If symbols do not display correctly change your browser character encoding to unicode CRUISE REPORT: P14S P15S (Updated 8 DEC 2004) A. HIGHLIGHTS CRUISE SUMMARY INFORMATION Leg 1 (Stns 1-93) Leg 2 (Stns 94-182) WOCE section P14S P15S Expedition (EXPOCODE) 31DSCG96_1 31DSCG96_2 Chief Scientists JOHN BULLISTER* RICHARD A. FEELY* Co Chief Scientists Gregory C. Johnson* Marilyn Roberts* Dates 1996 JAN 05 to 1996 FEB 04 1996 FEB 06 to 1996 MAR 10 Ship R/V DISCOVERER Ports of call Hobart, Tasmania Wellington, NZ to Wellington, NZ to Pago Pago, Samoa 40°23.58 S 0°0.01 S Geographic boundaries 169°59.27 E 169°58.3 W 173°2.13 W 168°36.87 W 67°0.03 S 40°23.66 S Number of Stations 29 144 Floats/drifters 14 ALACE floats deployed Moorings 0 deployed/recovered *all at NOAA-PMEL ________________________________________________________________________________ Contributing Authors John Bullister, Calvin Mordy, Kristy McTaggart, Greg Johnson, Kirk Hargreaves, Arnold Mantyla, Mark Rosenberg, David Wisegarver Chief Scientists' Contact Information Dr. John L. Bullister ph: (206) 526-6741 fx: (206) 526-6744 email: bullister@pmel.noaa.gov Dr. Richard A. Feely ph: (206) 526-6214 fx: (206) 526-6744 email: feely@pmel.noaa.gov Dr. Gregory C. Johnson ph: (206) 526-6806 fx: (206) 526-6744 email: gjohnson@pmel.noaa.gov Ms. Marilyn Roberts ph: (206)526-6252 fx: (206)526-6744 email: roberts@pmel.noaa.gov All at: National Oceanic and Atmospheric Administration Pacific Marine Environmental Laboratory (NOAA-PMEL) 600 Sand Point Way NE • Seattle WA 98115 USA SEE PDF REPORT FOR ALL FIGURES Cruise Report: WHP Lines P14S and P15S (CGC96 cruise) Prepared by: John Bullister, NOAA-PMEL Date of this (NOAA-PMEL) draft: 12 June 2000 Updated by WHPO: 12 July 2003 NOTE: The following topics are discussed in this file: A. HIGHLIGHTS Links Station Plot Station/Param/Floats Smry ADCP Atmospheric Chemistry Principal Investigators Narrative Problems Participating Scientists PI Contact Information Station Locations Leg 1 Station Locations Leg 2 Parameter Data Plots B. HYDROGRAPHIC DATA B.1. Oxygen Measurement Techniques B.1.1. Overview B.1.2. Sampling and Pickling B.1.3. Analysis B.1.4. Standardization B.1.5. Post- processing B.1.6. Reagents References Appendix 1: Replicate 0xqgen Measurements B.2. Nutrient Measurement Techniques B.3. CFC-11 and CFC-12 Measurement Techniques Appendix 2a: CFC Air Measurements Appendix 2b: Replicate CFC-11 measurements Appendix 2c: Replicate CFC-12 measurements B.4. Carbon Measurement Techniques B.4.1. pH B.4.2. Dissolved Inorganic Carbon B.4.3. Total Alkalinity B.4.4. Discrete fC02 Appendix 3: Listing of Bottle problems C. CTD DATA C.1. Introduction C.2. Standards and Pre-Cruise Calibrations C.2.1. Conductivity C.2.2. Temperature C.2.3. Pressure C.2.4. Oxygen C.3. Data Acquisition C.3.1. Data Acquisition Problems C.3.2. Salinity Analyses C.4. At Sea Processing C.5. Post-Cruise Calibrations C.5.1. Conductivity C.5.2. Temperature C.5.3. Oxygen Acknowledgements Table 1: CTD Cast Summary Table 2: STN groupings for CTD/O2 algorithm parameters D. DATA QUALITY EVALUATIONS D.1. Hydrographic Data DOE D.1.1. Rag Changes D.1.2. PI Responses to DQE D.2. CTD Data DOE D.2.1. Salinity D.2.2. Oxygen D.2.3. Temperature Intra-Cruise Comparison Table 3: Suspicious CTD salinity Table 4: Suspicious CTD oxygen data Table 5: Density inversions Table 6: Summary of lag changes CTD DOE Figures D.3. Response to CTD Data DOE Salinity Oxygen Temperature Despiking and Interpolation Density Inversions D.4. Final CFC Data DOE DATA PROCESSING NOTES CHIEF SCIENTISTS: Leg 1: Dr. John L. Bullister (Chief Scientist) Tel: (206)526-6741 FAX: (206)526-6744 Email: bullister@pmel.noaa.gov Dr. Gregory C. Johnson (co-chief scientist) Tel: (206)526-6806 FAX: (206)526-6744 Email: gjohnson@pmel.noaa.gov Leg 2: Dr. Richard A. Feely (Chief Scientist) Tel: (206)526-6214 FAX: (206)526-6744 Email: feely@pmel.noaa.gov Ms. Marilyn Roberts (co-chief scientist) Tel: (206)526-6252 FAX: (206)526-6744 Email: roberts@pmel.noaa.gov ---------------------------------------------------------- All at: National Oceanic and Atmospheric Administration Pacific Marine Environmental Laboratory (NOAA-PMEL) 7600 Sand Point Way, NE Seattle, WA 98115 USA Cruise Track: The station locations are shown in Fig. 1 and listed in Appendix 1 and in the P14SP15S.sum file. 182 Stations were completed: 3 test stations on the transit leg from Hobart to the start of the P14S section (2 thirty-six position rosette stations; 1 twenty-four position rosette station) 29 stations on the P14S section (17 thirty-six position rosette stations; 12 twenty-four position rosette stations) 144 stations on the P15S section (132 thirty-six position rosette stations; 10 twenty-four position rosette stations) 6 thirty-six position rosette stations in a short section across Samoa Passage 1 shallow primary productivity cast (with light meter) per day was made while on the P14S and P15S sections. Approximately number of water samples analysed: 5700 salinity 5700 oxygen 5700 nutrients 3300 CFC-11 and CFC-12 1000 CFC-113 and carbon tetrachloride 3100 Total CO2 3000 pCO2 5700 pH 3100 Alkalinity 1350 DOC Approximate number of water samples collected for shore-based analysis: 975 AMS carbon isotope samples (C-13 and C-14) 1025 DON FLOATS: 14 ALACE floats were deployed (8 standard and 6 stretched profilers). Lat Lon Date Time --------------------------------------------------------- 1 56 29.7 S 173 32.4 E 11 Jan 96 0323 2 59 27.5 S 173 57.9 E 12 Jan 96 0035 3 60 29.7 S 170 01.3 W 22 Jan 96 0606 Profiler 4 57 30.1 S 170 00.7 W 23 Jan 96 2120 Profiler 5 55 29.5 S 170 01.9 W 24 Jan 96 2321 Profiler 6 53 59.5 S 169 59.3 W 25 Jan 96 1545 Profiler 7 52 00.0 S 170 05.7 W 26 Jan 96 0155 Profiler 8 50 00.4 S 170 00.4 W 28 Jan 96 0502 Profiler 9 47 29.5 S 169 58.6 W 29 Jan 96 1505 10 45 10.6 S 172 43.8 W 31 Jan 96 0701 11 42 23.7 S 174 24.6 W 1 Feb 96 2143 12 39 04.4 S 172 06.8 W 14 Feb 96 1820 13 29 59.2 S 169 59.5 W 20 Feb 96 0125 14 24 29.9 S 170 00.1 W 22 Feb 96 0252 ADCP Lowered ADCP profiles were obtained at about 70 stations on Leg 1 using a rosette mounted lowered ADCP instrument on 36 position rosette frame. Continous underway ADCP measurements were made along the cruise track. ATMOSPHERIC CHEMISTRY DATA: Air samples were collected at approximately 3 degrees intervals for analyses of atmospheric CFCs. PARTICIPATING INSTITUTIONS: NOAA Pacific Marine Environmental Laboratory (PMEL) NOAA Atlantic Oceanographic and Meteorological Laboratory (AOML) Bermuda Biological Station for Research (BBSR) Monterey Bay Aquarium Research Institute (MBARI) Scripps Institution of Oceanography (SIO) Oregon State University (OSU) Institute of Ocean Sciences (IOS) University of Tennessee (UT) University of Hawaii (UH) University of Miami (UM) University of South Florida (USF) University of Charleston, South Carolina (UCSC) University of Washington (UW) PRINCIPAL INVESTIGATORS Insti- Funding Measurements Principal Investigators (PI) tution Agency ---------------------------- --------------------------------- ------ ------- CTD/O2 and bottle salinity Greg Johnson PMEL (NOAA) Chlorofluorocarbons (CFCs): John Bullister PMEL (NOAA) Total CO2 (DIC), pCO2: Dick Feely- PMEL/Rik Wanninkhof AOML (NOAA) C-14 (AMS radiocarbon), C-13 Paul Quay UW (NOAA) Nutrients: Calvin Mordy-PMEL/Zia-Zhong Zhang AOML (NOAA) Dissolved Oxygen (discrete) John Bullister PMEL (NOAA) Total Alkalinity: Frank Millero UM (NOAA) pH: Robert Byrne USF (NOAA) UW pH/DIC: Andrew Dickso SIO (NOAA) DOC/DON: Dennis Hansell BBSR (NOAA) ADCP: Peter Hacker/Eric Firing U Hawaii ALACE Float deployment: Russ Davis SIO Primary Productivity: Jack DiTullio-UCSC/Walker Smith UT (NOAA) UW Chlorophyll: F. Chavez MBARI (NOAA) Bathymetry: Ship personnel Underway thermosalinograph: Ship personnel NARRATIVE WOCE Hydrographic Sections P14S and P15S were completed on the NOAA Ship Discoverer in early 1996, measuring a wide suite of physical, chemical, and biological processes. A total of 182 full-water column CTD/O2 stations were made along the sections (Fig. 1). A 36 position rosette was used as the primary system. On Leg 1, a lowered ADCP system was mounted on the 36 position rosette, reducing the number of available 10-liter sample bottles to 34. Of the 182 stations, 159 stations were made with the 36-position, 10-liter bottle frame. The other 23 stations were made using a 24-position, 4-liter bottle frame, which was deployed primarily during bad weather. A Sea-Bird Electronics 911plus CTD was mounted in each frame. In addition to the set of temperature and conductivity sensors resident on each CTD, a mobile set of temperature and conductivity sensors with a dissolved oxygen sensor was always mounted on the CTD in use. This arrangement allowed redundant temperature and conductivity measurements for quality control and continuity of temperature and conductivity measurements while keeping each CTD mounted in its own frame. Water samples were collected at every station for analyses of salt, dissolved oxygen, and dissolved nutrients (silicate, nitrate, nitrite, and phosphate). Fig. 2a and 2b show locations where water samples were collected. Samples were drawn at selected locations for analysis of CFC-11, CFC-12, CFC-113, carbon tetrachloride, dissolved inorganic carbon (DIC), total alkalinity, pH, pCO2, dissolved organic carbon (DOC), carbon isotopes, oxygen isotopes, and other variables (see P14SP15s.sum file). Daily shallow casts were made for assessment of various biological parameters, including productivity. A total of 14 ALACE floats were deployed during the cruise, including 6 "Stretched T Profilers". For both sections sampled on this cruise, stations were occupied at a nominal spacing of 30 nm, closer over steeply sloped bathymetry, and never more distant than 60 nm. Stations 1-3 were test stations occupied to evaluate the CTD/O2 and rosette systems on the transit from Hobart, Australia to the start of P14S. Stations 177 to 182 were taken after the completion of P15S but prior to the final port stop in Pago-Pago, American Samoa. These profiles constitute a short, nearly zonal, section across the Samoan Passage, taken to investigate deep water-mass and transport variability there. These data are reported here. The cruise was broken up into two legs of roughly one month duration each by a port stop in Wellington, New Zealand after station 93. Station 94 was a reoccupation of station 93 to evaluate temporal variations that occurred during the port stop. WOCE section P14S began with station 4 at 53°S, 170°E in 200 m of water on the south edge of the Campbell Plateau and ended with station 32 at 66°S, 171°E, intersecting the zonal WHP section S4 occupied nominally along 67°S in 1992. The section consisted of 29 stations. It sampled the entire Antarctic Circumpolar Current between the edge of the Campbell Plateau and the crest of the Pacific-Antarctic Ridge. At the ridge crest it explored a deep passage between the Ross Sea and the Southwest Pacific Basin. South of the ridge crest, it entered the north side of the Ross Sea Gyre. WOCE section P15S began with station 33 at 67°S, 170°W, again intersecting the zonal WHP section S4 occupied nominally along 67°S in 1992. It proceeded north to station 72 at 47.5°S, 170°W, whereupon it followed a diagonal in towards the Chatham Rise until station 85 at 43.25°S, 175°E. From there it moved back away from the rise towards 170°W along a diagonal to station 104 at 36°S, 170°W. It then resumed north to station 154 at 10.5°S, 170°W, whereupon it shifted longitudes slightly to follow the axis of the Samoan Passage until station 164 at 7.5°S, 168.75°W. From there it continued north to station 174 at the equator, 168.75°W. Station 175 and 176 were added to the section to improve meridional resolution in the vicinity of the Samoan Passage. From 15°S to the equator the section overlapped WHP section P15N, occupied in 1994. The P15S section consisted of 143 stations, discounting the duplication after the Wellington port stop. It sampled the north end of the Ross Sea Gyre, the Antarctic Circumpolar Current, the Deep Western Boundary Current system on both flanks of the Chatham Rise, the Subtropical Gyre, and the Tropical Regime up to the equator. PROBLEMS: In general, the ship, winches and analytical systems performed well on this expedition. All of the major goals of the program were met. At the completion of the P14S and P15S sections, enough time remained to extend the P15S section from 5°S to the equator and to complete an additional 8 stations in Samoa Passage. Some time was lost at the beginning of Leg 1 due to problems with the level-wind mechanism on the primary winch. The wire was re-tensioned on the drum at sea by removing the CTD/rosette package, attaching a weight to the wire, and spooling the full length of the wire (except the last full wrap on the drum) behind the ship while underway. Level-wind problems were much reduced after this procedure. Figs. 3-18 show preliminary sections of bottle salinity, dissolved oxygen, phosphate, silicate, nitrate, CFC-11, CFC-12. These preliminary sections only utilize values listed in the P14S and P15S.sea file which are flagged as "good" (flags 2 or 6) and where the BTLNBR flag is also 2. Bathymetry shown in these figures is from depth recorded at each station. PARTICIPATING SCIENTISTS: Nationality Program Inst. Leg 1 Leg 2 (if non-US) ----------------------------------------------------------------------------- Chief Sci. PMEL John Bullister M Richard Feely M Co-Chief Sci. PMEL Greg Johnson M Marilyn Roberts F CTD/O2 PMEL Kristy McTaggart F Kristy McTaggart F OSU Jim Richman M IOS John Love M (CANADA) SeaBird Norge Larson M Nutrients PMEL Calvin Mordy M Calvin Mordy M AOML Zia-Zhong Zhang M Zia-Zhong Zhang M (PRC) Oxygen PMEL Kirk Hargreaves M Kirk Hargreaves M Salinity AOML Gregg Thomas M Gregg Thomas M CFC PMEL Dave Wisegarver M Dave Wisegarver M PMEL Craig Neill M Craig Neill M PMEL Wenlin Huang F (PRC) CFC/O2 IOS Carol Stewart F Carol Stewart F (NZ) TALK RSMAS David Purkinson M Mary Roche F RSMAS Jamie Goen F Jamie Goen F RSMAS Chris Edwards M Xiarong Zhu M pH USF Sean McElligott M Sean McElliogott M USF Wensheng Yao M Wensheng Yao M USF Johan Schijf M Xeuwu Liu M U/W pCO2 PMEL Cathy Cosca F DIC PMEL Marilyn Roberts F Kim Currie F (NZ) AOML Tom Lantry M Tom Lantry M pCO2 PMEL Dana Greeley M Dana Greeley M AOML Hua Chen M Rhonda Kelly F Primary Prod UTK Kendra Daly F Kendra Daly F USC David Jones M David Jones M MBARI Peter Walz M Tim Pennington M DOC BBSR Susan Becker F Susan Becker F BBSR Rachel Parsons F Rachel Parsons F Carbon Isotop. UW Brian Kleinhaus M Tanya Westby F Lowered ADCP UH Eric Firing M ADDRESSES of PIs: CFCs, DISSOLVED OXYGEN: | pH: Dr. John L. Bullister | Dr. Robert Byrne NOAA-PMEL | Marine Science Department 7600 Sand Point Way, NE | University of South Florida Seattle, WA 98115 USA | 140 7th Ave. South Phone: 206-526-6741 | St. Petersburg, FL 33701 FAX: 206-526-6744 | Phone: 813-893-9508 Email: bullister@pmel.noaa.gov | Email: byrne@msl1.marine.usf.edu | PRIMARY PRODUCTIVITY: | ALACE FLOATS: Dr. Francisco Chavez | Dr. Russ Davis MBARI | SIO-UCSD 160 Central Ave | MC 8030 Pacific Grove, CA 93950 | La Jolla, CA 92093 Phone: 408-647-3700 | Phone: 619-534-4415 Email: chfr@mbari.org | Email: davis@nemo.ucsd.edu | TCO2: | LADCP: Dr. Richard A. Feely | Dr. Eric Firing NOAA-PMEL | JIMAR 7600 Sand Point Way, NE | University of Hawaii Seattle, WA 98115 USA | 1000 Pope Road Phone: 206-526-6214 | Honolulu, HI 96822 FAX: 206-526-6744 | Phone: 808-734-8621 Email: feely@pmel.noaa.gov | Email: efiring@iniki.soest.hawaii.edu | CTD, SALINTY: | ALKALINITY: Dr. Gregory C. Johnson | Dr. Frank Millero NOAA-PMEL | University of Miami 7600 Sand Point Way, NE | RSMAS Seattle, WA 98115 USA | 4600 Rickenbacher Causeway Phone: 206-526-6806 | Miami, FL 33149 FAX: 206-526-6744 | Phone: 305-361-4707 Email: gjohnson@pmel.noaa.gov | Email: millero@rcf.rsmas.miami.edu | NUTRIENTS: | CARBON ISOTOPES: Dr. Calvin Mordy | Dr. Paul Quay NOAA-PMEL | University of Washington 7600 Sand Point Way, NE | School of Oceanography Seattle, WA 98115 USA | WB-10 Phone: 206-526-6870 | Seattle, WA 98195 FAX: : 206-526-6744 | Phone: 206-685-6081 Email: mordy@pmel.noaa.gov | Email: pdquay@u.washington.edu | TCO2, DISCRETE pCO2: | Dr, Rik Wanninkhof | Phone: 305-361-4379 AOML | Email: wanninkhof@ocean.aoml.noaa.gov 430 1Rickenbacher Causeway | Miami, FL 33149 | STATION LOCATIONS: LEG 1 STATION BOTTOM NUMBER Latitude Longitude Date DEPTH (M) ------------------------------------------------------- 1 45 49.5 S 153 05.1 E 6 Jan 96 4468 2 48 19.1 S 158 29.9 E 7 Jan 96 4850 3 50 05.0 S 162 29.3 E 8 Jan 96 4456 4 53 00.1 S 169 59.3 E 9 Jan 96 198 5 53 29.9 S 170 29.7 E 9 Jan 96 743 6 53 59.9 S 171 00.1 E 9 Jan 96 1175 7 54 10.2 S 171 10.8 E 9 Jan 96 1370 8 54 19.8 S 171 20.2 E 9 Jan 96 2615 9 54 30.3 S 171 29.8 E 9 Jan 96 4390 10 54 59.7 S 172 00.7 E 10 Jan 96 5345 11 55 30.4 S 172 27.0 E 10 Jan 96 5332 12 55 59.8 S 173 00.6 E 10 Jan 96 5415 13 56 29.2 S 173 30.2 E 11 Jan 96 5345 14 56 59.7 S 173 58.6 E 11 Jan 96 5430 15 57 30.3 S 173 58.5 E 11 Jan 96 5358 16 58 00.2 S 173 59.5 E 12 Jan 96 5205 17 58 30.2 S 173 58.2 E 12 Jan 96 5046 18 58 59.8 S 174 00.0 E 12 Jan 96 5110 19 59 28.7 S 173 59.7 E 12 Jan 96 5002 20 59 57.9 S 173 57.9 E 13 Jan 96 4346 21 60 30.3 S 173 57.8 E 13 Jan 96 5028 22 60 59.1 S 173 58.9 E 14 Jan 96 4712 23 61 30.0 S 174 00.2 E 14 Jan 96 5037 24 62 00.0 S 173 16.1 E 14 Jan 96 4450 25 62 26.9 S 172 35.2 E 14 Jan 96 4440 26 62 44.7 S 172 09.0 E 15 Jan 96 4450 27 62 60.0 S 171 44.9 E 15 Jan 96 2636 28 63 30.1 S 170 59.6 E 15 Jan 96 2422 29 63 59.8 S 171 06.6 E 16 Jan 96 2600 30 64 40.6 S 170 58.6 E 16 Jan 96 3475 31 65 20.2 S 170 60.0 E 16 Jan 96 3449 32 66 00.9 S 171 01.6 E 17 Jan 96 3151 33 66 59.6 S 170 00.0 W 18 Jan 96 3630 34 66 20.3 S 169 60.0 W 18 Jan 96 3430 35 65 39.8 S 170 00.3 W 19 Jan 96 3180 36 64 59.6 S 170 00.9 W 19 Jan 96 2880 37 64 30.1 S 169 59.9 W 19 Jan 96 2370 38 63 59.7 S 170 02.0 W 19 Jan 96 2783 39 63 30.1 S 170 00.3 W 20 Jan 96 2805 40 62 59.7 S 170 01.4 W 20 Jan 96 3085 41 62 30.0 S 169 59.8 W 20 Jan 96 2843 42 62 00.2 S 169 59.9 W 20 Jan 96 3422 43 61 29.5 S 169 60.0 W 21 Jan 96 3501 44 61 00.1 S 170 00.3 W 21 Jan 96 3630 45 60 29.7 S 169 59.6 W 22 Jan 96 3960 46 60 00.3 S 170 00.3 W 22 Jan 96 3738 47 59 30.2 S 169 59.9 W 22 Jan 96 4030 48 58 59.9 S 170 00.2 W 22 Jan 96 4780 49 58 29.6 S 170 00.8 W 23 Jan 96 5188 50 57 59.7 S 170 00.8 W 23 Jan 96 4140 51 57 30.1 S 170 00.4 W 23 Jan 96 5001 52 57 00.2 S 170 00.2 W 24 Jan 96 5165 53 56 29.9 S 169 59.8 W 24 Jan 96 5055 54 55 60.0 S 170 01.8 W 24 Jan 96 5157 55 55 29.9 S 170 00.0 W 24 Jan 96 4950 56 54 59.8 S 169 60.0 W 25 Jan 96 4820 57 54 29.4 S 170 00.1 W 25 Jan 96 4819 58 54 00.1 S 169 59.3 W 25 Jan 96 5013 59 53 39.9 S 169 59.4 W 25 Jan 96 5125 60 53 19.9 S 169 59.6 W 26 Jan 96 5276 61 52 60.0 S 170 00.5 W 26 Jan 96 5185 62 52 29.9 S 170 01.8 W 26 Jan 96 5065 63 52 00.1 S 170 07.8 W 26 Jan 96 4968 64 51 30.0 S 170 00.2 W 27 Jan 96 4757 65 51 00.2 S 170 00.4 W 27 Jan 96 5239 66 50 29.9 S 169 59.6 W 27 Jan 96 5041 67 50 00.4 S 169 59.9 W 28 Jan 96 5340 68 49 30.2 S 170 00.9 W 28 Jan 96 5200 69 48 59.6 S 169 59.4 W 28 Jan 96 5235 70 48 30.0 S 170 00.2 W 28 Jan 96 5280 71 47 59.8 S 170 00.3 W 29 Jan 96 5270 72 47 30.2 S 169 59.8 W 29 Jan 96 5285 73 47 06.5 S 170 27.7 W 29 Jan 96 5365 74 46 43.4 S 170 54.7 W 30 Jan 96 5268 75 46 20.0 S 171 22.2 W 30 Jan 96 5083 76 45 57.0 S 171 49.5 W 30 Jan 96 5136 77 45 33.6 S 172 16.7 W 30 Jan 96 4953 78 45 10.6 S 172 44.2 W 31 Jan 96 4652 79 44 50.1 S 173 08.2 W 31 Jan 96 3838 80 44 31.8 S 173 29.4 W 31 Jan 96 3408 81 44 19.2 S 173 44.7 W 31 Jan 96 3090 82 44 09.4 S 173 56.3 W 1 Feb 96 1908 83 43 50.9 S 174 17.7 W 1 Feb 96 950 84 43 38.8 S 174 32.2 W 1 Feb 96 790 85 43 15.2 S 174 59.9 W 1 Feb 96 790 86 42 55.9 S 174 47.2 W 1 Feb 96 1059 87 42 44.8 S 174 39.3 W 1 Feb 96 1590 88 42 24.1 S 174 24.4 W 1 Feb 96 2668 89 42 10.0 S 174 15.0 W 2 Feb 96 2875 90 41 42.8 S 173 56.5 W 2 Feb 96 3130 91 41 16.0 S 173 38.6 W 2 Feb 96 3330 92 40 49.5 S 173 19.5 W 2 Feb 96 4170 93 40 23.6 S 173 02.0 W 2 Feb 96 4568 STATION LOCATIONS: LEG 2 STATION BOTTOM NUMBER Latitude Longitude Date DEPTH (M) ------------------------------------------------------- 94 40 23.5 S 173 01.7 W 13 Feb 96 4568 95 39 57.7 S 172 42.2 W 14 Feb 96 4728 96 39 31.0 S 172 25.2 W 14 Feb 96 4751 97 39 04.3 S 172 07.7 W 14 Feb 96 4836 98 38 37.8 S 171 48.6 W 14 Feb 96 4901 99 38 11.4 S 171 30.2 W 15 Feb 96 4918 100 37 45.8 S 171 12.0 W 15 Feb 96 4980 101 37 18.6 S 170 53.7 W 15 Feb 96 5112 102 36 52.3 S 170 37.0 W 15 Feb 96 5254 103 36 27.0 S 170 17.2 W 16 Feb 96 5102 104 36 00.2 S 170 00.3 W 16 Feb 96 5050 105 35 40.3 S 170 00.9 W 16 Feb 96 4290 106 35 20.0 S 170 00.1 W 16 Feb 96 4880 107 35 00.5 S 169 59.6 W 17 Feb 96 5226 108 34 30.2 S 170 00.2 W 17 Feb 96 5457 109 33 59.8 S 169 60.0 W 17 Feb 96 5501 110 33 29.9 S 170 00.1 W 18 Feb 96 5387 111 33 00.1 S 170 00.1 W 18 Feb 96 5548 112 32 30.1 S 170 00.1 W 18 Feb 96 5501 113 31 59.8 S 169 59.8 W 18 Feb 96 5640 114 31 30.0 S 169 59.3 W 19 Feb 96 5496 115 31 00.4 S 169 59.7 W 19 Feb 96 5572 116 30 30.3 S 169 59.8 W 19 Feb 96 5505 117 30 00.2 S 169 59.8 W 19 Feb 96 5394 118 29 30.2 S 169 59.8 W 20 Feb 96 5127 119 29 00.8 S 169 59.9 W 20 Feb 96 5562 120 28 30.5 S 169 59.8 W 20 Feb 96 5425 121 28 00.3 S 169 59.6 W 21 Feb 96 4888 122 27 30.1 S 170 00.1 W 21 Feb 96 5318 123 27 00.3 S 169 59.5 W 21 Feb 96 5214 124 26 29.7 S 169 59.4 W 21 Feb 96 5575 125 26 00.3 S 169 59.7 W 22 Feb 96 5563 126 25 30.0 S 169 60.0 W 22 Feb 96 5787 127 25 00.1 S 169 59.9 W 22 Feb 96 5600 128 24 30.1 S 170 00.1 W 23 Feb 96 5610 129 23 59.8 S 170 00.1 W 23 Feb 96 5637 130 23 30.1 S 170 00.1 W 23 Feb 96 5626 131 22 59.8 S 169 59.7 W 23 Feb 96 5650 132 22 30.0 S 169 59.9 W 24 Feb 96 5609 133 22 00.0 S 169 59.9 W 24 Feb 96 5587 134 21 30.4 S 170 00.1 W 24 Feb 96 5388 135 20 59.7 S 169 59.6 W 25 Feb 96 5427 136 20 29.9 S 170 00.1 W 25 Feb 96 5560 137 20 00.0 S 170 00.1 W 25 Feb 96 5294 138 19 29.9 S 170 00.1 W 25 Feb 96 4885 139 19 00.1 S 170 03.4 W 26 Feb 96 3000 140 18 30.3 S 170 00.1 W 26 Feb 96 5232 141 17 60.0 S 169 60.0 W 26 Feb 96 4893 142 17 30.1 S 169 60.0 W 26 Feb 96 5002 143 17 00.1 S 169 59.8 W 27 Feb 96 4954 144 16 30.3 S 169 59.9 W 27 Feb 96 5109 145 16 00.2 S 169 59.9 W 27 Feb 96 5120 146 15 29.8 S 170 00.1 W 27 Feb 96 5064 147 15 00.2 S 170 00.0 W 28 Feb 96 4803 148 14 40.0 S 169 59.9 W 28 Feb 96 3322 149 14 16.9 S 169 59.8 W 28 Feb 96 3540 150 13 58.3 S 169 60.0 W 28 Feb 96 2947 151 13 49.1 S 170 00.1 W 28 Feb 96 4297 152 13 30.1 S 169 60.0 W 29 Feb 96 4860 153 12 59.9 S 170 00.0 W 29 Feb 96 4949 154 12 29.9 S 169 59.9 W 29 Feb 96 4979 155 12 00.1 S 170 00.1 W 29 Feb 96 5055 156 11 30.0 S 169 59.9 W 1 Mar 96 5035 157 11 00.1 S 169 59.9 W 1 Mar 96 5100 158 10 30.1 S 169 59.8 W 1 Mar 96 4858 159 09 55.6 S 169 37.7 W 1 Mar 96 5179 160 09 30.1 S 168 59.9 W 2 Mar 96 5310 161 08 59.9 S 168 52.6 W 2 Mar 96 4848 162 08 29.9 S 168 44.9 W 2 Mar 96 5129 163 08 00.0 S 168 37.0 W 2 Mar 96 5138 164 07 30.1 S 168 44.9 W 3 Mar 96 5244 165 06 60.0 S 168 44.9 W 3 Mar 96 5628 166 06 30.1 S 168 44.9 W 3 Mar 96 5498 167 06 00.0 S 168 45.0 W 4 Mar 96 5629 168 05 30.1 S 168 45.0 W 4 Mar 96 5347 169 05 00.0 S 168 44.9 W 4 Mar 96 5534 170 03 60.0 S 168 45.1 W 4 Mar 96 5191 171 03 00.0 S 168 45.0 W 5 Mar 96 5347 172 02 00.1 S 168 45.0 W 5 Mar 96 3293 173 01 00.1 S 168 45.2 W 6 Mar 96 5748 174 00 00.1 S 168 45.0 W 6 Mar 96 5542 175 07 44.8 S 168 40.2 W 8 Mar 96 5289 176 08 15.1 S 168 41.3 W 8 Mar 96 4944 177 10 08.7 S 168 58.8 W 8 Mar 96 4628 178 10 04.1 S 169 12.7 W 8 Mar 96 5226 179 09 55.2 S 169 37.7 W 9 Mar 96 5188 180 09 47.0 S 170 03.5 W 9 Mar 96 4993 181 09 41.6 S 170 19.5 W 9 Mar 96 4297 182 09 35.7 S 170 36.1 W 9 Mar 96 4038 ____________________________________________________________________________________________ ____________________________________________________________________________________________ B. HYDROGRAPHIC MEASUREMENT TECHNIQUES AND CALIBRATIONS B.1. OXYGEN MEASUREMENT TECHNIQUES (Kirk Hargreaves 15 May 1996) B.1.1 OVERVIEW Oxygen samples were drawn from every bottle for every station (except for some test casts and severely leaking bottles). A total of 5683 samples plus 516 duplicates were analyzed. Four people drew oxygen samples and three people ran analyses. The estimated accuracy, relative to the standards, is 0.1% (potentially 0.05%) plus an estimated precision of 0.2 µmol/kg. Note that precision is sampler dependent and was as good as 0.15 µmol/kg for some samplers. Also, discounting the 12 duplicates (2.5% of total) with more than three sigma error, the total precision is 0.15 µmol/kg. Individual sampler variation is from 0.14 to 0.19 µmol/kg. Water temperature was not measured at the time of sampling. Previous measurements have shown that even in the tropics, bottom water warms only a few degrees C before being sampled. For a rise in temperature from 0°C to 4°C, the change in the density of the water is 0.03%. Conversion to µmol/kg is calculated with potential density. Samples were titrated using Culberson's (Culberson, 1992) modifications to Carpenter's whole bottle technique (Carpenter, 1969). An auto-titrator based on a design by Gernot Friederich (Friederich, 1991) and using a modified version of Friederich's software was used to titrate the samples. The titrator consists of a Kloehn 50100 Syringe Drive with a 5 ml syringe, a custom- built photometer with two color channels, LM35 temperature sensors, an eight channel A/D board, and a computer. Post- processing software was used to add in temperature corrections and to analyze data. B.1.2 SAMPLING AND PICKLING Oxygen sampled immediately after CFC's. Samples were drawn in calibrated 125 ml nominal volume iodine determination flasks (Corning 5400-125). The sampling tube was inserted into the flask, allowed to flow freely and squeezed and tapped to remove bubbles, and then inverted. The tube was pinched to reduce flow and allow water in the flask to drain. A water sheet was formed on the inside of the flask, the sampling tube pinched to reduce flow, the flask drained, and then put right-side up. The sampling tube was slowly released to prevent turbulent flow and the flask allowed to fill. For best results, the sampling tube was kept pinched to keep the flow smooth throughout sampling. By counting, the fill time was measured and used to ensure at least two volumes overflow. Reagents were introduced shortly after sampling using Brinkmann 1.0 ml Fixed Volume Dispensette repipets. The tips of the repipets were lengthened using clear polyolefin shrink tubing. The MnCl2 was added at the midpoint of the flask, and NaOH/NaI just below the neck. Repipets were filled before inserting into the water. If necessary, a little was dispensed to ensure the tubes were full. Flasks were capped at this point and shaken while pushing on the stopper until the reagents were well mixed. The flask was inverted and checked for bubbles. Deionized water was added to the collar of the flask and the flask stowed. At least 20 minutes after sampling was finished, flasks were reshaken and deionized water added to the collars again. B.1.3 ANALYSIS Samples were analyzed no earlier than 20 minutes and no later than 8 hours after remixing. Liquid from the flask collar was aspirated with a transfer pipette and the stopper removed. ~1ml of 10°N sulfuric acid and a rinsed, pivotless stir bar were added (pivotless stir bars spin most easily). The flask was inserted into a water bath in the photometer and titrated with 0.05 N sodium thiosulfate. (The water path minimizes refractive effects). After titration, the sample was poured out and the flask rinsed with hot tap water. The typical sample-to-sample time was 1.5 to 2 minutes. B.1.4 STANDARDIZATION Titrant was standardized daily with ~0.01°N (actually 0.01 eq/kg) potassium iodate solution. The standard deviation of standardization is 0.05%, though one batch of thiosulfate solution showed a variation of 0.2%. Standards were mixed before the cruise and stored in upside down air tight Boston round bottles. All standards intercompared before the cruise to better than 0.02%. Standards were prepared by weight from two ~0.1 eq/kg stock solutions. The stock solutions were made from oven dried and vacuum desiccated KIO3 from two different manufacturers (Mallinckrodt Lot #1094-KHSR and Fisher Lot #951151). In addition, all standards were compared to a volumetrically prepared standard from Baker (pre-weighed KIO3 obtained from Oregon State University. Lot number unknown). Mixing standards by weight is both faster and more accurate than mixing standards volumetrically. Standard was dispensed using a spare Kloehn 50100 with a calibrated 25 ml buret or an Eppendorf Maxipettor with calibrated tip. Unfortunately, the Eppendorf Maxipettor has a large (0.02%/C) temperature dependence that needs to be taken into account. The measured precision of the dispensed standards is 0.6 uL and 2 uL for the Kloehn and Eppendorf, respectively. The temperature of the standard was measured directly with a calibrated thin film Pt-RTD (Sensycon GW2107-01) and thermometer (Cole-Parmer H-08497-00). Standard concentration was converted to normality by dividing by then density of pure water at temperature plus 0.03% (mass fraction of the potassium iodate). B.1.5 POST-PROCESSING Post-processing software written in Perl (Wall, 1991) and using algorithms from "Numerical Recipes in C" (Press, 1988) was used to add in temperature corrections and update standardization. Perl code was also used to generate the correct WOCE flags, average duplicate data, and generate the final output. Lotus 1-2-3 was used to plot curves, compare bottle data to oxygen sensor data, and analyze duplicates. B.1.6 REAGENTS Reagents were gravimetrically prepared before the cruise. 