CRUISE REPORT: P06W_2003, P06E_2003, I03_2003, A10_2003 
(Updated OCT 2005)

A.  HIGHLIGHTS

A.1.  CRUISE SUMMARY INFORMATION

          WOCE section designation  P06W_2003  (Leg 1)             
Expedition designation (ExpoCodes)  49NZ20030803                   
                  Chief Scientists  Fukasawa/JAMSTEC               
                      Cruise Dates  August 3, 2003 - September 5, 2003 
                              Ship  R/V MIRAI                      
                     Ports of call  Brisbane, Australia - Papeete, Tahiti 
                Number of Stations  121                            
                                                  29° 59.72' S  
             Geographic Boundaries  153° 29.00' E              144° 49.87' W 
                                                  32° 31.77' S 
      Floats and drifters deployed  10 Argo Floats 
    Moorings deployed or recovered  none


          WOCE section designation  P06E_2003 (leg 2)
Expedition designation (ExpoCodes)  49NZ20030909     
                  Chief Scientists  Watanabe/NIRE    
                      Cruise Dates  September 9, 2003 - October  16, 2003 
                              Ship  R/V MIRAI        
                     PORTS OF CALL  Papeete, Tahiti - Valparaiso, Chile
                Number of Stations  116 
                                                  32° 10.17' S
             Geographic Boundaries  149° 49.49' W              71° 29.94' W
                                                  32° 40.43' S 
      Floats and drifters deployed  18 Argo Floats 
    Moorings deployed or recovered  none


          WOCE section designation  A10_2003 (leg 4)               
Expedition designation (ExpoCodes)  49NZ200311060                  
                  Chief Scientists  Yoshikawa/JAMSTEC              
                             Dates  November  6, 2003 - December  5, 2003 
                              Ship  R/V MIRAI                      
                     PORTS OF CALL  Santos, Brazil - Cape Town, South Africa 
                Number of Stations  111 
                                                  27° 43.90' S  
             Geographic Boundaries  47° 23.27' W               15° 00.15' E
                                                  30° 13.21' S
      Floats and drifters deployed  21 Argo Floats 
    Moorings deployed or recovered  none



          WOCE section designation  I03_2003 (Leg 5)
Expedition designation (ExpoCodes)  49NZ20031209             
                  Chief Scientists  Fukasawa/JAMSTEC         
                      Cruise Dates  December  9, 2003 - January  24, 2004 
                              Ship  R/V MIRAI                
                     PORTS OF CALL  Cape Town, South Africa - Tamatave, Madagascar - 
                                    Port Louis, Mauritius - Fremantle, Australia 
                Number of Stations  145 
                                                  19° 58.06' S  
             Geographic Boundaries  35° 21.94' E               113° 45.52' E
                                                  24° 40.29' S
      Floats and drifters deployed  13 Argo Floats 
    Moorings deployed or recovered  none

                               CHIEF SCIENTISTS 

          MASAO FUKASAWA (Leg 1 and 5) 
           Japan Agency for Marine-Earth Science and Technology (JAMSTEC) 
           2-15, Natsushima, Yokosuka, 237-0061, Japan 
           Tel: +81-46-867-9470 Fax: +81-46-867-9455 
           E-mail: fksw@jamstec.go.jp 

          SHUICHI WATANABE (Leg 2) 
           Japan Agency for Marine-Earth Science and Technology (JAMSTEC)
           690 Kitasekine, Sekine, Mutsu City, Aomori, 035-0022, Japan 
           Tel: +81-175-45-1033 Fax: +81-175-45-1079 
           E-mail: swata@jamstec.go.jp 

          YASUSHI YOSHIKAWA (Leg 4) 
           Japan Agency for Marine-Earth Science and Technology (JAMSTEC) 
           2-15, Natsushima, Yokosuka, 237-0061, Japan 
           Tel: +81-46-867-9473 Fax: +81-46-867-9455 
           E-mail: yoshikaway@jamstec.go.jp 




                WHP P06, A10, I03/I04 REVISIT DATA BOOK 
             Blue Earth Global Expedition 2003 (BEAGLE2003)
                               Volume 1 



10, March, 2005 Published 
Edited by Hiroshi Uchida (JAMSTEC) and Masao Fukasawa (JAMSTEC) 

Published by (c) JAMSTEC, Yokosuka, Kanagawa, 2005 
Japan Agency for Marine-Earth Science and Technology 
2-15 Natsushima, Yokosuka, Kanagawa. 237-0061, Japan 
Phone +81-46-867-9474, Fax +81-46-867-9455 

Printed by Aiwa Printing Co., Ltd. 
3-22-4 Takanawa, Minato-ku, Tokyo 108-0074, Japan


CONTENTS (VOLUME 1) 
  Preface 
        M. Fukasawa (JAMSTEC) 
  Documents and .sum files 

  CRUISE NARRATIVE 
        M. Fukasawa, S. Watanabe and Y. Yoshikawa (JAMSTEC) 

  UNDERWAY MEASUREMENTS 
    Navigation and Bathymetry 
        S. Sueyoshi, S. Okumura, Y. Imai, K. Maeno, S. Okumura, 
        W. Tokunaga, R. Kimura (GODI) and T. Fujiwara (JAMSTEC) 
    Surface Meteorological Observation 
        K. Yoneyama (JAMSTEC), S. Okumura, S. Sueyoshi, Y. Imai, 
        S. Okumura, K. Maeno, W. Tokunaga, N. Nagahama 
        and R. Kimura (GODI) 
    Thermosalinograph and related measurements 
        M. Fukasawa, T. Kawano (JAMSTEC), T. Seike, T. Miyashita 
        and N. Komai (MWJ) 
    Underway pCO2 
        A. Murata (JAMSTEC), M. Kitada and M. Kamata (MWJ) 
    Acoustic Doppler Current Profiler 
        Y. Yoshikawa (JAMSTEC) and S. Sueyoshi (GODI) 

  STATION SUMMARY 
  BEAGLE2003 .sum files 

  Figures 
        Figure caption 
        Observation lines 
        Station locations 
        Bathymetry 
        Surface wind 
        Sea surface temperature and salinity 
        ∆pCO2 
        Surface current 

  .sum, .sea, .wct and other data files CD-ROM on the back cover


CONTENTS (VOLUME 2) 
  Documents 
    HYDROGRAPHIC MEASUREMENT TECHNIQUES AND CALIBRATIONS 
    CTD/O2 
        H. Uchida, M. Fukasawa (JAMSTEC), 
        W. Schneider (Univ. of Concepcion), M. Rosenberg (ACE CRC), 
        S. Ozawa, H. Matsunaga and K. Oyama (MWJ) 
    Salinity 
        T. Kawano (JAMSTEC), T. Matsumoto, N. Takahashi (MWJ) 
        and T. Watanabe (Nagasaki Univ.) 
    Oxygen 
        Y. Kumamoto, S. Watanabe (JAMSTEC), A. Nishina (Kagoshima Univ.), 
        K. Matsumoto (JAMSTEC), E. de Braga (Univ. of Sao Paulo), 
        T. Seike, I. Yamazaki, T. Miyashita and N. Komai (MWJ) 
    Nutrients 
        M. Aoyama (MRI/JMA), J. Hamanaka, A. Kubo, Y. Otsubo, 
        K. Sato, A. Yasuda and S. Yokogawa (MWJ) 
    Dissolved inorganic carbon (CT) 
        A. Murata (JAMSTEC), M. Kitada, M. Kamata, 
        M. Moro and T. Fujiki (MWJ) 
    Total alkalinity (AT) 
        A. Murata (JAMSTEC), F. Shibata and T. Ohama (MWJ) 
    pH 
        A. Murata (JAMSTEC), F. Shibata and T. Ohama (MWJ) 
    Lowered Acoustic Doppler Current Profiler 
        Y. Yoshikawa (JAMSTEC), L. Nonnato (Univ. of Sao Paulo) 
        and O. Sugimoto (JAMSTEC) 

  Figures 
    Figure caption 
    Observation lines 
    Station locations 
    Cross-sections 
        Potential temperature 
        Salinity 
        Salinity (with SSW correction) 
        Density (∑theta) 
        Density (∑4) 
        Neutral density (gamma n) 
        Oxygen 
        Silicate 
        Nitrate 
        Nitrite 
        Phosphate 
        Dissolved inorganic carbon 
        Total alkalinity 
        pH 
    Difference between WOCE and BEAGLE2003 
        Potential temperature 
        Salinity (with SSW correction) 
        Oxygen 


CONTENTS (VOLUME 3) 
  Documents 
    HYDROGRAPHIC MEASUREMENT TECHNIQUES AND CALIBRATIONS (continued) 
    CFCs 
        K. Sasaki (JAMSTEC), Y. Watanabe (Hokkaido Univ.), 
        M. Wakita (JAMSTEC), K. Sagishima, K. Wataki, H. Yamamoto, 
        Y. Sonoyama (MWJ), S. Tanaka (Hokkaido Univ.) 
        and S. Watanabe (JAMSTEC) 
    ∂13C and ∆14C of Dissolved Inorganic Carbon 
        Y. Kumamoto (JAMSTEC) 
    Total Organic Carbon 
        M. Wakita, A. Murata (JAMSTEC) and H. Ogawa (ORI, Univ. of Tokyo) 

  Figures 
    Figure caption 
    Observation lines 
    Station locations 
    Cross-sections 
        CFC-11 
        CFC-12 
        CFC113 
        ∆14C 
        ∂13C 
        Total organic carbon 

  Updated .sea files  CD-ROM on the back cover 

(Volume 3 will be published in 2007.)




                       DEDICATED TO LATE PROFESSOR YASUNOBU MATSUURA FROM SAO PAULO UNIVERSITY.



Zonal WOCE Hydrographic Program lines (WHP lines) of P06, A10, and I05 are located in the 
southern hemisphere and well known that they compose the Scorpio line in the southern 
hemisphere. Ocean Observation Research Department of Japan Marine Science and Technology 
Center, which was reformed as Institute of Observational Research for Global Change of Japan 
Agency for Marine-Earth Science and Technology (JAMSTEC) in 2004, planned an ambitious 
scientific cruise to occupy all of these lines at a time in order to investigate the possible 
decadal changes in the Antarctic Overturn System. They had reached a puzzling observational 
fact that the bottom water temperature increased along P01 and P17N, which were located at the 
terminal regions of the global overturn system in the northern-end of the North Pacific, 
through collaborative WHP revisits with IOS, Canada. Same warming of the bottom water as this 
one was also found at each WHP cross-point between P03 (23.5N) and several meridional WHP 
lines. The warming rate was so large that the increase in the temperature of bottom water 
corresponded to 0.5 degree Celsius warming for one century of duration. It was natural, at 
least for us, to suspect some non-linear and abrupt changes was taking place in the Antarctic 
Overturn System in the southern hemisphere which could have propagated in the bottom water at 
much faster phase speed than the advection of water itself.

This plan of the hydrographic observation around the southern hemisphere, which might compare 
with the global cruise of Magellan, was named as Blue Earth Global Expedition 2003 (BEAGLE2003) 
and promoted by JAMSTEC as a commemorative action of 30's anniversary of its establishment and 
also supported by the Partnership for Observation of the Global Ocean (POGO) as a following-up 
of the Sao Paulo Declaration in POGO2001 that recommended the enhancement of the ocean 
observation and the capacity building in the southern hemisphere. Although, during the 
preparation for the cruise, the Indian sector I05 in the original plan was substituted to I04 
and I03 in order to make the international collaboration of global hydrography more effective, 
JAMSTEC could invite more than 30 scientists and students from countries in the southern 
hemisphere as participants of BEAGLE2003 on the board of R/V Mirai. Also International Ocean 
Color Coordinating Group (IOCCG) dispatched eight trainees from various countries through POGO. 
The cruise was started on 3 August 2003 from Brisbane, Australia and finished 19 February 2004 
at Fremantle, Australia. During BEAGLE2003, four hundreds and ninety three (493) WOCE 
hydrographic stations were re-occupied, sixty Argo floats were launched and bottom cores were 
sampled at six stations.

This data book contains CTD data, bottle data and data from underway observations with their 
documentations along the circum southern hemispheric cruise track of BEAGLE2003. Also the 
bottom topography data measured by the multi narrow beam on R/V Mirai are included. At this 
stage, unfortunately, analyses of some radioactive carbon samples are not completed yet and 
they will be supplemented to this data book later. I heartily hope that BEAGLE2003 cruise will 
inspire young scientists with deep interests in the ocean science and that data from BEAGLE2003 
will help ocean scientists to have better understanding of the ocean through this data book.

Finally, it should be noted here that BEAGLE2003 was supported by many people in the world. 
Without their supports, we could not work out this ambitious cruise. I would like to express my 
heartfelt thanks to all people who supported BEAGLE2003 though I do not name all of them here 
because they are so many.  However, special thanks should be extended to Capt. Akamine from R/V 
Mirai with all crew members, Dr. Sathyendranath from POGO, Dr. Church from CSIRO, Dr. Stuardo 
from University of Conception, Dr. Weber from Sao Paulo University and Dr. Field from 
University of Cape Town because they were the first colleagues when we set sail into "the ocean 
of BEAGLE2003".


                                               at Mutsu Institute of Oceanography, 2005 Spring 

                                                                    BEAGLE2003 Chief Scientist 
                                                                                Masao Fukasawa  

                                      Ocean General Circulation Observational Research Program 
                                         Institute of Observational Research for Global Change 
                                          Japan Agency for Marine-Earth Science and Technology 




1 CRUISE NARRATIVE 

1.1 HIGHLIGHT 

WOCE LINE DESIGNATION:  P06W, P06C, P06E, A10, I03 and I04 

EXPEDITION DESIGNATION: MR03-K04 Leg 1, Leg 2, Leg 4 and Leg 5 

CHIEF SCIENTISTS AND AFFILIATION: 

                        MASAO FUKASAWA (Leg 1 and 5) 
                          Japan Agency for Marine-Earth Science and Technology (JAMSTEC) 
                          2-15, Natsushima, Yokosuka, 237-0061, Japan 
                          Tel: +81-46-867-9470 Fax: +81-46-867-9455 
                          E-mail: fksw@jamstec.go.jp 

                        SHUICHI WATANABE (Leg 2) 
                          Japan Agency for Marine-Earth Science and Technology (JAMSTEC)
                          690 Kitasekine, Sekine, Mutsu City, Aomori, 035-0022, Japan 
                          Tel: +81-175-45-1033 Fax: +81-175-45-1079 
                          E-mail: swata@jamstec.go.jp 

                        YASUSHI YOSHIKAWA (Leg 4) 
                          Japan Agency for Marine-Earth Science and Technology (JAMSTEC) 
                          2-15, Natsushima, Yokosuka, 237-0061, Japan 
                          Tel: +81-46-867-9473 Fax: +81-46-867-9455 
                          E-mail: yoshikaway@jamstec.go.jp 

SHIP:                   R/V MIRAI 

PORTS OF CALL:          Leg 1  Brisbane, Australia - Papeete, Tahiti 
                        Leg 2  Papeete, Tahiti - Valparaiso, Chile 
                        Leg 4  Santos, Brazil - Cape Town, South Africa 
                        Leg 5  Cape Town, South Africa - Tamatave, Madagascar - 
                               Port Louis, Mauritius - Fremantle, Australia 

CRUISE DATES:           Leg 1  August    3, 2003 - September 5, 2003 
                        Leg 2  September 9, 2003 - October  16, 2003 
                        Leg 4  November  6, 2003 - December  5, 2003 
                        Leg 5  December  9, 2003 - January  24, 2004 

NUMBER OF STATIONS:     Leg 1  121 CTD/Carousel Water Sampler 
                        Leg 2  116 CTD/Carousel Water Sampler 
                        Leg 4  111 CTD/Carousel Water Sampler 
                        Leg 5  145 CTD/Carousel Water Sampler 

GEOGRAPHIC BOUNDARIES:  Leg 1  153° 29.00' E  to 144° 49.87' W 
                                29° 59.72' S  to  32° 31.77' S 
                        Leg 2  149° 49.49' W  to  71° 29.94' W 
                                32° 10.17' S  to  32° 40.43' S 
                        Leg 4   47° 23.27' W  to  15° 00.15' E 
                                27° 43.90' S  to  30° 13.21' S 
                        Leg 5   35° 21.94' E  to 113° 45.52' E 
                                19° 58.06' S  to  24° 40.29' S

FLOATS AND DRIFTERS DEPLOYED: 
                        Leg 1   10 Argo Floats 
                        Leg 2   18 Argo Floats 
                        Leg 4   21 Argo Floats 
                        Leg 5   13 Argo Floats 
 
MOORING DEPLOYED OR RECOVERED MOORING:  NONE 


1.2  CRUISE SUMMARY 

(1) GEOGRAPHIC BOUNDARIES 

MR03-K04 leg 1 occupied stations along 32°30' S from 153°29' E to 144°50' W. MR03-K04 leg 2 
occupied stations along 32°30' S from 149°50' W to 71°30' W.  Two stations, No. 125 and 127, 
were revisited to be compared with leg 1.  MR03-K04 leg 4 occupied stations along 30° S from 
47°23' W to 15°E.  MR03-K04 leg 5a (Cape Town to Tamatave) occupied stations along 24°40' S 
from 35°22' E to 43°52' E.  MR03-K04 leg 5b (Tamatave to Fremantle via Port Louise) occupied 
stations along 20°S from 48°55' E to 113°46' E 


(2) Station occupied 

A total of 493 stations were occupied using a Sea-Bird Electronics 36 bottle Carousel equipped 
with 36 12 liter Niskin X water sample bottles, a SBE911plus equipped with SBE35 deep ocean 
standards thermometer, SBE43 oxygen sensor, Seapoint sensors Inc. Chlorophyll Fluorometer (except 
for Leg.2) and Benthos Inc Altimeter and RDI Workhorse Monitor ADCP.  Cruise track and station 
location are shown in Fig. 1.2.1 to Fig. 1.2.5 


(3) Sampling and measurements 

Water samples were analyzed for salinity, oxygen, nutrients, CFC11,12, 113, total alkalinity, 
DIC and pH.  The sampling layers in dbar were 10, 50, 100, 150, 200, 250, 300, 400, 500, 600, 
700, 800, 900, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 2800, 3000, 3250, 3500, 
3750, 4000, 4250, 4500, 4750, 5000, 5250, 5500, 5750 and bottom (minus 10 m).  Sample for Ar, 
14C, 13C, 3He/4He, 137Cs, Plutonium and 3H, TOC were also collected.  The bottle depth diagram 
is shown in Fig. 1.2.6.  Measurements of autotrophic biomass (epifluorescence and chlorophyll 
a) by surface LV and bio-optical measurement (scatter and transfer) were made in the day time.  
Underway measurements of pCO2, temperature, salinity, oxygen, surface current, bathymetry and 
meteorological parameters were made along the cruise track 

 
Figure 1.2.1.  Cruise track.
Figure 1.2.2.  Station location of leg 1.  Red dot and closed circle indicate 
               CTD station and Argo float deployment position, respectively.
Figure 1.2.3.  Same as Figure 1.2.2, but for leg 2.
Figure 1.2.4.  Same as Figure 1.2.2, but for leg 4.
Figure 1.2.5.  Same as Figure 1.2.2, but for leg 5.
Figure 1.2.6.  Bottle depth diagram.


(4) Floats and Drifters deployed 

62 ARGO floats were launched along the cruise track as a joint research program among JAMSTEC 
(FORGC), Scripps Institute of Oceanography (SIO), Atlantic Oceanographic and Meteorological 
Laboratory (AOML) and the Southampton Oceanography Centre (SOC).  The Launched positions of the 
ARGO floats are listed in Table.1.2.1.


Table 1.2.1.  Launched positions of the ARGO floats.
____________________________________________________________________________________________

        |      |      |  ARGOS  | Date and Time  | Date and Time  |
 Owner  | Type |  S/N |   PTT   |   of Reset     |   of Launch    |   Location of Launch
        |      |      |   ID    |    (UTC)       |    (UTC)       |  
 -------|------|------|---------|----------------|----------------|------------------------
 FORSGC | APEX |  927 |  25184  | 19:36, Aug. 21 | 20:42, Aug. 21 | 32-30.74 S, 171-55.13 W 
 SIO    | SOLO | 2185 | unknown | 00:08, Jul. 31 | 09:56, Aug. 23 | 32-31.01 S, 168-59.49 W 
 FORSGC | APEX |  928 |  25185  | 00:08, Jul. 31 | 18:24, Aug. 24 | 32-28.23 S, 165-48.00 W 
 SIO    | SOLO | 2199 | unknown | 00:08, Jul. 31 | 03:42, Aug. 27 | 32-29.45 S, 163-08.99 W 
 FORSGC | APEX |  929 |  25186  | 07:22, Aug. 28 | 09:13, Aug. 28 | 32-30.21 S, 159-48.14 W 
 FORSGC | APEX |  930 |  25187  | 03:21, Aug. 29 | 04:21, Aug. 29 | 32-30.38 S, 157-17.91 W 
 FORSGC | APEX |  931 |  25263  | 02:58, Aug. 30 | 05:19, Aug. 30 | 32-28.46 S, 154-01.00 W 
 SIO    | SOLO | 2202 | unknown | 08:35, Jul. 31 | 09:02, Aug. 31 | 32-30.95 S, 150-30.71 W 
 FORSGC | APEX |  932 |  25280  | 01:55, Sep. 01 | 03:25, Sep. 01 | 32-31.12 S, 148-08.70 W 
 SIO    | SOLO | 2203 | unknown | 00:11, Jul. 31 | 07:25, Sep. 02 | 32-31.12 S, 144-50.01 W 
 FORSGC | APEX |  933 |  25284  | 06:45, Sep. 14 | 08:05, Sep. 14 | 32-28.94 S, 142-20.93 W 
 SIO    | SOLO | 2204 | unknown | 22:52, Jul. 30 | 09:18, Sep. 15 | 32-30.46 S, 139-17.46 W 
 FORSGC | APEX |  934 |  25287  | 12:11, Sep. 16 | 13:25, Sep. 16 | 32-28.94 S, 136-00.61 W 
 SIO    | SOLO | 2205 | unknown | 22:55, Jul. 30 | 15:43, Sep. 17 | 32-29.30 S, 133-19.78 W 
 FORSGC | APEX |  935 |  25288  | 19:40, Sep. 18 | 20:41, Sep. 18 | 32-29.19 S, 129-59.26 W 
 SIO    | SOLO | 2206 | unknown | 22:57, Jul. 30 | 18:32, Sep. 19 | 32-28.75 S, 127-19.00 W 
 FORSGC | APEX |  936 |  25293  | 13:41, Sep. 21 | 14:53, Sep. 21 | 32-29.58 S, 124-00.23 W 
 SIO    | SOLO | 2207 | unknown | 22:59, Jul. 30 | 11:53, Sep. 22 | 32-29.87 S, 121-18.95 W 
 FORSGC | APEX |  660 |  11478  | 14:10, Sep. 23 | 15:27, Sep. 23 | 32-30.42 S, 117-59.04 W 
 SIO    | SOLO | 2208 | unknown | 23:00, Jul. 30 | 13:18, Sep. 24 | 32-29.33 S, 115-19.56 W 
 FORSGC | APEX |  938 |  25594  | 12:40, Sep. 25 | 14:00, Sep. 25 | 32-29.97 S, 111-59.55 W 
 SIO    | SOLO | 2209 | unknown | 23:02, Jul. 30 | 11:03, Sep. 26 | 32-28.79 S, 109-20.87 W 
 FORSGC | APEX |  940 |  25596  | 16:57, Sep. 27 | 17:30, Sep. 27 | 32-29.46 S, 106-01.87 W 
 SIO    | SOLO | 2210 | unknown | 23:59, Jul. 30 | 16:20, Sep. 28 | 32-30.13 S, 103-00.53 W 
 FORSGC | APEX |  939 |  25595  | 18:20, Sep. 30 | 20:06, Sep. 30 | 32-30.80 S, 100-00.49 W 
 SIO    | SOLO | 2211 | unknown | 00:02, Jul. 31 | 17:08, Oct. 01 | 32-30.67 S, 097-20.23 W 
 FORSGC | APEX |  941 |  25597  | 18:27, Oct. 02 | 19:50, Oct. 02 | 32-30.93 S, 093-59.28 W 
 SIO    | SOLO | 2212 | unknown | 00:04, Jul. 31 | 16:50, Oct. 03 | 32-31.49 S, 091-18.75 W 
 AOML   | SOLO |  262 | unknown | 04:47, Nov. 10 | 06:24, Nov. 10 | 29-23.73 S, 041-44.59 W
 AOML   | SOLO |  260 | unknown | 11:15, Nov. 11 | 12:32, Nov. 11 | 30-05.90 S, 039-01.21 W 
 AOML   | SOLO |  264 | unknown | 12:15, Nov. 17 | 13:46, Nov. 17 | 29-59.34 S, 025-51.76 W 
 AOML   | SOLO |  261 | unknown | 08:15, Nov. 18 | 09:44, Nov. 18 | 30-00.19 S, 023-18.64 W 
 AOML   | SOLO |  263 | unknown | 10:50, Nov. 19 | 12:03, Nov. 19 | 29-59.69 S, 019-53.28 W 
 AOML   | SOLO |  265 | unknown | 09:55, Nov. 20 | 11:22, Nov. 20 | 29-59.02 S, 017-01.38 W 
 SOC    | APEX |  865 | unknown | 06:35, Nov. 21 | 08:32, Nov. 21 | 29-59.55 S, 014-19.74 W 
 SOC    | APEX | 1190 | unknown | 21:48, Nov. 21 | 23:10, Nov. 21 | 29-58.61 S, 012-18.93 W 
 SOC    | APEX | 1191 | unknown | 13:26, Nov. 22 | 15:17, Nov. 22 | 29-59.65 S, 010-19.76 W 
 SOC    | APEX | 1192 | unknown | 07:02, Nov. 23 | 08:54, Nov. 23 | 29-59.62 S, 008-09.22 W 
 SOC    | APEX |  886 | unknown | 20:44, Nov. 23 | 21:52, Nov. 23 | 30-00.33 S, 006-28.91 W 
 SOC    | APEX | 1193 | unknown | 09:07, Nov. 24 | 10:27, Nov. 24 | 29-59.70 S, 004-48.50 W 
 SOC    | APEX | 1194 | unknown | 01:17, Nov. 26 | 02:39, Nov. 26 | 30-01.98 S, 002-18.17 W 
 SOC    | APEX | 1195 | unknown | 14:10, Nov. 26 | 15:13, Nov. 26 | 29-58.98 S, 000-43.56 W 
 SOC    | APEX | 1196 | unknown | 05:05, Nov. 27 | 06:51, Nov. 27 | 29-43.13 S, 001-08.20 E 
 SOC    | APEX |  887 | unknown | 01:47, Nov. 28 | 02:53, Nov. 28 | 29-27.83 S, 003-19.07 E 
 SOC    | APEX | 1197 | unknown | 18:58, Nov. 28 | 20:17, Nov. 28 | 29-44.82 S, 005-07.75 E 
 SOC    | APEX | 1198 | unknown | 08:07, Nov. 29 | 09:30, Nov. 29 | 29-43.79 S, 006-47.35 E 
 SOC    | APEX | 1199 | unknown | 22:12, Nov. 29 | 23:30, Nov. 29 | 29-44.65 S, 008-29.14 E 
 SOC    | APEX | 1200 | unknown | 10:39, Nov. 30 | 12:42, Nov. 30 | 29-43.97 S, 009-58.78 E 
 SOC    | APEX | 1201 | unknown | 06:25, Dec. 01 | 07:46, Nov. 01 | 29-44.47 S, 011-47.97 E 
 FORSGC | APEX | 1077 |  20647  | 00:21, Dec. 26 | 01:49, Dec. 26 | 20-22.87 S, 059-49.40 E 
 FORSGC | APEX | 1078 |  20724  | 16:45, Dec. 28 | 17:47, Dec. 28 | 20-21.16 S, 062-51.36 E 
 FORSGC | APEX | 1080 |  20773  | 18:42, Dec. 29 | 20:24, Dec. 29 | 19-59.85 S, 065-58.88 E 
 FORSGC | APEX | 1079 |  20725  | 17:37, Dec. 30 | 18:48, Dec. 30 | 19-59.81 S, 068-47.65 E 
 FORSGC | APEX | 1097 |  21997  | 20:16, Jan. 01 | 21:50, Jan. 01 | 19-58.97 S, 071-41.65 E 
 FORSGC | APEX | 1098 |  22083  | 05:47, Jan. 03 | 06:15, Jan. 03 | 19-59.11 S, 074-43.92 E 
 FORSGC | APEX | 1075 |  20590  | 07:39, Jan. 04 | 09:05, Jan. 04 | 19-59.74 S, 077-37.42 E 
 FORSGC | APEX | 1076 |  20644  | 09:53, Jan. 05 | 11:18, Jan. 05 | 19-58.41 S, 080-32.71 E 
 FORSGC | APEX | 1094 |  21341  | 12:04, Jan. 06 | 13:28, Jan. 06 | 19-59.53 S, 083-24.76 E 
 FORSGC | APEX | 1073 |  20572  | 18:39, Jan. 07 | 20:00, Jan. 07 | 19-58.51 S, 086-28.15 E 
 FORSGC | APEX |  947 |  26426  | 04:45, Jan. 10 | 06:20, Jan. 10 | 19-59.53 S, 089-59.70 E 
 FORSGC | APEX |  946 |  26080  | 14:05, Jan. 11 | 15:58, Jan. 11 | 19-58.80 S, 092-48.40 E 
 FORSGC | APEX | 1096 |  21561  | 18:35, Jan. 12 | 20:10, Jan. 12 | 19-59.36 S, 096-04.02 E 
____________________________________________________________________________________________


(5) MOORINGS DEPLOYED OR RECOVERED 
    No mooring was deployed nor recovered during the cruise.

 
1.3 List of Principal Investigator and Person in Charge on the Ship 
    The principal investigator (PI) and the person in charge responsible for the 
    major parameters measured on the cruise are listed in Table 1.3.1.


TABLE 1.3.1.  List of PI and person in charge.
___________________________________________________________________________________
  Item             Principal Investigator(s)           Person in Charge 
 ---------------------------------------------------------------------------------
 HYDROGRAPHY 
 CTDO             Hiroshi Uchida (JAMSTEC) 1-5        Mark Rosenberg (ACE CRC) 1,4 
                    huchida@jamstec.go.jp               mark.rosenberg@utas.edu.au 
                  Masao Fukasawa (JAMSTEC) 1-5        Satoshi Ozawa (MWJ) 1,4,5 
                    fksw@jamstec.go.jp                  satoshi@mwj.co.jp 
                  Wolfgang Schneider                  Hiroshi Matsunaga (MWJ) 2,5 
                    (Univ. of Concepcion) 4,5         matsunaga@mwj.co.jp 
                    wschneid@udec.cl 
 LADCP            Yasushi Yoshikawa (JAMSTEC) 1-5     Satoshi Ozawa (MWJ) 1 
                    yoshikaway@jamstec.go.jp            satoshi@mwj.co.jp 
                                                      Hiroshi Matsunaga (MWJ) 2 
                                                        matsunaga@mwj.co.jp 
                                                      On Sugimoto (JAMSTEC) 4 
                                                      Luiz Vianna Nonnato 
                                                        (Univ. of Sao Paulo) 4 
                                                        luiz@ceres.io.usp.br 
                                                      Masao Fukasawa (JAMSTEC) 5 
                                                        fksw@jamstec.go.jp 
 XCTD             Tamaryn Morris (MCM) 5              Yasutaka Imai (GODI) 5 
                    tmorris@mcm.wcape.gov.za            imai@godi.co.jp 
                  Masao Fukasawa (JAMSTEC) 5 
                    fksw@jamstec.go.jp 
 Salinity         Takeshi Kawano (JAMSTEC) 1-5        Naoko Takahashi (MWJ) 1,4 
                    kawanot@jamstec.go.jp               takahashi@mwj.co.jp 
                                                      Takeo Matsumoto (MWJ) 2 
                                                        takem@mwj.co.jp 
                                                      Ken-ichi Katayama (MWJ) 5 
                                                        katayama@mwj.co.jp 
 Oxygen           Shuichi Watanabe (JAMSTEC)1-4       Takayoshi Seike (MWJ) 1,4,5 
                    swata@jamstec.go.jp                 seike@mwj.co.jp 
                  Ayako Nishina (Kagoshima Univ.) 5   Tomoko Miyashita (MWJ) 2,5 
                    nishina@fish.kagoshima-u.ac.jp      miyashita@mwj.co.jp 
 Nutrients        Michio Aoyama (MRI/JMA) 1-5         Junko Hamanaka (MWJ) 1,4 
                    maoyama@mri-jma.go.jp               hamanaka@mwj.co.jp 
                                                      Ken-ichiro Sato (MWJ) 2,5 
                                                        satok@mwj.co.jp 
 TCO2             Akihiko Murata (JAMSTEC) 1-5        Minoru Kamata (MWJ) 1,4 
                    akihiko.murata@jamstec.go.jp        kamata@mwj.co.jp 
                                                      Mikio Kitada (MWJ) 2,5 
                                                        kitada@mwj.co.jp 
 Alkalinity       Akihiko Murata (JAMSTEC) 1-5        Fuyuki Shibata (MWJ) 1,4 
                    akihiko.murata@jamstec.go.jp        shibataf@mwj.co.jp
                                                      Taeko Ohama (MWJ) 2,5 
                                                        ohama@mwj.co.jp 
 pH               Akihiko Murata (JAMSTEC) 1-5        Toru Fujiki (MWJ) 1,4 
                    akihiko.murata@jamstec.go.jp        fujiki@mwj.co.jp 
                                                      Masaki Moro (MWJ) 2 
                                                        moro@mwj.co.jp 
                                                      Taeko Ohama (MWJ) 5 
                                                        ohama@mwj.co.jp 
 CFCs             Yutaka Watanabe (Hokkaido U) 1-5    Ken-ichi Sasaki (JAMSTEC) 1,4,5 
                    yywata@ees.hokudai.ac.jp            ksasaki@jamstec.go.jp 
                                                      Masahide Wakita (JAMSTEC) 2 
                                                        mwakita@jamstec.go.jp 
                                                      Katsuhiro Sagishima (MWJ) 4 
                                                        ksagi@mwj.co.jp 
                                                      Yuichi Sonoyama (MWJ) 5 
                                                        sonoyama@mwj.co.jp 
 ∆14C             Yuichiro Kumamoto (JAMSTEC) 1-5     Yuichiro Kumamoto (JAMSTEC) 1,2 
                    kumamoto@jamstec.go.jp              kumamoto@jamstec.go.jp 
                                                      Akihiko Murata (JAMSTEC) 4,5 
                                                        akihiko.murata@jamstec.go.jp 
 TOC              Akihiko Murata (JAMSTEC) 1-5        Akihiko Murata (JAMSTEC) 1,2 
                    akihiko.murata@jamstec.go.jp        akihiko.murata@jamstec.go.jp 
                                                      Minoru Kamata (MWJ) 4 
                                                        kamata@mwj.co.jp 
                                                      Mikio Kitada (MWJ)5 
                                                        kitada@mwj.co.jp 
 3He/4He          Shuichi Watanabe (JAMSTEC) 1,2,5    Yuichiro Kumamoto (JAMSTEC) 1 
                    swata@jamstec.go.jp                 kumamoto@jamstec.go.jp 
                                                      Shuichi Watanabe (JAMSTEC) 2 
                                                        swata@jamstec.go.jp 
                                                      Masahide Wakita (JAMSTEC) 5 
                                                        mwakita@jamstec.go.jp 
 Cs,Pu,3H,Sr      Michio Aoyama (MRI/JMA) 1-5         Akira Takeuchi (KANSO) 1,2 
                    maoyama@mri-jma.go.jp               takeuti_akira@kanso.co.jp 
                                                      Sang-Han Lee (IAEA) 4 
                                                        S.Lee@iaea.org 
                                                      Beniamino Oregioni (IAEA) 5 
                                                        B.Oregioni@iaea.org 
 Ar/N2            Yutaka Watanabe (Hokkaido U) 1-5    Shin-ichi Tanaka (Hokkaido Univ.) 1-5 
                    yywata@ees.hokudai.ac.jp            shinichi@ees.hokudai.ac.jp 
 N2O              Laura Farias (RP POC) 2             Mauricio Gallegos (RP POC) 2 
                    lfarias@profc.udec.cl               mauricio@profc.udec.cl 
 Primary          Brian Irwin (BIO) 1                 Brian Irwin (BIO) 1 
 Productivity       brian.Irwin@ns.sympatico.ca         brian.Irwin@ns.sympatico.ca 
                  Gadiel Alarcon (U of Concepcion) 2  Gadiel Alarcon (Univ. of Concepcion) 2 
                    gadiel@profc.udec.cl                gadiel@profc.udec.cl 
                  Vivian Lutz (INIDEP) 4              Vivian Lutz (INIDEP) 4 
                    vlutz@inidep.edu.ar                 vlutz@inidep.edu.ar
                  Prudence Bonham (CSIRO) 5           Prudence Bonham (CSIRO) 5 
                    Pru.Bonham@csiro.au                 Pru.Bonham@csiro.au 
 Chlorophyll-a    Brian Irwin (BIO) 1                 Brian Irwin (BIO) 1 
                    brian.Irwin@ns.sympatico.ca         brian.Irwin@ns.sympatico.ca 
                  Gadiel Alarcon (U of Concepcion) 2  Gadiel Alarcon (Univ. of Concepcion) 2 
                    gadiel@profc.udec.cl                gadiel@profc.udec.cl 
                  Vivian Lutz (INIDEP) 4              Vivian Lutz (INIDEP) 4 
                    vlutz@inidep.edu.ar                 vlutz@inidep.edu.ar 
                  Prudence Bonham (CSIRO) 5           Prudence Bonham (CSIRO) 5 
                    Pru.Bonham@csiro.au                 Pru.Bonham@csiro.au 
 
 ---------------------------------------------------------------------------------
 UNDERWAY 
 ADCP             Yasushi Yoshikawa (JAMSTEC) 1-5     Sou-ichiro Sueyoshi (GODI) 1,4 
                    yoshikaway@jamstec.go.jp            sueyoshi@godi.co.jp 
                                                      Satoshi Okumura (GODI) 2 
                                                        okumura@godi.co.jp 
                                                      Yasutaka Imai (GODI) 5 
                                                        imai@godi.co.jp 
 Bathymetry       Toshiya Fujiwara (JAMSTEC) 1-5      Sou-ichiro Sueyoshi (GODI) 1,4 
                    toshi@jamstec.go.jp                 sueyoshi@godi.co.jp 
                                                      Satoshi Okumura (GODI) 2 
                                                        okumura@godi.co.jp 
                                                      Yasutaka Imai (GODI) 5 
                                                        imai@godi.co.jp 
 Meteorology      Kunio Yoneyama (JAMSTEC) 1-5        Sou-ichiro Sueyoshi (GODI) 1,4 
                    yoneyamak@jamstec.go.jp             sueyoshi@godi.co.jp 
                                                      Satoshi Okumura (GODI) 2 
                                                        okumura@godi.co.jp 
                                                      Yasutaka Imai (GODI) 5 
                                                        imai@godi.co.jp 
 Thermo-          Takeshi Kawano (JAMSTEC) 1          Takayoshi Seike (MWJ) 1,4 
 salinograph        kawanot@jamstec.go.jp               seike@mwj.co.jp 
                  Masao Fukasawa (JAMSTEC) 2,4,5      Tomoko Miyashita (MWJ) 2,5 
                    fksw@jamstec.go.jp                  miyashita@mwj.co.jp 
 pCO2             Akihiko Murata (JAMSTEC) 1-5        Minoru Kamata (MWJ) 1,4 
                    akihiko.murata@jamstec.go.jp        kamata@mwj.co.jp 
                                                      Mikio Kitada (MWJ) 2,5 
                                                        kitada@mwj.co.jp 
 Fluorescence     Brian Irwin (BIO) 1                 Takayoshi Seike (MWJ) 1 
                    brian.Irwin@ns.sympatico.ca         seike@mwj.co.jp 
                  Gadiel Alarcon (U of Concepcion) 2  Tomoko Miyashita (MWJ) 2 
                    gadiel@profc.udec.cl                miyashita@mwj.co.jp 
 pN2O             Laura Farias (RP POC) 2             Mauricio Gallegos (RP POC) 2 
                    lfarias@profc.udec.cl               mauricio@profc.udec.cl 
 
 ---------------------------------------------------------------------------------
 FLOATS, DRIFTERS
 Argo float       Kensuke Takeuchi (JAMSTEC) 1-5      Tomoyuki Takamori (MWJ) 1,5 
                    takeuchi@fish-u.ac.jp               takamori@mwj.co.jp
                  Dean Roemmich (SIO) 1-5             Masao Fukasawa (JAMSTEC) 1,2,5 
                    droemmich@ucsd.edu                  fksw@jamstec.go.jp 
                                                      Takeo Matsumoto (MWJ) 2 
                                                        takem@mwj.co.jp 
                                                      Miki Yoshiike (MWJ) 4 
                                                      Yasushi Yoshikawa (JAMSTEC) 4 
                                                        yoshikaway@jamstec.go.jp 
                                                    
___________________________________________________________________________________
 
ACE CRC: Antarctic Climate and Ecosystems Cooperative Research Centre, Australia 
BIO:     Bedford Institute of Oceanography, Canada 
CSIRO:   Commonwealth Scientific and Industrial Research Organisation, Australia 
GODI:    Global Ocean Development Inc. 
IAEA:    International Atomic Energy Agency 
INIDEP:  Institute Nacional de Investigacion y Desarrollo Pesquero, Argentina 
JAMSTEC: Japan Marine Science and Technology Center 
KANSO:   Kansai Environmental Engineering Center Co., Ltd. 
MCM:     Marine and Coastal Management, South Africa 
MRI/JMA: Meteorological Research Institute, Japan Meteorological Agency 
MWJ:     Marine Works Japan, Ltd. 
RP POC:  Regional Program of Physical Oceanographic and Climate, 
           University of Concepcion, Chile 
SIO:     Scripps Institution of Oceanography, U.S.A.


1.4  SCIENTIFIC PROGRAM AND METHODS 

(1) NATURE AND OBJECTIVES OF MR03-K04 CRUISE PROJECT 

It has been a decade since WOCE (World Ocean Circulation Experiment under WCRP) Hydrographic 
Program (WHP) was carried out in the world ocean.  Not only accurate hydrographic sections but 
also mass transports and their divergence/convergence have been clarified on a basin scale.  On 
the other hand, skills of measurements, especially those for carbon and CFC parameters, have 
been developed remarkably since the WOCE period.  Thus, repeated land-to-land hydrography is 
recommended by CLIVAR and JGOFS strongly

At the same time, the repeated hydrography or WHP revisit is desirable to investigate long term 
changes in inventories of heat, water mass, materials and their transports; in fact, revisit of 
a WHP line in the North Pacific found a bottom water warming, which can be attributed to 
changes in the water column in the southern ocean.

The magnitude of the warming was significant along its path way although very small

Ocean Observation and Research Department of JAMSTEC plans to revisit WHP lines in the Southern 
Hemisphere as one of research actions of their project TAV-PI (Transport And Variability in the 
Pacific and the Indian) to detect long term changes in the hydrographic structure and the 
Antarctic overturn by surveying WHP lines in the Pacific, the Atlantic and the Indian at one 
cruise.  This southern hemispheric circum navigation was highlighted at POGO-3 (December, 2001) 
as a following-up of the Sao Paulo Declaration of POGO-2 (January, 2001) that encourages and 
promotes both oceanographic studies and scientific capacity building in the southern hemisphere

The main purpose of this research cruise is to detect and quantify temporal changes in the 
Antarctic overturn System corresponding to the global ocean and the Southern Ocean warming 
during the last decade through high quality and spatially dense observation along old WHP (WOCE 
Hydrographic Program: 1991-2002) lines.  Scientific priorities, which lead to the above 
interest, are (1) changes in inventories of heat and freshwater, (2) changes in production 
rate, mass and pathway, (3) carbon and nutrients transport, (4) data base for model validation, 
and (5) ARGO sensor calibration

The other purposes of this cruise are (1) to observe surface meteorological and hydrological 
parameters as a basic dataset of the meteorology and oceanography, (2) to launch ARGO floats in 
order to monitor the changes of sub-surface temperature and salinity, (3) to observe global 
warming gas distribution, (4) to observe sea bottom topography, gravity and magnetic fields 
along the cruise track in order to understand the dynamics of ocean plate and the accompanying 
geophysical activities, (5) to obtain data on global distribution and optical characteristics 
of aerosols and clouds for the climatology and for study of the feasibility of the satellite 
observations, (6) to construct a model to predict a primary production from satellite 
observation and (7) to observe concentration of cloud droplets for verification of satellite 
observation


(2) CRUISE OVERVIEW 

MR03-K04 cruise was carried out during the period from August 3, 2003 to February 19, 2004.  
The cruise was realized by the cooperation of Australia (CSIRO,ACE-CRC), Chile, Brazil, South 
Africa, IOCCG, Argo Science Team (Scripps, AOML, SOC) and IAEA.  The cruise contained six legs.  
Legs 1, 2, 4 and 5 were revisit of WOCE Hydrographic Program sections P06W, P06C, P06E, A10, I04 
and I03.  A total of 493 stations were set to agree with the 1990s WOCE hydrographic observation 
stations.  At each station, full-depth CTD profile and up to 36 water samples were taken and 
analyzed.  Water samples were obtained from fixed layers with 12-liter Niskin bottles attached 
to 36-position SBE carousel water sampler.  The layers were 10, 50, 100, 150, 200, 150, 200, 
250, 300, 400, 500, 600, 700, 800, 900, 1000, 1200, 1400, 1600, 1800, 2000, 2200, 2400, 2600, 
2800, 3000, 3250, 3500, 3750, 4000, 4250, 4500, 4750, 5000, 5250, 5500, 5750 dbar and about 10 
dbar above the bottom

Scientists from various institutions and technicians from Marine Works Japan Ltd. (MWJ) were 
responsible for analyzing water sample for salinity, dissolved oxygen, nutrients, CFCs, total 
carbon contents, alkalinity and pH

They also contributed sampling for total organic carbon, radiocarbon and He.  A student of 
Hokkaido University joined CFCs measurement.  We accepted 18 POGO trainees from Indonesia, Sri 
Lanka, Argentina, Chile, Turkey, Peru, Colombia, Uruguay, Brazil, Namibia, Tanzania and South 
Africa. POGO group mainly analyzed Chlorophyll-a contents and bioactivity in seawater.  Twelve 
scientists from Chile, Brazil, Namibia, South Africa, Kenya, Mozambique, Madagascar and 
Mauritius were invited to the cruise.  A part of Chilean group brought pN2O system and 
collected seawater samples for N2O analysis.  Technicians from Global Ocean Development Inc. 
(GODI) have responsibility on a part of underway measurements such as current velocity by 
Acoustic Doppler Current Profiler (ADCP), geological parameters (topography, geo-magnetic field 
and gravity), and meteorological parameters.  Sixty-two ARGO floats prepared by JAMSTEC, 
Scripps Institute of Oceanography (SIO), Atlantic Oceanographic and Meteorological Laboratory 
(AOML) and the Southampton Oceanography Centre (SOC) were launched by MWJ technicians and ship 
crew


(3) CRUISE NARRATIVE 

R/V Mirai departed Brisbane, (Australia) on August 3, 2003.  She arrived at the first station 
on the same day and made a cast for 93m.  Although the depth was so shallow to trip only three 
bottles for analysis, we tripped additional 33 bottles to drill the method of sample drawing 
into all watchstanders.  We made a cast at station P06-121 on September 2, 2003 and then went 
to Papeete, Tahiti.  We observed 121 stations during leg 1 along approximately 32°30'S, which 
is WHP P06E and a half of P06C.  She arrived at Papeete on September 5 and left on September 9, 
2003 for the hydrographic section.  She arrived at the first station, P06-127, on September 12, 
2003.  Although the station was observed once during leg 1, we observed the station again to 
confirm the continuity.  P06-125 was also observed again for the same purpose.  We made a cast 
at station P06-4 on 12 October, 2003 and then headed to Valparaiso, Chile.  We observed 116 
stations (excluding two doubled stations) along approximately 32°30'S, which corresponds to the 
rest half of P06C and P06W.  R/V Mirai left Valparaiso on October 19, 2003 for Santos, Brazil.  
She went through Magellan Strait and arrived at Santos on November 2, 2003.  She left Santos on 
November 6, 2003 for Cape Town, South Africa.  The first station of the leg 4 was A10-622 and 
observed on November 7, 2003.  We observed 111 stations along approximately 32°S, which 
corresponds to WHP A10.  We observed the last station of leg 4, A10-100 on December 2, 2003 and 
arrived at Cape Town on December 5, 2003.  She left Cape Town on December 9, 2003 and called at 
Tamatave, Madagascar on December 20 and Port Louise, Mauritius on December 27 on her way to 
Fremantle, Australia.  The navigation along approximately 24°40' S from Cape Town to Tamatave 
is called leg 5a and corresponds to WHP I04.  The navigation along approximately 20°S from 
Tamatave to Fremantle is called leg 5b and corresponds to WHP I03.

We observed 145 stations during leg 5 and arrived at Fremantle, Australia on January 24, 2004


1.5  MAJOR PROBLEMS AND GOALS NOT ACHIEVED 

Fluorometer attached to CTD was broken at Station P06-166.  We replaced it with new one from 
leg 4.  So fluoresence was not measured after P06-166 and during leg 2.

Since an instrument for CFCs did not work during leg 1 and a half of leg 2, CFCs were measured 
at selected layers during this period 


1.6  LIST OF PARTICIPANTS 

The members of the scientific party are listed in Table 1.6.1 to 1.6.5 along with their main 
tasks undertaken on the cruise


TABLE 1.6.1.  List of cruise participants in leg 1. 
______________________________________________________________________________________
 
 Name           Main tasks                       Affiliation 
 ------------------------------------------------------------------------------------
 A. Albertino   Sampling                         Bogor Agricultural University 
 E. Barberi     Sampling                         Estacion de Fotobiologia Playa Union 
 T. Fujiki      TCO2                             MWJ 
 M. Fujisaki    CTD                              MWJ 
 M. Fukasawa    LADCP, Thermosalinograph, ARGO   JAMSTEC 
 J. Hamanaka    Nutrients                        MWJ 
 Y. Iribe       Sampling                         MWJ 
 B. Irwin       Bio-Optics                       BIO 
 M. Kamata      TCO2                             MWJ 
 T. Kawano      Salinity                         JAMSTEC 
 A. Kubo        Nutrients                        MWJ 
 Y. Kumamoto    Oxygen,                          14C JAMSTEC 
 K. Maeno       ADCP, Bathymetry, Meteorology    GODI 
 A. Murata      pH, Alkalinity, TCO2, pCO2, TOC  JAMSTEC 
 T. Nishihashi  Sampling                         MWJ 
 S. Okumura     ADCP, Bathymetry, Meteorology    GODI 
 Y. Oyama       Sampling                         MWJ 
 S. Ozawa       CTD                              MWJ 
 M. Rosenberg   CTD Data Processing              ACE CRC 
 K. Sagishima   CFC                              MWJ 
 K. Sasaki      CFC                              JAMSTEC 
 T. Seike       Oxygen                           MWJ 
 F. Shibata     pH, Alkalinity                   MWJ 
 A. Shioya      Sampling                         MWJ 
 S. Sueyoshi    ADCP, Bathymetry, Meteorology    GODI 
 N. Takahashi   Salinity                         MWJ 
 T. Takamori    CTD Operation                    MWJ 
 A. Takeuchi    Radio Nuclides                   KANSO 
 S. Tanaka      Ar, N2, CFC                      Hokkaido University 
 T. Tanaka      Sampling, Salinity               MWJ 
 A. Wada        Sampling, CFC                    MWJ 
 M. Wakita      CFC                              JAMSTEC 
 K. Wataki      CFC                              MWJ 
 H. Yamazaki    Sampling                         MWJ 
 I. Yamazaki    Oxygen                           MWJ 
 K. Yapa        Sampling                         Univ. of Ruhuna, Matara, Sri Lanka 
 S. Yokogawa    Nutrients                        MWJ 
 M. Yokota      Sampling, CFC                    MWJ 
 Y. Yoshikawa   ADCP, LADCP                      JAMSTEC 
 
    ACE CRC:   Antarctic Climate and Ecosystems Cooperative Research Centre, Australia 
    BIO:       Bedford Institute of Oceanography, Canada 
    GODI:      Global Ocean Development Inc. 
    JAMSTEC:   Japan Marine Science and Technology Center 
    KANSO:     Kansai Environmental Engineering Center Co., Ltd. 
    MWJ:       Marine Works Japan, Ltd.
______________________________________________________________________________________


TABLE 1.6.2.   List of cruise participants in leg 2. 
______________________________________________________________________________________
 
 Name           Main tasks                       Affiliation 
 ------------------------------------------------------------------------------------
 G. Alarcon     Bio-Optics                       Univ. of Concepcion 
 T. Chihara     Sampling                         MWJ 
 R. Fuenzalida  Sampling                         Univ. of Concepcion 
 M. Fukasawa    Data Management, LADCP           JAMSTEC 
 K. Katayama    ARGO, Salinity                   MWJ 
 R. Kimura      ADCP, Bathymetry, Meteorology    GODI 
 M. Kitada      DIC, pCO2                        MWJ 
 N. Komai       Oxygen                           MWJ 
 Y. Kumamoto    Oxygen, 14C, Sampling            JAMSTEC 
 D.B. Matellini Bio-Optics                       Peruvian Marine Research Institute 
 K. Matsumoto   Sampling                         MWJ 
 T. Matsumoto   Salinity                         MWJ 
 H. Matsunaga   CTD                              MWJ 
 A.G. Mejia     Bio-Optics                       Univ. of Concepcion 
 T. Miyashita   Thermosalinograph, Oxygen        MWJ 
 M. Moro        TCO2                             MWJ 
 S.G. Munoz     Observer (Chile)                 Armada de Chile 
 A. Murata      Alkalinity, pH                   JAMSTEC 
 S. Okumura     ADCP, Bathymetry, Meteorology    GODI 
 Y. Otsubo      Nutrients                        MWJ 
 S. Sancak      Bio-Optics                       Middle East Technical University 
 W. Schneider   CTD                              Univ. of Concepcion 
 T. Ohama       Alkalinity, pH                   MWJ 
 K. Sato        Nutrients                        MWJ 
 Y. Sonoyama    CFC                              MWJ 
 O. Sugimoto    Sampling                         JAMSTEC 
 M. Gallegos    Nitrous Oxide                    RP POC 
 A. Takeuchi    Radio Nuclides                   KANSO 
 S. Tanaka      CFC, Ar, N2                      Hokkaido University 
 W. Tokunaga    ADCP, Bathymetry, Meteorology    GODI 
 H. Uchida      CTD                              JAMSTEC 
 V. Villagran   Elec. Engineer                   Univ. of Concepcion 
 M. Wakita      CFC                              JAMSTEC 
 S. Watanabe    CFC, 3He/4He                     JAMSTEC 
 T. Watanabe    Sampling                         MWJ 
 Hid Yamamoto   Data Management, LADCP, CFC      MWJ 
 Hir Yamamoto   Sampling                         JAMSTEC 
 A. Yasuda      Nutrients                        MWJ 
 M. Yoshiike    ARGO, CTD                        MWJ 
______________________________________________________________________________________

   Armada de Chile:  Servicio Hidrografico y Oceanografico de la Armada de Chile 
   GODI:             Global Ocean Development Inc. 
   JAMSTEC:          Japan Marine Science and Technology Center 
   KANSO:            Kansai Environmental Engineering Center Co., Ltd. 
   MWJ:              Marine Works Japan, Ltd. 
   RP POC:           Regional Program of Physical Oceanographic and Climate 
 

TABLE 1.6.3.   List of cruise participants in leg 4. 
______________________________________________________________________________________
 
 Name           Main tasks                       Affiliation 
 ------------------------------------------------------------------------------------
 E. Braga       Oxygen                           Univ. of Sao Paulo 
 A. Claudia     Sampling, Bio-Optics             Univ. of Sao Paulo 
 B. Currie      Sampling                         MFMR 
 T. Fujiki      TCO2                             MWJ 
 J. Hamanaka    Nutrients                        MWJ 
 J. Hashimoto   CTD Operation                    MWJ 
 S. Ikeda       Sampling                         MWJ 
 M. Kamata      TCO2                             MWJ 
 T. Kawano      Salinity                         JAMSTEC 
 A. Kubo        Nutrients                        MWJ 
 S. Lee         Radio Nuclides                   IAEA 
 V. Lutz        Bio-Optics                       INIDEP 
 J. Madruga     Sampling, Bio-Optics             Univ. of Sao Paulo 
 K. Maeno       ADCP, Bathymetry, Meteorology    GODI 
 K. Matsumoto   Oxygen, Sampling                 JAMSTEC 
 A. Murata      pH, Alkalinity, TOC, 14C         JAMSTEC 
 L. Nonnato     LADCP, Sampling                  Univ. of Sao Paulo 
 S. Okumura     ADCP, Bathymetry, Meteorology    GODI 
 S. Ozawa       CTD                              MWJ 
 K. Peard       Sampling                         LMR 
 M. Rosenberg   CTD, Data Processing             ACE CRC 
 K. Sagishima   CFC                              MWJ 
 K. Sasaki      CFC                              JAMSTEC 
 S. Sasaki      Sampling                         MWJ 
 V. Segura      Sampling, Bio-Optics             INIDEP 
 T. Seike       Oxygen                           MWJ 
 W. Schneider   CTD                              Univ. of Concepcion 
 F. Shibata     pH, Alkalinity                   MWJ 
 N. Silulwane   Sampling                         MCM 
 S. Sueyoshi    ADCP, Bathymetry, Meteorology    GODI 
 O. Sugimoto    Sampling                         JAMSTEC 
 N. Takahashi   Salinity                         MWJ 
 S. Tanaka      CFC, Ar, N2                      Hokkaido Univ. 
 H. Uchida      LADCP                            JAMSTEC 
 K. Wataki      CFC                              MWJ 
 S. Watanabe    CFC, 3He/4He                     JAMSTEC 
 S. Yokogawa    Nutrients                        MWJ 
 I. Yamazaki    Oxygen                           MWJ 
 M. Yokota      Sampling                         MWJ 
 M. Yoshiike    CTD Operation, ARGO              MWJ 
 Y. Yoshikawa   LADCP                            JAMSTEC 
______________________________________________________________________________________

   ACE CRC:   Antarctic Climate and Ecosystems Cooperative Research Centre, Australia 
   GODI:      Global Ocean Development Inc. 
   IAEA:      International Atomic Energy Agency 
   INIDEP:    Institute Nacional de Investigacion y Desarrollo Pesquero, Argentina 
   JAMSTEC:   Japan Marine Science and Technology Center 
   LMR:       Luederitz Marine Research, Namibia 
   MCM:       Marine and Coastal Management, South Africa 
   MFMR:      Ministry of Fisheries and Marine Resources, Namibia 
   MWJ:       Marine Works Japan, Ltd.


TABLE 1.6.4.   List of cruise participants in leg 5a. 
______________________________________________________________________________________
 
 Name           Main tasks                       Affiliation 
 ------------------------------------------------------------------------------------
 J. Bemiasa     Sampling                         IHSM 
 P. Bonham      Bio-Optics                       CSIRO 
 L. Bravo       Sampling                         Univ. of Concepcion 
 A. Forbes      LADCP                            CSIRO 
 T. Fujiki      TCO2                             MWJ 
 M. Fukasawa    LADCP, ARGO, Thermosalinograph   JAMSTEC 
 J. Githaiga-
    Mwicigi     Sampling                         MCM 
 A. Hoguane     Sampling                         Univ. of Eduardo Mondlane 
 Y. Imai        ADCP, Bathymetry, Meteorology, 
                XCTD                             GODI 
 K. Katayama    Salinity                         MWJ 
 T. Kawano      Salinity                         JAMSTEC 
 M. Kawazoe     Sampling                         MWJ 
 M. Kitada      TCO2, TOC                        MWJ 
 T. Kurokawa    Sampling                         MWJ 
 M. Kyewalyanga Sampling, Bio-Optics             Univ. of Dar es Salaam 
 K. Matsumoto   Sampling                         MWJ 
 H. Matsunaga   CTD                              MWJ 
 T. Miyashita   Oxygen, Thermosalinograph        MWJ 
 T. Morris      Sampling                         MCM 
 A. Murata      pH, Alkalinity, pCO2, TOC, 14C   JAMSTEC 
 Y. Naito       Sampling                         MWJ 
 A. Nishina     CTD, Oxygen                      Kagoshima University 
 T. Ohama       pH, Alkalinity                   MWJ 
 S. Okumura     ADCP, Bathymetry, Meteorology, 
                XCTD                             GODI 
 B. Oregioni    Radio Nuclides                   IAEA 
 S. Ozawa       CTD                              MWJ 
 S. Persand     Sampling                         Mauritius Oceanography Institute 
 T. Sagara      Sampling                         MWJ 
 K. Sasaki      CFC                              JAMSTEC 
 K. Sato        Nutrients                        MWJ 
 W. Schneider   CTD                              Univ. of Concepcion 
 T. Seike       Oxygen, Thermosalinograph        MWJ 
 Y. Sonoyama    CFC                              MWJ 
 T. Takamori    CTD Operation, ARGO              MWJ 
 S. Tanaka      CFC, Ar, N2                      Hokkaido University 
 W. Tokunaga    ADCP, Bathymetry, Meteorology, 
                XCTD                             GODI 
 M. Wakita      CFC, 3He/4He                     JAMSTEC 
 T. Watanabe    Salinity                         MWJ 
 B. Wigly       Sampling, Bio-Optics             Univ. of Cape Town 
 Hid. Yamamoto  LADCP                            MWJ 
 Hir. Yamamoto  Sampling                         JAMSTEC 
 A. Yasuda      Nutrients                        MWJ 
 S. Yokogawa    Nutrients                        MWJ 
______________________________________________________________________________________

   CSIRO:     Commonwealth Scientific and Industrial Research Organisation 
   GODI:      Global Ocean Development Inc. 
   IAEA:      International Atomic Energy Agency 
   IHSM:      Institut Halieutique et des Sciences Marines 
   JAMSTEC:   Japan Marine Science and Technology Center 
   MCM:       Marine and Coastal Management, South Africa 
   MWJ:       Marine Works Japan, Ltd.


