If symbols do not display correctly change your browser character encoding to unicode CRUISE REPORT: A16N_2003a (Updated MAY 2012) A. HIGHLIGHTS A.1. CRUISE SUMMARY INFORMATION WOCE section designation A16N_2003a Expedition designation 33RO200306_01 (ExpoCodes) 33RO200306_02 Chief Scientist JOHN BULLISTER/PMEL Co-Chief Scientist Nicolas GRUBER/UCLA Dates 2003 JUN 04 - 2003 AUG 11 Ship R/V RONALD H. BROWN Ports of call Reykjavik, Iceland to Natal, Brazil 63°17.58'N Geographic boundaries 29°00.00'W 19°59.99'W 6°0.64'S Stations 150 Floats and drifters deployed 6 ALACE profiling floats, 6 Surface drifters and 3 Carbon Explorer floats Moorings deployed or recovered 0 CONTRIBUTING AUTHORS E. Peltola, R. Wanninkhof, R. Feely, R. Castle, D. Greeley, J.-Z. Zhang, F. Millero, N.Gruber, J. Bullister, T. Graham CHIEF SCIENTIST CONTACT INFORMATION John L. Bullister (NOAA-PMEL) 7600 Sand Point Way N.E. • Seattle, WA 98115 • USA Tel: 206-526-6741 • Fax: 206-526-6744 e-mail: John.L.Bullister@noaa.gov Nicolas Gruber (UCLA) Institute of Geophysics & Planetary Physics & Department of Atmospheric Sciences 5853 Slichter Hall • Los Angeles, CA 90095-1567 • USA Tel: 310-825-4772 • Fax: 310-206-3051 e-mail: ngruber@igpp.ucla.edu SUMMARY: A hydrographic survey consisting of a meridional CTD/rosette section in the North Atlantic, nominally along 20°W from 63°N to 6°S was carried out on NOAA ship Ronald H. Brown (NOAA Cruise RB- 03-04) during July-August 2003 The expedition has been assigned the ExpoCode 33RO200306_01. This 2003 section repeated the A16N section occupied during the World Ocean Circulation Experiment (WOCE) period, hence this cruise is also designated A16N_2003. This was also a repeat of a NOAA cruise in 1993, during which a full suite of inorganic carbon, hydrographic and CFC measurements were made. This cruise was the first in a decadal series of repeat hydrography sections jointly funded by NOAA's Office of Global Programs (OGP) and the US National Science Foundation (NSF) as part of the CLIVAR/CO2/hydrography/tracer program. The program focuses on the need to monitor inventories of CO2, tracers, heat and freshwater and their transports in the ocean. Earlier programs under the World Ocean Circulation Experiment (WOCE) and Joint Global Ocean Flux Study (JGOFS) have provided a baseline observational field for these parameters. A total of 150 full water column CTD/rosette stations were occupied. Water samples (up to 34 at each station), LADCP, CTD and bio-optical data were collected on most casts to within ~20 m of the bottom. Salinity, dissolved oxygen, and nutrient samples were analyzed from every bottle sampled. Other parameters were sampled at a lower density, including a suite of carbon parameters (dissolved inorganic carbon-DIC, total alkalinity- Talk, pH and partial pressure of CO2- pCO2), chlorofluorocarbons (CFCs), dissolved organic carbon (DOC), 3He-tritium, and carbon isotopes. In addition to the CTD/rosette casts, separate trace metal casts were made at stations along the section, nominally at 60 nautical mile spacing. Measurements of near surface seawater properties (temperature, salinity, and pCO2), as well as atmospheric measurements (CO2, CFCs, aerosols) were made along the cruise track. Six ALACE-type profiling floats were deployed along the section, along with 6 surface drifters and 3 special 'Carbon Explorer' profiling floats designed to measure particulate inorganic carbon (PIC). This report describes the participants, scientific programs, and sampling details. Additional information on analytical methodologies are included in separate reports appended to this file. Further information and copies of the data from this cruise can be found at http://sts.ucsd.edu/cruise/a16n/hydro/. ACKNOWLEDGMENTS: The successful completion of the cruise relied on dedicated assistance from many individuals on shore and on the expedition. Funded investigators in the project and members of the Repeat Hydrography Oversight Committee, with Lynne Talley and Richard Feely as co-chairs, were instrumental in planning and executing the cruise. Officers and crew of the Ronald H. Brown exhibited a high degree of professionalism and assistance to accomplish the mission. The U.S. CLIVAR/CO2 Repeat Hydrography Program is jointly sponsored by the National Science Foundation's Physical and Chemical Oceanography Programs, and NOAA's Office of Climate Observation, with contributions from the National