600 g MnCl2 were added to 692.92 g water, and 320 g NaOH and 600 g NaI were added to 753.68 g water. At room temperature, these give molar concentrations equal to the WOCE specifications, but are much faster to mix. Reagents were stored in glass or HDPE bottles. OXYGEN REFERENCES Carpenter, J.H., "The Chesapeake Bay Institute Technique for the Winkler Dissolved Oxygen Method", Limnology and Oceanography, vol. 10, pp. 141-143. Culberson, C.H., "Dissolved Oxygen", WHP Operations and Methods, WHP Office Report WHPO 91-1, July 1992. Friederich, G.E., Codispoti, L.A., and Sakamoto, C.M., "An Easy- to-Construct Automated Winkler Titration System", MBARI Technical Report 91-6, August 1991. Press, W.H., Flannery, B.P., Teukolsky, S.A., and Vetterling, W.T., "Numerical Recipies in C", Cambridge University Press, Cambridge, 1988. Wall, L., and Schwartz, Randal L., "Programming Perl", O'Reilly & Associates, USA, 1991. APPENDIX 1: REPLICATE OXYGEN MEASUREMENTS These are the standard deviations of the oxygen data duplicates. The averaged data are in the oxygen data file and flagged with a '6'. Sta Smp StdDev | Sta Smp StdDev | Sta Smp StdDev --- --- ------ | --- --- ------ | --- --- ------ 5 104 0 | 35 104 0.31 | 57 107 0.11 6 104 0.15 | 35 107 0.19 | 57 113 0.02 6 107 0.16 | 35 110 0.36 | 57 119 0.13 10 204 0.01 | 40 108 0.21 | 57 125 0.14 10 208 0.17 | 40 119 0.18 | 58 213 0.1 11 105 0.11 | 41 109 0.04 | 58 227 0.39 11 110 0 | 41 115 0.13 | 58 231 0.01 11 115 0.06 | 41 121 0.79 | 59 106 0.32 11 120 0.47 | 41 127 0.01 | 59 109 0.33 14 112 0.16 | 42 107 0.79 | 60 104 0.31 14 120 0.27 | 42 113 0.19 | 60 106 0.78 14 128 0.14 | 42 119 0.22 | 60 109 0.07 15 207 0.08 | 42 125 0.23 | 61 105 0.05 15 214 0.19 | 46 103 0.17 | 61 109 0.19 15 221 0.74 | 46 109 0.02 | 61 115 0.12 15 229 0.35 | 46 115 0.53 | 61 119 0.05 16 104 0.64 | 46 121 0.19 | 62 217 0.05 16 108 0.75 | 47 213 0.09 | 62 219 0.02 17 104 0.08 | 47 217 0.06 | 62 225 0.09 17 108 0.05 | 47 221 0 | 62 231 0.07 17 122 0.01 | 47 225 0.01 | 65 121 0.4 18 105 0.01 | 48 104 0.44 | 65 123 0.05 18 111 0.04 | 48 108 0.34 | 66 110 0.08 18 117 0.04 | 49 113 0.01 | 66 117 0.3 18 123 0.84 | 49 117 0.26 | 66 122 0.03 28 111 0.05 | 50 105 0.16 | 66 128 0.06 28 118 0.38 | 50 115 0.05 | 67 207 0.15 29 203 0.08 | 50 121 0.15 | 67 209 0.21 29 206 0.08 | 50 129 0.03 | 67 213 0.24 29 210 0.31 | 51 108 0.02 | 68 107 0 29 214 0.63 | 51 114 0.09 | 68 115 0.07 30 105 0.1 | 51 120 0.03 | 68 123 0.2 30 107 0.18 | 51 126 0.14 | 68 131 0.06 30 117 0.21 | 52 105 0.08 | 69 208 0.06 30 127 0.12 | 52 108 0.11 | 69 213 0.12 31 207 0.03 | 52 112 0.43 | 69 221 0.03 31 215 0 | 53 105 0.21 | 69 229 0.01 31 223 0.24 | 53 111 0.04 | 70 106 0.35 31 227 0.09 | 53 117 0.03 | 70 109 0.01 32 104 0.2 | 53 121 0 | 70 111 0.08 32 107 0.2 | 54 103 0.09 | 71 105 0.22 32 114 0.02 | 54 109 0.13 | 71 113 0.06 33 105 0.3 | 54 115 0.13 | 71 119 0.03 33 111 0.91 | 54 121 0.05 | 71 123 0.08 33 117 0.05 | 55 107 0.11 | 72 103 0.16 33 123 0.04 | 55 110 0.16 | 72 113 0.06 34 107 0.1 | 55 113 0.06 | 72 119 0.02 34 113 0.14 | 56 106 0.09 | 72 127 0.06 34 119 0.02 | 56 108 0.16 | 73 110 0.13 34 125 0.02 | 56 110 0.16 | 73 118 0.07 Sta Smp StdDev | Sta Smp StdDev | Sta Smp StdDev --- --- ------ | --- --- ------ | --- --- ------ 73 126 0.12 | 92 234 0.07 | 106 109 0.03 74 205 0.39 | 93 101 0.36 | 106 121 0.28 74 211 0.24 | 93 105 0.36 | 106 129 0.09 74 216 0.06 | 93 108 0.12 | 107 101 0.2 74 220 0.2 | 93 113 0.12 | 107 112 0.17 75 107 0.38 | 94 105 0.01 | 107 124 0.09 75 115 0 | 94 111 0.24 | 108 107 0.05 75 123 0.41 | 94 117 0.03 | 108 117 0 75 131 0.07 | 94 123 0.24 | 108 127 0.01 76 213 0.04 | 95 101 0.17 | 108 135 0.15 76 219 0.35 | 95 112 0.59 | 109 105 0.04 76 225 0.34 | 95 124 0.14 | 109 121 0.19 76 231 0.08 | 96 107 0.03 | 109 129 0.12 77 106 0.01 | 96 123 0.05 | 110 212 0.63 77 110 0.08 | 97 209 0.18 | 110 215 0.03 77 112 0.05 | 97 215 0 | 110 219 0.15 77 115 0.08 | 97 221 0.27 | 110 227 0.01 78 104 0.1 | 97 227 0.06 | 111 107 0.07 78 107 0.05 | 98 107 0.01 | 111 109 0.01 78 111 0.01 | 98 113 0.05 | 111 115 0.03 78 115 0.05 | 98 122 0.11 | 111 123 0.1 79 111 0.04 | 98 130 0.05 | 112 105 0.03 79 117 0.03 | 99 101 0.03 | 112 113 0.06 79 123 0.09 | 99 112 0.19 | 112 121 0.15 79 129 0.14 | 99 124 0.01 | 112 129 0.07 80 215 0.04 | 99 136 0.09 | 114 112 0.1 80 221 0.05 | 100 107 0.12 | 114 123 0.05 80 227 0.56 | 100 113 0.08 | 114 134 0.04 81 105 0.06 | 100 119 0.07 | 115 107 0.11 81 108 0.09 | 100 125 0.25 | 115 115 0.04 81 113 0.06 | 101 204 0.52 | 115 123 0.18 82 104 0.15 | 101 211 0.02 | 115 131 0.25 82 107 0.15 | 101 219 0.12 | 116 205 0.03 82 110 0.07 | 101 231 0.06 | 116 213 0.09 88 101 0 | 102 105 0.1 | 116 221 0.17 88 104 0.11 | 102 115 0.11 | 116 229 0.06 88 106 0.07 | 102 121 0.03 | 117 103 0.18 89 201 0.14 | 102 129 0.03 | 117 109 0.05 89 204 0 | 103 101 0.18 | 117 125 0.1 89 208 0.11 | 103 119 0.21 | 117 135 0.12 90 101 0.07 | 103 136 0.01 | 118 101 0.13 90 104 0.04 | 104 105 0.09 | 118 112 0.04 90 108 0.17 | 104 115 0.03 | 118 124 0.13 91 107 0.03 | 104 125 0.09 | 118 136 0.03 91 115 0.16 | 104 135 0.13 | 119 101 0.1 91 121 0.05 | 105 209 0.07 | 119 111 0.02 91 127 0.06 | 105 213 0.01 | 119 121 0.06 92 209 0.12 | 105 223 0.06 | 119 133 0 92 217 0.03 | 105 232 0.13 | 120 201 0.05 92 225 0.03 | 106 105 0.04 | 120 211 0 Sta Smp StdDev | Sta Smp StdDev | Sta Smp StdDev --- --- ------ | --- --- ------ | --- --- ------ 120 221 0.04 | 133 113 0.15 | 146 128 0.09 120 231 0.04 | 133 125 0.11 | 147 101 0.26 121 205 0.09 | 133 135 0.07 | 147 112 0.21 121 211 0.21 | 134 201 0.05 | 147 125 0.11 121 223 0.08 | 134 211 0.09 | 147 136 0.08 121 231 0.63 | 134 221 0.11 | 148 101 0.08 122 101 0.02 | 134 231 0.03 | 148 111 0.09 122 112 0.01 | 135 203 0.11 | 148 119 0.02 122 124 0.16 | 135 212 0.06 | 148 131 0.12 122 136 0.02 | 135 219 0.08 | 150 201 0.01 123 103 0.03 | 135 229 0.01 | 150 207 0 123 113 0.05 | 136 101 0.11 | 150 215 0.04 123 123 0.19 | 136 107 0.1 | 150 225 0.04 123 135 0.08 | 136 113 0.08 | 151 105 0.01 124 102 0.13 | 136 119 0.01 | 151 111 0.23 124 112 0.06 | 137 103 0.04 | 151 118 0.06 124 122 0.65 | 137 109 0.13 | 151 125 0.1 124 132 0.21 | 137 115 0.06 | 152 103 0.14 125 301 0.01 | 137 123 0.14 | 152 112 0.12 125 312 0.13 | 138 105 0.24 | 152 124 0.2 125 325 0.05 | 138 111 0.01 | 152 125 0.25 126 101 0.03 | 138 119 0.09 | 153 105 0.05 126 111 0.06 | 138 127 0.06 | 153 113 0.05 126 121 0.12 | 140 104 0.22 | 153 121 0.03 126 131 0.07 | 140 111 0.08 | 153 129 0.07 127 205 0.01 | 140 121 0.01 | 154 101 0.06 127 215 0 | 140 131 0.06 | 154 107 0.06 127 225 0.64 | 141 101 0.08 | 154 117 0.04 127 233 0.25 | 141 113 0.11 | 154 131 0.07 128 205 0.11 | 141 125 0.02 | 155 105 0.07 128 211 0.14 | 141 135 0.12 | 155 111 0.01 128 221 0.21 | 142 105 0.21 | 155 119 0.18 128 229 0.25 | 142 111 0.01 | 155 125 0.01 129 102 0.07 | 142 119 0.02 | 156 103 0.29 129 115 0.05 | 142 129 0.11 | 156 109 0 129 122 0.18 | 143 105 0.02 | 156 123 0.01 129 131 0.06 | 143 111 0.12 | 156 129 0.06 130 101 0.49 | 143 121 0.27 | 157 109 0.01 130 109 0.12 | 143 129 0.07 | 157 115 0.06 130 117 0.05 | 144 104 0.24 | 157 118 0.09 130 125 0.05 | 144 110 0.11 | 157 119 0.07 131 105 0.08 | 144 117 0.02 | 158 104 0.2 131 111 0.05 | 144 125 0.1 | 158 115 0.04 131 119 0.01 | 145 101 0.06 | 158 119 0.01 131 127 0.07 | 145 107 0.01 | 158 125 0.16 132 101 0.06 | 145 113 0.17 | 159 105 0.06 132 113 0.14 | 145 119 0.04 | 159 111 0.03 132 124 0.03 | 146 103 0.14 | 159 119 0.07 132 136 0.03 | 146 111 0.28 | 159 125 0.17 133 101 0.01 | 146 119 0.14 | 160 101 0.09 || Sta Smp StdDev | Sta Smp StdDev | Sta Smp StdDev --- --- ------ | --- --- ------ | --- --- ------ 160 112 0.09 | 167 219 0.05 | 175 203 0.14 160 124 0.05 | 167 225 0.09 | 175 211 0.15 161 107 0.06 | 168 104 0.3 | 175 217 0.11 161 115 0.04 | 168 113 0.07 | 176 101 0.43 161 122 0 | 168 123 0.03 | 176 112 0.03 161 128 0.07 | 168 125 0.04 | 177 110 0.01 162 204 0.15 | 169 210 0.02 | 177 113 0.06 162 208 0.09 | 169 220 0.01 | 178 105 0.01 162 225 0.11 | 169 225 0.06 | 178 109 0.03 163 205 0.23 | 170 111 0.09 | 178 115 0.05 163 211 0.13 | 170 119 0.11 | 179 103 0.06 163 219 0.07 | 170 125 0.08 | 179 112 0.04 163 227 0.05 | 171 107 0.12 | 180 108 0.24 164 101 0.09 | 171 115 0.02 | 180 113 0.12 164 112 0.07 | 171 121 0.04 | 181 106 0.13 164 124 0.27 | 171 125 0.02 | 181 108 0.07 166 209 0.02 | 172 202 0.05 | 182 103 0.02 166 215 0.17 | 172 217 0.09 | 166 221 0.15 | 172 219 0.09 | 167 205 0.01 | 172 222 0 | 167 211 0.22 | | ____________________________________________________________________________________________ ____________________________________________________________________________________________ B.2. NUTRIENT MEASUREMENT TECHNIQUES (Calvin Mordy, NOAA-PMEL) Nutrient samples were analyzed for dissolved phosphate, silicic acid, nitrate, and nitrite using protocols of Gordon et al., 1993. Samples were collected in 20 ml high-density polyethylene scintillation vials closed with teflon lined polyethylene caps. All vials and caps were rinsed with 10% HCl prior to each station. Samples were usually analyzed immediately after collection; however, several samples were stored for up to 12 hours at 4-6°C. Samples were analyzed using an Alpkem RFA 300 modified with a custom heating coil and Spectro-100 UV/VIS detectors from Thermo Separation Products. Analytical temperatures were logged twice during every run and ranged from 16 to 25 degrees C. The following analytical methods were employed: Phosphate was converted to phosphomolybdic acid and reduced with ascorbic acid to form phosphomolybdous acid in a reaction stream heated to 42°C (Bernhardt and Wilhelms, 1967). Silicic acid was converted to silicomolybdic acid and reduced with stannous chloride to form silicomolybdous acid or molybdenum blue (Armstrong, 1967). Nitrite was diazotized with sulfanilamide and coupled with NEDA to form a red azo dye. (NO3- + NO2-) was measured by first reducing nitrate to nitrite in a copperized cadmium coil, and then analyzing for nitrite. Nitrate was determined from the difference of (NO3- + NO2-) and NO2- (Armstrong, 1967). Concentrations were converted to µmol/kg by calculating sample densities using the laboratory temperature during analysis, the bottle or CTD salinity, and the international equation of state (UNESCO, 1981). Primary standards were prepared by dissolving standard material in deionized water, and working standards were freshly made at each station in low nutrient seawater. Standard material for silicic acid was sodium fluorosilicate which had been referenced against a fused-quartz standard. All analysis were within the linear range of the instrument. Analytical precision was determined from replicate analysis (2 to 7 measurements) on one or more samples at almost every station. Average standard deviations (µmol/kg) for replicate analysis were 0.008 for phosphate (n = 205), 0.08 for silicic acid (n = 408), 0.05 for nitrate (n = 378) and 0.004 for nitrite (n = 15, for samples > 0.05 µmol/kg). REFERENCES: Armstrong, F.A.J., C.R. Stearns, and J.D.H. Strickland. 1967. The measurement of upwelling and subsequent biological processes by means of the Technicon Autoanalyzer and associated equipment. Deep-Sea Res. 14: 381-389. Bernhardt, H., and A. Wilhelms. 1967. The continuous determination of low level iron, soluble phosphate and total phosphate with the AutoAnalyzer. Technicon Symposia, Vol I, 385-389. Gordon LI, Jennings JC Jr., Ross AA, Krest JM. (1993) A suggested protocol for continuous flow automated analysis of seawater nutrients (phosphate, nitrate, nitrite and silicic acid) in the WOCE Hydrographic Program and the Joint Global Ocean fluxes Study. WOCE Operations Manual, Part 3.1.3 "WHP Operations and Methods" (WOCE Hydrographic Program Office, Methods Manual 91- 1) Bundesamt fur Seeschiffahrt und Hydrographie, Postfach 30 12 20, 2000 Hamburg 36 Germany UNESCO. (1981) The practical salinity scale 1978 and the international equation of state of seawater 1980. Tenth report of the Joint Panel on Oceanographic Tables and Standards.. UNESCO Technical Papers in Marine Science No. 36, UNESCO, Paris, France. ____________________________________________________________________________________________ ____________________________________________________________________________________________ B.3. CFC-11 AND CFC-12 MEASUREMENT TECHNIQUES (J.Bullister, NOAA-PMEL) Specially designed 10 liter water sample bottles were used on the cruise to reduce CFC contamination. These bottles have the same outer dimensions as standard 10 liter Niskin bottles, but use a modified end-cap design to minimize the contact of the water sample with the end-cap O-rings after closing. The O-rings used in these water sample bottles were vacuum-baked prior to the first station. Stainless steel springs covered with a nylon powder coat were substituted for the internal elastic tubing standardly used to close Niskin bottles. Water samples for CFC analysis were usually the first samples collected from the 10 liter bottles. Care was taken to co-ordinate the sampling of CFCs with other samples to minimize the time between the inital opening of each bottle and the completion of sample drawing. In most cases, dissolved oxygen, total CO2, alkalinity and pH samples were collected within several minutes of the initial opening of each bottle. To minimize contact with air, the CFC samples were drawn directly through the stopcocks of the 10 liter bottles into 100 ml precision glass syringes equipped with 2-way metal stopcocks. The syringes were immersed in a holding tank of clean surface seawater until analyses. To reduce the possibility of contamination from high levels of CFCs frequently present in the air inside research vessels, the CFC extraction/analysis system and syringe holding tank were housed in a modified 20' laboratory van on the deck of the ship. For air sampling, a ~100 meter length of 3/8" OD Dekaron tubing was run from the CFC lab van to the bow of the ship. Air was sucked through this line into the CFC van using an Air Cadet pump. The air was compressed in the pump, with the downstream pressure held at about 1.5 atm using a back-pressure regulator. A tee allowed a flow (~100 cc/min) of the compressed air to be directed to the gas sample valves, while the bulk flow of the air (>7 liter/minute) was vented through the back pressure regulator. Concentrations of CFC-11 and CFC-12 in air samples, seawater and gas standards on the cruise were measured by shipboard electron capture gas chromatography (EC-GC), using techniques similiar to those described by Bullister and Weiss (1988). For seawater analyses, a ~30-ml aliquot of seawater from the glass syringe was transferred into the glass sparging chamber. The dissolved CFCs in the seawater sample were extracted by passing a supply of CFC-free purge gas through the sparging chamber for a period of 4 minutes at ~70 cc/min. Water vapor was removed from the purge gas while passing through a short tube of magnesium perchlorate dessicant. The sample gases were concentrated on a cold-trap consisting of a 3-inch section of 1/8-inch stainless steel tubing packed with Porapak N (60-80 mesh) immersed in a bath of isopropanol held at -20°C. After 4 minutes of purging the seawater sample, the sparging chamber was closed and the trap isolated. The cold isopropanol in the bath was forced away from the trap which was heated electrically to 125°C. The sample gases held in the trap were then injected onto a precolumn (12 inches of 1/8-inch O.D. stainless steel tubing packed with 80-100 mesh Porasil C, held at 90°C), for the initial separation of the CFCs and other rapidly eluting gases from more slowly eluting compounds. The CFCs then passed into the main analytical column (10 feet, 1/8-inch stainless steel tubing packed with Porasil C 80-100 mesh, held at 90°C), and then into the EC detector. The CFC analytical system was calibrated frequently using standard gas of known CFC composition. Gas sample loops of known volume were thoroughly flushed with standard gas and injected into the system. The temperature and pressure was recorded so that the amount of gas injected could be calculated. The procedures used to transfer the standard gas to the trap, precolumn, main chromatographic column and EC detector were similar to those used for analyzing water samples. Two sizes of gas sample loops were present in the analytical system. Multiple injections of these loop volumes could be done to allow the system to be calibrated over a relatively wide range of CFC concentrations. Air samples and system blanks (injections of loops of CFC-free gas) were injected and analyzed in a similar manner. The typical analysis time for seawater, air, standard and blank samples was about 12 minutes. Concentrations of CFC-11 and CFC-12 in air, seawater samples and gas standards are reported relative to the SIO93 calibration scale (Cunnold, et. al., 1994). CFC concentrations in air and standard gas are reported in units of mole fraction CFC in dry gas, and are typically in the parts-per-trillion (ppt) range. Dissolved CFC concentrations are given in units of picomoles of CFC per kg seawater (pmol/kg). CFC concentrations in air and seawater samples were determined by fitting their chromatographic peak areas to multi-point calibration curves, generated by injecting multiple sample loops of gas from a CFC working standard (PMEL cylinder 33790) into the analytical instrument. The concentrations of CFC-11 and CFC-12 in this working standard were calibrated before and after the cruise versus a primary standard (36743) (Bullister, 1984). No measurable drift in the concentrations of CFC-11 and CFC-12 in the working standard could be detected during this interval. Full range calibration curves were run at intervals of ~ 3 days during the cruise. Single injections of a fixed volume of standard gas at one atmosphere were run much more frequently (at intervals of 1 to 2 hours) to monitor short term changes in detector sensitivity. Extremely low (<0.01 pmol/kg) CFC concentrations were measured in deep water (2000-3000 meters) from about 30°S to the equator along the P15S section, as expected from CFC measurements made during the earlier occupation of this section in 1990 (Wisegarveret al, 1995), and from other transient tracer studies made in this region of the southwest Pacific. Based on the median of CFC concentration measurements in the deep water of this region, which is believed to be nearly CFC-free, a blank correction of of 0.003 pmol/kg for CFC-11 and 0 pmol/kg for CFC-12 have been applied to the data set. For very low concentration water samples, subtraction of the water sample CFC-11 blank from the measured CFC-11 water sample concentration yields a small negative reported value. On this expedition, we estimate precisions (1 standard deviation) of about 1% or 0.005 pmol/kg (whichever is greater) for dissolved CFC-11 and CFC-12 measurements (see listing of replicate samples given at the end of this report). A number of water samples had clearly anomolous CFC-11 and/or CFC-12 concentrations relative to adjacent samples. These anomolous samples appeared to occur more or less randomly during the cruise, and were not clearly associated with other features in the water column (eg. elevated oxygen concentrations, salinity or temperature features, etc.). This suggests that the high values were due to individual, isolated low-level CFC contamination events. These samples are included in this report and are give a quality flag of either 3 (questionable measurement) or 4 (bad measurement). A total ~24 analyses of CFC-11 were assigned a flag of 3 and ~33 analyses of CFC-12 were assigned a flag of 3. A total of ~31 analyses of CFC-11 were assigned a flag of 4 and ~178 CFC-12 samples assigned a flag of 4. A value of -9.0 is used for missing values in the listings. CFC REFERENCES: Bullister, J.L. Anthropogenic Chlorofluoromethanes as Tracers of Ocean Circulation and Mixing Processes: Measurement and Calibration Techniques and Studies in the Greenland and Norwegian Seas, Ph.D. dissertation, Univ. Calif. San Diego, 172 pp. Bullister, J.L. and R.F. Weiss, Determination of CCl3F and CCl2F2 in seawater and air. Deep-Sea Research, 35 (5), 839-853, 1988. Cunnold, D.M., P.J. Fraser, R.F. Weiss, R.G. Prinn, P.G. Simmonds, B.R. Miller,F.N. Alyea, and A.J.Crawford. Global trends and annual releases of CCl3F and CCl2F2 estimated from ALE/GAGE and other measurements from July 1978 to June 1991. J. Geophys. Res., 99, 1107- 1126, 1994. Wisegarver, D.P., J.L. Bullister, F.A. Van Woy, F.A. Menzia, R.F. Weiss, A.H. Orsi, and PK. Salameh (1995). Chlorofluorocarbon Measurements in the Southwestern Pacific During the CGC-90 Expedition NOAA Data Report 1656 ____________________________________________________________________________________________ ____________________________________________________________________________________________ APPENDIX 2A: CFC AIR MEASUREMENTS (Interpolated to station locations) STATION F11 F12 NUMBER Latitude Longitude Date PPT PPT ------- --------- ---------- --------- ----- ----- 1 45 49.5 S 153 05.1 E 6 Jan 96 260.5 519.1 2 48 19.1 S 158 29.9 E 7 Jan 96 260.5 519.1 3 50 05.0 S 162 29.3 E 8 Jan 96 260.5 519.1 4 53 00.1 S 169 59.3 E 9 Jan 96 260.5 519.1 5 53 29.9 S 170 29.7 E 9 Jan 96 260.5 519.1 6 53 59.9 S 171 00.1 E 9 Jan 96 260.5 519.1 7 54 10.2 S 171 10.8 E 9 Jan 96 260.5 519.1 8 54 19.8 S 171 20.2 E 9 Jan 96 260.5 519.1 9 54 30.3 S 171 29.8 E 9 Jan 96 260.4 519.2 10 54 59.7 S 172 00.7 E 10 Jan 96 260.5 519.9 11 55 30.4 S 172 27.0 E 10 Jan 96 260.2 519.5 12 55 59.8 S 173 00.6 E 10 Jan 96 260.2 519.5 13 56 29.2 S 173 30.2 E 11 Jan 96 260.2 519.4 14 56 59.7 S 173 58.6 E 11 Jan 96 260.2 519.4 15 57 30.3 S 173 58.5 E 11 Jan 96 260.2 519.4 16 58 00.2 S 173 59.5 E 12 Jan 96 260.2 519.4 17 58 30.2 S 173 58.2 E 12 Jan 96 260.4 519.7 18 58 59.8 S 174 00.0 E 12 Jan 96 260.4 519.7 19 59 28.7 S 173 59.7 E 12 Jan 96 259.8 519.3 20 59 57.9 S 173 57.9 E 13 Jan 96 259.5 519.1 21 60 30.3 S 173 57.8 E 13 Jan 96 259.4 519.3 22 60 59.1 S 173 58.9 E 14 Jan 96 259.4 519.3 23 61 30.0 S 174 00.2 E 14 Jan 96 259.4 519.3 24 62 00.0 S 173 16.1 E 14 Jan 96 259.4 519.3 25 62 26.9 S 172 35.2 E 14 Jan 96 259.4 519.3 26 62 44.7 S 172 09.0 E 15 Jan 96 259.4 519.3 27 62 60.0 S 171 44.9 E 15 Jan 96 259.4 519.3 28 63 30.1 S 170 59.6 E 15 Jan 96 259.4 519.3 29 63 59.8 S 171 06.6 E 16 Jan 96 259.4 519.3 30 64 40.6 S 170 58.6 E 16 Jan 96 259.4 519.3 31 65 20.2 S 170 60.0 E 16 Jan 96 259.4 519.3 32 66 00.9 S 171 01.6 E 17 Jan 96 259.4 519.3 33 66 59.6 S 170 00.0 W 18 Jan 96 261.4 522.5 34 66 20.3 S 169 60.0 W 18 Jan 96 261.4 522.5 35 65 39.8 S 170 00.3 W 19 Jan 96 261.4 522.5 36 64 59.6 S 170 00.9 W 19 Jan 96 261.4 522.5 37 64 30.1 S 169 59.9 W 19 Jan 96 260.3 523.7 38 63 59.7 S 170 02.0 W 19 Jan 96 260.3 523.7 39 63 30.1 S 170 00.3 W 20 Jan 96 260.3 523.7 40 62 59.7 S 170 01.4 W 20 Jan 96 260.0 522.5 41 62 30.0 S 169 59.8 W 20 Jan 96 259.3 521.5 42 62 00.2 S 169 59.9 W 20 Jan 96 259.3 521.5 43 61 29.5 S 169 60.0 W 21 Jan 96 259.2 523.0 44 61 00.1 S 170 00.3 W 21 Jan 96 259.2 523.0 45 60 29.7 S 169 59.6 W 22 Jan 96 259.0 522.9 46 60 00.3 S 170 00.3 W 22 Jan 96 259.0 522.9 47 59 30.2 S 169 59.9 W 22 Jan 96 259.0 522.9 48 58 59.9 S 170 00.2 W 22 Jan 96 259.8 524.5 49 58 29.6 S 170 00.8 W 23 Jan 96 259.8 524.5 STATION F11 F12 NUMBER Latitude Longitude Date PPT PPT ------- --------- ---------- --------- ----- ----- 50 57 59.7 S 170 00.8 W 23 Jan 96 259.8 524.5 51 57 30.1 S 170 00.4 W 23 Jan 96 259.8 524.5 52 57 00.2 S 170 00.2 W 24 Jan 96 259.8 524.5 53 56 29.9 S 169 59.8 W 24 Jan 96 259.8 524.5 54 55 60.0 S 170 01.8 W 24 Jan 96 261.8 521.8 55 55 29.9 S 170 00.0 W 24 Jan 96 261.8 521.8 56 54 59.8 S 169 60.0 W 25 Jan 96 261.2 520.6 57 54 29.4 S 170 00.1 W 25 Jan 96 261.2 520.6 58 54 00.1 S 169 59.3 W 25 Jan 96 261.2 520.6 59 53 39.9 S 169 59.4 W 25 Jan 96 261.3 520.1 60 53 19.9 S 169 59.6 W 26 Jan 96 261.3 520.1 61 52 60.0 S 170 00.5 W 26 Jan 96 261.3 520.1 62 52 29.9 S 170 01.8 W 26 Jan 96 261.3 520.1 63 52 00.1 S 170 07.8 W 26 Jan 96 261.3 520.1 64 51 30.0 S 170 00.2 W 27 Jan 96 261.3 520.1 65 51 00.2 S 170 00.4 W 27 Jan 96 261.3 520.1 66 50 29.9 S 169 59.6 W 27 Jan 96 260.2 519.6 67 50 00.4 S 169 59.9 W 28 Jan 96 260.2 519.6 68 49 30.2 S 170 00.9 W 28 Jan 96 260.2 519.6 69 48 59.6 S 169 59.4 W 28 Jan 96 260.3 519.7 70 48 30.0 S 170 00.2 W 28 Jan 96 260.4 520.1 71 47 59.8 S 170 00.3 W 29 Jan 96 260.4 520.1 72 47 30.2 S 169 59.8 W 29 Jan 96 260.4 520.1 73 47 06.5 S 170 27.7 W 29 Jan 96 260.4 520.1 74 46 43.4 S 170 54.7 W 30 Jan 96 260.4 520.1 75 46 20.0 S 171 22.2 W 30 Jan 96 260.4 520.1 76 45 57.0 S 171 49.5 W 30 Jan 96 260.4 520.1 77 45 33.6 S 172 16.7 W 30 Jan 96 260.4 520.1 78 45 10.6 S 172 44.2 W 31 Jan 96 260.7 520.4 79 44 50.1 S 173 08.2 W 31 Jan 96 260.7 520.4 80 44 31.8 S 173 29.4 W 31 Jan 96 261.0 520.5 81 44 19.2 S 173 44.7 W 31 Jan 96 261.0 520.5 82 44 09.4 S 173 56.3 W 1 Feb 96 261.0 520.5 83 43 50.9 S 174 17.7 W 1 Feb 96 261.0 520.5 84 43 38.8 S 174 32.2 W 1 Feb 96 261.0 520.5 85 43 15.2 S 174 59.9 W 1 Feb 96 261.0 520.5 86 42 55.9 S 174 47.2 W 1 Feb 96 261.0 520.5 87 42 44.8 S 174 39.3 W 1 Feb 96 261.0 520.5 88 42 24.1 S 