TABLE 1.6.5.   List of cruise participants in leg 5b. 
______________________________________________________________________________________
 
 Name           Main tasks                       Affiliation 
 ------------------------------------------------------------------------------------
 P. Bonham      Bio-Optics                       CSIRO 
 L. Bravo       Sampling                         Univ. of Concepcion 
 A. Forbes      Bio-Optics                       CSIRO 
 M. Fukasawa    LADCP, ARGO, Thermosalinograph   JAMSTEC 
 J. Gasutaud    Radio Nuclides                   IAEA 
 Y. Imai        ADCP, Bathymetry, Meteorology,
                XCTD                             GODI 
 K. Katayama    Salinity                         MWJ 
 T. Kawano      Salinity                         JAMSTEC 
 M. Kawazoe     Sampling                         MWJ 
 R. Kimura      ADCP, Bathymetry, Meteorology, 
                XCTD                             GODI 
 M. Kitada      TCO2, TOC                        MWJ 
 N. Komai       Oxygen, Thermosalinograph        MWJ 
 A. Kubo        Nutrients                        MWJ 
 T. Kurokawa    Sampling                         MWJ 
 M. Kyewalyanga Sampling, Bio-Optics             Univ. of Dar es Salaam 
 K. Matsumoto   Sampling                         MWJ 
 H. Matsunaga   CTD                              MWJ 
 T. Miyashita   Oxygen, Thermosalinograph        MWJ 
 M. Moro        TCO2, TOC                        MWJ 
 A. Murata      pH, Alkalinity, pCO2, TOC, 14C   JAMSTEC 
 Y. Naito       Sampling                         MWJ 
 A. Nishina     CTD, Oxygen                      Kagoshima University 
 T. Ohama       pH, Alkalinity                   MWJ 
 Y. Okamoto     Sampling                         MWJ 
 T. Sagara      Sampling                         MWJ 
 K. Sasaki      CFC                              JAMSTEC 
 K. Sato        Nutrients                        MWJ 
 W. Schneider   CTD                              Univ. of Concepcion 
 A. Shioya      Sampling                         MWJ 
 Y. Sonoyama    CFC                              MWJ 
 T. Takamori    CTD Operation, ARGO              MWJ 
 S. Tanaka      CFC, Ar, N2                      Hokkaido University 
 W. Tokunaga    ADCP, Bathymetry, Meteorology,
                XCTD                             GODI 
 H. Uno         CTD                              MWJ 
 A. Wada        Sampling                         MWJ 
 M. Wakita      CFC, 3He/4He                     JAMSTEC 
 T. Watanabe    Salinity                         MWJ 
 Hid. Yamamoto  LADCP                            MWJ 
 Hir. Yamamoto  Sampling                         JAMSTEC 
 A. Yasuda      Nutrients                        MWJ 
 A. Yenluk      Sampling                         Mauritius Oceanography Institute 
______________________________________________________________________________________

   CSIRO:     Commonwealth Scientific and Industrial Research Organisation 
   GODI:      Global Ocean Development Inc. 
   IAEA:      International Atomic Energy Agency 
   JAMSTEC:   Japan Marine Science and Technology Center 
   MWJ:       Marine Works Japan, Ltd.



2 UNDERWAY MEASUREMENTS 


2.1 NAVIGATION AND BATHYMETRY 
    28 February 2005 

(1) Personnel 
    Souichiro Sueyoshi (GODI) 
    Satoshi Okumura (GODI) 
    Yasutaka Imai (GODI) 
    Katsuhisa Maeno (GODI) 
    Shinya Okumura (GODI) 
    Wataru Tokunaga (GODI) 
    Ryo Kimura (GODI) 
    Toshiya Fujiwara (JAMSTEC) 


(2) NAVIGATION 

(2.1) OVERVIEW OF THE EQUIPMENT 

Ship's position was measured by navigation system, made by Sena Co. Ltd, Japan.  The system has 
two 12-channel GPS receivers (Leica MX9400N).  GPS antennas located at Navigation deck, offset 
to starboard and portside, respectively.  We switched them to choose better state of receiving 
when the number of GPS satellites decreased or HDOP increased.  But the system sometimes lost 
the position while the receiving status became worse.  The system also integrates gyro heading 
(Tokimec TG-6000), log speed (Furuno DS-30) and other navigation devices data on HP workstation.  
The workstation keeps accurate time using GPS Time server (Datum Tymserv2100) via NTP (Network 
Time Protocol).  Navigation data was recorded as "SOJ" data every 60 seconds

The differential GPS (DGPS) system, THALES Geosolutions SkyFix, has also installed, but we had 
few chances to use this system because it needs reference stations within 2,000 km from the 
ship, so that differential corrections became available just before the end of this cruise.  
Two antennas for Leica GPS receiver located on the navigation deck, offset to starboard and 
portside, respectively.  We switched them to choose better state of receiving when the number 
of satellites decreased or HDOP increased.  But the system sometimes lost the position while 
the receiving status became worse


(2.2) DATA PERIOD 

      Leg 1: 01:00, 3 Aug. 2003 to 22:00,  5 Sep. 2003 
      Leg 2: 18:30, 9 Sep. 2003 to 12:08, 16 Oct. 2003 
      Leg 4: 11:20, 6 Nov. 2003 to 07:10,  5 Dec. 2003 
      Leg 5: 04:22, 9 Dec. 2003 to 00:52, 24 Jan. 2004 
      

(2.3) REMARKS 

Leg 1 
      None 
Leg 2 
      26 Sep. 2003 11:27 - 11:29                                           (GPS positioning error) 
      27 Sep. 2003 07:10 - 07:22                                           (GPS positioning error) 
      *  GPS system was changed at 07:22, 27 Sep. 2003, from GPS1 to GPS2
      28 Sep. 2003 11:25 - 11:30                                           (GPS positioning error) 
      03 Oct. 2003 08:09 - 08:13                                           (GPS positioning error) 
      03 Oct. 2003 09:22 - 09:27                                           (GPS positioning error) 
      03 Oct. 2003 13:03 - 13:18                                           (GPS positioning error) 
      04 Oct. 2003 12:16 - 12:21                                           (GPS positioning error) 
      09 Oct. 2003 12:01 - 12:04                                           (GPS positioning error) 
      11 Oct. 2003 11:56 - 11:58                                           (GPS positioning error)
      *  GPS system was changed at 15:50, 11 Oct. 2003, from GPS2 to DGPS1  
      *  GPS system was changed at 17:58, 11 Oct. 2003, from DGPS1 to GPS2
Leg 4 
      *  GPS system was changed at 10:24, 06 Nov. 2003, from GPS1 to DGPS2 
      *  GPS system was changed at 19:36, 06 Nov. 2003, from DGPS2 to GPS1 
      *  GPS system was changed at 16:17, 07 Nov. 2003, from GPS1 to DGPS2 
      *  GPS system was changed at 16:29, 08 Nov. 2003, from DGPS2 to GPS1 
      09 Nov. 2003 13:15 - 13:27                                           (SOJ logging program trouble) 
      10 Nov. 2003 10:35 - 10:37                                           (SOJ logging program trouble) 
      11 Nov. 2003 10:11 - 12:41                                           (GPS positioning error) 
      *  GPS system was changed at 12:42, 11 Nov. 2003, from GPS1 to GPS2 
      *  GPS system was changed at 14:59, 23 Nov. 2003, from GPS2 to GPS1 
      23 Nov. 2003 22:29 - 22:40                                           (GPS positioning error) 
      *  GPS system was changed at 22:51, 23 Nov. 2003, from GPS1 to GPS2 
      24 Nov. 2003 15:34 - 16:13                                           (Power failure) 
      *  GPS system was changed at 17:25, 24 Nov. 2003, from GPS2 to GPSN 
         26 Nov. 2003 15:05                                                (GPS positioning error) 
      *  GPS system was changed at 14:29, 27 Nov. 2003, from GPS2 to DGPS1 
      *  GPS system was changed at 15:23, 27 Nov. 2003, DGPS1 to GPS2 
Leg 5 
      21 Dec. 2003 13:16 - 13:46                                           (Network server trouble) 
      01 Jan. 2004 21:15 - 21:19                                           (GPS positioning error) 



(3) BATHYMETRY 


(3.1) Overview of the equipment 

R/V MIRAI equipped a Multi Narrow Beam Echo Sounding system (MNBES), SEABEAM 2112.004 (SeaBeam 
Instruments Inc.).  The main objective of MNBES survey is collecting continuous bathymetry data 
along ship's track to make a contribution to geological and geophysical investigations and 
global datasets.  Data interval along ship's track was max. 16 seconds at 6,000 m.  To get 
accurate sound velocity of water column for ray-path correction of acoustic multibeam, we used 
Surface Sound Velocimeter (SSV) data at the surface (6.2m), and sound velocity profiles 
calculated from temperature and salinity data obtained from the nearest CTD cast by the 
equation of Mackenzie (1981)


(3.2) SYSTEM CONFIGURATION AND PERFORMANCE 

      System:                SEABEAM2112.004 
      Frequency:              12 kHz 
      Transmit beam width:     2 degree 
      Transmit power:         20 kW 
      Transmit pulse length:   3 to 20 msec. 
      Depth range:           100 to 11,000 m 
      Beam spacing:            1 degree athwart ship 
      Swath width:           150 degree (max.) 
                             120 degree to 4,500 m 
                             100 degree to 6,000 m 
                              90 degree to 11,000 m 
      Depth accuracy:        Within < 0.5% of depth or +/-1m, whichever is greater, 
                             over the entire swath
                             (Nadir beam has greater accuracy; typically within  
                             < 0.2% of depth or +/-1m, whichever is greater) 


(3.3) DATA PERIOD 

We carried out bathymetric survey on the CTD observation lines during each leg

      Leg 1:  3 Aug. 2003 (P06_246) to  2 Sep. 2003 (P06_121) 
      Leg 2: 12 Sep. 2003 (P06_127) to 12 Oct. 2003 (P06_004) 
      Leg 4:  7 Nov. 2003 (A10_622) to  2 Dec. 2003 (A10_100) 
      Leg 5: 13 Dec. 2003 (I04_610) to 17 Dec. 2003 (I04_585) 
             19 Dec. 2003 (I03_562) to 20 Jan. 2004 (I03_444) 


(3.4) DATA PROCESSING 

(3.4.1) CHECKING THE NAVIGATION DATA 
Navigation data is checked and removed outliers identified.  Then the removed position data is 
interpolated

(3.4.2) SOUND VELOCITY CORRECTION 
The continuous bathymetry data is split into small area at the center of the adjoining CTD 
stations.  For each small area, the bathymetry data is corrected using sound velocity profile 
calculated by the CTD data in the area.  The equation of Mackenzie (1981) is used for the 
calculation of sound velocity in sea water.  These data processing are carried out using 
"mbbath" module of the mbsystem

(3.4.3) GRIDDING 
The data editing and gridding are carried out using the HIPS software version 5.4 (CARIS, 
Canada).  Firstly, low quality data during the CTD cast and the drift of the ship are removed.  
Secondly, the data is despiked by the function "Surface Cleaning" of the software using 
following parameters. 

Tiling: by size (Minimum size of tile: 163.84 [m]) 
Degree of polynomial: 1 (tiled plane) 
Cleaning 

      Shallow threshold: 3.000, ∑ = 99.74 [%] 
      Deep threshold:    3.000, ∑ = 99.74 [%] 
      Minimum residual required for rejection: 1.000 [m] 

Thirdly, remaining error data are removed manually and normal data, which removed by the 
function "Surface Cleaning" are returned manually by the function "Swath Editor" and "Subset 
Editor" of the software.  Finally, the data is gridded by the function "Interpolate" of the 
software using following parameters

      Matrix size: 5 x 5 
      Number of nearneighbors: 10 


REFERENCE 

Mackenzie, K.V. (1981): Nine-term equation for the sound speed in the oceans, 
    J. Acoust. Soc. Am., 70 (3), pp 807-812



2.2  SURFACE METEOROLOGICAL OBSERVATION 
     1 February 2005 

(1)  PERSONNEL 
     Kunio Yoneyama     (JAMSTEC) 
     Satoshi Okumura    (GODI) 
     Souichiro Sueyoshi (GODI) 
     Yasutaka Imai      (GODI) 
     Shinya Okumura     (GODI) 
     Katsuhisa Maeno    (GODI) 
     Wataru Tokunaga    (GODI) 
     Norio Nagahama     (GODI) 
     Ryo Kimura         (GODI) 


(2) OBJECTIVE 

As a basic dataset that describes weather conditions during the cruise, surface meteorological 
observation  had been continuously conducted


(3) METHODS 

There are two different surface meteorological observation systems on the R/V MIRAI.  One is 
the MIRAI surface meteorological measurement station (SMET), and the other is the Shipboard 
Oceanographic and Atmospheric Radiation (SOAR) system

Instruments of SMET whose data are used here are listed in Table 2.2.1.  All SMET data were 
collected and processed by KOAC-7800 weather data processor made by Koshin Denki, Japan.  Note 
that although SMET contains rain gauge, anemometer and radiometers in their system, we adopted 
those data from not SMET but SOAR due to the following reasons.  Namely, 1) since SMET rain 
gauge is located near the base of the mast, there is a possibility that its capture rate might 
be affected, 2) SOAR's anemometer has better starting threshold wind speed (1 m/sec) comparing 
to SMET's anemometer (2 m/sec), and 3) SMET's radiometers record data with 10 W/m2 unit, while 
SOAR takes 1 W/m2 unit

SOAR system was designed and constructed by the Brookhaven National Laboratory (BNL), USA for 
an accurate measurement of solar radiation on the ship.  Details of SOAR can be found at 
http://www.gim.bnl.gov/ soar/.  SOAR consists of 1) Portable Radiation Package (PRP) that 
measures short and long wave downwelling radiation, 2) Zeno meteorological system that measures 
pressure, air temperature, relative humidity, wind speed/direction, and rainfall, and 3) 
Scientific Computer System (SCS), that is developed by the National Oceanic and Atmospheric 
Administration (NOAA) of USA for data collection, management, real-time monitoring, and so on.  
Information on sensors used here are listed in Table 2.2.2


TABLE 2.2.1. Instruments and locations of SMET
__________________________________________________________________________________________________
 
 Sensor         Parameter              Manufacturer/type           Location/height from sea level  
 ------------------------------------------------------------------------------------------------
 Thermometer*1  air temperature        Vaisala, Finland/HMP45A     compass deck*2/21 m   
                relative humidity 
 Thermometer    sea temperature        Koshin Denki, Japan/RFN1-0  4th deck/-5 m 
 Barometer      pressure               Yokogawa, Japan/F-451       captain deck/13 m
__________________________________________________________________________________________________
 *1  Gill aspirated radiation shield 43408 made by R. M. Young, USA is attached
 *2  There are two thermometers at starboard and port sides.


TABLE 2.2.2. Instruments and locations of SOAR. 
__________________________________________________________________________________________________
 
 Sensor         Parameter              Manufacturer/type           Location/height from sea level  
 ------------------------------------------------------------------------------------------------
 Anemometer     wind speed/direction   R. M. Young, USA/05106      foremast/25 m 
 Rain gauge     rainfall accumulation  R. M. Young, USA/50202      foremast/24 m 
 Radiometer     short wave radiation   Eppley, USA/PSP             foremast/25 m 
 long wave      radiation              Eppley, USA/PIR             foremast/25 m 
__________________________________________________________________________________________________


(4) DATA PROCESSING AND DATA FORMAT 

All raw data were recorded every 6 seconds.  Datasets produced here are 1-minute mean values 
(time stamp at the beginning of the average).  They are simple mean of 8 samples (10 samples 
minus maximum/minimum values) to exclude singular values.  Liner interpolation onto missing 
values was applied only when their interval is less than 4 minutes

Since the thermometers are equipped on both starboard/port sides on the deck, we used air 
temperature/relative humidity (and dew point temperature) data taken at upwind side.  Dew point 
temperature was produced from relative humidity and air temperature data

No adjustment to sea level values is applied except pressure data

Data are stored as ASCII format and contain the following parameters

Time in UTC expressed as YYYYMMDDHHMM, time in Julian day (1.0000 = January 1, 0000Z), 
longitude (°E), latitude (°N), pressure (hPa), air temperature (°C), dew point temperature 
(°C), relative humidity (%), sea surface temperature (°C), zonal wind component (m/sec), 
meridional wind component (m/sec), precipitation (mm/hr), downwelling shortwave radiation 
(W/m2), and downwelling longwave radiation (W/m2)

Missing values are expressed as "9999"


(5) DATA QUALITY 

To ensure the data quality, each sensor was calibrated as follows.  It is remarked, however, 
since there is a possibility that fine time resolution data sets may have some noises caused 
by turbulence, it is recommended to create smoothed data sets (e.g., 1-hour mean) from this 
1-minute mean data sets depending on the scientific purpose

T/RH SENSOR: 
Temperature and humidity probes were calibrated before/after the cruise by the 
manufacturer.  Certificated accuracy for T/RH sensors are better than ± 0.2°C and ± 2%, 
respectively.  In addition, their time drifts between the leg 1 and the leg 5 were 0.0°C for T 
sensor and -1.3% for RH sensor

We also checked T/RH values using another calibrated portable T/RH sensor (Vaisala, HMP45A) 
before each cruise.  The results are listed below
          _________________________________________________________________________

           Check date          Jul.31   Sep.06   Oct.17   Nov.03   Dec.05   Jan.24 
          -----------------------------------------------------------------------
          Temperature (°C) 
            SMET               12.1     28.2     19.2     21.9     28.3     22.6 
            portable           12.4     28.3     19.4     21.8     28.8     22.3 
          Relative Humidity (%) 
            SMET               42       66       52       57       41       65  
            portable           38       65       51       56       41       66  

PRESSURE SENSOR: 
Using calibrated portable barometer (Vaisala, Finland / PTB220, certificated accuracy is better 
than ± 0.1 hPa, and it was calibrated at the manufacturer on Feb. 6, 2003), pressure sensor was 
checked before/after each cruise.  From the result listed below, pressure accuracy is better 
than ± 1 hPa
          _________________________________________________________________________

           Check date          Aug.02   Sep.02   Oct.17   Nov.03   Dec.05   Jan.24 
          -----------------------------------------------------------------------
          SMET                1023.3   1014.1   1015.3   1017.0   1009.4   1008.1 
          reference           1022.6   1013.6   1014.6   1016.4   1008.8   1007.5 
          difference             0.7      0.5      0.7      0.6      0.6      0.6 
           
ANEMOMETER: 
Using digital tester (Hioki, Japan / 3805), pre-/post calibration were conducted by the GODI 
technical staff

Pre-calibration date:            Apr. 09, 2003 
  Starting threshold wind speed: 0.2 m/sec for clockwise 
                                 0.4 m/sec for counter-clockwise 
  Wind direction check           better than ± 3° 

    Set value      0 30 60 90 120 150 180 210 240 270 300 330 
    Measured value 1 32 63 93 122 153 180 210 240 270 300 331 
    Difference    -1 -2 -3 -3  -2  -3   0   0   0   0   0  -1 
 
Post-calibration date:           Sep. 10, 2004 
  Starting threshold wind speed: 0.9 m/sec for clockwise 
                                 0.9 m/sec for counter-clockwise 
  Wind direction check:          better than ± 4° 

    Set value      0 30 60 90 120 150 180 210 240 270 300 330 
    Measured value 0 30 61 92 122 153 182 212 242 273 304 334 
    Difference     0  0 -1 -2  -2  -2  -2  -2  -2  -3  -4  -4 

PRECIPITATION: 
Before each cruise, we put the water into the rain gauge to check their linearity between the 
indicated values and water amount input. Expected accuracy is better than ± 1 mm that 
corresponds to sensor's specification

     ______________________________________________________________________________________
 
      Calibration date                Jul. 30  Sep. 05  Oct. 16  Nov. 04  Dec. 05  Jan. 24 
      ------------------------------------------------------------------------------------
      minimum input water volume (cc)    0.0      0.0      0.0      0.0      0.0      0.0 
      minimum measured value (mm)        1.0      0.9      0.8      0.9      0.9      0.1 
      maximum input water volume (cc)  513.7    511.0    512.3    511.7    513.0    511.7 
      maximum measured value (mm)       51.7     51.2     51.7     51.4     51.2     50.7 
     ______________________________________________________________________________________


RADIATION SENSORS: 
Short wave and long wave radiometers were calibrated at the Brookhaven National Laboratory 
prior to the cruise.  Sensors used here were calibrated in September 2002. Some results are 
shown below

For PSP:   y = 3.875 x + 0.2 
For PIR:   y = 1.228 x + 5.7,  where y = insolation (W/m2), and x = ADC value (mV). 
  1 / (T + T0) = p1 a3 + p2 a2 + p3 a + p4,  where a = ln(ADC mV), and T0 = 273.15 K 
  Case temperature fit: max error = 0.004°C 
      p1 = 3.0922e-6, p2 = -3.7240e-5, p3 = 4.3175e-4, p4 = 1.7014e-3 
  Dome temperature fit: max error = 0.004°C 
      p1 = 2.9703e-6, p2 = -3.6790e-5, p3 = 4.3686e-4, p4 = 1.6788e-3 


(6) DATA PERIODS 

    Leg 1           (Brisbane - Papeete):   2100Z, Aug.03, 2003 - 0700Z, Sep.02, 2003 
               Periods of missing values: 
                   wind speed / direction   0002Z, Aug.16, 2003 - 0010Z, Aug.16, 2003 
                            precipitation   0002Z, Aug.16, 2003 - 0010Z, Aug.16, 2003
                short/long wave radiation   0002Z, Aug.16, 2003 - 0010Z, Aug.16, 2003 
                                            2152Z, Aug.20, 2003 - 0020Z, Aug.21, 2003 
    Leg 2         (Papeete - Valparaiso):   0600Z, Sep.12, 2003 - 1100Z, Oct.16, 2003 
               Periods of missing values: 
                   wind speed / direction   0001Z, Sep.23, 2003 - 0012Z, Sep.23, 2003 
                                            0816Z, Oct.12, 2003 - 0821Z, Oct.12, 2003 
                            precipitation   0001Z, Sep.23, 2003 - 0012Z, Sep.23, 2003 
                                            0816Z, Oct.12, 2003 - 0821Z, Oct.12, 2003 
              short / long wave radiation   0001Z, Sep.23, 2003 - 0011Z, Sep.23, 2003 
                                            0816Z, Oct.12, 2003 - 0825Z, Oct.12, 2003 
    Leg 4           (Santos - Cape Town):   0000Z, Nov.09, 2003 - 0000Z, Dec.05, 2003 
               Periods of missing values: 
                   wind speed / direction   1534Z, Nov.24, 2003 - 1538Z, Nov.24, 2003 
                                            1544Z, Nov.24, 2003 - 1558Z, Nov.24, 2003 
                     short wave radiation   1548Z, Nov.09, 2003 - 1552Z, Nov.09, 2003 
                                            1411Z, Nov.19, 2003 - 1417Z, Nov.19, 2003 
                                            1427Z, Nov.19, 2003 - 1431Z, Nov.19, 2003 
    Leg 5 (Cape Town Tamatave-Fremantle):   0600Z, Dec.09, 2003 - 2100Z, Jan.23, 2004 
               Periods of missing values: 
                  sea surface temperature   0601Z, Jan.21, 2004 - 2100Z, Jan.23, 2004 
                                     wind   0008Z, Dec.24, 2003 - 0013Z, Dec.24, 2003 
                            precipitation   0008Z, Dec.24, 2003 - 0013Z, Dec.24, 2003 
                     short wave radiation   1201Z, Dec.09, 2003 - 1214Z, Dec.09, 2003 
                                            1029Z, Dec.15, 2003 - 1048Z, Dec.15, 2003 
                                            1022Z, Dec.17, 2003 - 1030Z, Dec.17, 2003 
                                            0953Z, Dec.22, 2003 - 0957Z, Dec.22, 2003 
                                            0933Z, Dec.23, 2003 - 0941Z, Dec.23, 2003 
                                            0008Z, Dec.24, 2003 - 0013Z, Dec.24, 2003 
                                            0804Z, Jan.03, 2004 - 0822Z, Jan.03, 2004 
                                            0726Z, Jan.06, 2004 - 0734Z, Jan.06, 2004 
                                            0743Z, Jan.06, 2004 - 0751Z, Jan.06, 2004 
                                            0720Z, Jan.07, 2004 - 0725Z, Jan.07, 2004 
                                            0741Z, Jan.07, 2004 - 0746Z, Jan.07, 2004 
                                            0419Z, Jan.15, 2004 - 0419Z, Jan.15, 2004 
                      long wave radiation   0008Z, Dec.24, 2003 - 0013Z, Dec.24, 2003 


(7) PRELIMINARY RESULTS 

Figures 2.2.1, 2.2.2, 2.2.3, and 2.2.4 show the time series of surface meteorological 
observation for each cruise. One hour mean values (time stamp at the medium of the average) 
instead of 1 minute mean are used to depict these figures


(8) POINT OF CONTACT 
    Kunio Yoneyama  (yoneyamak@jamstec.go.jp) 
    JAMSTEC / IORGC, 2-15, Natsushima, Yokosuka 237-0061, Japan 
 

FIGURE 2.2.1. Time series of (a) air and sea surface temperature, 
              (b) relative humidity, (c) precipitation, (d) pressure, 
              (e) zonal and meridional wind components, and 
              (e) short and long wave radiation for the leg 1 cruise.  
              Day216 corresponds to Aug. 3, 2003
FIGURE 2.2.2. Same as Figure 2.2.1, but for the leg 2 cruise.  Day255 
              corresponds to Sep. 12, 2003.
FIGURE 2.2.3. Same as Figure 2.2.1, but for the leg 4 cruise.  Day313 
              corresponds to Nov. 9, 2003
FIGURE 2.2.4. Same as Figure 2.2.1, but for the leg 5 cruise.  Day343 
              corresponds to Dec. 9, 2003. Day10 corresponds to Jan. 10, 2004.



2.3 THERMOSALINOGRAPH AND RELATED MEASUREMENTS 
    22 January 2004 


(1) PERSONNEL 
    Masao Fukasawa   (JAMSTEC) 
    Takeshi Kawano   (JAMSTEC) 
    Takayoshi Seike  (MWJ) 
    Tomoko Miyashita (MWJ) 
    Nobuharu Komai   (MWJ) 


(2) OBJECTIVE 

To measure salinity, temperature, dissolved oxygen, and fluorescence of near-sea surface water


(3) METHODS 

The Continuous Sea Surface Water Monitoring System (Nippon Kaiyo Co., Ltd.) has six kind of 
sensors and can automatically measure salinity, temperature, dissolved oxygen, fluorescence and 
particle size of plankton in near-sea surface water, continuously every 1-minute.  This system 
is located in the "sea surface monitoring laboratory" on R/V Mirai.  This system is connected 
to shipboard LAN-system.  Measured data is stored in a hard disk of PC every 1-minute together 
with time and position of ship, and displayed in the data management PC machine

Near-surface water was continuously pumped up to the laboratory and flowed into the Continuous 
Sea Surface Water Monitoring System through a vinyl-chloride pipe.  The flow rate for the 
system is controlled by several valves and was 12 L/min except with fluorometer (about 0.3 
L/min).  The flow rate is measured with two flow meters and each value was checked every day

Specification of the each sensor in this system of listed below

     a) Temperature and Salinity sensors 
          SEACAT THERMOSALINOGRAPH 
          Model:              SBE-21, Sea-Bird Electronics, Inc. 
          Serial number:      2118859-2641 (for leg 1 and 2) 
                              2118859-3126 (for leg 4 and 5) 
          Measurement range:  Temperature -5 to +35°C 
                              Salinity     0 to 6.5 S m-1 
          Accuracy:           Temperature  0.01°C 6 month-1 
                              Salinity     0.001 S m-1 month-1 
          Resolution:         Temperatures 0.001°C 
                              Salinity     0.0001 S m-1 
        
     b) Bottom of ship thermometer 
          Model:              SBE 3S, Sea-Bird Electronics, Inc. 
          Serial number:      032175 (for leg 1 and 2) 
                              032607 (for leg 4 and 5) 
          Measurement range:  -5 to +35°C 
          Resolution:         ± 0.001°C 
          Stability:          0.002°C year-1 
        
     c) Dissolved oxygen sensor 
          Model:              2127A, Oubisufair Laboratories Japan Inc. 
          Serial number:      44733 
          Measurement range:  0 to 14 ppm 
          Accuracy:           ± 1% at 5°C of correction range 
          Stability:          1% month-1
      
     d) Fluorometer  
          Model:              10-AU-005, Turner Designs 
          Serial number:      5562 FRXX 
          Detection limit:    5 ppt or less for chlorophyll-a 
          Stability:          0.5% month-1 of full scale 
         
     e) Particle Size sensor  
          Model:              P-05, Nippon Kaiyo Co., Ltd. 
          Serial number:      P5024 
          Measurement range:  0.02681 mmt to 6.666 mm 
          Accuracy:           ± 10% of range 
          Reproducibility:    ± 5% 
          Stability:          5% week-1 
      
     f) Flow meter  
          Model:              EMARG2W, Aichi Watch Electronics Ltd. 
          Serial number:      8672 
          Measurement range:  0 to 30 l min-1 
          Accuracy:           ± 1% 
          Stability:          ± 1% day-1 
 
The monitoring periods (UTC) are listed below. 

          Leg 1:   3 Aug. 2003, 11:00 to  3 Sep. 2003,  2:00 
          Leg 2:  11 Sep. 2003, 23:30 to 13 Oct. 2003, 14:00 
          Leg 4:   7 Nov. 2003, 11:07 to  2 Dec. 2003, 17:05 
          Leg 5:   9 Dec. 2003, 14:02 to 21 Jan. 2004, 01:16 
   

(4) COMPARISON OF SALINITY DATA WITH SAMPLED SALINITY 

We sampled about three times every day for salinity sensor calibration.  All salinity samples 
were collected from the course of the system while on station or from regions with weak 
horizontal gradients.  All samples were analyzed on the Guildline 8400B.  The results were 
shown in Table 2.3.1 to 2.3.4


TABLE 2.3.1. Comparison between salinity obtained from Continuous Sea 
             Surface Water Monitoring System and sampled salinity for Leg 1
             __________________________________________

                         |       |          | Sampled
                Date     | Time  | Salinity | Salinity
                (UTC)    | (UTC) |   Data   | (PSS-78)
              -----------|-------|----------|---------
              2003/08/03 | 18:54 | 35.5879  | 35.5776
              2003/08/04 |  2:25 | 35.6021  | 35.5977
              2003/08/04 |  9:59 | 35.6077  | 35.6023
              2003/08/04 | 18:01 | 35.6732  | 35.7100
              2003/08/05 |  1:54 | 35.6752  | 35.7049
              2003/08/05 |  9:50 | 35.6532  | 35.6842
              2003/08/05 | 18:01 | 35.6003  | 35.6289
              2003/08/06 |  1:51 | 35.5960  | 35.6247
              2003/08/06 | 10:27 | 35.6214  | 35.6512
              2003/08/06 | 20:40 | 35.6474  | 35.6757
              2003/08/06 | 21:50 | 35.6564  | 35.6859
              2003/08/07 |  6:14 | 35.6663  | 35.6854
              2003/08/07 | 15:20 | 35.6338  | 35.6642
              2003/08/07 | 22:00 | 35.6880  | 35.7229
              2003/08/08 |  6:01 | 35.6572  | 35.6895
              2003/08/08 | 21:10 | 35.6394  | 35.6733
              2003/08/09 |  5:05 | 35.7028  | 35.7333
              2003/08/09 | 12:57 | 35.6875  | 35.7201
              2003/08/09 | 20:58 | 35.6833  | 35.7181
              2003/08/10 |  5:00 | 35.6743  | 35.7086
              2003/08/10 | 21:54 | 35.6847  | 35.7183
              2003/08/11 |  4:50 | 35.6789  | 35.7130
              2003/08/11 | 17:09 | 35.6461  | 35.6810
              2003/08/11 | 20:55 | 35.6490  | 35.6857
              2003/08/12 |  5:03 | 35.6290  | 35.6705
              2003/08/12 | 12:55 | 35.6526  | 35.6881
              2003/08/12 | 20:54 | 35.6345  | 35.6703
              2003/08/13 |  5:04 | 35.6611  | 35.6964
              2003/08/13 | 11:57 | 35.6644  | 35.7019
              2003/08/13 | 20:58 | 35.6236  | 35.6593
              2003/08/14 |  4:11 | 35.6377  | 35.6739
              2003/08/14 | 12:04 | 35.6180  | 35.6571
              2003/08/14 | 20:08 | 35.6064  | 35.6447
              2003/08/15 |  3:57 | 35.6112  | 35.6496
              2003/08/15 | 12:15 | 35.5664  | 35.6030
              2003/08/15 | 20:18 | 35.5552  | 35.5950
              2003/08/16 |  7:48 | 35.4951  | 35.5322
              2003/08/16 | 16:16 | 35.4935  | 35.5294
              2003/08/16 | 23:56 | 35.4875  | 35.5251
              2003/08/17 |  7:55 | 35.4698  | 35.5070
              2003/08/17 | 15:40 | 35.5015  | 35.5427
              2003/08/18 |  0:33 | 35.4962  | 35.5350
              2003/08/18 |  8:14 | 35.4878  | 35.5273
              2003/08/18 | 16:05 | 35.4888  | 35.5312
              2003/08/19 |  0:05 | 35.5214  | 35.5527
              2003/08/19 |  7:54 | 35.5274  | 35.5679
              2003/08/19 | 16:00 | 35.5244  | 35.5650
              2003/08/19 | 23:56 | 35.5482  | 35.5841
              2003/08/20 |  8:08 | 35.4433  | 35.4880
              2003/08/20 | 16:08 | 35.5156  | 35.5571
              2003/08/20 | 19:58 | 35.4993  | 35.5407
              2003/08/21 |  3:58 | 35.5171  | 35.5598
              2003/08/21 | 11:33 | 35.5097  | 35.5511
              2003/08/21 | 18:55 | 35.4674  | 35.5105
              2003/08/22 |  2:57 | 35.3707  | 35.4655
              2003/08/22 | 10:50 | 35.3744  | 35.4391
              2003/08/22 | 18:56 | 35.2718  | 35.3405
              2003/08/23 |  2:48 | 35.3186  | 35.3660
              2003/08/23 | 10:51 | 35.4549  | 35.5079
              2003/08/23 | 18:44 | 35.4632  | 35.5062
              2003/08/24 |  3:01 | 35.4781  | 35.5308
              2003/08/24 | 10:57 | 35.4741  | 35.5188
              2003/08/24 | 18:58 | 35.4474  | 35.4910
              2003/08/25 |  3:05 | 35.4212  | 35.4646
              2003/08/25 | 11:09 | 35.4394  | 35.4823
              2003/08/25 | 18:54 | 35.4106  | 35.4549
              2003/08/26 |  2:54 | 35.3799  | 35.4229
              2003/08/26 | 11:31 | 35.4319  | 35.4754
              2003/08/27 |  7:00 | 35.4600  | 35.5030
              2003/08/27 | 14:57 | 35.4578  | 35.5008
              2003/08/27 | 23:07 | 35.3555  | 35.4095
              2003/08/28 |  6:58 | 35.4548  | 35.4993
              2003/08/28 | 15:09 | 35.4504  | 35.4941
              2003/08/28 | 23:00 | 35.3639  | 35.4040
              2003/08/29 |  6:54 | 35.3661  | 35.4016
              2003/08/29 | 15:27 | 35.4121  | 35.4533
              2003/08/29 | 23:05 | 35.3417  | 35.3944
              2003/08/30 | 11:23 | 35.2927  | 35.3342
              2003/08/30 | 15:00 | 35.2908  | 35.3325
              2003/08/30 | 22:58 | 35.4069  | 35.4482
              2003/08/31 |  6:58 | 35.3776  | 35.4200
              2003/08/31 | 23:04 | 35.2608  | 35.3023
              2003/09/01 |  7:00 | 35.3240  | 35.3648
              2003/09/01 | 14:55 | 35.3516  | 35.3940
              2003/09/01 | 22:57 | 35.3651  | 35.4015
              2003/09/02 |  6:56 | 35.0834  | 35.1256
              2003/09/02 | 21:59 | 35.3719  | 35.4129
             __________________________________________


TABLE 2.3.2. Comparison between salinity obtained from Continuous Sea 
             Surface Water Monitoring and sampled salinity for leg 2
             __________________________________________

                         |       |          | Sampled
                Date     | Time  | Salinity | Salinity
                (UTC)    | (UTC) |   Data   | (PSS-78)
              -----------|-------|----------|---------
              2003/09/12 |  0:04 | 35.4439  | 35.4388
              2003/09/12 |  4:50 | 35.3963  | 35.3872
              2003/09/12 | 13:57 | 35.4003  | 35.3969
              2003/09/12 | 21:53 | 35.3118  | 35.3038
              2003/09/13 |  5:50 | 35.4051  | 35.3944
              2003/09/13 | 14:12 | 35.3712  | 35.3756
              2003/09/13 | 21:49 | 35.3911  | 35.3844
              2003/09/14 |  5:55 | 35.3108  | 35.3050
              2003/09/14 | 13:57 | 35.3014  | 35.2981
              2003/09/14 | 21:54 | 35.3744  | 35.3707
              2003/09/15 |  6:06 | 35.2835  | 35.2799
              2003/09/15 | 13:58 | 35.1876  | 35.1810
              2003/09/15 | 21:51 | 35.1790  | 35.1674
              2003/09/16 |  6:14 | 34.9382  | 34.9259
              2003/09/16 | 12:41 | 35.0919  | 35.0850
              2003/09/16 | 20:51 | 35.1629  | 35.1564
              2003/09/17 |  4:51 | 35.0098  | 35.0148
              2003/09/17 | 13:00 | 35.0033  | 34.9987
              2003/09/17 | 20:51 | 35.0895  | 35.0844
              2003/09/18 |  5:08 | 35.1236  | 35.0788
              2003/09/18 | 13:04 | 35.1737  | 35.1689
              2003/09/18 | 20:57 | 34.9896  | 34.9934
              2003/09/19 |  5:05 | 35.1949  | 35.1894
              2003/09/19 | 13:45 | 35.1500  | 35.1461
              2003/09/19 | 20:49 | 34.9999  | 34.9976
              2003/09/20 |  4:54 | 34.8266  | 34.8203
              2003/09/20 | 12:04 | 35.0261  | 35.0190
              2003/09/20 | 19:50 | 34.9281  | 34.9238
              2003/09/21 | 15:52 | 35.1231  | 35.1174
              2003/09/21 | 20:12 | 35.1562  | 35.1505
              2003/09/22 | 12:01 | 34.7262  | 34.7236
              2003/09/22 | 19:47 | 34.6572  | 34.6524
              2003/09/23 |  3:54 | 34.5923  | 34.5870
              2003/09/23 | 11:54 | 34.6121  | 34.6025
              2003/09/23 | 19:44 | 34.7548  | 34.7495
              2003/09/24 |  3:28 | 34.6148  | 34.5793
              2003/09/24 | 11:52 | 34.6804  | 34.6772
              2003/09/24 | 19:56 | 34.6641  | 34.7457
              2003/09/25 |  3:24 | 35.1447  | 35.1417
              2003/09/25 | 11:54 | 34.9619  | 34.9601
              2003/09/25 | 19:53 | 34.7201  | 34.7183
              2003/09/26 |  3:47 | 34.8324  | 34.8302
              2003/09/26 | 11:52 | 34.5981  | 34.5895
              2003/09/26 | 19:51 | 34.6506  | 34.6458
              2003/09/27 |  3:29 | 34.7590  | 34.7481
              2003/09/27 | 10:46 | 34.5932  | 34.5780
              2003/09/27 | 18:53 | 34.7409  | 34.7540
              2003/09/28 |  2:42 | 34.5840  | 34.5791
              2003/09/28 | 10:54 | 34.2848  | 34.2899
              2003/09/28 | 18:54 | 34.3686  | 34.3644
              2003/09/29 |  3:09 | 34.4975  | 34.4959
              2003/09/29 | 10:58 | 34.8530  | 34.8501
              2003/09/29 | 18:57 | 34.8608  | 34.8580
              2003/09/30 | 14:52 | 34.8546  | 34.8509
              2003/09/30 | 18:50 | 34.7904  | 34.7903
              2003/10/01 |  2:39 | 34.6251  | 34.6164
              2003/10/01 | 10:54 | 34.8408  | 34.8399
              2003/10/01 | 18:53 | 34.8261  | 34.8265
              2003/10/02 |  2:10 | 34.6571  | 34.6547
              2003/10/02 | 10:53 | 34.9884  | 34.9745
              2003/10/02 | 18:54 | 34.4697  | 34.4692
              2003/10/03 |  2:50 | 34.2944  | 34.2984
              2003/10/03 | 10:00 | 34.2395  | 34.2355
              2003/10/03 | 17:48 | 34.2884  | 34.2893
              2003/10/04 |  1:11 | 34.3806  | 34.3789
              2003/10/04 |  9:55 | 34.4391  | 34.4373
              2003/10/04 | 17:50 | 34.4851  | 34.4850
              2003/10/05 |  2:00 | 34.2875  | 34.2835
              2003/10/05 | 10:01 | 34.3031  | 34.3025
              2003/10/05 | 17:50 | 34.4102  | 34.4096
              2003/10/06 |  1:27 | 34.4638  | 34.4738
              2003/10/06 |  9:56 | 34.5224  | 34.5197
              2003/10/06 | 17:49 | 34.5731  | 34.5723
              2003/10/07 |  0:34 | 34.4679  | 34.4655
              2003/10/07 | 10:11 | 34.4325  | 34.4312
              2003/10/07 | 17:50 | 34.4260  | 34.4274
              2003/10/08 | 12:54 | 34.4017  | 34.4126
              2003/10/08 | 17:06 | 34.4433  | 34.4455
              2003/10/09 |  0:04 | 34.2978  | 34.3073
              2003/10/09 |  8:49 | 34.3004  | 34.2992
              2003/10/09 | 16:55 | 34.2764  | 34.2782
              2003/10/10 |  0:27 | 34.1796  | 34.1775
              2003/10/10 |  8:56 | 34.1458  | 34.1464
              2003/10/10 | 16:50 | 34.2664  | 34.2686
              2003/10/11 |  0:11 | 34.2401  | 34.2395
              2003/10/11 |  8:58 | 34.2382  | 34.2358
              2003/10/11 | 16:49 | 34.2659  | 34.2650
              2003/10/11 | 23:26 | 34.6082  | 34..6093
             __________________________________________


TABLE 2.3.3. Comparison between salinity obtained from Continuous Sea 
             Surface Water Monitoring and sampled salinity for leg 4
             __________________________________________

                         |       |          | Sampled
                Date     | Time  | Salinity | Salinity
                (UTC)    | (UTC) |   Data   | (PSS-78)
              -----------|-------|----------|---------
              2003/11/07 | 17:55 | 36.1938  | 36.1807
              2003/11/08 |  1:58 | 36.2261  | 36.2155
              2003/11/08 |  9:59 | 36.5223  | 36.5107
              2003/11/08 | 18:02 | 37.1111  | 37.1012
              2003/11/09 |  2:10 | 36.9197  | 36.9104
              2003/11/09 |  9:51 | 36.1602  | 36.1485
              2003/11/09 | 17:53 | 35.9997  | 35.9989
              2003/11/10 |  1:59 | 36.0251  | 36.0113
              2003/11/10 |  9:49 | 35.7294  | 35.7069
              2003/11/10 | 17:57 | 35.7728  | 35.7581
              2003/11/11 |  1:58 | 36.0776  | 36.0665
              2003/11/11 |  9:56 | 36.0963  | 36.0859
              2003/11/11 | 17:58 | 36.4694  | 36.4562
              2003/11/12 |  1:54 | 36.1788  | 36.1679
              2003/11/12 |  9:56 | 36.0033  | 35.9918
              2003/11/12 | 18:02 | 36.0591  | 36.0479
              2003/11/13 |  1:57 | 36.0285  | 36.0178
              2003/11/13 | 10:02 | 36.0261  | 36.0285
              2003/11/13 | 17:53 | 35.8561  | 35.8478
              2003/11/14 |  2:04 | 35.9495  | 35.9412
              2003/11/14 |  9:58 | 35.9992  | 35.9889
              2003/11/14 | 18:01 | 36.0190  | 36.0086
              2003/11/15 |  1:57 | 35.9047  | 35.8949
              2003/11/15 |  9:57 | 35.9049  | 35.8949
              2003/11/15 | 17:58 | 35.9818  | 35.9718
              2003/11/16 |  1:54 | 36.0762  | 36.0671
              2003/11/16 | 10:01 | 36.1472  | 36.1375
              2003/11/16 | 18:00 | 36.0770  | 36.0673
              2003/11/17 |  2:08 | 35.4934  | 35.4839
              2003/11/17 |  9:53 | 35.8994  | 35.8891
              2003/11/17 | 17:57 | 35.7057  | 35.6967
              2003/11/18 |  1:58 | 36.0270  | 36.0165
              2003/11/18 | 10:06 | 35.9530  | 35.9444
              2003/11/18 | 18:02 | 35.8323  | 35.8216
              2003/11/19 |  2:01 | 36.0499  | 36.0429
              2003/11/19 |  9:59 | 35.9020  | 35.8931
              2003/11/19 | 18:01 | 36.0589  | 36.0523
              2003/11/20 |  0:56 | 35.9941  | 35.9846
              2003/11/20 |  8:50 | 36.0124  | 36.0030
              2003/11/20 | 17:03 | 36.1284  | 36.1210
              2003/11/21 |  1:00 | 36.1766  | 36.1659
              2003/11/21 |  8:49 | 36.0655  | 36.0578
              2003/11/21 | 16:56 | 36.0378  | 36.0288
              2003/11/22 |  0:56 | 35.8476  | 35.8372
              2003/11/22 |  8:48 | 35.9853  | 35.9764
              2003/11/22 | 17:03 | 35.8738  | 35.8642
              2003/11/23 |  0:55 | 35.8052  | 35.7957
              2003/11/23 |  8:47 | 35.7842  | 35.7746
              2003/11/23 | 16:59 | 36.1174  | 36.1141
              2003/11/24 |  0:59 | 36.0071  | 35.9972
              2003/11/24 |  8:45 | 35.9418  | 35.9332
              2003/11/24 | 17:05 | 35.9580  | 35.9500
              2003/11/24 | 23:56 | 36.0008  | 35.9927
              2003/11/25 |  7:57 | 35.9606  | 35.9538
              2003/11/25 | 16:00 | 36.0141  | 36.0069
              2003/11/25 | 23:58 | 35.8938  | 35.8864
              2003/11/26 |  8:09 | 35.8466  | 35.8371
              2003/11/26 | 15:59 | 35.8641  | 35.8579
              2003/11/26 | 23:59 | 35.7779  | 35.7695
              2003/11/27 |  7:52 | 35.9645  | 35.9598
              2003/11/27 | 16:08 | 35.8023  | 35.7946
              2003/11/27 | 23:57 | 35.7883  | 35.7797
              2003/11/28 |  8:01 | 35.7803  | 35.7724
              2003/11/28 | 15:57 | 35.6961  | 35.6885
              2003/11/29 |  0:01 | 35.7615  | 35.7524
              2003/11/29 |  7:53 | 35.8114  | 35.8036
              2003/11/29 | 16:02 | 35.6035  | 35.5984
              2003/11/29 | 23:56 | 35.3958  | 35.3908
              2003/11/30 |  7:54 | 35.6416  | 35.6358
              2003/11/30 | 15:57 | 35.5562  | 35.5515
              2003/12/01 |  6:45 | 35.5899  | 35.6257
              2003/12/01 | 14:54 | 35.4484  | 35.4906
              2003/12/01 | 21:55 | 35.4547  | 35.4953
              2003/12/02 |  5:43 | 35.3556  | 35.3501
              2003/12/02 | 13:59 | 35.2902  | 35.2840
             __________________________________________
             

TABLE 2.3.4. Comparison between salinity obtained from Continuous Sea 
             Surface Water Monitoring and sampled salinity for leg 5
             __________________________________________

                         |       |          | Sampled
                Date     | Time  | Salinity | Salinity
                (UTC)    | (UTC) |   Data   | (PSS-78)
              -----------|-------|----------|---------
              2003/12/09 | 14:31 | 35.5513  | 35.5438
              2003/12/10 |  7:03 | 35.6051  | 35.5966
              2003/12/10 | 15:21 | 35.6132  | 35.6084
              2003/12/10 | 23:10 | 35.6429  | 35.6401
              2003/12/11 |  7:06 | 35.5615  | 35.5515
              2003/12/11 | 16:43 | 35.4587  | 35.4493
              2003/12/11 | 22:11 | 35.3541  | 35.3453
              2003/12/12 |  5:49 | 35.3233  | 35.3163
              2003/12/12 | 14:09 | 35.3667  | 35.3576
              2003/12/13 |  6:05 | 35.1934  | 35.1889
              2003/12/13 | 17:25 | 35.2872  | 35.2744
              2003/12/13 | 21:55 | 35.3049  | 35.2942
              2003/12/14 |  6:05 | 35.3170  | 35.3018
              2003/12/14 | 14:29 | 35.3484  | 35.3395
              2003/12/14 | 22:17 | 35.2367  | 35.2346
              2003/12/15 |  6:10 | 35.3267  | 35.3150
              2003/12/15 | 22:02 | 35.1947  | 35.1857
              2003/12/16 |  6:03 | 35.2692  | 35.2608
              2003/12/16 | 22:14 | 35.2649  | 35.2563
              2003/12/17 |  6:10 | 35.1445  | 35.1364
              2003/12/17 | 14:02 | 35.1797  | 35.1685
              2003/12/17 | 22:09 | 35.2711  | 35.2556
              2003/12/18 |  6:05 | 35.1811  | 35.1779
              2003/12/18 | 14:04 | 34.5516  | 34.5406
              2003/12/18 | 22:00 | 34.7189  | 34.7142
              2003/12/19 |  5:42 | 33.9081  | 33.9088
              2003/12/19 | 14:33 | 34.8810  | 34.8727
              2003/12/21 |  5:36 | 35.0581  | 35.0529
              2003/12/21 | 21:15 | 35.0091  | 35.0119
              2003/12/22 |  5:24 | 35.0580  | 35.0516
              2003/12/22 | 13:01 | 34.9832  | 34.9781
              2003/12/22 | 21:07 | 35.0369  | 35.0310
              2003/12/23 |  4:52 | 34.9513  | 34.9449
              2003/12/23 | 12:59 | 34.9354  | 34.9188
              2003/12/23 | 21:23 | 34.9353  | 34.9256
              2003/12/24 |  5:18 | 34.9253  | 34.9196
              2003/12/24 | 12:53 | 34.9528  | 34.9435
              2003/12/24 | 21:06 | 35.0308  | 35.0188
              2003/12/25 |  5:44 | 35.0635  | 35.0560
              2003/12/25 | 13:11 | 35.1809  | 35.1728
              2003/12/25 | 21:28 | 34.9931  | 34.9905
              2003/12/26 |  5:00 | 35.0093  | 35.0030
              2003/12/28 |  2:55 | 35.0815  | 35.0731
              2003/12/28 | 11:16 | 34.9481  | 34.9407
              2003/12/29 |  3:13 | 35.0996  | 35.0946
              2003/12/29 | 11:13 | 35.1619  | 35.1544
              2003/12/29 | 17:58 | 35.0522  | 35.0443
              2003/12/30 |  3:13 | 35.0370  | 35.0297
              2003/12/30 | 10:51 | 34.9865  | 34.9810
              2003/12/30 | 18:54 | 34.8960  | 34.8873
              2003/12/31 |  3:05 | 35.0512  | 35.0462
              2003/12/31 | 10:51 | 34.9369  | 34.9289
              2004/01/01 |  2:19 | 35.0381  | 35.0326
              2004/01/01 | 10:01 | 35.0385  | 35.0325
              2004/01/01 | 17:45 | 35.0455  | 35.0376
              2004/01/02 |  2:04 | 35.0559  | 35.0509
              2004/01/02 |  9:52 | 35.0417  | 35.0360
              2004/01/02 | 17:53 | 35.1282  | 35.1227
              2004/01/03 |  1:59 | 35.0194  | 35.0694
              2004/01/03 |  9:49 | 35.1302  | 35.1237
              2004/01/03 | 17:54 | 35.0556  | 35.0494
              2004/01/04 |  3:54 | 35.2286  | 35.2220
              2004/01/04 |  9:50 | 35.0483  | 35.0443
              2004/01/04 | 17:22 | 35.2565  | 35.2510
              2004/01/05 |  2:08 | 35.1113  | 35.1068
              2004/01/05 |  9:49 | 34.8085  | 34.8027
              2004/01/05 | 17:32 | 34.5824  | 34.5768
              2004/01/06 |  2:06 | 34.5421  | 34.5342
              2004/01/06 |  9:48 | 34.5069  | 34.5013
              2004/01/06 | 17:08 | 34.5338  | 34.5289
              2004/01/07 |  1:56 | 34.6087  | 34.6038
              2004/01/07 |  9:53 | 34.5409  | 34.5364
              2004/01/07 | 17:41 | 34.9639  | 34.9567
              2004/01/08 |  2:08 | 34.9691  | 34.9635
              2004/01/08 |  8:52 | 34.9903  | 34.9846
              2004/01/08 | 16:41 | 34.9707  | 34.9652
              2004/01/09 |  0:53 | 34.9801  | 34.9741
              2004/01/09 | 13:03 | 35.0055  | 35.0031
              2004/01/09 | 16:37 | 34.9339  | 34.9278
              2004/01/10 |  0:58 | 34.7494  | 34.7441
              2004/01/10 |  8:56 | 35.1022  | 35.0979
              2004/01/10 | 16:46 | 35.0116  | 35.0046
              2004/01/11 |  0:57 | 34.9449  | 34.9392
              2004/01/11 |  8:56 | 35.0376  | 35.0314
              2004/01/11 | 16:04 | 35.2834  | 35.2772
              2004/01/12 |  0:59 | 35.1986  | 35.1942
              2004/01/12 |  9:00 | 34.9156  | 34.9097
              2004/01/12 | 16:27 | 34.6938  | 34.6848
              2004/01/13 |  1:07 | 34.8813  | 34.8761
              2004/01/13 |  8:50 | 35.0236  | 35.0229
              2004/01/13 | 16:57 | 35.1179  | 35.1127
              2004/01/14 |  0:59 | 35.1151  | 35.1101
              2004/01/14 |  8:48 | 35.0928  | 35.0882
              2004/01/14 | 16:36 | 35.0652  | 35.0609
              2004/01/15 |  0:59 | 34.9545  | 34.9496
              2004/01/15 |  8:44 | 34.9191  | 34.9075
              2004/01/15 | 15:55 | 35.0167  | 35.0112
              2004/01/16 |  0:10 | 34.9761  | 34.9714
              2004/01/16 |  8:15 | 34.9115  | 34.9055
              2004/01/16 | 16:05 | 34.9545  | 34.9495
              2004/01/16 | 23:55 | 34.8065  | 34.7996
              2004/01/17 |  7:42 | 35.0691  | 35.0653
              2004/01/17 | 15:50 | 35.2378  | 35.2319
              2004/01/18 |  0:03 | 34.9854  | 34.9813
              2004/01/18 |  7:53 | 35.1433  | 35.1390
              2004/01/18 | 16:05 | 35.2309  | 35.2260
              2004/01/19 |  0:01 | 35.0320  | 35.0272
              2004/01/19 |  7:49 | 35.1260  | 35.1202
              2004/01/19 | 15:46 | 35.3380  | 35.3321
              2004/01/19 | 23:58 | 35.3243  | 35.3150
              2004/01/20 |  7:55 | 35.2197  | 35.2148
              2004/01/20 | 15:24 | 35.1860  | 35.1802
              2004/01/21 |  0:04 | 35.0948  | 35.0942
             __________________________________________
             
             
2.4 UNDERWAY pCO2 
    3 February 2005 


(1) PERSONNEL 
    Akihiko Murata (IORGC, JAMSTEC) 
    Mikio Kitada (MWJ) 
    Minoru Kamata (MWJ) 


(2) INTRODUCTION 

Concentrations of CO2 in the atmosphere are now increasing at a rate of 1.5 ppmv y-1 due to 
human activities such as burning of fossil fuels, deforestation, cement production, etc.  It is 
an urgent task to estimate as accurately as possible the absorption capacity of the ocean 
against the increased atmospheric CO2, and to clarify the mechanism of the CO2 absorption, 
because the magnitude of the predicted global warming depends on the levels of CO2 in the 
atmosphere, and because the ocean currently absorbs 1/3 of the 6 Gt of carbon emitted into the 
atmosphere each year by human activities

In the BEAGLE, we were aimed at quantifying how much anthropogenic CO2 absorbed in the Southern 
Ocean, where intermediate and deep waters are formed, are transported and redistributed in the 
southern hemisphere subtropical oceans.  For the purpose, we measured CO2-system properties 
such as dissolved inorganic carbon (CT), total alkalinity (AT), pH and underway pCO2

In this section, we describe data on pCO2 in the atmosphere and surface seawater obtained in 
the BEAGLE in detail


(3) APPARATUS AND SHIPBOARD MEASUREMENT 

Continuous underway measurements of atmospheric and 
surface seawater pCO2 were made with the CO2 measuring system (Nippon ANS, Ltd) installed in 
the R/V Mirai of JAMSTEC.  The system comprises of a non-dispersive infrared gas analyzer 
(NDIR; BINOS(r) model 4.1, Fisher-Rosemount), an air-circulation module and a showerhead-type 
equilibrator.  To measure concentrations (mole fraction) of CO2 in dry air (xCO2a), air sampled 
from the bow of the ship (approx. 30 m above the sea level) was introduced into the NDIR 
through a dehydrating route with an electric dehumidifier (kept at ~2°C), a Perma Pure dryer 
(GL Sciences Inc.), and a chemical desiccant (Mg(ClO4)2).  The flow rate of the air was 500 ml 
min-1.  To measure surface seawater concentrations of CO2 in dry air (xCO2s), the air 
equilibrated with seawater within the equilibrator was introduced into the NDIR through the 
same flow route as the dehydrated air used in measuring xCO2a.  The flow rate of the 
equilibrated air was 600 - 800 ml min-1.  The seawater was taken by a pump from the intake 
placed at the approx. 4.5 m below the sea surface.  The flow rate of seawater in the 
equilibrator was 500 - 800 ml min-1

The CO2 measuring system was set to repeat the measurement cycle such as 4 kinds of CO2 
standard gases (Table 2.4.1), xCO2a (twice), xCO2s (7 times).  This measuring system was run 
automatically throughout the cruise by a PC control


(4) QUALITY CONTROL 

Concentrations of CO2 of the standard gases are listed in Table 2.4.1, 
which were calibrated by the JAMSTEC primary standard gases.  The CO2 concentrations of the 
primary standard gases were calibrated by C.D. Keeling of the Scripps Institution of 
Oceanography, La Jolla, CA, U.S.A

Since differences of concentrations of the standard gases between before and after the cruise 
were allowable (< 0.1 ppmv), the averaged concentrations (Table 2.4.1) were adopted for the 
subsequent calculations

In actual shipboard observations, the signals of NDIR usually reveal a trend.  The trends were 
adjusted linearly using the signals of the standard gases analyzed before and after the sample 
measurements

Effects of water temperature increased between the inlet of surface seawater and the 
equilibrator on xCO2s were adjusted based on Gordon and Jones (1973), although the temperature 
increases were slight, being ~ 0.1°C

We checked values of xCO2a and xCO2s by examining signals of the NDIR on recorder charts, and 
by plotting the xCO2a and xCO2s as a function of sequential day, longitude, sea surface 
temperature and sea surface salinity


TABLE 2.4.1. Concentrations of CO2 standard gases used in the BEAGLE
             _______________________________________________
              Cylinder no.  Concentrations (ppmv)   Leg no.
              --------------------------------------------
               CQB15429           270.08           1, 2, 4 
               CQB15808           268.84              5 
               CQB15428           328.87           1, 2, 4 
               CQB15809           330.16              5 
               CQB15434           359.10           1, 2, 4 
               CQB15810           369.37              5 
               CQB15426           409.23           1, 2, 4 
               CQB15811           414.39              5 
             _______________________________________________


REFERENCE 

Gordon, L. I. and L. B. Jones (1973): The effect of temperature on carbon 
    dioxide partial pressure in seawater. Mar. Chem., 1, 317-322.



