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