Aeronautics and Space Administration and the Department of Energy. In particular, we wish to thank program managers Eric Itsweire (NSF/OCE), Don Rice (NSF/OCE), Mike Johnson (NOAA/OCO), and Kathy Tedesco (NOAA/OGP) for their moral and financial support in the effort. A.2. INTRODUCTION: NOAA ship Ronald H. Brown departed Reykjavik Iceland on 19 June 2003. There was a port stop in Funchal Madeira from 10-15 July 2005. The cruise ended in Natal, Brazil on 11 Aug 2005. A sea- going science team from 14 institutions in the U.S. participated on the cruise. Several other science programs were supported with no dedicated cruise participants. PARTICIPATING INSTITUTIONS: AOML NOAA-Atlantic Ocean Marine Laboratory FSU Florida State University Hawaii University of Hawaii LDEO Lamont-Doherty Earth Observatory, Columbia University LBNL Lawrence-Berkeley National Laboratory NOAA National Oceanic and Atmospheric Agency RSMAS Rosenstiel School of Marine and Atmospheric Sciences, University of Miami PMEL NOAA-Pacific Marine Environmental Laboratory SIO Scripps Institution of Oceanography, University of California, San Diego TAMU Texas A&M University UCLA University of California, Los Angeles UW University of Washington UCB University of California, Berkeley UCI University of California, Irvine WHOI Woods Hole Oceanographic Institution A.3. CTD/HYDROGRAPHIC MEASUREMENT PROGRAM: Chief Scientists: John Bullister & Nicolas Gruber Survey Department: CST Jonathan Shannahoff Final Processing: Kristy McTaggart CTD Personnel: Regina Cesario, Elena Brambilla, Nicole Lovenduski, Kristy McTaggart A total of 150 CTD/rosette casts were made, usually to within 20 m of the bottom. Most of the casts were performed with a package consisting of a 36-position, 12-liter rosette frame designed at PMEL, a 36-place pylon (SBE32) and 34 12-liter 'Bullister' bottles. Two of the 36 bottle positions (positions 34 and 36) on the rosette frame were not available because of interference with the LADCP instruments mounted on the rosette frame. Because of inclement weather or winch/wire problems, a smaller 24-place 3- liter foul weather rosette package also designed at PME was deployed at 14 stations (Stations 35-42, 102-103, and 142-143). Water samples were collected from every bottle for analysis of salinity, dissolved oxygen, and nutrients. The distribution of water sample bottles is illustrated in the following figure. The basic CTD measurements were of pressure, temperature, salinity, and dissolved oxygen. Additional optical sensors were attached to the large rosette frame. Underwater electronic components on the 36 position frame consisted of a Sea-Bird Electronics (SBE) 9 plus CTD with dual pumps and the following sensors: dual temperature (SBE3plus), dual conductivity (SBE4), dissolved oxygen (SBE43), transmissometer (Wetlabs SeaStar), turbidity (Seapoint Sensors), and PIC (Wetlabs). The other underwater electronic components consisted of RDI LADCPs, a Simrad or Benthos altimeter, and a pinger. A detailed description of the sensors on the two (large and small) rosette frames is provided in the CTD section below. The CTD was mounted vertically in an SBE CTD frame attached to the bottom center of the rosette frame. All SBE4 conductivity and SBE3plus temperature sensors and their respective pumps were mounted vertically as recommended by SBE. The entire cage assembly was mounted on the bottom ring of the rosette frame, offset from center to accommodate the pylon, and also secured to frame struts at the top. The altimeter was mounted on the inside of a support strut adjacent to the bottom frame ring. The transmissometer, turbidity and PIC sensors were mounted horizontally along the rosette frame adjacent to the CTD. The LADCPs were vertically mounted inside the bottle rings on the opposite side of the frame from the CTD. The rosette system was suspended from a UNOLS-standard three- conductor 0.322" electro-mechanical sea cable. A load cell was installed between he rosette frame hanger and the sea cable to monitor the CTD/rosette package weight during casts. The load cell data stream was transmitted via the CTD unit and monitored in real time in the CTD lab. The R/V Brown's forward CTD winch was used during the cruise. The deck watch prepared the rosette within 40 minutes prior to each cast. All valves, vents, and lanyards were checked for proper orientation. The bottles were cocked and all hardware and connections rechecked. Once