2.5 ACOUSTIC DOPPLER CURRENT PROFILER 
    28 February 2005 


(1) PERSONNEL 
    Yasushi Yoshikawa (JAMSTEC) 
    Souichiro Sueyoshi (GODI) 


(2) INSTRUMENT AND METHOD 

The instrument used was the RDI broadband 76.8 kHz unit, hull-mounted on the centerline and 
approximately 23 m aft of the bow at the water line.  The firmware version was 5.59 and the 
data acquisition software was the VMDAS Ver. 1.3.  Operation was made from the first CTD 
station to the last CTD station in each leg.  The instrument was used in the water-tracking 
mode during the most of operations, recording each ping raw data in 100 x 8 m bins from 18.5 m 
to 818.5 m in deep.   Sampling interval was 9.01 seconds.  The bottom-tracking mode was added 
in the westernmost shallow water region, giving the data to evaluate the misalignment of the 
transducer on the hull.  In the course the scale factor of the ADCP was also evaluated

GPS gave the navigation data.  A compass we used was the INU (Inertial Navigation Unit) instead 
of the ship's gyrocompass.  Its accuracy was 1.0 mil (about 0.056 degree) and had already set 
on zero bias before the beginning of the cruise.  An electronic trouble occurred at 15:33 on 24 
November, between A10_67 and A10_68 in the Atlantic sector.  Though it recovered at 16:06, the 
INU compass had to be initialized.  The initialization on the sea brought the bias error as 2.0 
mil (about 0.112 degree) after the trouble.  The bias value was evaluated again at port of Cape 
Town again, and fortunately, we found these values are same each other.  Therefore the accuracy 
of the heading was same value of 0.056 degree during the cruise

The performance of the ADCP instrument was almost good throughout the cruise: on streaming, 
profiles usually reached to about 600 m, except in heaviest weather and except in whilst 
streaming.  Profiles were rather bad on CTD stations.  It is probably due to the babbles 
originated from the bow-thruster.  The profiles on the stations did not reach so far, from 200 
m to 500 m and the ADCP signal was weak typically at about 350 m in deep.  Echo intensity was 
relatively weak in the sea east of 160 W in the Pacific sector and Atlantic sector


(3) DATA PROCESSING 

The first processing was the evaluation both of the ADCP scale factor and the misalignment by 
using the bottom-tracking mode data between P6_246 and P6_244 in the westernmost Pacific 
sector.  The error velocity was less than 2.0 cm/s, and ratio ADCP/Navigation was 1.0259.  
Therefore the scale factor 1 / 1.0259 = 0.9748 was adopted to measured velocity magnitude of 
each ping.  The misalignment angle was calculated as -0.17 degree between the ADCP and the INU.  
The values are almost same to the values those were obtained near the African coast: the 
difference of misalignments is less than 0.02 degree.  The error of the heading, 0.056 degree, 
would give an estimation of the velocity error as 0.8 cm/s for the maximum ship speed 16 knots, 
and it would affect to the meridional velocity because the ship had almost zonal course

The second processing is applying misalignment correction to raw data, and then calculating 
flow field on time series as a preliminary result that would make us an overview.  Every ping 
data those error velocity, the difference between two vertical velocities, less than 20 cm/s 
and correlation value higher than 64 in the four beam solutions are used to the calculation.  
Median filter is used to make the 5 minutes mean field.  The grids are put at the interval of 
20 m.  The roll and pitch data of the INU are not used to compensate the tilt motion because 
the INU was not put near the ADCP transducer.  Therefore it would give a mismatch of the tilt 
motion.  Depth correction is also made using the CTD data.  The calculation is carried using 
less than about 100 independent data, 33 profiles x 3 bins.  The error roughly estimated by the 
difference of the vertical velocities in each composite field is reduced to less than 2.0 cm/s

We made the ADCP data set giving two types of profiles: one is at each CTD station and another 
is a mean profile on streaming between CTD stations.  The mean velocities and their standard 
deviation are calculated using the 5 minutes composite velocity field.  About 25 data on 
average are used in the calculation, which would reduce the error 0.4 cm/s, one fifth of the 
velocity error in each composite field.  Then the final estimation of the error should be 0.9 
cm/s, which is given by square root of [0.82  + 0.42].  The velocity in the data set has both 
of the temporal and spatial variations.  Its standard deviation is 7.6 cm/s on average.  It 
shows no significant difference between the standard deviations in each leg.  However, the 
standard deviation at streaming is about 9.1 cm/s, and it is somewhat greater than that at the 
CTD station, 6.2 cm/s



FIGURE CAPTIONS 

FIGURE 1: Observation lines for WHP P06, A10 and I03/I04 revisit in Blue Earth 
          Global Expedition 2003 (BEAGLE2003) with bottom topography based on 
          ETOPO5 (Data announcement 88-MGG-02, 1988)

FIGURE 2: Station locations for WHP P06, A10 and I03/I04 revisit in BEAGLE2003 with 
          bottom topography based on Smith and Sandwell (1997)

FIGURE 3: Bathymetry measured by Multi Narrow Beam Echo Sounding system.  Cross
          mark indicates CTD location

FIGURE 4: Surface wind measured at 25 m above sea level.  Wind data is averaged 
          over 1-hour and plotted every 1 degree in longitude

FIGURE 5: Sea surface temperature and salinity.  Temperature and salinity data
          are averaged over 1-hour

FIGURE 6: Difference in the partial pressure of CO2 between the ocean and 
          atmosphere, ∆pCO2

FIGURE 7: Surface current at 100 m depth measured by shipboard acoustic Doppler
          current profiler (ADCP)


REFERENCES 

Data Announcement 88-MGG-02 (1988): Digital relief of the Surface of the 
    Earth, NOAA, National Geophysical Data Center, Boulder, Colorado

Smith, W. H. F. and D. T. Sandwell (1997): Global seafloor topography from 
    satellite altimetry and ship depth soundings, Science, 277, 1956-1962.



________________________________________________________________________________________________

________________________________________________________________________________________________




                WHP P06, A10, I03/I04 REVISIT DATA BOOK 
             Blue Earth Global Expedition 2003 (BEAGLE2003)
                               Volume 2 



10, March, 2005 Published 
Edited by Hiroshi Uchida (JAMSTEC) and Masao Fukasawa (JAMSTEC) 

Published by (c) JAMSTEC, Yokosuka, Kanagawa, 2005 
Japan Agency for Marine-Earth Science and Technology 
2-15 Natsushima, Yokosuka, Kanagawa. 237-0061, Japan 
Phone +81-46-867-9474, Fax +81-46-867-9455 

Printed by Aiwa Printing Co., Ltd. 
3-22-4 Takanawa, Minato-ku, Tokyo 108-0074, Japan



CONTENTS (VOLUME 2) 
  Documents 
    HYDROGRAPHIC MEASUREMENT TECHNIQUES AND CALIBRATIONS 
    CTD/O2 
        H. Uchida, M. Fukasawa (JAMSTEC), 
        W. Schneider (Univ. of Concepcion), M. Rosenberg (ACE CRC), 
        S. Ozawa, H. Matsunaga and K. Oyama (MWJ) 
    Salinity 
        T. Kawano (JAMSTEC), T. Matsumoto, N. Takahashi (MWJ) 
        and T. Watanabe (Nagasaki Univ.) 
    Oxygen 
        Y. Kumamoto, S. Watanabe (JAMSTEC), A. Nishina (Kagoshima Univ.), 
        K. Matsumoto (JAMSTEC), E. de Braga (Univ. of Sao Paulo), 
        T. Seike, I. Yamazaki, T. Miyashita and N. Komai (MWJ) 
    Nutrients 
        M. Aoyama (MRI/JMA), J. Hamanaka, A. Kubo, Y. Otsubo, 
        K. Sato, A. Yasuda and S. Yokogawa (MWJ) 
    Dissolved inorganic carbon (CT) 
        A. Murata (JAMSTEC), M. Kitada, M. Kamata, 
        M. Moro and T. Fujiki (MWJ) 
    Total alkalinity (AT) 
        A. Murata (JAMSTEC), F. Shibata and T. Ohama (MWJ) 
    pH 
        A. Murata (JAMSTEC), F. Shibata and T. Ohama (MWJ) 
    Lowered Acoustic Doppler Current Profiler 
        Y. Yoshikawa (JAMSTEC), L. Nonnato (Univ. of Sao Paulo) 
        and O. Sugimoto (JAMSTEC) 

  Figures (see pdf report for all figures)
    Figure caption 
    Observation lines 
    Station locations 
    Cross-sections 
        Potential temperature 
        Salinity 
        Salinity (with SSW correction) 
        Density (∑theta) 
        Density (∑4) 
        Neutral density (gamma n) 
        Oxygen 
        Silicate 
        Nitrate 
        Nitrite 
        Phosphate 
        Dissolved inorganic carbon 
        Total alkalinity 
        pH 
    Difference between WOCE and BEAGLE2003 
        Potential temperature 
        Salinity (with SSW correction) 
        Oxygen 


3  HYDROGRAPHIC MEASUREMENT TECHNIQUES AND CALIBRATIONS 

the CTD data transmitted from a SBE 9plus underwater unit via a conducting cable to the SBE 11plus deck 
unit.  The SBE 11plus deck unit is a rack-mountable interface which supplies DC power to the underwater 
unit, decodes the serial data stream, formats the data under microprocessor control, and passes the data to a 
companion computer.  The serial data from the underwater unit is sent to the deck unit in RS-232 NRZ format 
using a 34,560 Hz carrier-modulated differential-phase-shift-keying (DPSK) telemetry link.  The deck unit 
decodes the serial data and sends them to a personal computer to display, at the same time, to storage in a disk 
file using SBE SEASOFT software.  

The SBE 911plus system acquires data from primary, secondary and auxiliary sensors in the form of binary 
numbers corresponding to the frequency or voltage outputs from those sensors at 24 samples per second.  The 
calculations required to convert from raw data to engineering units of the parameters are performed by the SBE 
SEASOFT in real-time.  The same calculations can be carried out after the observation using data stored in a 
disk file.  

The SBE 911plus system controls the 36-position SBE 32 Carousel Water Sampler.  The Carousel accepts 
12-litre water sample bottles.  Bottles were fired through the RS-232C modem connector on the back of the SBE 
11plus deck unit while acquiring real time data.  The 12-litre Niskin-X water sample bottle (General Oceanics, 
Inc., USA) is equipped externally with two stainless steel springs.  The external springs are ideal for applications 
such as the trace metal analysis because the inside of the sampler is free from contaminants from springs.  

SBE's temperature (SBE 3) and conductivity (SBE 4) sensor modules were used with the SBE 9plus 
underwater unit fixed by a single clamp and "L" bracket to the lower end cap.  The conductivity cell entrance is 
co-planar with the tip of the temperature sensor's protective steel sheath.  The pressure sensor is mounted in 
the main housing of the underwater unit and is ported to outside through the oil-filled plastic capillary tube.  A 
compact, modular unit consisting of a centrifugal pump head and a brushless DC ball bearing motor contained 
in an aluminum underwater housing pump (SBE 5T) flushes water through sensor tubing at a constant rate 
independent of the CTD's motion.  Motor speed and pumping rate (3,000 rpm) remain nearly constant over the 
entire input voltage range of 12-18 volts DC.  Flow speed of pumped water in standard TC duct is about 2.4 m/s.  


3.1 CTD/O2 
    28 FEBRUARY 2005 

(1) PERSONNEL 

    Hiroshi Uchida (JAMSTEC) 
    Masao Fukasawa (JAMSTEC) 
    Wolfgang Schneider (University of Concepcion) 
    Mark Rosenberg (ACE CRC) 
    Satoshi Ozawa (MWJ) 
    Hiroshi Matsunaga (MWJ) 
    Kentaro Oyama (MWJ) 


(2) WINCH ARRANGEMENTS 

The CTD package wad deployed using 4.5 Ton Traction Winch System (Dynacon, Inc., USA) which was 
installed on the R/V Mirai in April 2001.  The CTD Traction Winch System with the Heave Compensation 
Systems (Dynacon, Inc., USA) is designed to reduce cable stress resulting from load variation caused by wave 
or vessel motion.  The system is operated passively by providing a nodding boom crane that moves up or 
down in response to line tension variations.  Primary system components include a complete CTD Traction 
Winch System with up to 10 km of 9.53 mm armored cable (Ocean Cable and Communication Co.), cable rocker 
and Electro-Hydraulic Power Unit, nodding-boom crane assembly, two hydraulic cylinders and two hydraulic 
oil/nitrogen accumulators mounted within a single frame assembly.  The system also contains related electronic 
hardware interface and a heave compensation computer control program.  


(3) OVERVIEW OF THE EQUIPMENT 

The CTD system, SBE 911plus system (Sea-Bird Electronics, Inc., USA), is a real time data system with 
SBE's dissolved oxygen sensor (SBE 43) was placed between the conductivity sensor module and the pump.  

Auxiliary sensors, Deep Ocean Standards Thermometer (SBE 35), altimeter and fluorometer, were also used 
with the SBE 9plus underwater unit.  The SBE 35 position in regard to the SBE 3 is shown in Figure 3.1.1.  

It is known that the CTD temperature data is influenced by the motion (pitching and rolling) of the CTD 
package.  In order to reduce the motion of the CTD package, a heavy stainless frame (total weight of the CTD 
package without sea water in the bottles is about 1,000 kg) was used and an aluminum plate (54 x 90 cm) was 
attached to the frame (Figure 3.1.2).  

SUMMARY OF THE SYSTEM USED IN THIS CRUISE 

Leg 1 
     Deck unit: 
       SBE, Inc., SBE 11plus, S/N 0272 
     Under water unit: 
       SBE, Inc., SBE 9plus, S/N 79492 (Pressure sensor: S/N 0575) 
     Temperature sensor: 
       SBE, Inc., SBE 3plus, S/N 4188 (primary) 
       SBE, Inc., SBE 3, S/N 1464 (secondary) 
     Conductivity sensor: 
       SBE, Inc., SBE 4, S/N 1088 (primary) 
       SBE, Inc., SBE 4, S/N 1202 (secondary) 
     Oxygen sensor: 
       SBE, Inc., SBE 43, S/N 0390 (primary) 
       SBE, Inc., SBE 43, S/N 0205 (secondary) 
     Pump: 
       SBE, Inc., SBE 5T, S/N 3575 (primary) 
       SBE, Inc., SBE 5T, S/N 0984 (secondary) 
     Altimeter: 
       Benthos Inc., PSA-900D, S/N 1026 (except for P06_148) 
       Benthos Inc., 2110-2, S/N 206 (P06_148) 
     Deep Ocean Standards Thermometer: 
       SBE, Inc., SBE 35, S/N 0022 
     Fluorometer: 
       Seapoint sensors, Inc., S/N 2148 (from P06_246 to P06_166 cast 1) 
       (no fluorometer from P06_166 cast 2 to P06_004) 
     Carousel Water Sampler: 
       SBE, Inc., SBE 32, S/N 0278 
     Water sample bottle: 
       General Oceanics, Inc., 12-litre Niskin-X (no TEFLON coating) 

Leg 2 
     Deck unit: 
       SBE, Inc., SBE 11plus, S/N 0272 
     Under water unit: 
       SBE, Inc., SBE 9plus, S/N 42423 (Pressure sensor: S/N 0357) 
     Temperature sensor: 
       SBE, Inc., SBE 3, S/N 1524 (primary, P06_127) 
       SBE, Inc., SBE 3plus, S/N 4216 (primary, from P06_125 to P06_004) 
       SBE, Inc., SBE 3plus, S/N 2453 (secondary) 
     Conductivity sensor: 
       SBE, Inc., SBE 4, S/N 2240 (primary) 
       SBE, Inc., SBE 4, S/N 1206 (secondary)
     Oxygen sensor: 
       SBE, Inc., SBE 43, S/N 0391 (primary) 
       SBE, Inc., SBE 43, S/N 0069 (secondary, from P06_127 to P06_061) 
       (no secondary sensor from P06_060 to P06_004) 
     Pump: 
       SBE, Inc., SBE 5T, S/N 3575 (primary) 
       SBE, Inc., SBE 5T, S/N 0984 (secondary) 
     Altimeter: 
       Benthos Inc., PSA-900D, S/N 1026 
     Deep Ocean Standards Thermometer: 
       SBE, Inc., SBE 35, S/N 0022 
     Fluorometer: 
       None 
     Carousel Water Sampler: 
       SBE, Inc., SBE 32, S/N 0278 
     Water sample bottle: 
       General Oceanics, Inc., 12-litre Niskin-X (no TEFLON coating) 

Leg 4 
     Deck unit: 
       SBE, Inc., SBE 11plus, S/N 0272 
     Under water unit: 
       SBE, Inc., SBE 9plus, S/N 42423 (Pressure sensor: S/N 0357) 
     Temperature sensor: 
       SBE, Inc., SBE 3, S/N 1464 (primary) 
       SBE, Inc., SBE 3plus, S/N 4188 (secondary) 
     Conductivity sensor: 
       SBE, Inc., SBE 4, S/N 1203 (primary) 
       SBE, Inc., SBE 4, S/N 2435 (secondary) 
     Oxygen sensor: 
       SBE, Inc., SBE 43, S/N 0391 (primary) 
       SBE, Inc., SBE 43, S/N 0394 (secondary) 
     Pump: 
       SBE, Inc., SBE 5T, S/N 3575 (primary) 
       SBE, Inc., SBE 5T, S/N 0984 (secondary) 
     Altimeter: 
       Benthos Inc., PSA-900D, S/N 1026 
     Deep Ocean Standards Thermometer: 
       SBE, Inc., SBE 35, S/N 0045 
     Fluorometer: 
       Seapoint sensors, Inc., S/N 2579 
     Carousel Water Sampler: 
       SBE, Inc., SBE 32, S/N 0391 
     Water sample bottle: 
       General Oceanics, Inc., 12-litre Niskin-X (no TEFLON coating) 

Leg 5 
     Deck unit: 
       SBE, Inc., SBE 11plus, S/N 0272 (from I04_610 to I03_467) 
       SBE, Inc., SBE 11plus, S/N 0344 (from I03_466 to I03_444)
     Under water unit: 
       SBE, Inc., SBE 9plus, S/N 42423 (Pressure sensor: S/N 0357) 
     Temperature sensor: 
       SBE, Inc., SBE 3, S/N 1464 (primary) 
       SBE, Inc., SBE 3, S/N 4323 (secondary) 
     Conductivity sensor: 
       SBE, Inc., SBE 4, S/N 1088 (primary, from I04_610 to I03_503) 
       SBE, Inc., SBE 4, S/N 2435 (primary, from I03_502 to I03_444) 
       SBE, Inc., SBE 4, S/N 1202 (secondary) 
     Oxygen sensor: 
       SBE, Inc., SBE 43, S/N 0391 (primary) 
       SBE, Inc., SBE 43, S/N 0205 (secondary) 
     Pump: 
       SBE, Inc., SBE 5T, S/N 3575 (primary) 
       SBE, Inc., SBE 5T, S/N 0984 (secondary) 
     Altimeter: 
       Benthos Inc., PSA-900D, S/N 1026 (from I04_610 to I03_511) 
       Benthos Inc., PSA-900D, S/N 0396 
         (from I03_510 to I03_469, I03_466, I03_467, 
         from I03_463 to I03_444) 
       Benthos Inc., 2110-2, S/N 206 (from I03_468 to I03_467, I03_464) 
     Deep Ocean Standards Thermometer: 
       SBE, Inc., SBE 35, S/N 0045 
     Fluorometer: 
       Seapoint sensors, Inc., S/N 2579 
     Carousel Water Sampler: 
       SBE, Inc., SBE 32, S/N 0391 (from I04_610 to I03_514) 
       SBE, Inc., SBE 32, S/N 0278 (from I03_513 to I03_444) 
     Water sample bottle: 
       General Oceanics, Inc., 12-litre Niskin-X (no TEFLON coating) 


FIGURE 3.1.1.  The SBE 35 position in regard to the SBE 3 temperature sensors.
FIGURE 3.1.2.  The CTD package. 


(4) PRE-CRUISE CALIBRATION 

(4.1) PRESSURE 

The Paroscientific series 4000 Digiquartz high pressure transducer (Paroscientific, Inc., USA) uses a quartz 
crystal resonator whose frequency of oscillation varies with pressure induced stress with 0.01 per million 
of resolution over the absolute pressure range of 0 to 15,000 psia (0 to 10,332 dbar).  Also, a quartz crystal 
temperature signal is used to compensate for a wide range of temperature changes at the time of an observation.  

The pressure sensor (MODEL 415K-187) has a nominal accuracy of 0.015% FS (1.5 dbar), typical stability of 
0.0015% FS/month (0.15 dbar/month) and resolution of 0.001% FS (0.1 dbar).  

Pre-cruise sensor calibrations were performed at SBE, Inc., USA.  The following coefficients were used in 
the SEASOFT: 

S/N 0575 (Leg 1), 27 October 1999 
  c1 = -65706.8 
  c2 = -0.1758329 
  c3 = 2.04245e-02 
  d1 = 0.027146 
  d2 = 0.0 
  t1 = 29.92375 
  t2 = -2.63869e-04 
  t3 = 3.92132e-06 
  t4 = 1.35947e-09 
  t5 = 4.49704e-12 
  (The coefficients c1, c2, t1 and t2 were changed on 6 December 1999.) 

S/N 0357 (Leg 2, 4 and 5), 17 May 1994 
  c1 = -69582.91 
  c2 = -1.619244
  c3 = 2.34327e-02 
  d1 = 0.029679 
  d2 = 0 
  t1 = 28.12082 
  t2 = -4.595919e-04 
  t3 = 3.89464e-06 
  t4 = 0 
  t5 = 0 
Pressure coefficients are first formulated into 
  c = c1 + c2 * U + c3 * U2 
  d = d1 + d2 * U 
 t0 = t1 + t2 * U + t3 * U2 + t4 * U3 + t5 * U4 

where U is temperature in degrees Celsius.  The pressure temperature, U, is determined according to 
  U (°C) = M * (12 bit pressure temperature compensation word) - B 

The following coefficients were used in SEASOFT: 

S/N 0575 (Leg 1) 
  M = 0.01284934 
  B = -8.388034 
  (in the underwater unit system configuration sheet dated on 30 November 1999) 
S/N 0357 (Leg 2, 4 and 5) 
  M = 0.01161 
  B = -8.32759 
  (in the underwater unit system configuration sheet dated on 24 May 1994) 

Finally, pressure is computed as 
  P (psi) = c * [1 - (t02 / t2)] * {1 - d * [1 - (t02 / t2)]} 

where t is pressure period (μsec).  Since the pressure sensor measures the absolute value, it inherently 
includes atmospheric pressure (about 14.7 psi).  SEASOFT subtracts 14.7 psi from computed pressure above 
automatically.  

Pressure sensor calibrations against a dead-weight piston gauge (Bundenberg Gauge Co. Ltd., UK; Model 
480DA, S/N 23906) are performed at JAMSTEC (Yokosuka, Kanagawa, JAPAN) by Marine Works Japan Ltd. 
(MWJ), usually once in a year in order to monitor sensor time drift and linearity.  The pressure sensor drift is 
known to be primarily an offset drift at all pressures rather than a change of span slope.  The pressure sensor 
hysterisis is typically 0.2 dbar.  The following coefficients for the sensor drift correction were also used in 
SEASOFT through the software module SEACON: 

S/N 0575 (Leg 1), 21 April 2003 
  slope = 0.9999235 
  offset = 2.4157361 
S/N 0357 (Leg 2, 4 and 5), 18 April 2003 
  slope = 0.9999112 
  offset = -0.0295469 

The drift-corrected pressure is computed as 
  Drift-corrected pressure (dbar) = slope * (computed pressure in dbar) + offset 
Results of the pressure sensor calibrations against the dead weight piston gauge are shown in Figure 3.1.3 and 3.1.4.  
Time drifts of the pressure sensors based on the offset of the calibrations are also shown in Figure 3.1.5 and 3.1.6.  


FIGURE 3.1.3.  The residual pressures between the dead weight piston gauge and the CTD pressure (S/N 0575). 
FIGURE 3.1.4.  Same as FIGURE 3.1.3, but for the pressure sensor S/N 0357. 
FIGURE 3.1.5.  Pressure sensor (S/N 0575) time drift based on laboratory calibrations performed by MWJ. 
FIGURE 3.1.6.  Same as FIGURE 3.1.5, but for the pressure sensor S/N 0357.


(4.2) TEMPERATURE (SBE 3) 

The temperature sensing element is a glass-coated thermistor bead in a stainless steel tube, providing a 
pressure-free measurement at depths up to 10,500 (6,800) meters by titanium (aluminum) housing.  The sensor 
output frequency ranges from approximately 5 to 13 kHz corresponding to temperature from -5 to 35°C.  The 
output frequency is inversely proportional to the square root of the thermistor resistance, which controls the 
output of a patented Wien Bridge circuit.  The thermistor resistance is exponentially related to temperature.  

The SBE 3 thermometer has a nominal accuracy of 0.001°C, typical stability of 0.0002°C/month and resolution 
of 0.0002°C at 24 samples per second.  The premium temperature sensor, SBE 3plus, is a more rigorously 
tested and calibrated version of standard temperature sensor (SBE 3).  A sensor is designated as an SBE 3plus 
only after demonstrating drift of less than 0.001°C during a six-month screening period.  In addition, the time 
response is carefully measured and verified to be 0.065 ± 0.010 seconds.  

Pre-cruise sensor calibrations were performed at SBE, Inc., USA.  The following coefficients were used in 
SEASOFT:
 
S/N 4188 (Leg 1), 25 June 2003 
  g = 4.39868209e-03 
  h = 6.45272514e-04 
  i = 2.26066338e-05 
  j = 1.89127504e-06 
  f0 = 1000.000 
S/N 1464 (Leg 1), 24 June 2003 
  g = 4.84388979e-03 
  h = 6.80795615e-04 
  i = 2.70029675e-05 
  j = 2.13380253e-06 
  f0 = 1000.000 
S/N 1524 (Leg 2), 15 April 2003 
  g = 4.85928482e-03 
  h = 6.85560499e-04 
  i = 2.72682203e-05 
  j = 2.04591608e-06 
  f0 = 1000.000 
S/N 4216 (Leg 2), 29 July 2003 
  g = 4.35956769e-03 
  h = 6.45664029e-04 
  i = 2.25867675e-05 
  j = 1.88325427e-06 
  f0 = 1000.000 
S/N 2453 (Leg 2), 25 July 2003 
  g = 4.4010773e-03 
  h = 6.47307314e-04 
  i = 2.32721826e-05 
  j = 2.09881293e-06 
  f0 = 1000.000 
S/N 1464 (Leg 4 and 5), 23 September 2003 
  g = 4.84390595e-03 
  h = 6.80838076e-04 
  i = 2.70300539e-05 
  j = 2.13906165e-06 
  f0 = 1000.000
S/N 4188 (Leg 4), 23 September 2003 
  g = 4.39869651e-03 
  h = 6.45292266e-04 
  i = 2.26138218e-05 
  j = 1.89143037 e-06 
  f0 = 1000.000 
S/N 4323 (Leg 5), 29 October 2003 
  g = 4.36386026e-03 
  h = 6.48493108e-04 
  i = 2.28715193e-05 
  j = 1.84823185 e-06 
  f0 = 1000.000 
Temperature (ITS-90) is computed according to 
  Temperature (ITS-90) = 
    1 / {g + h * [ln(f0 / f)] + i * [ln2(f0 / f)] + j * [ln3(f0 / f)]} - 273.15 
  where f is the instrument frequency (kHz).  


(4.3) CONDUCTIVITY (SBE 4) 

The flow-through conductivity sensing element is a glass tube (cell) with three platinum electrodes to 
provide in-situ measurements at depths up to 10,500 meters.  The impedance between the center and the end 
electrodes is determined by the cell geometry and the specific conductance of the fluid within the cell.  The 
conductivity cell composes a Wien Bridge circuit with other electric elements of which frequency output is 
approximately 3 to 12 kHz corresponding to conductivity of the fluid of 0 to 7 S/m.  The conductivity cell SBE 4 
has a nominal accuracy of 0.0003 S/m, typical stability of 0.0003 S/m/month and resolution of 0.00004 S/m at 24 
samples per second.  

Pre-cruise sensor calibrations were performed at SBE, Inc., USA.  The following coefficients were used in 
SEASOFT: 

S/N 1088 (Leg 1), 3 July 2003 
  g = -4.01946189e+00 
  h = 5.50802658e-01 
  i = -1.68736617e-04 
  j = 3.83962022e-05 
  CPcor = -9.57e-08 (nominal) 
  CTcor = 3.25e-06 (nominal) 
S/N 1202 (Leg 1), 3 July 2003 
  g = -3.94210124e+00 
  h = 4.38993142e-01 
  i = -9.59762118e-06 
  j = 2.09906225e-05 
  CPcor = -9.57e-08 (nominal) 
  CTcor = 3.25e-06 (nominal) 
S/N 2240 (Leg 2), 30 July 2003 
  g = -1.06122361e+01 
  h = 1.51071990e+00 
  i = -2.24813805e-03 
  j = 2.43876786e-04 
  CPcor = -9.57e-08 (nominal) 
  CTcor = 3.25e-06 (nominal) 
S/N 1206 (Leg 2), 30 July 2003 
  g = -4.29002369+00
  h = 5.03379521e-01 
  i = 1.18152789e-04 
  j = 2.02164093e-05 
  CPcor = -9.57e-08 (nominal) 
  CTcor = 3.25e-06 (nominal) 
S/N 1203 (Leg 4), 25 September 2003 
  g = -4.05196392e+00 
  h = 4.93501401e-01 
  i = 8.12083631e-05 
  j = 2.24962840e-05 
  CPcor = -9.57e-08 (nominal) 
  CTcor = 3.25e-06 (nominal) 
S/N 2453 (Leg 4 and 5), 23 September 2003 
  g = -1.03013001e+00 
  h = 1.49755131e+00 
  i = 2.74099344e-04 
  j = 6.35607354e-05 
  CPcor = -9.57e-08 (nominal) 
  CTcor = 3.25e-06 (nominal) 
S/N 1088 (Leg 5), 4 November 2003 
  g = -4.02167245e+00 
  h = 5.51410012e-01 
  i = -2.94330837e-04 
  j = 4.48686818e-05 
  CPcor = -9.57e-08 (nominal) 
  CTcor = 3.25e-06 (nominal) 
S/N 1202 (Leg 5), 4 November 2003 
  g = -3.94477408e+00 
  h = 4.39537561e-01 
  i = -8.82455063e-05 
  j = 2.54499450e-05 
  CPcor = -9.57e-08 (nominal) 
  CTcor = 3.25e-06 (nominal) 

Conductivity of a fluid in the cell is expressed as: 
  C (S/m) = (g + h * f2 + i * f3 + j * f4) / [10 ( 1 + CTcor * t + CPcor * p)] 
where f is the instrument frequency (kHz), t is the water temperature (°C) and p is the water pressure (dbar).  

The value of conductivity at salinity of 35, temperature of 15°C (IPTS-68) and pressure of 0 dbar is 4.2914 S/m.  


(4.4) Oxygen (SBE 43) 

The SBE 43 oxygen sensor uses a Clark polarographic element to provide in-situ measurements at depths 
up to 7,000 meters.  Calibration stability is improved by an order of magnitude and pressure hysterisis is largely 
eliminated in the upper ocean (1,000 m) compared with the previous oxygen sensor (SBE 13).  Continuous 
polarization eliminates the wait-time for stabilization after power-up.  Signal resolution is increased by on-board 
temperature compensation.  The oxygen sensor is also included in the path of pumped sea water.  The oxygen 
sensor determines the dissolved oxygen concentration by counting the number of oxygen molecules per second 
(flux) that diffuse through a membrane, where the permeability of the membrane to oxygen is a function of 
temperature and ambient pressure.  Computation of dissolved oxygen in engineering units is done in SEASOFT 
software.  The range for dissolved oxygen is 120% of surface saturation in all natural waters; nominal accuracy 
is 2% of saturation; typical stability is 2% per 1,000 hours.  

Pre-cruise sensor calibrations were performed at SBE, Inc., USA.  The following coefficients were used in 
SEASOFT:

S/N 0390 (Leg 1), 14 July 2003 
  Soc = 0.3158 
  TCor = 0.0019 
  PCor = 1.350e-04 
  Offset = -0.5041 
S/N 0205 (Leg 1), 18 June 2003 
  Soc = 0.3982 
  TCor = 0.0003 
  PCor = 1.350e-04 
  Offset = -0.4885 
S/N 0391 (Leg 2, 4 and 5), 17 July 2003 
  Soc = 0.4108 
  TCor = 0.0012 
  PCor = 1.350e-04 
  Offset = -0.4851 
S/N 0069 (Leg 2), 7 August 2003 
  Soc = 0.3001 
  TCor = 0.0009 
  PCor = 1.350e-04 
  Offset = 0.5984 
S/N 0394 (Leg 4), 6 October 2003 
  Soc = 0.3003 
  TCor = 0.0016 
  PCor = 1.350e-04 
  Offset = 0.5016 
S/N 0205 (Leg 5), 17 November 2003 
  Soc = 0.3982 
  TCor = 0.0002 
  PCor = 1.350e-04 
  Offset = -0.4808 
Oxygen (ml/l) is computed as 
  Oxygen (ml/l) = {Soc * (v + offset)} * exp(TCor * t + PCor * p) * Oxsat(t, s) 
  Oxsat(t, s) = exp[A1 + A2 * (100 / t) + A3 * ln(t / 100) + A4 * (t / 100) 
    + s * {B1 + B2 * (t / 100) + B3 * (t / 100) * (t / 100)}] 
  A1 = -173.4292 
  A2 = 249.6339 
  A3 = 143.3483 
  A4 = -21.8482 
  B1 = -0.033096 
  B2 = -0.00170 
where p is pressure in dbar, t is absolute temperature and s is salinity in psu.  Oxsat is oxygen saturation value 
minus the volume of oxygen gas (STP) absorbed from humidity-saturated air.  


(4.5) DEEP OCEAN STANDARDS THERMOMETER 

The Deep Ocean Standards Thermometer (SBE 35) is an accurate, ocean-range temperature sensor that 
can be standardized against Triple Point of Water and Gallium Melt Point cells and is also capable of measuring 
temperature in the ocean to depths of 6,800 m.  

Temperature is determined by applying an AC excitation to reference resistances and an ultrastable aged 
thermistor with a drift rate of less than 0.001°C/year.  Each of the resulting outputs is digitized by a 20-bit A/D 
converter.  The reference resistor is a hermetically sealed, temperature-controlled VISHAY.  The switches are 
mercury wetted reed relays with a stable contact resistance.  AC excitation and ratiometric comparison using 
a common processing channel removes measurement errors due to parasitic thermocouples, offset voltages, 
leakage currents, and gain errors.  Maximum power dissipated in the thermistor is 0.5 μwatts, and contributes 
less than 200 μK of overheat error.  

The SBE 35 communicates via a standard RS-232 interface at 300 baud, 8 bits, no parity.  The SBE 35 
can be used with the SBE 32 Carousel Water Sampler and SBE 911plus CTD system.  The SBE 35 makes a 
temperature measurement each time a bottle fire confirmation is received, and stores the value in EEPROM.  

Calibration coefficients stored in EEPROM allow the SBE 35 to transmit data in engineering units.  Commands 
can be sent to SBE 35 to provide status display, data acquisition setup, data retrieval, and diagnostic test using 
terminal software.  

Following the methodology used for standards-grade platinum resistance thermometers (SPRT), the 
calibration of the SBE 35 is accomplished in two steps.  The first step is to characterize and capture the 
non-linear resistance vs temperature response of the sensor.  The SBE 35 calibrations are performed at SBE, 
Inc., in a low-gradient temperature bath and against ITS-90 certified SPRTs maintained at Sea-Bird's primary 
temperature metrology laboratory.  The second step is frequent certification of the sensor by measurements 
in thermodynamic fixed-point cells.  Triple point of water (TPW) and gallium melt point (GaMP) cells are 
appropriate for the SBE 35.  The SBE 35 resolves temperature in the fixed-point cells to approximately 25 μK.  

Like SPRTs, the slow time drift of the SBE 35 is adjusted by a slope and offset correction to the basic non-linear 
calibration equation.  

Pre-cruise sensor calibrations were performed at SBE, Inc., USA.  The following coefficients were stored in 
EEPROM: 

S/N 0022 (Leg 1 and 2), 12 October 1999 (1st step: linearization) 
  a0 =  4.320725498e-3 
  a1 = -1.189839279e-3 
  a2 =  1.836299593e-3 
  a3 = -1.032916769e-5 
  a4 =  2.225491125e-7 
S/N 0045 (Leg 4 and 5), 27 October 2002 (1st step: linearization) 
  a0 =  5.84093815e-03 
  a1 = -1.65529280e-03 
  a2 =  2.37944937e-04 
  a3 = -1.32611385e-05 
  a4 =  2.83355203e-07 
Linearized temperature (ITS-90) is computed according to 
  Linearized temperature (ITS-90) = 
    1 / {a0 + a1 * [ln(n)] + a2 * [ln2(n)] + a3 * [ln3(n)]+ a4 * [ln4(n)]} - 273.15 
where n is the instrument output.  Then the SBE 35 is certified by measurements in thermodynamic fixed-point 
cells of the TPW (0.0100°C) and GaMP (29.7646°C).  Like SPRTs, the slow time drift of the SBE 35 is adjusted 
by periodic recertification corrections.  

S/N 0022 (Leg 1 and 2), 26 March 2003 (2nd step: fixed point calibration) 
  Slope =   1.000012 
  Offset =  0.000052 
S/N 0045 (Leg 4 and 5), 26 September 2003 (2nd step: fixed point calibration) 
  Slope =   1.000007 
  Offset = -0.000376 
Temperature (ITS-90) is calibrated according to 
  Temperature (ITS-90) = Slope * Linearized temperature + Offset 

The SBE 35 has a time constant of 0.5 seconds.  The time required per sample = 1.1 * NCYCLES + 2.7 
seconds.  The 1.1 seconds is total time per an acquisition cycle.  NCYCLES is the number of acquisition cycles 
per sample.  The 2.7 seconds is required for converting the measured values to temperature and storing average 
in EEPROM.  Root mean square (rms) temperature noise for a SBE 35 in a Triple Point of Water cell is typically 
expressed as 82 / NCYCLES1/2 in μK.  In this cruise NCYCLES was set to 4 and the rms noise is estimated to be 
0.04 m°C.  

When using the SBE 911 system with SBE 35, the deck unit receives incorrect signal from the under water 
unit for confirmation of firing bottle #16.  In order to correct the signal, a module (Yoshi Ver. 1, EMS Co. Ltd., 
JAPAN) was used between the under water unit and the deck unit.  


(4.6) Altimeter 

The Benthos 2110 Series Altimeter (Benthos, Inc., USA) follows the basic principal of most echo ranging 
devices.  That is, a burst of acoustic energy is transmitted and the time until the first reflection is received is 
determined.  In this unit, a 400 microsecond pulse at 100 kHz is transmitted twice a second; concurrent with the 
transmission, a clock is turned off, thus the number of pulses out relates directly to the distance of the target 
from the unit.  The internal ranging oscillator has an accuracy of approximately 5% and is set assuring a speed of 
sound of 1,500 m/s.  Thus the unit itself, neglecting variations in the speed of sound, can be considered accurate 
to 5% or 0.1 meter, whichever is greater.  The unit is rated to a depth of 12,000 meters.  

The Benthos PSA-900 Programmable Sonar Altimeter (Benthos, Inc., USA) determines the distance of 
the target from the unit in almost the same way as the Benthos 2110.  PSA-900 also uses the nominal speed of 
sound of 1,500 m/s.  But, PSA-900 compensates for sound velocity errors due to temperature.  In a PSA-900 
operating at a 350 microsecond pulse at 200 kHz, the jitter of the detectors can be as small as 5 microseconds or 
approximately 0.4 centimeters total distance.  Since the total travel time is divided by two, the jitter error is 0.25 
centimeters.  The PSA-900D is rated to a depth of 6,000 meters.  

The following scale factors were used in SEASOFT: 

  PSA-900D, S/N 1026 and S/N 0396 
   FSVolt * 300 / FSRange = 10 
   Offset = 0.0 
  Model 2110-2, S/N 206 
   FSVolt * 300 / FSRange = 15 
   Offset = 0.0 


(4.7) FLUOROMETER 

The Seapoint Chlorophyll Fluorometer (Seapoint sensors, Inc., USA) is a high-performance, low power 
instrument to provide in-situ measurements of chlorophyll-a at depths up to 6,000 meters.  The instrument 
uses modulated blue LED lamps and a blue excitation filter to excite chlorophyll-a.  The fluorescent light 
emitted by the chlorophyll-a passes through a red emission filter and is detected by a silicon photodiode.  The 
low level signal is then processed using synchronous demodulation circuitry, which generates an output voltage 
proportional to chlorophyll-a concentration.  

 
The following coefficients were used in SEASOFT: 

  S/N 2148 (Leg 1) 
    Gain = 30 
  Offset = 0.0 
  S/N 2579 (Leg 4 and 5) 
    Gain = 30 
    Offset = 0.0 
  Chlorophyll-a concentration is computed as 
    Chlorophyll-a (μg/l) = (Voltage * 30 / Gain) + Offset 


(5) DATA COLLECTION AND PROCESSING 

(5.1) DATA COLLECTION 

CTD measurements were made using a SBE 9plus CTD equipped with two pumped temperature-conductivity (TC) sensors. 
The TC pairs were monitored to check drift and shifts by examining the differences between the two pairs.  
Dissolved oxygen sensor was placed between the conductivity sensor module and the pump.  Auxiliary sensors 
included Deep Ocean Standards Thermometer, altimeter and fluorometer.  The SBE 9plus CTD (sampling rate of 24 Hz) 
was mounted horizontally in a 36-position carousel frame.  

CTD system was powered on at least two minutes in advance of the operation and was powered off at least 
two minutes after the operation in order to acquire pressure data on ship's deck.  

The package was lowered into the water from the starboard side and held 10 m beneath the surface for 
about one minute in order to activate the pump.  After the pump was activated, the package was lifted to the 
surface and lowered at a rate of 0.5 m/s down to 100 m, where the package was stopped in order to operate 
the heave compensator of the crane.  The package was lowered again at a rate of 1.2 m/s to the bottom.  The 
position of the package relative to the bottom was monitored by the altimeter reading.  Also the bottom depth 
was monitored by the SEABEAM multi-narrow beam sounder on board.  For the up cast, the package was lifted 
at a rate of 1.2 m/s except for bottle firing stops.  At each bottle firing stops, the bottle was fired after waiting 30 
seconds and the package was stayed 7 seconds in order to sample temperature by the Deep Ocean Standards 
Thermometer.  At 100 m from the surface, the package was stopped in order to stop the heave compensator of 
the crane.  

Water samples were collected using a 36-bottle SBE 32 Carousel Water Sampler with 12-litre Nisken-X 
bottles.  Before a cast for CFCs, the 36-bottle frame and Niskin-X bottles were wiped with acetone.  

The SBE 11plus deck unit received the data signal from the CTD.  Digitized data were forwarded to a 
personal computer running the SEASAVE data acquisition software.  Temperature, conductivity, salinity, oxygen 
and descent rate profiles were displayed in real-time with the package depth and altimeter reading.  

Data acquisition software (Leg 1, 2, 4 and 5) 
  SBE, Inc., SEASAVE-Win32, version 5.27b 
After each CTD cast the SBE 35 data was retrieved using terminal software.  

Terminal software (Leg 1, 2, 4 and 5) 
  SBE, Inc., SEATERM-Win32, version 1.33 


(5.2) DATA COLLECTION PROBLEMS 

Leg 1 
  At station P06_X11, a small fish was found in the primary TC-duct after the CTD cast and influenced on the 
  primary salinity and oxygen data.  
  
  At station P06_166, communication between under water unit and deck unit broken at 1,800 m depth during 
  the up cast, so the CTD cast was aborted.  The system was checked after the cast and the fluorometer was found 
  to be broken.  Second cast was carried out at the site without fluorometer.  
  
  Frequently date and time of the SBE 35 (S/N 0022) did not change from "01 Jan 1980 00:00:-1" by the setup 
  commands "ddmmyy" and "hhmmss".  In such a case, test command (*rtctest) to reset date and time to default 
  value (01 Jan 1980 00:00:00) did not work and date and time of the samples in the data file did not change from " 
  01 Jan 1980 00:00:-1".  This problem was found at stations P06_126, 125, 123, 122 and 121.  It was found that the 
  lithium backup battery had reached the end of its life expectancy by the post-cruise calibration (19 November 
  2003).  

Leg 2 
  At station P06_127 second cast (first cast of this leg), frequent noise in primary temperature (its magnitude 
  was about one to two°C) was found during 400 to 900 m depths in the down cast.  So the cast was aborted and 
  the CTD package was lifted to the deck.  Primary temperature sensor was replaced from S/N 4216 to 1524 
  and the connection cable was also replaced.  A third cast was done at the site.  But similar noise in primary 
  temperature was found at about 600 m depths in the down cast.  So the cast was aborted.  After replacing SBE 
  9plus from S/N 0575 to S/N 0357 and all of the connection cables used, a fourth cast was done at the site.  After 
  the cast primary temperature sensor was replaced again from S/N 1524 to 4216.  
  
  At station P06_X17, the personal computer, which displays and stores the serial data from the deck unit, was 
  suddenly rebooted at about 1,500 m in the down cast.  So the cast was aborted and the CTD package was lifted 
  to the deck.  Connection of the AC power cable was checked and an AC power supply, CVFT1-500H (TOKYO 
  SEIDEN Co., JAPAN), was used in order to remove voltage fluctuations and irregularities in power lines.  A 
  second cast was done at the site.  
  
  After station P06_102, Niskin-X bottle #9 (NX(NC)12021) was replaced with bottle #3 (NX(NC)12015) in 
  order to check leakage or miss-trip of the bottle #9 that was guessed from analyzed values of salinity, oxygen 
  and nutrients at station P06_114.  
  
  After station P06_101, a hook that was connecting top and bottom caps of Niskin-X bottle #9 by nylon line 
  was away from the bottom cap.  So the bottle #9 was replaced from NX(NC)12015 to NX(NC)12012 after the 
  cast.  
  
  At station P06_061, output from secondary dissolved oxygen sensor (S/N 0069) showed unusual (negative) 
  value.  The secondary oxygen sensor was removed after the cast.  
  
  At the beginning of the down cast of station P06_044, the bottle confirmation signal correction module for 
  SBE 35 continued to display unusual signal during the package was lifting from 10 m beneath the surface after 
  activating the pump.  The status lamp did not change from red to green though the module was turned on again.  
  
  So the SEASAVE software was re-started from the surface in order to acquire the data in a new file, 044M02.  
  
  The SBE 35 (S/N 0022) backup battery problem was found at following stations: P06_119, 118, 117, 109, 
  108, X17, 106, 105, 104, 103, 102, 101, 100, 099, 098, 097, 096, 095, 094, 091, 089, 087, 086, 085, 084, 083, 082, 
  081, 080, 078, 077, 076, P06_069, 056, 055, 054, 053, 052, 050, 049, 045, 036, 031, 028, 027, 024, 023, 022, 021, 
  019, 016, 015, 014, 013, 012, 011, 010, 009, 008, 007, 006 and 005.  

Leg 4 
  At stations A10_043 and 068, the same bottle was fired by mistake.  Because the SEASAVE module didn' 
  t accept firing bottles more than 36 times, a bottle was fired using a fire button of the SBE 11plus deck unit in 
  order to close all bottles.  Bottles can be fired sequentially from its home position (#1) using the fire button of 
  the SBE 11plus deck unit.  Therefore the bottle #4 for the station A10_043 and #5 for the station A10_068 were 
  closed by pushing the fire button of the deck unit 4 and 5 times, respectively.  
  
  At station A10_089, abnormal value (greater than 37 psu) in primary salinity was found between 60 and 100 
  m depths.  Obtained data was carefully checked after the cast and unusual profiles in primary conductivity and 
  primary temperature were seen.  Therefore second cast was done at the site after the temperature, conductivity 
  and oxygen sensors were washed with Triton X for 10 minutes.  
  
  When the SBE 35 (S/N 0045) data was uploaded by SEATERM, transmission error occurred at all casts 
  except for A10_98, 99 and 100.  Randomly dropped one character in the SBE 35 data file was estimated and the 
  file was corrected manually.  

Leg 5 
  At station I04_597, a small fish was found in primary TC-duct after the cast and influenced 
  on the primary temperature, salinity and oxygen data shallower than 800 dbar of the up cast.  

  At station I03_529, the secondary conductivity sensor (S/N 1202) showed unusual value from 
  3,208 dbar of the up cast.  

  After station I03_551, a crack was found inside of the Niskin-X bottle #9 
  (NX(NC)12017) and the bottle was replaced to Niskin-X bottle (NX(NC)12021).  

  After station I03_513, carousel water sampler was replaced from S/N 0391 to S/N 0278.  

  At station I03_513 first cast, the scan number of the CTD data was not increased at 
  10 m beneath the surface.  Therefore the SEASAVE software was re-started and the data was 
  acquired from the surface in the same file, 513M01.  

  At station I03_511, the altimeter showed unusual values (negative).  So the altimeter 
  was replaced from S/N 1026 to S/N 0396.  

  At station I03_503, primary conductivity sensor (S/N 1088) showed unusual value from 
  4,995 dbar of the down cast.  So the primary conductivity sensor was replaced to 
  S/N 2435 after the cast.  

  At station I03_466, SEASAVE software was hung upped at about 120 m depths in the down cast.  
  So the cast was aborted and the CTD package was lifted to the deck.  The deck unit 
  (SBE 11plus) was replaced from 

  S/N 0272 to S/N 0344 and SEASAVE software was re-started.  The second cast was done at 
  the site in a new file, 466M03.  

  When the SBE 35 (S/N 0045) data was uploaded by SEATERM, transmission error occurred at
  all casts except for I03_524 and 448.  Randomly dropped one character in the SBE 35 data 
  file was estimated and the file was corrected manually.  


(5.3) DATA PROCESSING 

SEASOFT consists of modular menu driven routines for acquisition, display, processing, and archiving of 
oceanographic data acquired with SBE equipment, and is designed to work with a compatible personal computer.  

Raw data are acquired from instruments and are stored as unmodified data.  The conversion module DATCNV 
uses the instrument configuration and calibration coefficients to create a converted engineering unit data file that 
is operated on by all SEASOFT post processing modules.  Each SEASOFT module that modifies the converted 
data file adds proper information to the header of the converted file permitting tracking of how the various 
oceanographic parameters were obtained.  The converted data is stored in rows and columns of ascii numbers.  

The last data column is a flag field used to mark scans as good or bad.  

The following are the SEASOFT data processing module sequence and specifications used in the reduction 
of CTD data in this cruise.  


DATA PROCESSING SOFTWARE (Leg 1, 2, 4 and 5) 
  SBE, Inc., SEASOFT-Win32, version 5.27b 

DATCNV converted the raw data to scan number, pressure, depth, temperatures, conductivities, oxygen 
voltage, descent rate, altitude and fluorescence.  DATCNV also extracted bottle information where scans were 
marked with the bottle confirm bit during acquisition.  The duration was set to 4.4 seconds, and the offset was 
set to 0.0 seconds.  

ROSSUM created a summary of the bottle data.  The bottle position, date, time were output as the first two 
columns.  Scan number, pressure, depth, temperatures, conductivities, oxygen voltage, descent rate, altitude and 
fluorescence were averaged over 4.4 seconds.  And salinity, potential temperature, density (σθ) and oxygen were 
computed.  

ALIGNCTD converted the time-sequence of conductivity and oxygen sensor outputs into the pressure 
sequence to ensure that all calculations were made using measurements from the same parcel of water.  For a 
SBE 9plus CTD with the ducted temperature and conductivity sensors and a 3,000-rpm pump, the typical net 
advance of the conductivity relative to the temperature is 0.073 seconds.  So, the SBE 11plus deck unit was 
set to advance the primary conductivity for 1.73 scans (1.75/24 = 0.073 seconds).  As a result, the secondary 
conductivity was advanced 0.073 seconds relative to the temperature.  Oxygen data are also systematically 
delayed with respect to depth mainly because of the long time constant of the oxygen sensor and of an additional 
delay from the transit time of water in the pumped plumbing line.  This delay was compensated by 6 seconds 
advancing oxygen sensor output (oxygen voltage) relative to the temperature.  

WILDEDIT marked extreme outliers in the data files.  The first pass of WILDEDIT obtained an accurate 
estimate of the true standard deviation of the data.  The data were read in blocks of 1000 scans.  Data greater 
than 10 standard deviations were flagged.  The second pass computed a standard deviation over the same 1000 
scans excluding the flagged values.  Values greater than 20 standard deviations were marked bad.  This process 
was applied to all variables.  

CELLTM used a recursive filter to remove conductivity cell thermal mass effects from the measured 
conductivity.  Typical values used were thermal anomaly amplitude alpha = 0.03 and the time constant 1/beta = 7.0.  

FILTER performed a low pass filter on pressure with a time constant of 0.15 seconds.  In order to produce 
zero phase lag (no time shift) the filter runs forward first then backwards.  

WFILTER performed a median filter to remove spikes in the Fluorometer data.  A median value was 
determined from a window of 49 scans.  

SECTION selected a time span of data based on scan number in order to reduce a file size.  The minimum 
number was set to be the start time when the CTD package was beneath the sea-surface after activation of the 
pump.  The maximum number was set to be the end time when the package came up from the surface.  Data to 
check the CTD pressure drift were prepared before SECTION.  

LOOPEDIT marked scans where the CTD was moving less than the minimum velocity of 0.0 m/s (traveling 
backwards due to ship roll).  

DERIVE was used to compute oxygen.  

BINAVG averaged the data into 1 dbar pressure bins.  The center value of the first bin was set equal to the 
bin size.  The bin minimum and maximum values are the center value plus and minus half the bin size.  Scans 
with pressures greater than the minimum and less than or equal to the maximum were averaged.  Scans were 
interpolated so that a data record exists every dbar.  

DERIVE was re-used to compute salinity, potential temperature, and density (σθ).  

SPLIT was used to split data into the down cast and the up cast.  


(5.4) ADDITIONAL DATA PROCESSING 

After the data processing mentioned above the CTD data was carefully checked.  Fine-tuning adjustments 
between the temperature measurement and the conductivity measurement to the default advance (0.073 
seconds) were determined by looking for potential temperature - salinity plot as follows.  

  + 0.031 seconds for P06_227, P06_192 (leg 1, secondary conductivity) 
  - 0.021 seconds for P06_081 (leg 2, primary conductivity) 
  - 0.042 seconds for A10 all stations (leg 4, primary conductivity) 
  - 0.030 seconds for I3/I4 all stations (leg 5, primary conductivity) 
  + 0.045 seconds for I3/I4 all stations (leg 5, secondary conductivity) 

For these stations the CTD data were re-processed with the additions following the data processing sequence 
mentioned above.  Remaining spikes were removed by hand for the data file processed by LOOPEDIT and 
processed again following the data processing sequence after LOOPEDIT mentioned above.  


(6) POST-CRUISE CALIBRATION 

(6.1) PRESSURE 

The CTD pressure sensor drift in the period of the cruise is estimated from the pressure readings on 
the ship deck.  For best results the Paroscientific sensor has to be powered for at least 10 minutes before the 
operation and carefully temperature equilibrated.  However, CTD system was powered only several minutes 
before the operation at most of stations.  In order to get the calibration data for the pre- and post-cast pressure 
sensor drift, the CTD deck pressure is averaged over first and last two minutes, respectively.  Then the 
atmospheric pressure deviation from a standard atmospheric pressure (14.7 psi) is subtracted from the CTD 
deck pressure.  The atmospheric pressure was measured at the captain deck (20 m high from the base line) and 
sub-sampled one-minute interval for a meteorological data.  Time series of the CTD deck pressure are shown in 
Figure 3.1.7 - 3.1.10.  

The CTD pressure sensor drift is estimated from the deck pressure obtained above.  Mean of the pre- and 
the post-casts data over the whole period for each leg gave an estimation of the pressure sensor drift from the 
pre-cruise calibration date at each leg.  Mean residual pressure between the dead weight piston gauge and the 
calibrated CTD data at 0 dbar of the pre-cruise calibration is subtracted from the mean deck pressure.  Offset of 
the pressure data is estimated to be within ± 0.4 dbar (Table 3.1.1).  So the post-cruise calibration is not deemed 
necessary for the pressure sensors. 


TABLE 3.1.1. Offset of the pressure data.  Mean and standard deviation are calculated 
             from time series of the average of the pre- and the post-cast deck pressures.  
             ______________________________________________________________

                                 Mean deck  Standard   Residual  Estimated 
              Leg     S/N        pressure   deviation  pressure   offset
                                 (dbar)     (dbar)     (dbar)     (dbar)
              ----------------------------------------------------------
              Leg 1   0575        0.52       0.11       0.12      0.40 
              Leg 2   0357       -0.71       0.10      -0.57     -0.14 
              Leg 4   0357       -0.84       0.18      -0.57     -0.27 
              Leg 5   0357       -0.92       0.17      -0.57     -0.35
             ______________________________________________________________


FIGURE 3.1.7.  Time series of the CTD deck pressure for leg 1.  Pink dot indicates atmospheric 
               pressure anomaly.  Blue and green dots indicate pre- and post-cast deck pressures, 
               respectively.  Red dot indicates an average of the pre- and the post-cast deck pressures. 
FIGURE 3.1.8.  Same as Figure 3.1.7, but for leg 2. 
FIGURE 3.1.9.  Same as Figure 3.1.7, but for leg 4. 
FIGURE 3.1.10. Same as Figure 3.1.7, but for leg 5.


(6.2) TEMPERATURE 

The CTD temperature sensor (SBE 3) is made with a glass encased thermistor bead inside a needle.  The 
needle protects the thermistor from seawater.  If the thermistor bead is slightly large of specification, it receives 
mechanical stress when the needle is compressed at high pressure (Budeus and Schneider, 1998).  The pressure 
sensitivity for a SBE 3 sensor is usually less than +2 mK / 6000 dbar.  It is somewhat difficult to measure this 
effect in the laboratory and it is one of the primary reasons to use the SBE 35 at sea for critical work.  Also 
SBE 3 measurements may be affected by viscous heating that occurs in a TC duct and does not occur for 
un-pumped SBE 35 measurements (Larson and Pederson, 1996).  Furthermore the SBE 35 calibrations have 
some uncertainty (about 0.2 mK) and SBE 3 calibrations have some uncertainty (about 1 mK).  So the practical 
corrections for CTD temperature data can be made by using a SBE 35, correcting the SBE 3 to agree with 
the SBE 35 (a linear pressure correction, a viscous heating correction and an offset for drift and/or calibration 
uncertainty).  

Post-cruise sensor calibrations for the SBE 35 were performed at SBE, Inc., USA.  

S/N 0022 (Leg 1 and 2), 19 November 2003 (2nd step: fixed point calibration) 
   Slope =  1.000018 
  Offset =  0.000116 
S/N 0045 (Leg 4 and 5), 31 March 2004 (2nd step: fixed point calibration) 
   Slope =  1.000009 
  Offset = -0.000772 

Offsets of the SBE 35 data from the pre-cruise calibration are estimated to be 0.0 (leg 1), 0.1 (leg 2), 0.1 (leg 
4) and 0.2 (leg 5) m°C for temperature less than 4°C.  So the post-cruise calibration is not deemed necessary for 
the SBE 35 sensors.  

The discrepancy between the CTD temperature and the standard thermometer (SBE 35) is considered to be 
a function of pressure and time.  Since the pressure sensitivity is thought to be constant in time at least during 
observation period, the CTD temperature is calibrated as 

               Calibrated temperature = T - (c0 * P + c1 * t + c2 ) 

where T is CTD temperature in°C, P is pressure in dbar, t is time in days from pre-cruise calibration date of 
CTD temperature and c0, c1, and c2 are calibration coefficients.  The best fit sets of coefficients are determined 
by minimizing the sum of absolute deviation from the SBE 35 data.  The MATLAB® function FMINSEARCH is 
used to determine the sets.  The FMINSEARCH uses the simplex search method (Lagarias et al., 1998).  This is 
a direct search method that does not use numerical or analytic gradients.  

The calibration is performed for the following temperature data.  

 Leg 1: secondary (S/N 1464) 
 Leg 2: primary   (S/N 1254) for P06_127 
        primary   (S/N 4216) from P06_125 to P06_004 
 Leg 4: primary   (S/N 1464) 
 Leg 5: primary   (S/N 1464) except for I04_597 and I03_503 
        secondary (S/N 4323) for I04_597 and I03_503 

The CTD data created by the software module ROSSUM are used.  The deviation of CTD temperature from 
the SBE 35 at depth shallower than 2,000 dbar is large for determining the coefficients with sufficient accuracy 
since the vertical temperature gradient is strong in the regions.  So the coefficients are determined using the 
data in the depth deeper than 1,950 dbar.  

Since pressure sensitivity for the secondary temperature sensor (S/N 1464) is small compared with that of 
the primary temperature sensor (S/N 4188) in leg 1, data from the secondary temperature sensor are used in leg 
1.  Since the secondary temperature sensor (S/N 2453) had unusually large pressure sensitivity (+ 5m°C / 6,000 
dbar) in leg 2, data from the primary temperature sensor (S/N 1254 and S/N 4216) are used in leg 2 although the 
primary temperature sensor (S/N 4216) reading showed unusually large time drift (an order of 1 m°C / month).  

Since the difference between primary temperature (S/N 4216) and SBE 35 data showed different tendency of the 
time drift during leg 2, the data was divided four periods and the coefficients are determined for each period with 
fixed pressure sensitivity (c0 is constant).  For station I04_597 and I03_503 in leg 5, data quality of the primary 
conductivity sensor were bad, so the secondary temperature sensor is also calibrated and the data from the 
secondary temperature sensor are used for the two stations in leg 5.  

The number of data used for the calibration and the mean absolute deviation from the SBE 35 are listed in 
Table 3.1.2 and the calibration coefficients are listed in Table 3.1.3.  The results of the post-cruise calibration for 
the CTD temperature are summarized in Table 3.1.4 and shown in Figure 3.1.11 to Figure 3.1.14.  