174 24.4 W 1 Feb 96 261.0 520.5 89 42 10.0 S 174 15.0 W 2 Feb 96 261.0 520.5 90 41 42.8 S 173 56.5 W 2 Feb 96 261.0 520.5 91 41 16.0 S 173 38.6 W 2 Feb 96 261.0 520.5 92 40 49.5 S 173 19.5 W 2 Feb 96 261.0 520.5 93 40 23.6 S 173 02.0 W 2 Feb 96 261.0 520.5 94 40 23.5 S 173 01.7 W 13 Feb 96 260.4 521.7 95 39 57.7 S 172 42.2 W 14 Feb 96 260.4 521.6 96 39 31.0 S 172 25.2 W 14 Feb 96 260.1 521.7 97 39 04.3 S 172 07.7 W 14 Feb 96 260.1 521.7 98 38 37.8 S 171 48.6 W 14 Feb 96 260.1 521.7 99 38 11.4 S 171 30.2 W 15 Feb 96 260.1 521.7 STATION F11 F12 NUMBER Latitude Longitude Date PPT PPT ------- --------- ---------- --------- ----- ----- 100 37 45.8 S 171 12.0 W 15 Feb 96 260.1 521.7 101 37 18.6 S 170 53.7 W 15 Feb 96 260.1 521.7 102 36 52.3 S 170 37.0 W 15 Feb 96 260.1 521.7 103 36 27.0 S 170 17.2 W 16 Feb 96 260.8 521.9 104 36 00.2 S 170 00.3 W 16 Feb 96 260.8 521.9 105 35 40.3 S 170 00.9 W 16 Feb 96 260.8 521.9 106 35 20.0 S 170 00.1 W 16 Feb 96 260.8 521.9 107 35 00.5 S 169 59.6 W 17 Feb 96 260.8 521.9 108 34 30.2 S 170 00.2 W 17 Feb 96 260.8 521.9 109 33 59.8 S 169 60.0 W 17 Feb 96 260.8 521.9 110 33 29.9 S 170 00.1 W 18 Feb 96 260.8 521.9 111 33 00.1 S 170 00.1 W 18 Feb 96 260.8 521.9 112 32 30.1 S 170 00.1 W 18 Feb 96 260.8 521.9 113 31 59.8 S 169 59.8 W 18 Feb 96 260.8 521.9 114 31 30.0 S 169 59.3 W 19 Feb 96 260.6 521.7 115 31 00.4 S 169 59.7 W 19 Feb 96 260.6 521.9 116 30 30.3 S 169 59.8 W 19 Feb 96 260.6 521.9 117 30 00.2 S 169 59.8 W 19 Feb 96 260.6 521.9 118 29 30.2 S 169 59.8 W 20 Feb 96 260.6 521.9 119 29 00.8 S 169 59.9 W 20 Feb 96 260.6 521.9 120 28 30.5 S 169 59.8 W 20 Feb 96 260.6 521.9 121 28 00.3 S 169 59.6 W 21 Feb 96 260.6 521.9 122 27 30.1 S 170 00.1 W 21 Feb 96 260.6 521.9 123 27 00.3 S 169 59.5 W 21 Feb 96 260.8 522.1 124 26 29.7 S 169 59.4 W 21 Feb 96 260.6 521.9 125 26 00.3 S 169 59.7 W 22 Feb 96 260.6 521.9 126 25 30.0 S 169 60.0 W 22 Feb 96 260.6 521.9 127 25 00.1 S 169 59.9 W 22 Feb 96 260.9 522.3 128 24 30.1 S 170 00.1 W 23 Feb 96 260.9 522.3 129 23 59.8 S 170 00.1 W 23 Feb 96 261.3 522.7 130 23 30.1 S 170 00.1 W 23 Feb 96 261.3 522.7 131 22 59.8 S 169 59.7 W 23 Feb 96 261.3 522.7 132 22 30.0 S 169 59.9 W 24 Feb 96 261.3 522.7 133 22 00.0 S 169 59.9 W 24 Feb 96 261.3 522.7 134 21 30.4 S 170 00.1 W 24 Feb 96 261.3 522.7 135 20 59.7 S 169 59.6 W 25 Feb 96 262.1 524.4 136 20 29.9 S 170 00.1 W 25 Feb 96 262.1 524.4 137 20 00.0 S 170 00.1 W 25 Feb 96 262.1 524.4 138 19 29.9 S 170 00.1 W 25 Feb 96 262.1 524.4 139 19 00.1 S 170 03.4 W 26 Feb 96 262.1 524.4 140 18 30.3 S 170 00.1 W 26 Feb 96 262.1 524.4 141 17 60.0 S 169 60.0 W 26 Feb 96 262.1 524.4 142 17 30.1 S 169 60.0 W 26 Feb 96 262.1 524.4 143 17 00.1 S 169 59.8 W 27 Feb 96 262.3 525.0 144 16 30.3 S 169 59.9 W 27 Feb 96 262.7 525.9 145 16 00.2 S 169 59.9 W 27 Feb 96 262.7 525.9 146 15 29.8 S 170 00.1 W 27 Feb 96 262.8 525.6 147 15 00.2 S 170 00.0 W 28 Feb 96 262.8 525.6 148 14 40.0 S 169 59.9 W 28 Feb 96 262.9 525.5 149 14 16.9 S 169 59.8 W 28 Feb 96 262.9 525.5 STATION F11 F12 NUMBER Latitude Longitude Date PPT PPT ------- --------- ---------- --------- ----- ----- 150 13 58.3 S 169 60.0 W 28 Feb 96 262.9 525.5 151 13 49.1 S 170 00.1 W 28 Feb 96 262.9 525.5 152 13 30.1 S 169 60.0 W 29 Feb 96 262.9 525.5 153 12 59.9 S 170 00.0 W 29 Feb 96 262.9 525.5 154 12 29.9 S 169 59.9 W 29 Feb 96 262.9 525.5 155 12 00.1 S 170 00.1 W 29 Feb 96 262.9 525.5 156 11 30.0 S 169 59.9 W 1 Mar 96 262.9 525.5 157 11 00.1 S 169 59.9 W 1 Mar 96 262.9 525.5 158 10 30.1 S 169 59.8 W 1 Mar 96 262.9 525.5 159 09 55.6 S 169 37.7 W 1 Mar 96 262.6 525.3 160 09 30.1 S 168 59.9 W 2 Mar 96 262.6 525.3 161 08 59.9 S 168 52.6 W 2 Mar 96 262.6 525.0 162 08 29.9 S 168 44.9 W 2 Mar 96 262.6 525.0 163 08 00.0 S 168 37.0 W 2 Mar 96 262.6 525.0 164 07 30.1 S 168 44.9 W 3 Mar 96 262.6 525.0 165 06 60.0 S 168 44.9 W 3 Mar 96 262.8 526.1 166 06 30.1 S 168 44.9 W 3 Mar 96 262.7 526.5 167 06 00.0 S 168 45.0 W 4 Mar 96 262.7 526.5 168 05 30.1 S 168 45.0 W 4 Mar 96 262.7 526.5 169 05 00.0 S 168 44.9 W 4 Mar 96 262.7 526.5 170 03 60.0 S 168 45.1 W 4 Mar 96 262.7 526.5 171 03 00.0 S 168 45.0 W 5 Mar 96 263.0 527.3 172 02 00.1 S 168 45.0 W 5 Mar 96 263.5 528.4 173 01 00.1 S 168 45.2 W 6 Mar 96 263.5 528.4 174 00 00.1 S 168 45.0 W 6 Mar 96 263.5 528.4 175 07 44.8 S 168 40.2 W 8 Mar 96 262.7 526.5 176 08 15.1 S 168 41.3 W 8 Mar 96 262.7 526.5 177 10 08.7 S 168 58.8 W 8 Mar 96 262.7 526.5 178 10 04.1 S 169 12.7 W 8 Mar 96 262.7 526.5 179 09 55.2 S 169 37.7 W 9 Mar 96 262.7 526.5 180 09 47.0 S 170 03.5 W 9 Mar 96 262.7 526.5 181 09 41.6 S 170 19.5 W 9 Mar 96 262.7 526.5 182 09 35.7 S 170 36.1 W 9 Mar 96 262.7 526.5 APPENDIX 2B: REPLICATE CFC-11 MEASUREMENTS STATION SAMP F11 F11 NUMBER NO. pM/kg Stdev ---------------------------------- 1 112 0.092 0.007 4 110 4.157 0.012 5 113 4.117 0.008 9 202 0.136 0.015 9 234 4.672 0.035 10 201 0.155 0.003 10 211 0.050 0.001 10 214 0.095 0.004 11 101 0.148 0.007 14 101 0.143 0.000 14 134 4.542 0.030 15 201 0.144 0.001 15 234 4.674 0.009 16 101 0.148 0.002 16 110 0.047 0.003 17 103 0.134 0.002 17 133 5.035 0.037 18 134 4.864 0.061 21 123 5.464 0.042 25 110 0.087 0.001 28 101 0.180 0.005 28 112 0.226 0.001 28 124 6.359 0.131 29 201 0.496 0.001 29 212 0.250 0.001 29 230 6.393 0.097 30 101 1.373 0.007 30 133 6.172 0.033 31 203 1.422 0.021 31 225 0.662 0.019 32 111 0.091 0.006 32 115 0.124 0.006 33 103 0.664 0.002 33 131 4.790 0.014 34 101 0.579 0.006 34 103 0.542 0.001 34 107 0.190 0.003 35 101 0.524 0.004 35 103 0.512 0.000 35 133 6.287 0.029 39 101 0.128 0.001 39 121 6.277 0.107 39 124 6.638 0.087 40 101 0.108 0.005 40 133 6.720 0.006 41 103 0.077 0.007 41 133 6.678 0.030 42 101 0.093 0.001 42 133 6.521 0.013 43 111 0.186 0.000 43 120 5.799 0.006 45 110 0.184 0.002 45 115 1.009 0.013 45 123 5.791 0.022 46 103 0.049 0.007 46 129 5.699 0.029 48 101 0.060 0.001 48 110 0.034 0.001 49 101 0.080 0.001 49 111 0.044 0.005 49 120 0.727 0.001 49 129 4.880 0.019 STATION SAMP F11 F11 NUMBER NO. pM/kg Stdev ---------------------------------- 50 104 0.045 0.008 50 116 0.198 0.008 50 132 5.214 0.038 52 101 0.090 0.000 52 110 0.040 0.009 52 113 0.058 0.002 52 121 1.006 0.009 52 132 5.044 0.006 53 103 0.084 0.003 53 125 3.138 0.019 54 102 0.082 0.007 54 114 0.074 0.000 54 132 4.758 0.088 56 103 0.078 0.000 56 111 0.039 0.001 56 132 4.654 0.025 57 103 0.073 0.004 58 211 0.035 0.006 58 232 4.508 0.036 61 103 0.086 0.006 61 113 0.083 0.003 61 123 3.373 0.011 61 131 4.015 0.003 62 203 0.068 0.003 63 103 0.052 0.002 63 122 4.015 0.021 65 101 0.090 0.002 65 110 0.103 0.003 65 114 2.096 0.021 65 122 4.111 0.004 66 101 0.082 0.001 66 133 3.836 0.007 67 202 0.071 0.000 67 233 3.457 0.002 68 102 0.067 0.003 69 201 0.080 0.001 69 231 3.791 0.000 70 101 0.072 0.001 70 107 0.026 0.000 71 104 0.051 0.001 71 128 4.000 0.007 72 101 0.084 0.003 73 103 0.070 0.005 73 115 0.290 0.003 73 133 3.444 0.008 74 202 0.088 0.006 75 102 0.095 0.001 75 128 3.592 0.027 76 201 0.101 0.003 76 203 0.082 0.001 76 208 0.037 0.003 77 102 0.089 0.000 77 112 0.063 0.002 77 133 3.101 0.001 78 101 0.094 0.005 79 102 0.045 0.001 79 132 2.876 0.002 80 203 0.030 0.004 81 109 0.796 0.004 83 101 0.372 0.002 83 105 1.986 0.003 86 101 0.199 0.006 87 101 0.030 0.003 88 101 0.016 0.001 88 104 0.005 0.001 88 113 1.807 0.007 88 125 3.050 0.021 89 202 0.018 0.000 89 206 0.012 0.003 89 232 2.466 0.001 90 103 0.012 0.003 92 201 0.054 0.004 93 102 0.058 0.000 94 102 0.055 0.002 94 112 0.009 0.002 94 130 2.911 0.013 95 101 0.065 0.000 96 102 0.055 0.001 96 119 0.344 0.008 96 135 2.563 0.001 97 201 0.068 0.002 98 102 0.046 0.002 98 134 2.506 0.007 STATION SAMP F11 F11 NUMBER NO. pM/kg Stdev ---------------------------------- 100 101 0.067 0.006 100 118 0.095 0.000 101 227 2.735 0.014 102 102 0.031 0.000 102 124 1.114 0.008 104 101 0.029 0.001 104 132 3.014 0.022 105 201 0.018 0.002 105 203 0.006 0.001 105 205 0.002 0.002 106 102 0.029 0.000 106 134 2.344 0.013 108 101 0.024 0.002 108 134 2.594 0.013 109 101 0.021 0.001 110 202 0.016 0.001 110 234 2.336 0.023 112 102 0.020 0.000 112 132 2.632 0.008 113 101 0.015 0.000 114 104 0.012 0.000 114 135 2.035 0.006 115 101 0.014 0.001 116 201 0.013 0.001 116 204 0.012 0.000 116 223 0.596 0.005 116 234 1.946 0.007 117 101 0.013 0.002 117 107 0.005 0.000 118 103 0.011 0.000 118 128 2.240 0.001 119 103 0.014 0.002 120 201 0.012 0.000 120 205 0.008 0.001 120 227 1.996 0.040 120 234 2.237 0.008 121 201 0.010 0.001 122 102 0.011 0.000 122 105 0.004 0.002 122 132 2.404 0.000 123 101 0.009 0.000 124 101 0.009 0.000 124 130 2.283 0.015 124 135 1.766 0.003 125 303 0.009 0.001 125 334 1.959 0.018 126 101 0.008 0.001 126 132 2.142 0.012 127 201 0.013 0.000 127 210 0.001 0.001 127 226 1.524 0.002 127 235 1.814 0.013 128 201 0.013 0.002 129 102 0.009 0.000 129 135 1.755 0.020 130 101 0.011 0.001 130 107 0.007 0.001 130 125 1.222 0.006 131 134 1.935 0.008 132 102 0.013 0.001 132 119 0.003 0.001 132 133 1.930 0.011 133 101 0.011 0.001 134 201 0.012 0.000 134 235 1.630 0.005 135 201 0.013 0.002 135 215 -0.001 0.000 135 234 1.919 0.001 136 103 0.010 0.000 137 101 0.011 0.002 137 121 0.003 0.002 137 133 1.892 0.002 140 102 0.009 0.000 140 133 1.872 0.004 141 101 0.011 0.001 142 102 0.015 0.002 142 123 0.071 0.000 142 135 1.641 0.007 143 101 0.011 0.000 144 102 0.006 0.001 144 129 1.962 0.011 145 103 0.005 0.002 146 102 0.007 0.001 146 125 0.351 0.001 146 131 1.827 0.011 147 101 0.009 0.000 148 121 0.719 0.000 STATION SAMP F11 F11 NUMBER NO. pM/kg Stdev ---------------------------------- 150 234 1.566 0.003 151 102 0.006 0.001 151 135 1.552 0.018 152 101 0.007 0.002 153 102 0.006 0.000 153 132 1.689 0.002 154 101 0.006 0.001 154 103 0.006 0.000 155 102 0.006 0.000 155 122 0.009 0.001 155 134 1.566 0.003 156 102 0.008 0.002 157 104 0.004 0.001 158 102 0.006 0.000 159 102 0.008 0.002 159 103 0.005 0.001 159 134 1.553 0.012 160 103 0.006 0.001 161 103 0.003 0.001 161 131 1.715 0.014 162 201 0.005 0.001 163 201 0.005 0.000 163 229 1.620 0.002 164 104 0.002 0.001 166 201 0.003 0.001 167 201 0.003 0.002 167 230 1.936 0.007 169 201 0.004 0.001 169 226 0.055 0.002 169 235 1.666 0.013 170 101 0.004 0.001 170 129 1.045 0.003 171 101 0.005 0.001 171 128 0.343 0.003 172 221 0.176 0.000 172 233 1.741 0.001 173 201 0.003 0.002 173 225 0.056 0.004 173 231 1.689 0.001 174 101 -0.000 0.000 175 204 0.003 0.000 176 101 0.005 0.001 177 101 0.003 0.000 177 104 0.000 0.000 178 101 0.005 0.000 179 101 0.005 0.000 180 101 0.005 0.001 181 101 0.006 0.000 182 101 0.006 0.001 APPENDIX 2C: REPLICATE CFC-12 MEASUREMENTS STATION SAMP F12 F12 NUMBER NO. pM/kg Stdev --------------------------------- 1 112 0.043 0.007 4 110 2.188 0.007 5 113 2.131 0.012 9 202 0.070 0.007 9 234 2.408 0.013 10 201 0.080 0.003 10 214 0.050 0.002 11 101 0.083 0.010 14 101 0.070 0.001 14 134 2.317 0.007 15 201 0.072 0.002 15 234 2.395 0.011 16 101 0.070 0.003 16 110 0.021 0.002 17 103 0.066 0.001 17 133 2.571 0.031 18 134 2.457 0.015 21 123 2.772 0.035 25 110 0.038 0.004 28 101 0.082 0.003 28 112 0.106 0.001 28 124 3.075 0.054 29 201 0.228 0.003 29 212 0.115 0.002 29 230 3.072 0.048 30 101 0.646 0.013 30 133 2.976 0.021 31 203 0.682 0.008 31 225 0.415 0.084 33 103 0.321 0.003 33 131 2.343 0.018 34 101 0.286 0.001 34 103 0.306 0.033 34 107 0.104 0.004 35 101 0.265 0.008 35 103 0.245 0.001 35 133 3.094 0.002 39 101 0.061 0.001 39 121 3.011 0.075 39 124 3.165 0.026 40 101 0.064 0.004 40 133 3.191 0.001 41 103 0.039 0.003 41 133 3.186 0.005 42 101 0.053 0.002 42 133 3.133 0.007 43 111 0.090 0.004 43 120 2.826 0.011 45 101 0.033 0.002 45 110 0.088 0.008 45 115 0.472 0.002 45 123 2.837 0.029 46 103 0.025 0.001 46 129 2.800 0.030 48 101 0.028 0.001 48 110 0.025 0.002 49 101 0.040 0.001 49 111 0.027 0.004 49 120 0.349 0.003 49 129 2.413 0.021 STATION SAMP F12 F12 NUMBER NO. pM/kg Stdev --------------------------------- 50 104 0.027 0.000 50 116 0.097 0.001 50 132 2.642 0.018 52 101 0.044 0.001 52 110 0.021 0.006 52 113 0.030 0.004 52 121 0.476 0.008 52 132 2.556 0.008 53 103 0.046 0.000 53 125 1.531 0.004 54 102 0.044 0.002 54 114 0.042 0.008 54 132 2.414 0.032 56 103 0.043 0.004 56 111 0.021 0.001 56 132 2.422 0.007 57 103 0.032 0.002 58 211 0.019 0.001 58 232 2.323 0.020 61 103 0.038 0.005 61 113 0.041 0.002 61 123 1.680 0.011 61 131 2.128 0.030 62 203 0.034 0.004 63 103 0.028 0.000 63 122 2.119 0.011 65 101 0.049 0.003 65 110 0.050 0.002 65 114 1.009 0.016 65 122 2.133 0.012 66 101 0.046 0.008 66 133 2.050 0.001 67 202 0.040 0.000 67 233 1.864 0.013 68 102 0.037 0.002 69 201 0.041 0.001 69 231 2.000 0.005 70 101 0.039 0.003 70 107 0.014 0.001 71 104 0.032 0.001 72 101 0.045 0.000 73 103 0.043 0.002 73 115 0.144 0.000 73 133 1.841 0.009 74 202 0.056 0.007 75 128 1.863 0.011 76 201 0.053 0.004 76 203 0.059 0.004 77 102 0.058 0.002 77 133 1.695 0.012 78 101 0.076 0.007 79 132 1.610 0.013 81 109 0.474 0.008 83 101 0.235 0.007 83 105 1.014 0.014 86 101 0.153 0.005 88 113 0.959 0.018 88 125 1.701 0.001 89 232 1.394 0.025 90 103 0.004 0.003 93 102 0.035 0.001 94 102 0.031 0.004 94 130 1.535 0.001 95 101 0.034 0.000 96 102 0.028 0.000 96 119 0.182 0.003 96 135 1.402 0.008 97 201 0.037 0.004 98 102 0.030 0.000 98 134 1.365 0.011 STATION SAMP F12 F12 NUMBER NO. pM/kg Stdev --------------------------------- 100 101 0.041 0.005 100 118 0.058 0.005 100 135 1.310 0.003 101 227 1.374 0.025 102 102 0.018 0.002 102 124 0.565 0.005 104 101 0.017 0.000 104 132 1.615 0.018 105 201 0.014 0.001 105 203 0.006 0.000 105 205 0.003 0.000 106 102 0.018 0.003 106 134 1.288 0.015 108 101 0.012 0.001 108 134 1.382 0.000 109 101 0.013 0.003 110 202 0.011 0.000 110 234 1.267 0.024 112 102 0.012 0.001 112 132 1.398 0.006 113 101 0.010 0.001 114 104 0.009 0.000 114 135 1.135 0.012 115 101 0.009 0.001 116 201 0.010 0.000 116 204 0.009 0.001 116 223 0.306 0.000 116 234 1.094 0.017 117 101 0.009 0.003 117 107 0.004 0.001 118 103 0.007 0.000 118 128 1.166 0.003 119 103 0.007 0.000 120 201 0.008 0.000 120 205 0.007 0.000 120 227 0.988 0.002 120 234 1.227 0.003 121 201 0.007 0.001 122 102 0.007 0.001 122 105 0.004 0.000 122 132 1.295 0.003 123 101 0.005 0.000 124 101 0.006 0.001 124 130 1.213 0.009 124 135 1.000 0.005 125 303 0.004 0.000 125 334 1.081 0.004 126 101 0.004 0.000 126 132 1.174 0.011 127 201 0.007 0.000 127 210 0.002 0.001 127 226 0.755 0.002 127 235 1.029 0.004 128 201 0.007 0.000 129 102 0.005 0.000 129 135 0.996 0.006 130 101 0.005 0.000 130 107 0.004 0.001 130 125 0.600 0.004 131 134 1.077 0.006 132 102 0.006 0.001 132 119 0.004 0.001 133 101 0.006 0.000 134 201 0.007 0.001 134 235 0.935 0.018 135 201 0.008 0.000 135 215 0.001 0.001 135 234 1.073 0.004 136 103 0.005 0.000 137 101 0.006 0.001 137 121 0.002 0.000 137 133 1.059 0.005 140 102 0.004 0.000 140 133 1.056 0.003 141 101 0.006 0.000 142 102 0.006 0.001 142 123 0.045 0.007 142 135 0.946 0.012 143 101 0.005 0.001 144 102 0.003 0.000 144 129 1.056 0.009 145 103 0.002 0.001 146 102 0.003 0.001 146 125 0.192 0.003 146 131 1.012 0.006 147 101 0.003 0.000 148 121 0.369 0.007 STATION SAMP F12 F12 NUMBER NO. pM/kg Stdev --------------------------------- 150 234 0.914 0.004 151 102 0.001 0.002 151 135 0.888 0.006 152 101 0.005 0.002 153 102 0.003 0.000 153 132 0.946 0.003 154 101 0.001 0.002 154 103 0.001 0.000 155 102 0.002 0.001 155 122 0.004 0.001 155 134 0.892 0.013 156 102 0.003 0.001 157 104 0.001 0.000 158 102 0.003 0.001 159 102 0.002 0.000 159 103 0.002 0.001 159 134 0.910 0.038 160 103 0.002 0.001 161 103 0.000 0.001 161 131 0.935 0.008 162 201 0.003 0.000 163 201 0.002 0.001 163 229 0.848 0.001 164 104 0.000 0.001 167 201 0.002 0.000 167 230 1.042 0.006 169 201 0.002 0.001 169 226 0.029 0.002 169 235 0.937 0.004 170 101 0.009 0.000 170 129 0.551 0.002 171 101 0.000 0.001 171 128 0.180 0.002 172 221 0.089 0.001 172 233 0.949 0.006 173 201 0.000 0.000 173 225 0.020 0.002 173 231 0.879 0.007 174 101 0.000 0.000 178 101 0.003 0.000 179 101 0.002 0.000 180 101 0.004 0.002 181 101 0.004 0.000 182 101 0.004 0.001 ____________________________________________________________________________________________ ____________________________________________________________________________________________ B.4. CARBON MEASUREMENT TECHNIQUES B.4.1 pH Seawater samples were drawn from the PVC bottles with a 25-cm length of silicon tubing. One end of the tubing was fit over the petcock of the PVC bottle and the other end was attached over the opening of a 10-cm glass spectrophotometric cell. The spectrophotometric cell was rinsed three to four times with a total volume of approximately 200 mL of seawater; the Teflon(tm) endcaps were also rinsed and then used to trap a sample of seawater in the glass cell. While drawing the sample, care was taken to make sure that no air bubbles were trapped within the cell. Seawater pH was measured using a three-wavelength spectrophotometric procedure (Byrne, 1987) and the indicator calibration of Clayton and Byrne (1993). The indicator was a 8.0-mM solution of Kodak(tm) m-cresol purple sodium salt (C21H17O5Na) in a 10% ethanol solution; the absorbance ratio of the concentrated indicator solution (RI = 578A/434A) was 1.00. All absorbance ratio measurements were obtained in the thermostatted (25.0 +/- 0.05°C) cell compartments of HP 8453 diode array spectrophotometers. Periodically the spectrophotometric cells were cleaned with a 1 N HCl solution to preclude biological growth. Measurements of pH were taken at 25°C on the total hydrogen ion concentration ([H+]t) scale, in mol/kg soln. B.4.2 DISSOLVED INORGANIC CARBON (DIC) The DIC analytical equipment was set up in a seagoing container modified for use as a laboratory. The analysis was done by coulometry; two analytical systems were used simultaneously on the cruise, each consisting of a coulometer (UIC, Inc.) coupled with a SOMMA (Single Operator Multiparameter Metabolic Analyzer) inlet system developed by Ken Johnson (Johnson et al., 1985,1987,1993; Johnson, 1992) of Brookhaven National Laboratory (BNL). Pipette volume was determined based on the procedures described in Handbook of Methods for CO2 Analysis (DOE, 1994). In the coulometric analysis of DIC, all carbonate species are converted to CO2 (gas) by addition of excess hydrogen to the seawater sample, and the evolved CO2 gas is carried into the titration cell of the coulometer, where it reacts quantitatively with a proprietary reagent based on ethanolamine to generate hydrogen ions. These are subsequently titrated with coulometrically generated OH-. CO2 is thus measured by integrating the total charge required to achieve this. Samples were drawn from the PVC bottles into cleaned, precombusted 500-mL Pyrex(tm) bottles using Tygon(tm) tubing according to procedures outlined in the Handbook of Methods for CO2 Analysis (DOE, 1994). Bottles were rinsed once and filled from the bottom, overflowing half a volume, and care was taken not to entrain any bubbles. The tube was pinched off and withdrawn, creating a 5-mL headspace, and 0.2 mL of saturated HgCl2 solution was added as a preservative. The sample bottles were sealed with glass stoppers lightly covered with Apiezon-L(tm) grease, and were stored at room temperature for a maximum of 12 hours prior to analysis. The coulometers were calibrated by injecting aliquots of pure CO2 (99.995%) by means of an 8-port valve outfitted with two sample loops that had been calibrated at BNL (Wilke, 1993). All DIC values were corrected for dilution by 0.2 mL of HgCl2; total water volume was 540 mL. The correction factor used was 1.00037. The instruments were calibrated at the beginning, middle, and end of each coulometer cell solution with a set of the gas loop injections. CRMs (Batch 29) were provided by Dr. Andrew Dickson (SIO), and was analyzed on both instruments over the duration of the cruise. The CRM certified value was 1902.54 +/-1.05 (n=14). The overall accuracy and precision for the CRMs on both instruments combined was -1.1 +/-0.9 (n=153). Replicate measurements from different PVC bottles tripped at the same depth, along with replicate measurements from the same PVC bottle was within +/-1.9 mol/kg DIC. DIC data reported for this cruise have been corrected to the Batch 29 CRM value by adding the difference between the certified value and the mean shipboard CRM value (certified value - shipboard analyses) on a per instrument/per leg basis. B.4.3. TOTAL ALKALINITY (TA) The titration system used to determine TA consisted of a Metrohm 665 Dosimat(tm) titrator and an Orion(tm) 720A pH meter controlled by a personal computer (Millero et al., 1993). The acid titrant, in a water-jacketed burette, and the seawater sample, in a water-jacketed cell, were kept at 25 +/- 0.1°C with a Neslab(tm) constant-temperature bath. The plexiglass water-jacketed cells were similar to those used by Bradshaw et al. (1988), except that a larger volume (200 mL) was used to increase the precision. The cells had fill and drain valves with zero dead-volume to increase the reproducibility of the cell volume. The HCl solutions used throughout the cruise were made, standardized, and stored in 500-mL glass bottles in the laboratory for use at sea. The 0.2487 M HCl solutions were made from 1 M Mallinckrodt(tm) standard solutions in 0.45 M NaCl to yield an ionic strength equivalent to that of average seawater (0.7 M). The acid was independently standardized using a coulometric technique (Taylor and Smith, 1959; Marinenko and Taylor, 1968) by the University of Miami and by Dr. Dickson. The two standardization techniques agreed to +/-0.0001 N. The volume of HCl delivered to the cell is traditionally assumed to have a small uncertainty (Dickson, 1981) and is equated with the digital output of the titrator. Calibrations of the Dosimat(tm) burettes with Milli Q(tm) water at 25°C indicated that the systems deliver 3.000 mL (the value for a titration of seawater) to a precision of 0.0004 mL. This uncertainty resulted in an error of 0.4 mol/kg in TA. Internal consistency of each cell was checked before, during, and after the cruise by titrating CRM Batches 29 and 30 prepared by Dr. Dickson. The TA of CRM was determined by open cell (weighed) titration in the laboratory prior to the cruise and was found to be 2184.8 +/- 1.3 mol/kg (n= 15) and 2201.9 +/- 1.0 mol/kg (n = 21), respectively. A total of 85 CRM measurements made at sea yielded 2173.8 +/- 1.6 mol/kg for Batch 29 and 2190.8 +/- 1.7 mol/kg for Batch 30 on three different cells. This offset was due to changes in the volume of the cells. All TA data have been corrected to laboratory CRM values for each cell and each leg. ____________________________________________________________________________________________ ____________________________________________________________________________________________ B.4.4. DISCRETE FCO2 (FUGACITY OF CO2) MEASUREMENTS DURING CGC-96 Principal Investigator: Rik Wanninkhof (Wanninkhof@aoml.noaa.gov) Analysts: Dana Greeley and Hua Chen Note: all data is fCO2 data but labeled as pCO2 Approximately 2900 discrete fCO2 samples from 168 station were taken and analyzed on the cruise using an analysis system based on gas chromatography (Neill et al., 1997). The measurement was performed by equilibrating 10-mL headspace with 120-mL seawater sample at 20°C in a bottle with crimp seal and Teflon lined cap. The headspace was injected into a gas chromatographic column that separates CO2 from the other gases in the headspace. The CO2 is subsequently quantitatively converted to methane using a ruthenium catalyst. The methane is measured at high sensitivity with a flame ionization detector. The data obtained from the cruise has an uncertainty proportional to the gas concentration in contrast to our previous system that was based on infrared analysis using larger samples (Wanninkhof and Thoning, 1993). The current system has slightly worse precision for surface water samples but better precision for samples with high pCO2. During leg 1, 38 duplicate samples had a precision of 0.9% (1- st. dev.); during leg 2, 41 duplicates yielded a precision of 1%. The quality control steps were as follows. All samples that had sampling irregularities such as leakage, detachment of the sample bottle from the intake line etc. were flagged as questionable during analysis on the cruise. During data reduction the following checks were performed: (1) Plotting fCO2 against depth (2) Plotting fCO2 against DIC (3) Plotting fCO2 against pH (4) Performing internal consistency calculations using the Lewis and Wallace (1998) program and calculating TA(TC,fCO2) and TA(TC,pH) and {TA(meas)- TA(TC,fCO2)} and {TA(meas)- TA(TC,pH)}. These differences were then plotted for four consecutive stations against depth. Based on these comparisons a subjective assessment was made as to the quality of the data and quality control flags were adjusted as deemed proper. fCO2 REFERENCES: Lewis, E., and D.W.R. Wallace, Program developed for CO2 system calculations, Oak Ridge National Laboratory, Oak Ridge, 1998. Neill, C., K.M. Johnson, E. Lewis, and D.W.R. Wallace, Small volume, batch equilibration measurement of fCO2 in discrete water samples., Limnol. Oceanogr., 42, 1774-1783, 1997. Wanninkhof, R., and K. Thoning, Measurement of fugacity of CO2 in surface water using continuous and discrete sampling methods, Mar. Chem., 44 (2-4), 189-205, 1993. ____________________________________________________________________________________________ ____________________________________________________________________________________________ APPENDIX 3: LISTING OF CGC96 BOTTLE PROBLEMS, WITH QC EVALUATIONS * indicates no nutrient sample. initial Stn Samp Cast Fbtl Problem as annotated; fbtlnbr Nbr no no nbr Ctdprs on deck logs Comments re-set to: --- --- ---- --- ------ ------------------------------------ ---------------------------------------- --------- 1 106 1 3 3001.9 Leaking, * ctd-sal < .001,no O2,cfc,sil 2 2 110 1 3 3997.2 Leaking, * ctd-sal = 0,no O2,cfc,sil 2 2 121 1 3 1600.5 Leaking, * ctd-sal < .0014,no O2,sil, cfc=good 2 2 129 1 3 2235.5 Leaking, * no sal,O2,cfc,sil 3 2 133 1 3 2236.5 Leaking, * no sal,O2,sil cfc=OK 3 3 129 1 3 37.5 Leaking, * NO BOTTLE DATA FO STA=3 3 4 104 1 3 117.7 Leaking, high nutrients ctd-sal < .001, O2=OK,cfc=OK,sil=high 3 4 109 1 3 9.3 Leaking ctd-sal = -.0085,O2=OK, cfc=OK 2 5 107 1 3 465.9 Stopcock pushed in ctd-sal < 0.001,no O2,cfc 3 5 113 1 3 207.4 Leaking ctd-sal = -.0011,others=OK 2 5 114 1 3 180.8 Top endcap cracked ctd-sal=0.001,sil=OK,no cfc,O2 3 6 103 1 4 1070.5 Did not trip properly, * no samples 4 6 110 1 3 490.8 Leaking ctd-sal=-0.0004,sil=OK, no others 2 7 108 1 3 724.9 Leaking ctd-sal=.0003,O2,sil=OK,no cfc 2 7 120 1 3 154.8 Leaking ctd-sal=.0003,O2,sil=OK, no cfc 2 8 108 1 3 1213.6 Huge Leak at top cap, * ctd-sal=.0007,no O2,cfc,sil 3 8 132 1 3 11.1 Stopcock open, 131/132 nut reps look OK ctd-sal=0.0001,o2=OK,no cfc 3 11 103 1 3 5120 Stopcock pushed in,102/103 nut reps=ok ctd-sal=-.0006,O2,nuts=OK,no cfc 2 11 117 1 3 1317.8 Leaking, * no sal,nuts,cfc; O2=high BAD 3 12 203 2 4 4900.2 no comment ctd-sal=0.5,nuts-very low, o2=very high fbtlnbr 4 12 206 2 3 3699.8 Leaking ctd-sal=0.0009,o2,sil=OK 2 12 209 2 3 2504.4 Leaking ctd-sal=.0017,o2,sil=OK 2 13 106 1 3 3498.8 Leaking ctd-sal=0.0010,no o2,cfc,sil=OK 2 13 109 1 3 2293.5 Leaking ctd-sal=0.0017,no O2,cfc;sil=OK 2 14 117 1 3 1214 Leaking, * no sal,cfc,sil;O2 a little high? 3 15 208 2 3 3561.8 Leaking ctd-sal=0.0013;no cfc;o2,sil=OK 2 15 213 2 3 2316.3 Band broken on btm ctd-sal=0.001;o2,cfc,sil=OK 2 15 217 2 3 1310 Leaking, * no sal,cfc,nuts; o2=high 3 15 225 2 3 427.1 Stopcock pushed in ctd-sal=-0.0009;no cfc,sil;o2-ctd=low 3 15 233 2 4 31.2 Did not trip, * 4 16 109 1 3 