TABLE 3.1.2. Number of data used for the calibration (pressure > 1,950 dbar) and mean 
             absolute deviation (ADEV) between the CTD temperature and the SBE 35. 
             ___________________________________________

              Leg    S/N   Number   ADEV   Note 
                          of data  (m°C)
             -----------------------------------------
             Leg 1  1464  1724     0.15 
             Leg 2  1254  16       0.10   only P06_127 
                    4216  1108     0.11 
             Leg 4  1464  1136     0.17 
             Leg 5  1464  1659     0.14 
                    4323  1659     0.18 
             ___________________________________________


TABLE 3.1.3. Calibration coefficients for the CTD temperature sensor 
             ___________________________________________________________________________

               Leg    S/N          c0              c1           c2          Note
                              (°C/dbar)        (°C/day)       (°C) 
              -------------------------------------------------------------------------
              Leg 1  1464  -8.26735877e-008   1.48131e-005   0.37e-3 
              Leg 2  1254   2.65640509e-007         -       -0.68e-3  P06_127 
                     4216  -5.25359666e-008   1.09403e-004  -3.18e-3  P06_125 - P06_094 
                           -5.25359666e-008  -2.08090e-005   4.01e-3  P06_093 - P06_055 
                           -5.25359666e-008  -3.24966e-005   5.12e-3  P06_054 - P06_024 
                           -5.25359666e-008   3.14971e-005   0.79e-3  P06_023 - P06_004 
              Leg 4  1464  -7.07002361e-008   9.73776e-006  -0.03e-3  
              Leg 5  1464  -6.97861330e-008  -1.26196e-006   0.83e-3  
                     4323   2.51539456e-007  -1.65317e-005   0.95e-3  I04_597, I03_503 
             ___________________________________________________________________________


TABLE 3.1.4. Difference between the CTD temperature and the SBE 35 after the post-cruise 
             calibration.  Mean and standard deviation (Sdev) are calculated below and 
             above 2,000 dbar for each leg.  Number of data used is also shown. 
             _____________________________________________________________________

               Leg    Pressure >= 2,000 dbar          Pressure < 2,000 dbar 
                     Num   Mean (m°C)  Sdev (m°C)    Num   Mean (m°C)  Sdev (m°C) 
              -------------------------------------------------------------------
              Leg 1  1687   0.01       0.21          2660  -0.26       2.74 
              Leg 2  1087   0.00       0.18          3027   0.20       3.75 
              Leg 4  1113  ?0.01       0.33          2795  -0.01       4.64 
              Leg 5  1624   0.00       0.22          3140   0.27       6.61
             _____________________________________________________________________


FIGURE 3.1.11. Difference between the CTD temperature and the Deep Ocean Standards 
               thermometer (SBE 35) for leg 1.  Blue and red dots indicate before 
               and after the post-cruise calibration using the SBE 35 data, respectively.  
               Lower two panels show histogram of the difference after the calibration. 
FIGURE 3.1.12. Same as FIGURE 3.1.11, but for leg 2.
FIGURE 3.1.13. Same as FIGURE 3.1.11, but for leg 4. FIGURE 3.1.14.  
               Same as FIGURE 3.1.11, but for leg 5.


(6.3) SALINITY 

The discrepancy between the CTD salinity and the bottle salinity is considered to be a function of 
conductivity and pressure.  The CTD salinity is calibrated as 
 
             Calibrated salinity = S - (c0 * P + c1 * C + c2 * C * P + c3) 

where S is CTD salinity, P is pressure in dbar, C is conductivity in S/m and c0, c1, c2 and c3 are calibration 
coefficients.  The best fit sets of coefficients are determined by minimizing the sum of absolute deviation with a 
weight from the bottle salinity data.  The MATLAB® function FMINSEARCH is used to determine the sets.  The 
weight is given as a function of vertical salinity gradient and pressure as 

             Weight = min[4, exp{log(4) * Gr / Grad}] * min[4, exp{log(4) * P2 / PR2}] 

where Grad is vertical salinity gradient in PSU dbar-1, P is pressure in dbar.  Gr and PR are threshold of the 
salinity gradient (default value is 0.5 mPSU dbar-1) and pressure (1,000 dbar), respectively.  When salinity 
gradient is small (large) and pressure is large (small), the weight is large (small) at maximum (minimum) value 
of 16 (1).  The salinity gradient is calculated using up-cast CTD salinity data.  The up-cast CTD salinity data is 
low-pass filtered with a 3-point (weights are 1/4, 1/2, 1/4) triangle filter before the calculation.  

  The calibration is performed for the salinity derived from the following conductivity sensor.  

    Leg 1: secondary (S/N 1202) 
    Leg 2: primary   (S/N 2240) 
    Leg 4: primary   (S/N 1203) 
    Leg 5: primary   (S/N 1088) from I04_610 to  I03_504 except for I04_597 
           secondary (S/N 1202) for  I04_597 and I03_503 
           primary   (S/N 2435) from I03_502 to  I03_444 

The CTD data created by the software module ROSSUM are used after the post-cruise calibration for the CTD 
temperature.  For station I04_597 and I03_503 in leg 5, data quality of the primary conductivity sensor were bad, 
so the data from the secondary conductivity sensor are used for the two stations in leg 5.  

The coefficients are basically determined for each station.  Some stations, especially for shallow stations, are 
grouped for determining the calibration coefficients.  In order to obtain better result, the threshold of the salinity 
gradient is changed to 0.3 mPSU/dbar for P06_206, P06_205, P06_056, I03_554, I03_518, I03_517, I03_506, 
I03_500, I03_490, I03_488, I03_480, I03_X09 and changed to 0.2 mPSU/dbar for I04_604, I04_588, I03_562, 
I03_561, I03_560, I03_599, I03_557, I03_556, I03_555.  An example of the calibration is shown in Figure 3.1.15.  

The results of the post-cruise calibration for the CTD salinity are summarized in Table 3.1.5 and shown in 
Figure 3.1.16 to Figure 3.1.19.  And the calibration coefficients, the mean absolute deviation (ADEV) from the 
bottle salinity and the number of the data (NUM) used for the calibration are listed in Table 3.1.6 to 
Table 3.1.9 Please see PDF version of this report for these tables).  


TABLE 3.1.5. Difference between the CTD salinity and the bottle salinity after the 
             post-cruise calibration.  Mean and standard deviation (Sdev) are calculated 
             below and above 1,000 dbar for each leg.  Number of data used is also shown.  
             _______________________________________________________________________

               Leg Pressure >= 1,000 dbar             Pressure < 1,000 dbar 
                     Num   Mean (mPSU)  Sdev (mPSU)  Num   Mean (mPSU)  Sdev (mPSU) 
              ---------------------------------------------------------------------
              Leg 1  1789  -0.01        0.34         1579  -0.24        1.25 
              Leg 2  1612   0.04        0.33         1427  -0.27        1.44 
              Leg 4  1433  -0.02        0.55         1336  -0.10        1.90 
              Leg 5  2070  -0.01        0.57         1822   0.42        4.46
             _______________________________________________________________________


FIGURE 3.1.15. An example of difference between the CTD salinity and the bottle salinity (leg 1, P06_174).  
               Upper panel shows vertical profile of bottle salinity (blue) and calibrated CTD salinity (red).  
               Middle panel shows vertical distribution of the difference (blue dot: before the calibration, 
                 red dot: after the calibration).  
               Lower panel shows histogram of the difference after the calibration.
FIGURE 3.1.16. Difference between the CTD salinity and the bottle salinity for leg 1.  Blue and red dots indicate 
               before and after the post-cruise calibration using the bottle salinity data, respectively.  
               Lower two panels show histogram of the difference after the calibration. 
FIGURE 3.1.17. Same as Figure 3.1.16, but for leg 2.
FIGURE 3.1.18. Same as Figure 3.1.16, but for leg 4. 
Figure 3.1.19. Same as Figure 3.1.16, but for leg 5.


TABLE 3.1.6.   Calibration coefficients of CTD salinity for leg 1. (see pdf report for these tables)
TABLE 3.1.7.   Same as Table 3.1.6, but for leg 2.
TABLE 3.1.8.   Same as Table 3.1.6, but for leg 4.
TABLE 3.1.9.   Same as Table 3.1.6, but for leg 5.



(6.4) OXYGEN 

The CTD oxygen is calibrated using the oxygen model (see 4.4) as 

  Calibrated oxygen (ml/l) 
  = {(Soc + dSoc) * {v + offset + doffset} * exp{(TCor + dTCor) * t + (PCor + dPCor) * p}} * Oxsat(t, s) 

where p is pressure in dbar, t is absolute temperature and s is salinity in psu.  Oxsat is oxygen saturation value 
minus the volume of oxygen gas (STP) absorbed from humidity-saturated air (see 4.4).  Soc, offset, TCor and 
PCor are the pre-cruise calibration coefficients (see 4.4) and dSoc, doffset, dTCor and dPCor are calibration 
coefficients.  The best fit sets of coefficients are determined by minimizing the sum of absolute deviation with a 
weight from the bottle oxygen data.  The MATLAB® function FMINSEARCH is used to determine the sets.  The 
weight is given as a function of vertical oxygen gradient and pressure as 

  Weight = min[4, exp{log(4) * Gr / Grad}] * min[4, exp{log(4) * P2 / PR2}] 

where Grad is vertical oxygen gradient in μmol kg-1 dbar-1, P is pressure in dbar.  Gr and PR are threshold of the 
oxygen gradient (default value is 0.3 μmol kg-1 dbar-1) and pressure (1,000 dbar), respectively.  When oxygen 
gradient is small (large) and pressure is large (small), the weight is large (small) at maximum (minimum) value 
of 16 (1).  The oxygen gradient is calculated using up-cast CTD oxygen data.  The up-cast CTD oxygen data is 
low-pass filtered with a 3-point (weights are 1/4, 1/2, 1/4) triangle filter before the calculation.  

The calibration is performed for the output from following oxygen sensor.  

 Leg 1: primary   (S/N 0390) with secondary temperature and salinity data 
 Leg 2: primary   (S/N 0391) 
 Leg 4: primary   (S/N 0391) 
 Leg 5: primary   (S/N 0391) except for I04_597 and I03_503 
        secondary (S/N 0205) for I04_597 and I03_503 

The down-cast CTD data sampled at same density of the CTD data created by the software module ROSSUM are 
used after the post-cruise calibration for the CTD temperature and salinity.  

The coefficients are basically determined for each station.  Some stations, especially for shallow stations, 
are grouped for determining the calibration coefficients.  Following stations are exceptionally grouped with fixing 
only the coefficient dTCor in order to obtain better result.  

    P06_175 & P06_174, P06_122 & P06_121, P06_011 & P06_010 & P06_009, 
    I03_546 & I03_545, I03_531 & I03_530, I03_528 & I03_527, I03_515 & I03_514, 
    I03_505 & I03_504 & I03_503, I03_452 & I03_451 & I03_450 

Two examples of the calibration are shown in Figure 3.1.15 and Figure 3.1.16.  For leg 1, the secondary 
oxygen sensor (S/N 0205) data could not be calibrated with sufficient accuracy through this calibration method 
(Figure 3.1.15).  Therefore the primary oxygen sensor (S/N 0390) data are used with secondary temperature and 
salinity data (Figure 3.1.16).  

The results of the post-cruise calibration for the CTD oxygen are summarized in Table 3.1.10 and shown in 
Figure 3.1.22 to Figure 3.1.25.  And the calibration coefficients, the mean absolute deviation (ADEV) from the 
bottle oxygen and the number of the data (NUM) used for the calibration are listed in Table 3.1.11 to Table 3.1.14.  


TABLE 3.1.10. Difference between the CTD oxygen and the bottle oxygen after the post-cruise calibration.  Mean 
              and standard deviation (Sdev) are calculated below and above 1,000 dbar for each leg.  Number of 
              data used is also shown.  
              __________________________________________________________________

               Leg    Pressure >= 1,000 dbar           Pressure < 1,000 dbar 
                      Num     Mean     Sdev            Num    Mean      Sdev 
               ----------------------------------------------------------------
                           (µmol/kg) (µmol/kg)              (µmol/kg) (µmol/kg) 
               Leg 1  1776    0.00     0.59            1581   -0.25     2.58 
               Leg 2  1570    0.09     0.71            1532    0.00     2.98 
               Leg 4  1438   -0.06     0.76            1412   -0.02     2.78 
               Leg 5  2088    0.00     1.14            1881    0.34     3.27
              __________________________________________________________________

FIGURE 3.1.20. An example of difference between the CTD oxygen and the bottle oxygen (leg 1, P06_174) 
               for secondary oxygen sensor (S/N 0205).  Upper panel shows vertical profile of bottle oxygen 
               (blue) and calibrated CTD oxygen (red).  Middle panel shows vertical distribution of the 
               difference (blue: before the calibration, red: after the calibration).  Lower panel shows 
               histogram of the difference after the calibration. 
FIGURE 3.1.21. Same as Figure 3.1.20, but for primary oxygen sensor (S/N 0390).
FIGURE 3.1.22. Difference between the CTD oxygen and the bottle oxygen for leg 1.  Blue and red dots indicate 
               before and after the post-cruise calibration using the bottle oxygen data, respectively.  Lower 
               two panels show histogram of the difference after the calibration. 
FIGURE 3.1.23. Same as Figure 3.1.22, but for leg 2.
FIGURE 3.1.24. Same as Figure 3.1.22, but for leg 4. Figure 3.1.25.  Same as Figure 3.1.22, but for leg 5.


TABLE 3.1.11.  Calibration coefficients of CTD oxygen for leg 1. (see pdf report for these tables)
TABLE 3.1.12.  Same as Table 3.1.11, but for leg 2.
TABLE 3.1.13.  Same as Table 3.1.11, but for leg 4.
TABLE 3.1.14.  Same as Table 3.1.11, but for leg 5.



REFERENCES 

Budeus, G. and W. Schneider (1998): In-situ temperature calibration: A remark on instruments and methods, Intl. 
    WOCE Newsletter, 30, 16-18.  
Lagarias, J.C., J.A. Reeds, M.H. Wright and P. E. Wright (1998): Convergence properties of the Nelder-Mead 
    simplex method in low dimensions, SIAM Journal of Optimization, 9, 112-147. 
Larson, N. and A. Pederson (1996): Temperature measurements in flowing water: Viscous heating of sensor tips, 
    1st IGHEM Meeting, Montreal, Canada.  

                (http://www.seabird.com/technical_references/paperindex.htm)


3.2 SALINITY 
    8 FEBRUARY 2005 

(1) PERSONNEL 

    Takeshi Kawano (JAMSTEC) 
    Takeo Matsumoto (MWJ) 
    Naoko Takahashi (MWJ) 
    Tomomi Watanabe (Nagasaki University) 


(2) OBJECTIVES 

Bottle salinities were measured in order to be compared with CTD salinities to identify leaking bottles and 
calibrate CTD salinities.  


(3) INSTRUMENT AND METHOD 

(3.1) SALINITY SAMPLE COLLECTION 

The bottles in which the salinity samples are collected and stored are 250 ml Phoenix brown glass bottles 
with screw caps.  Each bottle was rinsed three times with sample water and was filled to the shoulder of the 
bottle.  The caps were also thoroughly rinsed.  Salinity samples were stored for about 24 hours in the same 
laboratory as the salinity measurement was made.  


(3.2) INSTRUMENTS AND METHOD 

The salinity analysis was carried out on two sets of Guildline Autosal salinometers model 8400B (S/N 
62556 and S/N 62827), which were modified by addition of an Ocean Science International peristaltic-type 
sample intake pump and two Guildline platinum thermometers model 9450.  One thermometer monitored an 
ambient temperature and the other monitored a bath temperature.  The resolution of the thermometers was 
0.001°C.  The measurement system was almost same as Aoyama et al (2003).  The salinometer was operated 
in the air-conditioned ship's laboratory at a bath temperature of 24°C.  An ambient temperature varied from 
approximately 19°C to 23°C, while a bath temperature is very stable and varied within +/- 0.002°C on rare 
occasion.  A measure of a double conductivity ratio of a sample is taken as a median of thirty-one reading.  Data 
collection was started after 5 seconds and it took about 10 seconds to collect 31 readings by a personal computer.  

Data were sampled for the sixth and seventh filling of the cell.  In case the difference between the double 
conductivity ratio of this two fillings is smaller than 0.00003, the average value of the two double conductivity 
ratios was used to calculate the bottle salinity with the algorithm for practical salinity scale, 1978 (UNESCO, 
1981).  If the difference was grater than or equal to the 0.0003, we measured eighth filling of the cell.  In case the 
double conductivity ratio of eighth filling did not satisfy the criteria above, we measured ninth and tenth filling of 
the cell and the median of the double conductivity ratios of five fillings are used to calculate the bottle salinity.  

The measurement was conducted 16 hours per day (typically from noon to 04:00 in the next day in leg 
1, from 17:00 to 04:00 in the next day in leg 2, from 8:00 to 24:00 in leg 4, from 7:00 to 23:00 in leg 5) and the 
cell was rinsed by pure water every day and cleaned by ethanol or soap or both almost every day after the 
measurement of the day.  


(3.3) PRELIMINARY RESULT 

(i) Leg 1 

STAND SEAWATER 
Standardization control was set to 638 and all the measurements were done by this setting.  During the 
whole measurement, the STANDBY was 6107 +/- 0001 and ZERO was 0.00000 to 0.00001.  We used IAPSO 
Standard Seawater batch P142 whose conductivity ratio was 0.99991 (double conductivity ratio is 1.99982) as the 
standard for salinity.  We measured 178 ampoules of P142 and the average of the double conductivity ratio was 
1.99978 and the standard deviation was 0.000014, which is equivalent to 0.0003 in salinity.  Figure 3.2.1 shows 
the history of double conductivity ratio of the Standard Seawater batch P142.  Since there was no significant 
trend in Figure 3.2.1 and the average of the double conductivity ratio was 1.99978, we add 0.00004 to all of the 
measured double conductivity ratio.  


Figure 3.2.1. The history of double conductivity ratio of the Standard Seawater batch P142. 


SUB-STANDARD SEAWATER 
We also used sub-standard seawater which was deep-sea water filtered by pore size of 0.45 micrometer and 
stored in a 20 liter cubitainer made of polyethylene and stirred for at least 24 hours before measuring.  It was 
measured every six samples in order to check the possible sudden drift of the salinometer.  During the whole 
measurements, there was no detectable sudden drift of the salinometer.  

REPLICATE AND DUPLICATE SAMPLES 
We took 692 pairs of replicate and 49 pairs of duplicate samples.  Figure 3.2.2 (a) and (b) shows the histogram 
of the absolute difference between replicate samples and duplicate samples, respectively.  There were seven bad 
measurements and six questionable measurements of replicate samples.  As for questionable measurements, 
one of the pair is extremely high (more than 0.01 in salinity).  This might be cause insufficient seal of the sample 
bottles.  Excluding these bad and questionable measurements, the standard deviation of the absolute deference 
of 679 pairs of replicate samples was 0.0002 in salinity and that of 49 pairs of duplicate samples was 0.0003 in 
salinity. 
  

FIGURE 3.2.2 (a).  The histogram of the absolute difference between replicate samples.
FIGURE 3.2.2 (b).  The histogram of the absolute samples between duplicate samples. 


(ii) Leg 2 

STAND SEAWATER 
Standardization control was set to 506 and all the measurements were done by this setting.  During the 
whole measurement, the STANDBY was 6110 +/- 0001 and ZERO was -0.00001 to 0.00001.  We used IAPSO 
Standard Seawater batch P142 which conductivity ratio was 0.99991 (double conductivity ratio is 1.99982) as the 
standard for salinity.  We measured 157 ampoules of P142.  Figure 3.2.3 shows the history of double conductivity 
ratio of the Standard Seawater batch P142.  The values are rather scattered during the period from the beginning 
to the serial number 47 (from station 127 to 95).  The average of double conductivity ratio was 1.99976 and 
the standard deviation was 0.00018, which is equivalent to 0.0004 in salinity.  We add 0.00006 to the measured 
double conductivity ratio during this period.  As mentioned above, the cell of Autosal was removed and washed 
thoroughly between the serial number 47 and 48 (between station 94 and 95).  The measurement system 
became stable after washing.  The average became 1.99978 and the standard deviation became 0.00001, which is 
equivalent to 0.0002 in salinity.  We add 0.00004 to the measured double conductivity ratio after station 94.  


FIGURE 3.2.3.  The history of double conductivity ratio of the Standard Seawater batch P142.


SUB-STANDARD SEAWATER 
We also used sub-standard seawater which was deep-sea water filtered by pore size of 0.45 micrometer and 
stored in a 20 liter cubitainer made of polyethylene and stirred for at least 24 hours before measuring.  It was 
measured every six samples in order to check the possible sudden drift of the salinometer.  During the whole 
measurements, there was no detectable sudden drift of the salinometer.  

REPLICATE AND DUPLICATE SAMPLES 
We took 685 pairs of replicate and 67 pairs of duplicate samples.  Figure 3.2.4 (a) and (b) shows the histogram 
of the absolute difference between replicate samples and duplicate samples, respectively.  There were 11 bad 
measurements and 7 questionable measurements of replicate samples.  As for questionable measurements, one 
of the pairs is extremely high (more than 0.01 in salinity).  This might be cause insufficient seal of the sample 
bottles.  Excluding these bad and questionable measurements, the standard deviation of the absolute deference 
of 667 pairs of replicate samples was 0.0002 in salinity and that of 67 pairs of duplicate samples was 0.0003 in 
salinity.  


FIGURE 3.2.4 (a). The histogram of the absolute difference between replicate samples.
FIGURE 3.2.4 (b). The histogram of the absolute samples between duplicate samples. 


(iii) Leg 4 

STAND SEAWATER 
Standardization control was set to 638 and all the measurements were done by this setting.  During the 
whole measurement, the STANDBY was 6106 +/- 0001 and ZERO was 0.00000 to 0.00001.  We used IAPSO 
Standard Seawater batch P142 whose conductivity ratio was 0.99991 (double conductivity ratio is 1.99982) as the 
standard for salinity.  We measured 141 ampoules of P142 and the average of the double conductivity ratio was 
1.99974 and the standard deviation was 0.000009, which is equivalent to 0.0002 in salinity.  Figure 3.2.5 shows 
the history of double conductivity ratio of the Standard Seawater batch P142.  Since there was no significant 
trend in Figure 3.2.5 and the average of the double conductivity ratio was 1.99974, we add 0.00008 to all of the 
measured double conductivity ratios.  

SUB-STANDARD SEAWATER 
We also used sub-standard seawater which was deep-sea water filtered by pore size of 0.45 micrometer and 
stored in a 20 liter cubitainer made of polyethylene and stirred for at least 24 hours before measuring.  It was 
measured every six samples in order to check the possible sudden drift of the salinometer.  During the whole 
measurements, there was no detectable sudden drift of the salinometer.  


FIGURE 3.2.5. The history of double conductivity ratio of the Standard Seawater batch P142.


REPLICATE AND DUPLICATE SAMPLES 
We took 627 pairs of replicate and 55 pairs of duplicate samples.  Figure 3.2.6 (a) and (b) shows the 
histogram of the absolute difference between replicate samples and duplicate samples, respectively.  There 
were one bad measurement and five questionable measurements in replicate samples and five questionable 
measurements in duplicate samples.  As for questionable measurements, one of the pair is extremely high.  This 
might be cause insufficient seal of the sample bottles.  Excluding these bad and questionable measurements, the 
standard deviation of the absolute deference of 621 pairs of replicate samples was 0.0002 in salinity and that of 50 
pairs of duplicate samples was 0.0003 in salinity.  


FIGURE 3.2.6 (a). The histogram of the absolute difference between replicate samples. 
FIGURE 3.2.6 (b). The histogram of the absolute difference between duplicate samples. 


(iv) Leg.5 

STAND SEAWATER 
Standardization control of the salinometer with serial number of 62827 and 62556 was set to 508 and 638, 
respectively.  During the measurement, the STANDBY of 62827 was 5410 +/- 0001 and ZERO was 0.00000 
to 0.00001.  The STANBY of 62556 was 6107 +/- 0001 and ZERO was 0.00000 to 0.00001.  We used IAPSO 
Standard Seawater batch P142 whose conductivity ratio was 0.99991 (double conductivity ratio is 1.99982) as the 
standard for salinity.  We measured 194 ampoules of P142.  There were 7 bad ampoules whose conductivities are 
extremely high.  Data of these 7 ampoules is not taken into consideration hereafter.  

Figure 3.2.7 shows the history of double conductivity ratio of the Standard Seawater batch P142.  The 
average of double conductivity ratio from Stn.610 to Stn.555 was 1.99977 and the standard deviation was 0.00008, 
which is equivalent to 0.0002 in salinity.  We add 0.00005 to the measured double conductivity ratio during this 
period.  The average from Stn.554 to Stn.444 was 1.99974 and the standard deviation was 0.00008.  We add 
0.00008 to the measured double conductivity ratio during this period.  


FIGURE 3.2.7. The history of double conductivity ratio of the Standard Seawater batch P142. 


SUB-STANDARD SEAWATER 
We also used sub-standard seawater which was deep-sea water filtered by pore size of 0.45 micrometer and 
stored in a 20 liter cubitainer made of polyethylene and stirred for at least 24 hours before measuring.  It was 
measured every six samples in order to check the possible sudden drift of the salinometer.  During the whole 
measurements, there was no detectable sudden drift of the salinometer.  

REPLICATE AND DUPLICATE SAMPLES 
We took 830 pairs of replicate and 66 pairs of duplicate samples.  Figure 3.2.8 (a) and (b) shows the histogram 
of the absolute difference between replicate samples and duplicate samples, respectively.  There were eight bad 
measurements and 20 questionable measurements of replicate samples and eight questionable measurements 
of duplicate samples.  As for questionable measurements, one of the pair is extremely high (more than 0.01 in 
salinity).  This might be cause insufficient seal of the sample bottles.  Excluding these bad and questionable 
measurements, the standard deviation of the absolute deference of 802 pairs of replicate samples was 0.0002 in 
salinity and that of 58 pairs of duplicate samples was 0.0003 in salinity.  



REFERENCES 

Aoyama, M., T. Joyce, T. Kawano and Y. Takatsuki: Standard seawater comparison up to P129. 
    Deep-Sea Research, I, Vol. 49, 1103~1114, 2002 
UNESCO: Tenth report of the Joint Panel on Oceanographic Tables and Standards. UNESCO Tech. 
    Papers in Mar. Sci., 36, 25 pp., 1981


FIGURE 3.2.8 (a). The histogram of the absolute difference between replicate samples. FIGURE 3.2.8 (b).  
                  The histogram of the absolute samples between duplicate samples.


3.3 OXYGEN 
    28 JANUARY 2005 

(1) PERSONNEL 

    Yuichiro Kumamoto (JAMSTEC) 
    Shuichi Watanabe (JAMSTEC, Principal Investigator for leg 1, 2, 4) 
    Ayako Nishina (Kagoshima University, Principal Investigator for leg 5) 
    Kazuhiko Matsumoto (JAMSTEC) 
    Elisabete de Braga (Institute of Oceanography, University of Sao Paulo) 
    Takayoshi Seike (MWJ) 
    Ichiro Yamazaki (MWJ) 
    Tomoko Miyashita (MWJ) 
    Nobuharu Komai (MWJ) 


(2) OBJECTIVES 

Dissolved oxygen is one of the most significant tracers for the ocean circulation study.  Recent studies 
indicated that dissolved oxygen concentration in intermediate layers changed in basin wide scale.  The causes 
of the change, however, are still unclear.  During MR03-K04, we measured dissolved oxygen concentration at all 
the stations along WHP P06 in the South Pacific, WHP A10 in the South Atlantic, and WHP I03 and I04 in the 
Indian Ocean.  Our purposes are to evaluate decadal change of dissolved oxygen in the southern hemisphere.  



(3) METHODS 

Reagents 
  Pickling Reagent I: Manganous chloride solution (3M) 
  Pickling Reagent II: Sodium hydroxide (8M) / sodium iodide solution (4M) 
  Sulfuric acid solution (5M) 
  Sodium thiosulfate (0.025M) 
  Potassium iodate (0.001667M) 
  CSK standard solution of potassium iodate: Lot TCK8677, 0.0100N, 
    Wako Pure Chemical Industries Ltd. 

INSTRUMENTS 
  Burette for sodium thiosulfate: 
  APB-510 manufactured by Kyoto Electronic Co. Ltd. / 10 cm3 of titration vessel 
  Burette for potassium iodate: 
  APB-410 manufactured by Kyoto Electronic Co. Ltd. / 20 cm3 of titration vessel 
  Detector and Software: Automatic photometric titrator manufactured by Kimoto Electronic Co. Ltd. 

SAMPLING 
  Following procedure is based on the WHP Operations and Methods (Dickson, 1996).  Seawater samples 
  were collected with Niskin bottle attached to the CTD-system.  Seawater for oxygen measurement was 
  transferred from Niskin sampler bottle to a volume calibrated flask (ca. 100 cm3).  Three times volume of the 
  flask of seawater was overflowed.  Temperature was measured by digital thermometer during the overflowing.  
  
  Then two reagent solutions (Reagent I, II) of 0.5 cm3 each were added immediately into the sample flask and the 
  stopper was inserted carefully into the flask.  The sample flask was then shaken vigorously to mix the contents 
  and to disperse the precipitate finely throughout.  After the precipitate has settled at least halfway down the 
  flask, the flask was shaken again vigorously to disperse the precipitate.  The sample flasks containing pickled 
  samples were stored in a laboratory until they were titrated.  

SAMPLE MEASUREMENT 
  At least two hours after the re-shaking, the pickled samples were measured on board.  A magnetic stirrer 
  bar and 1 cm3 sulfuric acid solution were added into the sample flask and stirring began.  Samples were titrated 
  by sodium thiosulfate solution whose molarity was determined by potassium iodate solution.  Temperature of 
  sodium thiosulfate during titration was recorded by a digital thermometer.  During this cruise we measured 
  dissolved oxygen concentration using two sets of the titration apparatus (DOT-1 and DOT-2).  Dissolved oxygen 
  concentration (μmol kg-1) was calculated by sample temperature during seawater sampling, salinity of the sample, 
  and titrated volume of sodium thiosulfate solution.  
  
Standardization 
  Concentration of sodium thiosulfate titrant (ca. 0.025M) was determined by potassium iodate solution.  

  Pure potassium iodate was dried in an oven at 130°C.  1.7835 g potassium iodate weighed out accurately was 
  dissolved in deionized water and diluted to final volume of 5 dm3 in a calibrated volumetric flask (0.001667M).  
 
  10 cm3 of the standard potassium iodate solution was added to a flask using a calibrated dispenser.  Then 90 cm3 
  of deionized water, 1 cm3 of sulfuric acid solution, and 0.5 cm3 of pickling reagent solution II and I were added into 
  the flask in order.  Amount of sodium thiosulfate titrated gave the molarity of sodium thiosulfate titrant.  


TABLE 3.3.1, 3.3.2, 3.3.3, and 3.3.4 show result of the standardization during leg 1, 2, 4, and 5, respectively.  


Reproducibility (C.V.) of each standardization was less than 0.1% (n = 5).  Moreover a series of the 
standardizations using same sodium thiosulfate also gave errors (C.V.) less than 0.1%.  


DETERMINATION OF THE BLANK 

The oxygen in the pickling reagents I (0.5 cm3) and II (0.5 cm3) was assumed to be 3.8 x 10-8 mol (Dickson, 
1996).  The blank from the presence of redox species apart from oxygen in the reagents was determined as 
follows.  1 cm3 of the standard potassium iodate solution was added to a flask using a calibrated dispenser.  Then 
100 cm3 of deionized water, 1 cm3 of sulfuric acid solution, and 0.5 cm3 of pickling reagent solution II and I 
were added into the flask in order.  Just after titration of the first potassium iodate, a further 1 cm3 of standard 
potassium iodate was added and titrated.  The blank was determined by difference between the first and second 
titrated volumes of the sodium thiosulfate.  

The results are shown in Table 1, 2, 3, and 4.  The blank was ranged from -0.012 to 0.003 cm3 (c.a. -0.7 ~ 
0.2 μmol/kg).  Most of them are negative, implying that there are deoxidizers in the reagents.  We also found that 
the blank of DOT-2 is systematically larger than that of DOT-1 by about 0.003 cm3 (c.a. 0.2 μmol/kg).  Because 
we could not explain the deoxidizers in the reagents and the systematic difference between DOT-1 and DOT-2, 
we assumed that the reagent blank due to redox species was negligible.  


TABLE 3.3.1. Results of the standardization and the blank determinations during MR03-K04 leg 1. 

__________________________________________________________________________________________________________

 Date     | Time  | | KIO3      |        DOT-1 (cm3)        |        DOT-2 (cm3)        |    Samples
          |-------|#|-----------|----------|-------|--------|----------|-------|--------|----------------
 (UTC)    | (UTC) | | bottle    | Na2S2O3  | E.P.  | blank  | Na2S2O3  | E.P.  | blank  |    (Stations)
          |-------|#|-----------|----------|-------|--------|----------|-------|--------|----------------
 08-03-03 | 18:44 | | 030414-31 | 030411-7 | 3.969 | -0.004 | 030411-8 | 3.969 | -0.003 | 246,245,244  
 08-04-03 | 09:43 | | 030414-32 | 030411-7 | 3.967 | -0.008 | 030411-8 | 3.967 | -0.002 | 243,242  
 08-04-03 | 15:57 | | 030414-33 | 030411-7 | 3.964 | -0.005 | 030411-8 | 3.968 | -0.003 | 241  
 08-04-03 | 22:38 | | 030414-34 | 030804-1 | 3.971 | -0.006 | 030804-2 | 3.968 | -0.006 | 240  
 08-05-03 | 05:09 | | 030414-35 | 030804-1 | 3.968 | -0.003 | 030804-2 | 3.966 | -0.004 | 239  
 08-05-03 | 11:07 |1| 030414-36 | 030804-1 | 3.968 | -0.003 | 030804-2 | 3.968 | -0.003 | 238  
 08-05-03 | 16:53 | | 030414-37 | 030804-1 | 3.966 | -0.005 | 030804-2 | 3.968 | -0.005 | 237  
 08-05-03 | 21:18 | | 030414-38 | 030804-1 | 3.965 | -0.005 | 030804-2 | 3.970 | -0.004 | X11  
 08-06-03 | 02:44 | | 030414-39 | 030804-1 | 3.965 | -0.002 | 030804-2 | 3.968 | -0.005 | 235  
 08-06-03 | 09:50 | | 030414-40 | 030804-3 | 3.970 | -0.003 | 030804-4 | 3.971 | -0.004 | 234,232  
 08-06-03 | 18:02 | | 030414-41 | 030804-3 | 3.970 | -0.005 | 030804-4 | 3.969 | -0.005 | 231,230
 08-06-03 | 23:48 |1| 030414-42 | 030804-3 | 3.967 | -0.005 | 030804-4 | 3.969 | -0.003 | 229,228  
 08-07-03 | 05:04 | | 030414-43 | 030804-3 | 3.962 | -0.006 | 030804-4 | 3.965 | -0.004 | 227,226  
 08-07-03 | 14:14 | | 030415-1  | 030804-5 | 3.968 | -0.003 | 030807-1 | 3.958 | -0.004 | 225,224,223  
 08-07-03 | 23:10 | | 030415-2  | 030804-5 | 3.968 | -0.008 | 030807-1 | 3.957 | -0.005 | 222,221,220  
 08-08-03 | 07:11 | | 030415-3  | 030804-5 | 3.965 | -0.004 | 030807-1 | 3.957 | -0.005 | 219,218  
 08-08-03 | 16:21 | | 030415-4  | 030804-5 | 3.963 | -0.007 | 030807-1 | 3.956 | -0.005 | 217,216  
 08-09-03 | 01:30 | | 030415-5  | 030804-5 | 3.963 | -0.007 | 030807-1 | 3.951 | -0.003 | 216  
 08-09-03 | 05:17 |2| 030415-6  | 030807-2 | 3.957 | -0.006 | 030807-3 | 3.958 | -0.004 | 215,214,213  
 08-10-03 | 13:48 | | 030415-7  | 030807-2 | 3.954 | -0.006 | 030807-3 | 3.956 | -0.005 | 212,211  
 08-11-03 | 02:49 | | 030415-8  | 030807-2 | 3.953 | -0.005 | 030807-3 | 3.950 | -0.003 | 210  
 08-11-03 | 06:31 | | 030415-9  | 030807-2 | 3.953 | -0.005 | 030807-3 | 3.951 | -0.003 | 209,208  
 08-11-03 | 15:28 | | 030415-10 | 030807-2 | 3.954 | -0.007 | 030807-3 | 3.953 | -0.003 | 207  
 08-11-03 | 21:44 | | 030415-11 | 030807-4 | 3.957 | -0.006 | 030807-5 | 3.959 | -0.003 | 206,205  
 08-12-03 | 04:55 | | 030415-12 | 030807-4 | 3.957 | -0.008 | 030807-5 | 3.956 | -0.002 | 204,203  
 08-12-03 | 12:36 | | 030415-13 | 030807-4 | 3.954 | -0.007 | 030807-5 | 3.955 | -0.003 | 202,201  
 08-12-03 | 22:14 | | 030415-16 | 030810-1 | 3.960 | -0.008 | 030810-2 | 3.961 | -0.003 | 200,199  
 08-13-03 | 04:12 | | 030415-17 | 030810-1 | 3.959 | -0.007 | 030810-2 | 3.958 | -0.004 | 198,197  
 08-13-03 | 12:43 | | 030415-18 | 030810-1 | 3.958 | -0.007 | 030810-2 | 3.958 | -0.002 | 196,195  
 08-13-03 | 23:12 | | 030415-19 | 030810-1 | 3.958 | -0.007 | 030810-2 | 3.959 | -0.003 | 194,X14  
 08-14-03 | 12:08 |3| 030415-20 | 030810-3 | 3.961 | -0.005 | 030810-4 | 3.961 | -0.002 | 192,191  
 08-15-03 | 00:50 | | 030415-21 | 030810-3 | 3.960 | -0.007 | 030810-4 | 3.959 | -0.002 | 190,186  
 08-15-03 | 10:32 | | 030415-22 | 030810-3 | 3.960 | -0.006 | 030810-4 | 3.959 | -0.001 | 185,184  
 08-15-03 | 19:00 | | 030415-23 | 030810-3 | 3.961 | -0.006 | 030810-4 | 3.959 | -0.002 | 183,182  
 08-16-03 | 05:06 | | 030415-24 | 030810-5 | 3.963 | -0.002 | 030815-1 | 3.960 | -0.002 | 181,180  
 08-16-03 | 11:14 | | 030415-25 | 030810-5 | 3.960 | -0.006 | 030815-1 | 3.957 | -0.002 | 179,178  
 08-17-03 | 23:02 |3| 030415-26 | 030810-5 | 3.960 | -0.007 | 030815-1 | 3.953 |  0.001 | 177  
 08-18-03 | 04:19 | | 030415-27 | 030810-5 | 3.960 | -0.004 | 030815-1 | 3.951 | -0.003 | 176  
 08-18-03 | 12:31 | | 030415-31 | 030815-2 | 3.959 | -0.007 | 030815-3 | 3.959 | -0.003 | 175  
 08-18-03 | 17:45 | | 030415-32 | 030815-2 | 3.960 | -0.005 | 030815-3 | 3.955 | -0.001 | 174  
 08-19-03 | 03:37 | | 030415-33 | 030815-2 | 3.958 | -0.006 | 030815-3 | 3.958 | -0.001 | 173,172  
 08-19-03 | 18:00 | | 030415-34 | 030815-2 | 3.958 | -0.005 | 030815-3 | 3.958 | -0.001 | 171  
 08-20-03 | 11:12 |4| 030415-36 | 030815-4 | 3.958 | -0.005 | 030815-5 | 3.959 | -0.002 | 170,169,168,167 
 08-20-03 | 21:21 | | 030415-37 | 030815-4 | 3.960 | -0.006 | 030815-5 | 3.960 |  0.001 | 166-1,2  
 08-21-03 | 03:54 | | 030815-38 | 030815-4 | 3.960 | -0.004 | 030815-5 | 3.959 |  0.001 | 165  
 08-21-03 | 12:46 | | 030415-39 | 030819-1 | 3.960 | -0.006 | 030819-2 | 3.961 |  0.000 | 164,163,162  
 08-22-03 | 03:43 | | 030415-41 | 030819-1 | 3.957 | -0.008 | 030819-2 | 3.958 | -0.001 | 161,160  
 08-22-03 | 13:35 | | 030415-42 | 030819-1 | 3.958 | -0.008 | 030819-2 | 3.960 | -0.001 | 159  
 08-22-03 | 19:24 | | 030415-43 | 030819-1 | 3.959 | -0.008 | 030819-2 | 3.958 | -0.001 | 158  
 08-23-03 | 05:01 | | 030417-1  | 030819-3 | 3.960 | -0.006 | 030819-4 | 3.961 |  0.000 | X15,156  
 08-23-03 | 12:01 | | 030417-2  | 030819-3 | 3.961 | -0.005 | 030819-4 | 3.961 |  0.000 | 155,154  
 08-24-03 | 23:08 | | 030417-3  | 030819-3 | 3.960 | -0.006 | 030819-4 | 3.961 |  0.001 | 153,152  
 08-24-03 | 09:21 | | 030417-4  | 030819-3 | 3.959 | -0.006 | 030819-4 | 3.960 |  0.001 | 151  
 08-24-03 | 17:22 |5| 030417-5  | 030819-5 | 3.959 | -0.008 | 030823-1 | 3.960 |  0.002 | 150,149  
 08-26-03 | 05:30 | | 030417-6  | 030819-5 | 3.959 | -0.007 | 030823-1 | 3.959 | -0.002 | 148  
 08-26-03 | 16:05 | | 030417-7  | 030819-5 | 3.957 | -0.006 | 030823-1 | 3.959 |  0.000 | 147  
 08-26-03 | 22:48 | | 030417-8  | 030819-5 | 3.958 | -0.006 | 030823-1 | 3.960 |  0.000 | 146  
 08-27-03 | 05:13 | | 030417-9  | 030819-5 | 3.957 | -0.005 | 030823-1 | 3.956 |  0.002 | 145  
 08-27-03 | 12:49 | | 030417-10 | 030823-2 | 3.959 | -0.007 | 030823-3 | 3.957 | -0.005 | 144,143
 08-27-03 | 23:51 | | 030417-11 | 030823-2 | 3.959 | -0.007 | 030823-3 | 3.960 | -0.004 | 142  
 08-28-03 | 04:50 |5| 030417-12 | 030823-2 | 3.959 | -0.006 | 030823-3 | 3.958 | -0.006 | 140  
 08-28-03 | 10:06 | | 030417-13 | 030823-2 | 3.958 | -0.004 | 030823-3 | 3.957 | -0.004 | 139,138  
 08-28-03 | 02:25 | | 030417-16 | 030823-4 | 3.961 | -0.005 | 030823-5 | 3.962 | -0.002 | 137,136  
 08-29-03 | 11:54 | | 030417-17 | 030823-4 | 3.959 | -0.005 | 030823-5 | 3.960 | -0.003 | 135  
 08-29-03 | 19:00 | | 030417-18 | 030823-4 | 3.961 | -0.008 | 030823-5 | 3.963 |  0.001 | 134,133  
 08-30-03 | 06:30 | | 030417-19 | 030823-4 | 3.959 | -0.006 | 030823-5 | 3.960 | -0.001 | 132,131  
 08-30-03 | 21:51 | | 030417-20 | 030828-1 | 3.960 | -0.005 | 030828-2 | 3.962 | -0.003 | 130,129  
 08-31-03 | 07:44 |6| 030417-21 | 030828-1 | 3.960 | -0.006 | 030828-2 | 3.963 | -0.001 | X16  
 08-31-03 | 15:51 | | 030417-22 | 030828-1 | 3.961 | -0.005 | 030828-2 | 3.962 | -0.001 | 127  
 08-31-03 | 22:59 | | 030417-23 | 030828-1 | 3.961 | -0.005 | 030828-2 | 3.963 | -0.001 | 126  
 09-01-03 | 04:50 | | 030417-24 | 030828-1 | 3.962 | -0.005 | 030828-2 | 3.963 | -0.001 | 125  
 09-01-03 | 11:54 | | 030417-25 | 030828-3 | 3.958 | -0.007 | 030828-4 | 3.961 | -0.002 | 124,123  
 09-02-03 | 00:17 | | 030417-26 | 030828-3 | 3.959 | -0.007 | 030828-4 | 3.962 |  0.000 | 122  
 09-02-03 | 06:12 | | 030417-27 | 030828-3 | 3.958 | -0.007 | 030828-4 | 3.958 | -0.002 | 121  
__________________________________________________________________________________________________________

                      #: Batch number of the KIO3 standard series. 


TABLE 3.3.2. Results of the standardization and the blank determinations during MR03-K04 leg 2. 
_______________________________________________________________________________________________________________

 Date     | Time  |  | KIO3      |        DOT-1 (cm3)        |        DOT-2 (cm3)        |    Samples
          |-------| #|-----------|----------|-------|--------|----------|-------|--------|--------------------
(UTC)     | (UTC) |  | bottle    | Na2S2O3  | E.P.  | blank  | Na2S2O3  | E.P.  | blank  |    (Stations)
          |-------| #|-----------|----------|-------|--------|----------|-------|--------|--------------------
 09-12-03 | 05:11 |  | 030417-31 | 030828-4 | 3.960 | -0.006 | 030828-5 | 3.962 | -0.001 | 127,125  
 09-13-03 | 12:38 |  | 030417-32 | 030910-1 | 3.961 | -0.006 | 030910-2 | 3.964 |  0.000 | 120,119  
 09-14-03 | 11:22 |  | 030417-33 | 030910-1 | 3.959 | -0.006 | 030910-2 | 3.963 |  0.000 | 118,117,116 
 09-15-03 | 07:24 |  | 030417-45 | 030910-3 | 3.961 | -0.004 | 030910-4 | 3.963 |  0.001 | 115,114,113 
 09-15-03 | 20:23 |7 | 030417-34 | 030910-3 | 3.961 | -0.005 | 030910-4 | 3.963 |  0.001 | 112,111,110 
 09-16-03 | 16:05 |  | 030417-35 | 030910-5 | 3.962 | -0.005 | 030910-6 | 3.961 |  0.002 | 109,108,X17 
 09-17-03 | 10:15 |  | 030417-36 | 030910-5 | 3.959 | -0.004 | 030910-5 | 3.962 |  0.002 | 106,105,104 
 09-18-03 | 08:31 |  | 030417-37 | 030916-1 | 3.961 | -0.004 | 030916-2 | 3.965 |  0.001 | 103,102,101 
 09-18-03 | 23:02 |  | 030417-38 | 030916-1 | 3.961 | -0.005 | 030916-2 | 3.963 |  0.000 | 100,099,098 
 09-19-03 | 17:34 |  | 030417-39 | 030916-3 | 3.962 | -0.005 | 030916-4 | 3.965 | -0.002 | 097,096,095,09  
 09-21-03 | 03:48 |  | 030418-1  | 030916-6 | 3.966 | -0.005 | 030916-7 | 3.970 |  0.002 | 093,092,091 
 09-21-03 | 21:40 |  | 030418-2  | 030916-6 | 3.966 | -0.005 | 030916-7 | 3.968 | -0.001 | 090,089,088,087 
 09-22-03 | 18:21 |  | 030418-3  | 030916-6 | 3.965 | -0.004 | 030916-7 | 3.965 | -0.001 | 086,085,084 
 09-23-03 | 11:27 |  | 030418-4  | 030921-1 | 3.966 | -0.004 | 030921-2 | 3.968 | -0.001 | 083,082,081 
 09-24-03 | 05:36 |8 | 030418-5  | 030921-1 | 3.964 | -0.005 | 030921-2 | 3.969 |  0.001 | 080,079,078,077 
 09-25-03 | 07:20 |  | 030418-6  | 030921-3 | 3.965 | -0.004 | 030921-4 | 3.968 |  0.002 | 076,075,072,071 
 09-25-03 | 19:31 |  | 030418-7  | 030921-3 | 3.962 | -0.003 | 030921-4 | 3.963 |  0.002 | 070,069,068,067 
 09-26-03 | 18:45 |  | 030418-9  | 030921-6 | 3.964 | -0.005 | 030921-7 | 3.970 | -0.001 | 066,065,064 
 09-27-03 | 13:12 |  | 030418-10 | 030921-6 | 3.968 | -0.004 | 030921-7 | 3.971 |  0.001 | 063,062,061,060 
 09-28-03 | 12:29 |  | 030418-11 | 030925-1 | 3.967 | -0.004 | 030925-2 | 3.969 |  0.000 | 059,X18,056 
 09-29-03 | 10:52 |  | 030418-12 | 030925-1 | 3.964 | -0.005 | 030925-2 | 3.969 | -0.001 | 055
 09-30-03 | 16:58 |  | 030418-16 | 030925-1 | 3.961 |    -   | 030925-2 | 3.967 |   -    | 054,053 
 10-01-03 | 05:09 |  | 030418-17 | 030925-3 | 3.964 | -0.004 | 030925-4 | 3.970 |  0.000 | 052,051,050 
 10-01-03 | 18:34 |  | 030418-18 | 030925-3 | 3.967 | -0.003 | 030925-4 | 3.967 |  0.000 | 049,048,047 
 10-02-03 | 11:46 |  | 030418-19 | 030925-6 | 3.963 | -0.006 | 030925-7 | 3.968 |  0.000 | 046,045,044 
 10-03-03 | 03:43 |  | 030418-20 | 030925-6 | 3.964 | -0.005 | 030925-7 | 3.970 |  0.003 | 043,042,041 
 10-03-03 | 19:06 |9 | 030418-21 | 030930-1 | 3.963 | -0.005 | 030930-2 | 3.968 |  0.002 | 040,039,038 
 10-04-03 | 10:37 |  | 030418-22 | 030930-1 | 3.963 | -0.003 | 030930-2 | 3.965 | -0.001 | 037,036,X19 
 10-05-03 | 06:03 |  | 030418-23 | 030930-3 | 3.964 | -0.003 | 030930-4 | 3.970 | -0.001 | 034,033,032 
 10-05-03 | 18:54 |  | 030418-24 | 030930-3 | 3.961 | -0.003 | 030930-4 | 3.964 | -0.002 | 031,030,029 
 10-06-03 | 12:07 |  | 030418-25 | 030930-6 | 3.964 | -0.005 | 030930-7 | 3.966 | -0.001 | 028,027,026 
 10-07-03 | 05:19 |  | 030418-26 | 030930-6 | 3.965 | -0.005 | 030930-7 | 3.967 |  0.003 | 025,024 
 10-08-03 | 13:45 |  | 030418-32 | 031005-1 | 3.966 | -0.005 | 031005-2 | 3.971 |  0.001 | 023,022,021 
 10-09-03 | 08:02 |  | 030418-33 | 031005-1 | 3.968 | -0.004 | 031005-2 | 3.969 |  0.000 | 020,019,018 
 10-10-03 | 01:15 |10| 030418-34 | 031005-3 | 3.965 | -0.006 | 031005-4 | 3.969 | -0.001 | 017,016,015 
 10-10-03 | 15:13 |  | 030418-35 | 031005-3 | 3.966 | -0.006 | 031005-4 | 3.970 |  0.000 | 014,013,012 
 10-11-03 | 09:23 |  | 030418-36 | 031005-6 | 3.966 | -0.005 | 031005-7 | 3.969 | -0.001 | 011,010,009 
 10-11-03 | 23:31 |  | 030418-37 | 031005-6 | 3.966 | -0.003 | 031005-7 | 3.970 |  0.002 | 008,007,006,005,004 
_______________________________________________________________________________________________________________

                      #: Batch number of the KIO3 standard series. 


TABLE 3.3.3.  Results of the standardization and the blank determinations during MR03-K04 leg 4. 
___________________________________________________________________________________________________________________

 Date     | Time  |  | KIO3      |        DOT-1 (cm3)        |        DOT-2 (cm3)        |    Samples
          |-------| #|-----------|----------|-------|--------|----------|-------|--------|--------------------
(UTC)     | (UTC) |  | bottle    | Na2S2O3  | E.P.  | blank  | Na2S2O3  | E.P.  | blank  |    (Stations)
          |-------| #|-----------|----------|-------|--------|----------|-------|--------|--------------------
 11-07-03 | 06:09 |  | 030418-47 | 031010-2 | 3.961 | -0.005 | 031010-3 | 3.956 | -0.007 | 622,623,624,625  
 11-07-03 | 23:26 |  | 030418-48 | 031010-2 | 3.960 | -0.005 | 031010-3 | 3.957 | -0.003 | 626,627,628 
 11-08-03 | 16:33 |  | 030418-49 | 031010-4 | 3.964 | -0.005 | 031010-5 | 3.963 | -0.004 | 629,630,631 
 11-09-03 | 00:46 |  | 030418-50 | 031010-4 | 3.965 | -0.006 | 031010-5 | 3.964 | -0.003 | 632,001,002 
 11-09-03 | 14:35 |  | 030418-51 | 031108-1 | 3.965 | -0.005 | 031108-2 | 3.964 | -0.004 | 003,004,005 
 11-10-03 | 08:15 |11| 030418-52 | 031108-1 | 3.963 | -0.004 | 031108-2 | 3.963 | -0.004 | 006,007,008 
 11-10-03 | 23:27 |  | 030418-53 | 031108-3 | 3.964 | -0.006 | 031108-4 | 3.962 | -0.005 | 009,010,011 
 11-11-03 | 14:49 |  | 030418-54 | 031108-3 | 3.962 | -0.004 | 031108-4 | 3.960 | -0.004 | X17,013,014 
 11-12-03 | 05:04 |  | 030418-55 | 031108-5 | 3.963 | -0.011 | 031111-1 | 3.959 | -0.004 | 015,016,X.23,018,019 
 11-12-03 | 21:01 |  | 030418-56 | 031108-5 | 3.964 | -0.006 | 031111-1 | 3.959 | -0.005 | 020,021,022,023,024 
 11-13-03 | 15:35 |  | 030418-57 | 031111-2 | 3.964 | -0.005 | 031111-3 | 3.961 | -0.010 | 025,026,027 
 11-14-03 | 04:13 |  | 030418-58 | 031111-2 | 3.963 | -0.004 | 031111-3 | 3.961 | -0.004 | 028,029,030 
 11-14-03 | 21:52 |  | 030418-61 | 031111-4 | 3.962 | -0.006 | 031111-5 | 3.959 | -0.004 | 031,032,033 
 11-15-03 | 15:48 |  | 030418-63 | 031111-4 | 3.959 | -0.006 | 031111-5 | 3.958 | -0.004 | some samples of 031  
 11-16-03 | 07:14 |  | 030418-64 | 031111-4 | 3.958 | -0.008 | 031111-5 | 3.954 | -0.005 | 034,035,036 
 11-16-03 | 01:21 |  | 030418-65 | 031115-1 | 3.957 | -0.008 | 031115-2 | 3.957 | -0.004 | 037,038,039 
 11-17-03 | 18:47 |  | 030418-66 | 031115-1 | 3.956 | -0.006 | 031115-2 | 3.957 | -0.004 | X16,041,042 
 11-18-03 | 18:16 |12| 030418-67 | 031115-3 | 3.960 | -0.007 | 031115-4 | 3.959 | -0.003 | 043,044,045 
 11-19-03 | 10:36 |  | 030418-68 | 031115-3 | 3.959 | -0.006 | 031115-4 | 3.958 | -0.003 | 046,X15,048 
 11-20-03 | 08:01 |  | 030418-69 | 031115-5 | 3.960 | -0.006 | 031119-1 | 3.956 | -0.004 | 049,050,051 
 11-20-03 | 22:47 |  | 030418-70 | 031115-5 | 3.950 | -0.007 | 031119-1 | 3.948 | -0.004 | 052,053,054 
 11-21-03 | 14:43 |  | 030418-71 | 031119-2 | 3.957 | -0.006 | 031119-3 | 3.954 | -0.004 | 055,056,057,058 
 11-22-03 | 10:19 |  | 030418-72 | 031119-2 | 3.953 | -0.009 | 031119-3 | 3.952 | -0.007 | 059,060,061 
 11-23-03 | 23:49 |  | 030418-75 | 031119-4 | 3.956 | -0.010 | 031119-5 | 3.955 | -0.007 | X14,063,064,065,066,067
 11-25-03 | 10:00 |  | 030418-76 | 031125-1 | 3.963 | -0.009 | 031125-2 | 3.961 | -0.007 | 068,069,070 
 11-26-03 | 07:54 |  | 030418-77 | 031125-1 | 3.959 | -0.009 | 031125-2 | 3.957 | -0.006 | 071,072,073 
 11-27-03 | 04:47 |  | 030418-78 | 031125-3 | 3.958 | -0.008 | 031125-4 | 3.959 | -0.006 | 074,075,076 
 11-27-03 | 17:17 |  | 030418-79 | 031125-3 | 3.958 | -0.011 | 031125-4 | 3.959 | -0.006 | 077,078,079 
 11-28-03 | 10:24 |13| 030418-80 | 031125-5 | 3.957 | -0.010 | 031128-1 | 3.959 | -0.007 | 080,081,082 
 11-29-03 | 01:19 |  | 030418-81 | 031125-5 | 3.955 | -0.010 | 031128-1 | 3.959 | -0.006 | 083,084,085 
 11-30-03 | 01:21 |  | 030418-82 | 031128-2 | 3.961 | -0.011 | 031128-3 | 3.960 | -0.004 | 086,087,X13 
 11-30-03 | 18:09 |  | 030418-83 | 031128-2 | 3.958 | -0.009 | 031128-3 | 3.960 | -0.006 | 089,090,091 
 12-01-03 | 19:56 |  | 030418-84 | 031128-4 | 3.960 | -0.011 | 031128-5 | 3.963 | -0.004 | 092,093,094 
 12-02-03 | 06:02 |  | 030418-85 | 031128-4 | 3.962 | -0.008 | 031128-5 | 3.962 | -0.005 | 095,096,097,098,099,100 
___________________________________________________________________________________________________________________

                      #: Batch number of the KIO3 standard series. 


TABLE 3.3.4.  Results of the standardization and the blank determinations during MR03-K04 leg 5. 
___________________________________________________________________________________________________________________

 Date     | Time  |  | KIO3       |        DOT-1 (cm3)        |        DOT-2 (cm3)        |    Samples
          |-------| #|------------|----------|-------|--------|----------|-------|--------|--------------------
(UTC)     | (UTC) |  | bottle     | Na2S2O3  | E.P.  | blank  | Na2S2O3  | E.P.  | blank  |    (Stations)
          |-------| #|------------|----------|-------|--------|----------|-------|--------|--------------------
 12-13-03 | 02:32 |  | 030418-91  | 031209-1 | 3.961 | -0.008 | 031209-2 | 3.962 | -0.006 | 610,609,608,607,606,605  
 12-14-03 | 01:07 |  | 030418-92  | 031209-1 | 3.957 | -0.009 | 031209-2 | 3.959 | -0.007 | 604,603,602  
 12-14-03 | 12:06 |  | 030418-93  | 031209-6 | 3.959 | -0.012 | 031209-7 | 3.960 | -0.008 | 601,600,599  
 12-15-03 | 01:14 |  | 030418-94  | 031209-6 | 3.960 | -0.011 | 031209-7 | 3.961 | -0.008 | 598,597,596  
 12-16-03 | 00:43 |14| 030418-96  | 031209-6 | 3.958 | -0.008 | 031209-7 | 3.959 | -0.008 | 595,594  
 12-16-03 | 01:59 |  | 030418-96  | 031209-4 | 3.955 | -0.011 | 031209-5 | 3.959 | -0.010 | 593,592,591  
 12-16-03 | 15:28 |  | 030418-97  | 031209-4 | 3.957 | -0.012 | 031209-5 | 3.960 | -0.007 | 590,589,588  
 12-17-03 | 05:40 |  | 030418-98  | 031209-4 | 3.959 | -0.011 | 031209-5 | 3.960 | -0.008 | 587,586,585  
 12-19-03 | 05:30 |  | 030418-100 | 031215-1 | 3.957 | -0.011 | 031215-2 | 3.959 | -0.008 | 562,561,560,559 
 12-20-03 | 22:34 |  | 030418-102 | 031215-1 | 3.953 | -0.011 | 031215-2 | 3.955 | -0.009 | 558,557,556 
 12-21-03 | 18:52 |  | 030418-106 | 031215-3 | 3.955 | -0.012 | 031215-4 | 3.956 | -0.008 | 555,554,553 
 12-22-03 | 06:22 |  | 030418-107 | 031215-3 | 3.958 | -0.012 | 031215-4 | 3.958 | -0.009 | 552,551,550 
 12-23-03 | 02:12 |  | 030418-108 | 031215-5 | 3.956 | -0.012 | 031221-1 | 3.955 | -0.008 | 549,X07,547 
 12-23-03 | 17:53 |  | 030418-109 | 031215-5 | 3.958 | -0.011 | 031221-1 | 3.955 | -0.009 | 546,545,544 
 12-24-03 | 10:01 |15| 030418-110 | 031221-2 | 3.955 | -0.011 | 031221-3 | 3.957 | -0.007 | 543,542,541,540 
 12-24-03 | 23:05 |  | 030418-111 | 031221-2 | 3.956 | -0.011 | 031221-3 | 3.957 | -0.007 | 539,538,537,536 
 12-25-03 | 21:06 |  | 030418-112 | 031221-4 | 3.956 | -0.011 | 031221-5 | 3.956 | -0.009 | 535,534,533 
 12-28-03 | 01:07 |  | 030418-114 | 031221-4 | 3.955 | -0.010 | 031221-5 | 3.957 | -0.008 | 532,531,530 
 12-28-03 | 22:01 |  | 030418-115 | 031224-1 | 3.953 | -0.009 | 031224-2 | 3.954 | -0.010 | 529,528,527 
 12-29-03 | 09:07 |  | 030418-116 | 031224-1 | 3.955 | -0.011 | 031224-2 | 3.955 | -0.008 | 526,525,524,523
 12-30-03 | 01:45 |15| 030418-117 | 031224-3 | 3.956 | -0.009 | 031224-4 | 3.957 | -0.008 | 522,521,520 
 12-30-03 | 16:51 |  | 030418-118 | 031224-3 | 3.954 | -0.009 | 031224-4 | 3.956 | -0.008 | 519,518,517 
 12-31-03 | 05:55 |  | 030418-121 | 031224-5 | 3.957 | -0.012 | 031229-1 | 3.961 | -0.008 | 516,515,514 
 01-01-04 | 15:35 |  | 030418-123 | 031224-5 | 3.954 | -0.009 | 031229-1 | 3.958 | -0.007 | 513,512,511 
 01-02-04 | 09:30 |  | 030418-124 | 031229-2 | 3.961 | -0.009 | 031229-3 | 3.961 | -0.007 | 510,509,508 
 01-03-04 | 23:45 |16| 030418-125 | 031229-2 | 3.960 | -0.009 | 031229-3 | 3.959 | -0.008 | 507,506,505 
 01-03-04 | 21:41 |  | 030418-126 | 031229-4 | 3.958 | -0.010 | 031229-5 | 3.958 | -0.008 | 504,503,502 
 01-04-04 | 17:47 |  | 030418-127 | 031229-4 | 3.959 | -0.009 | 031229-5 | 3.958 | -0.009 | 501,500,X08 
 01-05-04 | 10:36 |  | 030418-128 | 031229-6 | 3.956 | -0.008 | 040102-1 | 3.958 | -0.007 | 498,497,496 
 01-06-04 | 04:57 |  | 030418-129 | 031229-6 | 3.958 | -0.009 | 040102-1 | 3.958 | -0.008 | 495,494,493 
 01-07-04 | 01:09 |  | 030418-130 | 040102-2 | 3.960 | -0.010 | 040102-3 | 3.959 | -0.008 | 492,491,490,489 
 01-08-04 | 19:31 |  | 030418-136 | 040102-2 | 3.961 | -0.009 | 040102-3 | 3.961 | -0.007 | 488,487,486,485 
 01-09-04 | 16:37 |  | 030418-137 | 040102-4 | 3.961 | -0.009 | 040102-5 | 3.960 | -0.008 | 484,483,482 
 01-10-04 | 04:46 |  | 030418-138 | 040102-4 | 3.959 | -0.010 | 040102-5 | 3.959 | -0.008 | 481,480,479 
 01-11-04 | 00:24 |  | 030418-139 | 040108-1 | 3.960 | -0.009 | 040108-2 | 3.960 | -0.007 | 478,477,476 
 01-11-04 | 17:58 |17| 030418-140 | 040108-1 | 3.959 | -0.009 | 040108-2 | 3.959 | -0.008 | 475,474,473 
 01-13-04 | 08:41 |  | 030418-142 | 040108-3 | 3.958 | -0.009 | 040108-4 | 3.960 | -0.007 | X09,471,470,469,468 
 01-14-04 | 04:55 |  | 030418-144 | 040108-5 | 3.956 | -0.010 | 040112-1 | 3.958 | -0.007 | 467,466,465 
 01-16-04 | 04:38 |  | 030418-146 | 040108-5 | 3.958 | -0.009 | 040112-1 | 3.960 | -0.008 | 464,463,462 
 01-17-04 | 04:00 |  | 030418-147 | 040112-2 | 3.958 | -0.010 | 040112-3 | 3.959 | -0.008 | 461,460,459 
 01-18-04 | 02:31 |  | 030418-148 | 040112-2 | 3.959 | -0.010 | 040112-3 | 3.959 | -0.008 | 458,457,456 
 01-19-04 | 01:40 |  | 030418-151 | 040112-4 | 3.959 | -0.008 | 040112-5 | 3.959 | -0.008 | 455,454,X10 
 01-19-04 | 20:27 |18| 030418-152 | 040112-4 | 3.959 | -0.008 | 040112-5 | 3.960 | -0.008 | 452,451,450 
 01-20-04 | 21:05 |  | 030418-155 | 040112-4 | 3.962 | -0.009 | 040112-5 | 3.961 | -0.007 | 449,448,447(DOT-02) 
___________________________________________________________________________________________________________________

                      #: Batch number of the KIO3 standard series. 
 

(4) REPRODUCIBILITY OF SAMPLE MEASUREMENT 

Replicate samples were taken at every CTD cast.  These were 5 - 10% of seawater samples of each cast.  

Results of the replicate samples were shown in Table 3.3.5.  The standard deviation of the replicate measurement 
was about 0.1 µmol/kg during the whole legs (leg 1, 2, 4, and 5) and there was no significant difference between 
DOT-1 and DOT-2 measurements.  The standard deviation was calculated by a procedure (SOP23) in DOE (1994).  


TABLE 3.3.5. Results of the replicate sample measurements. 
             _______________________________________________________________________

                                               | Leg 1 | Leg 2 | Leg 4 | Leg 5 
              ---------------------------------|-------|-------|-------|------
              Number of replicate sample pairs | 388   |  380  | 368   |  489 
              Standard deviation (µmol/kg)     | 0.09  |  0.13 | 0.09  |  0.08 
             _______________________________________________________________________


(5) CSK STANDARD MEASUREMENTS 

During the whole legs (leg 1, 2, 4, and 5), we car ried out measurement of the CSK standard solution 
of potassium iodate ever y the KIO3 standard series (# in Table 1) in order to trace stability of our oxygen 
measurement on board.  Table 3.3.6 shows the result of the CSK standard measurements.  Averaged values all 
through the legs of DOT-1 and DOT-2 are 0.009991 ± 0.000006 N and 0.009991 ± 0.000005 N respectively, 
suggesting that there was no systematic difference between DOT-1 and DOT-2 measurements.  Furthermore, 
these results indicate stability of oxygen measurement during the whole legs.  The averaged value of the CSK 
standard solution is so close to the certified value (0.0100 N) that we did not correct sample measurements with 
the CSK standard measurements.  


TABLE 3.3.6. Results of the CSK standard measurements. 
             ___________________________________________________________________________

                  |          |       |    |         DOT-1        |          DOT-2 
                  | Date     | Time  |KIO3|----------------------|---------------------
              Leg | (UTC)    | (UTC) | #  | Conc. (N) | error (N)| Conc. (N) | error (N) 
              ----|----------|-------|----|-----------|----------|-----------|---------
                1 | 08-03-03 | 17:49 |  1 |  0.009998 | 0.000008 | -0.009989 | 0.000003 
                1 | 08-08-03 | 06:11 |  2 |  0.009990 | 0.000005 |  0.009990 | 0.000009 
                1 | 08-13-03 | 11:28 |  3 |  0.009988 | 0.000003 |  0.009987 | 0.000007 
                1 | 08-19-03 | 02:58 |  4 |  0.009983 | 0.000003 |  0.009994 | 0.000005 
                1 | 08-23-03 | 22:26 |  5 |  0.009988 | 0.000002 |  0.009993 | 0.000004 
                1 | 09-02-03 | 12:42 |  6 |  0.009989 | 0.000002 |  0.009989 | 0.000004 
                2 | 09-12-03 | 14:35 |  7 |  0.009994 | 0.000003 |  0.009988 | 0.000004 
                2 | 09-21-03 | 22:42 |  8 |  0.009983 | 0.000003 |  0.009984 | 0.000008 
                2 | 10-01-03 | 18:01 |  9 |  0.009985 | 0.000007 |  0.009983 | 0.000007 
                2 | 10-09-03 | 07:23 | 10 |  0.009985 | 0.000004 |  0.009990 | 0.000003 
                4 | 11-07-03 | 08:21 | 11 |  0.009991 | 0.000004 |  0.009985 | 0.000008 
                4 | 11-17-03 | 21:15 | 12 |  0.009993 | 0.000012 |  0.009997 | 0.000004 
                4 | 11-27-03 | 18:37 | 13 |  0.009985 | 0.000003 |  0.009988 | 0.000006 
                5 | 12-13-03 | 06:29 | 14 |  0.009996 | 0.000002 |  0.009994 | 0.000002 
                5 | 12-23-03 | 17:00 | 15 |  0.010002 | 0.000001 |  0.009997 | 0.000001 
                5 | 01-03-04 | 02:24 | 16 |  0.009999 | 0.000002 |  0.009997 | 0.000004 
                5 | 01-10-04 | 05:51 | 17 |  0.009997 | 0.000003 |  0.009994 | 0.000002 
                5 | 01-19-04 | 22:35 | 18 |  0.009999 | 0.000001 |  0.009996 | 0.000002 
                                  average |  0.009991 | 0.000006 |  0.009991 | 0.000005 
             ___________________________________________________________________________


(6) QUALITY CONTROL FLAG ASSIGNMENT 

Quality flag values were assigned to oxygen measurements using the code defined in Table 0.2 of WHP 
Office Report WHPO 91-1 Rev.2 section 4.5.2 (Joyce et al., 1994).  Measurement flags of 2, 3, 4, and 5 have been 
assigned (Table 3.3.7).  For the choice between 2 (good), 3 (questionable) or 4 (bad), we basically followed a 
flagging procedure as listed below:  
  a. On a station-by-station basis, a datum was plotted against depth.  Any points not lying on a generally smooth 
     trend were noted. 
  b. If the bottle flag was marked with "problem", a datum was noted and flagged 3.  
  c. Dissolved oxygen was then plotted against nitrate concentration and CTD oxygen.  If a datum deviated from 
     both the depth and plots, it was flagged 3.  
  d. Vertical sections against depth and potential density were drawn.  If a datum was anomalous on the section 
     plots, datum flag was degraded from 2 to 3, or from 3 to 4.  
  e. We did not use flag of 6 for the replicate samples.  If both of replicate sample data were flagged 2, averaged 
     value was shown with flag of 2.  If either of them was flagged 3 or 4, a datum with a younger flag was shown.  


Table 3.3.7. Summary of assigned quality control flags. 
             _____________________________________________________

              Flag Definition          Leg 1  Leg 2  Leg 4  Leg 5 
              ---------------------------------------------------
              2   Good                3373   3101   2850   3969 
              3   Questionable           9      9     15      1 
              4   Bad                   18     29     17     23 
              5   Not report (missing)   8      8      3      6 
              ---------------------------------------------------
                               Total  3408   3147   2885   3999
             _____________________________________________________



REFERENCES 

Dickson, A. (1996): Dissolved Oxygen, in WHP Operations and Methods, Woods Hole, 
    pp 1-13.  
DOE (1994): Handbook of methods for the analysis of the various parameters of the 
    carbon dioxide system in sea water; version 2. A.G. Dickson and C. Goyet (eds), 
    ORNL/CDIAC-74.  
Joyce, T., and C. Corry, eds., C. Corry, A. Dessier, A. Dickson, T. Joyce, M. Kenny, 
    R. Key, D. Legler, R. Millard, 
R. Onken, P. Saunders, M. Stalcup, contrib. (1994): Requirements for WOCE Hydrographic 
    Programme Data Reporting, WHPO Pub. 90-1 Rev. 2, 145 pp.  



3.4 NUTRIENTS 
    3 FEBRUARY 2005 

(1) PERSONNEL 

    Michio Aoyama (Meteorological Research Institute / Japan Meteorological Agency, (Principal Investigator) 
    Junko Hamanaka (Marine Works Japan Ltd.) 
    Asako Kubo (Marine Works Japan Ltd.) 
    Yuki Otsubo (Marine Works Japan Ltd.) 
    Kenichiro Sato (Marine Works Japan Ltd.) 
    Ai Yasuda (Marine Works Japan Ltd.) 
    Shinichiro Yokogawa (Marine Works Japan Ltd.) 


(2) OBJECTIVES 

The objectives of nutrients analyses during the R/V Mirai around the world cruises along ca. 30°S in the 
Southern Hemisphere are as follows:
 
•Describe the present status of nutrients in 2003-2004 in good traceability throughout the cruises.  The 
 target nutrients are nitrate, nitrite, phosphate and silicate (Although silicic acid is correct, we use silicate 
 because a term of silicate is widely used in oceanographic community.).  

•Study the temporal and spatial variation of nutrients based on the previous high quality experiments data of 
 WOCE, GOESECS, IGY and so on.  

•Study of temporal and spatial variation of nitrate: phosphate ratio, so called Redfield ratio.  

•Obtain more accurate estimation of total amount of nitrate, phosphate and silicate in the interested area.  

•Provide more accurate nutrients data for physical oceanographers to use as tracers of water mass 
 movement.  


(3) EQUIPMENT AND TECHNIQUES 

A.  ANALYTICAL DETAIL USING TRAACS 800 SYSTEMS (BRAN+LUEBBE) 

    The phosphate analysis is a modification of the procedure of Murphy and Riley (1962).  

    Molybdic acid is added to the seawater sample to form phosphomolybdic acid which is in turn reduced to 
    phosphomolybdous acid using L-ascorbic acid as the reductant.  

    Nitrate + nitrite and nitrite are analyzed according to the modification method of Grasshoff (1970).  
    
    The sample nitrate is reduced to nitrite in a cadmium tube inside of which is coated with metallic copper.  
    
    The sample stream with its equivalent nitrite is treated with an acidic, sulfanilamide reagent and the nitrite forms 
    nitrous acid which reacts with the sulfanilamide to produce a diazonium ion.  N1-Naphthylethylene-diamine 
    added to the sample stream then couples with the diazonium ion to produce a red, azo dye.  With reduction of the 
    nitrate to nitrite, both nitrate and nitrite react and are measured; without reduction, only nitrite reacts.  Thus, for 
    the nitrite analysis, no reduction is performed and the alkaline buffer is not necessary.  Nitrate is computed by 
    difference.  

    The silicate method is analogous to that described for phosphate.  The method used is essentially that of 
    Grasshoff et al. (1983), wherein silicomolybdic acid is first formed from the silicic acid in the sample and added 
    molybdic acid; then the silicomolybdic acid is reduced to silicomolybdous acid, or "molybdenum blue," using 
    ascorbic acid as the reductant.  

    The flow diagrams and regents for each parameter are shown in Figures 3.4.1-3.4.4.  

NITRATE REAGENTS 
    Imidazole (buffer), 0.06M (0.4% w/v) 
    Dissolve 4 g imidazole, C3H4N2, in ca. 900 ml DIW; add 2ml concentrated HCl; make up to 1000 ml with DIW.  

    After mixing, 1 ml Triton(R)X-100 (50% solution in ethanol) is added.  
    
    Sulfanilamide, 0.06M (1% w/v) in 1.2M HCl 
    Dissolve 10 g sulfanilamide, 4-NH2C6H4SO3H, in 1000ml of 1.2M (10%) HCl.  After mixing, 1 ml Triton(R)X-100 
    (50% solution in ethanol) is added.  
    
    N-1-Napthylethylene-diamine dihydrochloride, 0.004 M (0.1% w/v) 
    Dissolve 1 g NEDA, C10H7NHCH2CH2NH2 · 2HCl, in 1000 ml of DIW; containing 10 ml concentrated HCl.  Stored 
    in a dark bottle.  
    
NITRITE REAGENTS 
    Sulfanilamide, 0.06M (1% w/v) in 1.2M HCl 
    Dissolve 10 g sulfanilamide, 4-NH2C6H4SO3H, in 1000 ml of 1.2M (10%) HCl. After mixing, 1 ml Triton(R)X-100 
    (50% solution in ethanol) is added. 
    N-1-Napthylethylene-diamine dihydrochloride , 0.004 M (0.1% w/v) 
    Dissolve 1 g NEDA, C10H7NHCH2CH2NH2 · 2HCl, in 1000 ml of DIW; containing 10 ml concentrated HCl. Stored 
    in a dark bottle. 


FIGURE 3.4.1.  1ch. (NO3+NO2) flow diagram.
FIGURE 3.4.2.  2ch. (NO2) flow diagram.

 
SILICIC ACID REAGENTS 
    Molybdic acid, 0.06M (2% w/v) 
    Dissolve 15 g Disodium Molybdate (VI) Dihydrate, Na2MoO4 · 2H2O, in 1000 ml DIW containing 6 ml H2SO4.  

    After mixing, 20 ml sodium dodecyl sulphate (15% solution in water) is added.  
    
Oxalic acid, 0.6M (5% w/v) 
    Dissolve 50 g Oxalic Acid Anhydrous, HOOC: COOH, in 1000 ml of DIW.  
    
Ascorbic acid, 0.01M (3% w/v) 
    Dissolve 2.5 g L (+)-Ascorbic Acid, C6H8O6, in 100 ml of DIW.  Stored in a dark bottle and freshly prepared before 
    every measurement.  


FIGURE 3.4.3.  3ch. (SiO2) flow diagram. 


PHOSPHATE REAGENTS 
    Stock molybdate solution, 0.03M (0.8% w/v) 
    Dissolve 8 g Disodium Molybdate (VI) Dihydrate, Na2MoO4 · 2H2O, and 0.17 g Antimony Potassium Tartrate, 
    C8H4K2O12Sb2 · 3H2O, in 1000 ml of DIW containing 50 ml concentrated H2SO4.  
    
MIXED REAGENT 
    Dissolve 0.8 g L (+)-Ascorbic Acid, C6H8O6, in 100 ml of stock molybdate solution.  After mixing, 2 ml sodium 
    dodecyl sulphate (15% solution in water) is added.  Stored in a dark bottle and freshly prepared before every 
    measurement.  
    
PO4 DILUTION 
    Dissolve Sodium Hydrate, NaCl, 10 g in ca. 900 ml, add 50 ml Acetone and 4 ml concentrated H2SO4, make up to 
    1000 ml. After mixing, 5 ml sodium dodecyl sulphate (15% solution in water) is added.  


FIGURE 3.4.4.  4ch. (PO4) flow diagram. 


B.  SAMPLING PROCEDURES 
    Sampling of nutrients followed that oxygen, trace gases and salinity.  Samples were drawn into two of virgin 
    10 ml polyacrylates vials without sample drawing tubes.  These were rinsed three times before filling and vials 
    were caped immediately after the drawing.  The vials are put into water bath at 23°C in 10 minutes before use to 
    stabilize the temperature of samples.  

    No transfer was made and the vials were set an auto sampler tray directly.  Samples were analyzed as rapidly 
    as possible after collection, and then the samples were analyzed within 5 hours.  

C.  DATA PROCESSING 
    Raw data from TRAACS800 were treated as follows;  
    Check baseline shift.  

    Check the shape of each peak and positions of peak values taken, and then change the positions of peak 
    values taken if necessary.  

    Carriover correction and baseline drift correction were applied to peak heights of each samples followed by 
    sensitivity correction.  

    Baseline correction and sensitivity correction were done basically using liner regression.  
    
    Load pressure and salinity from CTD data to calculate density of seawater.  
    
    Calibration curves to get nutrients concentration were assumed second order equations.  
    

(4) NUTRIENTS STANDARDS 

A.  IN-HOUSE STANDARDS 

  (i) Volumetric Laboratory Ware 
      All volumetric glass- and plastic (PMP)-ware used were gravimetrically calibrated.  Plastic volumetric flasks 
      were gravimetrically calibrated at the temperature of use within 2-3 K.  
      
      Volumetric flasks 
      Volumetric flasks of Class quality (Class A) are used because their nominal tolerances are 0.05% or less 
      over the size ranges likely to be used in this work.  Class A flasks are made of borosilicate glass, and the 
      standard solutions were transferred to plastic bottles as quickly as possible after they are made up to volume 
      and well mixed in order to prevent excessive dissolution of silicic acid from the glass.  High quality plastic 
      (polymethylpentene, PMP, or polypropylene) volumetric flasks were gravimetrically calibrated and used only 
      within 2-3 K of the calibration temperature.  
      
      The computation of volume contained by glass flasks at various temperatures other than the calibration 
      temperatures were done by using the coefficient of linear expansion of borosilicate crown glass.  
      
      Because of their larger temperature coefficients of cubical expansion and lack of tables constructed for these 
      materials, the plastic volumetric flasks were gravimetrically calibrated over the temperature range of intended 
      use and used at the temperature of calibration within 2 K.  The weights obtained in the calibration weightings 
      were corrected for the density of water and air buoyancy.  
 
      Pipettes and pipettors 
      All pipettes have nominal calibration tolerances of 0.1% or better.  These were gravimetrically calibrated in 
      order to verify and improve upon this nominal tolerance.  
    
 (ii) Reagents, General considerations 
      General Specifications 
      All reagents were of very high purity such as "Analytical Grade," "Analyzed Reagent Grade" and others.  And 
      assay of nitrite was determined according JISK8019 and assays of nitrite salts were 98.9%.  We use that value to 
      adjust the weights taken.  
    
      For the silicate standards solution, we use commercial available silicon standard solution for atomic 
      absorption spectrometry of 1000 mg L-1.  Since this solution is alkaline solution of 0.5 M KOH, an aliquot of 70 
      ml solution were diluted to 500 ml as B standard together with an aliquot of 35 ml of 1M HCl.  Then the pH of B 
      standard for silicate prepared to be 6.9.  
 
      ULTRA PURE WATER 
      Ultra pure water (MilliQ water) freshly drawn was used for preparation of reagents, higher concentration 
      standards and for measurement of reagent and system blanks.  
       
      LOW-NUTRIENT SEAWATER (LNSW) 
      Surface water having low nutrient concentration was taken and filtered using 0.45 μm pore size membrane 
      filter.  This water is stored in 20 liter cubitainer with paper box.  The concentrations of nutrient of this water 
      were measured carefully in May 2003.  
 
(iii) Concentrations of nutrients for A, B and C standards 
      Concentrations of nutrients for A, B and C standards are set as shown in Table 3.4.1.  The C standard is 
      prepared according recipes as shown in Table 3.4.2.  All volumetric laboratory tools were calibrated prior the cruise 
      as stated in chapter (i).  Then the actual concentration of nutrients in each fresh standard was calculated based on 
      the ambient, solution temperature and determined factors of volumetric lab. wares.  


TABLE 3.4.1. Nominal concentrations of nutrients for A, B and C standards. 
             ____________________________________________________

                          A     B    C-1  C-2   C-3   C-4   C-5 
                        -----  ----  ---  ----  ----  ----  ----
              NO3 (µM)  45000  1350  0.0  13.5  27.0  40.5  54.0 
              NO2 (µM)   4000    40  0.0  0.4   0.8   1.2   1.6 
              SiO2 (µM) 36000  5040  0.0  50    100   150   200 
              PO4 (µM)   4500    90  0.0  0.9   1.8   2.7   3.6
             ____________________________________________________


TABLE 3.4.2. Working calibration standard recipes. 
             ________________________________

              C-STD  B-1STD  B-2 STD  MAT 
              -----  ------  -------  ------
              C-1    0 ml    0 ml     40  ml 
              C-2    5 ml    5 ml     30  ml 
              C-3    10 ml   10 ml    20  ml 
              C-4    15 ml   15 ml    10  ml 
              C-5    20 ml   20 ml    0 ml 
             ________________________________

               B-1 STD: Mixture of nitrate, silicate and phosphate 
               B-2 STD: Nitrite 


 (iv) Renewal of in-house standard solutions 
In-house standard solutions as stated in (iii) were renewed as shown in Table 3.4.3.  


Table 3.4.3. Timing of renewal of in-house standards. 
             ___________________________________________________________

               NO3, SiO2, PO4               Renewal 
              ---------------------------  ----------------------------
              A-1 Std. (NO3)               maximum 10 days 
              A-3 Std. (SiO2)              commercial prepared solution 
              A-4 Std. (PO4)               maximum 14 days 
              B-1 Std. 
              (mixture of NO3, SiO2, PO4)  2 days 

              ---------------------------------------------------------
              NO2                          Renewal 
              ---------------------------  ----------------------------
              A-2 Std. (NO2)               maximum 14 days 
              B-2 Std. (NO2)               maximum 14 days 

              ---------------------------------------------------------
              C Std                        Renewal
              ---------------------------  ----------------------------
              C-1 ~ C-5 Std (mixture of    24 hours
                B1 and B2 Std.) 
              ---------------------------------------------------------

              ---------------------------------------------------------
              Reduction estimation Renewal 
              ---------------------------------------------------------
              D-1 Std.                     when A-1renewed 
              44 µM NO3                    when C-std renewed 
              47 µM NO2                    when C-std renewed 
             ___________________________________________________________


B.  RMNS 

To get the more accurate and high quality nutrients data to achieve the objectives stated above, huge 
numbers of the bottles of the reference material of nutrients in seawater (hereafter RMNS) are prepared 
(Aoyama et al., submitted).  In the previous world wide expeditions, such as WOCE cruises, the higher 
reproducibility and precision of nutrients measurements were required (Joyce and Corry, 1994).  Since no 
standards were available for the measurement of nutrients in seawater at that time, the requirements were 
described in term of reproducibility.  The required reproducibility was 1%, 1-2%, 1-3% for nitrate, phosphate 
and silicate, respectively.  Although nutrient data from the WOCE one-time survey was of unprecedented quality 
and coverage due to much care in sampling and measurements, the differences of nutrients concentration at 
crossover points are still found among the expeditions (Aoyama and Joyce, 1996, Mordy et al., 2000, Gouretski 
and Jancke, 2001).  For instance, the mean offset of nitrate concentration at deep waters was 0.5 μmol kg-1 for 
345 crossovers at world oceans, though the maximum was 1.7 μmol kg-1 (Gouretski and Jancke, 2001).  At the 31 
crossover points in the Pacific WHP one-time lines, the WOCE standard of reproducibility for nitrate of 1% was 
fulfilled at about half of the crossover points and the maximum difference was 7% at deeper layers below 1.6°C 
in potential temperature (Aoyama and Joyce, 1996).  

 (i) RMNS preparation 
     RMNS preparation and homogeneity for previous lots 
     The study on reference material for nutrients in seawater (RMNS) on the seawater base has been carried 
     out to establish traceability on nutrient analyses in seawater since 1994 in Japan.  Autoclaving to produce RMNS 
     has been studied (Aminot and Kerouel, 1991, 1995) and autoclaving was used to stabilize the samples for the 5th 
     intercompariosn exercise in 1992/1993 (Aminot and Kirkwood, 1995).  Aminot and Kerouel (1995) concluded that 
     nitrate and nitrite were extremely stable throughout their 27 months storage experiment with overall standard 
     deviations lower than 0.3% (range 5-50 μmol l-l) and 0.8% (range 0.5-5 μmol l-1), respectively.  For phosphate, 
     slight increase by 0.02-0.07 μmol l-1 per year was observed due to the leaching from the container glass.  The 
     main source of nutrient variation in seawater is believed to be microorganism activity, hence, production 
     of RMNS depends on biological inactivation of samples.  In this point of view, previous study showed that 
     autoclaving to inactivate the biological activity is acceptable for RMNS preparation.  

     The seawater for RMNS production was sampled in the North Pacific Ocean at the depths of surface where 
     the nutrients are almost depleted and 1500-2000 meters depth where the nutrients concentrations are the 
     maximum.  The seawater was gravity-filtered through a membrane filter with a pore size of 0.45 μm (Millipore 
     HA).  The latest procedure of autoclaving for RMNS preparation is that the seawater in a stainless steel container 
     of 40 liters was autoclaved at 120°C, 2 hours, 2 times during two days.  The filling procedure of autoclaved 
     seawater was basically same throughout our study.  Following cooling at room temperature in two days, 
     polypropylene bottle of 100 ml capacity were filled by the autoclaved seawater of 90 ml through a membrane 
     filter with a pore size of 0.2 μm (Millipore HA) at a clean bench in a clean room.  The polypropylene caps were 
     immediately tightly screwed on and a label containing lot number and serial number of the bottle was attached on 
     all of the bottles.  Then the bottles were vacuum-sealed to avid potential contamination from the environment.  
     
     180 RMNS packages and 500 bottles of lot AH for this cruise 
     RMNS lots T, AN, AK, AM and O are prepared to cover the nutrients concentrations in the interested sea 
     area.  About 180 sets of 5 RMNS lots are prepared.  These packages will be used daily when in-house standard 
     solutions renewed daily.  500 bottles of RMNS lot AH are prepared to use every analysis at every hydrographic 
     stations planed about 500 during the cruise.  These RMNS assignment were completely done based on random 
     number.  The RMNS bottles were stored at a room, REGENT STORE, where the temperature was maintained 
     around 22°C.  
     
(ii) The homogeneity of RMNS and consensus values of the lot AH 
     The homogeneity of lot AH and analytical precision are shown in Table 3.4.4. These are for the assessment 
     of the magnitude of homogeneity of the RMNS bottles those are used during the cruise.  As shown in Table 3.4.4, 
     the homogeneity of RMNS lot AH for nitrate and silicate are the same magnitude of analytical precision derived 
     from fresh raw seawater.  The homogeneity for phosphate, however, exceeded the analytical precision at about 
     factor two.  The homogeneity for lot AH is same order of magnitude for previous RMNS of lot K.  


Table 3.4.4. Homogeneity of lot AH derived from 30 samples measurements and analytical precision onboard 
             R/V Mirai in May 2003. 
             ________________________________________

                         Phosphate  Nitrate  Silcate 
                         CV% 
              ---------  ---------  -------  -------
              RMNS 
                AH       0.83%       0.39%    0.13% 
                (K)     (1.0%)      (0.3%)   (0.2%) 
              Precision  0.39%       0.36%    0.13% 
              --------------------------------------
                   Note: N = 30 x 2
             ________________________________________


(5) QUALITY CONTROL 

A.  Precision of nutrients analyses during the cruise 

Precision of nutrients analyses during the cruise was evaluated based on the 13 measurements, which are 
measured every 10-15 samples, during a run at the concentration of C-5.  We also evaluated the reproducibility 
based on the replicate analyses of five samples in each run.  Summary of precisions are shown in Table 
3.4.5.  As shown in Table 3.4.5 and Figures 3.4.5-3.4.7, the precisions for each parameter are generally good 
considering the analytical precisions estimated from the simultaneous analyses of 60 samples in May 2003.  

Analytical precisions previously evaluated were 0.39% for phosphate, 0.36% for nitrate and 0.13% for silicate, 
respectively.  During leg 5, analytical precisions were 0.17% for phosphate, 0.13% for nitrate and 0.12% for 
silicate in terms of median, respectively.  Then we can conclude that the analytical precisions for phosphate, 
nitrate and silicate were maintained or better throughout leg 5 comparing the pre-cruise evaluations.  


TABLE 3.4.5. Summary of precision based on the replicate analyses of 13 samples in each run through out cruise. 
             _______________________________________

                       Nitrate  Phosphate  Silicate 
                       CV%      CV%        CV% 
                       -------  ---------  --------
              Median   0.15     0.18       0.15 
              Mean     0.16     0.19       0.16 
              Maximum  1.37     1.10       0.4 
              Minimum  0.04     0.06       0.04 
              N        491      490        490 
              -------------------------------------
               The time series of precision are 
                 shown in Figures 3.4.5-3.4.7. 
             _______________________________________


FIGURE 3.4.5. Time series of precision of nitrate.
Figure 3.4.6. Time series of precision of phosphate. Figure 3.4.7.  Time series of precision of silicate.


B.  CARRY OVER 

We can also summarize the magnitudes of carry over throughout the cruise.  These are as shown in Table 
3.4.6.  The average of carry over for nitrate was 0.45, which is relatively high rather than those of Phosphate and 
Silicate.  


TABLE 3.4.6. Summary of carry over through out cruise. 
             ________________________________________

                       Nitrate  Phosphate  Silicate 
                       CV%      CV%        CV% 
              ----------------  ---------  --------
              Median   0.49     0.20       0.12 
              Mean     0.48     0.20       0.10 
              Maximum  0.94     1.25       0.47 
              Minimum  0.03     0.00       0.00 
              N        491      491        491 
             ________________________________________


C.  CONCENTRATIONS OF LOW NUTRIENTS SEAWATER 

Concentrations of low nutrients seawater obtained from each measurement were summarized in Table 3.4.7.  

As shown in Table 3.4.7, the concentrations of low nutrients seawater used in this cruise are well reproduced 
against nominal concentrations given in May 2003.  The phosphate concentration of low nutrients seawater was 
calculated as 0.15 μmol kg-1 while nominal concentration was 0.16 μmol kg-1.  This discrepancy might be caused 
by the difference of automated decision process of peak positions of baseline between "base" and others.  Then, 
we concluded that this difference as shown in Table 3.4.7 will not affect on the samples.  


Table 3.4.7. Summary of low nutrients seawater through out cruise. 
             __________________________________________

                       Nitrate    Phosphate  Silicate 
                       µmol kg-1  µmol kg-1  µmol kg-1 
              ------------------  ---------  ---------
              Median   0.01       0.15       0.99 
              Mean     0.01       0.15       0.98 
              Maximum  0.15       0.35       1.36 
              Minimum -0.13       0.08       0.01 
              Nominal  0.00       0.16       1.01 
              ----------------------------------------
               The numbers of analysis were 490 for 
                         three parameters. 
             __________________________________________


(6) EVALUATION OF TRUENESS OF NUTRIENTS CONCENTRATIONS USING RMNSS 

We have been using RMNS for all runs, then, we can evaluate the trueness of nutrients concentration 
throughout cruise.  Results of RMNS measurements are shown in Figures 3.4.8-3.4.13.  

The uncertainties of nitrate, phosphate and silicate measurements for this cruise were evaluated as 
functions of concentrations of those.  Uncertainties of nitrate measurement are expressed by equation (1).  

    Uncertainties (%) = 0.28 + 3.28 / Cnitrate (1) 
Where Cnitrate is nitrate concentration in µmol kg-1.  

    Uncertainties of phosphate measurement are expressed equation (2).  
      Uncertainties (%) = 0.26 + 0.942 / Cphos + 0.125 / (Cphos x Cphos) (2) 
Where Cphos is phosphate concentration in μmol kg-1.  

Uncertainties of silicate measurement are expressed equation (3).  

    Uncertainties (%) = 0.22 + 11.9 / Csilicate (3) 
Where Csilicate is silicate concentration in μmol kg-1.  

Then, we add new three columns to show the uncertainties of nutrients measurement in the sea file of this 
cruise.  


FIGURE 3.4.8.  Time series of nitrate concentration for RMNS lot AH ordered as measurement. 
Figure 3.4.9.  Time series of nitrate concentration for RMNS lot AH sorted by RMNS serial number.
Figure 3.4.10. Same as Figure 3.4.8, but for phosphate. Figure 3.4.11.  Same as Figure 3.4.9, but for phosphate.
Figure 3.4.12. Same as Figure 3.4.8, but for silicic acid. Figure 3.4.13.  Same as Figure 3.4.9, but for silicic acid.


(7) LEG-TO-LEG TRACEABILITY 

Leg-to-leg traceability was examined based on the results of the statistics of RMNS-AH concentrations.  As 
shown in Table 3.4.8 and 3.4.9, the medians and averages of the nutrients concentration of RMNS-AH were in 
good agreement among leg 1, 2, 4 and 5.  The deviations among four legs were less than 0.3% for nitrate, 0.2% 
for silicate and 0% for phosphate, respectively.  


TABLE 3.4.8. Results of the statistics of RMNS-AH concentrations. 
             _________________________________________________

                       NO3_Pacific  SiO2_Pacific  PO4_Pacific 
                       -----------  ------------  -----------
              median   35.33        133.95        2.11 
              mean     35.32        133.94        2.11 
              stdev    0.15         0.45          0.02 
              CV%      0.42         0.34          1.00 
              max      35.88        137           2.15 
              min      34.64        132.74        1.97 
              max-min  1.24         4.26          0.18 
              count    537          535           535 


                       NO3_Leg 1    SiO2_Leg 1    PO4_Leg 1 
                       -----------  ------------  -----------
              median   35.25        133.75        2.11 
              mean     35.25        133.88        2.11 
              stdev    0.12         0.62          0.02 
              CV%      0.33         0.46          1.13 
              max      35.64        137           2.15 
              min      34.96        132.86        1.97 
              max-min  0.68         4.14          0.18 
              count    166          165           165 


                       NO3_Leg 2    SiO2_Leg 2    PO4_Leg 2 
                       -----------  ------------  -----------
              median   35.37        134.00        2.11 
              mean     35.36        133.96        2.11 
              stdev    0.15         0.35          0.02 
              CV%      0.43         0.26          0.94 
              max      35.88        134.94        2.15 
              min      34.64        132.74        1.98 
              max-min  1.24         2.2           0.17 
              count    371          370           370 


                       NO3_Leg 4    SiO2_Leg 4    PO4_Leg 4 
                       -----------  ------------  -----------
              median   35.37        134.02        2.11 
              mean     35.37        134.02        2.11 
              stdev    0.07         0.30          0.02 
              CV%      0.21         0.23          1.02 
              max      35.61        134.90        2.15 
              min      35.10        133.19        2.00 
              max-min  0.51         1.71          0.15 
              count    181          183           183


                       NO3_Leg 5    SiO2_Leg 5    PO4_Leg 5 
                       -----------  ------------  -----------
              median   35.34        133.93        2.11 
              average  35.34        133.95        2.11 
              stdev    0.13         0.51          0.02 
              cv%      0.38         0.38          1.14 
              max      35.82        137.02        2.39 
              min      34.76        131.99        2.01 
              max-min  1.06         5.03          0.38 
              count    267          267           267 
             _________________________________________________


TABLE 3.4.9. Summary of leg-to-leg traceability. 
             ______________________________________________

                       Nitrate      Phosphate     Silicate 
                       -----------  ------------  -----------
              Leg 1    35.25        2.11          133.75 
              Leg 2    35.37        2.11          134.00 
              Leg 4    35.37        2.11          134.02 
              Leg 5    35.34        2.11          133.93 
             ______________________________________________


(8) PROBLEMS/IMPROVEMENTS OCCURRED AND SOLUTIONS 

LEG 1 

a. Silicate concentration decrease in 3-4 days in B-standard solution 
   A decrease of silicate concentration in B-standard solution was found three to four days after its renewal.  

   This was found by the apparent change of RMNS-AH silicate concentrations.  

   We, then, decided to renew B-std solution of silicate every two days from the measurements of the sample 
   at station P06C-166.  We, also, did additional measurements of RM-AH to monitor the stability of B-std.  After 
   introducing this new procedure, the apparent stability of RMNS-AH silicate concentration becomes better.  

b. Base line shift at 3 and 4 ch, silicate and phosphate channels, of #2 machine of TRAACS800 
   Base line shift at 3 and 4 ch, silicate and phosphate channels, of #2 machine of TRAACS800 were observed 
   during leg 1.  From station P06C-123, we had stopped to use #2 machine of TRAACS800.  The measurements 
   were continued using #1 machine of TRAACS800 until the station P06C-121.  

   At Tahiti, #2 machine of TRAACS800 were checked and a board and two cables were replaced.  

c. Silicate concentration drift related with the direct flow from air conditioner in the laboratory 
   Silicate concentration drift related with the direct flow from air conditioner in the laboratory were observed 
   in the results of #1 TRAACS.  We, then, put temporally shield from the measurements of the sample at station 
   P06C-160.  The drift of the results of #1 TRAACS, however, did not become smaller after station P06X-160 
   during leg 1.  

d. Nitrate concentration might decrease within a few weeks in A-standard solution after preparation 
   A decrease of nitrate concentration in A-standard solution was found within a few weeks after its renewal.  

   This was found by the apparent change of RMNS-AH nitrate concentrations.  

   We, then, decided to renew A-std solution of nitrate every 10 days. 

LEG 2 

a. At Tahiti, a slave unit of #2 machine of TRAACS800 were checked and a board, a drive belt and 
   two cables were replaced because baseline shift were occurred frequently at the end of leg 1 
   During the leg 2, baseline shift occurred few due to a same reason as that during leg 1 at the salve unit of 
   #2 machine of TRAACS800, which were for silicate and phosphate.  This might contribute an improvement of 
   reproducibility of silicate analyses during leg 2, as shown in Table 3.4.8.  

b. Decrease a reproducibility of nitrate analyses 
   Since the interval of pump tubes was relatively long rather than expected due to the heavy load of analyses, 
   this might decrease the reproducibility of nitrate analyses.  We also got a problem that air had invaded into 
   sample lines through a four-way valve at a reduction column and it was replaced at station P06C-105.  
   
c. Lower phosphate concentration for a few RMNS-AH bottles 
   We found that phosphate concentrations for 4 bottles of RM-AH during leg 2 were unreasonably low 
   comparing the concentrations of RMNS bottles.  Those are AH-34, 218, 802 and 895, respectively.  

LEG 4 

a. Lower phosphate concentration for a few RMNS-AH bottles 
   We found that phosphate concentrations for 4 bottles of RM-AH during leg 4 were unreasonably low 
   comparing the concentrations of RMNS bottles.  Those are AH-4, 720, 801 and 805, respectively.  

b. Simultaneous base line shift at 3 and 4 ch, silicate and phosphate channels, of #2 machine of TRAACS800 
   Simultaneous base line shift at 3 and 4 ch, silicate and phosphate channels, of #2 machine of TRAACS800 
   were occurred seven times during leg 4.  Although, #2 machine of TRAACS800 were checked at Tahiti and a 
   board, two cables and a drive belt were replaced and base line shift becomes less, these simultaneous base line 
   shifts may be caused by different reason.  

c. Preventive replacements of pump tubes and flow cells, and careful treatment of the peak position 
   determination might contribute excellent results on analytical precision 
   We did preventive replacements of pump tubes before baseline noise would increase due to the aging of 
   pump tubes.  We also did preventive replacements of flow cells to maintain good condition of the TRAACS800s.  
   
   We pay more attention to determine peak positions before the calculation of concentrations of nutrients.  
   
LEG 5 

a. Silicate TRAACS800s #1 #2 systematic difference between two machines about 0.7% 
b. Pump tube replacement interval ca. 5days same as leg 4 lead better precision 
c. A pump and a drive belt for ch3, ch4 were replaced prior leg 5, then, no shift occurred during leg 5 



REFERENCES 

Aminot, A. and R. Kerouel, 1991, Autoclaved seawater as a reference material for the determination of nitrate 
    and phosphate in seawater, Anal. Chim. Acta, 248 : 277-283. 
Aminot, A. and D.S. Kirkwood, 1995, Report on  the results of the fifth ICES intercomparison exercise for 
    nutrients in sea water, ICES coop. Res. Rep. Ser., 213. 
Aminot, A. and R. Kerouel, 1995, Reference material for nutrients in seawater : stability of nitrate, nitrite, 
    ammonia and phosphate in autoclaved samples. Mar. Chem., 49 : 221-232. 
Aoyama, M. and T.M. Joyce, 1996, WHP property comparisons from crossing lines in North Pacific. In Abstracts, 
    1996 WOCE Pacific Workshop, Newport Beach, California. 
Aoyama, M., H. Ota, S. Iwano, H. Kamiya, M. Kimura, S. Masuda, N. Nagai, K. Saito and H. Tubota, 2004, 
    Reference material for nutrients in seawater in a seawater matrix, Mar. Chem., submitted. 
Grasshoff, K., M. Ehrhardt, K. Kremling et al., 1983, Methods of seawater anylysis. 2nd ref. ed. Verlag Chemie 
    GmbH, Weinheim. 419. 
Joyce, T. and C. Corry, 1994, Requirements for WOCE hydrographic programmed data reporting. WHPO 
    Publication, 90-1, Revision 2, WOCE Report No. 67/91. 
Kirkwood, D.S., 1992, Stability of solutions of nutrient salts during storage. Mar. Chem., 38 : 151-164. 
Kirkwood, D.S., A. Aminot and M. Perttila, 1991, Report on the results of the ICES fourth intercomparison 
    exercise for nutrients in sea water. ICES coop. Res. Rep. Ser., 174. 
Mordy, C.W., M. Aoyama, L.I. Gordon, G.C. Johnson, R.M. Key, A.A. Ross, J.C. Jennings and J. Wilson, 2000, 
    Deep water comparison studies of the Pacific WOCE nutrient data set. Eos Trans-American Geophysical 
    Union. 80 (supplement), OS43. 
Murphy, J. and J.P. Riley, 1962, Analytica chim. Acta 27, 31-36. 
    Gouretski, V.V. and K. Jancke, 2001, Systematic errors as the cause for an apparent deep water property 
    variability: global analysis of the WOCE and historical hydrographic data, REVIEW ARTICLE, Progress In 
    Oceanography, 48 : Issue 4, 337-402.


3.5 DISSOLVED INORGANIC CARBON (CT) 
    5 FEBRUARY 2005 

(1) PERSONNEL 

    Akihiko Murata (IORGC, JAMSTEC) 
    Mikio Kitada (MWJ) 
    Minoru Kamata (MWJ) 
    Masaki Moro (MWJ) 
    Toru Fujiki (MWJ) 

(2) INTRODUCTION 

Concentrations of CO2 in the atmosphere are now increasing at a rate of 1.5 ppmv y-1 due to human 
activities such as burning of fossil fuels, deforestation, cement production, etc.  It is an urgent task to estimate as 
accurately as possible the absorption capacity of the oceans against the increased atmospheric CO2, and to clarify 
the mechanism of the CO2 absorption, because the magnitude of the predicted global warming depends on the 
levels of CO2 in the atmosphere, and because the ocean currently absorbs 1/3 of the 6 Gt of carbon emitted into 
the atmosphere each year by human activities.  

In this cruise (BEAGLE), we were aimed at quantifying how much anthropogenic CO2 absorbed in the 
Southern Ocean, where intermediate and deep waters are formed, are transported and redistributed in the 
southern hemisphere subtropical oceans.  For the purpose, we measured CO2-system properties such as 
dissolved inorganic carbon (CT), total alkalinity (AT), pH and underway pCO2.  

In this section, we describe data on CT obtained in the BEAGLE in detail.  


(3) APPARATUS 

Measurements of CT were made with two total CO2 measuring systems (systems A and B; Nippon ANS, 
Inc.), which are slightly different from each other.  The systems comprise of a seawater dispensing system, a CO2 
extraction system and a coulometer (Model 5012, UIC Inc.).  

The seawater dispensing system has an auto-sampler (6 ports), which takes seawater in a 300 ml 
borosilicate glass bottle and dispenses the seawater to a pipette of nominal 20 ml volume by a PC control.  The 
pipette is kept at 20°C by a water jacket, in which water from a water bath set at 20°C is circulated.  

CO2 dissolved in a seawater sample is extracted in a stripping chamber of the CO2 extraction system by 
adding phosphoric acid (10% v/v).  The stripping chamber is approx. 25 cm long and has a fine frit at the bottom.  

To degas CO2 as quickly as possible, a heating wire kept at 40°C was rolled from the bottom to a 1/3 height of the 
stripping chamber.  The acid is added to the stripping chamber from the bottom of the chamber by pressurizing 
an acid bottle for a given time to push out the right amount of acid.  The pressurizing is made with nitrogen 
gas (99.9999%).  After the acid is transferred to the stripping chamber, a seawater sample kept in a pipette 
is introduced to the stripping chamber by the same method as in adding an acid.  The seawater reacted with 
phosphoric acid is stripped of CO2 by bubbling the nitrogen gas through a fine frit at the bottom of the stripping 
chamber.  The CO2 stripped in the stripping chamber is carried by the nitrogen gas (flow rates of 130 ml min-1 
and 140 ml min-1 for the systems A and B, respectively) to the coulometer through a dehydrating module.  For 
the system A, the module consists of two electric dehumidifiers (kept at 1 - 2°C) and a chemical desiccant 
(Mg(ClO4)2).  For the system B, it consists of three electric dehumidifiers with a chemical desiccant.  


(4) SHIPBOARD MEASUREMENT 

SAMPLING 

All seawater samples were collected from depth with 12 liter Niskin bottles basically at every other stations.  

The seawater samples for CT were taken with a plastic drawing tube (PFA tubing connected to silicone rubber 
tubing) into a 300 ml borosilicate glass bottle.  The glass bottle was filled with seawater smoothly from the 
bottom following a rinse with a seawater of 2 full, bottle volumes.  The glass bottle was closed by a stopper, 
which was fitted to the bottle mouth gravimetrically without additional force.  

At a chemical laboratory on the ship, a headspace of approx. 1% of the bottle volume was made by removing 
seawater using a plastic pipette.  A saturated mercuric chloride of 100 μl was added to poison seawater samples.  

The glass bottles were sealed with a greased (Apiezon M, M&I Materials Ltd) ground glass stopper and the clips 
were secured.  The seawater samples were kept at 4°C in a refrigerator until analysis.  A few hours just before 
analysis, the seawater samples were kept at 20°C in a water bath.  

ANALYSIS 

At the start of each leg, we calibrated the measuring systems by blank and 5 kinds of Na2CO3 solutions 
(nominally 500, 1000 1500, 2000, 2500 μmol/L).  As it was empirically known that coulometers do not show 
a stable signal (low repeatability) with fresh (low absorption of carbon) coulometer solutions.  Therefore we 
measured 2% CO2 gas repeatedly until the measurements became stable. Then we started the calibration.  

The measurement sequence such as system blank (phosphoric acid blank), 2% CO2 gas in a nitrogen base, 
seawater samples (6) was programmed to repeat.  The measurement of 2% CO2 gas was made to monitor 
response of coulometer solutions (from UIC, Inc.).  For every renewal of coulometer solutions, certified 
reference materials (CRM, batch 60) provided by Prof. A. G. Dickson of Scripps Institution of Oceanography were 
analyzed.  In addition, reference materials (RM) provided by JAMSTEC (2 kinds) and KANSO were measured at 
the initial, intermediate and end times of a coulometer solution's lifetime.  

The preliminary values were reported in a data sheet on the ship.  Repeatability and vertical profiles of CT 
based on raw data for each station helped us check performances of the measuring systems.  

In each leg, we finished all the analyses for CT on board the ship.  As we used two systems, we had 
not encountered such a situation as we had to abandon the measurement.  However, we experienced some 
malfunctions of the measuring systems during the cruise, which are described in the followings: 
In the leg 1, due to malfunction of the coulometer of the system B, we replaced it to a back-up coulometer; 
There occurred lowering of repeatability, mostly due to dirt.  This situation was recovered by cleaning the 
measuring systems; 
The "undershooting" of coulometer detection was often found.  This happened in measuring seawater 
samples subsequent to the measurement of phosphoric acid blank.  To avoid the "undershooting" occurred in 
seawater sample measurement, we measured a dummy seawater sample subsequent to the bank measurement.  


(5) QUALITY CONTROL 

LEG 1 
  Calibration factors of the systems A and B were listed in Table 3.5.1.  With these factors, we calculated 
  CT of CRM (batch 60), and plotted the values as a function of sequential day (Fig. 3.5.1).   From Fig. 3.5.1, it is 
  found that there were no trends of CRM measurements for the system A during the leg 1.  The average and 
  standard deviation were 1991.0 and 1.5 μmol kg-1 (n = 40), respectively.  Since the certified value of the batch 60 
  is 1991.24 μmol kg-1, very close to the average, it implies that the measurement had been conducted in a good 
  condition.  
  
  For the system B, however, we had to replace the coulometer with a back-up one, because repeatability for 
  the system B had been worse (3.0 μmol kg-1 for CRM measurements) than usually expected value (~1.5 μmol 
  kg-1).  Before and after the replacement, the calibration factor changed largely from 0.31322 to 0.31644 (Table 
  3.5.1).  This change of a calibration factor caused CRM measurements to be 2011.7±1.5 μmol kg-1, which were 
  1991.9 µmol kg-1 before the replacement.  
  
  Based on the results of CRM measurements stated above, we re-calculated the calibration factors so that 
  measurements of seawater samples become traceable to the certified value of batch 60.  For example, the initial 
  factor of 0.31322 for the system A became 0.31333 by such a calculation as 0.31322/(1990.24/1991.0).  
  
  Temporal variations of RM measurements are shown in Fig. 3.5.2.  From Fig. 3.5.2, it is evident that RM 
  measurements included a linear trend, implying that measurements of seawater samples also have the trend.  
  
  The trend was also found in temporal changes of 2% CO2 gas measurements.  The trend seems to be due to "cell 
  age" change (Johnson et al., 1998) of a coulometer solution.  
  
  Considering the trends, we adjusted measurements of seawater samples so as to be traceable to the certified 
  value of batch 60, although the adjustments were usually slight.  
  
  Finally we surveyed vertical profiles of CT.  In particular, we examined whether systematic differences 
  between measurements of the systems A and B existed or not.  Then taking other information of analyses into 
  account, we determined a flag of each value of CT.  
  
  The average and standard deviation of absolute values of differences of CT analyzed consecutively were 1.5 
  and 1.3 μmol kg-1 (n = 203), respectively.  

LEG 2 
  Calibration factors of the systems A and B for the leg 2 are listed in Table 3.5.1, and temporal variations of 
  CRM CT are shown in Fig. 3.5.3.  
  
  From Fig. 3.5.3, it is found that the CRM CT for the system A changes discontinuously at the 268th 
  sequential day.  In the former period, no trends are found, while in the latter period, a significant trend exists.  
  
  We do not know the causes of this discontinuity and the subsequent trend.  For the system B, no such a variation 
  of CRM CT is found (Fig. 3.5.3).  
  
  The average and standard deviation of CRM CT in the former period (before the 268 sequential day) for the 
  system A were calculated to be 1990.9 and 1.2 μmol kg-1 (n = 16), respectively.  Those in the latter period were 
  1990.7 and 1.4 µmol kg-1 (n = 20), respectively.  For the system B, the average and standard deviation were 
  1994.1 and 1.9 µmol kg-1 (n = 34), respectively.  
  
  Based on the information of CRM CT stated above, we re-calculated the calibration factors as made for the 
  leg 1, considering the trend.  
  
  Based on RM measurements, we adjusted the trend of CT of seawater samples as conducted for the data on 
  leg 1.  Then, we checked the vertical profiles of CT, and determined a flag of each CT value.  
  
  The average and standard deviation of absolute values of differences of CT analyzed consecutively were 1.5 
  and 1.4 µmol kg-1 (n = 188), respectively.  

LEG 4 
  Calibration factors of the systems A and B for the leg 4 are listed in Table 3.5.1, and temporal variations of 
  CRM CT are shown in Fig. 3.5.4.  
  
  From Fig. 3.5.4, it is found that there existed no trends for the system A, but a slight decreasing trend for 
  the system B, which was not significant statistically.  
  
  The average and standard deviation of CRM CT for the system A were 1988.2 and 1.1 μmol kg-1 (n = 35), 
  respectively, while those for the system B were 1998.6 and 0.9 µmol kg-1 (n = 28), respectively.  
  
  Based on the information of CRM CT stated above, we re-calculated the calibration factors as made for the 
  leg 1.  
  
  Based on RM measurements, we adjusted the trend of CT of seawater samples as conducted for the data on 
  leg 1.  Then, we checked the vertical profiles of CT, and determined a flag of each CT value.  
  
  The average and standard deviation of absolute values of differences of CT analyzed consecutively were 1.0 
  and 0.8 µmol kg-1 (n = 166), respectively.  
  
LEG 5 
  Calibration factors of the systems A and B for the leg 5 are listed in Table 3.5.1, and temporal variations 
  of CRM CT are shown in Fig. 3.5.5.  From this figure, if is found that for both the systems, the CRM CTs show 
  statistically significant increasing trends, but in a discontinuous manner.  Therefore we divided the time series 
  into the two periods.  Then we calculated the averages and standard deviations of each period separately.  
  
  The average and standard deviation of CRM CT for the former period (before the 367th sequential day) of the 
  system A were 1989.7 and 1.3 μmol kg-1 (n = 25), respectively, while those for the latter period were 1990.1 and 
  1.0 µmol kg-1 (n = 17), respectively.  For the system B, the average and standard deviation for the former period 
  (before 377th sequential day) were 1988.6 and 0.9 μmol kg-1 (n = 29), respectively, while those for the latter 
  period were 1990.1 and 0.5 µmol kg-1 (n = 6), respectively.  
  
  Based on RM measurements, we adjusted the trend of CT of seawater samples as conducted for the data on 
  leg 1.  Then, we checked the vertical profiles of CT, and determined a flag of each CT value.  
  
  The average and standard deviation of absolute values of differences of CT analyzed consecutively were 0.9 
  and 0.7 µmol kg-1 (n = 229), respectively.  



REFERENCE 

Johnson, K.M., A.G. Dickson, G. Eischeid, C. Goyet, P. Guenther, R.M. Key, F. J. Millero, D. Purkerson, C.L. 
    Sabine, R.G. Schottle, D.W.R. Wallace, R.J. Wilke and C.D. Winn (1998): Coulometric total carbon dioxide 
    analysis for marine studies: assessment of the quality of total inorganic carbon measurements made during 
    the US Indian Ocean CO2 survey 1994-1996, Mar. Chem., 63, 21-37.  


Table 3.5.1. Calibration factors determined from Na2CO3 solutions. 
             _________________________________________________________

                      Calibration factors 
              Leg no.    A        B     Remarks
              ------  -------  -------  -----------------------------
                 1    0.31322  0.31322  Replacement of coulometer was 
                      0.31644           conducted for the system B. 
                 2    0.31281  0.31589  
                 4    0.31399  0.30895  
                 5    0.31398  0.31140  
             _________________________________________________________
            

FIGURE 3.5.1. Temporal variations of CRM CT measured by the systems A and B in the leg 1. 
FIGURE 3.5.2. An example of temporal variations of RM CT.
FIGURE 3.5.3. Temporal variations of CRM CT measured by the systems A and B in the leg 2. 
FIGURE 3.5.4. Temporal variations of CRM CT measured by the systems A and B in the leg 4. 
FIGURE 3.5.5. Temporal variations of CRM CT measured by the systems A and B in the leg 5.


3.6 TOTAL ALKALINITY (AT) 
    3 FEBRUARY 2005 

(1) PERSONNEL 
    Akihiko Murata (IORGC, JAMSTEC) 
    Fuyuki Shibata (MWJ) 
    Taeko Ohama (MWJ) 


(2) INTRODUCTION 

Concentrations of CO2 in the atmosphere are now increasing at a rate of 1.5 ppmv y-1 due to human 
activities such as burning of fossil fuels, deforestation, cement production, etc.  It is an urgent task to estimate as 
accurately as possible the absorption capacity of the oceans against the increased atmospheric CO2, and to clarify 
the mechanism of the CO2 absorption, because the magnitude of the predicted global warming depends on the 
levels of CO2 in the atmosphere, and because the ocean currently absorbs 1/3 of the 6 Gt of carbon emitted into 
the atmosphere each year by human activities.  

In the BEAGLE, we were aimed at quantifying how much anthropogenic CO2 absorbed in the Southern 
Ocean, where intermediate and deep waters are formed, are transported and redistributed in the southern 
hemisphere subtropical oceans.  For the purpose, we measured CO2-system properties such as dissolved 
inorganic carbon (CT), total alkalinity (AT), pH and underway pCO2.  

In this section, we describe data on AT obtained in the BEAGLE in detail.  


(3) APPARATUS 

The measuring system for AT (customized by Nippon ANS, Inc.) comprises of a water dispensing unit 
with an auto-sampler (6 ports), an auto-burette (Metrohm) and a pH meter (Thermo Orion).  They are 
automatically controlled by a PC.  We prepared two systems for the BEAGLE, but a single system was enough 
for the measurement except for the leg 1, because the system could perform a high speed titration (5-6 min.).  

Combined electrodes (Model 8103BN ROSSTM) were used through the cruise.  

A seawater of approx. 40 ml is transferred from a sample bottle (borosilicate glass bottle; 130 ml) into a 
water-jacketed (25°C) pipette by pressurized N2 gas, and is introduced into a water-jacketed (25°C) titration cell.  

Next, a given volume of a titrant is injected into the titration cell so that pH of a seawater sample becomes 4.5 - 
4.0.  The seawater sample mixed with the titrant is stirred for three minutes by a stirring chip.  Then an aliquot 
of titrant (~0.1 ml) is added consecutively until pH or e.m.f. reaches a given value.  The concentration of the acid 
titrant is nominally 0.05 M HCl in 0.65 M NaCl.  

Calculation of AT is made based on a modified Gran approach.  


(4) SHIPBOARD MEASUREMENT 

SAMPLING 

All seawater samples were collected from depth using 12 liter Niskin bottles basically at every other 
stations.  The seawater samples for AT were taken with a plastic drawing tube (PFA tubing connected to silicone 
rubber tubing) into borosilicate glass bottles of 130 ml.  The glass bottle was filled with seawater smoothly from 
the bottom after rinsing it with a seawater of half a or a full bottle volume.  A few hours before analysis, the 
seawater samples were kept at 25°C in a water bath.  

ANALYSIS 

For the AT measurement, we selected electrodes, which showed signals close to theoretical Nernstian 
behavior.  

At the start of each leg, we conducted calibration of the acid titrant, which was prepared on land.  The 
calibration was made by measuring AT of 5 solutions of Na2CO3 in 0.7 M NaCl solutions (nominally 0, 100, 1000, 
2000 and 2500 μmol kg-1).  The measured values of AT (calculated by assuming 0.05 M acid titrant) should be a 
linear function of the AT computed from concentrations of the Na2CO3 solutions.  The linear function was fitted by 
the method of least squares.  Theoretically, the slope of the linear function should be unity.  If the measured slope 
is not equal to one, the acid normality should be adjusted by dividing initial normality by the slope, and the whole 
set of calculations is repeated until the slope = 1.  