3188.9 Leaking ctd-sal=0.0010;o2,sil=OK,no cfc 2 16 117 1 3 1224.3 Leaking ctd-sal=0.0015;o2,sil=OK,no cfc 2 17 120 1 3 926.4 Leaking ctd-sal=0.00008;o2,cfc,sil=OK 2 17 131 1 3 78.5 Leaking ctd-sal=0.0012;o2,sil=OK;no cfc 2 18 103 1 3 4878.1 Leaking ctd-sal=0.0013;o2,sil,cfc=OK;ph? 3 18 133 1 4 19.4 Did not close, * 4 19 106 1 3 3093.8 Leaking ctd-sal=-0.0012;f12 a little high,no pH 2 19 110 1 3 1504.9 Leaking ctd-sal=0.0029; 2 19 117 1 3 420.1 Stopcock pushed in * 3 20 105 1 4 2889.9 Empty, * 4 20 106 1 3 2502.3 Leaking ctd-sal <0.001;sil=OK 3 20 109 1 3 1355.7 Damaged bottle 3 20 114 1 3 577 Stopcock pushed in 3 21 103 1 4 4702.5 Did not trip properly, * 4 21 106 1 3 3502 Leaking, PO4 high, sil & NO3 ok ctd-sal=0.0009;cfc,sil=OK 2 21 122 1 4 67.2 Empty, * 4 22 205 2 4 3300.8 Did not trip properly, * no sal,o2,cfc,sil 4 22 206 2 3 2899.0 Did not trip properly, * ctd-sal=0.0049;no cfc;o2,sil=OK 3 23 109 1 3 2299.5 Vent open ctd-sal=0.0010;o2,cfc,sil=OK 2 23 115 1 3 603 Bottom open, * 4 25 104 1 3 3496.2 Stopcock pushed in ctd-sal<<0.001;cfc,o2,sil,ph=OK 2 25 105 1 4 3096.6 Did not trip properly, * 4 27 111 1 4 722.4 Did not close-lanyard hung up, * 4 28 117 1 3 191.3 Stopcock pushed in ctd-sal=-0.001;o2,sil=OK;no cfc 2 29 209 2 3 1029.4 Leaking ctd-sal=0.0011;no cfc,o2;sil=OK 2 29 220 2 3 269.6 Leaking ctd-sal=0.0002;sil,o2=OK;no cfc 2 29 226 2 3 106.1 Leaking ctd-sal=0.0025;sil,o2,cfc=OK 2 30 104 1 3 3185.7 Leaking ctd-sal=0.0003;sil,o2,cfc=OK 2 30 120 1 3 436.3 Leaking ctd-sal = 0.0006;no cfc;o2,sil=OK 2 31 229 2 4 -9 Did not trip properly, * 4 31 230 2 4 -9 Did not trip properly, * 4 31 231 2 4 -9 Did not trip properly, * 4 31 232 2 4 -9 Did not trip properly, * 4 31 233 2 4 -9 Did not trip properly, * 4 31 234 2 4 -9 Did not trip properly, * 4 32 131 1 3 45.1 Leaking 3 33 113 1 3 1136.4 Stopcock pushed in ctd-sal=-0.0002;o2,cfc,sil,ph=OK 2 34 110 1 3 1439.2 Leaking ctd-sal=0.0004;o2,sil=OK;no cfc,ph 2 35 131 1 3 59.1 Leaking ctd-sal=0.0176;no cfc,o2;sil=OK 3 36 101 1 3 2901 Stopcock pushed in no sal,cfc;o2,sil,ph=OK 3 36 102 1 3 2752.2 Stopcock pushed in no sal,cfc;o2,sil,ph=OK 3 37 107 1 3 1030.9 Top may be been cracked by tag lines ctd-sal=0.0002;o2,sil,cfc,ph=OK 2 37 108 1 3 921 Top may be been cracked by tag lines ctd-sal=0.0002;o2,sil,cfc,ph=OK 2 37 109 1 3 820 Top may be been cracked by tag lines ctd-sal=0.0067 3 38 103 1 3 2099.4 Stopcock pushed in ctd-sal=-0.0012;o2,sil,ph=OK;no cfc; 2 38 122 1 3 41.4 Leaking ctd-sal=-0.0051;sil=OK;no cfc,ph,o2 2 39 104 1 3 1897.4 Stopcock pushed in ctd-sal=-0.0005;o2,sil,ph=OK;no cfc 2 39 109 1 3 919.5 Stopcock pushed in no sal,cfc;sil,ph,o2=OK 3 40 131 1 3 43.3 ctd-sal=-0.0025;o2,ph,sil=OK;no cfc 2 40 134 1 3 10.7 bottom leaking ctd-sal=-0.0034;sil=OK;no cfc,o2,ph 2 41 130 1 3 8.3 Leaking ctd-sal=-0.0036;sal,o2,sil,ph=OK;no cfc 2 42 110 1 3 1693.4 Stopcock pushed in ctd-sal=-0.0009;o2,sil=OK;no cfc,ph 2 42 131 1 3 45.1 Stopcock pushed in ctd-sal = -0.0011;o2,sil=OK;no cfc,ph 2 43 103 1 3 2706.8 no comment sal,o2,cfc,nuts flagged 3 45 120 1 3 166.3 Stopcock pushed in ctd-sal=-0.0013;sil=OK;no cfc,ph,o2 3 46 126 1 3 193.2 Leaking ctd-sal=-0.0010;o2,cfc,sil,ph=OK 2 46 131 1 3 67 Leaking ctd-sal=0.0042;sil=OK;no cfc,ph 3 47 201 2 3 4100.7 Leaking cts-sal=0.0011;o2-ctd high,sil=OK 3 47 231 2 3 82.1 Leaking ctd-sal=-0.0006;o2,sil=OK 2 48 106 fo2=4 4% lower than surrounding points 49 120 1 3 927 Stopcock pushed in ctd-sal=0.0011;o2,cfc,sal=OK,no ph 2 50 101 1 3 4489.5 Leaking ctd-sal=0.0008;o2,ph,sil=OK;no cfc 2 50 102 fo2=3:1.5% higher than rep and surrounding points 50 111 1 3 2440 Leaking ctd-sal=0.0013;o2,cfc,sil,ph=OK 2 50 114 1 3 1661.4 Leaking ctd-sal=0.0004;o2,sil,ph=OK;no cfc 2 51 104 1 3 4566.8 Leaking ctd-sal=0.0012;o2,sil,ph=OK;no cfc 2 52 112 1 3 2437.5 Vent valve left open ctd-sal=0.0021; 3 53 101 1 3 5144.9 Stopcock pushed in ctd-sal=0.0007;o2,ph,sil=OK;no cfc 2 53 133 1 3 29.7 Did not trip properly, * 3 55 133 1 4 31.3 "Bottom open, lanyard hung up",* 4 56 116 1 3 1440.2 Leaking, * 3 56 117 1 3 1216.5 Leaking, * 3 57 104 1 3 4565.9 Leaking 3 57 116 1 3 1562.5 Leaking 3 57 133 1 4 28.4 Did not trip properly, * 4 59 103 1 3 4814.1 Leaking 3 60 128 1 3 189.2 Leaking 3 60 133 1 4 19.1 "Empty, lanyard hung up", * 4 61 127 1 3 261.3 Leaking ctd-sal=0.0008;o2,sil=OK;no cfc,ph 2 62 201 2 3 5171 Leaking ctd-sal=-0.0005;o2,sil=OK,no cfc,ph 2 62 204 2 4 4439.4 Stopcock pushed in ctd-sal=0.0003;o2,sil=OK,no cfc,ph 2 63 105 1 3 3495.9 no comment ctd-sal=0.0083;o2,cfc=high hp-high? 3 64 116 1 4 478.4 Did not trip properly, low nuts 4 64 117 1 4 365.8 "Empty, lanyard hung up", * 4 66 116 1 3 1436.3 Stopcock pushed in 3 66 126 1 3 291.2 Leaking 3 67 219 2 3 1027.4 no comment ctd-sal=0.0056; 3 67 226 2 3 319.9 Leaking ctd-sal=-0.0003;o2-ctd=4;ph,sil=OK 2 67 231 2 3 79 Leaking ctd-sal=-0.011;o2,sil,ph,cfc=OK 2 68 101 1 3 5334.9 Leaking ctd-sal=0.0003;sil,ph=OK;no cfc,o2=high 3 69 227 2 3 265.5 "Large leak, top" 4 70 116 1 3 1441.3 Minor btm leak sal,o2,ph,sil=OK 2 71 131 1 3 79.2 sal,o2,ph,sil=OK 2 71 134 1 4 9.7 lanyard hangup 4 72 131 1 3 69.6 ctd-sal=-0.006 3 73 131 1 3 80.1 sal,o2,cfc,ph,sil=OK 2 73 134 1 3 10.1 leak bottom cap no sal,o2,cfc,sil,ph 3 74 201 2 3 5385.3 Leaking, NO3 & sil low, PO4 n/a=bad sal 4 77 101 1 3 5056.0 fo2=3;O2 >2% high 77 107 1 3 3565.6 fo2=3; O2 high 79 133 1 3 13.4 Leaking 3 80 212 2 3 1075.3 Leaking 2 80 228 2 4 119.4 Leaking, high nutrients BAD sal 4 80 229 2 4 93.6 Did not trip-no sample 4 80 230 2 4 69.1 Did not trip-no sample 4 80 231 2 4 -9 Did not trip-no sample 4 80 232 2 4 -9 Did not trip-no sample 4 80 233 2 4 -9 Did not trip-no sample 4 80 234 2 4 -9 Did not trip-no sample 4 81 104 1 3 2555.9 Leaking sal,o2,ph,sil=OK no cfc 2 81 133 1 3 9.6 Leaking, * no samp 3 83 103 1 3 725.5 Small leak sal,o2,sil,ph=OK;no cfc 2 83 104 1 3 624.9 Small leak sal,o2,sil=OK;no cfc,ph 2 83 116 1 3 130.9 Leaking sal,o2,sil,ph=OK;no cfc 2 85 104 1 3 565.8 "Small leak, bottom cap" sal,o2,sil,ph-OK;no cfc 2 85 121 1 3 10 "Small leak, bottom cap" sal,o2,sil,phcfc=OK 2 87 103 1 3 1314.2 "Small leak, bottom cap" sal,o2,ph,sil,cfc=OK 2 89 222 2 3 230.6 "Small leak, bottom cap" sal,sil,ph=OK;o2 low,no cfc 2 90 116 1 3 590.8 Leaking sal,o2,sil,ph=OK;no cfc 2 91 116 1 3 623.8 Small leak, bottom cap sal:OK;o2sil,ph,cfc=OK 2 91 133 1 3 9.2 Leaking, * 3 92 222 2 3 474.9 Small leak, bottom cap sal,o2,sil=OK;no cfc.ph 2 92 226 2 3 240.5 Small leak, bottom cap 2 92 233 2 3 20.5 Large leak, bottom cap sal,o2=OK 2 93 133 1 3 30.1 Leaking sal,o2,sil,cfc=OK;no ph 2 94 101 1 3 4655.3 Stopcock pushed in sal,o2,sil=OK 2 94 119 1 4 874.6 sal=high,o2,cfc,ph=low,sil=high 4 94 121 1 3 676.8 Leaking sal,o2,cfc,sil,ph=OK 2 95 136 1 3 2.4 Leaking, * sal OK, no other sample data 3 97 224 2 3 525.8 Leaking sal,o2,sil,ph=OK;no cfc 2 97 233 2 3 79.3 Leaking sal,o2,ph,sil=OK; no cfc 2 99 116 1 3 1350.2 Small leak, bottom cap sal,o2,sil.ph=OK;no cfc 2 99 133 1 3 79.6 Small leak, bottom cap sal,o2,sil.ph=OK;no cfc 2 100 129 1 4 190.3 Did not trip, lanyard hung up", * 4 100 130 1 4 145.7 Did not trip, lanyard hung up", * 4 100 131 1 4 -9 "Did not trip, lanyard hung up", * 4 100 132 1 4 -9 "Did not trip, lanyard hung up", * 4 103 107 1 4 3564.9 Vent left open sal=OK,sil=BAD 4 105 233 2 4 56.4 "Did not trip, lanyard hung up", * 4 106 124 1 3 478 Possible leak sal,cfc,sil,ph=OK;no o2 2 106 133 1 4 69.9 Did not trip properly, * 4 107 129 1 3 190.4 Leaking sal=ok;sil,ph,o2=OK;no cfc 2 107 130 1 3 143.9 Leaking sal=ok;sil,ph,o2=OK;no cfc 2 107 133 1 4 69.9 Lanyard hung up 4 107 136 1 4 4.7 leaking badly 4 109 103 1 2 fo2=3; 4%higher than surrounding points 109 111 1 3 3064.2 Leaking 3 110 216 2 3 1939.3 Leaking, * no sal,o2,sil,ph;cfc=OK 3 110 218 2 3 1440.5 Spigot leaking sal,o2,cfc,sil,ph=OK 2 114 111 1 3 3191 "Small leak, bottom cap sal,o2.cfc.sil.ph+OK 2 114 124 1 3 669 Leaking sal,o2.cfc.sil.ph+OK 2 114 136 1 4 5.3 Vent open only sal,sil; OK 2 115 126 1 3 524.1 "Small leak, bottom cap sal,o2,sil=OK 2 116 210 2 3 3440.6 no comment sal,o2,=low 3 117 116 1 3 1814.5 Leaking sal,o2,sil,ph=OK;no cfc 2 118 131 1 3 120.4 "Small leak, bottom cap sal,o2,sil=OK 2 119 109 1 3 3561.9 "Large leak, top cap" sal,o2,ph,sil=OK;no cfc 2 119 126 1 3 526.8 Leaking sal,o2,sil=OK;no cfc,ph 2 119 131 1 3 163.9 "Large leak, bottom cap" 3 120 226 2 3 474.6 "Small leak, bottom cap" sal,o2,sil,cfc=OK 2 120 231 2 3 140.1 Slight leak sal,o2,sil,cfc,ph=OK 2 121 203 2 3 4565 Vent left open sal,o2,sil,ph=OK;no cfc 2 121 209 2 3 3065.5 Leaked before vent open sal,o2,sil,ph=OK;no cfc 2 121 218 2 3 1125.5 Leaking sal,o2,sil,ph=OK;no cfc 2 123 133 1 3 80.5 Slight leak sal,o2,sil=OK;no cfc 2 124 117 fo2=3; high 124 124 1 3 677.8 Leaking, * no sal,cfc,sil,ph 3 125 324 3 3 720.1 Leaking sil,ph=OK 2 126 124 1 3 670.5 "Small leak, bottom cap" sal,cfc,sil=OK 2 127 207 2 4 4316.1 Stopcock pushed in sal,o2,sil=OK 2 127 209 2 3 3815.3 Leaking sal=BAD,no cfc,ph 3 127 224 2 3 719.5 Major leaker 3 129 104 ph l0oks low ???? 129 111 1 3 3314.1 Leaking sal,o2,sil=OK;no cfc,ph 2 130 104 phlooks low ???? 130 126 1 3 476.6 Leaking ctd-sal=-0.007;no cfc,ph 3 131 104 ph looks low ???? 131 136 1 3 3.6 "Leaker, top cap", * o2,ph=OK 2 132 110 1 3 3437.4 "Leaker, top cap" sil,sal=OK 2 132 112 1 3 2939.4 "Small leak, top cap" sil,sal=OK 2 132 131 1 3 140.7 Small leak sal,o2,cfc,sil=OK 2 133 104 1 3 5067.6 Bottom leak sal,o2,cfc,sil=OK 2 133 107 1 3 4314.1 Small bottom leak sal,o2,cfc,sil=OK 2 134 224 2 3 673.6 Leaking sal,o2,cfc,sil=OK 2 135 209 2 3 3565.1 Leaking sal,o2,sil=OK 2 136 109 1 3 3671.3 "Leaker, top cap" sal,o2,sil=OK 2 136 130 1 3 190.4 Small bottom leak sal,o2,sil=OK 2 137 124 1 3 726.1 Major leak sal,sil=OK;no cfc,o2,ph 3 137 130 1 3 217.6 "Large leak, bottom cap" sal,sil=OK; no cfc,ph,o2 3 139 109 1 3 1814.7 Leaking sal,o2,sil=OK;no cfc,ph 2 140 109 1 3 3439.6 "Small leak, bottom cap" sal,o2,sil=OK;no cfc,ph 2 140 135 1 3 18.5 "Small leak, bottom cap" sal,o2,sil=OK;no cfc,ph 2 141 102 1 3 4814.8 Small leak sal,o2,sil=OK;no ph,cfc 2 141 103 1 3 4566.3 Small leak sal,o2,cfc,sil=OK;no ph 2 141 109 1 3 3065.8 Small leakk sal,o2,cfc,sil=OK;no ph 2 141 131 1 3 129.3 Leaking sal,o2,sil=OK;no ph,cfc 2 144 125 1 3 475.7 Small leak sal,cfc,sil=ok; no,ph.o2 2 144 133 1 3 69.8 Leaking sal,sil=ok;o2=high?,no cfc,ph 3 146 102 1 3 4940.2 Leaking sal,o2,cfc,sil,ph"OK 2 147 133 1 3 79.2 Leaking sal,o2,sil=OK;no cfc,ph 2 147 135 1 3 28.4 Leaking sal,o2,sil=OK;no cfc,ph 2 152 126 1 4 375.1 Did not trip properly, * 4 152 133 1 3 70.1 "Small leak, bottom cap" sal,o2,sil=OK;no cfc,ph 2 152 136 1 3 4.3 Leaking sal,o2,sil=OK;no cfc,ph 2 153 133 1 3 78.6 Leaking sal,o2,sil=ok;no cfc,ph 2 158 111 1 3 2441.2 Stopcock pushed in sal,o2,sil,ph=OK;no cfc 2 160 102 1 4 5247.9 Stopcock pushed in sal,sil=OK;nocfc,o2,ph 2 160 105 1 3 4866.2 Stopcock pushed in sal,o2,sil=OK; no cfc,ph 2 160 106 1 3 4738.1 Stopcock pushed in sal,o2,sil=OK; no cfc,ph 2 160 128 1 4 290.7 Leaking ctd-sal=-0.007,sil=OK;no cfc,ph,o2 4 160 136 1 4 5.1 Vent left open sal,sil=OK,no o2,cfc,ph 2 161 106 1 3 4288.5 Stopcock pushed in sal,o2,sil=OK;no cfc,ph 2 163 206 2 3 4564.4 Stopcock pushed in sal,o2,sil=OK;no cfc,ph 2 163 228 2 3 324.5 Leaking from top sal,o2,sil,ph=OK;no cfc 2 163 232 2 3 117.1 Leaking from top sal,o2,sil,ph=OK;no cfc 2 163 234 2 3 57.9 Vent left open sal,o2,sil,ph=OK;no cfc 2 163 235 2 3 29.6 Vent left open sal,o2,sil,ph=OK;no cfc 2 163 236 2 3 5.3 Vent left open sal,o2,sil,ph,cfc=OK 2 164 102 1 3 5179.4 Stopcock pushed in sal,o2,sil=OK;no cfc,ph 2 164 136 1 3 4 Leaking sal,sil=ok;no o2,cfc,ph 3 165 102 1 3 5599.4 Small bottom leak sal,o2,sil=OK;no cfc,ph 2 165 106 1 3 4564.3 Stopcock pushed in sal,o2,sil=OK;no cfc,ph 2 165 129 1 3 265.1 Stopcock pushed in 3 166 228 2 3 286.8 Stopcock pushed in sal,o2,sil,ph=OK;no cfc 2 167 206 2 3 4566 Stopcock pushed in sal,o2,sil=OK no cfc,ph 2 167 228 2 3 326.4 Stopcock pushed in sal,sil=OK;no o2,cfc,ph 3 168 109 1 3 3686.8 Small bottom leak sal,o2,sil=OK;no cfc,ph 2 168 131 1 3 140.1 Small bottom leak sal,o2,sil=OK;no cfc,ph 2 171 112 1 3 2812.9 Stopcock pushed in sal,o2,sil=OK;no cfc,ph 2 171 113 1 3 2562.7 Stopcock pushed in sal,o2,sil=OK;no cfc,ph 2 171 117 1 3 1564 Small bottom leak sal,o2,sil,ph=OK;no cfc 2 171 127 1 3 421.6 Stopcock pushed in sal,sil=OK;no o2,cfc,ph 3 172 235 2 3 10 Small bottom leak sal,o2,sil=OK,no cfc,ph 2 173 226 2 3 525.3 Small bottom leak sal,o2,cfc,sil=OK;no ph 2 174 105 1 3 4689 Leaking sal,o2,sil=OK;no cfc,ph 2 174 117 1 3 1690.4 Leaking sal,o2,sil=OK;no cfc,ph 2 174 127 1 3 374.2 Stopcock pushed in sal,sil=OK;no o2,cfc,ph 3 174 135 1 3 20.4 Small bottom leak sal,o2,cfc,sil=OK;no ph 2 175 205 2 3 4899.9 Leaking from top sal,o2,sil=OK;no cfc,ph 2 178 110 1 3 4098.9 Leaking stopcock sal,o2,sil=OK;no cfc,ph 2 181 110 1 3 3253 Leaking, * 3 ____________________________________________________________________________________________ ____________________________________________________________________________________________ C. CTD/O2 TECHNIQUES McTaggart, K.E. and and G.C. Johnson (1997). CTD/O2 Measurements Collected on a Climate & Global Change Cruise (WOCE Sections P14S and P15S) During January - March, 1996. NOAA Data Report ERL PMEL-63, Pacific Marine Environmental Laboratory, Seattle. Washington, September 1997. ABSTRACT Summaries of CTD/O2 measurements and hydrographic data acquired on a Climate and Global Change cruise during the winter of 1996 aboard the NOAA ship DISCOVERER are presented. The majority of these data were collected along WOCE section P14S from 53°S, 170°E to 66°S, 171°E and WOCE section P15S from 67°S, 170°W to 0, 169°W. Also presented are data collected along a short section across the Samoa Passage. Data acquisition and processing systems are described and calibration procedures are documented. Station location, meteorological conditions, CTD/O2 summary data listings, profiles, and potential temperature- salinity diagrams are included for each cast. Section plots of oceanographic variables and hydrographic data listings are also given. C.1. INTRODUCTION The long-term objective of the Climate and Global Change Program is to provide reliable predictions of climate change and associated regional implications on time scales ranging from seasons to centuries. In support of NOAA's Climate Program, PMEL scientists have been measuring the growing burden of greenhouse gases in the Pacific Ocean and the overlying atmosphere since 1980. The NOAA Office of Global Programs (OGP) sponsors the Ocean Tracers and Hydrography Program and Ocean-Atmosphere Carbon Exchange Study (OACES) to study ocean circulation, mixing processes, and the rate at which CO2 and chloro- fluorocarbons (CFCs) are taken up and released by the oceans. Work on this cruise was cooperative with the World Ocean Circulation Experiment (WOCE) and the Joint Global Ocean Flux Study (JGOFS). Data from this cruise will allow quantification of the zonal currents and meridional distribution of water masses throughout the full water column in the southwestern Pacific. Tracer measurements will be used to study the rates of mass formation and transport processes throughout the water column. For both sections sampled on this cruise, stations were occupied at a nominal spacing of 30 nm, closer over steeply sloped bathymetry, and never more distant than 60 nm. Stations 1-3 were test stations occupied to evaluate the CTD/O2 and rosette systems on the transit from Hobart, Australia to the start of P14S. These profiles were not processed and are not included in this data report. Stations 177 to 182 were taken after the completion of P15S but prior to the final port stop in Pago-Pago, American Samoa. These profiles constitute a short, nearly zonal, section across the Samoan Passage, taken to investigate deep water-mass and transport variability there. These data are reported here. The cruise was broken up into two legs of roughly one month duration each by a port stop in Wellington, New Zealand after station 93. Station 94 was a reoccupation of station 93 to evaluate temporal variations that occurred during the port stop. Full water column CTD/O2 profiles were collected at all stations. Lowered Acoustic Doppler Current Profiler (ADCP) measurements were also collected on most casts of leg 1. In addition, underway salinity, temperature, and CO2 measurements were taken along the cruise track. Shallow productivity casts were made daily, and ALACE floats were deployed during the cruise. Water samples were analyzed for a suite of natural and anthropogenic tracers including salinity, dissolved oxygen, inorganic nutrients, CFCs, carbon tetrachloride, dissolved inorganic carbon, total alkalinity, pH, pCO2, dissolved organic carbon, dissolved organic nitrogen, carbon isotopes, and oxygen isotopes. Samples were collected from productivity casts for chlorophyll and primary productivity. Fig. 1 shows station locations. Table 1 provides a summary of cast information. WOCE section P14S began with station 4 at 53°S, 170°E in 200 m of water on the south edge of the Campbell Plateau and ended with station 32 at 66°S, 171°E, intersecting the zonal WHP section S4 occupied nominally along 67°S in 1992. The section consisted of 29 stations. It sampled the entire Antarctic Circumpolar Current between the edge of the Campbell Plateau and the crest of the Pacific-Antarctic Ridge. At the ridge crest it explored a deep passage between the Ross Sea and the Southwest Pacific Basin. South of the ridge crest, it entered the north side of the Ross Sea Gyre. WOCE section P15S began with station 33 at 67°S, 170°W, again intersecting the zonal WHP section S4 occupied nominally along 67°S in 1992. It proceeded north to station 72 at 47.5°S, 170°W, whereupon it followed a diagonal in towards the Chatham Rise until station 85 at 43.25°S, 175°E. From there it moved back away from the rise towards 170°W along a diagonal to station 104 at 36°S, 170°W. It then resumed north to station 154 at 10.5°S, 170°W, whereupon it shifted longitudes slightly to follow the axis of the Samoan Passage until station 164 at 7.5°S, 168.75°W. From there it continued north to station 174 at the equator, 168.75°W. Station 175 and 176 were added to the section to improve meridional resolution in the vicinity of the Samoan Passage. From 15°S to the equator the section overlapped WHP section P15N, occupied in 1994. The section consisted of 143 stations, discounting the duplication after the Wellington port stop. It sampled the north end of the Ross Sea Gyre, the Antarctic Circumpolar Current, the Deep Western Boundary Current system on both flanks of the Chatham Rise, the Subtropical Gyre, and the Tropical Regime up to the equator. C.2. STANDARDS AND PRE-CRUISE CALIBRATIONS The CTD/O2 system is a real time data system with the data from a Sea-Bird Electronics, Inc. (SBE) 9plus underwater unit transmitted via a conducting cable to the SBE 11plus deck unit. The serial data from the underwater unit is sent to the deck unit in RS-232 NRZ format using a 34560 Hz carrier-modulated differential-phase-shift-keying (DPSK) telemetry link. The deck unit decodes the serial data and sends it to a personal computer for display and storage in a disk file using Sea-Bird SEASOFT software. The SBE 911plus system transmits data from primary and auxiliary sensors in the form of binary number equivalents of the frequency or voltage outputs from those sensors. The calculations required to convert from raw data to engineering units of the parameters being measured are performed by software, either in real-time, or after the data has been stored in a disk file. The SBE 911plus system is electrically and mechanically compatible with standard unmodified rosette water samplers made by General Oceanics (GO), including the 1016 36-position sampler, which was used for most stations on this cruise. An optional modem and rosette interface allows the 911plus system to control the operation of the rosette directly without interrupting the data from the CTD, eliminating the need for a rosette deck unit. The SBE 9plus underwater unit uses Sea-Bird's standard modular temperature (SBE 3) and conductivity (SBE 4) sensors which are mounted with 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 inside the underwater unit main housing and is ported to outside pressure through the oil-filled plastic capillary tube seen protruding from the main housing bottom end cap. A compact, modular unit consisting of a centrifugal pump head and a brushless DC ball bearing motor contained in an aluminum underwater housing pump flushes water through sensor tubing at a constant rate independent of the CTD's motion. This improves dynamic performance. Motor speed and pumping rate (3000 rpm) remain nearly constant over the entire input voltage range of 12-18 volts DC. 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. It provides access to the modem channel and control of the rosette interface. Output data is in RS-232 (serial) format. C.2.1 CONDUCTIVITY The flow-through conductivity-sensing element is a glass tube (cell) with three platinum electrodes. The resistance measured between the center electrode and end electrode pair is determined by the cell geometry and the specific conductance of the fluid within the cell, and controls the output frequency of a Wien Bridge circuit. The sensor has a frequency output of approximately 3 to 12 kHz corresponding to conductivity from 0 to 7 S/m (0 to 70 mmho/cm). The SBE 4 has a typical accuracy/stability of +/- 0.0003 S/m/month; resolution of 0.00004 S/m at 24 samples per second; and 6800 meter anodized aluminum housing depth rating. Pre-cruise sensor calibrations were performed at Sea-Bird Electronics, Inc. in Bellevue, Washington. The following coefficients were entered into SEASOFT using software module SEACON: S/N 748 S/N 1561 S/N 1562 December 14, 1995 December 14, 1995 December 14, 1995 ------------------------ ----------------------- ----------------------- g = -4.13299236 g = -4.09205330 g = -4.16899749 h = 4.36576287e-01 h = 5.28538155e-01 h = 5.53740992e-01 i = -1.39236118e-04 i = -1.56949585e-04 i = -5.94323544e-05 j = 2.59599092e-05 j = 3.46776288e-05 j = 3.11836344e-05 ctcor = 3.2500e-06 ctcor = 3.2500e-06 ctcor = 3.2500e-06 cpcor = -9.5700e-08 cpcor = -9.5700e-08 cpcor = -9.5700e-08 Conductivity calibration certificates show an equation containing the appropriate pressure-dependent correction term to account for the effect of hydrostatic loading (pressure) on the conductivity cell: C (S/m) = (af^m + bf^2 + c + dt) / [10 (1 - 9.57e-08 p)] where a, b, c, d, and m are the calibration coefficients above, f is the instrument frequency (kHz), t is the water temperature (C), and p is the water pressure (dbar). SEASOFT automatically implements this equation. C.2.2 TEMPERATURE The temperature-sensing element is a glass-coated thermistor bead, pressure-protected by a stainless steel tube. The sensor output frequency ranges from approximately 5 to 13 kHz corresponding to temperature from -5 to 35°C. The output frequency is inversly 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 typical accuracy/stability of +/- 0.004°C per year; and resolution of 0.0003°C at 24 samples per second. The SBE 3 thermometer has a fast response time of 70 ms. It's anodized aluminum housing provides a depth rating of 6800 m. Pre-cruise sensor calibrations were performed at Sea-Bird Electronics, Inc. in Bellevue, Washington. The following coefficients were entered into SEASOFT using software module SEACON: S/N 1370 S/N 2038 S/N 2037 November 22, 1995 December 14, 1995 December 14, 1995 ------------------- ------------------- ------------------- g = 4.84042876e-03 g = 4.11396861e-03 g = 4.13135090e-03 h = 6.74974915e-04 h = 6.20923913e-04 h = 6.33482482e-04 i = 2.38622986e-05 i = 1.98024796e-05 i = 2.11340704e-05 j = 1.66698127e-06 j = 1.99224715e-06 j = 2.16252937e-06 f0 = 1000.0 f0 = 1000.0 f0 = 1000.0 Temperature (IPTS-68) is computed according to T (C) = 1/{a+b[ln(f0/f)]+c[ln^2(f0/f)]+d[ln^3(f0/f)]}-273.15 where a, b, c, d, and f0 are the calibration coefficients above and f is the instrument frequency (kHz). SEASOFT automatically implements this equation. C.2.3 PRESSURE The Paroscientific series 4000 Digiquartz high pressure transducer uses a quartz crystal resonator whose frequency of oscillation varies with pressure induced stress measuring changes in pressure as small as 0.01 parts per million with an absolute range of 0 to 10,000 psia (0 to 6885 dbar). Also, a quartz crystal temperature signal is used to compensate for a wide range of temperature changes. Repeatability, hysteresis, and pressure conformance are 0.005% FS. The nominal pressure frequency (0 to full scale) is 34 to 38 kHz. The nominal temperature frequency is 172 kHz + 50 ppm/degree Celsius. Pre-cruise sensor calibrations were performed at Sea-Bird Electronics, Inc. in Bellevue, Washington. The following coefficients were entered into SEASOFT using software module SEACON: S/N 53960 S/N 53586 April 11, 1995 October 29, 1993 ------------------ ------------------ c1 = -4.315048e+04 c1 = -3.920451e+04 c2 = 4.542800e-01 c2 = 6.234560e-01 c3 = 1.344380e-02 c3 = 1.350570e-02 d1 = 3.795200e-02 d1 = 3.894300e-02 d2 = 0.0 d2 = 0.0 t1 = 3.034230e+01 t1 = 3.046303e+01 t2 = -1.809380e-04 t2 = -9.018862e-05 t3 = 4.616150e-06 t3 = 4.528890e-06 t4 = 2.084220e-09 t4 = 3.309590e-09 Pressure coefficients are first formulated into c = c1 + c2*U + c3*U^2 d = d1 + d2*U t0 = t1 + t2*U + t3*U^2 + t4*U^3 where U is temperature in degrees Celsius. Then pressure is computed according to P (psia) = c * [1 - (t0^2/t^2)] * {1 - d[1 - (t0^2/t^2)]} where t is pressure period (us). SEASOFT automatically implements this equation. C.2.4 OXYGEN The SBE 13 dissolved oxygen sensor uses a Beckman polarographic element to provide in-situ measurements at depths up to 6800 meters. This auxiliary sensor is also included in the path of pumped sea water. Oxygen sensors determine the dissolved oxygen concentration by counting the number of oxygen molecules per second (flux) that diffuse through a membrane. By knowing the flux of oxygen and the geometry of the diffusion path the concentration of oxygen can be computed. The permeability of the membrane to oxygen is a function of temperature and ambient pressure. The interface electronics outputs voltages proportional to membrane current (oxygen current) and membrane temperature (oxygen temperature). Oxygen temperature is used for internal temperature compensation. Computation of dissolved oxygen in engineering units is done in the software. The range for dissolved oxygen is 0 to 650 µmol/kg; accuracy is 4 µmol/kg; resolution is 0.4 µmol/kg. Response times are 2 s at 25°C and 5 s at 0°C. The following oxygen calibrations were entered into SEASOFT using SEACON: S/N 130309 September 28, 1995 ------------------- m = 2.4544 e-07 b = -4.6633 e-10 soc = 2.6721 boc = -0.0178 tcor = -3.3e-02 pcor = 1.5e-04 tau = 2.0 wt = 0.67 k = 8.9224 c = -6.9788 The use of these constants in linear equations of the form I = mV + b and T = kV + c will yield sensor membrane current and temperature (with a maximum error of about 0.5°C) as a function of sensor output voltage. These scaled values of oxygen current and oxygen temperature were carried through the SEASOFT processing stream unaltered. C.3. DATA ACQUISITION CTD/O2 measurements were made using one of two Seabird 9plus CTDs each equipped with a fixed pumped temperature-conductivity (TC) sensor pair. A mobile pumped TC pair with dissolved oxygen sensor was mounted on whichever CTD was in use so that dual TC measurements and dissolved oxygen measurements were always collected. The TC pairs were monitored for calibration drift and shifts by examining the differences between the two pairs on each CTD and comparing CTD salinities with bottle salinity measurements. PMEL's Sea-Bird 9plus CTD/O2 S/N 09P8431-0315 (sampling rate 24 Hz) was mounted in a 36-position frame and employed as the primary package. Auxiliary sensors included a lowered ADCP, Metrox load cell, and Benthos altimeter. Water samples were collected using a General Oceanics 36-bottle rosette and 10-liter Nisken bottles. The primary package was used for the majority of 182 casts. PMEL's Sea-Bird 9plus CTD/O2 S/N 329053-0209 (sampling rate 24 Hz) was mounted in a 24-position frame and employed as the backup package. Auxiliary sensors included a Metrox load cell and Benthos altimeter. Water samples were collected using a Sea-Bird 24-bottle rosette, and 4-liter Niskin bottles. One test cast and 22 bad-weather stations were made using the smaller backup package. The package entered the water from the stern of the ship and was held 5-15 m beneath the surface for one minute in order to activate the pump and attach tag lines for package recovery. Under ideal conditions the package was lowered at a rate of 30 m/min to 50 m, 45 m/min to 200 m, and 60 m/min to depth. Ship heave often caused substantial variation about these mean lowering rates, especially at southern ocean stations. Load cell values were monitored in real-time during each cast. The position of the package relative to the bottom was monitored on the ship's Precision Depth Recorder (PDR) and an altimeter. A bottom depth was estimated from bathymetric charts and the PDR ran during the bottom 1000 m of the cast. Stations were generally made to within 10 m of the bottom, sometimes farther away in heavy weather. Fig. 2 shows the depths of bottle closures during the upcast. Upon completion of the cast, sensors were flushed with deionized water and stored with a dilute Triton-X solution in the plumbing. Niskin bottles were then sampled for various water properties detailed in the introduction. Sample protocols conformed to those specified by the WOCE Hydrographic Programme. A Sea-Bird 11plus deck unit received the data signal from the CTD. The analog data stream was recorded onto video cassette tape as a backup. Digitized data were forwarded to a 286-AT personal computer equipped with SEASOFT acquisition and processing software version 4.216. Temperature, salinity, and oxygen profiles were displayed in real-time. Raw data files were transferred to a 486 personal computer using Laplink version 3 and backed up to optical disk. C.3.1 DATA ACQUISITION PROBLEMS Some time was lost at the beginning of leg 1 owing to level-wind problems on the primary winch. The sea cable was retensioned on the drum at sea by removing the CTD/rosette package, attaching a weight to the cable, and spooling the full length of cable behind the ship while underway to within the last full wrap on the drum . Level-wind problems were much reduced after this procedure. No useful data from the secondary TC pair and dissolved oxygen sensor was collected during station 12 owing to biological fouling of the mobile sensors. Data from the primary TC pair were processed for station 12, as well as for stations 69, 78, 79, 128, 130, 131, and 159 owing to noise. No oxygen data are available for stations 132, 133, 134, and 144 during which problems with the dissolved oxygen sensor were being diagnosed and repaired. C.3.2 SALINITY ANALYSES Bottle salinity analyses were performed in the ship's salinity laboratory using two Guildline Model 8400A inductive autosalinometers standardized with IAPSO Standard Seawater batch P114. The autosalinometer in use was standardized before each run and either at the end of each run or after no more than 48 samples. The drift between standardizations was monitored and the individual samples were corrected for that drift by linear interpolation. Duplicate samples taken from the deepest bottle on each cast were analyzed on a subsequent day. Bottle salinities were compared with preliminary CTD salinities to aid in identification of leaking bottles as well as to monitor the CTD conductivity cells' performance and drift. The expected precision of the autosalinometer with an accomplished operator is 0.001 PSS, with an accuracy of 0.003. To assess the precision of discrete salinity measurements on this cruise, a comparison was made for data from the instances in which two bottles were tripped within 10 dbar of each other at the same station below a depth of 2000 dbar. For the 124 instances in which both bottles of the pair have acceptable salinity measurements, the standard deviation of the differences is 0.0008 PSS. This value is below the expected precision. C.4. AT SEA PROCESSING SEASOFT consists of modular menu driven routines for acquisition, display, processing, and archiving of oceanographic data acquired with Sea-Bird equipment and is designed to work with an IBM or compatible personal computer. Raw data is acquired from the instruments and is 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 information to the header of the converted file permitting tracking of how the various oceanographic parameters were obtained. The converted data is stored in either rows and columns of ascii numbers or as a binary data stream with each value stored as a 4 byte binary floating point number. The last data column is a flag field used to mark scans as good or bad. The following are the SEASOFT processing module sequence and specifications used in the reduction of P14S/P15S CTD/O2 data: DATCNV converted the raw data to pressure, temperature, conductivity, oxygen current, and oxygen temperature; and computed salinity and the time rate of change of oxygen current. DATCNV also extracted bottle information where scans were marked with the bottle confirm bit during acquisition. ROSSUM created a summary of the bottle data. Bottle position, date, and time were output as the first two columns. Pressure, temperature, conductivity, salinity, oxygen current, oxygen temperature, and time rate of change of oxygen current were averaged over a 2-s interval (48 scans). For the primary package, the time interval was from 5 to 3 s prior to the confirm bit in order to avoid spikes in conductivity and oxygen current owing to minor incompatibilities between the Sea-Bird 911plus CTD/O2 system and General Oceanics 1016 rosette. Bottle data from the backup package were averaged from 1 s prior to the confirm bit to 1 s after the confirm bit in the data stream. ROSSUM computed CTD oxygen, potential temperature, and sigma-theta. 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 200 scans. Data greater than two standard deviations were flagged. The second pass computed a standard deviation over the same 200 scans excluding the flagged values. Values greater than 16 standard deviations were marked bad. SPLIT removed decreasing pressure records from the data files leaving only the downcast. FILTER performed a low pass filter on pressure with a time constant of 0.15 s. In order to produce zero phase (no time shift) the filter first runs forward through the file and then runs backwards through the file. ALIGNCTD aligned conductivity in time relative to pressure to ensure that all calculations were made using measurements from the same parcel of water. Conductivity for the primary sensor on the 36-bottle package was advanced by -0.020 s. Conductivity for the primary sensor on the 24-bottle package was advanced by -0.010 s. Conductivity for the secondary, mobile sensor on either package was advanced 0.055 s. CELLTM used a recursive filter to remove conductivity cell thermal mass effects from the measured conductivity. For C748 with an epoxy coating, the thermal anomaly amplitude (alpha=0.03) and the time constant (1/beta=9.0) were higher than for C1561 and C1562 with no coating (alpha=0.02, 1/beta=7.0). DERIVE was used to compute fall rate (m/s) with a time window size for fall rate and acceleration of 2.0 seonds. LOOPEDIT marked scans where the CTD was moving less than the minimum velocity of 0.25 m/s or travelling backwards due to ship roll. BINAVG averaged the data into 1-dbar pressure bins starting at 1 dbar with no surface bin. The center value of the first bin was set equal to the bin size. The bin minimum and maximum values are the center value +/- 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 decibar. STRIP removed scan number and fall rate from the data files. TRANS converted the data file format from binary to ascii. C.5. POST-CRUISE CALIBRATIONS Post-cruise sensor calibrations were done at Sea-Bird Electronics, Inc. during May 1996. Mobile, secondary sensor pair T1370 and C748 were selected for final data reduction for all stations except 12, 69, 128, 130, 131, and 159. Post-cruise calibrations showed T1370 to have drifted by 0.43e-03°C over the 3.2 months between calibrations. Station 12 data are from sensors T2037 and C1562. Post-cruise calibrations showed T2037 to have drifted by -0.28e-03°C over the 3.2 months between calibrations. The remaining station data are from sensors T2038 and C1561. Post-cruise calibrations showed T2038 to have drifted by 0.11e-03°C over the 3.3 months between calibrations. C.5.1 CONDUCTIVITY SEASOFT module ALIGNCTD was used to align conductivity measurements in time relative to pressure. Measurements can be misaligned due to the inherent time delay of the sensor response, the water transit time delay in the pumped plumbing line, and the sensors being physically misaligned in depth. Because SBE 3 temperature response is fast (0.06 s), it is not necessary to advance temperature relative to pressure. When measurements are properly aligned, salinity spiking and density errors are minimized. For a SBE 9 CTD with ducted TC sensors and a 3000 rpm pump the typical net advance of conductivity relative to temperature is 0.073 s. The SBE 11 deck units advanced primary conductivity 0.073 s but do not advance secondary conductivity. Therefore the alignment of C748 conductivity data, which was from the secondary sensor channel (except for stations 78 and 79), was much larger, typically 0.06 s versus coming from a primary sensor channel, typically 0.02 s. Conductivity slope and bias, along with a linear pressure term (modified beta), were computed by a least-squares minimization of CTD and bottle conductivity differences. The function minimized was BC - m * CC - b - beta * CP where BC is bottle conductivity (S/m), CC is pre-cruise calibrated CTD conductivity (S/m), CP is the CTD pressure (dbar), m is the conductivity slope, b is the bias (S/m), and beta is a linear pressure term (S/m/dbar). The final CTD conductivity (S/m) is m * CC + b + beta * CP The slope term m is a fourth-order polynomial function of station number to allow the entire cruise to be fit at once with a smoothly-varying station- dependent slope correction. For sensors C748 and C1561 a series of fits were made, each fit throwing out bottle values for locations having a residual between CTD and bottle conductivities greater than three standard deviations. This procedure was repeated with the remaining bottle values until no more bottle values were thrown out. For C748, the slope correction ranged from 1.0000501 to 1.0001274, the bias applied was -7.5e-04, and the beta term was -9.01e-09. Of 5680 bottles, the percentage of bottles retained in the fit was 85.2 with a standard devia- tion of CTD versus bottle conductivity differences of 9.88e-05 S/m. For C1561, the slope correction ranged from 1.0001481 to 1.0002849, the bias applied was -3.8e-04, and the beta term was -3.16e-09. Of 5118 bottles, the percentage of bottles retained in the fit was 88.1 with a standard deviation of 9.93e-05 S/m. For station 12, station 13 calibrated secondary salinity data was used as a reference. A slope, bias, and pressure correction was determined that matched station 13 uncalibrated primary salinity (C1562,T2037) to station 13 calibrated secondary salinity (C748,T1370). These coefficients (slope=1.004, bias=-0.0011, beta=-2.49e-08) were used to calibrate station 12 primary salinity (C1562,T2037). CTD-bottle conductivity are plotted against cast number to show the stability of the calibrated CTD conductivities relative to the bottle conductivities (McTaggart and Johnson, 1997; Fig. 3, upper panel). CTD-bottle conductivity differences are plotted against pressure to show the tight fit below 800 m and the increasing scatter above 800 m (McTaggart and Johnson, 1997; Fig. 3, lower panel). C.5.2 TEMPERATURE Adjustments were made to the bias of the thermistors as deviations from the pre-cruise calibrations on a station by station basis. These deviations were obtained from a linear fit of the pre-cruise and post-cruise temperature residuals from the pre-cruise calibration versus time. A pressure correction was then applied to each sensor such that CT = CT * pcor * CP where CT is CTD temperature (C) with the bias adjustment, pcor is the pressure correction (dbar) for each sensor, and CP is CTD pressure (dbar). pcor1370 = -2.6e-03/9000 = -2.8889e-007 pcor2037 = -2.3e-03/9000 = -2.5556e-007 pcor2038 = -1.7e-03/9000 = -1.8889e-007 Also, a uniform correction is applied for heating of the thermistor owing to viscous effects. All the thermistors are biased high by this effect and were adjusted down accordingly. An adjustment of 0.6e-03°C results in errors of no more than +-0.15°C from this effect for the full range of oceanographic temperature and salinity. Post-cruise temperature and conductivity calibrations were applied to all sensor pairs using PMEL program CALCTD (STA12CAL for station 12). Surface values were filled using PMEL program FILLSFC. FILLSFC copied the first good value of salinity and potential temperature back to the surface and then back- calculated temperature and conductivity. Primary and secondary sensor differences were examined. Data from the secondary sensor pair (T1370/C748) was chosen for all stations except 12, 69, 78, 79, 128, 130, 131, and 159. Primary sensor data chosen for these 8 stations were within .001 psu of the secondary sensor data of the surrounding stations. All profiles were despiked and data linearly interpolated using PMEL program DESPIKE. Package slowdowns and reversals owing to ships heave can move mixed water in tow to in front of the CTD sensors and obscure measurements. In addition to SEASOFT module LOOPEDIT (see below), PMEL program DELOOP computed values of density locally referenced between every 1 dbar of pressure to compute N^2 = (-g/rho)(drho/dz) and linearly interpolated over those records where N^2 <= -1.0e-05 s^(-2). Post-cruise calibrations were applied to CTD data associated with bottle data using PMEL program CALMSTR. CALMSTR also ammended WOCE quality flags associated with CTD and bottle salinities. Eighteen CTD salinities were flagged as bad during station 78 likely owing to clogged plumbing of the primary sensors during the up-cast. Of the 5640 bottle salinities, 0.33% were flagged as bad and 2.68% were flagged as questionable. 5.3 OXYGEN In situ oxygen samples collected during CTD profiles are used for post-measurement calibration. Calibrated CTD data associated with bottle data were merged with bottle oxygen data flagged as 'good'. Because the dissolved oxygen sensor has an obvious hysteresis, program OXDWNP replaced up-profile water sample data with corresponding down-profile CTD/O2 data at common pressure levels. The time rate of change of oxygen current was computed using 2 second intervals in SEASOFT and smoothed using a median filter of width 5 dbar prior to OXDWNP. Oxygen saturation values were computed according to Benson and Krause (1984) in units of µmol/kg. The algorithm used for converting oxygen sensor current and probe temperature measurements to oxygen as described by Owens and Millard (1985) requires a non-linear least squares regression technique in order to determine the best fit coefficients of the model for oxygen sensor behavior to the water sample observations. WHOI program OXFITMR uses Numerical Recipes (Press et al., 1986) Fortran routines MRQMIN, MRQCOF, GAUSSJ, and COVSRT to perform non-linear least squares regression using Levenberg-Marquardt method. A Fortran subroutine FOXY describes the oxygen model with the derivatives of the model with respect to six coefficients in the following order: oxygen current slope, temperature correction, pressure correction, weight, oxygen current bias, and oxygen current lag. Program OXFITMR reads the data for a group of stations. The data are editted to remove spurious points where values are less than zero or greater than 1.2 times the saturation value. The routine varies the six (or fewer) parameters of the model in such a way as to produce the minimum sum of squares in the difference between the calibration oxygens and the computed values. Individual differences between the calibration oxygens and the computed oxygen values (residuals) are then compared with the standard deviation of the residuals. Any residual exceeding an edit factor of 2.8 standard deviations is rejected. A factor of 2.8 will have a 0.5% chance of rejecting a valid oxygen value for a normally distributed set of residuals. The iterative fitting process is continued until none of the data fail the edit criteria. The best fit to the oxygen probe model coefficients is then determined. Coefficents were applied by PMEL program CALOX2W and CTD oxygen was computed using subroutine OXY6W. By plotting the oxygen residuals versus station, appropriate station groupings for further refinements of fitting were obtained by looking for abrupt station to station changes in the residuals. For each grouping, two sets of coefficients were determined, one fitting all the bottles and a second fitting only bottles deeper than just above the median bottle oxygen minimum. Sometimes it was necessary to fix values of some oxygen algorithm parameters to keep those parameters within a reasonable range (noted by asterisks in Table 2). Final coefficients were applied to downcast data using PMEL program OXYCALC; and to bottle data using OXYCALB. The two sets of coefficients were blended at the oxygen minimum using a set of hyperbolic tangent functions with 250-dbar decay scales. CTD oxygen values were despiked using PMEL program CLEANOX. Bad CTD oxygen data were flagged for all of station 12 owing to clogged plumbing, parts of stations 127-131 where the dissolved oxygen module failed in the deep water (the dissolved oxygen module was replaced prior to station 135), and stations 177-182 above 2850 dbar where no shallow bottle data were available to calibrate the sensor. CTD-bottle oxygen differences are plotted against station number to show the stability of the calibrated CTD oxygens relative to the bottle oxygens (McTaggart and Johnson, 1997; Fig. 4, upper panel). CTD-bottle oxygen differences are plotted against pressure to show the tight fit below 1200 m and the increasing scatter above 1200 m (McTagart and Jihnson, 1997; Fig. 4, lower panel). PMEL program P15_EPIC converted finalized CTD data files into EPIC format (Soreide, 1995); and computed ITS-90 temperature, ITS-90 potential temperature, and dynamic height. EPIC datafiles contain a WOCE quality flag parameter associated with pressure, temperature, salinity, and CTD oxygen. Quality flag definitions can be found in the WOCE Operations Manual (1994). TABLE 1. CTD CAST SUMMARY. STN LATITUDE LONGITUDE DATE TIME W/D W/S DEPTH† HAB* CAST T (kts) (m) (m) (db) -------------------------------------------------------------------- 4 53 0.1S 169 59.3E 9 JAN 96 13 270 5 195 12 185 5 53 29.9S 170 29.6E 9 JAN 96 342 275 8 732 10 733 6 53 59.9S 171 0.1E 9 JAN 96 736 275 10 1159 10 1172 7 54 10.2S 171 10.9E 9 JAN 96 1022 320 9 1346 10 1368 8 54 19.8S 171 20.2E 9 JAN 96 1338 315 15 2583 11 2582 9 54 30.3S 171 29.8E 9 JAN 96 1852 355 16 4373 9 4503 10 54 59.7S 172 0.7E 10 JAN 96 203 260 19 5350 5 5469 11 55 30.4S 172 27.0E 10 JAN 96 904 250 38 10 5453 12 55 59.8S 173 0.6E 10 JAN 96 1750 240 27 5448 10 5544 13 56 29.2S 173 30.2E 11 JAN 96 42 220 20 5350 0 5466 14 56 59.7S 173 58.6E 11 JAN 96 908 230 17 5437 10 5549 15 57 30.3S 173 58.5E 11 JAN 96 1731 275 23 5368 11 5425 16 58 0.2S 173 59.5E 12 JAN 96 1 300 18 5206 16 5308 17 58 30.3S 173 58.2E 12 JAN 96 641 315 21 5043 5 5108 18 58 59.8S 174 0.0E 13 JAN 96 1344 265 25 5109 8 5216 19 59 28.7S 173 59.7E 13 JAN 96 2208 280 30 4998 18 5077 20 59 57.9S 173 57.9E 13 JAN 96 530 270 34 40 4419 21 60 30.3S 173 57.8E 13 JAN 96 1958 285 25 5016 22 5107 22 60 59.1S 173 58.8E 14 JAN 96 257 315 19 4692 9 4774 23 61 30.0S 174 0.2E 14 JAN 96 856 340 27 5025 10 5134 24 62 0.0S 173 16.1E 14 JAN 96 1631 330 23 4450 10 4538 25 62 26.9S 172 35.2E 14 JAN 96 2249 305 26 4414 12 4499 26 62 44.7S 172 9.0E 15 JAN 96 424 270 30 4425 39 4052 27 63 0.0S 171 44.9E 15 JAN 96 1135 295 23 10 2644 28 63 30.1S 170 59.6E 15 JAN 96 1744 5 16 2374 12 2391 29 63 59.8S 171 6.6E 16 JAN 96 29 10 26 2551 25 2534 30 64 40.6S 170 58.6E 16 JAN 96 737 330 24 3430 10 3457 31 65 20.2S 171 0.0E 16 JAN 96 1459 35 14 3403 6 3461 32 66 0.9S 171 1.6E 17 JAN 96 11 355 12 3103 7 3159 33 66 59.6S 170 0.0W 18 JAN 96 1150 340 18 3587 10 3668 34 66 20.3S 170 0.0W 18 JAN 96 1930 325 12 3384 10 3431 35 65 39.8S 170 0.3W 19 JAN 96 114 305 17 3142 7 3190 36 64 59.6S 170 0.9W 19 JAN 96 815 265 23 6 2905 37 64 30.1S 169 59.9W 19 JAN 96 1333 230 32 2332 11 2357 38 63 59.7S 170 2.0W 19 JAN 96 1858 240 28 2744 19 2922 39 63 30.1S 170 0.3W 20 JAN 96 57 280 23 2766 12 2842 40 62 59.7S 170 1.4W 20 JAN 96 630 255 17 3046 12 3064 41 62 30.0S 169 59.8W 20 JAN 96 1206 310 15 17 2473 42 62 0.2S 169 59.9W 20 JAN 96 1806 330 28 3384 11 3431 43 61 29.5S 170 0.0W 21 JAN 96 37 315 33 3463 12 3434 44 61 0.1S 170 0.3W 21 JAN 96 2105 300 15 4169 30 4190 45 60 29.7S 169 59.6W 22 JAN 96 410 280 34 3926 10 4013 46 60 0.3S 170 0.3W 22 JAN 96 1030 310 17 3702 12 3747 47 59 30.2S 169 59.9W 22 JAN 96 1702 315 20 4007 10 4104 48 58 59.9S 170 0.2W 22 JAN 96 2311 310 18 4771 10 4860 49 58 29.6S 170 0.8W 23 JAN 96 547 315 17 5188 10 5295 STN LATITUDE LONGITUDE DATE TIME W/D W/S DEPTH† HAB* CAST T (kts) (m) (m) (db) -------------------------------------------------------------------- 50 57 59.7S 170 0.8W 23 JAN 96 1212 290 13 4119 8 4492 51 57 30.1S 170 0.4W 23 JAN 96 1858 240 9 4998 7 5110 52 57 0.2S 170 0.2W 24 JAN 96 122 250 14 5165 8 5261 53 56 29S 169 59.8W 24 JAN 96 751 250 21 5052 9 5159 54 56 0.0S 170 1.8W 24 JAN 96 1352 220 20 5157 7 5236 55 55 29.9S 170 0.0W 24 JAN 96 2050 240 5 4945 9 5049 56 54 59.8S 170 0.0W 25 JAN 96 307 285 11 4812 7 4916 57 54 29S 170 0.1W 25 JAN 96 900 285 13 4811 3 4929 58 54 0.1S 169 59.3W 25 JAN 96 1545 290 16 5009 8 5138 59 53 39S 169 59.4W 25 JAN 96 2122 270 17 5131 5 5253 60 53 19.9S 169 59.6W 26 JAN 96 320 280 22 5286 8 5459 61 53 0.0S 170 0.5W 26 JAN 96 925 275 22 5193 9 5298 62 52 29.9S 170 1.8W 26 JAN 96 1643 270 27 5070 7 5173 63 52 0.1S 170 7.8W 26 JAN 96 2325 275 26 4970 10 5067 64 51 30.0S 170 0.2W 27 JAN 96 606 270 26 4754 20 4876 65 51 0.2S 170 0.4W 27 JAN 96 1221 250 20 5249 12 5321 66 50 29S 169 59.6W 27 JAN 96 1937 220 10 5052 15 5129 67 50 0S 169 59.4W 28 JAN 96 225 210 11 5361 8 5479 68 49 30.3S 170 0.9W 28 JAN 96 917 265 15 5217 15 5337 69 48 59.6S 169 59.4W 28 JAN 96 1633 270 18 5253 10 5340 70 48 30.0S 170 0.2W 28 JAN 96 2248 310 10 5303 5 5409 71 47 59.8S 170 0.3W 29 JAN 96 531 340 10 5293 10 5400 72 47 30.3S 169 59.8W 29 JAN 96 1148 45 13 5309 5 5474 73 47 6.5S 170 27.7W 29 JAN 96 1902 70 6 5391 8 5500 74 46 43S 170 54.7W 30 JAN 96 124 45 6 5292 9 5387 75 46 20.0S 171 22.2W 30 JAN 96 743 50 10 5101 8 5196 76 45 57.0S 171 49.5W 30 JAN 96 1446 100 15 5156 9 5250 77 45 33.6S 172 16.7W 30 JAN 96 2127 110 9 4968 7 5057 78 45 10.6S 172 44.2W 31 JAN 96 443 180 10 4660 10 4738 79 44 50.1S 173 8.2W 31 JAN 96 1035 230 15 3832 10 3869 80 44 31.8S 173 29.4W 31 JAN 96 1707 230 16 3397 10 3452 81 44 19.2S 173 44.7W 31 JAN 96 2119 225 10 3077 9 3115 82 44 9S 173 56.3W I FEB 96 106 280 5 1897 10 1911 83 43 50S 174 17.7W 1 FEB 96 434 250 11 946 10 959 84 43 38.8S 174 32.2W 1 FEB 96 710 0 0 790 10 789 85 43 15.2S 174 59.9W 1 FEB 96 1023 280 9 788 12 785 86 42 55S 174 47.2W 1 FEB 96 1328 270 5 1054 10 1055 87 42 44.8S 174 39.3W 1 FEB 96 1627 300 4 1581 9 1595 88 42 24.1S 174 24.4W 1 FEB 96 2014 315 7 2654 10 2677 89 42 10.1S 174 15.0W 2 FEB 96 6 350 10 2862 7 2889 90 41 42.8S 173 56.5W 2 FEB 96 520 330 12 3118 6 3162 91 41 16.0S 173 38.7W 2 FEB 96 1014 325 12 3319 6 3353 92 40 49.5S 173 19.5W 2 FEB 96 1545 330 14 4169 6 4239 93 40 23.6S 173 2.0W 2 FEB 96 2056 345 18 4574 9 4652 94 40 23.5S 173 1.7W 13 FEB 96 2049 130 15 4574 4 4658 95 39 57.7S 172 42.2W 14 FEB 96 326 150 22 4738 8 4823 96 39 31-0S 172 25.2W 14 FEB 96 937 190 23 4761 8 4848 97 39 4.3S 172 7.7W 14 FEB 96 1612 160 18 4835 10 4929 98 38 37.8S 171 48.6W 14 FEB 96 2202 140 12 4914 10 5003 99 38 11S 171 30.2W 15 FEB 96 423 140 8 4932 10 5031 STN LATITUDE LONGITUDE DATE TIME W/D W/S DEPTH† HAB* CAST T (kts) (m) (m) (db) -------------------------------------------------------------------- 100 37 45.8S 171 12.0W 15 FEB 96 1033 130 14 4997 7 5119 101 37 18.6S 170 53.7W 15 FEB 96 1727 145 14 5130 5 5230 102 36 52.3S 170 37.0W 15 FEB 96 2306 210 12 5278 6 5384 103 36 27.0S 170 17.2W 16 FEB 96 513 220 15 5122 8 5219 104 36 0.2S 170 0.3W 16 FEB 96 1135 200 19 5069 8 5156 105 35 40.3S 170 0.9W 16 FEB 96 1727 205 24 4292 5 4329 106 35 20.0S 170 0.1W 16 FEB 96 2233 170 21 4895 7 4981 107 35 0.5S 169 59.6W 17 FEB 96 415 140 19 5250 5 5348 108 34 30.3S 170 0.2W 17 FEB 96 1137 160 20 5487 6 5591 109 33 59.8S 170 0.0W 17 FEB 96 1849 150 16 5533 6 5640 110 33 29.9S 170 0.1W 18 FEB 96 119 150 10 5416 6 5509 111 33 0.1S 170 0.1W 18 FEB 96 736 115 10 5582 10 5677 112 32 30.1S 170 0.1W 18 FEB 96 1404 115 8 5533 7 5651 113 31 59.8S 169 59.8W 18 FEB 96 2055 140 6 5677 7 5790 114 31 30.0S 169 59.3W 19 FEB 96 330 90 7 5526 8 5645 115 31 0S 169 59.7W 19 FEB 96 951 80 15 5606 7 5725 116 30 30.3S 169 59.8W 19 FEB 96 1640 90 14 5537 9 5640 117 30 0.2S 169 59.8W 19 FEB 96 2259 80 12 5413 7 5514 118 29 30.2S 169 59.8W 20 FEB 96 503 90 15 5148 12 5190 119 29 0.8S 169 59.9W 20 FEB 96 1113 70 18 5596 15 5684 120 28 30.5S 169 59.8W 20 FEB 96 1809 90 10 5459 9 5555 121 28 0.3S 169 59.6W 21 FEB 96 10 90 13 4907 10 4966 122 27 30.1S 170 0.1W 21 FEB 96 600 100 20 5349 7 5485 123 27 0.3S 169 59.5W 21 FEB 96 1202 95 13 5241 7 5331 124 26 29.7S 169 59.4W 21 FEB 96 1906 110 24 5613 8 5710 125 26 0.3S 169 59.7W 22 FEB 96 321 100 20 5601 9 5695 126 25 30.0S 170 0.0W 22 FEB 96 1005 105 17 5833 9 5944 127 25 0.1S 169 59.9W 22 FEB 96 1734 100 20 5640 3 5818 128 24 30.0S 170 0.1W 23 FEB 96 16 90 16 5650 10 5757 129 23 59.8S 170 0.1W 23 FEB 96 720 80 16 5678 10 5780 130 23 30.1S 170 0.1W 23 FEB 96 1404 100 18 5666 7 5781 131 22 59.8S 169 59.7W 23 FEB 96 2139 120 9 5691 9 5799 132 22 30.0S 169 59.9W 24 FEB 96 448 120 13 5649 7 5752 133 22 0.0S 169 59.9W 24 FEB 96 1127 160 12 5626 8 5731 134 21 30S 170 0.1W 24 FEB 96 1837 150 7 5421 6 5514 135 20 59.7S 169 59.6W 25 FEB 96 107 160 5 5461 4 5566 136 20 29S 170 0.1W 25 FEB 96 739 175 5 5598 40 5722 137 20 0.0S 170 0.1W 25 FEB 96 1354 170 6 5315 7 5429 138 19 29.9S 170 0.1W 25 FEB 96 2023 80 4 4904 8 4982 139 19 0.1S 170 3.4W 26 FEB 96 159 350 5 2991 10 3047 140 18 30.3S 170 0.1W 26 FEB 96 730 330 9 5260 3 5343 141 18 0.0S 170 0.0W 26 FEB 96 1324 350 3 4912 9 4991 142 17 30.1S 170 0.0W 26 FEB 96 1948 