Before starting analyses of seawater samples, we measured AT of dummy seawater samples to confirm 
a condition of the measuring systems.  If repeat measurements of AT were constant within ~3 μmol kg-1, we 
initiated measurement of seawater samples.  We analyzed reference materials (RM), which were produced for 
CT by JAMSTEC and KANSO, but were efficient also for the monitor of AT measurement.  In addition, certified 
reference materials (CRM, batch 60, certified value = 2199.55 μmol kg-1) were also analyzed periodically to 
monitor systematic differences of measured AT.  

The preliminary values were reported in a data sheet on the ship.  Repeatability calculated from replicate 
samples and vertical profiles of AT based on raw data for each station helped us check performances of the 
measuring systems.  

In each leg, we finished all the analyses for AT on board the ship.  We did not encounter so serious a problem 
as we had to give up the analyses.  However, we experienced some malfunction of the system during the cruise, 
which are listed in the followings: 
Small bubbles were often found in a pipette, probably due to stagnation of a seawater flow in the joint at an 
inlet of a pipette.  In this case, we re-sealed the joint properly; 
After analyses of a large number of samples, we often experienced a drift of an electrode, which appeared as 
differences of pH or e.m.f. in spite of an injection of a constant volume of an acid titrant into a seawater sample of 
almost a same AT.  In this case, we changed ranges of pH or e.m.f. used for the determination of AT.  


(5) QUALITY CONTROL 

LEG 1 
  We used two systems (systems A and B) in this leg, but about 2/3 of the all the samples were analyzed by 
  the system A.  
  
  Temporal variations of CRM AT are displayed in Fig. 3.6.1.  From this figure, it is found that for both the 
  systems, such characteristic patterns as trend, discontinuity, etc. do not exist in the variations.  Therefore, we 
  re-calculated AT of seawater samples using the concentration of HCl, which was re-calculated from the average of 
  measured CRM AT and the certified value of CRM AT.  
  
  We surveyed vertical profiles of AT. In particular, we examined whether systematic differences between 
  measurements of the systems A and B existed or not.  Then taking other information of analyses into account, 
  we determined a flag of each value of AT.  
  
  The average and standard deviation of absolute values of differences of AT analyzed consecutively were 2.2 
  and 1.8 µmol kg-1 (n = 188), respectively.  
  
  We compared AT measured in the BEAGLE with AT calculated from CT and pCO2 measured in the WOCE P6 
  (Fig. 3.6.5).  We judged that differences of AT between the two observation periods are due to analytical errors, 
  because the differences are also found in the deep layer.  


LEG 2 
  We analyzed all seawater samples by the system B.  
  
  Temporal variations of CRM AT are displayed in Fig. 3.6.2.  From this figure, it is found that there exists a 
  decreasing trend of AT.  In addition, we also found some gaps of measured AT, when we examined the vertical 
  profiles of AT.  Considering these results, we decided to calculate averages of CRM AT separating the data into 
  three periods.  Since in the first period (before the 270th sequential day, Fig. 3.6.2), the AT includes a decreasing 
  trend, we determined the values of CRM AT at each sequential day of measurements of seawater samples 
  considering the trend.  Then we determined concentration of HCl from the corrected values of CRM AT and the 
  certified value of CRM AT.  
  
  We surveyed vertical profiles of AT.  Then taking other information of analyses into account, we determined 
  a flag of each value of AT.  
  
  The average and standard deviation of absolute values of differences of AT analyzed consecutively were 2.5 
  and 2.0 µmol kg-1 (n = 168), respectively.  
  
  We compared AT measured in the BEAGLE with AT calculated from CT and pCO2 measured in the WOCE P6 
  (Fig. 3.6.5).  We judged that differences of AT (5 - 10 μmol kg-1) between the two observation periods are due to 
  analytical errors, because the differences are also found in the deep layer.  

LEG 4 
  We analyzed all seawater samples by the system B.  
  
  Temporal variations of CRM AT are displayed in Fig. 3.6.3.  From this figure, it is found that there exists a 
  discontinuous change of AT.  That is, before the 320 sequential day, the AT shows a decreasing trend, but after 
  the day, the AT displays a stationary variation.  From this characteristics of temporal variation, we re-calculated 
  concentrations of HCl, separating the data for CRM AT into two periods, as conducted in the quality control for 
  the leg 2.  
  
  We surveyed vertical profiles of AT.  Then taking other information of analyses into account, we determined 
  a flag of each value of AT.  
  
  The average and standard deviation of absolute values of differences of AT analyzed consecutively were 2.2 
  and 1.7 µmol kg-1 (n = 162), respectively.  
  
  We compared AT measured in the BEAGLE with AT measured in the WOCE A10 (Fig. 3.6.6).  We judged that 
  differences of AT (5 - 10 µmol kg-1) between the two observation periods are due to analytical errors, except for 
  the upper layer.  The differences in the upper layer might be related to seasonal differences.  

LEG 5 
  We analyzed all seawater samples by the system B.  
  
  Temporal variations of CRM AT are displayed in Fig. 3.6.4.  The AT shows a decreasing trend.  Therefore, we 
  reflected the trend in re-determining concentration of HCl, as conducted in the quality control for the leg 2.  
  
  We surveyed vertical profiles of AT.  Then taking other information of analyses into account, we determined 
  a flag of each value of AT.  
  
  The average and standard deviation of absolute values of differences of AT analyzed consecutively were 2.0 
  and 1.8 µmol kg-1 (n = 220), respectively.  
  
  We compared AT measured in the BEAGLE with AT measured in the WOCE I3 and I4 (Fig. 3.6.7).  It is 
  evident that ATs obtained in the BEAGLE are systematically lower by 5 - 10 µmol kg-1 than those in the WOCE.  
  
  At present, we do not know the reason why such a difference occurs.  


FIGURE 3.6.1. Temporal variations of CRM AT measured in the leg 1.  The sequential day is counted from 1 
              January, 2003.  The "A" and "B" indicate results of the systems A and B, respectively. 
FIGURE 3.6.2. Temporal variations of CRM AT measured in the leg 2. 
FIGURE 3.6.3. Temporal variations of CRM AT measured in the leg 4. 
FIGURE 3.6.4. Temporal variations of CRM AT measured in the leg 5.
FIGURE 3.6.5. Comparisons of AT measured in the BEAGLE with AT calculated from CT and pCO2 measured along 
              the WOCE P6 on isopycnal surfaces of 26.1 σθ (top panel), 27.1 σθ (middle panel) and 
              27.5 σθ (bottom panel). 
FIGURE 3.6.6. Comparisons of AT measured in the BEAGLE with AT calculated from CT and pCO2 measured along 
              the WOCE A10 on isopycnal surfaces of 26.1 σθ (top panel), 27.1 σθ (middle panel) and 
              27.5 σθ (bottom panel).
FIGURE 3.6.7. Comparisons of AT measured in the BEAGLE with AT calculated from CT and pCO2 measured along 
              the WOCE I3/I4 on isopycnal surfaces of 26.1 σθ (top panel), 27.1 σθ (middle panel) and 
              27.5 σθ (bottom panel).


3.7 pH 
    3 FEBRUARY 2005 

(1) PERSONNEL 

    Akihiko Murata (IORGC, JAMSTEC) 
    Fuyuki Shibata (MWJ) 
    Taeko Ohama (MWJ) 


(2) INTRODUCTION 

Concentrations of CO2 in the atmosphere are now increasing at a rate of 1.5 ppmv y-1 due to human 
activities such as burning of fossil fuels, deforestation, cement production, etc.  It is an urgent task to estimate as 
accurately as possible the absorption capacity of the oceans against the increased atmospheric CO2, and to clarify 
the mechanism of the CO2 absorption, because the magnitude of the predicted global warming depends on the 
levels of CO2 in the atmosphere, and because the ocean currently absorbs 1/3 of the 6 Gt of carbon emitted into 
the atmosphere each year by human activities.  

In the BEAGLE, we were aimed at quantifying how much anthropogenic CO2 absorbed in the Southern 
Ocean, where intermediate and deep waters are formed, are transported and redistributed in the southern 
hemisphere subtropical oceans.  For the purpose, we measured CO2-system properties such as dissolved 
inorganic carbon (CT), total alkalinity (AT), pH and underway pCO2.  

In this section, we describe data on pH obtained in the BEAGLE in detail.  


(3) APPARATUS 

Measurement of pH was made by a pH measuring system (Nippon ANS, Inc.), which adopts a method of 
the spectrophotometric determination.  The measuring system comprises of a water dispensing unit with an 
auto-sampler and a spectrophotometer (Carry 50 Scan, Varian).  

Seawater is transferred from borosilicate glass bottle (300 ml) to a sample cell in the spectrophotometer.  

The length and volume of the cell are 8 cm and 13 ml, respectively, and the sample cell is kept at 25.00 ± 0.05° 
C in a thermostatic compartment.  First, absorbance of seawater is measured at three wavelengths (730, 578 
and 434 nm).  Then an indicator solution is injected and circulated for about 4 minutes to mix the indicator 
solution and seawater sufficiently by a peristaltic pump.  After the pump is stopped, the absorbance of seawater 
+ indicator solution is measured at the three wavelengths.  The pH is calculated based on the following equation 
(Clayton and Byrne, 1993): 
                               ,               (1) SEE PAGE 89 OF PDF
where A1 and A2 indicate absorbance at 578 and 434 nm, respectively, and pK2 is calculated as a function of water 
temperature and salinity.  


(4) SHIPBOARD MEASUREMENT 

SAMPLING 
All seawater samples were collected from depth with 12 liter Niskin bottles basically at every other stations.  

The seawater samples for pH were taken with a plastic drawing tube (PFA tubing connected to silicone rubber 
tubing) into a 300 ml borosilicate glass bottle, which is the same as used for CT sampling.  The glass bottle was 
filled with seawater smoothly from the bottom following a rinse with a sea water of 2 full, bottle volumes.  The 
glass bottle was closed by a stopper, which was fitted to the bottle mouth gravimetrically without additional force.  

We analyzed seawater samples as soon as possible within half a day.  

ANALYSIS 
For an indicator solution, m-cresol purple (2 mM) was used.  NaCl was added to the indicator solution so that 
the solution had a density close to seawater.  The indicator solution was produced on board the ship, and retained 
in a 1000 ml DURAN® laboratory bottle.  To minimize absorption of CO2 in an indicator solution, a holder of soda 
lime was attached.  We renewed an indicator solution periodically when the headspace of the bottle became large, 
and monitored pH or absorbance ratio of the indicator solution by another spectrophotometer (Carry 50 Scan, 
Varian) using a cell with a short path length of 0.5 mm.  In most indicator solutions, the absorbance ratios were 
initially in the range 1.4 - 1.6, and decreased to 1.1.  

It is difficult to mix seawater with an indicator solution sufficiently under no headspace condition.  However, 
by circulating the mixed solution with a peristaltic pump and by increasing density of indicator solutions, a 
well-mixed condition came to be attained rather shortly, leading to a rapid stabilization of absorbance (Fig. 
3.7.1).  We renewed a TYGON® tube of a peristaltic pump periodically, when the tube deteriorated in an impaired 
condition.  

Absorbance of seawater only and seawater + indicator solutions was measured 12 and 30 times, respectively, 
and the last five values of absorbance were used for the calculation of pH (Equation 1).  

The preliminary values of pH were reported in a data sheet on the ship.  Repeatability calculated from 
replicate samples and vertical profiles of pH based on raw data for each station helped us check performance of 
the measuring system.  

In each leg, we finished all the analyses for pH on board the ship.  We did not encounter so serious a problem 
as we had to give up the analyses.  However, we sometimes experienced malfunction of the system during the 
cruise: 
The difference between absorbance of seawater only and absorbance of seawater + indicator solution was 
infrequently greater than ± 0.001.  This implies dirt of the cell. In this case, we cleaned or replaced the cell.  


(5) QUALITY CONTROL 

It is recommended that correction for pH change resulting from addition of indicator solutions is made 
(DOE, 1994).  To check the perturbation of pH due to the addition, we measured absorbance ratios by changing 
the volume of indicator solutions added to a same seawater sample. We corrected absorbance ratios based on an 
empirical method (DOE, 1994).  

We surveyed vertical profiles of pH.  In particular, we examined whether systematic differences between 
before and after the renewal of indicator solutions existed or not.  Then taking other information of analyses into 
account, we determined a flag of each value of pH.  

The average and standard deviation of absolute values of differences of pH analyzed consecutively are listed 
in Table 3.7.1.  



REFERENCES 

Clayton, T.D. and R.H. Byrne (1993): Spectrophotometric seawater pH measurements: total hydrogen ion 
    concentration scale calibration of m-cresol purple and at-sea results. Deep-Sea Research 40, 2115-2129. 
DOE (1994): Handbook of methods for the analysis of the various parameters of the carbon dioxide system in sea 
    water, version 2, A. G. Dickson & C. Goyet, eds. (unpublished manuscript). 


Table 3.7.1. Averages and standard deviations (s.t.d.) of absolute values differences of pH analyzed 
             consecutively, separately for legs 1, 2, 4 and 5. 
             _______________________________

              Leg no.   N   Average  s.t.d 
              -------  ---  -------  ------
                 1     140  0.0014   0.0017 
                 2     176  0.0017   0.0014 
                 4     155  0.0010   0.0009 
                 5     208  0.0008   0.0007
             _______________________________


FIGURE 3.7.1. An example of temporal changes of absorbances.  
              A unit of sequence corresponds to about 5 seconds.


3.8 LOWERED ACOUSTIC DOPPLER CURRENT PROFILER 
    28 FEBRUARY 2005 

(1) PERSONNEL 

    Yasushi Yoshikawa (JAMSTEC) 
    Luiz Nonnato (University of Sao Paulo) 
    On Sugimoto (JAMSTEC) 


(2) INSTRUMENT AND METHOD 

Direct flow measurement from sea surface to the bottom was carried out using a lowered acoustic 
Doppler current profiler (LADCP).  The instrument used was the RDI Workhorse Monitor 307.2 kHz unit (RD 
Instruments, USA).  The instrument was attached on the CTD/RMS frame, orientating downward.  The CPU 
firmware version was 16.20.  

One ping raw data were recorded, where the bin number was 32 and the bin length was 8 m, except 4m at 
CTD stations from P6_246 to P6_232 in the beginning of the cruise.  The accuracies of each ping were 2.0 cm/s 
for 8 m bin and 3.0 cm/s for 4 m bin, respectively.  Sampling interval was 1.29 seconds originally, and then it was 
changed to 1.20 seconds in leg 5.  The bottom-tracking mode was used, which made the LADCP capture the sea 
floor 200 m above.  Salinity value in the sound speed calculation was set as a constant value 34 PSU.  We found 
the one of the four beams sounded weak signal during the cruise, and then we replaced another instrument at 
A10_37 station in the Atlantic sector.  A pressure sensor was added to the first instrument.  

A total of 118 operations were made with the CTD observations in the leg 1.  Because the depth was too 
deep, operation was not made at the CTD stations, P6_175, P6_174 and P6_148.  The performance of the 
LADCP instrument was good in western stations.  Profiles were obtained over 100 m distance in shallow depth 
and almost 60 m in deeper depth.  On the other hand in eastern stations in the leg 1 the performance was bad.  

In the deeper depth good quality data were obtained only 3 or 4 bins, which means the LADCP could observe 
only 25 m.  It would due to a weak echo intensity, which agreed with ship's ADCP.  A total of 112 operations 
are made in the leg 2.  In the leg 4 a total of 111 operations were made.  As mentioned above, we replace the 
instrument at A10_37.  For the first instrument, the performance was bad; profiles were obtained less than 60 m 
in deeper depth.  Three beam solutions gradually appeared more, sometimes in the leg 1, and often in the leg 2 
and leg 4 before the replacement.  After the replacement the profile was obtained about 80 m in deeper depth, as 
a four-beam solution.  The sea bottom was detected during the instrument was lowered less than 200 m above 
the bottom.  A total of 142 operations were made in the leg 5.  The LADCP measurement was not operated at 
the station I3_468 where the depth was too deep.  The performance of the instrument was relatively better in 
the shallow ocean, where profiles were obtained over 100 m.  In the deep ocean it reached almost 60 m.  The 
performance looked unchanged during the leg.  Data transfer errors were often occurred during upload process 
from the LADCP to PC.  


(3) PRELIMINARY RESULTS 

Vertical profiles of velocity field are analyzed by the inverse method (Visbeck, 2002).  The bottom-track data 
and GPS navigation data are used in the calculation.  Shipboard ADCP data are not included in the calculation.  

At this stage the CTD data are used for the sound speed and depth calculation.  Figure 3.8.1 and 3.8.2 show the 
results at station A10_087 and A10_010, respectively, in the Atlantic.  They would be a typical good and bad 
result, respectively.  The results are somewhat sensitive to parameters.  It is probably due to the short range of 
the LADCP signal, which makes less overlap in the inversion.  More three-beam solution should affect it worse.  

On the other hand the bottom tracking was valid even if the sound did not reach so long.  



REFERENCE 

Visbeck, M. (2002): Deep velocity profiling using Lowered Acoustic Doppler Current Profilers: Bottom track and 
    inverse solutions. J. Atmos. Oceanic Technol., 19, 794-807.


Figure 3.8.1. Vertical profiles of velocity at station A10_87. 
Figure 3.8.2. Vertical profiles of velocity at station A10_10.


FIGURE CAPTIONS 

Figure 1:  Observation lines for WHP P6, A10 and I3/I4 revisit in Blue Earth Global Expedition 2003 
           (BEAGLE2003) with bottom topography based on ETOPO5 (Data announcement 88-MGG-02, 1988).  

Figure 2:  Station locations for WHP P6, A10 and I3/I4 revisit in BEAGLE2003 with bottom topography based 
           on Smith and Sandwell (1997).  

Figure 3:  Potential temperature (°C) cross section calculated using CTD temperature and salinity data 
           calibrated by bottle salinity measurements.  Vertical exaggeration of the 0-6,500 m section is 1000:1.  
           Expanded section of the upper 1000 m is made with a vertical exaggeration of 2500:1.  

Figure 4:  CTD salinity (psu) cross section calibrated by bottle salinity measurements.  Vertical exaggeration 
           is same as Figure 3.  

Figure 5:  Same as Figure 4 but with SSW batch correction1.  

Figure 6:  Density (σ0) (kg/m3) cross section calculated using CTD temperature and calibrated salinity data 
           with SSW batch correction.  Vertical exaggeration is same as Figure 3.  

Figure 7:  Same as Figure 6 but for σ4 (kg/m3).  

Figure 8:  Neutral density ( γ n) (kg/m3) cross section calculated using CTD temperature and calibrated salinity 
           data with SSW batch correction.  Vertical exaggeration is same as Figure 3.  

Figure 9:  Cross section of bottle sampled dissolved oxygen (μmol/kg).  Data with quality flags of 2 were 
           plotted.  Vertical exaggeration is same as Figure 3.  

Figure 10: Silicate (μmol/kg) cross section.  Data with quality flags of 2 were plotted.  Vertical exaggeration is 
           same as Figure 3.  

Figure 11: Nitrate (μmol/kg) cross section.  Data with quality flags of 2 were plotted.  Vertical exaggeration of 
           the upper 1000 m section is same as Figure 3.  

Figure 12: Nitrite (μmol/kg) cross section.  Data with quality flags of 2 were plotted.  Vertical exaggeration is 
           same as Figure 3.  

Figure 13: Phosphate (μmol/kg) cross section.  Data with quality flags of 2 were plotted.  Vertical exaggeration 
           is same as Figure 3.  

Figure 14: Dissolved inorganic carbon (μmol/kg) cross section.  Data with quality flags of 2 were plotted.  
           Vertical exaggeration is same as Figure 3.  

Figure 15: Total alkalinity (μmol/kg) cross section.  Data with quality flags of 2 were plotted.  Vertical 
           exaggeration is same as Figure 3.  

Figure 16: pH cross section.  Data with quality flags of 2 were plotted.  Vertical exaggeration is same as 
           Figure 3.  

Figure 17: Difference in potential temperature (°C) between results from WOCE (from May to Jul. 1992 for 
           P6, from Dec. 1992 to Jan. 1993 for A10, from Apr. to June 1995 for I3/I4) and BEAGLE2003 (from 91 
           Jul. to Oct. 2003 for P6, from Nov. to Dec. 2003 for A10, from Dec. 2003 to Jan. 2004 for I3/I4).  Red 
           and blue areas show areas where potential temperature increased and decreased in BEAGLE2003, 
           respectively.  On white areas differences in temperature do not exceed the detection limit of 
           0.002°C.  Vertical exaggeration is same as Figure 3.  
 
Figure 18: Difference in salinity (psu) between results from WOCE and BEAGLE2003.  Red and blue areas 
           show areas where salinity increased and decreased in BEAGLE2003, respectively.  CTD salinity 
           data with SSW batch correction1 are used.  On white areas differences in salinity do not exceed the 
           detection limit of 0.002 psu.  Vertical exaggeration is same as Figure 3.  

Figure 19: Difference in dissolved oxygen (μmol/kg) between results from WOCE and BEAGLE2003.  Red and 
           blue areas show areas where salinity increased and decreased in 2001, respectively.  CTD oxygen 
           data2 are used.  On white areas differences in salinity do not exceed the detection limit of 2 μmol/kg.  
           Vertical exaggeration is same as Figure 3.  

Note 
          1. As for the traceability of SSW to Mantyla's value, the offset for the batches P116 (WOCE P6), P120 (WOCE 
             A10), P126 (WOCE I3/I4) and P142 (BEAGLE2003) are +0.0001, -0.0022, -0.0007 and -0.0011, respectively 
             (Aoyama et al, 2002, Aoyama, 2005).  

          2. As for the WOCE A10 data, there are systematic differences between CTD oxygen and bottle oxygen data 
             (Millard, 2000).  Therefore the CTD oxygen of WOCE A10 was modified as 
               Modified CTD oxygen = CTD oxygen - (a0 + b0 * p)  [where p < 2,000 dbar] 
                                   = CTD oxygen - (a1 + b1 * p)  [where p >= 2,000 dbar] 
                        a0 + b0 * pr = a1 + b1 * pr  [where pr = 2,000 dbar] 
             where p is CTD pressure in dbar.  The best fit sets of coefficients 
             (a0, b0, a1 and b0) were determined by minimizing the sum of absolute deviation 
             from the bottle oxygen data as follows.  

                a0 = -3.9577e-4 
                b0 = 6.4409 
                a1 = 6.3317e-4 
                b1 = 4.3830 



REFERENCES 

Data Announcement 88-MGG-02 (1988): Digital relief of the Surface of the Earth, NOAA, National Geophysical 
    Data Center, Boulder, Colorado. 
Jackett, D. R. and R. J. McDougall (1997): A neutral density variable for the world's oceans, Journal of Physical 
    Oceanography, 27, 237-263.  
Smith, W. H. F. and D. T. Sandwell (1997): Global seafloor topography from satellite altimetry and ship depth 
    soundings, Science, 277, 1956-1962. 
Aoyama, M., T. M. Joyce, T. Kawano and Y. Takatsuki (2002): Standard seawater comparison up to P129, 
    Deep-Sea Res. I, 49, 1103-1114. 
Aoyama, M. (2005): Study on the traceability of reference material for salinity in seawater, Report of Research 
    Project, Grant-in-Aid for Scientific Research (C)(2), 2002-2004, pp. 24.  
Millard, R. (2000): DQE of CTD & water sample salinity and oxygen data of WOCE section A10, Cruise and data 
    documentation for WHP A10, AR04EW, AR15, 
    http://whpo.ucsd.edu/data/onetime/atlantic/a10/index.htm


3.9. CHLOROFLUOROCARBONS (CFCs)
     7 December 2006

(1) PERSONNEL

Ken'ichi Sasaki:     Mutsu Institute of Oceanography, Japan Agency of 
                     Marine Science and Technology  (MIO, JAMSTEC)
Yutaka W. Watanabe:  Hokkaido University
Shuichi Watanabe:    MIO, JAMSTEC
Masahide Wakita:     MIO, JAMSTEC
Shinichi Tanaka:     Hokkaido University
Katsunori Sagishima: Marine Works Japan LTD (MWJ)
Yuichi Sonoyama:     MWJ
Hideki Yamamoto:     MWJ
Keisuke Wataki:      MWJ


(2) INTRODUCTION

Chlorofluorocarbons (CFCs) are completely man-made gasses that are chemically 
and biologically stable gasses in the environment. The CFCs have been 
accumulated in the atmosphere since 1930's (Walker et al., 2000) and the 
atmospheric CFCs can slightly dissolve in sea surface water. The dissolved 
CFC concentrations in sea surface water should have changed year by year and 
then penetrated into the ocean interior by water circulation. Three chemical 
species of CFCs, namely CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)) and CFC-113 
(C(2)Cl(3)F(3)), dissolved in seawater are useful transient tracers for the 
ocean circulation with time scale on the order of decades. 

In this cruise, we determined the concentrations of these CFCs in seawater on 
board.


(3) APPARATUS

Dissolved CFCs were measured by a method modified from the original design of 
Bullister and Weiss (1988). Two systems were used for CFCs measurement. A 
custom made purging and trapping system was attached to gas chromatograph 
(GC-14B: Shimadzu Ltd) having an electron capture detector (ECD-14: Shimadzu 
Ltd). Porapak T® filler was packed in a 1/8" stainless steel trap column. 
PoraPlot Q-HT capillary columns [i.d.: 0.53mm, length: 2m, film layer 
thickness: 20µml was used as a pre-column. PoraPlot Q-HT capillary columns 
[i.d.: 0.53mm, length: 20m, film layer thickness: 20µm] was used as a 
main analytical column in leg 1 and 2. The main analytical column was 
replaced by PoraBond Q capillary columns [i.d.: 0.53mm, length: 25m, film 
layer thickness: 10µm] in legs 4 and 5. 

The change in main analytical columns has been due to serious problems found 
in the columns used in legs 1 and 2. The main columns used in legs 1 and 2 
were clogged by particles peeled from column wall and carrier gas could not 
flow sufficiently. This problem affected to separation of compounds and 
analytical time.


(4) SHIPBOARD MEASUREMENT

SAMPLING

Seawater sub-samples for CFCs measurement were collected from 12 litter 
Niskin bottles to 300ml subsampling glass bottles which were developed for 
CFCs analyses in JAMSTEC. The sub-sampling bottles have stainless steel union 
altered from original design of Swagelok® on the top. A 1/4" ϕ stainless 
steel tube goes through the union into the bottle interior and reaches to 
near the bottom of bottle. A small plastic stop valve was on the upper tip of 
stainless steel tube. The bottles were filled by nitrogen gas before 
sampling. The valve was connected to Niskin bottle. The sub-sampling bottles 
were filled by seawater sample from the bottom. Two times of the bottle 
volumes of seawater sample were overflowed from vent valve put on side of the 
union and then the all valves closed from downstream. The bottles filled by 
seawater sample were kept in water bathes roughly controlled on sample 
temperature. The CFC concentrations were determined as soon as possible after 
sampling. These procedures were needed in order to minimize contamination 
from atmospheric CFCs.

ANALYSIS

The CFCs analytical system is modified from the original design of Bullister 
and Weiss (1988). Constant volume of sample water is taken into the purging & 
trapping system. The volume of sample was 150 ml in legs 1 and 2 and 100 ml 
in legs 4 and 5. Dissolved CFCs are de-gassed by N2 gas purge and 
concentrated in a 1/8" SUS packed trap column (Porapak T) cooled to -40 
degree centigrade. The CFCs are desorbed by electrically heating the trap 
column to 130°C, and lead into the pre-column. CFCs and other compounds are 
roughly separated in the pre-column and the compounds having earlier 
retention time than CFC-113 are sent to main analytical column. And then the 
pre-column is flushed buck by counter flow of pure nitrogen gas (Back flush 
system). The back flush system is prevent to enter any compounds that have 
higher retention time than CFC-113 into main analytical column and permits 
short time analysis. CFCs which are sent into main column are separated 
further and detected by an electron capture detector (ECD). 

In legs 1 and 2, temperature rising analysis has been used because of too 
long of retention times of CFCs to use temperature constant analysis. The 
long retention time was due to problems on main analytical column mentioned 
above.

In legs 4 and 5, we can use temperature constant analysis due to applying new 
column for main analytical column. Analytical conditions are listed in Table 
3.9.1. 

Gas loops that the volumes were around 1, 3 and 10 ml were used for 
introducing standard gases into the analytical system.


TABLE 3.9.1. Analytical conditions of dissolved CFCs in seawater.
______________________________________________________________________________

 Leg 1

 Temperature
     Analytical Column:         70 or 100°C constant for 10 minutes 
                                followed by temperature changing 
                                stage in10 °C/min of the rate to 140°C.
     Detector (ECD):            200 or 250°C
     Trap column:               -45°C (at adsorbing) & 130°C (at desorbing)

 Mass flow rate of nitrogen gas (99.9999%)
     Carrier gas:               3-7 ml/min
     Detector make-up gas:       17 ml/min
     Back flush gas:            >10 ml/min
     Sample purge gas:          100 ml/min

 Leg 2
 
 Temperature
     Analytical Column:        75°C constant for 5 minutes followed by 
                               temperature changing stage in 20°C/min 
                               of the rate to 130°C.
     Detector (ECD):            270 or 290°C
     Trap column:               -45°C (at adsorbing) & 130°C (at desorbing)

 Mass flow rate of nitrogen gas (99.9999%)
     Carrier gas:               8-9 ml/min
     Detector make-up gas:    16-21 ml/min

 Back flush gas:                4-7 ml/min
 Sample purge gas:              200 ml/min

 Legs 4 and 5
     Temperature
     Analytical Column:          95°C constant.
     Detector (ECD):            290°C
     Trap column:               -45°C (at adsorbing) & 130°C (at desorbing)

 Mass flow rate of nitrogen gas (99.9999%)
     Carrier gas:                27 ml/min
     Detector make-up gas:       28 ml/min
     Back flush gas:            >15 ml/min
     Sample purge gas:          300 ml/min

 Standard gas (Taiyo Toyo Sanso co. ltd.) in all legs
     Base gas: Nitrogen
     CFC-11:                    850 ppt (v/v)
     CFC-12:                    500 ppt (v/v)
     CFC-113:                    90 ppt (v/v)
______________________________________________________________________________



(5) QUALITY CONTROL

Analytical conditions of CFCs have been changed among legs. Data qualities 
are mentioned for each leg.

LEG 1

One of two analytical systems had serious problem in cold trap heating 
system. We needed considerable time for repairing the problem and we could 
not obtain CFCs data in around half of planed stations. Another system
also had some problems in the analytical columns. It was closed by the resins 
and considerable high pressure of carrier gas had been needed to obtain the 
mass flow rate of 5 ml/min. Additionally, the column cannot separate
CFC-11 peak from unknown interference peaks. Almost all CFC-11 data was bad 
in the quality and flag was "4".

Considerable numbers of CFC-12 and -113 data were also not good in quality 
due to unstable condition of analytical systems and were given flag of "4".

LEG 2

Before starting leg 2, analytical conditions have been coordinated again. The 
peaks of CFC-11 and -113 cannot separate from unknown interference peaks. 
Separation of CFC-12 peak was better than that in leg 1. Most CFC-12 data was 
good in quality and given flag of "2". The analytical precision was estimated 
from replicate sample analysis of CFC-12. The precision was estimated from 
average of absolute difference to be 0.009 ± 0.011 pmol/kg (n = 24).

LEG 4

We got new analytical columns at before Leg 3 that did not have plan for CFCs 
analyses. During Leg 3, we have tested the columns and successfully decided 
the analytical condition for CFC-11 and 12. CFC-113 however had been 
interfered by unknown large peak. We tried to calculate CFC-113 peak by post 
analyses of the chromatogram and gave the data flag "4". In the case of that 
the CFC-113 peak had completely been covered by interference peaks, we could 
not calculate the area of peak and given the data flag "5". The analytical 
precisions are estimated from replicate sample analyses for CFC-11 and -12. 
The precisions were estimated from average of absolute difference to be 0.012 
± 0.013 (n = 98) and 0.007 ± 0.008 pmol/kg (n = 98) for CFC-11 and -12, 
respectively.

LEG 5

Analytical conditions were same as that in leg 4. In the one of the 
analytical systems, serious problem has been found in several stations of 
this leg. The problem was considerable high blank for CFC-12 chromatogram
peak. We could not find the causes of the problems by end of this leg. The 
problems interfered in determination of CFC-12. This problem was remarkable 
in 5 stations namely stations of I03-557, I03-480, I03-455, I03-451 and
I03-447. Although we tried to correct the blank, quality of the data is not 
good. CFC-12 data in these stations had been given flag of "4". In CFC-113 
analyses, there are same problems as that of leg 4 and almost all quality 
flags were "4". The precisions were estimated from average of absolute 
difference to be 0.009 ± 0.010 pmol/kg (n = 131) and 0.006 ± 0.006 pmol/kg 
(n = 122) for CFC-11 and -12, respectively.

STANDARD GASSEES

Standard gasses used in this cruise have been made by Taiyo Nissan Co. Ltd. 
CFC mixing ratios of the standard gases have been determined by the maker 
using gravimetric method. The standard gases used in this cruise have not 
been calibrated to SIO scale standard gases yet because SIO scale standard 
gasses is hard to obtain due to legal difficulties for CFCs import into 
Japan. The data will be corrected as soon as possible when we will obtain the 
standard gasses.

BLANK CORRECTION

CFCs concentrations in deep water which was one of oldest water masses of the 
ocean were low but not zero for CFC-11 and -12. In leg 2, Average 
concentrations of CFC-12 in water samples collected from density range of
27.5 - 27.8 sigma-theta were 0.009 ± 0.004 (n = 226). Average concentrations 
of CFC-11 and -12 in water samples collected from density range of sigma-
theta > 27.8 and sigma-4 < 45.87 were 0.029 ± 0.005 (n = 195), 0.011 ± 0.003 
(n = 195) in leg 4 except data from western region where relatively new deep 
water mass could come by western boundary current (on Santos Plateau and Vema 
Channel). Average concentrations of CFC-11 and -12 in water samples collected 
from density range of sigma-theta > 27.76 and sigma-4 < 45.87 were 0.021 
± 0.006 (n = 251), 0.011 ± 0.003 (n = 243) in leg 5 except data from I04 
section where relatively new deep water mass could come (on Mozambique 
Basin). These values would be sampling blanks which was contaminations from 
Niskin bottle and/or during sub-sampling and were subtracted from all 
measurements.


(6) REFERENCES

Walker, S.J., Weiss, R.F. and Salameh, P.K., Reconstructed histories of the 
    annual mean atmospheric mole fractions for the halocarbons CFC-11, CFC-
    12, CFC-113 and Carbon Tetrachloride, Journal of Geophysical Research, 
    105, 14,285-14,296, (2000).
Bullister, J.L and Weiss, R.F. Determination of CCl3F and CCl2F2 in seawater 
    and air. Deep Sea Research, 35, 839-853 (1988).


3.10. δ^(13)C AND Δ^(14)C OF DISSOLVED INORGANIC CARBON
      25 December 2006

(1) PERSONNEL

Yuichiro Kumamoto: Institute of Observational Research for Global Change, 
Japan Agency for Marine-Earth Science and Technology (IORGC, JAMSTEC)

(2) INRTRODUCTION

Stable and radioactive carbon isotopic ratios (δ^(13)C and Δ^(14)) of 
dissolved inorganic carbon (DIC) are good tracers for the anthropogenic 
carbon in the ocean. During MR03-K04 cruise, named BEAGLE2003, we collected 
seawater samples δ^(13)C and Δ^(14) for analyses at stations along the WOCE-
P6 (Leg-1&2), WOCE-A10 (Leg-4), and WOCE-I3&I4 (Leg-5) lines in the southern 
hemisphere. Here we report the final results of δ^(13)C and Δ^(14) of DIC.
Our preliminary reports of δ^(13)C and Δ^(14) measurements are replaced by 
this final report. General information and other hydrographic data of 
BEAGLE2003 cruise have already published in our previous data books of 
BEAGLE2003 (Uchida and Fukasawa, 2005a,b)

(3) SAMPLE COLLECTION

The sampling stations are summarized in Figure 3.10.1 and Table 3.10.1-4. A 
total of 3,060 seawater samples, including 233 replicate samples, were 
collected between surface (about 10 m depth) and near bottom at 97 stations 
using 12-liter X-Niskin bottles. The seawater in the X-Niskin bottle was 
siphoned into a 250 cm^3 glass bottle with enough seawater to fill the glass 
bottle 2 times. Immediately after sampling, 10 cm^3 of seawater was removed 
from the bottle and poisoned by 50 µl of saturated HgCl(2) solution. Then the 
bottle was sealed by a glass stopper with Apiezon M grease and stored in a 
cool and dark space on board. Theses procedures on board basically follow the 
methods described in WOCE Operation Manual (McNichol and Jones, 1991).

(4) SAMPLE PREPARATION

In our laboratory, DIC in the seawater samples were stripped cryogenically 
and split into three aliquots: Accelerator Mass Spectrometry (AMS) ^(14)C 
measurement (about 200 µmol), ^(13)C measurement (about 100 µmol), and 
archive (about 200 µmol). Efficiency of the CO2 stripping from seawater 
sample was more than 95 % that was calculated from concentration of DIC in 
the seawater samples. The stripped CO2 gas for ^(14)C was then converted to 
graphite catalytically on iron powder with pure hydrogen gas. Yield of 
graphite powder from CO2 gas was estimated to be 73 ± 9 % in average by 
weighing of sample graphite powder. Details of these preparation procedures 
were described by Kumamoto et al. (2000).


Figure 3.10.1. Sampling stations for δ^(13)C and Δ^(14) of dissolved 
inorganic carbon during BEAGLE2003 Leg-1(August-September, 2003), Leg-2 
(September-October, 2003), Leg-4 (November-December, 2003), and Leg-
5(December, 2003-January, 2004).


TABLE 3.10.1. The sampling dates, locations, number of samples, and maximum 
              sampling pressure for carbon isotopes in DIC during BEAGLE2003 
              Leg-1.
__________________________________________________________________________________


 Station   Date (UTC)   Latitude  Longitude  Number of  Number of      Max.
                                              samples   replicates  pressure/db
 --------  -----------  --------  ---------  ---------  ----------  -----------
 P06W-239  04/Aug/2003  30.087 S  154.165 E     31          3         4,680
 P06W-234  05/Aug/2003  30.081 S  156.533 E     32          3         4,898
 P06W-227  06/Aug/2003  30.079 S  158.682 E     24          3         3,235
 P06W-221  07/Aug/2003  30.086 S  161.500 E     15          1         1,185
 P06W-215  08/Aug/2003  30.086 S  164.834 E     26          2         3,419
 P06W-211  10/Aug/2003  30.084 S  166.999 E     23          2         2,873
 P06W-207  11/Aug/2003  30.084 S  168.999 E     25          3         3,153
 P06W-201  12/Aug/2003  30.089 S  171.501 E     20          2         2,264
 P06W-195  13/Aug/2003  30.083 S  174.497 E     27          3         3,689
 P06W-191  14/Aug/2003  30.582 S  177.000 E     30          3         4,353
 P06C-182  15/Aug/2003  32.501 S  179.917 E     24          3         2,872
 P06C-174  18/Aug/2003  32.502 S  177.251 W     36          3         6,503
 P06C-168  20/Aug/2003  32.497 S  174.330 W     36          3         5,958
 P06C-162  21/Aug/2003  32.500 S  171.909 W     29          3         4,200
 P06C-X15  22/Aug/2003  32.504 S  170.001 W     34          3         5,610
 P06C-150  24/Aug/2003  32.497 S  166.500 W     33          3         5,357
 P06C-146  26/Aug/2003  32.491 S  163.832 W     34          3         5,630
 P06C-142  27/Aug/2003  32.500 S  161.164 W     33          3         5,221
 P06C-137  28/Aug/2003  32.500 S  158.166 W     35          3         5,781
 P06C-133  29/Aug/2003  32.504 S  154.847 W     32          3         5,076
 P06C-X16  31/Aug/2003  32.499 S  150.499 W     33          3         5,234
 P06C-125  01/Sep/2003  32.501 S  148.160 W     30          3         4,626
 P06C-121  02/Sep/2003  32.508 S  144.831 W     33          3         5,354
 --------  -----------  --------  ---------  ---------  ----------  -----------
 Total                                         675         64
__________________________________________________________________________________



TABLE 3.10.2. As same as Table 3.10.1 but for Leg-2.
__________________________________________________________________________________


 Station   Date (UTC)   Latitude  Longitude  Number of  Number of      Max.
                                              samples   replicates  pressure/db
 --------  -----------  --------  ---------  ---------  ----------  -----------
 P06C-117  14/Sep/2003  32.497 S  141.494 W     31          3         4,762
 P06C-113  15/Sep/2003  32.501 S  138.665 W     31          3         4,640
 P06C-109  16/Sep/2003  32.499 S  136.003 W     31          3         4,456
 P06C-105  17/Sep/2003  32.502 S  133.344 W     29          3         4,306
 P06C-101  18/Sep/2003  32.494 S  130.660 W     27          3         3,650
 P06C-097  19/Sep/2003  32.494 S  127.997 W     28          3         3,988
 P06C-093  21/Sep/2003  32.509 S  125.336 W     20          2         2,183
 P06C-089  21/Sep/2003  32.492 S  122.658 W     22          2         2,625
 P06C-085  22/Sep/2003  32.501 S  119.992 W     24          3         3,089
 P06C-081  23/Sep/2003  32.499 S  117.320 W     26          3         3,352
 P06C-077  24/Sep/2003  32.500 S  114.668 W     24          2         2,970
 P06E-071  25/Sep/2003  32.499 S  111.999 W     23          2         2,722
 P06E-067  26/Sep/2003  32.500 S  109.343 W     30          3         4,496
 P06E-063  27/Sep/2003  32.501 S  106.674 W     26          3         3,343
 P06E-X18  28/Sep/2003  32.500 S  103.000 W     27          3         3,617
 P06E-055  29/Sep/2003  32.503 S  101.332 W     27          3         3,622
 P06E-051  01/Oct/2003  32.501 S   98.667 W     28          3         3,847
 P06E-047  02/Oct/2003  32.498 S   96.000 W     28          3         4,012
 P06E-043  02/Oct/2003  32.501 S   93.338 W     23          2         2,691
 P06E-039  03/Oct/2003  32.500 S   90.682 W     27          3         3,741
 P06E-X19  04/Oct/2003  32.503 S   87.994 W     27          3         3,774
 P06E-031  05/Oct/2003  32.497 S   85.334 W     28          3         4,054
 P06E-027  06/Oct/2003  32.501 S   82.664 W     28          3         3,934
 P06E-023  08/Oct/2003  32.502 S   79.997 W     23          2         2,811
 P06E-019  09/Oct/2003  32.495 S   77.328 W     26          3         3,608
 P06E-015  10/Oct/2003  32.497 S   74.673 W     28          3         3,886
 P06E-011  11/Oct/2003  32.495 S   72.716 W     36          3         6,054
 --------  -----------  --------  ---------  ----------  ---------  -----------
 Total                                         728         75
__________________________________________________________________________________



TABLE 3.10.3. As same as Table 3.10.1 but for Leg-4.
__________________________________________________________________________________


 Station   Date (UTC)   Latitude  Longitude  Number of  Number of      Max.
                                              samples   replicates  pressure/db
 --------  -----------  --------  ---------  ---------  ----------  -----------
 A10-629   08/Nov/2003  28.044 S  46.127 W      22          2         2,429
 A10-003   09/Nov/2003  28.832 S  43.593 W      28          3         3,935
 A10-007   10/Nov/2003  29.613 S  41.161 W      28          3         3,835
 A10-X17   11/Nov/2003  30.098 S  39.037 W      30          2         4,249
 A10-021   12/Nov/2003  30.001 S  35.488 W      22          1         2,328
 A10-029   14/Nov/2003  30.000 S  32.007 W      28          2         3,862
 A10-035   16/Nov/2003  29.998 S  29.003 W      26          2         3,199
 A10-038   17/Nov/2003  29.999 S  26.716 W      35          2         5,368
 A10-X16   17/Nov/2003  30.220 S  25.049 W      31          2         4,411
 A10-043   18/Nov/2003  30.000 S  22.482 W      32          2         4,660
 A10-X15   19/Nov/2003  30.109 S  19.007 W      31          2         4,671
 A10-051   20/Nov/2003  30.002 S  16.334 W      28          2         3,741
 A10-055   21/Nov/2003  30.003 S  13.665 W      22          2         2,317
 A10-059   22/Nov/2003  30.000 S  11.001 W      28          2         3,767
 A10-X14   22/Nov/2003  30.003 S  08.999 W      29          2         3,981
 A10-067   24/Nov/2003  30.000 S  04.829 W      31          2         4,302
 A10-071   26/Nov/2003  30.001 S  01.505 W      32          2         4,789
 A10-075   27/Nov/2003  29.732 S  01.122 E      28          2         3,747
 A10-079   27/Nov/2003  29.467 S  03.302 E      32          2         4,816
 A10-083   29/Nov/2003  29.746 S  05.931 E      34          2         5,204
 A10-087   30/Nov/2003  29.745 S  09.288 E      34          2         5,067
 A10-093   01/Dec/2003  29.372 S  12.790 E      28          3         3,250
 --------  -----------  --------  ---------  ---------  ----------  -----------
 Total                                         639         46    
__________________________________________________________________________________



TABLE 3.10.4. As same as Table 3.10.1 but for Leg-5.
__________________________________________________________________________________


 Station   Date (UTC)   Latitude  Longitude  Number of  Number of      Max.
                                             samples    replicates  pressure/db
 --------  -----------  --------  ---------  ---------  ----------  -----------
 I04-601   14/Dec/2003  24.673 S  036.991 E     25          2         3,084
 I04-595   15/Dec/2003  24.661 S  039.996 E     27          2         3,578
 I04-589   16/Dec/2003  24.665 S  042.997 E     28          2         3,725
 I03-557   21/Dec/2003  19.997 S  050.060 E     31          2         4,401
 I03-551   22/Dec/2003  19.985 S  052.777 E     34          1         5,002
 I03-545   23/Dec/2003  19.999 S  056.092 E     31          2         4,441
 I03-535   25/Dec/2003  20.380 S  059.228 E     33          2         4,823
 I03-531   28/Dec/2003  20.368 S  061.631 E     28          2         3,650
 I03-525   29/Dec/2003  20.089 S  064.934 E     27          1         2,935
 I03-519   30/Dec/2003  19.998 S  068.213 E     23          1         2,541
 I03-513   01/Jan/2004  19.997 S  071.256 E     30          1         4,240
 I03-507   02/Jan/2004  20.000 S  074.167 E     33          2         5,032
 I03-503   03/Jan/2004  19.987 S  076.908 E     34          2         5,168
 I03-X08   05/Jan/2004  19.996 S  079.998 E     34          2         4,928
 I03-495   06/Jan/2004  19.996 S  082.736 E     34          2         5,305
 I03-491   07/Jan/2004  19.990 S  085.304 E     33          2         4,951
 I03-487   09/Jan/2004  20.000 S  087.333 E     20          1         2,022
 I03-480   10/Jan/2004  19.992 S  090.288 E     35          2         5,251
 I03-474   11/Jan/2004  19.991 S  093.533 E     35          2         5,410
 I03-470   13/Jan/2004  19.991 S  096.953 E     35          2         5,419
 I03-466   14/Jan/2004  19.990 S  100.466 E     36          2         6,067
 I03-463   16/Jan/2004  19.992 S  103.129 E     36          2         5,751
 I03-459   17/Jan/2004  19.996 S  106.625 E     36          3         5,617
 I03-455   18/Jan/2004  20.932 S  109.445 E     34          3         5,140
 I03-451   20/Jan/2004  21.825 S  111.902 E     33          3         5,019
 --------  -----------  --------  ---------  ---------  ----------  -----------
 Total                                         785         48 
__________________________________________________________________________________



(5) SAMPLE MEASUREMENTS

δ^(13)C of the sample CO2 gas was measured using Finnigan MAT252 mass 
spectrometer. The δ^(13)C value was calculated by a following equation:

               δ^(13)C(‰) = (R(sample)/R(standard) -1) X 1000,            (1)

where R(sample) and R(standard) denote ^(13)C/^(12)C ratios of the sample CO2 
gas and the standard CO2 gas, respectively. The working standard gas was 
purchased from Oztech Gas Co. with assigned δ^(13)C value of -3.64 ‰ versus 
VPDB (Lot No. SHO-873C). The gas has been calibrated relative to the 
appropriate internationally accepted IAEA primary standards. ∆^(14)C in the 
graphite sample was measured in AMS facilities of Institute of Accelerator 
Analysis Ltd in Shirakawa (Pelletron 9SDH-2, NEC) and Paleo Labo Co. Ltd in 
Kiryu (Compact-AMS, NEC), Japan. The ∆^(14)C value was calculated by:

                δ^(14)C(‰) = (R(sample)/R(standard) -1) X 1000,           (2)

        ∆^(14)C(‰) = δ^(14)C -2 (δ^(13)C + 25) (1 + δ^(14)C/1000),        (3)

where R(sample) and R(standard) denote, respectively, ^(14)C/^(12)C ratios of 
the sample and the international standard, NIST Oxalic Acid SRM4990-C 
(HOxII). R(standard) was corrected for decay since A.D. 1950 (Stuiver and 
Polach, 1977; Stuiver, 1983). Equation 3 is normalization for isotopic 
fractionation. When quality of δ^(13)C data was not "good", ∆^(14)C was 
calculated by interpolated δ^(13) value derived from data at just above and 
below layers. Finally ∆^(14)C value was corrected for radiocarbon decay 
between the sampling and the measurement dates. Individual errors of δ^(13)C 
were given by standard deviation of repeat measurements. Errors of ∆^(14)C 
were derived from larger of the standard deviation of repeat measurements 
and the counting error. Means of the δ^(13)C and ∆^(14)C errors were 
calculated to be 0.004 ‰ and 3.6 ‰ that probably correspond to 
"repeatabilities" of our δ^(13)C and ∆^(14)C measurements. It should be noted 
that these errors did not include error due to sample preparation.

(6) REPLICATE MEASUREMENTS

Replicate samples were taken at all the 97 stations. Results of 233 pairs of 
the replicate samples are shown in Table 3.10.5. The standard deviations of 
the δ^(13)C and ∆^(14)C replicate analyses were calculated to be 0.020 ‰ (n = 
217) and 3.9 ‰ (n = 214), respectively. The standard deviations of δ^(13)C 
replicate analyses during Leg-1, Leg-2, Leg-4, and Leg-5 were 0.021 (n = 58), 
0.019 (n = 74), 0.020 (n = 42), and 0.019 ‰ (n = 43), respectively. The 
standard deviation of ∆^(14)C replicate analyses during Leg-1, Leg-2, Leg-4, 
and Leg-5 were 3.6 (n = 62), 3.7 (n = 68), 4.4 (n = 37), and 3.9 ‰ (n = 47), 
respectively.