65 5 5024 8 5097 143 17 0.1S 169 59.8W 27 FEB 96 156 80 12 4974 7 5081 144 16 30.3S 169 59.9W 27 FEB 96 746 80 17 5134 6 5208 145 16 0.2S 169 59.9W 27 FEB 96 1343 90 13 5145 5 5233 146 15 29.8S 170 0.1W 27 FEB 96 2028 70 10 5087 8 5172 147 15 0.2S 170 0.0W 28 FEB 96 250 0 10 4820 8 4884 148 14 40.0S 169 59.9W 28 FEB 96 800 80 14 3315 8 3365 149 14 16.9S 169 59.8W 28 FEB 96 1225 20 10 3535 8 3578 STN LATITUDE LONGITUDE DATE TIME W/D W/S DEPTH† HAB* CAST T (kts) (m) (m) (db) -------------------------------------------------------------------- 150 13 58.3S 170 0.0W 28 FEB 96 1648 355 11 2938 9 2986 151 13 49.1S 170 0.1W 28 FEB 96 2111 40 7 4303 7 4367 152 13 30.1S 170 0.0W 29 FEB 96 231 280 6 4878 8 4952 153 12 59S 170 0.0W 29 FEB 96 821 95 11 4969 10 5047 154 12 29.9S 169 59.9W 29 FEB 96 1403 20 7 5000 5 5084 155 12 0.1S 170 0.1W 29 FEB 96 2018 310 11 5078 9 5016 156 11 30.0S 170 0.0W 1 MAR 96 217 330 13 5057 9 5138 157 11 0.1S 170 0.0W 1 MAR 96 807 20 9 5124 10 5205 158 10 30.1S 169 59.8W 1 MAR 96 1345 350 7 4876 5 4964 159 9 55.5S 169 37.7W 1 MAR 96 2112 20 20 5205 10 5285 160 9 30.1S 168 59.4W 2 MAR 96 429 60 18 5340 5 5432 161 9 0.0S 168 52.6W 2 MAR 96 1036 70 19 4866 9 4973 162 8 29S 168 44.9W 2 MAR 96 1726 40 10 5154 6 5243 163 8 0.0S 168 37.0W 2 MAR 96 2343 40 5 5164 8 5260 164 7 30.0S 168 45.0W 3 MAR 96 542 70 10 5273 7 5364 165 7 0.0S 168 44.9W 3 MAR 96 1141 100 10 5670 8 5767 166 6 30.1S 168 44.9W 3 MAR 96 1854 70 10 5535 10 5646 167 6 0.0S 168 45.0W 4 MAR 96 123 30 10 5671 8 5769 168 5 30.1S 168 45.0W 4 MAR 96 803 50 10 5379 8 5522 169 5 0.0S 168 45.0W 4 MAR 96 1441 50 9 5572 10 5666 170 4 0.0S 168 45.1W 4 MAR 96 2242 40 14 5208 8 5290 171 3 0S 168 45.0W 5 MAR 96 712 30 20 5379 4 5467 172 2 0S 168 45.0W 5 MAR 96 1555 40 17 3285 10 3447 173 1 0S 168 45.2W 6 MAR 96 12 80 17 5786 8 5891 174 0 0.1S 168 45.0W 6 MAR 96 828 70 16 5581 10 5683 175 7 44.8S 168 40.2W 8 MAR 96 14 80 14 5319 3 5414 176 8 15.1S 168 41.3W 8 MAR 96 549 75 10 4964 6 5051 177 10 8.7S 168 58.8W 8 MAR 96 1642 100 12 4640 8 4709 178 10 4.1S 169 12.7W 8 MAR 96 2108 100 10 5254 10 5336 179 9 55.2S 169 37.7W 9 MAR 96 248 70 11 5215 4 5306 180 9 47.0S 170 3.5W 9 MAR 96 1024 95 7 5014 8 5097 181 9 41.6S 170 19.5W 9 MAR 96 1459 30 6 4293 8 4372 182 9 35.7S 170 36.1W 9 MAR 96 1900 90 9 4038 7 4090 ___________________________ * height above bottom depth † corrected water depth TABLE 2A: FULL WATER COLUMN STATION GROUPINGS FOR CTD OXYGEN ALGORITHM PARAMETERS. Station StdDev #Obs 2.8*sd 1:Bias 2:Slope 3:Pcor 4:Tcor 5:Wt 6:Lag -------------------------------------------------------------------------------------------------------------------------- 4-9 0.1351E+01 96 3.782 0.014 0.3616E-02 0.1350E-03* -0.3149E-01 0.8702E+00* 0.3275E+01* 10-13 0.1732E+01 73 4.849 0.026 0.3561E-02 0.1350E-03* -0.3003E-01 0.8702E+00* 0.3275E+01* 14-18 0.9219E+00 145 2.581 0.007 0.3815E-02 0.1350E-03* -0.3797E-01 0.8702E+00* 0.3275E+01* 19-24 0.1207E+01 108 3.380 0.020 0.3702E-02 0.1350E-03* -0.3494E-01 0.8702E+00* 0.3275E+01* 25-31 0.8802E+00 149 2.465 0.019 0.3738E-02 0.1350E-03* -0.3822E-01 0.8702E+00* 0.3275E+01* 32-45 0.1088E+01 322 3.045 0.017 0.3772E-02 0.1338E-03 -0.3540E-01 0.6807E+00 0.7588E+01 46-53 0.9705E+00 237 2.718 0.023 0.3676E-02 0.1345E-03 -0.3174E-01 0.6084E+00 0.6309E+01 54-62 0.1516E+01 273 4.244 0.021 0.3675E-02 0.1361E-03 -0.3032E-01 0.8185E+00 0.1341E+01 63-77 0.2001E+01 430 5.603 0.045 0.3481E-02 0.1310E-03 -0.2757E-01 0.8358E+00 0.2439E+01 78-87 0.2184E+01 231 6.114 0.044 0.3320E-02 0.1449E-03 -0.2536E-01 0.7788E+00 0.2021E+01 88-95 0.1724E+01 255 4.827 0.050 0.3271E-02 0.1409E-03 -0.2511E-01 0.7474E+00 0.2745E+01 96-113 0.1770E+01 574 4.956 0.034 0.3472E-02 0.1389E-03 -0.2739E-01 0.8249E+00 0.2537E+01 114-131 0.1687E+01 587 4.724 0.034 0.3479E-02 0.1390E-03 -0.2703E-01 0.8737E+00 0.3543E+01 135-154 0.1714E+01 624 4.800 0.045 0.2938E-02 0.1476E-03 -0.2465E-01 0.8803E+00 0.5267E-01 155-171 0.1929E+01 558 5.402 0.009 0.3289E-02 0.1508E-03 -0.2794E-01 0.8965E+00 0.1374E-01 172-176 0.1494E+01 124 4.182 -0.006 0.3554E-02 0.1474E-03 -0.3070E-01 0.7925E+00 0.0000E+00* 177 0.4873E+00 13 1.364 0.021 0.3213E-02 0.1474E-03* -0.4386E-01 0.7925E+00* 0.0000E+00* 178 0.8195E+00 16 2.295 -0.009 0.3443E-02 0.1474E-03* -0.8431E-01 0.7925E+00* 0.0000E+00* 179 0.5936E+00 15 1.662 -0.019 0.3316E-02 0.1474E-03* -0.9472E-01 0.7925E+00* 0.0000E+00* 180 0.5059E+00 13 1.416 -0.040 0.3283E-02 0.1474E-03* -0.1163E+00 0.7925E+00* 0.0000E+00* 181 0.3037E+00 10 0.850 -0.041 0.3268E-02 0.1474E-03* -0.1508E+00 0.7925E+00* 0.0000E+00* 182 0.1928E+01 7 5.398 -0.098 0.3711E-02 0.1474E-03* -0.1875E+00 0.7925E+00* 0.0000E+00* fixed parameter TABLE 2B: DEEP WATER COLUMN STATION GROUPINGS FOR CTD OXYGEN ALGORITHM PARAMETERS. Station StdDev #Obs 2.8*,sd 1:Bias 2:Slope 3:Pcor 4:Tcor 5:Wt 6:Lag -------------------------------------------------------------------------------------------------------------------------- 10-18 0.8233E+00 119 2.305 0.000 0.3918E-02 0.1350E-03* -0.4539E-01 0.8702E+00* 0.3275E+01* 19-31 0.8240E+00 187 2.307 0.016 0.3754E-02 0.1350E-03* -0.3740E-01 0.8702E+00* 0.3275E+01* 32-45 0.8000E+00 237 2.240 0.021 0.3735E-02 0.1338E-03* -0.3460E-01 0.6807E+00* 0.7588E+01* 46-53 0.5762E+00 131 1.613 0.010 0.3846E-02 0.1345E-03* -0.3893E-01 0.6084E+00* 0.6309E+01* 54-62 0.4671E+00 139 1.308 -0.001 0.3939E-02 0.1361E-03* -0.3908E-01 0.8185E+00* 0.1341E+01* 63-77 0.5677E+00 190 1.590 0.008 0.3972E-02 0.1310E-03* -0.4515E-01 0.8358E+00* 0.2439E+01* 78-95 0.8477E+00 90 2.374 -0.011 0.3991E-02 0.1409E-03* -0.3776E-01 0.7474E+00* 0.2745E+01* 96-113 0.7719E+00 196 2.161 -0.001 0.3901E-02 0.1389E-03* -0.3079E-01 0.8249E+00* 0.2537E+01* 114-131 0.7562E+00 213 2.117 -0.008 0.4008E-02 0.1390E-03* -0.3101E-01 0.8737E+00* 0.3543E+01* 135-154 0.8193E+00 180 2.294 -0.003 0.3476E-02 0.1476E-03* -0.2547E-01 0.8803E+00* 0.5267E-01* 155-171 0.8459E+00 225 2.368 -0.013 0.3480E-02 0.1508E-03* -0.6254E-02 0.8965E+00* 0.1374E-01* 172-176 0.1120E+01 64 3.135 -0.009 0.3524E-02 0.1474E-03* -0.1246E-01 0.7500E+00* 0.0000E+00* 8. ACKNOWLEDGEMENTS The assistance of the officers, crew, and survey department of the NOAA ship DISCOVERER is gratefully acknowledged. Funds for the CTD/O2 program were provided to PMEL by the Climate and Global Change program under NOAA's Office of Global Programs. 9. REFERENCES Benson, B.B. and D. Krausse Jr., 1984 : The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnology and Oceanography, 29, 620- 632. Denbo, D.W., 1992 : PPLUS Graphics, P.O. Box 4, Sequim, WA, 98382. McTaggart, K.E. and and G.C. Johnson, 1997. CTD/O2 Measurements Collected on a Climate & Global Change Cruise (WOCE Sections P14S and P15S) During January - March, 1996. NOAA Data Report ERL PMEL-63, Pacific Marine Environmental Laboratory, Seattle. Washington, September 1997. Owens, W.B. and R.C. Millard Jr., 1985 : A new algorithm for CTD oxygen calibration. J. Physical Oceanography, 15, 621-631. Press, W., B. Flannery, S. Teukolsky, and W. Vetterling, 1986 : Numerical Recipes: The Art of Scientific Computing, Cambridge University Press, 818 pp. Seasoft CTD Aquisition Software Manual, 1994 : Sea-Bird Electronics, Inc., 1808 136th Place NE, Bellevue, Washington, 98005. Soreide, N.N., M.L. Schall, W.H. Zhu, D.W. Denbo and D.C. McClurg, 1995 : EPIC: An oceanographic data management, display and analysis system. Proceedings, 11th International Conference on Interactive Information and Processing Systems for Meteorology, Oceanography, and Hydrology, January 15-20, 1995, Dallas, TX, 316-321. WOCE Operations Manual, 1994 : Volume 3: The Observational Programme, Section 3.1: WOCE Hydrographic Programme, Part 3.1.2: Requirements for WHP Data Reporting. WHP Office Report 90-1, WOCE Report No. 67/91, Woods Hole, MA, 02543. ____________________________________________________________________________________________ ____________________________________________________________________________________________ D. DATA QUALITY EVALUATIONS D.1. HYDROGRAPHIC DATA DQE (Arnold Mantyla - 1998.NOV.18) The first leg, P14S, was along approximately 170°E southward from Campbell Island to about 66°S, providing an excellent section across the main flow of the Antarctic Circumpolar Current. Data from WOCE section S04 stations 769 to 783 could be tacked onto this section to complete the section to the Antarctic coast at Victoria Land. The cruise continued to 67°S, 170°W to start a long northward section, providing another crossing of the ACC; and then extending through the Samoan Passage on to the equator. There was considerable overlap with P15N. Crossings of P06, P21, p31 and S04 provided comparisons with other WOCE sections as well. The sampling density and data quality for this cruise was quite good on the stations where the 34 place rosette could be used. On the stations where the larger rosette could not be used because of rough weather, the 24 place rosette was still able to get a reasonable profile for the full water column. The data originators have looked over the data quite thoroughly but they have flagged quite a bit more data as questionable than I would have. In the case of phosphate, many profile bumps of only .01, which is well within measurement uncertainty or even round off truncations, were flagged as uncertain. Unless there was some problem in the measurement, those values should have been accepted as ok. In the case of salinity, most of the flagged values were in high gradient regions or near sharp extrema in the profiles. There are a number of reasons why the CTD and water samples may not agree perfectly, and yet neither may be "wrong". The two measurements are quite different snapshots of the water column. Ray Weiss's study on the flushing characteristics of oceanographic samplers (DSR 18: 653-656) points out water samples are really "an integration of the water column through which the sampling bottle has been passed"; while the CTD is an instantaneous measure of the ocean that is in the wake of the rosette package. In high gradient regions either measurement can have problems. If the rosette bottle is tripped too quickly, some water will be entrained from below, so the operators usually wait a bit at each stop so as to collect a more representative sample from the target depth, but even a slightly smeared out sample with respect to depth will be acceptable to most data users. CTD processing routines have a number of checks to result in smoother data: pressure reversals (common when a rosette stops), gradient "spikes", statistical tests, and various averaging schemes that can result in a number that is not equivalent to what the rosette bottle is seeing, not to mention that the two types of samplers are usually physically separated in depth. Ideally, the CTD check should be an average of the CTD data just prior to the rosette trip so as to be equivalent to when the rosette sampler is integrating the water column (though stopped, the package moves up and down with the ship roll and changing wire angle). The purpose of the salinity samples from every rosette bottle is to confirm that the water samples really come from the target depth and verify correct trips and tight seals, or no leakage during the cast. Comparison of the salinometer salinity with the CTD salinity provides a very sensitive validation of the quality of the water samples, and they were usually very good on this cruise. Where differences are greater than that expected from the combined precisions of the two measurements, one looks to see if there could have been a trip problem, leakage, sample collection errors, or analytical errors. It's often a judgement call, but it is not reasonable to believe that sample handling errors occur primarily in the upper water column, where the majority of the u'd values were. A little more care should have been taken to evaluate those apparent salt errors to see if they were possible, given the local gradients. I have not changed many of the quality flags, tending to accept the originator's call, but these data are clearly over-edited. The following are a few specific comments that should be looked into: STATIONS 111-127: Most have isolated mid-depth bottle salts flagged "u", but examination of the density curves and theta/s curves compared to adjacent stations indicate the bottle salinity is more likely to be correct and the CTD slightly off. I asked Mark Rosenberg to check out stations 116, 117, and 120 and he confirmed that the down CTD trace agreed with the bottle data, so I switched the flags on those stations. However, single values at depths between 1800 and 2400db on the other stations should also be changed to accept the bottle salts as ok (if verified by the down CTD trace). STATIONS 100, 104, 139, and 163: These stations have negative oxygen values, either -.78, -.88, or - .98, that may be just a computation residual from a busted analyses. They are flagged as "bad" data, but they are not data at all and should be omitted, and flagged missing or lost. There are quite a few stations (listed below) that have lines without any data, not even a CTD pressure. Some have nutrients or a salinity, but without a location for the data, they have no value and should not be left in to clutter eventual global archives. I suggest the lines without any pressure information be deleted on stations 25, 26, 31, 36, 37, 39, 41 43-45, 48, 63, 66, 68, 69, 71, 73, 77, 78, 80-83, 91, 95-97, 106, 107, 114, 131, 134, 155, 160, 164, 170, 175-182. Most of these are single lines labeled sample 140 or 240, but others have numerous empty fields. STATIONS 30-32 PO4's: Station 32 phosphates below 970db were u'd, apparently because they differ from station 31. However, 32 agrees well with 30, so could station 31 be off instead? All are lower than WOCE S04 PO4's. STATION 26: Station 26 is an unusual one; it is in a mid ocean ridge fracture zone and the deep temperatures are much colder than the previous station, indicating the passage is open to the south to the next basin. All phosphates were flagged "u", but if there is not analytical reason to do so, I would change them to ok. They agree well at the same potential temperatures with nearby stations. Low surface PO4's: Ten stations have zero surface phosphates, unlike any other cruise that I have seen and unlike the NODC Atlas NESDIS 1 for nutrients. Plots of PO4 vs NO3 usually have a positive PO4 intercept at zero NO3 around 0.2 PO4, although values of less than 0.1 (but non-zero) are seen in the western subtropical gyres of the northern hemisphere. PO4/NO3 plots for this cruise compare well with P06 and P15N, except at the surface. Could there be a low level detection problem with the Alpkem Autoanalyzer? The zero values are suspect, and should be flagged "u". The problem stations are between stations 79 and 147. STATION 116, 3441db: The water samples are clearly poor and are not from this level. Salt and 3 of 4 nutrients were u'd, but O2 and NO2 were accepted as ok. The CTD confirms the O2 is poor also, and even though the NO2 would "fit" at this level, the water did not come from this depth, so all water samples should be u'd. Below is a list of the lines in the .sea file where the DQE has made changes to the QUALT2 flags. EXPOCODE 31DSCG96_1, 31DSCG96_2 WHP-ID P14S & P15S DATE 010596 to 031096 19980930WHPOSIOSA STN CAST SAMP BTL CTD NIT NIT PHS DEL DEL C14 C13 NBR NO NO NBR RAW CTDPRS CTDTMP CTDSAL CTDOXY THETA SALNTY OXYGEN SILCAT RAT RIT PHT CFC-11 CFC-12 C14 C13 ERR ERR QUALT1 QUALT2 c16 1 1 112 404 -9 1604.8 2.8508 34.5703 154.04 2.7359 34.5732 162.52 -9.00 -9.00 -9.00 -9.00 0.091 0.043 -9.0 -9.0 -9.0 -9.0 2212411916699 2212311916699 c127 4 1 104 1003 -9 117.7 7.1622 34.3993 281.42 7.1512 34.3992 282.10 6.21 17.55 0.35 1.30 4.298 2.228 -9.0 -9.0 -9.0 -9.0 3222233332299 3222222222299 c153 5 1 101 1022 -9 730.0 6.1802 34.3576 237.54 6.1144 34.3574 32.62 15.77 24.36 0.02 1.67 2.780 1.395 -9.0 -9.0 -9.0 -9.0 2222423322299 2222422222299 c180 7 1 127 1234 -9 8.4 7.3430 34.1401 301.74 7.3422 34.1480 298.43 3.36 18.71 0.20 1.28 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222222229999 2223222229999 c296 10 2 211 1114 -9 2690.5 1.6186 34.7383 198.84 1.4278 34.7371 196.92 98.99 31.13 0.00 2.11 0.049 0.022 -9.0 -9.0 -9.0 -9.0 2222266636299 2222266626299 c358 12 2 203 439 -9 4900.2 0.9043 34.7045 174.10 0.5018 34.2147 269.69 13.40 24.68 0.00 1.66 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 4244333239999 4244333339999 c364 13 1 121 417 -9 113.0 6.0008 34.2096 289.67 5.9913 34.2109 280.74 7.60 21.73 0.10 1.43 4.245 2.139 -9.0 -9.0 -9.0 -9.0 2222222222299 2222333332299 c402 14 1 117 1104 -9 1214.0 2.4670 34.5815 177.31 2.3874 -9.0000 179.15 -9.00 -9.00 -9.00 -9.00 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 3225299991199 3225399991199 c528 18 1 127 1234 -9 237.8 4.7880 34.1270 287.94 4.7701 34.1274 294.64 9.21 22.91 0.22 1.56 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222222229999 2222322229999 c532 18 1 123 1250 -9 575.3 3.4305 34.2090 234.77 3.3917 34.2078 241.92 29.11 30.39 0.01 2.05 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222622229999 2222322229999 c543 18 1 112 1217 -9 2440.0 1.7297 34.7410 194.51 1.5594 34.7401 195.95 95.54 31.14 0.00 2.10 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222232229999 2222222229999 c547 550 18 1 108 1263 -9 3443.3 1.0807 34.7185 204.15 0.8305 34.7166 204.31 116.24 32.00 0.00 2.16 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222232229999 2222222229999 18 1 107 1245 -9 3687.7 0.9947 34.7139 205.88 0.7223 34.7121 206.06 119.55 32.10 0.00 2.17 0.064 0.034 -9.0 -9.0 -9.0 -9.0 2222232222299 2222222222299 18 1 106 1262 -9 3937.1 0.9228 34.7104 207.69 0.6266 34.7081 207.52 121.94 32.22 0.00 2.18 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222232229999 2222222229999 18 1 105 1113 -9 4189.5 0.8652 34.7069 208.63 0.5439 34.7046 209.27 124.13 32.30 0.00 2.18 0.101 0.053 -9.0 -9.0 -9.0 -9.0 2222632222299 2222622222299 c645 22 2 206 441 -9 2899.0 1.1234 34.7217 203.40 0.9240 34.7266 202.17 110.16 31.78 0.00 2.16 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 3223266629999 3223366629999 c881 31 2 240 -9 -9 -9.0 -9.0000 -9.0000 -9.00 -9.0000 -9.0000 -9.00 -9.00 -9.00 -9.00 -9.00 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2999999999999 4999999999999 c1038 35 1 108 1263 -9 1819.9 0.5258 34.7017 208.35 0.4248 34.7015 212.68 123.89 32.50 0.00 2.20 0.169 0.098 -9.0 -9.0 -9.0 -9.0 2222222222299 2222322222299 c1070 36 1 101 406 -9 2901.0 0.3685 34.6982 214.11 0.1853 -9.0000 217.54 124.83 32.55 0.00 2.21 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 3229266669991 3229366669991 c1084 37 1 112 404 -9 523.9 1.8990 34.7181 182.81 1.8698 -9.0000 190.80 84.50 31.80 0.00 2.16 0.179 0.121 -9.0 -9.0 -9.0 -9.0 2229222222499 2229322222499 c1118 1119 38 1 102 414 -9 2496.9 0.6984 34.7055 206.81 0.5426 34.7072 212.39 126.37 32.40 0.00 2.19 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222266649999 2222366649999 38 1 101 406 -9 2918.1 0.7321 34.7056 207.56 0.5395 34.7068 221.63 126.37 32.20 0.00 2.20 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222266669999 2222366669999 c1254 43 1 119 416 -9 164.0 -1.0130 33.9776 282.03 -1.0174 33.9684 347.50 48.12 29.28 0.13 2.06 6.051 2.960 -9.0 -9.0 -9.0 -9.0 2222422222210 2222322222210 c1270 43 1 103 439 -9 2706.8 0.8684 34.7112 206.25 0.6914 34.7334 198.77 103.13 31.53 0.00 2.14 0.058 0.117 -9.0 -9.0 -9.0 -9.0 3224233232410 3224333232410 c1315 1317 45 1 108 440 -9 1502.3 1.9898 34.7290 188.46 1.8930 34.7301 188.18 86.44 31.32 0.00 2.16 0.077 0.038 -9.0 -9.0 -9.0 -9.0 2222222232299 2222222222299 45 1 107 436 -9 1897.2 1.7051 34.7401 194.05 1.5811 34.7395 194.98 94.56 31.16 0.00 2.15 0.059 0.030 -9.0 -9.0 -9.0 -9.0 2222222232299 2222222222299 45 1 106 441 -9 2297.6 1.4063 34.7339 198.76 1.2541 34.7337 198.67 103.62 31.43 0.00 2.16 0.049 0.021 -9.0 -9.0 -9.0 -9.0 2222222232299 2222222222299 c1345 46 1 112 1217 -9 1437.1 2.0886 34.7170 184.93 1.9957 34.7161 184.19 83.94 31.87 0.00 2.15 0.098 0.078 -9.0 -9.0 -9.0 -9.0 2222222232490 2222222222490 c1390 47 2 201 1022 -9 4100.7 0.8609 34.7068 209.34 0.5492 34.7057 209.96 123.01 32.27 0.00 2.21 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 3222266669999 3222236669999 c1539 52 1 123 1250 -9 577.2 2.9835 34.2949 212.74 2.9465 33.8992 216.19 41.70 32.55 0.00 2.21 1.930 0.927 -9.0 -9.0 -9.0 -9.0 2224422222290 2224222222290 c1922 63 1 105 423 -9 3495.9 1.2560 34.7237 203.08 0.9961 34.7155 206.36 107.43 31.21 0.00 2.13 0.077 0.043 -9.0 -9.0 -9.0 -9.0 3223233334499 3223333334499 c1935 64 1 116 409 -9 478.4 5.1715 34.2241 262.54 5.1331 34.2565 276.72 7.77 20.14 0.07 1.50 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 4223322229911 4223333339911 c2229 73 1 124 1218 -9 525.8 7.2659 34.4211 251.35 7.2149 34.4244 251.23 8.37 20.71 0.01 1.45 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2223222221199 2222222221199 c2286 74 2 201 1022 -9 5385.3 0.9691 34.7041 209.79 0.5060 34.6873 209.27 119.27 31.77 0.00 -9.00 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 4224233659910 4224333659910 c2492 80 2 201 1022 -9 3448.0 1.2375 34.7220 203.06 0.9829 34.7214 210.74 111.48 31.99 0.00 2.18 0.042 0.151 -9.0 -9.0 -9.0 -9.0 2222266662499 2222366662499 c2512 81 1 116 1211 -9 564.0 7.8179 34.4918 235.88 7.7606 34.5526 229.52 -9.00 -9.00 -9.00 -9.00 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2224299999999 2224399999999 c2843 92 2 202 1030 -9 4190.2 0.9208 34.7076 206.04 0.5978 34.7072 206.36 122.04 32.15 0.00 2.22 0.043 0.028 -9.0 -9.0 -9.0 -9.0 2222222232299 2222222222299 c2845 92 2 201 1022 -9 4237.3 0.9014 34.7065 206.26 0.5738 34.7072 208.69 122.85 32.28 0.00 2.22 0.054 0.126 -9.0 -9.0 -9.0 -9.0 2222266636499 2222266626499 c2968 96 1 122 1265 -9 673.0 7.4823 34.4927 210.85 7.4152 34.4913 211.30 11.27 23.17 0.00 1.57 1.218 0.613 -9.0 -9.0 -9.0 -9.0 2222422222299 2222222222299 c2970 96 1 120 1015 -9 872.8 6.4577 34.4489 198.18 6.3762 34.4482 199.99 20.43 26.40 0.00 1.79 0.548 0.288 -9.0 -9.0 -9.0 -9.0 2222422222299 2222222222299 c2989 96 1 101 1022 -9 4846.1 0.9441 34.7053 208.33 0.5467 34.7049 207.72 123.20 32.39 0.00 2.22 0.069 0.031 -9.0 -9.0 -9.0 -9.0 2222466622299 2222266622299 c3167 3169 101 2 203 999 -9 4807.7 1.0028 34.7083 206.98 0.6078 34.7074 206.16 121.68 32.53 0.00 2.21 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222263629910 2222262629910 101 2 202 1030 -9 5063.7 1.0137 34.7072 207.80 0.5881 34.7064 202.95 122.18 32.56 0.00 2.21 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222223229910 2222322229910 101 2 201 1022 -9 5227.8 1.0189 34.7065 207.81 0.5733 34.7066 207.33 122.58 32.54 0.00 2.21 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222263669910 2222262669910 c3344 106 1 107 1263 -9 3443.7 1.6337 34.7153 184.89 1.3697 34.7159 190.60 108.72 32.38 0.00 2.23 0.003 0.002 -9.0 -9.0 -9.0 -9.0 2222222222299 2222322222299 c3462 110 2 234 1216 -9 44.6 20.1116 35.6224 228.82 20.1034 35.6264 233.32 1.22 0.01 0.00 0.10 2.336 1.267 -9.0 -9.0 -9.0 -9.0 2222422226699 2222222226699 c3464 110 2 232 1039 -9 95.7 15.2980 35.4279 240.33 15.2833 35.4331 243.71 1.48 0.28 0.03 0.21 2.748 1.455 -9.0 -9.0 -9.0 -9.0 2222222232299 2222222222299 c3536 112 1 132 1039 -9 94.1 15.8199 35.4880 217.81 15.8051 35.4889 240.41 1.91 0.40 0.05 0.22 2.632 1.398 -9.0 -9.0 -9.0 -9.0 2222222236610 2222222226610 c3556 112 1 112 1217 -9 2689.1 1.9488 34.6579 147.63 1.7520 34.6581 148.39 125.52 36.04 0.00 2.49 -0.001 0.002 -9.0 -9.0 -9.0 -9.0 2222422222210 2222222222210 c3582 113 1 122 1265 -9 927.1 5.4371 34.3316 214.11 5.3575 34.4098 213.22 19.78 28.09 0.00 1.90 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2224322229999 2224222229999 c3587 113 1 117 1267 -9 1816.7 2.4545 34.6015 152.77 2.3269 34.6016 153.95 101.60 35.60 0.00 2.46 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222322229999 2222222229999 c3589 113 1 115 1041 -9 2315.8 2.1241 34.6384 146.58 1.9583 34.6407 146.54 119.45 36.13 0.00 2.51 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222422229999 2222222229999 c3645 115 1 132 1039 -9 113.5 16.2967 35.5503 215.22 16.2784 35.5536 227.46 1.63 1.03 0.10 0.24 2.549 1.354 -9.0 -9.0 -9.0 -9.0 2222222232299 2222222222299 c3651 115 1 126 1025 -9 524.1 8.6264 34.5883 207.21 8.5701 34.5836 207.43 7.19 20.17 0.00 1.38 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2223222229999 2222222229999 c3677 3678 116 2 236 1245 -9 4.0 23.5176 35.8167 223.52 23.5167 35.8274 212.22 1.15 0.05 0.00 0.03 1.946 1.078 -9.0 -9.0 -9.0 -9.0 2222222222210 2223222222210 116 2 235 1113 -9 19.4 23.5276 35.8183 213.91 23.5236 35.8183 222.57 1.16 0.06 0.00 0.03 1.948 1.095 -9.0 -9.0 -9.0 -9.0 2222222222299 2222322222299 c3689 116 2 224 1013 -9 675.2 7.0551 34.4163 227.11 6.9900 34.4164 226.59 8.82 22.83 0.00 1.55 0.966 0.477 -9.0 -9.0 -9.0 -9.0 2222422222299 2222222222299 c3698 116 2 215 1041 -9 2189.2 2.1769 34.6255 146.99 2.0215 34.6341 145.96 117.20 36.20 0.00 2.50 -0.002 0.002 -9.0 -9.0 -9.0 -9.0 2223222222299 2322222222299 c3703 116 2 210 1301 -9 3440.6 1.6287 34.7042 175.73 1.3652 34.6753 157.91 123.48 35.26 0.00 2.43 -0.001 0.003 -9.0 -9.0 -9.0 -9.0 3224233232299 3224333332299 c3734 3735 117 1 115 1041 -9 2046.1 2.2843 34.6220 147.78 2.1395 34.6262 147.52 112.57 35.84 0.00 2.49 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2223222229990 2322222229990 117 1 114 1017 -9 2315.9 2.1070 34.6356 146.42 1.9415 34.6419 145.76 120.96 36.08 0.00 2.51 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2223222229990 2322222229990 c3744 117 1 105 1264 -9 4564.6 1.0366 34.7103 206.04 0.6685 34.7127 205.87 119.61 32.11 0.00 2.21 0.009 0.006 -9.0 -9.0 -9.0 -9.0 2222222232290 2222222222290 c3821 120 2 236 1245 -9 4.7 23.9467 35.8507 213.93 23.9457 35.8641 211.66 1.30 0.02 0.00 0.03 1.933 1.119 -9.0 -9.0 -9.0 -9.0 2222222222210 2323222222210 c3843 3844 120 2 214 1017 -9 2189.3 2.1045 34.6325 145.78 1.9501 34.6400 145.96 120.13 36.07 0.00 2.51 -0.001 0.004 -9.0 -9.0 -9.0 -9.0 2223222222299 2222222222299 120 2 213 1302 -9 2439.1 1.9871 34.6471 146.09 1.8126 34.6520 145.47 125.28 36.18 0.00 2.51 0.001 0.003 -9.0 -9.0 -9.0 -9.0 2223222222299 2222222222299 c3951 123 1 114 1017 -9 2064.3 2.1895 34.6222 145.70 2.0447 34.6315 145.77 117.53 36.25 0.00 2.50 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2223222229999 2222222229999 c4013 125 3 324 1013 -9 720.1 6.9901 34.4017 230.38 6.9208 34.4056 228.05 8.70 22.71 0.00 1.55 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2223222229999 2222222229999 c4095 4107 127 2 214 1017 -9 2559.0 1.8973 34.6520 145.97 1.7135 34.6590 145.66 128.66 36.13 0.00 2.53 -0.001 0.000 -9.0 -9.0 -9.0 -9.0 2223222222290 2322222222290 127 2 213 1302 -9 2810.0 1.8188 34.6602 146.34 1.6132 34.6661 146.63 131.92 36.18 0.00 2.52 0.002 0.002 -9.0 -9.0 -9.0 -9.0 2223222222290 2322222222290 127 2 212 1217 -9 3065.2 1.7567 34.6679 147.91 1.5279 34.6704 148.97 132.89 35.94 0.00 2.51 0.003 0.001 -9.0 -9.0 -9.0 -9.0 2222222222290 2322222222290 127 2 211 1114 -9 3315.0 1.6346 34.6811 155.99 1.3838 34.6830 158.01 131.06 35.28 0.00 2.46 0.002 0.002 -9.0 -9.0 -9.0 -9.0 2222222222290 2322222222290 127 2 210 1301 -9 3565.8 1.5221 34.6942 175.79 1.2485 34.7028 178.44 119.58 33.49 0.00 2.32 0.001 0.002 -9.0 -9.0 -9.0 -9.0 2223222226690 2322222226690 127 2 209 1233 -9 3815.3 1.4040 34.7125 193.65 1.1073 34.7205 194.88 111.50 32.14 0.00 2.21 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 3223222229990 3322222229990 127 2 208 1227 -9 3992.6 1.3077 34.7164 198.57 0.9948 34.7185 199.26 112.17 31.94 0.00 2.20 0.005 0.003 -9.0 -9.0 -9.0 -9.0 2222222222290 2322222222290 127 2 207 1263 -9 4316.1 1.1466 34.7123 203.32 0.8030 34.7144 203.93 115.99 32.01 0.00 2.20 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222222229990 2322222229990 127 2 206 1262 -9 4566.6 1.0717 34.7095 205.05 0.7023 34.7111 205.58 118.71 32.16 0.00 2.21 0.011 0.005 -9.0 -9.0 -9.0 -9.0 2222222222290 2322222222290 127 2 205 1264 -9 4811.8 1.0511 34.7077 205.50 0.6540 34.7093 206.36 119.83 32.19 0.00 2.21 0.012 0.006 -9.0 -9.0 -9.0 -9.0 2222622222290 2322622222290 127 2 204 1003 -9 5061.5 1.0523 34.7067 206.09 0.6257 34.7085 206.26 120.78 32.22 0.00 2.21 0.009 0.005 -9.0 -9.0 -9.0 -9.0 2222222222290 2322222222290 127 2 203 1035 -9 5321.2 1.0691 34.7067 190.77 0.6103 34.7088 206.65 121.16 32.25 0.00 2.22 0.009 0.006 -9.0 -9.0 -9.0 -9.0 2242222222290 2342222222290 127 2 202 1030 -9 5602.1 1.0978 34.7062 206.37 0.6028 34.7089 208.01 121.36 32.27 0.00 2.21 0.012 0.007 -9.0 -9.0 -9.0 -9.0 2242222222290 2342222222290 c4254 132 1 136 1245 -9 5.1 27.8460 34.7999 -9.00 27.8448 34.8053 199.16 1.02 0.02 0.00 0.00 1.637 0.959 -9.0 -9.0 -9.0 -9.0 2292622222210 2293622222210 c4373 4374 135 2 226 1025 -9 527.7 8.4781 34.5337 201.07 8.4221 34.5336 204.22 9.11 22.92 0.00 1.58 1.131 0.555 -9.0 -9.0 -9.0 -9.0 2222222222210 2222233332210 135 2 225 1119 -9 625.5 6.9897 34.4038 223.91 6.9299 34.4054 224.06 9.13 22.96 0.00 1.58 0.942 0.466 -9.0 -9.0 -9.0 -9.0 2222222222210 2222233332210 c4793 146 1 102 1030 -9 4940.2 1.0523 34.7090 206.05 0.6401 34.7097 207.91 120.70 32.25 0.00 2.21 0.007 0.003 -9.0 -9.0 -9.0 -9.0 2222222226610 2222322226610 c4811 147 1 120 1015 -9 829.0 4.7780 34.4723 148.90 4.7114 34.4689 147.28 53.59 33.97 0.00 2.36 0.023 0.009 -9.0 -9.0 -9.0 -9.0 2223222222299 2222222222299 c5059 154 1 124 1244 -9 575.5 6.6821 34.4886 153.19 6.6285 34.4854 148.48 30.37 30.54 0.00 2.11 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2223222229999 2222222229999 c5114 155 1 106 1262 -9 3815.6 1.4825 34.6898 165.83 1.1838 34.6922 166.18 132.95 35.15 0.00 2.40 -0.001 0.000 -9.0 -9.0 -9.0 -9.0 2222222222299 2222223222299 c5452 165 1 130 1257 -9 213.6 20.5119 35.8367 145.40 20.4715 35.9834 150.40 2.31 6.96 0.01 0.71 1.965 1.055 -9.0 -9.0 -9.0 -9.0 2224222222210 2223222222210 c5483 166 2 235 1113 -9 21.7 28.8105 35.4380 194.94 28.8053 35.5323 196.00 1.52 0.10 0.01 0.22 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2223222229999 2322222229999 c5637 170 1 125 1119 -9 573.6 7.4558 34.6053 47.04 7.3990 34.6018 44.01 44.91 39.55 0.00 2.75 0.011 0.005 -9.0 -9.0 -9.0 -9.0 2223622222299 2222622222299 c5688 171 1 110 1301 -9 3314.3 1.5556 34.6817 148.42 1.3068 34.6842 153.44 140.83 35.86 0.00 2.47 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222222221199 2223333331199 c5699 172 2 235 1113 -9 10.0 26.5125 35.3942 201.31 26.5102 35.4018 201.33 2.84 4.37 0.32 0.48 -9.000 -9.000 -9.0 -9.0 -9.0 -9.0 2222222229910 2223222229910 c5737 173 2 233 1021 -9 81.0 26.6480 35.5076 200.63 26.6296 35.5114 200.45 2.55 4.02 0.32 0.49 1.719 1.101 -9.0 -9.0 -9.0 -9.0 2222322223399 2222222223399 c5742 173 2 228 1230 -9 326.4 10.8877 34.7808 69.58 10.8475 34.7792 70.52 25.57 29.37 0.00 2.05 0.379 0.223 -9.0 -9.0 -9.0 -9.0 2222322222399 2222222222399 c5866 176 1 112 1217 -9 3648.1 1.4940 34.6875 162.59 1.2126 34.6827 157.82 135.40 35.75 0.00 2.46 -0.002 -0.001 -9.0 -9.0 -9.0 -9.0 2223666662499 2223366662499 c5947 178 1 103 1302 -9 5100.1 1.0852 34.7087 205.62 0.6528 34.7089 201.39 120.21 32.46 0.00 2.21 0.003 0.001 -9.0 -9.0 -9.0 -9.0 2222222222299 2222322222299 ____________________________________________________________________________________________ ____________________________________________________________________________________________ APPENDIX 9B: RESPONSES TO WOCE DQE COMMENTS ON INITIAL .SEA FILE We have removed 4 oxygen values that were 'lost' data. We have removed samples where no CTD pressures or other parameters were reported. We have left in some samples (typically sample '140') which were surface samples collected from the underway pumping system while on station. These samples we analysed for tcarbn and alkali, and although no CTD values are available, we feel it is useful to include them in th file for completeness. We have adopted most of the suggested changes in the salnty, ctdsal and oxygen flags suggested by A. Mantyla. The following response to the Nutrient DQE comments was provided by Calvin Mordy: Changes to Version 8 of P15/P14S Nutrient Data (6/8/00) CWM initiated edits 45 102-105 Changed PO4 flag from 2 to 6 (oversight) 139 108 Changed PO4 flag from 5 to 3 (typo) A. Mantyla initiated edits PO4 32 REJECTED Deep water remains flagged as 4 due to DOC phosphoric acid contamination 26 ACCEPTED Changed flag to 2 or 6 except for bottle 3 (QF=3) 83-142 ACCEPTED Shallow PO4s less than 0.4 µmol/kg were flagged as questionable. ACCEPTED changes suggested by A. Mantyla (FLAG = SIL/NO3/NO2/PO4) STA BOTTLE OLD FLAG NEW FLAG --- ---------- -------- -------- 4 104 3333 2222 5 101 2332 2222 12 203 3323 3333 13 121 2222 3333 18 105-108,112 3222 2222 Reruns due to bubble in flowcell look ok. 45 106-108 2223 2222 46 112 2223 2222 64 116 2222 3333 92 201,202 2223 2222 110 232 2223 2222 112 132 2223 2222 115 132 2223 2222 116 210 3323 3333 117 105 2223 2222 135 225,226 2222 3333 171 110 2222 3333 REJECTED changes suggested by A. Mantyla (FLAG = SIL/NO3/NO2/PO4) STA BOT FLAG Rejected COMMENT Flag --- --- ---- -------- ------------------------------------------------- 10 211 6663 6662 Air bubble in PO4 peak, rerun was suspect 47 201 6666 3666 No problem with silicic acid peak or concentraton 101 201 6366 6266 Peak corrected for severe bubble drift, still questionable 101 202 2322 2222 Peak corrected for severe bubble drift, still questionable 101 203 6362 6262 Peak corrected for severe bubble drift, still questionable 155 106 2222 2322 NO3 peak is ok, not a flier ____________________________________________________________________________________________ ____________________________________________________________________________________________ D.2. CTD DATA DQE (Mark Rosenberg - October 1998) This report contains a data quality evaluation of the CTD data files for the Pacific sector cruise along WOCE meridional sections P14S and P15S (Figure 1) on the RV Discoverer in January to March, 1996. Bottle data are evaluated by Arnold Mantyla in a separate report. The data are in general of good quality, and help to fill a former sampling void for the Southern Ocean in particular. Notably, the P15S section provides a contiguous high density sampling through tropical, subtropical and Antarctic waters, crossing several major fronts. The most significant problem is the biasing of CTD salinity data for individual stations, as detailed below. Note that the comments in this report are offered as suggestions (hopefully helpful ones) from an outside perspective, focussing on various data and methodology problems. They are not intended to detract from the general high standard and usefulness of the data set. STATION SUMMARY FILE (.sum) • Stations 21 and 77 are listed as cast 2 in .sum and .ctd files, but cast 1 in .sea file - needs clarification. • The uncorrected sounder depth at the bottom of the cast appears wrong for stations 44 and 50, as follows (N.B. depth from CTD = altimeter reading + maximum pressure recalculated in meters): Station depth from wire out sounder depth at CTD (m) (m) bottom of cast (m) ------- ---------- -------- ------------------ 44 4134 4114 3630 50 4409 4423 4140 • Sound speed and transducer depth information for the ship's sounder were not provided in the documentation. "Corrected depth" in the .sum file was therefore calculated from the CTD at the bottom of the cast i.e. altimeter reading + maximum CTD pressure recalculated in meters (using the method of Saunders and Fofonoff, 1976). For stations with no altimeter reading, no corrected depth was calculated. These corrected depth values are in an ascii file corrdepth.dat, and have not been merged into the .sum file. D.2.1 SALINITY In the following discussion, only CTD and bottle values with a quality flag of 2 are considered (i.e. QUALT1=2 for CTDSAL and SALNTY in the .sea file). See Table 3 for a station by station summary of data problems. SCATTER OF SALINITY RESIDUALS The salinity residual data delta-S (where delta-S = bottle - CTD salinity difference) for all depths is shown in Figure 2. Outliers were rejected iteratively by the data processors, as described in the cruise report. Below 500 dbar, scatter of delta-S is greatly reduced (Figure 3), so the outliers are from samples shallower than 500 dbar. Much of the scatter for the shallower samples is no doubt due to sampling errors in steep vertical gradients. However, the sign of delta-S can not always be reconciled with the direction of the vertical salinity gradient (assuming here that the CTD sensors are below the Niskin bottles on the rosette package). It may be possible to improve this scatter by increasing the averaging period for the upcast CTD burst data from 2 seconds to 10 seconds. This larger averaging period more closely matches the swell wave period, and may better average out the effect of the rolling ship during bottle stops. BIASING OF CTD SALINITY DATA FOR INDIVIDUAL STATIONS Standard deviations for delta-S for the whole cruise were calculated from data in the .sea file ("uncorrected data" in Table 1). The value of 0.0018, calculated using all sampling depths and |delta-S| ≤ 0.008, is a reasonable estimate of the salinity accuracy for the cruise (note that 0.008 ~ 2.8*0.0029, where 0.0029 is the standard deviation for all bottles from Table 1). When the cruise is viewed as a whole, this salinity accuracy meets WOCE requirements and delta-S varies about a mean of zero (Figures 2 and 3). However when individual stations are examined, there is a significant problem with biasing of the CTD salinity data (Table 3). This is clearly evident through visual examination of Figures 2 and 3: the mean value of delta-S for each station varies (a good example is for stations 46 to 53, where delta-S is clearly negative). The biasing is a direct result of the conductivity calibration method as described in the cruise report, where the whole cruise is fitted in one group and the fourth order station dependent slope correction fails to fully track the variation of conductivity sensor behaviour over the cruise. Breaking down the stations into smaller calibration groups is strongly recommended - this would allow the station dependent slope correction to remove the bias for individual stations. To prove this point, I've done an extra fit to the delta-S data to minimize the residuals and biasing, as follows. Note that back-calculating conductivity made no difference to the resulting corrections, so salinity was used. Firstly, Figure 3 was examined and station groups formed to reflect the variation through the cruise of mean delta-S for each station (Table 2). Next, samples for which |deltaS| > 0.008 were rejected. A linear fit of CTD to bottle salinity (i.e. Sctd to Sbtl) was then found for each station group: Sctd = a1 Sbtl + a2 for fit coefficients a1 and a2. Lastly, corrected salinity Scor was calculated each station group: Scor = (Sctd - a2)/a1 The resulting Sbtl - Scor residuals are plotted in Figure 4 (all depths) and Figure 5 (deeper than 500 dbar). Standard deviation calculations for these "corrected" data are shown in Table 1. As expected, there is only a small improvement to standard deviations calculated for the whole cruise (Table 1). The important point is the marked improvement to the biasing of individual stations, revealed by comparing Figure 5 to Figure 3. Corrected and uncorrected delta-S vertical profiles for a few example stations are plotted in Figure 6. Stations for which the correction improves salinity biasing are indicated in Table 3. I hope this does not put too fine a point on the conductivity calibration. True, the salinity biasing errors for the submitted data are less than 0.002, however delta-S values for each station ought to be scattered around a mean value of zero. Clearly, breaking down a cruise into smaller station groups for the calibration of CTD conductivity significantly improves the calibration. Note that the correction done here is only a rough version - for a real calibration on selected station groups, groups would be selected with a linear variation of station mean delta-S, allowing the station dependent slope correction to take effect within each group and giving even better calibration results. TABLE 1: Standard deviations for salinity residuals _S (using only bottle and CTD data for which the quality flag=2), where "uncorrected data" are as submitted to WHPO, and corrected data are with additional delta-S fit applied. standard deviation standard deviation of delta-S, of delta-S data uncorrected data corrected data --------------------------- ------------------ ------------------ all depths 0.0029 0.0028 deeper than 500 dbar 0.0010 0.0009 all depths, |delta-S|≤0.008 0.0018 0.0017 Table 2: Station grouping used for additional fit of salinity residuals. 1-3 41-45 75-80 133-137 162-174 4-8 46-53 81-99 138-146 175-182 9-18 54-59 100-105 147-148 19-25 60-62 106-109 149-151 26-30 63-65 110-121 152-154 31-35 66-70 122-129 155-157 36-40 71-74 130-132 158-161 PROBLEM SALINITY BOTTLE DATA Comparing bottle salinity values for adjacent stations on deepwater theta-S curves, the following problems were found: station problem recommendation ------- --------------------------- ------------------------ 19 bottle salts high by ~0.002 don't use in calibration 49 bottle salts low by ~0.001 don't use in calibration 117 bottle salts high by ~0.002 don't use in calibration 164 bottle salts low by ~0.001 don't use in calibration D.2.2. OXYGEN The CTD oxygen data are of the highest quality. Calibration results are excellent, and oxygen profiles are remarkably free of noise. The Seabird design of constant flow past the oxygen sensor membrane appears to have merit. Due to the inherent small scale variability of membrane-type oxygen sensors, I do not believe the concerns expressed about data despiking later in this report are relevant here. Oxygen residual data are plotted in Figure 7, noting that large outliers lie beyond the axis limits on the graph. Many stations appear to have suspicious oxygen data for the top few bins, due to transient sensor errors as the instrument enters the water and the pump winds up, combined with the despiking errors discussed below. Stations where these errors are greater than ~4 µmol/kg, and where there is no matching T/S feature, are summarised in Table 4, and a quality flag of "3" is recommended for bins not already flagged as "7" in the .ctd files. Also listed in Table 4 are a few stations where most of the CTD oxygen profile has a constant offset from the bottle values. In all cases the offset is small (~1%), however given the high quality of the CTD oxygen data set these stations are worth pointing out. D.2.3. TEMPERATURE The following temperature spikes were identified in the .ctd files: station 43: very spikey T structure between 100 and 300 dbar on downcast, not reflected in salinity - would like to confirm with upcast CTD temperature station 45: temperature spike at 9 dbar, flag as 3 in .ctd file station 49: temperature spike at 8-11 dbar, flag as 3 in .ctd file station 54: small temperature spike at 7 dbar, status uncertain due to despiking of salinity data station 60: small temperature spike at 5-6 dbar, status uncertain due to despiking of salinity data station 64: small temperature spike at 7-8 dbar, status uncertain due to despiking of salinity data station 106:small temperature spike at 7 dbar, status uncertain due to despiking of salinity data station 108:small temperature spike at 4 dbar, status uncertain due to despiking of salinity data D.2.3.1. DESPIKING AND INTERPOLATION There is a large number of interpolated CTD temperature and salinity values in the .ctd files, flagged as "6". This needs an explanation i.e. is it due to fouling of the pump line, data dropouts from the instrument or some other electronic problem? Or is it mainly due to interpolations from the program DELOOP mentioned in the cruise report? I have concerns about despiking of the temperature and salinity data (program DESPIKE mentioned in the cruise report). In particular, salinity data near the surface is often continued to the surface as an identical value from the first good data bin a few decibars down, and flagged as "7" (program FILLSFC mentioned in the cruise report). As a result, temperature features are often not relected in the salinity data (e.g. Figure 8), and density inversions can occur. In some instances, erroneous salinity features may appear (e.g. station 159, top 9 dbar in Figure 8). Rather than inserting these fictional salinity data near the surface, it might be preferable to leave the original bad data there and flag as "3" or "4", or else remove the data entirely. In general, all data in the top 15 dbar with a "7" flag should be regarded as questionable. D.2.3.2. DENSITY INVERSIONS Locations of unstable vertical density gradients are shown in Figure 9; only gradients more unstable than -0.003 kg/m3/dbar are shown. Unstable density gradient values are summarised in Table 5. All except for station 40 occur in the top 20 dbar. In addition, almost all occur where the CTD salinity data has been "despiked" (flag 7 in the .ctd file). The worst instance is for station 78 at 9 dbar: a temperature feature occurs at this level, however the salinity data has been artificially smoothed, leaving a large density instability. D.2.4. INTRA-CRUISE COMPARISON Deepwater theta-S and theta-oxygen curves compare well for the coincident station pair 93/94. More variability is evident for the station pair 159/179. COMPARISONS WITH OTHER CRUISES Deepwater theta-S and theta-oxygen curves were compared for P15S stations coincident with other cruise data sets, as follows. In general, there is reasonable consistency between the different data sets. P15S and P15N (P.I. H. Freeland) (Figure 10) P15N salinity lower than P15S by on average 0.001. No CTD oxygen data for P15N. P15S and P31 (P.I. D. Roemmich) (Figure 11) P31 salinity lower than P15S by on average 0.001. Oxygen data compare well. P15S and P21 (P.I. H. Bryden on western leg) (Figure 12) Limited data only for comparison, and stations separated longitudinally by 19 miles. P21 salinity higher than P15S by ~0.001 above (theta=1.3o; compare well at bottom. Oxygen data compare well below theta=1.25o P15S and P6 (P.I. M.McCartney on central leg) (Figure 12) Limited data only for comparison, and stations separated longitudinally by up to 12 miles. Salinity data compare well. Oxygen data compare well around the oxygen minimum; at the bottom, P6 is higher by ~2 µmol/kg P15S and S4P (P.I. Koshlyakov) (Figure 12) Limited data only for comparison, and stations separated longitudinally by up to 17.5 miles. S4P salinity lower by ~0.0015. Oxygen data a bit variable, but within ~1%. DOCUMENTATION The documentation is good and thorough. It would be useful to add the following information: • PDR sound speed used for sounder readings, and whether or not readings have been corrected for transducer depth below the waterline; • criteria used for despiking. REFERENCES Saunders, P.M. and Fofonoff, N.P., 1976. Conversion of pressure to depth in the ocean. Deep Sea Research, 23:109-111. TABLE 3: SUSPICIOUS CTD SALINITY (SCTD) DATA. * Indicates calibration improved by additional correction described in the text (i.e. using smaller station groupings). stn comment recommendation --- -------------------------------------------------- --------------------------------- *8 Sctd high by ~0.001 below 1500 dbar use smaller station groupings (impressive interfingering for this station!) *9 Sctd high by ~0.0015 for whole profile use smaller station groupings *10 Sctd high by ~0.001 for whole profile use smaller station groupings *11 Sctd high by ~0.001 for whole profile use smaller station groupings *13 Sctd high by ~0.001 below 1500 dbar use smaller station groupings *15 Sctd high by ~0.001 below 2000 dbar use smaller station groupings *16 Sctd high by ~0.001 below 2000 dbar use smaller station groupings *17 Sctd high by ~0.001 for whole profile use smaller station groupings *18 Sctd high by ~0.0015 for whole profile use smaller station groupings 23 Sctd high by ~0.001 below 1000 dbar possibly due to bottles *26 Sctd high by ~0.001 for whole profile use smaller station groupings (interesting T feature at 2600 dbar on downcast) *27 Sctd high by ~0.001 for whole profile use smaller station groupings *29 Sctd high by ~0.001 below 800 dbar, low at surface use smaller station groupings 37 Sctd low by ~0.001 below 1000 dbar 38 Sctd low by ~0.001 for whole profile *41 Sctd high by ~0.001 below 500 dbar, low at surface use smaller station groupings *46 Sctd high by ~0.001 below 1000 dbar use smaller station groupings *47 Sctd high by ~0.001 below 1000 dbar use smaller station groupings *48 Sctd high by ~0.001 for whole profile use smaller station groupings *50 Sctd high by ~0.001 below 1000 dbar use smaller station groupings *51 Sctd high by ~0.001 for whole profile use smaller station groupings *52 Sctd high by ~0.001 for 1000 to 4000 dbar use smaller station groupings *53 Sctd high by ~0.001 below 2000 dbar use smaller station groupings *54 Sctd low by ~0.001 below 2000 dbar use smaller station groupings *57 Sctd low by ~0.001 for whole profile use smaller station groupings *58 Sctd low by ~0.001 for whole profile use smaller station groupings 61 1 to 5 dbar transient/despiking error in Sctd 63 1 to 10 dbar transient/despiking error in Sctd *63 Sctd low by ~0.001 for whole profile use smaller station groupings *64 Sctd low by ~0.001 for whole profile use smaller station groupings *65 Sctd low by ~0.001 for whole profile use smaller station groupings 69 Sctd high by ~0.001 below 1500 dbar 70 Sctd low by ~0.001 for whole profile 73 Sctd high by ~0.001 below 1500 dbar 74 Sctd high by ~0.001 below 2500 dbar (interesting S in top 120 m) 75 Sctd high by ~0.001 for whole profile *76 Sctd high by ~0.001 below 1000 dbar use smaller station grouping *77 Sctd high by ~0.001 below 2000 dbar use smaller station grouping *79 Sctd high by ~0.001 below 1000 dbar use smaller station grouping *80 Sctd high by ~0.001 for 2500 to 3500 dbar use smaller station grouping 90 Sctd low by ~0.001 for whole profile 95 Sctd high by ~0.001 for whole profile 96 Sctd high by ~0.001 for top 3000 dbar *100 Sctd high by ~0.001 for whole profile use smaller station groupings *101 Sctd high by ~0.001 below 500 dbar use smaller station groupings *102 Sctd high by ~0.001 below 500 dbar use smaller station groupings *103 Sctd high by ~0.001 below 500 dbar use smaller station groupings *105 Sctd high by ~0.001 below 500 dbar use smaller station groupings *111 Sctd low by ~0.0008 for whole profile use smaller station groupings *112 Sctd low by ~0.001 for whole profile use smaller station groupings *115 Sctd low by ~0.001 for whole profile use smaller station groupings *119 Sctd low by ~0.001 below 3500 dbar use smaller station groupings *120 Sctd low by ~0.001 below 1200 dbar use smaller station groupings *121 Sctd low by ~0.0015 below 2000 dbar use smaller station groupings 124 Sctd low by ~0.001 below 3000 dbar 126 1 to 13 dbar transient/despiking error in Sctd 126 Sctd low by ~0.001 for whole profile 127 upcast CTDSAL values in .sea file bad flag as 3 in .sea file the CTDSAL below 2500 dbar (possible fouling) values for samples 202 to 214 128 Sctd high by ~0.001 for 1000 to 5000 dbar *130 Sctd high by ~0.001 for whole profile use smaller station groupings *132 Sctd high by ~0.001 for 2000 to 5000 dbar use smaller station groupings 133 Sctd low by ~0.001 below 1500 dbar *138 Sctd high by ~0.0008 below 2000 dbar use smaller station groupings *140 Sctd high by ~0.001 for 1000 to 4000 dbar use smaller station groupings *143 Sctd high by ~0.001 for 1500 to 4000 dbar use smaller station groupings 144 Sctd high by ~0.0015 below 2000 dbar 146 1 to 6 dbar transient/despiking error in Sctd *147 Sctd high by ~0.0015 for whole profile use smaller station groupings *148 Sctd high by ~0.001 below 500 dbar use smaller station groupings *154 Sctd high by ~0.001 for 1200 to 3500 dbar use smaller station groupings *155 Sctd low by ~0.001 below 1000 dbar use smaller station groupings *156 Sctd low by ~0.001 below 1000 dbar use smaller station groupings *158 Sctd high by ~0.001 below 500 dbar use smaller station groupings 159 1 to 9 dbar transient/despiking error in Sctd 160 1 to 10 dbar transient/despiking error in Sctd 160 Sctd high by ~0.001 for 500 to 4000 dbar, low below 4000 dbar 168 Sctd high by ~0.001 for 800 to 4500 dbar 173 Sctd low by ~0.001 below 1000 dbar TABLE 4: Suspicious CTD oxygen data station comment recommendation ------- ------------------------------------- ------------------------------ 8 high by ~2 µmol/kg below 500 dbar calibrate station individually 10 high by ~2 µmol/kg below 1000 dbar calibrate station individually 13 1 to 5 dbar transient/despiking error 16 1 to 8 dbar transient/despiking error 17 1 to 7 dbar transient/despiking error 18 1 to 8 dbar transient/despiking error 19 1 to 7 dbar transient/despiking error 21 1 to 7 dbar transient/despiking error 22 to 25 1 to 8 dbar transient/despiking error 27 55 to 57 dbar spike flag as 3 in .ctd file 29 1 to 8 dbar transient/despiking error 32 1 to 11 dbar transient/despiking error 40 1 to 8 dbar transient/despiking error 43 1 to 10 dbar transient/despiking error 44 1 to 11 dbar transient/despiking error 45 1 to 12 dbar transient/despiking error 46, 47 1 to 10 dbar transient/despiking error 52 1 to 11 dbar transient/despiking error 54 1 to 10 dbar transient/despiking error 55 1 to 11 dbar transient/despiking error 63 1 to 11 dbar transient/despiking error 112 1 to 12 dbar transient/despiking error 119 12 dbar spike flag as 3 in .ctd file 135 high by ~2.5 µmol/kg for whole profile calibrate station individually 148 1 to 5 dbar transient/despiking error 152, 153 1 to 4 dbar transient/despiking error 155 1 to 4 dbar transient/despiking error 161 1 to 11 dbar transient/despiking error 164 1 to 3 dbar transient/despiking error 165 1 to 6 dbar transient/despiking error TABLE 5: DENSITY INVERSIONS < -0.003 kg/m3/dbar, AND QUALITY FLAG FOR SALINITY IN .CTD FILE FOR THE PRESSURE BIN. stn pres. density sal. | stn pres. density sal. | stn pres. density sal. (dbar) gradient flag | (dbar) gradient flag | (dbar) gradient flag --- ------ -------- ---- | --- ------ -------- ---- | --- ------ -------- ---- 8 7 -0.0057 7 | 106 8 -0.0163 7 | 155 10 -0.0048 6 8 8 -0.0032 7 | 107 2 -0.0059 7 | 155 11 -0.0048 2 10 7 -0.0058 7 | 107 3 -0.0046 7 | 157 5 -0.0099 7 20 4 -0.0047 7 | 107 9 -0.0190 7 | 159 6 -0.0052 7 22 6 -0.0061 7 | 107 12 -0.0099 6 | 162 5 -0.0036 7 40 105 -0.0031 6 | 107 13 -0.0099 6 | 162 12 -0.0030 6 40 106 -0.0031 6 | 107 14 -0.0100 2 | 162 13 -0.0030 6 40 107 -0.0032 2 | 108 5 -0.0108 7 | 162 14 -0.0030 2 45 9 -0.0102 7 | 109 2 -0.0193 7 | 165 4 -0.0050 7 49 8 -0.0181 7 | 110 2 -0.0037 7 | 167 4 -0.0125 7 54 8 -0.0044 7 | 111 2 -0.0094 7 | 169 3 -0.0053 7 57 2 -0.0041 7 | 112 2 -0.0122 7 | 169 5 -0.0034 7 60 7 -0.0114 7 | 113 3 -0.0037 7 | 170 2 -0.0035 7 64 8 -0.0054 7 | 113 4 -0.0034 7 | 174 4 -0.0036 7 64 9 -0.0040 7 | 117 3 -0.0046 7 | 176 2 -0.0130 7 68 2 -0.0052 7 | 117 7 -0.0059 7 | 176 5 -0.0033 7 69 11 -0.0061 7 | 