TABLE 3.10.5. Summary of replicate analyses.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06W-239  32    0.949     0.002     0.930       0.028             79.5   3.8        78.0      3.0
                 0.910     0.002                                   75.7   4.8
 P06W-239  21    0.484     0.003     0.482       0.003           -170.4   3.3      -171.0      2.3
                 0.483     0.003                                 -171.4   3.1
 P06W-239  13    0.437     0.005     0.408       0.028           -165.5   3.2      -167.7      3.0
                 0.397     0.003                                 -169.8   3.2
 P06W-234  32    1.135     0.004     1.124       0.012             83.6   3.8        81.9      2.7
                 1.118     0.003                                   80.1   3.8  
 P06W-234  21    0.608     0.003     0.615       0.009           -147.3   3.2      -146.1      2.3
                 0.621     0.003                                 -144.9   3.2  
 P06W-234  13    0.385     0.004     0.471       0.064           -155.8   4.4      -159.2      4.7
                 0.476     0.001                                 -162.5   4.4
 P06W-227  32    0.918     0.002     0.914       0.006             92.8   5.4        91.1      3.7
                 0.910     0.002                                   89.5   5.2
 P06W-227  21    0.542     0.002     0.540       0.007           -166.9   4.4      -165.6      3.1
                 0.532     0.004                                 -164.2   4.4
 P06W-227  13    0.440     0.003     0.394       0.036           -165.9   4.4      -164.9      3.1
                 0.389     0.001                                 -163.9   4.4
 P06W-221  32    0.956     0.004     0.941       0.022              -      -         -          -
                 0.925     0.004                                    -      -
 P06W-215  32    0.979     0.003     0.963       0.023              -      -         -          -
                 0.947     0.003                                    -      -
 P06W-215  21    0.530     0.002     0.531       0.002           -142.7   4.2      -140.1      3.7
                 0.533     0.003                                 -137.4   4.3
 P06W-211  32    0.994     0.002     0.975       0.043             88.6   4.0        91.1      3.5
                 0.933     0.003                                   93.6   4.0
 P06W-211  21    0.546     0.006     0.542       0.004           -158.5   3.3      -161.4      3.7
                 0.541     0.003                                 -163.7   2.9
 P06W-207  32    1.086     0.003     1.091       0.005             85.3   4.0        83.2      3.1
                 1.093     0.002                                   80.9   4.1
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06W-207  21    0.615     0.005     0.594       0.025           -148.3   3.4      -153.7      7.6
                 0.580     0.004                                 -159.1   3.4
 P06W-207  13    0.197     0.003     0.182       0.022           -208.4   3.1      -207.4      2.2
                 0.166     0.003                                 -206.3   3.1
 P06W-201  32      -         -         -           -               80.7   3.8        80.8      2.7
                   -         -                                     80.9   3.7
 P06W-201  21    0.548     0.002     0.579       0.044           -149.4   3.3      -151.6      4.5
                 0.610     0.002                                 -155.8   4.5 
 P06W-195  32    0.984     0.002     0.985       0.005             86.9   6.1        89.9      3.1
                 0.991     0.005                                   90.9   3.6 
 P06W-195  21    0.533     0.003     0.547       0.020           -163.2   3.2      -163.1      2.3
                 0.561     0.003                                 -162.9   3.2
 P06W-195  13      -         -         -           -             -202.6   3.1      -206.8      5.9
                   -         -                                   -211.0   3.1
 P06W-191  32    0.987     0.004     0.988       0.002             77.3   3.7        74.6      4.0
                 0.988     0.003                                   71.7   3.8
 P06W-191  21    0.540     0.002     0.539       0.003           -173.5   3.1      -171.9      2.3
                 0.536     0.004                                 -170.3   3.1
 P06W-191  13    0.190     0.003     0.173       0.017           -209.3   3.0      -212.1      4.2
                 0.166     0.002                                 -215.2   3.2
 P06C-182  32    1.039     0.004     1.033       0.009             73.3   4.0        71.9      3.1
                 1.026     0.004                                   69.5   5.0
 P06C-182  21    0.653     0.005     0.645       0.013           -143.8   3.4      -148.5      6.2
                 0.634     0.006                                 -152.5   3.1
 P06C-182  13    0.294     0.003     0.297       0.006           -197.8   3.2      -201.3      4.8
                 0.303     0.004                                 -204.6   3.1
 P06C-174  32    1.043     0.002     1.047       0.009             73.4   4.2        74.6      3.0
                 1.056     0.003                                   75.7   4.3   
 P06C-174  21    0.664     0.005     0.657       0.006           -147.0   3.4      -150.9      5.4
                 0.656     0.002                                 -154.6   3.3
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06C-174  13      -         -         -           -             -177.3   3.1      -180.1      4.3
                   -         -                                   -183.4   3.4
 P06C-168  32    1.067     0.002     1.070       0.013             75.1   4.5        75.4      3.0
                 1.086     0.005                                   75.6   4.1
 P06C-168  21    0.619     0.004     0.636       0.015           -150.4   3.4      -153.2      4.1
                 0.640     0.002                                 -156.2   3.5
 P06C-168  13    0.202     0.005     0.215       0.013           -219.0   3.1      -218.7      2.3
                 0.220     0.003                                 -218.3   3.3
 P06C-162  32    1.077     0.005     1.077       0.002             71.6   4.5        73.4      3.1
                 1.077     0.002                                   75.0   4.4
 P06C-162  21    0.639     0.002     0.636       0.018           -143.0   3.6      -144.7      2.6
                 0.614     0.005                                 -146.6   3.7
 P06C-162  13    0.255     0.005     0.263       0.008           -204.1   3.4      -207.2      4.4
                 0.266     0.003                                 -210.3   3.4
 P06C-X15  32    1.106     0.003     1.098       0.021             69.7   3.7        69.1      2.7
                 1.077     0.005                                   68.4   4.0
 P06C-X15  21    0.595     0.003     0.615       0.021           -146.2   3.2      -152.2      8.8
                 0.624     0.002                                 -158.7   3.3
 P06C-X15  13    0.228     0.004     0.226       0.001           -210.4   3.1      -208.4      3.0
                 0.226     0.001                                 -206.2   3.2
 P06C-150  32    1.138     0.004     1.126       0.017             78.6   3.8        77.1      2.7
                 1.114     0.004                                   75.5   3.7
 P06C-150  21    0.659     0.005     0.657       0.004           -151.7   3.4      -148.8      4.0
                 0.654     0.005                                 -146.1   3.3
 P06C-150  13    0.212     0.001     0.210       0.011           -214.2   3.2      -214.9      2.2
                 0.196     0.003                                 -215.5   3.1
 P06C-146  32    1.178     0.004     1.152       0.037             81.2   4.2        80.4      2.9
                 1.126     0.004                                   79.6   4.1
 P06C-146  21      -         -         -           -             -142.7   3.5      -143.5      2.5
                   -         -                                    144.3   3.5
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06C-146  13    0.168     0.004     0.191       0.033           -222.9   3.3      -220.6      3.4
                 0.214     0.004                                 -218.1   3.4
 P06C-142  32    1.163     0.003     1.151       0.018             76.4   3.8        71.3      7.7
                 1.138     0.003                                   65.5   4.1
 P06C-142  21    0.671     0.004     0.654       0.015           -144.7   3.4      -142.4      3.2
                 0.650     0.002                                 -140.2   3.4    
 P06C-142  13    0.182     0.005     0.185       0.005           -212.2   2.9      -213.3      2.1
                 0.189     0.006                                 -214.7   3.1
 P06C-137  32    1.131     0.003     1.120       0.029             84.7   3.6        82.9      2.5
                 1.090     0.005                                   81.2   3.5
 P06C-137  21    0.597     0.003     0.600       0.005           -145.7   3.0      -142.0      5.2
                 0.604     0.004                                 -138.3   3.0
 P06C-137  13    0.210     0.003     0.227       0.023           -209.3   3.0      -213.1      5.6
                 0.243     0.003                                 -217.2   3.1
 P06C-133  32      -         -         -           -               86.7   4.3        89.8      4.3
                   -         -                                     92.8   4.2  
 P06C-133  21    0.639     0.004     0.615       0.034           -146.7   3.6      -144.9      2.5
                 0.591     0.004                                 -143.1   3.6
 P06C-133  13    0.232     0.002     0.234       0.008           -214.9   3.5      -212.7      3.0
                 0.244     0.005                                 -210.7   3.4
 P06C-X16  32    1.230     0.004     1.222       0.008             99.8   3.7       100.9      2.7
                 1.218     0.003                                  102.0   3.8
 P06C-X16  21    0.573     0.004     0.596       0.032           -145.1   3.2      -147.7      3.6
                 0.618     0.004                                 -150.2   3.2
 P06C-X16  13    0.198     0.003     0.228       0.031           -210.8   3.2      -211.8      2.2
                 0.242     0.002                                 -212.7   3.0 
 P06C-125  32    1.282     0.002     1.278       0.006             83.6   3.8        83.0      2.7
                 1.274     0.002                                   82.5   3.7   
 P06C-125  21    0.607     0.004     0.619       0.009           -155.4   3.1      -158.9      5.4
                 0.620     0.001                                 -163.0   3.3
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06C-125  13    0.245     0.007     0.263       0.017           -214.7   3.0      -212.5      3.0
                 0.269     0.004                                 -210.5   2.9
 P06C-121  32      -         -         -           -               79.9   3.8        80.3      2.7
                   -         -                                     80.7   3.8
 P06C-121  21    0.571     0.003     0.587       0.016           -154.9   4.2      -151.0      4.4
                 0.594     0.002                                 -148.7   3.2
 P06C-121  13    0.258     0.002     0.262       0.013           -211.2   3.0      -208.9      3.4
                 0.277     0.004                                 -206.4   3.1
 P06C-117  32    1.236     0.004     1.249       0.023             -       -          -         -
                 1.269     0.005                                   -       -    
 P06C-117  21    0.592     0.003     0.571       0.021           -148.1   3.3      -153.5      7.6
                 0.562     0.002                                 -158.8   3.3
 P06C-117  13    0.261     0.005     0.260       0.003           -205.8   3.0      -206.9      2.1
                 0.260     0.003                                 -207.8   2.9
 P06C-113  32    1.257     0.004     1.221       0.040             92.5   3.7        91.6      2.6
                 1.201     0.003                                   90.6   3.7
 P06C-113  21    0.585     0.005     0.630       0.033           -145.1   3.2      -145.6      2.3
                 0.632     0.001                                 -146.2   3.3
 P06C-113  13    0.262     0.002     0.266       0.013           -213.1   3.0      -210.3      4.2
                 0.280     0.004                                 -207.2   3.2
 P06C-109  32    1.323     0.004     1.276       0.052             91.1   3.8        86.1      7.4
                 1.250     0.003                                   80.7   4.0
 P06C-109  21    0.532     0.003     0.542       0.013           -160.6   3.4      -156.2      6.2
                 0.551     0.003                                 -151.9   3.4
 P06C-109  13    0.293     0.002     0.295       0.004           -213.6   3.2      -213.9      2.3
                 0.299     0.003                                 -214.2   3.3
 P06C-105  32    1.359     0.002     1.348       0.025             88.4   3.9        84.6      5.4
                 1.323     0.003                                   80.7   4.0 
 P06C-105  21    0.552     0.005     0.569       0.016           -158.2   3.3      -157.0      2.3
                 0.575     0.003                                 -156.0   3.2
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06W-207  21    0.615     0.005     0.594       0.025           -148.3   3.4      -153.7      7.6
                 0.580     0.004                                 -159.1   3.4
 P06W-207  13    0.197     0.003     0.182       0.022           -208.4   3.1      -207.4      2.2
                 0.166     0.003                                 -206.3   3.1
 P06W-201  32      -         -         -           -               80.7   3.8        80.8      2.7
                   -         -                                     80.9   3.7
 P06W-201  21    0.548     0.002     0.579       0.044           -149.4   3.3      -151.6      4.5
                 0.610     0.002                                 -155.8   4.5
 P06W-195  32    0.984     0.002     0.985       0.005             86.9   6.1        89.9      3.1
                 0.991     0.005                                   90.9   3.6
 P06W-195  21    0.533     0.003     0.547       0.020           -163.2   3.2      -163.1      2.3
                 0.561     0.003                                 -162.9   3.2    
 P06W-195  13      -         -         -           -             -202.6   3.1      -206.8      5.9
                   -         -                                   -211.0   3.1
 P06W-191  32    0.987     0.004     0.988       0.002             77.3   3.7        74.6      4.0
                 0.988     0.003                                   71.7   3.8  
 P06W-191  21    0.540     0.002     0.539       0.003           -173.5   3.1      -171.9      2.3
                 0.536     0.004                                 -170.3   3.1
 P06W-191  13    0.190     0.003     0.173       0.017           -209.3   3.0      -212.1      4.2
                 0.166     0.002                                 -215.2   3.2
 P06C-182  32    1.039     0.004     1.033       0.009             73.3   4.0        71.9      3.1
                 1.026     0.004                                   69.5   5.0
 P06C-182  21    0.653     0.005     0.645       0.013           -143.8   3.4      -148.5      6.2
                 0.634     0.006                                 -152.5   3.1
 P06C-182  13    0.294     0.003     0.297       0.006           -197.8   3.2      -201.3      4.8
                 0.303     0.004                                 -204.6   3.1
 P06C-174  32    1.043     0.002     1.047       0.009             73.4   4.2        74.6      3.0
                 1.056     0.003                                   75.7   4.3
 P06C-174  21    0.664     0.005     0.657       0.006           -147.0   3.4      -150.9      5.4
                 0.656     0.002                                 -154.6   3.3
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06C-105  13    0.276     0.005     0.328       0.038           -208.5   3.1      -210.8      3.3
                 0.330     0.001                                 -213.2   3.1
 P06C-101  32    1.231     0.004     1.244       0.014             95.0   3.8        92.5      6.6
                 1.251     0.003                                   85.7   6.3
 P06C-101  21    0.555     0.006     0.562       0.005           -145.8   3.2      -147.4      2.3
                 0.562     0.001                                 -149.0   3.2
 P06C-101  13    0.297     0.005     0.259       0.044           -208.6   2.9      -207.3      2.1
                 0.235     0.004                                 -206.0   3.0 
 P06C-097  32      -         -         -           -              100.4   3.8       105.7      7.6
                   -         -                                    111.2   3.9
 P06C-097  21    0.617     0.005     0.577       0.033           -138.7   3.1      -138.8      2.2
                 0.571     0.002                                 -138.8   3.0
 P06C-097  13    0.303     0.003     0.297       0.009           -198.7   2.9      -201.7      4.0
                 0.290     0.003                                 -204.4   2.8
 P06C-093  32    1.208     0.001     1.209       0.007             83.7   3.6        87.5      5.4
                 1.218     0.003                                   91.4   3.7 
 P06C-093  21    0.515     0.004     0.517       0.002           -155.6   3.1      -156.8      2.2
                 0.518     0.003                                 -157.8   3.0   
 P06C-089  32    1.267     0.007     1.251       0.013             90.6   3.7        89.5      2.6
                 1.248     0.003                                   88.4   3.7
 P06C-089  21    0.578     0.003     0.562       0.042           -157.9   3.1      -156.8      2.2
                 0.519     0.005                                 -155.6   3.2
 P06C-085  32    1.374     0.002     1.375       0.004             90.4   3.5        91.7      2.5
                 1.379     0.006                                   93.1   3.7
 P06C-085  21    0.543     0.003     0.548       0.005           -151.6   2.9      -153.7      3.1
                 0.550     0.002                                 -156.0   3.0 
 P06C-085  13    0.283     0.004     0.282       0.002           -204.5   2.9      -206.8      3.3
                 0.282     0.003                                 -209.2   3.0
 P06C-081  32    1.275     0.005     1.271       0.004             87.4   3.5        83.2      6.4
                 1.270     0.003                                   78.4   3.7
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06C-081  21    0.565     0.003     0.565       0.003           -155.3   4.2      -146.6      9.3
                 0.565     0.005                                 -142.2   3.0
 P06C-081  13    0.287     0.004     0.286       0.002           -204.0   2.9      -203.5      2.1
                 0.286     0.002                                 -202.9   3.0
 P06C-077  32    1.450     0.004     1.444       0.018             69.9   3.7        70.2      2.6
                 1.425     0.007                                   70.4   3.7 
 P06C-077  21    0.473     0.004     0.496       0.032           -150.5   3.1      -150.3      2.1
                 0.518     0.004                                 -150.1   2.9   
 P06E-071  32    1.294     0.004     1.290       0.006             90.6   4.0        91.0      2.8
                 1.286     0.004                                   91.4   4.0
 P06E-071  21    0.477     0.004     0.481       0.006           -153.8   3.4      -157.2      4.7
                 0.486     0.005                                 -160.4   3.3     
 P06E-067  32    1.296     0.004     1.293       0.003             89.5   4.0        92.2      3.6
                 1.292     0.002                                   94.6   3.8
 P06E-067  21    0.383     0.002     0.375       0.007           -173.5   3.2      -174.8      2.3
                 0.373     0.001                                 -176.3   3.4
 P06E-067  13    0.322     0.004     0.300       0.031           -202.9   3.2      -201.6      2.3
                 0.278     0.004                                 -200.3   3.2
 P06E-063  32    1.356     0.002     1.358       0.008             98.1   3.9        97.5      2.8
                 1.368     0.004                                   96.7   4.0
 P06E-063  21    0.337     0.005     0.352       0.018           -175.2   3.3      -174.7      2.8
                 0.362     0.004                                 -173.2   5.6
 P06E-063  13    0.329     0.003     0.331       0.004           -197.9   3.3      -195.8      3.0
                 0.334     0.004                                 -193.6   3.3
 P06E-X18  21    0.353     0.001     0.352       0.023           -182.0   3.0      -179.1      4.1
                 0.320     0.005                                 -176.2   3.0
 P06E-X18  13    0.314     0.002     0.319       0.018           -198.1   2.9      -194.6      5.2
                 0.340     0.004                                 -190.7   3.0
 P06E-X18   1    1.417     0.004     1.407       0.008             88.3   3.6        87.5      2.5
                 1.405     0.002                                   86.7   3.6
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06E-055  32    1.393     0.007     1.366       0.023             93.0   3.7        89.       5.4
                 1.361     0.003                                   85.3   3.6
 P06E-055  21    0.310     0.004     0.310       0.002           -185.6   3.2      -186.0      2.2
                 0.310     0.003                                 -186.3   3.1
 P06E-055  13    0.319     0.006     0.321       0.003              -      -          -         -
                 0.322     0.004                                    -      -
 P06E-051  32    1.330     0.001     1.332       0.011             85.9   3.6        88.9      4.5
                 1.346     0.003                                   92.2   3.8
 P06E-051  21    0.297     0.004     0.303       0.013           -187.3   3.0      -183.7      5.0
                 0.315     0.006                                 -180.2   2.9
 P06E-051  13    0.304     0.001     0.308       0.013           -196.6   2.9      -195.5      2.1
                 0.322     0.002                                 -194.3   3.0
 P06E-047  32    1.456     0.004     1.466       0.008             75.3   3.6        76.2      2.9
                 1.468     0.002                                   77.8   5.0
 P06E-047  21    0.313     0.003     0.326       0.025           -186.7   3.0      -183.9      4.1
                 0.348     0.004                                 -180.9   3.1
 P06E-047  13    0.305     0.003     0.316       0.021           -190.8   2.9      -188.5      3.3
                 0.335     0.004                                 -186.1   2.9
 P06E-043  32    1.389     0.004     1.401       0.021             85.8   3.5        87.1      2.9
                 1.419     0.005                                   89.7   5.0
 P06E-043  21    0.272     0.002     0.275       0.011              -      -          -         -
                 0.288     0.004                                    -      -
 P06E-039  32    1.326     0.007     1.365       0.030             83.1   2.5        82.2      1.8
                 1.368     0.002                                   81.4   2.6 
 P06E-039  21    0.298     0.004     0.288       0.018           -191.1   2.3      -192.4      1.7
                 0.273     0.005                                 -193.5   2.2       
 P06E-039  13    0.286     0.002     0.277       0.020           -196.8   2.2      -195.0      2.3
                 0.258     0.003                                 -193.5   2.0
 P06E-X19  32    1.515     0.003     1.521       0.011             83.8   3.6        84.0      2.5
                 1.531     0.004                                   84.3   3.6
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06E-X19  21    0.266     0.004     0.270       0.004           -184.8   3.0      -184.4      2.1
                 0.272     0.003                                 -184.1   2.9   
 P06E-X19  13    0.304     0.003     0.305       0.003              -      -          -         -
                 0.306     0.005                                    -      -
 P06E-031  32    1.402     0.004     1.430       0.030             80.2   4.1        82.4      2.9 
                 1.445     0.003                                   84.4   4.0
 P06E-031  21    0.244     0.003     0.274       0.031           -190.7   3.3      -194.6      5.5
                 0.288     0.002                                 -198.5   3.3
 P06E-031  13    0.276     0.002     0.290       0.032           -198.4   3.3      -201.8      4.8
                 0.321     0.003                                 -205.2   3.3
 P06E-027  32    1.357     0.004     1.352       0.008             54.4   4.0        50.8      5.3
                 1.345     0.005                                   46.9   4.1
 P06E-027  21    0.227     0.002     0.234       0.009           -212.8   3.5      -210.2      3.5
                 0.240     0.002                                 -207.8   3.4
 P06E-027  13    0.229     0.003     0.233       0.008           -215.2   3.3      -218.6      4.7
                 0.240     0.004                                 -221.8   3.2
 P06E-023  32    1.310     0.005     1.316       0.006              -      -          -         -
                 1.318     0.003                                    -      -
 P06E-023  21    0.204     0.003     0.204       0.003           -189.3   3.2      -188.9      2.3
                 0.203     0.005                                 -188.4   3.2
 P06E-019  32    0.474     0.003     0.461       0.025             21.7   3.5        22.8      2.5
                 0.438     0.004                                   24.0   3.6
 P06E-019  21    0.211     0.004     0.214       0.004           -193.5   3.1      -195.8      3.1
                 0.216     0.004                                 -197.9   3.0
 P06E-019  13    0.206     0.004     0.210       0.006           -224.3   3.0      -219.8      6.4
                 0.215     0.005                                 -215.3   3.0
 P06E-015  32    0.084     0.004     0.076       0.011             -6.9   3.5        -7.4      2.5
                 0.068     0.004                                   -8.0   3.5
 P06E-015  21    0.177     0.005     0.184       0.013           -207.2   3.2      -206.3      2.2
                 0.195     0.006                                 -205.4   3.0
______________________________________________________________________________________________________________




TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06E-015  13     0.249    0.004      0.246      0.009           -215.0   2.9      -217.7      3.9
                  0.236    0.007                                 -220.5   3.0
 P06E-011  32    -0.082    0.003     -0.078      0.010              -      -          -         -
                 -0.068    0.005                                    -      -
 P06E-011  21     0.208    0.003      0.203      0.014           -200.1   3.1      -199.5      2.1
                  0.188    0.005                                 -198.9   2.9
 P06E-011  13     0.211    0.003      0.202      0.013              -      -          -         -
                  0.193    0.003                                    -      -
 A10-629   32     1.098    0.003      1.091      0.010              -      -          -         -
                  1.084    0.003                                    -      -
 A10-629    1       -        -          -          -             -114.9   3.5      -113.7      2.5
                    -        -                                   -112.5   3.5
 A10-003   32     1.251    0.005      1.250      0.003            103.0   4.1       102.3      3.0
                  1.250    0.003                                  101.6   4.3
 A10-003   21     0.655    0.003      0.670      0.030           -118.6   3.3      -117.3      3.7
                  0.697    0.004                                 -113.3   5.9
 A10-003   13     1.043    0.004      1.009      0.030            -99.7   3.3      -100.0      2.8
                  1.000    0.002                                 -100.6   5.1
 A10-007   32     1.174    0.003      1.180      0.015             83.9   4.0        81.3      3.7
                  1.195    0.005                                   78.6   4.0
 A10-007   21     0.677    0.001      0.677      0.006           -128.1   3.5      -131.8      5.0 
                  0.668    0.005                                 -135.2   3.4
 A10-007   13     0.992    0.005      1.002      0.021           -104.6   3.7      -103.9      2.6
                  1.022    0.007                                 -103.2   3.6
 A10-X17   21     0.694    0.003      0.686      0.012           -119.3   3.3      -121.7      3.5
                  0.677    0.003                                 -124.2   3.3
 A10-X17    1     1.028    0.004      1.046      0.033              -      -          -         -
                  1.074    0.005                                    -      -
 A10-021   32     1.238    0.002      1.237      0.002             83.9   4.0        83.0      2.8
                  1.235    0.004                                   82.1   4.0
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 A10-029   32    1.217     0.002     1.213       0.026             88.9   4.1        90.2      3.7
                 1.180     0.006                                   94.1   7.1
 A10-029   21    0.670     0.003     0.995       0.004              -      -          -         -
                 0.681     0.003                                    -      -
 A10-035   21    0.671     0.003     0.660       0.016           -120.0   3.3      -117.3      3.8
                 0.648     0.003                                 -114.6   3.4
 A10-035   13      -         -         -           -             -107.0   3.3      -103.4      5.1
                   -         -                                    -99.8   3.3
 A10-038   32    1.173     0.004     1.171       0.004              -      -          -         -
                 1.168     0.004                                    -      -
 A10-038   21    0.678     0.004     0.661       0.019           -123.7   3.3      -120.7      4.2
                 0.651     0.003                                 -117.7   3.3
 A10-X16   32    1.204     0.002     1.203       0.006             74.4   6.0        77.6      3.3
                 1.195     0.005                                   79.0   4.0
 A10-X16   13    0.983     0.006     0.935       0.037            -99.1   3.4       -98.5      2.4 
                 0.930     0.002                                  -97.9   3.4
 A10-043   21    0.648     0.004     0.654       0.008           -130.0   3.3      -126.9      4.5
                 0.660     0.004                                 -123.7   3.4 
 A10-043   13    0.954     0.004     0.935       0.021            -98.2   3.3      -103.9      8.6
                 0.924     0.003                                 -110.4   3.5 
 A10-X15   32    1.233     0.002     1.209       0.034             88.3   3.9        83.9      6.4
                 1.185     0.002                                   79.3   4.0
 A10-X15   13    0.927     0.004     0.950       0.032           -113.1   3.6      -113.7      2.5
                 0.972     0.004                                 -114.3   3.4 
 A10-051   32    1.092     0.004     1.123       0.034             70.3   3.9        70.3      2.8
                 1.140     0.003                                   70.3   3.9
 A10-051   21    0.576     0.002     0.581       0.025           -127.9   3.2      -123.2      7.0
                 0.612     0.005                                 -118.0   3.4
 A10-055   21    0.600     0.003     0.574       0.037           -121.2   3.6      -119.5      2.5
                 0.548     0.003                                 -117.8   3.6
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 A10-059   32    1.191     0.002     1.190       0.002             71.6   3.8        74.4      6.6
                 1.188     0.003                                   80.9   5.8
 A10-059   13    0.880     0.003     0.871       0.009           -111.2   3.4      -112.2      2.9
                 0.867     0.002                                 -114.9   5.4 
 A10-X14   32    1.219     0.005     1.215       0.004              -      -          -         -
                 1.214     0.003                                    -      -
 A10-X14   21    0.623     0.003     0.580       0.044           -120.9   3.5      -116.7      5.7
                 0.561     0.002                                 -112.8   3.4
 A10-067   21    0.618     0.003     0.595       0.033           -129.4   3.4      -125.1      5.5
                 0.571     0.003                                 -121.6   3.1 
 A10-067   13    0.904     0.002     0.893       0.016           -115.7   3.4      -117.1      2.4
                 0.882     0.002                                 -118.5   3.4
 A10-071   32    0.917     0.003     0.925       0.011             89.6   3.7        88.2      2.7
                 0.933     0.003                                   86.7   3.8
 A10-071   13    0.874     0.004     0.872       0.002           -118.4   3.5      -112.6      7.4
                 0.872     0.002                                 -107.9   3.2
 A10-075   32    1.030     0.003     1.034       0.006             94.3   3.8        93.4      2.7
                 1.038     0.003                                   92.5   3.7
 A10-075   21    0.661     0.007     0.649       0.010           -122.3   3.3      -122.1      2.3
                 0.647     0.003                                 -121.9   3.3
 A10-079   21    0.653     0.002     0.655       0.010              -      -          -         -
                 0.667     0.005                                    -      -
 A10-079   13    0.846     0.004     0.850       0.005           -128.8   3.4      -123.8      6.8
                 0.853     0.004                                 -119.2   3.3
 A10-083   32    1.042     0.002     1.035       0.016              -      -          -         -
                 1.020     0.003                                    -      -
 A10-083   13    0.852     0.002     0.850       0.004           -117.2   3.3      -114.4      4.2
                 0.847     0.003                                 -111.3   3.5
 A10-087   32    1.034     0.005     1.027      0.006               -      -          -         -
                 1.026     0.002                                    -      -
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 A10-087    1    0.593     0.004     0.591       0.004           -126.1   3.4      -123.5      3.6
                 0.587     0.005                                 -121.0   3.4 
 A10-093   32    1.032     0.005     1.026       0.007             74.6   4.0        81.1      9.5
                 1.022     0.004                                   88.0   4.1
 A10-093   21      -         -         -           -             -124.2   5.3      -119.7      4.5
                   -         -                                   -117.8   3.5
 A10-093   13    0.877     0.003     0.882       0.007           -114.5   3.7      -113.8      2.5
                 0.887     0.003                                 -113.3   3.5
 I04-601   21    0.683     0.005     0.683       0.004           -141.4   3.1      -141.2      2.3
                 0.683     0.007                                 -140.8   3.3
 I04-601   13    0.681     0.003     0.696       0.015           -144.0   3.3      -147.0      4.2
                 0.702     0.002                                 -150.0   3.3
 I04-595   32    0.671     0.006     0.632       0.047             67.4   3.8        64.9      3.6
                 0.605     0.005                                   62.3   3.9
 I04-595   13    0.723     0.005     0.705       0.018           -142.6   3.2      -144.3      2.3
                 0.698     0.003                                 -145.8   3.1 
 I04-589   32      -         -         -           -               80.2   3.7        81.7      2.7
                   -         -                                     83.3   3.8
 I04-589   21    0.377     0.002     0.378       0.004           -153.3   4.3      -150.4      3.2
                 0.382     0.004                                 -148.7   3.3
 I03-557   21    0.467     0.003     0.469       0.008           -165.7   3.0      -163.9      2.5
                 0.479     0.006                                 -162.2   3.0 
 I03-557   13    0.293     0.004     0.288       0.008           -184.3   3.0      -184.9      2.2
                 0.281     0.005                                 -185.7   3.2
 I03-551   13    0.339     0.003     0.333       0.012           -190.5   3.0      -189.7      2.2
                 0.322     0.004                                 -188.9   3.1
 I03-545   32    0.512     0.006     0.502       0.010             51.4   3.5        49.5      2.8
                 0.498     0.004                                   47.4   3.6    
 I03-545   21    0.416     0.001     0.418       0.008           -153.9   3.0      -156.4      3.7
                 0.427     0.002                                 -159.2   3.1
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 I03-535   21    0.384     0.003     0.383       0.003           -172.6   3.1      -168.4      6.0
                 0.380     0.004                                 -164.1   3.2
 I03-535   13    0.378     0.003     0.379       0.003           -186.1   3.3      -185.9      2.3
                 0.382     0.004                                 -185.7   3.3
 I03-531   32    0.735     0.006     0.679       0.044             67.3   3.9        64.1      4.5
                 0.673     0.002                                   61.0   3.8
 I03-531   13    0.380     0.004     0.379       0.003           -172.9   3.2      -171.8      2.3
                 0.377     0.005                                 -170.8   3.3
 I03-525   32    0.860     0.005     0.870       0.013             68.9   3.7        63.9      6.9
                 0.879     0.005                                   59.2   3.6
 I03-519   21      -         -         -           -             -167.6   3.1       -172.1     6.2
                   -         -                                   -176.4   3.0
 I03-513   32    0.736     0.003     0.712       0.035              -      -           -        -
                 0.687     0.003                                    -      -
 I03-513   21    0.274     0.004     0.244       0.026           -170.2   2.9       -167.6     3.7
                 0.237     0.002                                 -165.0   2.9
 I03-507   21    0.234     0.003     0.222       0.017           -163.5   3.1       -168.8     7.6
                 0.210     0.003                                 -174.3   3.2
 I03-507   13    0.435     0.003     0.432       0.003           -175.9   3.3       -179.2     4.5
                 0.431     0.002                                 -182.2   3.2
 I03-503   32    0.825     0.002     0.823       0.004             75.0   3.6         75.9     2.6
                 0.819     0.003                                   76.8   3.8
 I03-503   13    0.415     0.005     0.433       0.021           -184.7   3.0       -183.5     2.1
                 0.445     0.004                                 -182.3   3.0
 I03-X08   32    0.869     0.004     0.846       0.017             61.8   3.5         61.6     2.5
                 0.845     0.001                                   61.3   3.5
 I03-X08   21    0.255     0.001     0.255       0.006           -175.6   3.1       -176.1     2.2
                 0.264     0.005                                 -176.6   3.1
 I03-495   21    0.308     0.005     0.307       0.003           -174.6   3.0       -177.9     4.6
                 0.306     0.004                                 -181.1   3.0
______________________________________________________________________________________________________________



TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 -------   ---   --------  --------  ----------  -------------   -------  -------  ----------  -------------
 I03-495   13      -         -         -           -             -186.1   3.0      -183.0      4.5
                   -         -                                   -179.8   3.0
 I03-491   32    0.856     0.003     0.854       0.002             68.4   3.7        70.2      2.6
                 0.853     0.002                                   72.0   3.6
 I03-491   13    0.415     0.002     0.414       0.003           -184.2   3.1      -182.7      2.3
                 0.411     0.003                                 -181.0   3.2
 I03-487    1    0.304     0.005     0.324       0.019           -179.1   3.3      -180.6      2.3
                 0.331     0.003                                 -181.8   3.1
 I03-480   32    0.934     0.008     0.926       0.007             65.7   3.7        66.4      2.6
                 0.924     0.004                                   67.1   3.6
 I03-480   21    0.287     0.004     0.291       0.006           -180.8   3.1      -179.6      2.2
                 0.295     0.004                                 -178.3   3.2
 I03-474   32    0.845     0.003     0.852       0.014             63.5   3.6        66.4      4.1
                 0.865     0.004                                   69.3   3.6     
 I03-474   13    0.362     0.003     0.351       0.008           -190.3   2.8      -193.1      4.1
                 0.350     0.001                                 -196.1   2.9
 I03-470   32    0.785     0.007     0.764       0.018             77.6   3.4        78.4      2.4
                 0.760     0.003                                   79.3   3.3
 I03-470   21    0.290     0.003     0.293       0.008           -171.4   2.9      -170.9      2.1
                 0.302     0.005                                 -170.4   2.9
 I03-466   21    0.255     0.005     0.257       0.003           -177.6   3.1      -175.8      2.6
                 0.259     0.004                                 -173.9   3.1
 I03-466   13    0.326     0.006     0.352       0.027           -196.7   2.9      -194.5      3.3
                 0.364     0.004                                 -192.0   3.0
 I03-463   32    0.717     0.005     0.695       0.016             71.4   3.5        73.0      2.5
                 0.694     0.001                                   74.7   3.5
 I03-463    1    0.318     0.004     0.325       0.013           -183.9   3.1      -183.6      2.2
                 0.337     0.005                                 -183.3   3.0
 I03-459   32    0.788     0.004     0.775       0.015             57.3   3.7        62.6      7.2
                 0.767     0.003                                   67.5   3.6
______________________________________________________________________________________________________________

 

TABLE 3.10.5. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 I03-459   21    0.277     0.004     0.280       0.004           -187.8   3.1      -180.5      10.3
                 0.282     0.003                                 -173.2   3.1
 I03-459   13    0.397     0.003     0.374       0.045           -190.3   3.1      -188.8       2.7
                 0.334     0.004                                 -186.5   3.9
 I03-455   32      -         -         -           -               38.0   3.7        43.0       7.2
                   -         -                                     48.2   3.8
 I03-455   21    0.284     0.005     0.269       0.022           -192.9   3.1      -188.3       6.5
                 0.253     0.005                                 -183.7   3.1
 I03-455   13    0.349     0.001     0.343       0.042           -186.1   3.1      -186.5       2.2
                 0.290     0.003                                 -187.0   3.2
 I03-451   32    0.826     0.004     0.825       0.003              -      -          -          -
                 0.824     0.006                                    -      -
 I03-451   21      -         -         -           -             -177.7   3.2      -177.0       2.3
                   -         -                                   -176.4   3.2
 I03-451   13      -         -         -           -             -189.5   3.2      -192.5       4.3
                   -         -                                   -195.6   3.2
______________________________________________________________________________________________________________

a. Standard deviation of repeat measurements.
b. Error weighted mean of the replicate pair.
c. Larger of the standard deviation of the error weighted standard deviation 
   of the replicate pair.
d. Larger of the standard deviation of repeat measurements and the counting
   errors.


(7) DUPLICATE MEASUREMENTS

At 48 stations, seawater samples were taken from two X-Niskin bottles that 
were collected at same depth(duplicate sampling). Most of the duplicate 
samples were collected in deep layers below 1,000 dbar. Results of the 
duplicate pair analyses are shown in Table 3.10.6. The standard deviations of 
the δ^(13)C and Δ^(14)C duplicate analyses in good measurement were 
calculated to be 0.014 ‰ (n = 39) and 3.7 ‰ (n = 40), respectively. These 
deviations are almost same as those obtained by the replicate analyses (0.020 
‰ for δ^(13)C and 3.9 ‰ for Δ^(14)C).

The results of replicate and duplicate measurements suggested that 
"reproducibilities" of our δ^(13)C and Δ^(14)C measurements including errors 
due to the sample preparation were less than 0.02 ‰ and 4 ‰, respectively.


TABLE 3.10.6. Summary of duplicate analyses.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                    ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 P06W-201  35    1.206     0.002     1.201       0.024             91.5   3.9        87.7      5.4
           16    1.172     0.005                                   83.9   3.9
 P06E-039  22    0.321     0.001     0.320       0.006           -196.6   2.5      -193.6      3.7
           11    0.313     0.003                                 -191.3   2.2
 P06E-X19  20    0.274     0.002     0.278       0.006           -190.4   3.0      -191.2      2.1
           11    0.282     0.002                                 -191.9   3.0
 P06E-027  16    0.274     0.006     0.256       0.016           -208.7   3.2      -210.7      2.9
           10    0.252     0.003                                 -212.8   3.3
 P06E-023  14    0.201     0.004     0.200       0.002           -210.0   3.1      -213.7      5.2
            1    0.199     0.003                                 -217.3   3.1
 P06E-019  12    0.250     0.004     0.236       0.016           -218.0   3.0      -217.2      2.1
            1    0.228     0.003                                 -216.4   2.9
 A10-629   21    1.035     0.003     1.026       0.018              -      -          -         -
           17    1.010     0.004                                    -      -
 A10-007   16    1.014     0.004     0.994       0.018            -99.6   3.6      -101.2      2.5
           15    0.989     0.002                                 -102.9   3.6 
 A10-X17   13    0.727     0.006     0.729       0.004           -136.5   3.3      -136.5      2.3
            9    0.730     0.006                                 -136.6   3.3
 A10-021   17    0.882     0.004     0.876       0.011           -126.8   3.4      -125.2      2.4
            8    0.866     0.005                                 -123.6   3.5
 A10-035   23    0.974     0.005     0.967       0.006              -      -          -         -
           13    0.965     0.003                                    -      -
 A10-038   22    0.639     0.002     0.634       0.011              -      -          -         -
            4    0.623     0.003                                    -      -
 A10-X16   21    0.664     0.005     0.651       0.013              -      -          -         -
            8    0.646     0.003                                    -      -
 A10-043   20    0.650     0.003     0.668       0.018           -145.2   3.5      -146.6      2.4
            7    0.676     0.002                                 -147.9   3.4
 A10-X15   18    0.794     0.003     0.805       0.016           -124.5   3.4      -122.8      2.4
            9    0.816     0.003                                 -121.3   3.3
 A10-051   16    0.880     0.005     0.869       0.016           -117.3   3.4      -116.1      2.5
           11    0.858     0.005                                 -114.9   3.6
______________________________________________________________________________________________________________


 

TABLE 3.10.6. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 I03-535   22    0.444     0.004     0.424       0.015           -167.0   3.1      -171.0      5.7
            7    0.423     0.001                                 -175.1   3.1
 I03-535   23    0.622     0.005     0.637       0.021           -125.8   3.4      -123.7      3.0
            3    0.652     0.005                                 -121.6   3.4
 I03-525   17      -         -         -           -             -177.9   3.0      -176.8      2.2
           14      -         -                                   -175.8   3.1
 I03-519   16    0.445     0.002     0.446       0.004           -162.9   3.0      -165.1      3.0
           14    0.451     0.004                                 -167.2   3.0
 I03-513   11      -         -         -           -             -177.1   3.0      -176.6      2.1
            9      -         -                                   -176.2   2.9
 I03-507    8      -         -         -           -             -193.3   3.1      -189.1      6.1
            6      -         -                                   -184.6   3.2
 I03-503    6    0.411     0.003     0.396       0.022           -189.7   2.9      -189.4      2.1
            1    0.380     0.003                                 -189.0   2.9
 I03-X08    6    0.357     0.003     0.364       0.009           -191.3   2.9      -189.2      3.3
            4    0.370     0.003                                 -186.7   3.1 
 I03-495    5      -         -         -           -             -187.6   3.0      -186.8      2.1
            2      -         -                                   -186.0   3.0
 I03-491   23    0.381     0.002     0.384       0.003           -193.5   3.0      -191.5      2.9
            6    0.385     0.001                                 -189.4   3.1
 I03-487   21    0.321     0.003     0.322       0.002           -189.4   3.1      -188.9      2.2
           19    0.322     0.003                                 -188.4   3.1
 I03-480   18    0.484     0.004     0.481       0.004           -179.2   3.2      -175.7      5.1
            4    0.478     0.004                                 -172.0   3.3
 I03-474   16      -         -         -           -             -163.7   2.8      -170.0      9.3
            6      -         -                                   -176.8   2.9
 I03-470   14    0.451     0.002     0.453       0.006           -161.8   2.9      -162.6      2.0
            4    0.459     0.003                                 -163.4   2.8
 I03-463   13    0.430     0.004     0.434       0.004           -170.1   2.9      -166.9      5.1
            3    0.436     0.003                                 -162.9   3.2
 I03-455   10    0.437     0.004     0.436       0.003           -176.2   3.2      -173.8      3.3
            5    0.434     0.004                                 -171.6   3.1
______________________________________________________________________________________________________________



TABLE 3.10.6. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 A10-055   17    0.796     0.002     0.801       0.007              -      -          -         -
           14    0.806     0.002                                    -      -
 A10-059   12      -         -         -           -             -105.9   3.5      -106.5      2.5
           11      -         -                                   -107.3   3.6
 A10-X14   10    0.844     0.002     0.885       0.036           -105.0   3.5      -107.9      4.2
            1    0.895     0.001                                 -110.9   3.5
 A10-067    9    0.884     0.004     0.867       0.025           -111.8   3.3      -113.0      2.3
            8    0.849     0.004                                 -114.3   3.2
 A10-071    7    0.788     0.004     0.793       0.006           -121.3   3.4      -117.9      4.7
            6    0.797     0.004                                 -114.7   3.3
 A10-075   11    0.842     0.001     0.846       0.013           -125.9   3.5      -121.7      5.6
            4    0.860     0.002                                 -118.0   3.3
 A10-079    7      -         -         -           -             -148.5   3.4      -150.9      3.4
            2      -         -                                   -153.3   3.3
 A10-083   23    0.554     0.005     0.546       0.009              -      -          -         -
            5    0.541     0.004                                    -      -
 A10-087   21    0.576     0.002     0.553       0.021              -      -          -         -
            5    0.547     0.001                                    -      -
 A10-093   12    0.855     0.003     0.835       0.021              -      -          -         -
            8    0.826     0.002                                    -      -
 I04-601   21    0.683     0.004     0.684       0.002           -141.2   2.3      -141.1      1.8
           14    0.684     0.002                                 -141.0   3.2
 I04-595   18    0.668     0.003     0.676       0.016           -137.5   3.3      -142.8      7.1
           12    0.690     0.004                                 -147.6   3.2
 I04-589   15       -         -        -           -             -142.7   3.1      -142.8      2.2
           11       -         -                                  -142.9   3.1
 I03-557   10    0.474     0.002     0.480       0.015           -174.8   3.1      -170.7      5.6
            8    0.495     0.003                                 -166.9   3.0
 I03-551    7    0.502     0.008     0.490       0.010           -161.3   3.1      -160.2      2.3
            6    0.488     0.003                                 -159.0   3.3
 I03-545    8       -         -        -           -             -170.5   3.2      -168.7      2.5
            4       -         -                                  -166.9   3.2
 ______________________________________________________________________________________________________________



TABLE 3.10.6. continued.
______________________________________________________________________________________________________________


 Station   Btl                   δ^(13)C/‰                                     ∆^(14)C/‰
                 δ^(13)C  Error ^a  E.W.Mean^b  Uncertainty^c   ∆^(14)C  Error^d  E.W.Mean^b  Uncertainty^c
 --------  ---   -------  --------  ----------  -------------   -------  -------  ----------  -------------
 I03-535   22    0.444     0.004     0.424       0.015           -167.0   3.1      -171.0      5.7
            7    0.423     0.001                                 -175.1   3.1
 I03-535   23    0.622     0.005     0.637       0.021           -125.8   3.4      -123.7      3.0
            3    0.652     0.005                                 -121.6   3.4
 I03-525   17      -         -         -           -             -177.9   3.0      -176.8      2.2
           14      -         -                                   -175.8   3.1
 I03-519   16    0.445     0.002     0.446       0.004           -162.9   3.0      -165.1      3.0
           14    0.451     0.004                                 -167.2   3.0 
 I03-513   11      -         -         -           -             -177.1   3.0      -176.6      2.1
            9      -         -                                   -176.2   2.9 
 I03-507    8      -         -         -           -             -193.3   3.1      -189.1      6.1
            6      -         -                                   -184.6   3.2
 I03-503    6    0.411     0.003     0.396       0.022           -189.7   2.9      -189.4      2.1
            1    0.380     0.003                                 -189.0   2.9
 I03-X08    6    0.357     0.003     0.364       0.009           -191.3   2.9      -189.2      3.3
            4    0.370     0.003                                 -186.7   3.1
 I03-495    5      -         -         -           -             -187.6   3.0      -186.8      2.1
            2      -         -                                   -186.0   3.0
 I03-491   23    0.381     0.002     0.384       0.003           -193.5   3.0      -191.5      2.9
            6    0.385     0.001                                 -189.4   3.1
 I03-487   21    0.321     0.003     0.322       0.002           -189.4   3.1      -188.9      2.2
           19    0.322     0.003                                 -188.4   3.1
 I03-480   18    0.484     0.004     0.481       0.004           -179.2   3.2      -175.7      5.1
            4    0.478     0.004                                 -172.0   3.3
 I03-474   16      -         -         -           -             -163.7   2.8      -170.0      9.3
            6      -         -                                   -176.8   2.9
 I03-470   14    0.451     0.002     0.453       0.006           -161.8   2.9      -162.6      2.0
            4    0.459     0.003                                 -163.4   2.8 
 I03-463   13    0.430     0.004     0.434       0.004           -170.1   2.9      -166.9      5.1
            3    0.436     0.003                                 -162.9   3.2
 I03-455   10    0.437     0.004     0.436       0.003           -176.2   3.2      -173.8      3.3
            5    0.434     0.004                                 -171.6   3.1
______________________________________________________________________________________________________________

a. Standard deviation of repeat measurements.
b. Error weighted mean of the replicate pair.
c. Larger of the standard deviation and the error weighted standard deviation 
   of the replicate pair.
d. Larger of the standard deviation of repeat measurements and the counting 
   errors.


(8) REFERENCE SEAWATER MEASUREMENTS

During the sample measurements period from May 2004 to October 2006, we 
synchronously carried out δ^(13)C and Δ^(14)C measurements of reference 
seawaters. The reference seawater was prepared from a large volume of surface 
seawater collected in open ocean. The surface seawater was filtered, exposed 
to ultraviolet irradiation, poisoned by HgCl2, and then dispensed in 250 cm^3 
glass bottles. The δ^(13)C and Δ^(14)C of the reference seawater was 
measured at every 40 samples analyses approximately. The results are shown in 
Figure 3.10.2 and Table 3.10.7. The standard deviations of δ^(13)C and 
Δ^(14)C were 0.027 ‰ and 5.8 ‰, respectively. These deviations were slightly 
larger than those obtained by the replicate and duplicate measurements (0.02 
‰ for δ^(13)C and 4 ‰ for Δ^(14)C). Finally we concluded that "precisions" 
of our δ^(13)C and Δ^(14)C analyses including error due to the sample 
preparation and storage were about 0.03 ‰ and 6 ‰, respectively.


TABLE 3.10.7. Summary of reference seawaters measurements.
_____________________________________________________________________________________________


 NO.  RS No.                 δ^(13)C/‰                           ∆^(14)C/‰
                   Measurement date  δ^(13)C  Error^b   Measurement date  ∆^(14)C  Error^c
 ---  ----------   ----------------  -------  -------   ----------------  -------  -------
  1   RM0204-026   17-May-04         -1.978    0.005     18-May-04         60.2     4.6
  2   RM0204-156   20-May-04         -1.966    0.004     14-Jun-04         62.3     5.3
  3   RM0204-093   24-May-04         -1.988    0.005     14-Jun-04         57.5     5.3
  4   RM0204-103   25-May-04         -2.049    0.003     18-Jun-04         69.5     5.2
  5   RM0204-028   04-Jun-04         -2.012    0.002     16-Jul-04         71.9     4.1
  6   RM0204-148   15-Jun-04         -1.972    0.002     16-Jul-04         55.7     3.9
  7   RM0204-022   16-Jun-04         -2.034    0.004     16-Jul-04         63.8     3.8
  8   RM0204-152   17-Jun-04         -1.987    0.002     21-Jul-04         55.2     3.5
  9   RM0204-064   01-Jul-04         -1.937    0.006     21-Jul-04         59.6     3.8
 10   RM0204-076   02-Aug-04         -2.016    0.004     23-Aug-04         60.3     5.7
 11   RM0204-115   05-Aug-04         -2.023    0.001     06-Sep-04         62.2     4.2
 12   RM0204-092   10-Aug-04         -1.945    0.002     26-Sep-04         67.2     4.6
 13   RM0204-027   12-Aug-04         -2.014    0.006     26-Sep-04         64.7     4.5
 14   RM0204-018   31-Aug-04         -1.950    0.002     29-Sep-04         57.1     3.7
 15   RM0204-169   17-Jun-04         -1.981    0.002     29-Oct-04         59.2     3.8
 16   RM0204-062   12-Jul-05         -2.032    0.004     08-Nov-04         69.2     6.2
 17   RM0204-048   09-Aug-04         -2.031    0.003     08-Nov-04         67.5     3.9
 18   RM0204-004   15-Nov-04         -1.977    0.005     27-Dec-04         60.5     3.9
 19   RM0204-119   26-Nov-04         -2.009    0.006     27-Dec-04         63.5     3.9
 20   RM0204-108   09-Aug-04         -2.012    0.003     27-Dec-04         63.3     3.8
 21   RM0204-123   30-Nov-04         -1.959    0.004     03-Feb-05         68.8     4.0
 22   RM0204-065   01-Dec-04         -1.994    0.005     03-Feb-05         71.8     4.2
 23   RM0204-159   22-Feb-05         -2.005    0.003     24-May-05         65.3     3.8
 24   RM0204-055   18-Feb-05         -1.966    0.006     24-May-05         66.9     3.9
 25   RM0204-177   23-Feb-05         -1.984    0.007     09-Jun-05         58.3     3.7
 26   RM0204-111   01-Mar-05         -1.954    0.004     09-Jun-05         65.7     3.6
 27   RM0204-138   07-Sep-04         -2.012    0.003     22-Jun-05         69.0     3.5
 28   RM0204-058   17-Sep-04         -2.010    0.003     22-Jun-05         63.5     3.7
 29   RM0204-165   17-Sep-04         -1.976    0.005     22-Jun-05         67.3     6.0
 30   RM0204-183   17-Sep-04         -1.988    0.005     29-Jun-05         70.7     3.5
_____________________________________________________________________________________________



TABLE 3.10.7. continued.
_____________________________________________________________________________________________


 NO.  RS No.                 δ^(13)C/‰                           ∆^(14)C/‰
                   Measurement date  δ^(13)C  Error^b   Measurement date  ∆^(14)C  Error^c
 ---  ----------   ----------------  -------  -------   ----------------  -------  -------
 31   RM0204-135   05-Nov-04         -2.006    0.003     29-Jun-05         74.4     3.6
 32   RM0204-070   05-Nov-04         -1.923    0.002     06-Jul-05         65.9     3.8
 33   RM0204-081   05-Nov-04         -1.950    0.004     06-Jul-05         71.5     3.8
 34   RM0204-179   15-Nov-04         -1.964    0.004     06-Jul-05         74.4     4.0
 35   RM0204-016   27-Dec-04         -1.949    0.004     06-Jul-05         72.0     3.5
 36   RM0204-075   27-Dec-04         -1.995    0.002     06-Jul-05         66.4     3.7
 37   RM0204-133   27-Dec-04         -1.994    0.003     06-Jul-05         64.7     3.6
 38   RM0204-098   18-Feb-05         -2.007    0.003     14-Jul-05         71.6     3.6
 39   RM0204-087   18-Feb-05         -1.964    0.005     19-Oct-05         58.5     2.5
 40   RM0204-014   18-Feb-05         -1.988    0.004     31-Aug-05         71.1     3.5
 41   RM0204-182   18-Feb-05         -1.975    0.005     31-Aug-05         71.5     4.1
 42   RM0204-145   18-Feb-05         -2.005    0.002     31-Aug-05         69.9     3.9
 43   RM0204-106   18-Feb-05         -1.974    0.004     31-Aug-05         65.5     3.9
 44   RM0204-035   29-Mar-05         -1.989    0.001     31-Aug-05         71.2     4.1
 45   RM0204-147   29-Mar-05         -2.019    0.003     29-Sep-05         63.9     4.1
 46   RM0204-061   06-Apr-05         -1.990    0.005     29-Sep-05         72.5     4.0
 47   RM0204-132   23-Jun-05         -1.978    0.003     17-Nov-05         71.0     3.8
 48   RM0204-044   02-Aug-05         -1.980    0.004     17-Nov-05         73.3     4.1
 49   RM0204-176   03-Aug-05         -1.992    0.002     17-Nov-05         71.2     4.0
 50   RM0204-053   17-Aug-05         -1.987    0.003     16-Jan-06         75.5     3.9
 51   RM0204-097   22-Sep-05         -1.983    0.002     23-Jan-06         75.0     4.0
 52   RM0204-160   05-Oct-05         -1.972    0.004     24-Feb-06         63.7     4.2
 53   RM0204-034   05-Dec-05         -1.996    0.002     14-Mar-06         75.9     3.9
 54   RM0204-141   07-Dec-05         -2.004    0.003     14-Mar-06         74.2     3.9
 55   RM0204-188   19-Dec-05         -1.953    0.005     24-Mar-06         62.4     3.9
 56   RM0204-083   20-Dec-05         -1.977    0.005     24-Mar-06         67.0     3.8
 57   RM0204-010   26-Dec-05         -1.949    0.005     24-Mar-06         76.7     4.1
 58   RM0204-173   30-Jan-06         -2.015    0.003     23-May-06         59.0     3.8
 59   RM0204-001   01-Feb-06         -1.949    0.006     23-May-06         57.3     4.0
 60   RM0204-172   02-Feb-06         -1.940    0.003     26-May-06         62.1     3.6
_____________________________________________________________________________________________



TABLE 3.10.7. continued.
_____________________________________________________________________________________________


 NO.  RS No.                 δ^(13)C/‰                           ∆^(14)C/‰
                   Measurement date  δ^(13)C  Error^b   Measurement date  ∆^(14)C  Error^c
 ---  ----------   ----------------  -------  -------   ----------------  -------  -------
 61   RM0204-144   20-Feb-06         -1.979    0.001     26-May-06         56.0     4.6
 62   RM0204-080   23-Feb-06         -1.949    0.006     05-Jun-06         71.4     3.9
 63   RM0204-146   27-Mar-06         -1.981    0.003     05-Jun-06         68.6     3.8
 64   RM0204-126   28-Mar-06         -1.957    0.005     29-Jun-06         63.1     3.6
 65   RM0204-021   30-Mar-06         -1.951    0.003     29-Jun-06         72.3     3.4
 66   RM0204-039   06-Jun-06         -1.973    0.002     29-Jun-06         72.3     3.8
 67   RM0204-105   07-Jun-06         -1.937    0.003     29-Jun-06         60.8     5.6
 68   RM0204-178   10-Jan-06         -1.992    0.004     25-Jul-06         64.4     3.8
 69   RM0204-029   20-Feb-06         -1.995    0.004     02-Aug-06         72.0     3.5
 70   RM0204-167   20-Mar-06         -2.002    0.003     02-Aug-06         64.3     3.7
 71   RM0204-117   20-Mar-06         -1.965    0.001     06-Oct-06         63.2     3.6
 72   RM0204-024   27-Mar-06         -1.961    0.006     06-Oct-06         74.2     3.7
 73   RM0204-067   22-Jun-06         -1.954    0.003     13-Oct-06         57.6     3.7
 74   RM0204-107   26-Jun-06         -1.977    0.003     13-Oct-06         63.9     3.5
 75   RM0204-153   28-Jun-06         -2.023    0.004     27-Oct-06         71.6     3.5
 76   RM0204-051   30-Jun-06         -1.995    0.004     27-Oct-06         55.9     3.5
 ---  ----------   ----------------  --------  -------   ----------------  -------  ------
                               mean  -1.983                          mean  66.3
                 standard deviation   0.027            standard deviation   5.8
_____________________________________________________________________________________________

a. Decay corrected for 01/May/2004.
b. Standard deviation of repeat measurements.
c. Larger of the standard deviation and the counting error.


(9) QUALITY CONTROL FLAG ASSIGNMENT

Quality flag values were assigned to all δ^(13)C and Δ^(14)C measurements 
using the code defined in Table 0.2 of WHP Office Report WHPO 91-1 Rev.2 
section 4.5.2 (Joyce et al., 1994). Measurement flags of 2, 3, 4, 5, and 6 
have been assigned (Table 3.10.8). For the choice between 2 (good), 3 
(questionable) or 4 (bad), we basically followed a flagging procedure in Key 
et al. (1996) as listed below:

a. On a station-by-station basis, a datum was plotted against pressure. Any 
   points not lying on a generally smooth trend were noted.

b. δ^(13)C (Δ^(14)C) was then plotted against dissolved oxygen (silicate) 
   concentration and deviant points noted. If a datum deviated from both the 
   depth and oxygen (silicate) plots, it was flagged 3.

c. Vertical sections against depth were prepared using the Ocean Data View 
   (Schlitzer, 2006). If a datum was anomalous on the section plots, datum 
   flag was degraded from 2 to 3, or from 3 to 4.


TABLE 3.10.8.  Summary of assigned quality control flags.
               ________________________________________________
               
                Flag  Definition                 Number
                                            δ^(13)C  ∆^(14)C
                ----  --------------------  -------  -------
                2     Good                   2,486    2,518
                3     Questionable              94       80
                4     Bad                       19        3
                5     Not report (missing)      11       12
                6     Replicate                217      214
                ----  --------------------  -------  -------
                      Total                  2,827    2,827
               ________________________________________________



(10) DATA SUMMARY

Figure 3.10.3 and 3.10.4 show vertical sections of δ^(13)C and Δ^(14)C 
against depth, respectively. Maximum of δ13C was observed in the mode waters 
(SAMW: Subantarctic Mode Water) in the Pacific and Indian Oceans. In the 
Southwest Pacific Basin (180° - 130°W), Madagascan Basin (50°E - 60°E), and 
West Australian Basin (90°E - 110°E), high δ13C waters near bottom well 
correspond to the Circumpolar Deep Water (CDW). In the South Atlantic Ocean, 
one can distinguish low-δ^(13)C water of the Antarctic Bottom Water (AABW) 
from high-δ^(13)C water of the North Atlantic Deep Water (NADW). Low δ^(13)C 
was found in deep waters in the Indian Ocean (IDW: Indian Deep Water) and in 
the Pacific Ocean (PDW: Pacific Deep Water) from 1,000 to 4,000 m depth 
approximately. The global distribution of δ13C well agree with that presented 
in a previous study (Kroopnick, 1985). Temporal increase of the anthropogenic 
CO2 inventory can be estimated by comparison the BEAGLE2003 δ^(13)C with 
historical data because atmospheric δ13C decrease, named "13C-Suess Effect", 
has been imprinted in δ13C of DIC in surface ocean.

Higher Δ^(14)C values were observed in the thermocline (< about 1,000 m 
depth) of the three basins because of the bomb-produced radiocarbon 
penetration. Deep Δ^(14)C data clearly indicate the global pattern of 
thermohaline circulation. Relative higher Δ^(14)C was measured in CDW where 
the high-δ^(13)C water was found. In the South Atlantic Ocean, one can 
distinguish low-Δ^(14)C water of AABW from high-Δ^(14)C water of NADW. 
Minimum of Δ^(14)C was measured in IDW and PDW where the δ^(13)C minimum was 
found. The global distribution of Δ^(14)C in deep and bottom waters supports 
a previous study (Key et al., 2004). Difference between BEAGLE2003 and 
historical radiocarbon data will suggest temporal change of bomb radiocarbon 
in the thermocline.


FIGURE 3.10.3. Vertical sections of δ^(13)C against depth during BEAGLE2003 
               cruise in 2003/2004.
FIGURE 3.10.4. Vertical sections of Δ^(14)C against depth during BEAGLE2003 
               cruise in 2003/2004.


References

Joyce, T., and C. Corry, eds., C. Corry, A. Dessier, A. Dickson, T. Joyce, M. 
    Kenny, R. Key, D. Legler, R. Millard, R. Onken, P. Saunders, M. Stalcup, 
    contrib., 1994. Requirements for WOCE Hydrographic Programme Data 
    Reporting, WHPO Pub. 90-1 Rev. 2, 145pp.
Key, R.M., A. Kozyr, C.L. Sabine, K. Lee, R. Wanninkhof, J.L. Bullister, R.A. 
    Feely, F.J. Millero, C. Mordy, T.H. Peng, 2004. A global ocean carbon 
    climatology: Results from Global Data Analysis Project (GLODAP), Global 
    Biogeochemical Cycles, 18, GB4031, doi:10.1029/2004GB002247.
Key, R.M., P.D. Quay, G.A. Jones, A.P. McNichol, K.F. von Reden, R.J. 
    Schneider, 1996. WOCE AMS radiocarbon I: Pacific Ocean results (P6, P16, 
    P17), Radiocarbon 38, 425-518.
Kroopnick, P.M., 1985. The distribution of 13C of Σ CO2 in the world oceans, 
    Deep-Sea Research, 32, 57-84.
Kumamoto, Y., M.C. Honda, A. Murata, N. Harada, M. Kusakabe, K. Hayashi, N. 
    Kisen, M. Katagiri, K. Nakao, and J.R. Southon, 2000. Distribution of 
    radiocarbon in the western North Pacific: preliminary results from 
    MR97-02 cruise in 1997, Nuclear Instruments and Methods in Physics 
    Research B172, 495-500.
McNichol, A.P. and G.A. Jones, 1991. Measuring 14C in seawater CO2 by 
    accelerator massspectrometry, WOCE Operations Manual, WOCE Report 
    No.68/91, Woods Hole, MA.
Schlitzer, R., 2006. Ocean Data View, http://www.awi-bremerhaven.de/GEO/ODV.
Stuiver. M., 1983. International agreements and the use of the new oxalic 
    acid standard, Radiocarbon, 25, 793-795.
Stuiver, M. and H.A. Polach, 1977. Reporting of 14C data. Radiocarbon 19, 
    355-363.
Uchida, H. and M. Fukasawa, 2005a. WHP P6, A10, I3/I4 Revisit Data Book, Blue 
    Earth Global Expedition 2003 (BEAGLE2003) Volume 1. JAMSTEC. Yokosuka. pp 
    115.
Uchida, H. and M. Fukasawa, 2005b. WHP P6, A10, I3/I4 Revisit Data Book, Blue 
    Earth Global Expedition 2003 (BEAGLE2003) Volume 2. JAMSTEC. Yokosuka. pp 
    129.


3.11. ANTHROPOGENIC RADIONUCLIDES
      23 January 2007

3.11.1. General information
        M. Aoyama (MRI), A. Takeuchi (KANSO), S. Lee (IAEA-MEL), B. Oregioni 
        (IAEA-MEL), and J. Gasutaud (IAEA-MEL)

(1) Personnel

M. Aoyama:   Meteorological Research Institute (MRI)
A. Takeuchi: The General Environmental Technos Co., LTD (KANSO)
S. Lee:      International Atomic Energy Agency, Marine Environmental 
             Laboratories (IAEA-MEL)
B. Oregioni: IAEA-MEL
J. Gasutaud: IAEA-MEL


(2) Objectives

    1) Geochemical studies of global fallout, anthropogenic radionuclides 
       such as ^(137)Cs, ^(90)Sr and Pu isotopes, including studies on the 
       long term behaviour of ^(137)Cs in the world ocean, and to learn more 
       about the present geographical distribution of 137Cs in the oceans in 
       the southern hemisphere.
    2) Use of anthropogenic radionuclides as tracers for oceanographic and 
       climate change studies. Development of the anthropogenic radionuclides 
       database for validation and update of ocean general circulation models.


(3) Target radionuclides

Main target radionuclides are ^(137)Cs, Pu isotopes and tritium. In some 
samples analysis of ^(90)Sr will be carried out as well.


(4) Sampling procedures

Seawater sampling for analysis of radionuclides in the water column was 
carried out using adopted procedures. If additional Niskin bottles filled 
with samples were available, volumes of water column samples varied from 6 L 
to 20 L. The samples were drawn from Niskin bottles into 20 L cubitainers. 
The samples were then filtered through 0.45 µm pore size filters and filled 
into cubitainers or bottles of appropriate sizes. Filters were also archived. 
Concentrated nitric acid was added to the samples to keep pH at 1.6, except 
for tritium samples.

Surface water samples were drawn through an intake pump located several 
meters below the sea surface.

Volumes up to 85 L were collected for ^(137)Cs and Pu analysis. For tritium 
analysis, samples of 1 L were collected.

All samples were stored in a storage room at a stable temperature by the end 
of the cruise. In March 2004 the samples were loaded on land and transported 
to MRI at Tsukuba for the analysis of radionuclides on land. In June 2004, 
selected samples were sent to IAEA-MEL at Monaco for the analysis of 
radionuclides on land, too.


(5) Samples accomplished during the cruises

A total of 91 samples were collected for surface seawater samples. At the 56 
stations, a total of 777 samples were collected for water column samples 
(Table 3.11.1). The sampling locations and depths are shown in Figure 3.11.1. 
A total weight of the samples was around 22,000 kg.


TABLE 3.11.1. Number of stations for each ocean.
________________________________________________________________________________


               The Pacific Ocean  The Atlantic Ocean  The Indian Ocean  Total 
 ------------  -----------------  ------------------  ----------------  -----
 Surface       51                 18                  22                91
 Water column  27                 12                  17                56
________________________________________________________________________________



FIGURE 3.11.1. locations and depths of sampling sites.


(6) Problems during the cruise and solutions

No serious problems occurred during the cruise.


(7) Comparability on the analysis of radionuclides among the laboratories on 
    land

Since the samples were measured by several laboratories on land, we checked 
the comparability of the measurements. Results are presented in Table 3.11.2, 
3.11.3 and 3.11.4.


TABLE 3.10.8.  Summary of assigned quality control flags.
               _________________________________________________

                Flag  Definition                  Number
                                            δ^(13)C  ∆^(14)C
                ----  --------------------  -------  -------
                2     Good                  2,486     2,518
                3     Questionable             94        80
                4     Bad                      19         3
                5     Not report (missing)     11        12
                6     Replicate               217       214
               ----  --------------------  --------  -------
                      Total                 2,827     2,827
               _________________________________________________



TABLE 3.11.2.  Results of intercomparison of ^(137)Cs measurements.
               _____________________________________________________________________

                                  MRI         MEL         LLRL     Comenius Univ.
                               (Bq m^-3)   (Bq m^-3)   (Bq m^-3)     (Bq m^-3)
                ------------  -----------  ----------  ----------  --------------
                P06C-127      1.23±0.00    1.24±0.06
                              1.20±0.04
                I03-507       1.36±0.07                              1.32±0.07
                              1.19±0.05
                A10-X15       1.23±0.06    1.15±0.03
                              1.20±0.04
                165E-33-800   0.97±0.03                1.14±0.05
                165E-33-900   0.63±0.02                0.78±0.04
                165E-33-1000  0.50±0.05                0.66±0.06
                165E-37-800   0.55±0.03                0.69±0.05
               _____________________________________________________________________



TABLE 3.11.3.  Results of measurements of ^(137)Cs in IAEA-381 reference 
               material (Irish seawater).
               _____________________________________________________________________

                                                       Certified 
                                  MRI         MEL        value
                               (Bq kg-1)   (Bq kg-1)   (Bq kg-1)
                ------------  -----------  ----------  ----------
                IAEA381       0.445±0.002              0.49±0.01
               _____________________________________________________________________



TABLE 3.11.4.  Results of intercomparison of Pu measurements.
               _____________________________________________________________________
               
                                  MRI         MEL         KINS
                               (mBq m^-3)  (mBq m^-3)  (mBq m^-3)
                ------------  -----------  ----------  ----------
                P06C-175      1.1±0.3                  1.41±0.24
                P06C-124      1.5±0.4
                P06C-127
               _____________________________________________________________________



3.11.2. Analyses at Meteorological Research Institute (MRI) and Low Level
        Radioactivity Laboratory , Kanazawa University (LLRL) in Japan
        M. Aoyama (MRI), K. Hirose (MRI, LLRL), K. Komura (LLRL), and 
        Y. Hamajima (LLRL)


(1) Personnel

    M. Aoyama:   MRI
    K. Hirose:   MRI, Low Level Radioactivity Laboratory, Kanazawa University 
                 (LLRL)
    K. Komura:   LLRL
    Y. Hamajima: LLRL


(2) Analytical method of ^(137)Cs analysis in seawater at MRI and LLRL

Cs is one of the alkali metals, which exists in ionic form in natural water, 
and chemically shows less affinity than other chemicals. Known adsorbents to 
collect Cs in seawater are ammonium phosphomolybdate (AMP) and 
hexacyanoferrate compounds (Folsom and Sreekumaran, 1966; La Rosa et al., 
2001). The AMP has been an effective ion exchanger of alkali metals (Van R. 
Smit et al., 1959). Aoyama et al. (2000) re-examined the AMP procedure and 
their experiments revealed that the stable Cs carrier of the same equivalent 
amount as AMP is required to form insoluble Cs-AMP compounds in an acidic 
solution (pH from 1.2 to 2.2). The improved method has achieved high chemical 
yields of more than 95% for sample volumes of less than 100 L. Another 
improvement is a reduction of the amount of AMP from ~10 g to 4 g to adsorb 
^(137)Cs from seawater samples. As a result, it has been possible to reduce 
the sample volumes from ~100 L to less than 20 L, so after final sample 
treatment high-efficiency well-type Ge-detectors can be used for analysis of 
^(137)Cs. These improvements have enabled to apply ^(137)Cs as a chemical 
tracer for studying oceanographic processes in much larger scales, as has 
been documented during the BEAGLE cruise.