120 2 -0.0032 7 | 177 3 -0.0049 7 69 12 -0.0030 6 | 121 2 -0.0040 7 | 177 4 -0.0035 7 69 13 -0.0030 6 | 124 3 -0.0135 7 | 180 2 -0.0108 7 69 14 -0.0031 2 | 124 4 -0.0047 7 | 181 2 -0.0073 7 70 4 -0.0058 7 | 125 2 -0.0042 7 | 182 2 -0.0034 7 70 6 -0.0046 7 | 126 2 -0.0055 7 | 182 3 -0.0078 7 71 7 -0.0054 7 | 131 7 -0.0033 7 | 78 5 -0.0094 7 | 131 11 -0.0053 7 | 78 8 -0.0080 7 | 132 2 -0.0034 7 | 78 9 -0.0254 7 | 134 4 -0.0030 7 | 82 3 -0.0032 7 | 134 7 -0.0033 7 | 83 8 -0.0089 7 | 135 2 -0.0063 7 | 84 2 -0.0042 7 | 136 2 -0.0125 7 | 85 5 -0.0082 7 | 139 9 -0.0103 7 | 86 2 -0.0031 7 | 140 6 -0.0134 7 | 87 2 -0.0036 7 | 143 2 -0.0073 7 | 88 5 -0.0173 7 | 143 3 -0.0067 7 | 89 4 -0.0063 7 | 143 4 -0.0038 7 | 89 5 -0.0075 7 | 144 2 -0.0066 7 | 90 5 -0.0071 7 | 148 2 -0.0084 7 | 90 9 -0.0151 7 | 152 3 -0.0047 7 | 91 4 -0.0057 7 | 153 2 -0.0136 7 | 99 3 -0.0042 7 | 154 2 -0.0054 7 | 101 4 -0.0033 7 | 154 4 -0.0059 7 | 101 8 -0.0046 7 | 155 6 -0.0047 6 | 102 7 -0.0040 7 | 155 7 -0.0048 6 | 105 4 -0.0054 7 | 155 8 -0.0048 6 | 106 4 -0.0038 7 | 155 9 -0.0048 6 | TABLE 6: Summary of flag changes recommended in .ctd (i.e. .wct) files. Note that for all cases shallower than 15 dbar, all data above the reflagged values was already flagged as "7" (i.e. despiked) - "7" flags were not changed. station parameter pressure old flag new flag ------- --------- -------- -------- -------- 45 T 9 2 3 49 T 8 to 11 2 3 61 S 5 2 3 63 S 6 to 10 2 3 126 S 11 2 3 126 S 12 to 13 6 3 146 S 6 2 3 159 S 8 to 9 2 3 160 S 11 6 3 13 O 5 2 3 19 O 7 2 3 25 O 8 2 3 27 O 55 to 57 2 3 52 O 11 2 3 63 O 11 2 3 119 O 12 2 3 ____________________________________________________________________________________________ ____________________________________________________________________________________________ D.3. RESPONSE TO CTD DATA DQE (Kristy McTaggart and Greg Johnson) We considered each of the suggestions and the following is an itemized explanation of what we did or didn't change in our data files, as well as answers to DQE's questions. STATION SUMMARY FILE (.sum) Stations 21 and 77 should be listed as cast 1. The .sum and .ctd files should be corrected. We've corrected our files here. The uncorrected sounder depth at the bottom of the cast for stations 44 and 55 may appear erroneous. However, these are not typos. They are the values calculated from the ship's PDR during acquisition. The bottom at station 44 in particular was noted to be strongly sloping. We did not change these values in our files. The PDR sound speed used for sounder readings was 1500 m/s. The readings were not corrected for transducer depth below the waterline. The depth of the transducer would've been about 5.5 +/- 0.6 m. We would prefer to use the PDR depths as listed and correct them using Carter's tables so that they serve as independent measurements and can be used as a check on CTD pressure. SALINITY Scatter Of Salinity Residuals There is an incompatibility between the General Oceanics rosette sampler and the Sea-Bird 911plus CTD system that generates a spike in the data stream at the moment a bottle is confirmed as tripped. Because of this, upcast CTD burst data had to be averaged prior to the bottle confirm bit. Two-second averages were chosen over a longer interval because the CTD operators did not always let the package sit at bottle depth for at least 10 seconds before firing the rosette. Hence no changes were made. Biasing Of CTD Salinity Data For Individual Stations Of course one can seemingly make a (very slight) improvement in the CTD-bottle residual statistics by allowing more degrees of freedom in the fit as the DQE has suggested (that is, breaking up the fit into small station groupings). One could get the best statistics by individually fitting each station to its bottles, but most experts would argue that this would be a bad choice, because one would not be taking advantage of the CTD calibration as a way to average out station-to-station bottle salinity noise. We believe that the SBE-9/11 CTD conductivity slope drifts gradually, and is actually more stable than the day-to-day fluctuations in the autosal- inometer salinities owing to small temperature drifts in the laboratory and the fact that severe budgetary constraints on these cruises forced us to economize even on such things as standard sea water. We suspect that the "biasing of the CTD salinity data" mentioned in the DQE evaluations is actually noise in the bottle data. Somewhat suspicious is that the station groupings recommended by the DQE of the correct size (most often 3-5 stations per group) that they could easily be owing to daily drift problems in the autosalinometer. For our original calibrations we deliberately chose to model the conductivity slope adjustments of the entire data sets for P14S/P15S and P18 using 4th-order polynomial functions of station number to average out bottle salinity noise. We did this because we saw no obvious jumps in the CTD calibration for either cruise, just gradual drifts. Statistical support for our philosophy over that of the DQE is given by the following exercise: The 2°C potential isotherm is well within the oldest Pacific Deep Water, and has some of the tightest Theta-S relation- ships in the Pacific Ocean (and probably the world). For both P18 and P14S/P15S, we looked at the absolute values of station-to-station changes in CTD salinity on Theta=2.0°C (Figure 1) for our original calibration, creating a histogram of station-to-station differences for each cruise in 0.001 bins. We then applied the DQE's suggested ad-hoc calibrations for smaller station groupings to the data and conducted the same analysis. When the histograms are differenced (Figure 2), one can see that the Theta-S relations at 2°C after the DQE's corrections are noisier for both cruises. For P18, after the DQE's suggested correction there are four less station pairs in the 0.000 difference bin and one less in the 0.001 difference bin whereas there are three more in the 0.002 difference bin and two more in the 0.003 difference bin. For P15S/P15S there are four less stations in the 0.000 difference bin after the DQE's suggested correction, with one more in the 0.001 difference bin and three more in the 0.002 difference bin. Since the DQE's "corrections" actually introduce more noise in the CTD Theta-S relation at 2°C than our original calibration, we decline application of them. The small groups do not improve the calibraiton, they degrade, perhaps by introducing autosalinometer drift noise. Regarding suspicious CTD salinity data listed in Table 3, no changes were made to any profile data (see above) nor flags associated with "transient/ despiking errors". As for CTDSAL values in the .sea file for station 127, we agree that they should be flagged as 3 for samples 202 to 214. Also, BOTSAL flags for samples 209, 210, 213, and 214 should then be changed to 2. PROBLEM SALINITY BOTTLE DATA Excluding stations 19, 49, 117, and 164 bottle salinity values from the calibration of this data set as a whole would not significantly change the fit as we have done it, thus we didn't make this adjustment. OXYGEN Quality flags should be ammended as suggested in Table 4. However, stations 8, 10, and 135 will not be recalibrated individually as they are among the first casts with a new sensor module. As a rule, the first few casts with a new module are problematic, and this cruise was no exception. TEMPERATURE The very spikey temperature structure between 100 and 300 dbar at station 43 is also seen in salinity and has been identified as Antarctic Intermediate Water interleaving at the front. It is also seen at adjacent stations 42 and 44. Nothing should be done to this profile. Temperature spikes listed were examined but not changed. Neither were their flags changed. DESPIKING AND INTERPOLATION Interpolated temperature and salinity data are the result of processing programs and not instrument or electronic problems. In program DESPIKE salinity profiles are viewed and interactively despiked using linear interpolation. Conductivity, theta, and sigma-theta are recomputed for the interpolated records. Only the salinity quality flag is ammended to 6. In program DELOOP Brunt-Vaisala Frequency squared (N^2) is computed at the mid depths and bracketed between two vectors, one padded with zeros at the surface and one padded with zeros at depth. If the first and second points of a -N^2 fail the criteria (<=-1e-05), then temperature and conductivity are linearly interpolated and salinity, theta, and sigma- theta are recomputed. The quantity of interpolated points is large because we were working with a large package off the stern of the ship, often in the Southern Ocean. Hence, there was a lot of wake problems. As for the filled surface records flagged as 7, we maintain that this is more useful than leaving flagged bad or questionable data or removing the data entirely. It should be noted in the documentation that all data in the top 15 dbar with a flag of 7 should be regarded as questionable. DENSITY INVERSIONS Density inversions listed in Table 5 were examined and salinity quality flags were changed to '3' for the following records. Station Pressure Station Pressure ------- -------- ------- -------- 8 5-7 108 4 10 1-7 109 1 20 1-3 110 1 22 1-5 111 1 45 1-8 112 1 49 1-7 113 1-3 54 7 117 1-6 57 1 120 1 60 5-6 121 1 64 7-8 124 1-3 68 1 125 1-3 69 1-14 126 1-13 70 3,5 131 3,5,6,10 71 6 132 1-9 78 1-9 134 1-3,6 82 1-4 135 1 83 7 136 1 84 1-2 139 8 85 4 140 4,5 86 1 143 1-3 87 1 144 1 88 3,4 146 1-6 89 3,4 148 1-3 90 4,8 152 1-2 91 1-4 153 1-2 99 1-2 154 1-3 101 1,3,7 155 1-15 102 6 157 1-4 105 1-3 159 1-6 106 1-3,6,7 160 1-12 107 1-2,8,11-13 162 1-13 165 1-3 167 1-3 169 1-7 170 1-3 174 1-3 176 1-4 177 1-3 180 1-3 181 1 182 1-2 DOCUMENTATION Again, the PDR sound speed was 1500 m/s, and the readings have not been corrected for transducer depth (5.5 +/- 0.6 m) below the waterline. The criteria used for despiking are explained above under DESPIKING AND INTERPOLATION. ____________________________________________________________________________________________ ____________________________________________________________________________________________ D.3. Final CFC Data DQE (David Wisegarver - Dec 2000) During the initial DQE review of the CFC data, a small number of samples were given QUALT2 flags which differed from the initial QUALT1 flags assigned by the PI. After discussion, the PI concurred with the DQE assigned flags and updated the QUAL1 flags for these samples. The CFC concentrations have been adjusted to the SIO98 calibration Scale (Prinn et al. 2000) so that all of the Pacific WOCE CFC data will be on a common calibration scale. For further information, comments or questions, please, contact the CFC PI for this section J. Bullister, (johnb@pmel.noaa.gov) or David Wisegarver (wise@pmel.noaa.gov). Additional information on WOCE CFC synthesis may be available at: http://www.pmel.noaa.gov/cfc. ******************************************************************************** Prinn, R. G., R. F. Weiss, P. J. Fraser, P. G. Simmonds, D. M. Cunnold, F. N. Alyea, S. O'Doherty, P. Salameh, B. R. Miller, J. Huang, R. H. J. Wang, D. E. Hartley, C. Harth, L. P. Steele, G. Sturrock, P. M. Midgley, and A. McCulloch, A history of chemically and radiatively important gases in air deduced from ALE/GAGE/AGAGE. Journal of Geophysical Research, 105, 17,751-17,792, 2000. ******************************************************************************** ____________________________________________________________________________________________ ____________________________________________________________________________________________ WHPO DATA PROCESSING NOTES Date Contact Data Type Data Status Summary ========================================================================== 05/06/98 Bullister SUM/SEA/DOC Submitted for DQE P14S & P15S data are combined. P14s/p15s has been updated with a new SUMfile, SEA-HYDfile and additional documentation from John Bullister. 10/06/98 Anderson CTD/BTL/SUM Reformatted by WHPO Reformatted .sum file: Changed EXPOCODE from 31DICG96/1 to 31DSCG96_1 and 31DICG96/2 to 31DSCG96_2. Ran over sumchk, no problems. .sea file ok except for first header. Changed EXPCODE to EXPOCODE. Changed 31DICG96/1 to 31DSCG96_1 and 31DSCG96_2 to 31DSCG96_2. Reordered pressures so they are shallowest to deepest. For stas. 21 and 77 .sum file had only cast 2, .sea file had only cast 1. I don't know which is correct so I did not change. Ran over wocecvt, only problem above mentioned cast number discrepancies. CTD - ctd data was ok except for EXPOCODE. Changed from 31DICG96/1 and 31DICG96/2 to 31DSCG96_1 and 31DSCG96_2. Dates in .sum and .wct files for sta/cast 13/1, 16/1, 29/2, 32/1, 39/1, 43/1, 52/1, 74/2, 89/2, 110/2, 121/2, 128/2, 135/2, 167/2, 173/2, and 175/2 do not agree. In all cases the BE time is before midnight and the BO time is after midnight so the day is different. The originator used the BE dates for the ctd's. I did not change the .wct files. 10/15/98 Mantyla NUTs/S/O DQE Begun 10/15/98 Rosenberg CTD DQE Begun at WHPO/SIO 11/16/98 Rosenberg CTD DQE Complete 11/18/98 Rosenberg CTD DQE Report sent to Chief Scientist 11/18/98 Mantyla NUTs/S/O DQE Report Complete 01/11/99 Bullister CTD/BTL*/CFC Data are Public NUTs, S/O, c14 collected and sent to WHOI. Checking w/ Quay re c14 data status 01/11/99 Johnson CTD/S/O DQE Report sent to Chief Scientist ctdoxy data are public, all else nonpublic 04/29/99 Bartolocci DELC13 Data and/or Status info Requested (P.Quay) 07/15/99 Johnson CTD/HYD DQE Reports rcvd by PI Kristy will be mailing you our responses to both reports (and submitting some revised data) shortly. Please don't make any changes to the CTD data for these cruises until you have our replies in hand. 08/17/99 Anderson SUM/HYD Data Files Reformatted p14ssu.txt: Reformatted to conform with the WHPO standard .sum format. Mostly adding and/or deleting spaces. p14shy.txt: Reordered pressures that were not in descending order. Changed station 21 cast 1 to cast 2 to conform with the sum file: Changed station 77 cast 1 to cast 2 to conform with the .sum file. Ran over wocecvt and sumchk without any errors. 03/20/00 Diggs SUM/HYD Website Updated SUM and HYD files are now out on the website, and all tables have been updated. 04/19/00 Bartolacci DELC14 Website Updated: no samples collected However I'd like to clarify this with you, because the DOC file that we have indicates that some 900 or so samples were taken for both C14 and C113, did they not get processed? (There are columns in the data file for both of these parameters that will need to be edited out.) 04/20/00 Key DELC14 No Data Submitted; Not Processed P14S15S is problematic. Paul did collect samples which could have been used for C-13 and C-14. I'm pretty sure that many of the C-13 samples have been analyzed. Unfortunately, in his proposal, Paul did not request funding for C-14 analysis. Paul saved an aliquot of the extracted CO2 gas which can be analyzed for C-14 if we can get the funds. We plan on submitting a proposal which, if funded, will cover C-14 anlaysis costs on a few cruises including: P14S15S EqPac (Fall and Spring; NOAA) P1 (Japanese E-W transect) Unnamed German cruise in the upwelling region west of S. Am. 06/13/00 Bullister BTL/SUM/DOC Final Data Submitted w/ DQE-related updates. I just re-sent p14sp15s .sea, .sum and .doc files to the WHPO ftp site. The file names are: p14sp15s.doc.senttoWHPO12jun2000 p14sp15s.sea.senttoWHPO12jun2000 p14sp15s.sum.senttoWHPO12jun2000 These files have a number of updates compared to the 'p14s' files now posted at the WHPO web site. Please note that the data in these files (and in the old 'p14s' posted at the WHPO web site) are for both p14s AND p15s- both sections were done on the same expedition. The .sea file now ncludes tcarbn, alkali and pH data; the CFC data are reported on the SI093 calibration scale. We have incorporated most of the changes recommended in A. Mantyla's DQE recommendations. Details of these changes are included at the end of the p14sp15s.doc.senttoWHPO12jun2000 file. PS: Please note that the formatting instructions given for delc13 in the WHPO 90-1 manual posted at the WHPO web site still ask for F8.1. This should be F8.2. A lot of the value of the delc13 data is lost if they are only reported to 1 decimal precision. 06/16/00 Bartolacci BTL/SUM/DOC Website Updated • Re-aligned column headings and date, lat/lon columns. • Changed expocode backslashes to underscores. • Changed expocode from 31DICG96_ to 31DSCG96_ • Added time/name stamp. • ran sumck a second time with no errors. New file named p14sp15s.sum.edt BOT: • ran wocecvt, warnings on pressure and depth sequencing problems. • Inverted all samples to be in increasing pressure order. • Changed expocode backslashes to underscores. • Changed expocode from 31DICG96_ to 31DSCG96_ • Added time/name stamp. • ran wocecvt a second time with only duplicate depth warnings. New file named p14sp15s.sea.edt DOC: new doc file will replace current online version. 06/17/00 Bartolacci BTL/SUM/DOC Final data files put online I have updated the current sumfile and doc file for this cruise as well as the bottle file. The new bottle file contains: CTDRAW CTDPRS CTDTMP CTDSAL CTDOXY THETA SALNTY OXYGEN SILCAT NITRAT NITRIT PHSPHT CFC-11 CFC-12 DELC14 DELC13 C14ERR C13ERR TCARBN ALKALI PCO2 PCO2TMP PH PHTEMP There are no data in the columns for DELC14, DELC13 C14ERR, C13ERR, PCO2TMP and PHTEMP Bullister has been notified via email that the above changes have been made. 06/24/00 Bullister PCO2 Submitted I just received a revised pCO2 data file for the P14SP15S cruise, along with a short description of the analytical methods used, all from the PI (Rik Wanninkhof wanninkhof@aoml.noaa.gov) I just put 2 files at the WHPO INCOMING ftp site: p14sp15spco2.dat p14sp15spco2.txt Could you please merge the pco2 data into the p14sp15shy.txt file at your site, and include the text of p14sp15spco2.txt in the cruise documentation file? 07/05/00 McNichol DELC13 Submitted csv for p15s leg only I have just uploaded three files p15sbmt2.csv, p15submt.des, and p13submt.des to your ftp site. The csv file contains the following fields in a comma-delimited file: LabID, Trackline, Station, cast, niskin, del13C, QC The LabID is to distinguish between the two laboratories where the majority of the measurements were made--University of Washington and NOSAMS, WHOI. The files labelled des describe the samples flagged with a "6" in greater detail. Can you accept these as well? Paul Quay and I would like to append a statement *somewhere* indicating the status of our laboratory data comparisons. Do you have an appropriate place for this? 09/29/00 McNichol DELC13 Data are Public; See Note: All the Pacific data (most of which I still need to send you) is public. I should be sending you a pile of data next month. Also, if the future, if you have a question that you need answered immediately, the best person to get in contact with besides me is Dana Stuart. Her contact info is dstuart@whoi.edu 11/21/00 Uribe DOC Submitted See Note: 2000.11.21 KJU File contained here is CRUISE SUMMARIES and NOT sumfiles. Files listed below should be considered WHP DOC files. Documention is online. 2000.10.11 KJU Files were found in incoming directory under whp_reports. This directory was zipped, files were separated and placed under proper cruise. All of them are sumfiles. Received 1997 August 15th. 03/15/01 Key DELC14 Measured as per .DOC Funding now available to analyze Got word from Eric this A.M. that he will fund NOSAMS at the rate of 1000/year to analyze previously collected, but unfunded C14 samples. Highest priority will be to fill in Pacific "holes" starting with P14S15S (NOAA), P15N (Wong) and P1 (Japan). Policy decision supported by WOCE SSC. Eric would, if possible, like these data to be included in the atlas. In reality I don't know if this is possible/practical, but I will do everything possible to expedite. Scheduling at NOSAMS will be complicated, but order listed above is the "scientific" priority as of now. 06/22/01 Uribe CTD/BTL Website Updated; CSV File Added CTD and Bottle files in exchange format have been put online. 10/01/01 Muus CFC/BTL/SUM Data Merged into BTL file CFCs merged into BTL, SUM file modified, CSV file updated Merged July 2001 CFCs into bottle file, modified SUM file WOCE SECT column to allow conversion to exchange format, made new exchange file and place all on web. Notes on P14S CFC merging Sept 26, 2001. D. Muus 1. New CFC-11 and CFC-12 from: /usr/export/html-public/data/onetime/pacific/p14/p14s/original/ 20010709_CFC_UPDT_WISEGARVER_P14SP15S/20010709.173406_ WISEGARVER_P14SP15S/20010709.173406_WISEGARVER_P14SP15S_p14s_ CFC_DQE.dat merged into SEA file taken from web Sept 26, 2001 (20000616SIOWHPODMB) Most "1"s in QUALT1 changed to "9"s and QUALT2 replaced by new QUALT1 prior to merging. CTDOXY has values for Stations 1 through 3 but QUALT1 code is "1". Bottle oxygens taken on Station 1 and from Station 4 on. No bottle oxygens on Stations 2 and 3. QUALT1 code for CTDOXY is "2" from Station 4 on. Left "1"s as quality codes for Station 1 - 3 CTDOXY as caution to users. 2. Conversion from woce bottle format to exchange format failed using the web SUMMARY file (20000616SIOWHPODMB). Modified SUM file by replacing blanks in WOCE SECT columns for Stations 1 - 3 with "x"s. Moved WOCE SECT header so column is left justified. Conversion to exchange file worked after these modifications made. 3. Exchange file checked using Java Ocean Atlas. 01/22/02 Uribe CTD Website Updated CSV File Added; see note: CTD has been converted to exchange using the new code and put online. Files for station 21 and 77 has a mismatch in the cast number in the sumfile. The sumfile contained data for a cast 1 but the CTD files said cast 2 so the CTD files were modified for the purpose of the conversion. 06/21/02 Kappa Doc PDF & TXT files updated, new sections added: New sections include a CTD cast summary and CTD oxygen algorithm parameters tables, HYD DQE report, CTD DQE report, PI response to CTD DQE report, CFC DQE report, Report on CO2fugacity Measurements, and WHPO data processing notes. PDF Cruise Report includes all the above, plus figures and internal links between figures and table of contents and relevant text. 06/26/02 Tibbetts DOC Website Updated pdf, txt versions online New txt & pdf docs online 03/05/03 Muus DELC13 Website Updated; Data Merged into OnLine File Notes on P14S/P15S Mar, 5, 2003 D. Muus 1. Merged DELC13 with 2-decimal-place DELC13 from: /usr/export/html-public/data/onetime/pacific/p15/p15s/original/ 2000.07.05_P15S_MCNICHOL/p15submt2_reformat.csv into p14shy.txt (20010927WHPOSIODM) 2. No DELC13 in P14S part of cruise (Stations 1-32). 3. Both QUALT1 and QUALT2 set to QC value given in original data file. 4. C13ERR column was in web bottle with all missing value indicators. No C13ERR data in C13 data file. 5. 6 samples in data file have 2 delc13 values. First was used in merge. Second values follow: STNNBR CASTNO SAMPNO DELC13 QC ------ ------ ------ ------ -- 53 1 124 1.03 2 62 2 224 1.41 2 67 2 228 2.12 2* 84 1 105 1.13 2 101 2 202 0.43 2 112 1 132 1.3 2 *First value for 67/2/228 is 1.32, QC=6. Second value looks high. 6. Made new exchange file for Bottle data. 7. Checked new bottle file with Java Ocean Atlas. 06/24/03 Swift PH Data Update Code is cutting 4 decimals to 2, will have to be fixed After checking P15S and P14N I am guessing that whatever code were are using to convert 'original WOCE' format to 'WHP Exchange' format is truncating pH to two decimal places. Steve will have to fix the code, and then the staff will have to update every Exchange data file with pH data. '90-1' clearly shows that there is a 4-decimal place specification for pH. 07/12/03 Kappa DOC PDF and Text docs updated CTD DQE report by R. Millard added Data Processing Notes Expanded 07/16/03 Coartney DOC Website Updated; New PDF and text docs online 03/02/04 Key DELC14 Final Data DQE'd, Submitted; No Report I just finished uploading the c14 data (DELC14, C14ERR, C14FLAG) for p14s15s (the noaa cruise). As usual, my software hasn't truncated to the correct number of decimal places, it does, on the other hand drop trailing zeroes. These analyses were funded by a special NSF grant obtained to measure some of the samples which were collected, but without c14 analysis money. The C14 PI for these data is Paul Quay. Paul also measured the C13 values which are currently in the WHP files. NOSAMS reran the C13, but the NOSAMS c13 values will not replace Paul's values. I did the QC on the C14 and have already sent copies (merged) back to NSOAMS and to Quay. I have not written a final report for this cruise, and probably won't. As noted on the submission form (Data quality somewhat lower than norm for WOCE), the data from this cruise (especially the lower station numbers) are noiser than normal for WOCE, but the number of "fliers" is not too bad. Cause is probably extra storage and handling, but that's just a guess. Given the geographic location, these certainly need to be included in any updated versions of the WHP files - that is, they fill a giant data hole. 03/03/04 Anderson DELC14 Data Reformatted/OnLine Merged the DELC14 and C14ERR from file 20040302.100353_KEY_P14S15S_p14s15s.c14.WHP submitted by Bob Key into online file 20030305SIOWHPODM. See email below. The file Key sent had station, cast, and bottle number. The bottle number did not agree with the bottle number in the online bottle file. They did agree with the sample no in the online file if you added the cast number, ie 24 in Key's file was 124 in the online file if it was cast 1 (or 224 if cast 2, 324 if cast 3, etc). Key's file had quite a few stations with sample numbers that were not in the online file, but since there were no DELC14 values for these I ignored them. The online file had -9.0 for all DELC14 values so the QUALT1 and QUALT2 flags were all 9. Key's file had only one Q flag. When I merged the data I used Key's Q flag for both Q1 and Q2. Also, Key's file had a Q flag of 2 for all the -999.0 values, I changed those to 9. Had to add P14S under WOCE SECT for stas. 1-3 in the .sum files in order to get the exchange file made. 06/29/04 Kozyr PH Correct pH values truncated in exchange file Andrew Dickson of SIO recently send me a message that for WOCE P14N and P14S sections pH was reported to 2 decimal points in exchange formatted files, but to 3 and 4 decimal points in old WHP formatted files. I did not check other files where pH is reported but I think that it is probably a mistake in that pearl code that converts the data. Could you please check this out. It is very important to have pH reported to 3 or 4 decimal points and many users now copy the data in exchange format. 07/07/04 Diggs PH Exchange values corrected from 2 to 4 decimal points I have fixed the code that produces the Exchange files and subsequent NetCDF files. PH is now an F9.4 number. Danie, Jim and I are working on a strategy to re-do all of the files online in the near future. 11/12/04 Kappa DOC Cruise Report Updated • Deleted CTD DQE Report by Bob Millard. [Report belonged with P15N Leg 1 CTD data] • Added figures for McTaggart & Johnson's response to the CTD DQE • Added bookmarks to PDF version • Added table of contents to text version • Added introduction to CTD report by K.E. McTaggart and G.C. Johnson • Expanded these Data Processing Notes • Updated OnLine Data History