Recently Komura (Komura, 2004; Komura and Hamajima, 2004) has established an 
underground facility (Ogoya Underground Laboratory, OUL) to achieve an 
extremely low background of γ-spectrometers, operating with Ge detectors of 
high efficiency. The OUL has been constructed in 1995 by Low Level 
Radioactivity Laboratory of the Kanazawa University in the tunnel of former 
Ogoya copper mine (235 m above the sea level, Ishikawa prefecture). The 
shielding depth of the OUL is 270 m of water equivalent, where contributions 
of meaon are more than four orders of magnitude lower than at the ground 
level. In order to achieve an extremely low background of γ-spectrometers, 
high efficiency well type Ge detectors specially designed for low level γ-ray
spectrometry were shielded with low background lead prepared from old roof 
tiles of the Kanazawa Castle. As a result, the background of γ-ray 
spectrometers in the energy range of ^(137)Cs is two orders of magnitude 
lower than that in ground-level facilities, as shown in Table 3.11.5. A 
detection limit of ^(137)Cs at the OUL is 0.18 mBq for a counting time of 
10000 minutes (Hirose et al., 2005).

There is a residual problem in low-level γ-spectrometry for ^(137)Cs 
measurements as AMP adsorbs trace amounts of potassium when Cs is extracted 
from seawater. Potassium is a major component in seawater, and natural 
potassium compounds contains 0.0118% of radioactive potassium (40K) to stable 
potassium. Therefore even trace amounts of 40K cause elevation of background 
in the ^(137)Cs energy window due to Compton scattering of gamma-rays from 
40K. If 40K can be removed from AMP(Cs) compound samples, a better 
sensitivity of underground γ-spectrometers for ^(137)Cs measurements can be 
achieved. To remove 40K from AMP(Cs) compounds, a precipitation method 
including insoluble platinate salt of Cs was developed for purification of 
Cs. This method helped to remove trace amounts of 40K from from AMP(Cs) 
compounds with a chemical yield of around 90% for ^(137)Cs (Hirose et al., 
2007). This method has been applied for seawater samples collected below the 
1200 m water depth.

MATERIALS AND PROCEDURES OF CHEMICAL SEPARATION

All reagents used for ^(137)Cs, ^(90)Sr and Pu assay are special (G.R.) grade 
for analytical use. All experiments and sample treatments have been carried 
out at ambient temperatures. It is very important to know background 
γ-activity of reagents. The ^(137)Cs activity of CsCl and AMP reagents was 
less than 0.03 mBq g^-1 and 0.008 mBq g^-1, respectively. There has not been 
any ^(137)Cs contamination observed from other reagents.

An improved AMP procedure of chemical separation of ^(137)Cs from seawater 
samples for the ground-level γ-spectrometry was as follows:

 (1) Measure the seawater volume (5-100 L) and put the sample into a tank of 
     appropriate size.

 (2) pH should be adjusted to be 1.6-2.0 by adding concentrated HNO(3) 
     (addition of 40 mL conc. HNO(3) for 20 L seawater sample makes pH of 
     seawater sample about 1.6).

 (3) Add CsCl of 0.26 g to form an insoluble compound, and stir at a rate of 
     25 L per minute for several minutes.

 (4) Weigh AMP of 4 g and pour it into a tank to disperse the AMP with 
     seawater.

 (5) 1 hour stirring at the rate of 25 L air per minute.

 (6) Settle until the supernate becomes clear. A settling time is usually 6 
     hours to overnight, but no longer than 24 hours.

 (7) Take an aliquot of 50 mL supernate to calculate the amount of the 
     residual caesium in the supernate.

 (8) Loosen the AMP(Cs) compound from the bottom of the tank and transfer 
     into a 1-2 L beaker, if it is necessary do an additional step of 
     decantation.

 (9) Collect the AMP/Cs compound onto 5 B filter by filtration and wash the 
     compound with 1 M HNO(3)

(10) Dry up the AMP(Cs) compound for several days in room temperature

(11) Weigh the AMP(Cs) compound and determine weight yield

(12) Transfer the AMP(Cs) compound into a teflon tube of 4 mL volume and 
     analyze in a γ-ray spectrometer.

^(137)Cs measurements were carried out by γ-spectrometry using well-type Ge 
detectors coupled with multichannel pulse height analyzers. The performance 
of the well-type Ge detectors is summarized in Table 3.11.5. The detector 
energy calibration was done using IPL mixed γ-ray sources, while the geometry 
calibration was done using an internal reference material of similar density, 
placed in the same sample tube.


TABLE 3.11.5. The performance of HPGe coaxial well-type detectors (Hirose et 
              al., 2007).
___________________________________________________________________________


 Institute  Type      Active volume  Absolute efficiency^a  Background^b
                          (cm3)              (%)             (cpm/1keV)
 ---------  --------  -------------  ---------------------  ------------
 MRI        ORTEC 6        280               20.5              0.092
                  7         80               10.8              0.033
                  8        280               16.5              0.109
                  9        600               23.7              0.074

 Ogoya      Canberra       199               14.5              0.0005
            EYRISYS        315               20.0              0.0016
___________________________________________________________________________

a: The absolute efficiencies of HPGE are calculated at 662 keV photo-peak of 
   ^(137)Cs.
b: The background values were calculated as a sum from 660 keV to 664 keV 
   corresponding to 662 keV photo-peak of ^(137)Cs.


For samples collected deeper than 1200 m, an additional treatment using 
Cs2Pt(Cl)(6) precipitate was applied to remove traces of 40K. These samples 
were analyzed for ^(137)Cs in the underground facility at Ogoya.

 (1) the same procedure from step 1) to step 12).

 (2) Dissolve the AMP(Cs) compound by adding alkali solution.

 (3) pH should be adjusted to 8.1 by adding 2 M HCl and adjust the volume of 
     solution to 70-100 mL.

 (4) Perform precipitation of Cs2Pt (Cl)(6) adding chloroplatinic acid 
     (1g/5mL DW) at pH = 8.1 and keep in refrigerator during a half-day.

 (5) Collect the Cs2Pt (Cl)6 precipitate onto a filter by filtration and wash 
     the compound with solution (pH = 8.1).

(10) Dry up the Cs2Pt (Cl)(6) precipitate for several days at room 
     temperature.

(11) Weigh the Cs2Pt (Cl)(6) precipitate and determine weight yield.

(12) Transfer the Cs2Pt (Cl)6 precipitate into a teflon tube of 4 mL volume 
     and analyze by underground γ-spectrometry.


(3) Analytical method of 239+240Pu in seawater at MRI

PRECONCENTRATION OF Pu

Co-precipitation method of Pu with Fe hydroxides was used as a 
preconcentration method. Seawater sample of 60 L was acidified to pH=2 with 
12 M HCl (60 mL). After addition of ferric chloride (0.6 g), a known amount 
of tracer (^(242)Pu) and K(2)S(2)O(5) (30 g), the solution was stirred for 1 
h. In this stage, all Pu species in solution were reduced to Pu(III). 
Coprecipitation of Pu with ferric hydroxide was formed at pH=10 to adding 
dilute NaOH solution (0.5-1 M). The formed ferric oxide precipitation 
contained small amounts of Ca(OH)(2) and Mg(OH)(2).

RADIOCHEMICAL SEPARATION

Precipitates (Fe, Mg, Ca hydroxides) were dissolved with 12 M HCl and added 
to bring the acid strength to 9 M (three times of the dissolved materials). 
One drop of 30% H(2)O(2) was added for each 10 mL solution, and the solution 
was heated just below boiling for 1 h. After the solution had cooled, Pu was 
isolated by anion exchange techniques (Dowex 1-X2 resin, 100 mesh; a large 
column (15 mm of diameter and 250 mm long) was used.) The sample solution 
passed through the column and was washed with 50 ml 9 M HCl. In this stage, 
Pu, Fe and U were retained onto resin, whereas Am and Th were in effluents. 
Fe and U fractions were sequentially eluted with 8 M HNO(3). After elution of 
U, the column was washed with 5 ml 1.2 M HCl. Finally Pu fraction was eluted 
with 1.2 M HCl (100 ml) containing 2 ml of 30% H2O2. The solution was dried 
onto hot plate. The chemical yield was around 70 %.

ELECTRODEPOSITION

Pu samples for α-spectrometry were electroplated onto stainless steel disks. 
The diameter of stainless steel disk depends on the active surface area of 
detectors. The electrodeposition was performed using an electrolysis 
apparatus with electrodeposition cell consisting of teflon cylinder, a 
cathode of platinum electrode and an anode of stainless steel disk.

The purified Pu fraction was dissolved in 1 mL of 2 M HCl and transferred 
into an electrodeposition cell using 20 mL ethanol. Pu was then electroplated 
onto a stainless steel disk (30 mm in diameter) at 15 V and 250 mA for 2 
hours.

α-spectrometry

The α-spectrometers consist of several vacuum chambers with solid-state 
detectors, a pulse height analyzer and a computer system. The detector, which 
is silicone surface barrier type (PIPS, energy resolution: <25 keV(FWHM), 
counting efficiency: 15-25%), has an active surface area of 450-600 mm^2 and 
a minimum depletion thickness of 100 µm. The vacuum in the chamber is less 
than 100 mTorr by using a vacuum pump. The counting time was more than 800000 
s. Counting uncertainties (1σ) for BEAGLE samples were 10-20%.


3.11.3. Analyses at Marine Environmental Laboratories (IAEA-MEL) in Monaco,
        Comenius University of Bratislava in Slovakia, and Risoe National 
        Laboratory (RNL) in Denmark
        J. A. Sanchez-Cabeza (IAEA-MEL), P. P. Povinec (Comenius Univ. of 
        Bratislava), P. Ross (RNL), J. Gastaud (IAEA-MEL), M. Eriksson (IAEA-
        MEL), I. Levy-Palomo (IAEA-MEL), S. Rezzoug (IAEAMEL), and I. Sykora 
        (Comenius Univ. of Bratislava)


(1) Personnel

J. A. Sanchez-Cabeza: International Atomic Energy Agency, Marine 
                      Environmental Laboratories (IAEA-MEL)
P. P. Povinec:        Comenius University of Bratislava
P. Ross:              Risoe National Laboratory (RNL)
J. Gastaud:           IAEA-MEL
M. Eriksson:          IAEA-MEL
I. Levy-Palomo:       IAEA-MEL
S. Rezzoug:           IAEA-MEL
I. Sykora:            Comenius University of Bratislava


(2) Introduction

IAEA-MEL performed the radiochemical separation of samples from the Atlantic 
and Indian Oceans. The seawater samples were filtered (0.45 µm) and acidified 
on board RV Mirai and sent to Monaco. In average, the volumes received were 
80 L for surface and 20 L for deeper samples. For all samples, plutonium and 
caesium were analyzed. Strontium was analyzed all surface samples and 4 
profiles. Therefore, 3 separation processes were sequentially performed based 
on co-precipitation techniques. Also, selected samples were analyzed for 
tritium.


(3) Sample preparation

When transferring the acidified filtered sea water samples to the 
precipitation containers, sample volume and weight were determined. After 
adjusting pH to 1, plutonium tracer (242Pu: 1,022 dpm per sample) and 
carriers (caesium: 40 to 800 mg, depending on sample volume; strontium: 1 g) 
were added.

PRE-CONCENTRATION OF PLUTONIUM WITH MANGANESE DIOXIDE

After mixing of the tracer and the carriers to equilibrium, saturated KMnO(4) 
(0.5 mL per liter of sample) was added to the samples and stirred. To 
precipitate MnO(2), 0.5 M MnCl(2) (1 mL per liter of sample) was added to the
sample and pH was increased to 9 with 10M NaOH. After precipitation and 
stirring, the pH was readjusted to 8.

The precipitate was allowed to settle overnight. The supernatant was 
carefully siphoned and transferred to another container for the caesium 
separation. The MnO(2) (Pu) precipitate was poured into a beaker for further
chemical separation.

PRE-CONCENTRATION OF CAESIUM WITH AMMONIUM MOLYBDOPHOSPHATE (AMP)

The supernatant solution was re-acidified to pH 1.5 - 2 with concentrated HCl 
(1 to 1.5 mL per liter of sample). Addition of a few ml of 30% H(2)O(2) was 
needed to dissolve a small amount of MnO(2) suspension carried over from the 
previous step. A slurry of AMP (0.2 g per liter of sample) in water was added 
and the suspension stirred for 30 minutes. The AMP was let to settle in the 
tank. For the subsequent precipitation of Ca(Sr) oxalate, the samples were 
transferred to another container. The AMP(Cs) precipitate was poured into a 
beaker for further chemical processing.

PRE-CONCENTRATION OF STRONTIUM WITH CALCIUM OXALATE

The strontium is co-precipitated with calcium as an insoluble oxalate from 
solution containing excess oxalic acid and adjusted to pH 5 - 6. As the Sr 
chemical recovery is estimated by X-Ray fluorescence, an aliquot of the 
seawater was collected kept before the Ca(Sr) precipitation. The mixed Ca(Sr) 
oxalate precipitation was carried out by adding an appropriate quantity of 
oxalic acid dissolved in very hot de-ionized water (10g per liter of sample) 
to the AMP(Cs) supernatant solution, mixing well and adjusting to a final pH 
5 - 6 with 10M NaOH. The Ca(Sr) oxalate precipitate was let to settle 
overnight. Afterwards, the supernate was pumped out. The Ca(Sr) mixed oxalate 
precipitate was recovered from the tank bottom and transferred into a beaker 
for further separation.

The schematic diagram of pre-concentration of radionuclides in seawater is 
shown in Figure 3.11.2.


FIGURE 3.11.2. Pre-concentration of radionuclides in sea water.


(4) Plutonium analysis

DISSOLUTION OF MANGANESE DIOXIDE

After the precipitate settled in the beaker, the supernatant was siphoned 
out. The solution containing the MnO(2) precipitate was acidified to pH 1 and 
a solution of hydroxylammonium hydrochloride (NH(2)OH•HCl, 0.1 g/ml) was 
added in small portions to the hot suspension until all of the manganese 
dioxide had dissolved by reduction from Mn(IV) dioxide to soluble Mn(II).

OXIDATION STATE ADJUSTMENT OF PLUTONIUM 

Fifty milligrams of Fe(III) were added. A few mL of NH(2)OH•HCl solution were 
added and the manganese-iron-Pu solution was heated to reduce Fe(III) to 
Fe(II). The Fe(II) rapidly reduced all soluble Pu species to Pu(III). After 
the reduction to Fe(II) and Pu(III), 2 g of NaNO(2) dissolved in 20 mL of 
water was added to the hot solution in order to oxidize the excess 
NH(2)OH•HCl and to convert Fe(II) and Pu(III) to Fe(III) and Pu(IV), 
respectively.

IRON HYDROXIDE PRECIPITATION

NH(4)OH was added to the hot solution to make the pH 8 - 9, causing 
precipitation of Fe(OH)(3) and coprecipitation of Pu(IV). The freshly 
precipitated iron hydroxide was flocculated by heating. After heating, the pH 
of the suspension was adjusted to 6 - 7 with HCl. At this pH, manganese will 
stay in solution but the flocculated iron hydroxide and its co-precipitated 
Pu(IV) remain insoluble.

The iron hydroxide (Pu) was left to settle overnight. The Fe(OH)(3) (Pu) was 
separated from the supernatant solution by siphoning and the precipitate was 
separated by centrifugation of the suspension left in the precipitating 
vessel. Hot, concentrated HCl was used to dissolve the separated iron 
hydroxide, including that on the wall of the precipitating beaker. 
Concentrated nitric acid additions and evaporations were used to convert
this to a nitrate salt residue. (Figure 3.11.3)


FIGURE 3.11.3. Dissolution and treatment of MnO(2)•xH(2)O (Pu) concentrate.


PREPARATINS FOR Pu SEPARATION BY ANION EXCHANGE

The Fe(Pu) precipitate was dissolved in 1 M HNO(3) and after adding 
hydrazinium hydrate (1 to 2 mL). The solution was heated to facilitate the 
reduction of Fe(III) to Fe(II). Successful conversion of the iron to the 
ferrous state ensures that the dissolved Pu species are brought to their 
lower oxidation states of III and IV. Excess N(2)H(4)•H(2)O was destroyed by 
adding 70% HNO(3) and heating the solution strongly. At this stage, Pu was in 
the Pu(IV) oxidation state, but this was further assured by adding NaNO(2) to 
the cooled solution and boiled. Finally, the solution was adjusted to 7 - 8 M 
HNO(3) with 70% HNO(3).

PLUTONIUM SEPARATION BY COLUMN CHROMATOGRAPHY

The anion exchange resin used was analytical grade AG 1-X8, 100 - 200 mesh 
bead size, supplied in the chloride form from Bio-Rad. A water slurry of the 
resin (10 mL) was loaded into a 30 cm glass column (1 cm inner diameter). The 
resin was conditioned from chloride to nitrate form by passing 8 M HNO(3) (50 
mL) through the resin bed.

The sample solution (7 - 8 M HNO(3)) from the previous step and the rinse 
solution of the beaker were loaded into the column reservoir. This was 
followed by 50 ml of 8 M HNO(3) "wash" to rinse the feed solution thoroughly 
out of the column (removing non-retained species such as Am, Fe, Al, Ca, K). 
After this wash, 100 mL of 10 M HCl were passed through the column to elute 
thorium. The plutonium was eluted with freshly prepared 0.1 M NH(4)I-9M HCl. 
The so-called "Pu strip" was collected in a beaker. This solution was 
evaporated down. Iodine was removed as volatile iodine (I(2)) vapour by 
repeated additions of concentrated HNO(3) with small portions of 30% 
H(2)O(2). (Figure 3.11.4)


FIGURE 3.11.4. Separation of Plutonium by oxidation state adjustment and 
               anion exchange chromatography.


NEODYNIUM FLUORIDE PRECIPITATE

Considering that Pu was to be measured by ICP-MS, it is important to 
efficiently remove the uranium with NdF3 precipitations. The solution residue 
(Pu) was dissolved in 1 M HNO(3) and transferred to a centrifuge tube with 
the rinsing solution of the beaker. 10 mg of Nd (from a neodymium oxide 
solution) was added and a sequence of reduction-oxidation of the Pu was done 
by adding Mohr's salts followed by 25% NaNO(2) solution. The Pu was co-
precipitated as NdF(3) by adding concentrated HF (5 ml). This precipitate was 
centrifuged to remove the supernatant. The dissolution of the precipitate was 
done with 4 M HNO(3)-H(3)BO(3) (10mg/ml). A second precipitation was carried 
out in the same conditions. Finally, after dissolution, the precipitate was 
conditioned in 3 M HNO(3). (Figure 3.11.5)


FIGURE 3.11.5. Separation of Plutonium by NdF(3) precipitation.


PLUTONIUM SEPARATION BY EICHROM-TEVA COLUMN

The purpose is to separate thorium traces in the solution. The pre-packed 
TEVA column (2 mL) was conditioned in 3 M HNO(3) and the solution was passed 
through it. The rinsing and following cleaning steps were processed with 
Ultra-Pure (UP) acids. First, thorium was eluted with 10 M HCL UP. Then Pu 
was eluted with a 0.1 M HCl-0.1 M HF UP solution in a Teflon beaker. (Figure 
3.11.6)

PREPARATION OF SAMPLES FOR ICP-MS MEASUREMENTS

The final solution was evaporated to dryness, treated a few times with 
concentrated HNO(3) UP and dried. The residue was diluted and the walls of 
the beaker were rinsed with 1 M HNO(3) UP. The 3 successively small volumes 
(0.5mL, 0.5 mL and 0.25 mL) used were transferred to closed plastic tubes for 
further analysis by ICP-MS.


FIGURE 3.11.6. Plutonium separation by Eichrom-TEVA column and preparation 
               for ICP-MS analysis.

ICP-MS ANALYSIS

Samples were analyzed using a high resolution ICP-MS at Risoe National 
Laboratory. An ultrasonic nebuliser was used for introduction of samples into 
the spectrometer. The settings of the system were as follow:

  Xs- cones with Cetac USN 5000+. Heater 140°C, cooler 3°C
  Extraction voltage             -694 V
  Lens 1                         -1019 V
  Lens 2                         -69 V
  Auxiliary gas                   0.70 lpm
  Nebuliser gas                   0.92 lpm
  RF power                        1405 W
  Hexapole bias                  -2 V
  Sample uptake rate:             0.5 ml/min
  Sensitivity 238U:               4.5 MHz/ppb
  Number of points per peak:      1
  Dwell time:                     50 ms (239&240Pu), 1ms (238U), 2ms (242Pu)
  Number of sweeps:               250
  Repetitions per sample:         20
 
Reagent blanks and reference materials were analyzed together with the 
seawater samples. An example of the mass spectrum obtained is shown in Figure 
3.11.7.


FIGURE 3.11.7. mass spectrum of plutonium solutions.


(5) Caesium analysis

AMP(Cs) was transferred into a beaker, decanted and the supernatant was 
siphoned. The AMP(Cs) was finally centrifuged. The separated AMP was 
dissolved in a minimum amount of 10 M NaOH. As some fine particle suspension 
of MnO(2) was carried over in the supernatant solution from the first pre-
concentration step(MnO(2) precipitation for Pu) and subsequently scavenged by 
the AMP, the insoluble fraction was separated by centrifugation. The AMP(Cs) 
solution in NaOH was transferred to a beaker, heated and boiled to drive off 
ammonia in order to minimize precipitation of AMP when the solution is re-
acidified.

The boiled Cs-AMP-NaOH solution was cooled and diluted to about 500 mL with 
water. Concentrated HCl was added to adjust the solution to pH 2. Then, 1 g 
of fresh AMP was added and stirred to collect the Cs (2nd AMP-Cs 
precipitation). After settling and decantation, the 2nd AMP-Cs was separated 
by centrifugation and washed. It was again dissolved in a minimum amount of 
10 M NaOH, and any eventual insoluble fraction was discarded by 
centrifugation. The solution was introduce into a standard geometry for 
gamma-ray counting. (Figure 3.11.8)

The recovery of this process was finally estimated by AAS from a small 
aliquot of the final solution.


FIGURE 3.11.8. Caesium separation for gamma-spectrometry.


GAMMA-SPECTROMETRY AT IAEA-MEL

The AMP(Cs) samples were analyzed with high-purity well-type germanium 
detectors in the underground laboratory at IAEA-MEL. Ultra-low background is 
achieved by using very old lead and an anticosmic shield(Figure 3.11.9, 
Povinec et al., 2005). The detectors used had relative efficiencies ranging 
from 100 to 200%, and 40K background count rates ranging from 1-5 10-4 s-1. A 
typical spectrum from a sample taken at 1000 m water depth is shown in Figure 
3.11.10.


FIGURE 3.11.9.  Schematic diagram of the IAEA-MEL underground (CAVE) facility 
                (Povinec et al., 2005).
FIGURE 3.11.10. Gamma-ray spectrum of a sweater sample collected at 1000 m 
                water depth in the Atlantic Ocean.


^(137)Cs GAMMA-RAY SPECTROMETRY OF SEAWATER SAMPLES FROM THE INDIAN OCEAN 
CARRIED OUT AT THE COMENIUS UNIVERSITY OF BRATISLAVA, SLOVAKIA

Indian Ocean seawater samples prepared in IAEA-MEL as AMP(Cs) samples were 
analyzed in the Comenius University of Bratislava, Slovakia. Two shields for 
low background gamma-ray spectrometers located at about 10 m of water 
equivalent were built in the Department of Nuclear Physics of the Comenius 
University of Bratislava, Slovakia (Figure 3.11.11; Sykora et al., 1992; 
Sykora et al. 2006). The larger one has the outer dimensions of 2X1.5X1.5 m. 
It is composed of the following layers (from the outside to the inside): 10 
cm of lead, 10 cm of electrolytic cooper, 10 cm of polyethylene with boric 
acid, 0.1 cm of electrolytic cooper, 0.1 cm of cadmium and 1cm of perspex. On 
the top, a layer of 12 cm of iron is added. The inner dimensions of the 
shield are 80X90X172 cm. To further reduce the detector background, and to 
decrease the radon contribution and stabilize its content in the shield (by 
flushing the detector chamber with nitrogen evaporated from a cooling Dewar), 
an extra copper shield (12X20X30 cm) has been inserted inside the large 
shield (Figure 3.11.11).


FIGURE 3.11.11. Small (left) and large (centre and right) shields for low-
                level gamma-ray spectrometry constructed in the Department of 
                Nuclear Physics of the Comenius University of Bratislava, 
                Slovakia.
FIGURE 3.11.12. Schematic diagram of electronic circuits of the coincidence-
                anticoincidence spectrometer.


The copper has been used because of its low radioactive contamination by 
uranium and thorium and their decay products. A HPGe coaxial detector 
produced by PGT (USA) with 70% relative efficiency (for 1332.5 keV and 
relative to 75X75 mm NaI(Tl) crystal) and of 270 cm^3 sensitive volume 
operates in this shield. The smaller shield (Figure 3.11.11) has a similar 
composition of layers to the large shield, however, its inner dimensions are
38X38X62 cm only.


FIGURE 3.11.13. Comparison of background and sample counting rates in the old 
                and in the additional Cu shield under the 661.6 keV peak of 
                137Cs.


A HPGe coaxial detector of 50% relative efficiency produced by Canberra 
(USA), or a HPGe detector of 6% relative efficiency with Be window produced 
by ORTEC (USA), operates in this shield. A block scheme of electronics used 
for coincidence-anticoincidence measurements, anti-Compton (with NaI(Tl) well 
detector) and/or with anti-cosmic shielding (with plastic scintillation 
detector) is shown in Figure 3.11.12. A background reduction in the ^(137)Cs 
window after introduction of the additional copper shield into the large 
shield is shown in Figure 3.11.13.

Typical applications have included non-destructive analysis of natural and 
anthropogenic radionuclides (mainly cosmogenic ^(7)Be, radiogenic ^(210)Pb 
and anthropogenic ^(137)Cs) in marine and terrestrial samples.


(6) Strontium analysis

STRONTIUM PURIFICATION

The calcium oxalate suspension was allowed to settle after transferring into 
a large beaker. The supernatant solution was siphoned off and the precipitate 
was centrifuged. It was then dried and ashed at 600°C to convert the oxalate 
to carbonate. The ashed sample was weighed to determine the amount of 70% 
HNO(3) to be added. A volume of 70% HNO(3) in mL equal to seven times the ash 
weight in grams was slowly added to the calciumstrontium carbonate ash in an 
appropriate beaker. Strontium nitrate (1st) precipitates from this medium 
while the calcium remains in solution. Barium, radium and lead are expected 
to accompany the strontium nitrate.

The 1st strontium nitrate precipitate was separated from the mother solution 
containing the dissolved calcium-strontium ash by decanting the supernatant 
solution after settling. Heating the strontium nitrate suspension for some 
hours before allowing it to settle improves the separation by producing a 
Sr(NO(3))(2) precipitate of larger crystal size. This 1st Sr(NO(3))(2) 
precipitate was transferred to a pre-weighed 150 ml beaker, then washed with 
three 30 - 50 mL portions of acetone to remove HNO3 and more soluble calcium 
nitrate. The washed Sr(NO(3))(2) was dried under a heat lamp and weighed. A 
volume of water in ml equal to 1.5 times the weight of dried precipitate in 
grams was added. This precipitate of Sr(NO(3))(2) will easily dissolve to 
give a clear solution.

After the salt was dissolved, a second Sr(NO(3))(2) precipitate was obtained 
by adding a volume of 70% HNO(3) equal to ten times the volume of water used 
to dissolve the salt. This 2nd Sr(NO(3))(2) was separated by decantation of 
the supernatant liquid and washed again with small portions of acetone. After 
drying and weighing, the dissolution, concentrated nitric acid addition and 
acetone washings steps were repeated to give a 3rd Sr(NO(3))(2) precipitate.

Further purification of the Sr from barium, radium and lead contaminants was 
performed by a Ba chromate precipitation from an acetate-buffered solution at 
pH 5. A final clean-up of the Sr from ingrown Y-90 and some other possible 
beta-emitting radionuclides (e.g., Bi-210) was made by an iron hydroxide 
scavenge using 10 - 50 mg of Fe(III) and concentrated ammonia to pH 9. The 
iron hydroxide precipitate was centrifuged off and the Sr-acetate-chromate 
solution was acidified with concentrated HCl to pH 1. The purified Sr 
fraction was diluted with 0.1 M HCl. The chemical recovery of the Sr was 
determined by X-Ray fluorescence on a sample aliquot.

MILKING OF ^(90)Y FROM THE PURIFIED STRONTIUM FRACTION

This step consists in the separation of the produced ^(90)Y from the ^(90)Sr 
contained in the solution. For that reason, an ingrowth period of 2 - 3 weeks 
was allowed before separation of the ^(90)Y. Then, the Sr solution was 
transferred to a beaker. An accurately known amount of yttrium carrier (10 
mg) was added and the solution was evaporated down to 20 ml. The solution was 
transferred to a centrifuge tube, 1 g of NH(4)Cl was dissolved in it and 
concentrated NH(4)OH was added to pH 9 to precipitate yttrium hydroxide. The 
supernatant solution was decanted away from the Y hydroxide precipitate. The 
time at which the decantation occurred was noted as the Y-Sr separation time.

After the Y hydroxide dissolution with concentrated HCl, the solution was 
diluted to 25 mL, and 1 g of NH(4)Cl was dissolved in it. Ten mg of stable Sr 
holdback carrier were added and a second mixed Y hydroxide was precipitated 
with NH(4)OH. The flocculated precipitate was centrifuged and the supernatant 
solution was decanted. This 2nd Y hydroxide was dissolved in concentrated 
HCl, diluted and filtered through a membrane filter to remove any insoluble 
material.

To the Y solution, 0.5 g of oxalic acid was added, the solution was heated 
and a white yttrium oxalate was precipitated by the addition of NH(4)OH to pH 
1.5 - 2. This preliminary yttrium oxalate is separated from the solution by 
filtration through a membrane filter. Then it was dissolved by treatment with 
concentrated HCl and passed through the filter with rinses into a 100 ml 
beaker. The final yttrium oxalate precipitate was obtained from 40 - 50 mL of 
hot solution by dissolving 0.1 g of oxalic acid and adding concentrated 
ammonia until pH 1.5 - 2.

The yttrium oxalate was digested for about 30 minutes to obtain a crystalline 
form. Then it was filtered onto a pre-washed, pre-weighed 0.2 μm polysulfone 
membrane filter (22 mm diameter, Gellman Sciences, Inc.). Theyttrium oxalate 
was washed with 0.5% ammonium oxalate solution and 80% ethanol.

The final filtered yttrium oxalate was dried in a 70°C oven for ca. 30 
minutes and weighed to determine the yttrium chemical recovery from the 
stable weighing form of Y(2)(C(2)O(4))(3) . 9 H2O (10 mg of Y gives 34 mg of 
yttrium oxalate). Then, the yttrium oxalate-loaded filter was mounted to fit 
in a Risoe GM-25-5 Beta Multicounter System (Riso National Laboratory, 
Roskilde, Denmark), a gas-flow proportional counter with anti-coincidence 
background reduction. Counting generally starts 6 to 8 hours after the Y-Sr 
separation time. The measured betaactivity decay curve must be consistent 
with the known 64 hour half-life of ^(90)Y which indicates the high 
radiochemical purity of the yttrium sources.


(7) Tritium analysis

One liter seawater samples were collected in plastic bottles, tightly sealed 
and transferred to MEL for storage before analysis. Samples were then sent to 
Dr. Jurgen Sültenfuß, , University of Bremen, for analysis in the Bremen Mass 
Spectrometric Facility for tritium analysis using the He-3 ingrowth method 
(Figure 3.11.14, Sültenfuß et al., 2005). For ingrowth of tritiugenic ^(3)He 
in the laboratory, typically 500 mL are sucked into an evacuated 1-L soda-
glass bulb. The contained helium is removed (to < 10-6 of solubility 
equilibrium concentration) by flushing the head space with water vapour under 
heavy shaking for 30 min, where after the bulb is flame sealed. The shaking 
ensures timely escape of dissolved helium into the head space. The 
flushing(50 mL/s) is enforced by pumping through a capillary connection that 
regulates the flow, and, together with a narrowing in the bulb's head tubing, 
prevents any diffusion back into the bulb; the resulting water loss amounts 
to about 2 g, so that isotopic tritium fractionation remains negligible. 
Beforehand, the bulb's walls are made helium-free by heating the bulb in 
vacuo to 400°C for 24 hours. After typically a six-month storage, enough 
tritiugenic ^(3)He has been generated to obtain a tritium detection limit of 
10 mTU. Any ^(3)He other than tritiugenic is corrected for using a concurrent 
measurement of ^(4)He (the ^(3)He/^(4)He ratio is approximately the 
atmospheric one). That correction is a prerequisite for precise measurement 
of the minute amounts of tritiugenic ^(3)He produced.


FIGURE 3.11.14. Scheme of the mass spectrometry system used for tritium 
                analysis (Sültenfuß et al., 2005).


3.11.4. Analyses at Korean Institute of Nuclear Safety (KINS) in South Korea
        C. S. Kim (KINS)


(1) Personnel

C. S. Kim: Korean Institute of Nuclear Safety (KINS)


(2) Sample preparation

IRON HYDROXIDE PRECIPITATION

Weight of the acidified and filtered seawater was determined and poured into 
the seawater treatment cistern, and then 30 mg of Fe^(3+) carrier added. 
After stirring for 1 hour, Pu was co-precipitated with Fe(OH)(3) by addition 
of NH(4)OH up to pH 8-9. Fe(OH)(3) precipitate was collected with 5 L beaker 
and then heated until boiling on a hot plate. With heating, the pH of 
suspension was re-adjusted to pH 8 with HCl. After cooling, supernatant was 
discarded by decantation and the Fe(OH)3 was recovered on a glass fiber 
filter by suction filtration, and then the precipitate was dissolved with 
conc. HCl. The dissolved solution was dried on a hot plate and then dissolved
with 12 mL 5 M HNO(3). The solution was filtered with a membrane filter (0.45 
μm) and then the oxidation state of Pu was adjusted according to next 
procedure prior to loading to an on-line automated separation system.


FIGURE 3.11.15. Pre-treatment of seawater for Pu chemical purification.


ADJUSTMENT OF OXIDATION STATE OF PLUTONIUM

The oxidation state of Pu in the loading solution was kept to +4 oxidation 
state by dissolving with 5 M HNO(3) and extra high oxidation state (VI) was 
reduced to (IV) by the treatment of ascorbic acid. The loading solution was 
treated with ascorbic acid for at least 20 minutes before loading to on-line 
separation system.


(3) Chemical purification

PLUTONIUM PURIFICATION BY ON-LINE SEPARATION

Chemical separation was carried out by on-line automated purification system 
as shown schematically in Figure 3.11.15, which is developed by Kim et al. 
(2002). The on-line automated purification process consist of 10 purification 
steps including the sample loading, rinsing and elution, which is described 
in Table 3.11.6. The 5 M HNO(3), 1 M HNO(3) and 9 M HCl solutions were used 
to remove U, Th and bulk matrix elements in sample solution, which were 
injected into TEVA-Spec resin by two peristaltic tubing pumps. Separation 
column (3 mm i.d. X 25 mm long) of borosilicate column (Omnifit, Cambridge, 
England) packed with TEVA resin (Eichrom Industries, Inc., Darien, IL, USA) 
was installed in the on-line purification system.

To minimize the interference effect of ^(238)U on 239 m/z, the 1st purified 
Pu fraction was treated once more by the 2nd on-line purification procedure. 
The 2nd separation is the same as that of the 1st separation process. To 
adjust matrix and oxidation state of Pu, 3 mg of Fe^(3+) carrier, 1.2 mL 10 M 
HNO(3), 10 mg of ascorbic acid and 2.6 mL 5 M HNO(3) were sequentially added 
to the 1st Pu fraction. Approximately 5 mL 5 M HNO(3) was injected into the 
2nd on-line purification system.


FIGURE 3.11.16. Schematic diagram of the on-line separation system for Pu 
                isotopes. P1 and P2, peristaltic pump; SS1 and SS2, six-fort 
                solvent selector; TW, two-way valve; SV1 ~ SV4, isolation 
                valve. The circled numbers indicate the procedure order, as 
                described in Table 3.11.6.


TABLE 3.11.6. Description of sequential separation steps in on-line automated 
              purification for Pu.
____________________________________________________________________________________________


                    two-way  two-way   Flow rate/
 Step   Pumped       6 port  6 port     ml min^-1    SV1     SV2     SV3      SV4    Time/s
        medium      valve 1  valve 2  Pump1  Pump2
 ---- ------------  -------  -------  -----  -----  ------  ------  ------   ------  ------
   1  0.5 M HCl        2        1      0.0   0.83     -       -      -       Bottom   40
   2  1.4 M HF         2        1      0.0   0.83     -       -      -       Top      90
   3  5.0 M HNO(3)     1        2      1.6   0.00     -       -      -       Bottom   50
   4  5.0 M HNO(3)     1        2      1.6   0.00   Bottom    -     Top        -     240
   5  5.0 M HNO(3)     1        1      1.6   0.00   Top       -     Top        -     700
   6  5.0 M HNO(3)     1        2      1.6   0.00   Bottom    -     Top        -     240
   7  9.0 M HCl        2        1      0.0   0.83     -     Bottom  Bottom     -     100
   8  1.0 M HNO(3)     1        1      1.6   0.00     -     Top     Bottom     -     160
   9  0.5 M HCl        2        1      0.0   0.83     -       -       -      Bottom    6
  10  0.5 M HCl        2        2      0.0   0.83     -       -       -      Bottom   75
 ------------------------------------------------------------------------------------------

                                Description of step
 ------------------------------------------------------------------------------------------
   1  0.5 M HCl is pumped through resin to rinse residual elements.
   2  1.4 M HF is pumped through resin to rinse residual elements.
   3  0.5 M HCl is pumped through resin to fill the eluent line and exchange HF solution
   4  5.0 M HNO(3) is pumped through column to pre-treat resin at 1.6 ml min^-1.
   5  Sample is loaded to TEVA-Spec at 1.6 ml min-1.
   6  5.0 M HNO(3) is pumped to rinse residual sample and interference materials.
   7  9.0 M HCl is pumped through resin to clean Th in resin.
   8  1.0 M HNO(3) is pumped to rinse residual U.
   9  0.5 M HCl is pumped through TEVA-Spec to elute Np at 0.83 ml min^-1 for 6 seconds 
      until 0.5 M HCl reach the two-way valve.
  10  About 1.1 ml 0.5 M HCl is pumped to elute Np and Pu on TEVA-Spec.
____________________________________________________________________________________________



(4) ICP-MS analysis

Sample was measured by ICP-SF-MS, a PlasmaTrace 2 (Micromass, Manchester, 
UK), under the optimum sensitivity and stability. Approximately 1 mL of final 
Pu fraction was injected into plasma by an Aridus desolvating introduction 
system (Cetac Technologies, Omaha, NE, USA) involving a T1-H microconcentric 
nebulizer. The Pu isotopes (^(239)Pu, ^(240)Pu, ^(242)Pu) and ^(238)U were 
measured three times in peak hopping mode. The details of operation condition 
used for ICP-SFMS and the sample introduction system are described in Table 
3.11.7. To increase integrated count, eluent completely used up and sample 
was measured three runs to get relative standard deviation. Sample blank was 
positioned in the first row before samples and ^(242)Pu standard solutions 
were finally measured to check the chemical recovery. An example of the mass 
spectrum for Pu isotopes and ^(238)U obtained by ICP-SF-MS is shown in Figure 
3.11.17. The concentration of Pu isotopes was calculated base on the isotope 
dilution analysis (IDA) using following equation.


       C ± σ(c) = [(R(s)-R(t)) ± √((σ(R(s))^2 + (σ(R(t))^2)](T/W)

C:     Concentration of ^(239)Pu or ^(240)Pu (pg/g)

R(s):  ([^(239)Pu](s) - [^(239)Pu](b))/([^(242)Pu](s) - [^(242)Pu](b)) or
       ([^(240)Pu](s) - [^(240)Pu](b))/([^(242)Pu](s) - [^(242)Pu](b))

R(t):  ([^(239)Pu](t) - [^(239)Pu](b))/([^(242)Pu](t) - [^(239)Pu](b)) or
       ([^(240)Pu](t) - [^(240)Pu](b))/([^(242)Pu](t) - [^(242)Pu](b))
       s; sample, b; blank sample, t; tracer (^(242)Pu)
       [^(239)Pu], [^(240)Pu], [^(242)Pu] : ^(239)Pu, ^(240)Pu, ^(242)Pu 
       count rate (cps)

T:     Amounts of tracer added (^(242)Pu)(pg)

W:     Sample amounts (g)

σ(c):  ^(239)Pu or ^(240)Pu standard deviation (pg/g)

σ(Rs): [^(239)Pu](s)/[^(242)Pu](s) or [^(240)Pu](s)/[^(242)Pu](s) standard 
       deviation of sample

σ(Rt): [^(239)Pu](t)/[^(242)Pu](t) or [^(240)Pu](t)/[^(242)Pu](t) standard 
       deviation of tracer


TABLE 3.11.7. Operation condition of ICP-SF-MS (PT2).
_________________________________________________________________________________________

                                                     ICP and interface
 RF power, W                                               1350
 Coolant gas flow, L/min                                   14
 Auxiliary gas flow, L/min                                 2.2
 Carrier gas flow, L/min                                   1.1
 Expansion chamber pressure, mbar                          1.6
                                                          Aridus
 Sweeping gas flow. L/min                                  2.4
 Spray chamber temp., °C                                   80
 Membrane desolvator temp., °C                             160
 Sample uptake rate, mL/min                                0.1
 Type of nebulizer                                         T1
                                                     date acquisition
                                 -------------------------------------------------------
 Element                           ^(238)U     ^(239)Pu          ^(240)Pu     ^(242)Pu
 Mass range, amu                 237.8-238.6  238.4-239.6       239.4-240.6  241.4-242.6
 Dwell time, ms                       7           60                120          15
 Width Points                        100         100                100         100
 Peak widths                         1.7         1.6                1.6         1.8
 Sweep no.                                                  3
 Runs                                                       3
 Resolving Power                                           430
 Total analysis time, s/sample       3.57       28.8               57.6         8.1
_________________________________________________________________________________________



FIGURE 3.11.17. Mass spectrum of plutonium isotopes and ^(238)U in deep (600 
                meter) seawater.


3.11.5. Preliminary results of ^(137)Cs and Pu isotopes in the surface layers
        M. Aoyama (MRI), M. Eriksson (IAEA-MEL), J. Gastaud (IAEA-MEL), K. 
        Hirose (MRI, LLRL), Y. Hamajima (LLRL), C. S. Kim (KINS), K. Komura 
        (LLRL), I. Levy-Palomo (IAEA-MEL), P. P. Povinec (Comenius Univ. of 
        Bratislava), S. Rezzoug (IAEA-MEL), P. Ross (RNL), J. A. Sanchez-
        Cabeza (IAEAMEL), and I. Sykora (Comenius Univ. of Bratislava)


(1) Personnel

M. Aoyama:            MRI
M. Eriksson:          IAEA-MEL
J. Gastaud:           IAEA-MEL
K. Hirose:            MRI, LLRL
Y. Hamajima:          LLRL
C. S. Kim:            KINS
K. Komura:            LLRL
I. Levy-Palomo:       IAEA-MEL
P. P. Povinec:        Comenius University of Bratislava
S. Rezzoug:           IAEA-MEL
P. Ross:              RNL
J. A. Sanchez-Cabeza: IAEA-MEL
I. Sukora:            Comenius University of Bratislava


(2) Preliminary results of ^(137)Cs along the BEAGLE lines

^(137)Cs concentrations in surface waters in the mid latitude region of the 
Southern Ocean along P06, A10 and I03/4 lines are shown in Figure 3.11.18. 
Those were in the range from 0.1 to 2.3 Bq m^-3, which is no significant 
difference with that in the North Pacific mid-latitude region (Aoyama et 
al., 2004, 2006; Povinec et al., 2003). Large ^(137)Cs concentration 
gradients, with high values in the North Pacific mid-latitude region, and low 
ones in the South Pacific were observed in the 1970s and 1980s (Bowen et al., 
1980; Hirose and Aoyama, 2003).


FIGURE 3.11.18. ^(137)Cs concentration in the surface layers, surface and 100 
                m depth, along BEAGLE lines in 2003/2004.


The high density ^(137)Cs data revealed a typical longitudinal distribution 
as shown in Fig. 3.11.18, which depends on sea areas. In the Pacific Ocean, 
the ^(137)Cs concentrations in the Tasman Sea, 155 deg. E to 180 deg. E, 
ranged from 1.37 to 1.74 Bq m^-3, showing higher values compared with that in 
the subtropical gyre in the South Pacific. In the Tasman Sea, the ^(137)Cs 
concentrations gradually decreased from west to east, which corresponds from 
upstream and downstream of East Australian Current System (EAC),respectively. 
The surface ^(137)Cs concentration was high in the upstream of EAC and low in 
the downstream of EAC. In the subtropical gyre, there was no longitudinal 
gradient of the surface ^(137)Cs concentrations, which ranged from 0.91 to 
1.53 Bq m^-3, although the surface ^(137)Cs levels varied spatially. In the 
Eastern South Pacific, the ^(137)Cs concentrations, ranged from 0.07 to 1.14 
Bq m^-3, showing lower values than that in the Tasman Sea and subtropical 
gyre.

In the Indian Ocean, the ^(137)Cs concentrations ranged from 1.5 to 2.2 Bq 
m^-3, showing higher values compared with that in the Southern Hemisphere. 
The ^(137)Cs concentrations in the Mozambique Channel ranged from 0.4 to 1.2 
Bq m^-3, showing lower values than those in the Indian Ocean and Tasman Sea.

In the Atlantic Ocean, the ^(137)Cs concentrations ranged from 1.1 to 1.6 Bq 
m^-3, showing similar with that in the subtropical gyre in the Pacific Ocean.


FIGURE 3.11.19. ^(137)Cs section in the surface layers, surface - 1000 m 
                depth, along P6 line.


The ^(137)Cs concentrations in the layers between the surface to 1000 m depth 
are shown in Figure 3.11.19.

As well as the general trend of ^(137)Cs concentration in the surface layers 
(Figure 3.11.18), the ^(137)Cs concentrations in the Tasman Sea was higher 
than 1.5 Bq m^-3 between surface to 200 m depth, showing higher values than 
those in the subtropical gyre and the Eastern South Pacific. The ^(137)Cs 
concentrations in the layers between surface to 200 m depth ranged from 1.0 
to 1.5 Bq m^-3 in the subtropical gyre and it decreased rapidly in the 
Eastern South Pacific. This tendency that ^(137)Cs decreased from west to 
east in general is observed for the depths between the surface to 1000 m 
depth throughout the Pacific sector.


(3) Preliminary results of Pu isotopes along the BEAGLE lines

^(239,240)Pu concentrations in surface water in the mid-latitudes of the 
South Pacific were in the range of 0.5 to 4.1 mBq m^-3. The surface 
^(239,240)Pu in the South Pacific was the same order of magnitude as that in 
the subtropical gyre in the North Pacific (1.5 to 9.2 mBq m^-3) (Hirose et 
al., 2001, 2006; Povinec et al., 2003; Yamada et al., 2006). The observation 
of the current surface ^(239,240)Pu concentrations suggests that there has 
not been a marked inter-hemisphere distribution in the Pacific, although 
rather large spatial variation of surface 239,240Pu concentration has been 
observed.

Close sampling spacing revealed that the surface ^(239,240)Pu concentration 
shows a different longitudinal distribution from that of ^(137)Cs (seen in 
Fig. 3.11.18). The ^(239,240)Pu concentrations in the Tasman Sea, ranged from
1.0 to 2.9 mBq m^-3, showed a similar longitudinal distribution as did 
^(137)Cs. In the subtropical gyre, there was no longitudinal gradient of the 
surface ^(239,240)Pu concentrations, which ranged from 0.8 to 4.1 mBq m^-3, 
although peaks of the higher ^(239,240)Pu concentrations were observed near 
165°W and 135°W. In the Eastern South Pacific, the surface ^(239,240)Pu 
concentrations which ranged from 0.5 to 3.2 mBq m^-3, showed a larger 
variation than that in the Tasman Sea and subtropical gyre. The surface 
^(239,240)Pu concentrations in the mid-latitude region of the South Pacific 
broadly decreased from west to east.


FIGURE 3.11.20. ^(239,240)Pu concentration in the surface layers along P6 
                line.


References

Aoyama, M., K. Hirose, T. Miyao, Y. Igarashi, 2000, Low level ^(137)Cs 
    measurements in deep seawater samples, Appl. Radiat. Isot. 53: 159-162.
Aoyama, M., Hirose, K., Komura, K., & Nemoto, K., 2004. Temporal variation of 
    ^(137)Cs Distribution and Inventory along 165 deg. E in the North Pacific 
    since 1960s to the Present, International Conference on Isotopes in 
    Environmental Studies - Aquatic Forum 2004, BOOK OF EXTENDED SYNOPSES. 
    IAEA-CN-118, 256-257.
Aoyama, M., Fukasawa, M., Hirose, K., Mantoura, R. F. C., Povinec, P. P., 
    Kim, C. S., & Komura, K., 2006. Southern Hemisphere Ocean Tracer Study 
    (SHOTS): An overview and preliminary results, INTERNATIONAL CONFERENCE ON 
    ISOTOPES AND ENVIRONMENTAL STUDIES, Radionuclides in the Environment, 
    Vol.8, Ed., P. P. Povinec and J.A. Sanchez-Cabeza, Elsevier, London, pp 
    53-66.
Bojanowski, R. and D. Knapinska-Skiba, 1990, Determination of low-level Sr-90 
    in environmental materials: a novel approach to the classical method, J. 
    Radioanal. Nuclear Chem., 138: 207-218.
Bowen, V. T., Noshkin, V. E., Livingston. H. D., & Volchok, H. L, 1980. 
    Fallout radionuclides in the Pacific Ocean: Vertical and horizontal 
    distributions, largely from GEOSECS stations. Earth Planet. Sci. Lett., 
    49, 411-434.
Folsom T. R. and C. Sreekumaran, 1966, Some reference methods for determining 
    radioactive and natural cesium for marine studies. In: Reference methods 
    for marine radioactivity studies, Annex IV, IAEA, Vienna.
Hirose, K. , Aoyama, M., Miyao T. & Igarashi Y., 2001. Plutonium in seawaters 
    of the western North Pacific. J. Radioana. Nucl. Chem. Articles 248, 771-
    776.
Hirose, K. , & Aoyama, M., 2003. Analysis of ^(137)Cs and ^(239,24)0Pu 
    concentrations in surface waters of the Pacific Ocean. Deep Sea Res. II, 
    50, 2675-2700.
Hirose, K., M. Aoyama, Y. Igarashi, K. Komura, 2005, Extremely low background 
    measurements of ^(137)Cs in seawater samples using an underground 
    facility (Ogoya), J. Radioanal. Nucl. Chem., 263: 349-353.
Hirose, K., Aoyama, M., Kim, C. S., Kim, C. K., & Povinec, P. P., 2006. 
    Plutonium isotopes in seawater of the North Pacific: effect of close-in 
    fallout. Radionuclides in the Environment, Vol. 8, Ed., P. P. Povinec and 
    J. A. Sanchez-Cabeza, pp.67-82.
Hirose, K., M. Aoyama, Y. Igarashi, K. Komura, 2007, Oceanic ^(137)Cs: 
    Improvement of ^(137)Cs Analysis in Small Volumes Seawater Samples Using 
    The Underground Facility (Ogoya), J. Radioanal. Nucl. Chem. (in press).
Kim, C. S., C. K. Kim, K. J. Lee, 2002, Determination of Pu Isotopes in 
    Seawater by an On-Line Sequential Injection Technique with Sector Field 
    Inductively Coupled Plasma Mass Spectrometry, Anal. Chem. 74(15):3824-
    3832.
Komura, K., Y. Hamajima, 2004, Ogoya Underground Laboratory for the 
    measurement of extremely low levels of environmental radioactivity: 
    Review of recent projects carried out at OUL, Appl. Radiat. Isot. 61: 
    164-189.
La Rosa, J. J., W. Burnett, S-H. Lee, I. Levy, J. Gastaud, P. P. Povinec, 
    2001, Separation of actinides, cesium and strontium from marine samples 
    using extraction chromatography and sorbents. J. Radioanal. Nucl. Chem. 
    248: 765-770.
Povinec, P. P., Livingston, H. D., Shima, S., Aoyama, M. Gastaud, J., 
    Goroncy, I., Hirose, K., Hynh-Ngoc, L., Ikeuchi, Y., Ito, T., LaRosa, J., 
    Kwong, L. L. W., Lee, S.-H., Moriya, H., Mulsow, S., Oregioni, B., 
    Pettersson H. & Togawa, T. 2003. IAEA '97 expedition to the NW Pacific 
    Ocean-results of oceanographic and radionuclide investigations of the 
    water column. Deep-Sea Res. Part II, 50, 2607-2637.
Povinec, P. P., J-F. Commanducci, I. Levy-Palomo, 2005, IAEA-MEL's 
    underground counting laboratory (CAVE) for the analysis of radionuclides 
    in the environment at very low-levels. J. Radioanal. Nucl. Chem., 
    263/2:441-445.
Sültenfuß, J., W. Roether, M. Rhein, 2005, The Bremen Mass Spectrometric 
    Facility for the Measurement of Helium Isotopes, Neon, and Tritium in 
    Water, IAEA-CN-119/7.
Sykora, I., Durcik M., Stanicek J., Povinec P., 1992, Radon problem in low-
    level gamma-ray spectrometry. In: Rare Nuclear Processes (Ed.P. Povinec), 
    World Sci., Singapore, p. 321-326.
Sykora, I., M. R. Jeskovsky, R. Janik, K. Holy´, M. Chudy´, P. P. Povinec, 
    2006, Low-level single and coincidence gamma-ray spectrometry. J. 
    Radioanal. Nucl. Chem. (in press).
Van R. Smit, J., W. Robb, J. J. Jacobs, 1959, AMP-Effective ion exchanger for 
    treating fission waste. Nucleonics 17, 116-123.
Yamada, M., Zheng, J., & Wang, Z.-L., 2006. ^(137)Cs, ^(239+240)Pu and 
    ^(240)Pu/^(239)Pu atom ratios in the surface waters of the western North 
    Pacific Ocean, eastern Indian Ocean and their adjacent seas. Sci. Total 
    Environ., 366, 242-252.



4. ERRATA AND UPDATED DATA OF THE DATA BOOKS VOLUME 1 AND 2

4.1. ERRATA IN THE DOCUMENTS

Coefficients of Note 2 in Figure caption of Volume 2 (p. 91) should be 
corrected as follows.

          a(0)=6.4409, b(0)=-3.9577e-4, a(t)=4.3830, b(t)=6.3317e-4


4.2. MISTAKES IN THE FIGURES

In Figures 14, 15 and 16 in Volume 2 (vertical sections for dissolved 
inorganic carbon, total alkalinity and pH), data with quality flags of 6 
(mean of replicate measurements) were not included.


4.3. UPDATES IN THE DATA FILES

(1) FLUOR in the CTD data

Flags for FLUOR in the CTD exchange format files were wrong (flags for CTDOXV 
were set by mistake) and corrected.

(2) pH

Reporting precision for pH increased from F7.3 to F7.4 (FORTRAN format).

(3) Total alkalinity and dissolved inorganic carbon

Following flags and a value for carbon related parameters were revised.

_____________________________________________________________________

 EXPOCODE     STNNBR  CASTNO  SAMPNO  PARAMETER:          Change
 -----------  ------  ------  ------  -------------- ---------------
 49MR03K04_1  172     1        4      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_1  172     1        1      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_1  X15     1        6      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_1  150     1       16      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_1  137     1        1      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_2   95     1        1      ALKALI:        2291.3 -> 2381.2
 49MR03K04_2   59     1       33      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_2   59     1       14      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_2   47     1       27      ALKALI_FLAG_W:    2   ->    4
 49MR03K04_2   11     1        9      TCARBN_FLAG_W:    2   ->    3
 49MR03K04_4    7     1       17      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_4    9     1       19      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_4   11     1       19      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_4   11     1       15      ALKALI_FLAG_W:    6   ->    3
 49MR03K04_4  X17     1       13      ALKALI_FLAG_W:    2   ->    4
 49MR03K04_4   18     1       16      TCARBN_FLAG_W:    2   ->    3
 49MR03K04_4   27     1       32      TCARBN_FLAG_W:    2   ->    3
 49MR03K04_4   27     1       12      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_4   33     1        1      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_4   38     1       22      ALKALI_FLAG_W:    2   ->    3
 49MR03K04_4   38     1       15      ALKALI_FLAG_W:    6   ->    3
 49MR03K04_4   38     1        3      ALKALI_FLAG_W:    2   ->    4
_____________________________________________________________________



4.4. PLANNED UPDATES

In the future, data of total organic carbon (TOC) will be available through 
our web site:

        http://www.jamstec.go.jp/iorgc/ocorp/data/beagle2003/index.html. 

In addition, data of the artificial radionuclides will be updated.


Figure Captions

Figure 1  Observation lines for WHP P6, A10 and I3/I4 revisit in Blue Earth 
          Global Expedition 2003(BEAGLE2003) with bottom topography based on 
          ETOPO5 (Data announcement 88-MGG-02,1988).

Figure 2  Station locations for WHP P6, A10 and I3/I4 revisit in BEAGLE2003 
          with bottom topography based on Smith and Sandwell (1997).

Figure 3  CFC-11 (CCl(3)F ; pmol kg^-1) cross section. Data with quality 
          flags of 2 and 6 were plotted. Vertical exaggeration of the 0-6,500 
          m section is 1000:1. Expanded section of the upper 1000 m is made 
          with a vertical exaggeration of 2500:1.

Figure 4  Same as Figure 3 but for CFC-12 (CCl(2)F(2); pmol kg^-1)

Figure 5  Same as Figure 3 but for Δ^(14)C of dissolved inorganic carbon (‰).

Figure 6  Same as Figure 3 but for δ^(13)C of dissolved inorganic carbon (‰).


References

Data Announcement 88-MGG-02 (1988): Digital relief of the Surface of the 
    Earth, NOAA, National Geophysical Data Center, Boulder, Colorado.
Smith, W. H. F. and D. T. Sandwell (1997): Global seafloor topography from 
    satellite altimetry and ship depth soundings, Sciense, 277, 1956-1962.



___________________________________________________________________________________________________________________________
___________________________________________________________________________________________________________________________



CCHDO DATA PROCESSING NOTES

Date      Contact     Data Type      Data Status Summary
--------  ----------  -------------  ------------------------------------------
07/11/05  Anderson    CTD/BTL/SUM    Initial CCHDO evaluation
          I took a quick look at the p06 west files.  There are woce and 
          exchange format files.  The only odd thing I can find is that in the 
          bottle file a parameter called SBE35 uses 9 cols, it is reported to 5 
          decimal places.

          The ctd files have CTDCND (conductivity), also 9 cols, 5 decimal 
          places. There is also a parameter CTDOXV, I assume oxygen, units are 
          volts, and FLOUR. 

          I'll be happy to check all the file and get them ready and put them 
          online if someone will let me know where they should go and if we are 
          going to change the EXPOCODEs the Japanese have assigned to them.
07/11/05  Swift       CTD/BTL/SUM    Initial CCHDO evaluation
          The SBE35 is a reference temperature probe.  It's data should look 
            like bottle in-site temperature data (not theta), and are useful to 
            4 decimal places (accurate to about 1 decimal place).
          The FLOUR can be changed to FLUOR.
          I presume we round the decimal places to better match reality?

07/11/05  Fukasawa    CTD/BTL/SUM    Submitted; available via ftp
          It is truly my great pleasure to tell you that QC'd data with 
          documentations from BEAGLE2003 cruise are completed to be opened at 
          last. I asked Dr. Hiroshi Uchida to send them to Jim and Alex 
          electrically as soon as possible. We also prepared beautiful data 
          books for BEAGLE2003 with a CD ROM. 

07/11/05  Uchida      CTD/BTL/SUM    Submitted; available via ftp
          I prepared CD-ROM contents (documents, data, and figures) of the 
          BEAGLE2003 data book for you on a following web page in advance of 
          sending the data book with the CD-ROM to you. You can access to the 
          web page using following user_id and password.

10/12/05  Bartolacci  Cruise ID      Data Ready to go online
          We decided to call the Beagle cruises by their individual WOCE lines.  
          Directories are set up for p6 and a10, however the directory for 
          i03/i04 (which we decided was to be all together under i03) isn't set 
          up correctly, there needs to be a subdirectory for it (i03_2003a).

02/17/06  Kappa       Cruise ID      changed fist 4 characters to 49NZ
          According to Francis Mitchell at NOAA the "NODC Code for the Mirai is 
          49NZ."  Therefore, I changed the first 4 characters of the expocode 
          from 49MR to 49NZ.

05/10/06  Kappa       Cruise Report  Submitted; Ready to go online
          I just put pdf and text docs for the Beagle cruises in my directory.  
          Please put them online with p06_2004, a10_2004, and i03/i04_2004.

10/04/06  Kappa       Cruise ID      changed to 49NZ200308_1 
          Following a discussion with Justin, I changed the expocode for line 
          P06W_2003 from 49NZ03K04_1 to 49NZ200308_1 to match the expocode in 
          the data files.

10/04/06  Kappa       Cruise ID      changed expocode to 49NZ200309_2 
          Following a discussion with Justin, I changed the expocode for line 
          P06E_2003 from 49NZ03K04_2 to 49NZ200309_2 to match the expocode in 
          the data files.

10/04/06  Kappa       Cruise ID      changed the expocode to 49NZ200311_4 
          Following a discussion with Justin, I changed the expocode for line 
          A10_2003 from 49NZ03K04_4 to 49NZ200311_4 to match the expocode in 
          the data files.

10/04/06  Kappa       Cruise Report  Updated Cruise Report; Combined Vols 1 & 2
          Combined Volumes 1 and 2 in both the PDF and ASCII formatted reports
          Added CCHDO Summary pages (pages 1 and 2)
          Added these Data Processing Notes
          Added links and bookmarks to the PDF version