stopped on station, the LADCP was turned on and syringes were removed from the CTD sensor intake ports. As directed by the deck watch leader, the CTD was powered- up and the data acquisition system started. Two stabilizing taglines were threaded through rings on the rosette frame. The deck watch leader directed the winch operator to raise the package, the squirt boom and rosette were extended outboard, and the package quickly lowered into the water. The tag lines were removed and the package was lowered to 10 m. The CTD console operator waited for the CTD sensor pumps to turn on, waited an additional 60 seconds for sensors to stabilize, then directed the winch operator to bring the package close to the surface, pause for typically 10 seconds, and begin the descent. Each rosette cast was usually lowered to within 20 m of the bottom, using the altimeter and pinger to determine a safe distance. On the up cast, the winch operator was directed to stop at each bottle trip depth. The CTD console operator waited 30 seconds before tripping a bottle, then an additional 10 seconds after receiving the trip confirmation before directing the winch to proceed to the next bottle stop. Sampling depths and the total number of bottles tripped on each cast were adjusted depending the overall water depth. Typically all 34 bottles were closed for casts deeper than ~3000 m. Sample spacing was closer in the upper water column, with typically ~20 bottles closed in the upper 1000 meters of the water column. The bottle depths were staggered to reduce data contouring artifacts (see sample distribution figure). Recovering the package at the end of the deployment was essentially the reverse of launching, with the additional use of poles and snap-hooks to attach tag lines for added safety and stability. The rosette was left outside on deck for sampling. The bottles and rosette were examined before samples were taken, and anything unusual noted on the sample log. Each bottle on the rosette had a unique serial number. This bottle identification was maintained independently of the bottle position on the rosette, which was used for sample identification. Routine CTD maintenance included soaking the conductivity and DO sensors in fresh water between casts to maintain sensor stability. Rosette maintenance was performed on a regular basis. O-rings were changed as necessary and bottle maintenance was performed each day to insure proper closure and sealing. Valves were inspected for leaks and repaired or replaced as needed. A.4. BOTTLE SAMPLING: A.4.1. BOTTLE SAMPLING PROCEDURES A station log sheet was maintained in the CTD lab for each sample team to indicate their sampling plans for the upcoming ~10-20 stations. This allowed groups which did not sample every station fully to better co-ordinate sampling plans with other groups. Planned deployments of floats at upcoming stations were also entered in this table. At each station, a sample log sheet was prepared prior to the arrival of the case on deck. Each sampling group filled out a column on this log sheet, indicating which rosette bottles were to be sampled, and the ID numbers of their individual sample containers. At the end of each rosette deployment, water samples were drawn from the bottles in the order listed below. This log also included any comments or anomalous conditions noted about the rosette and bottles. One member of the sampling team was designated the "sample cop," whose responsibility was to maintain this log sheet, check the correspondence between individual sample containers and the rosette bottle as the samples were drawn, and insure that sampling progressed in the proper drawing order. Normal bottle sampling practice included initially pushing in the drain valve petcock prior to opening the air vent screw. The release of any water from the petcock indicated an air leak. This observation, together with other diagnostic comments (e.g., "lanyard caught in lid," "valve left open") that might later prove useful in determining sample integrity, were routinely noted on the sample log and are included below. Once individual samples had been drawn and properly prepared, they were distributed for analysis. SAMPLING AND ANALYSES OF BOTTLE DATA The order of drawing samples was: CFCs, helium isotopes (3He), oxygen (O2), hydrochlorofluorocarbon (HCFCs), pCO2, DIC, pH, TAlk, radiocarbon (DI14C), tritium, DOC, particulate inorganic/organic carbon (PIC/POC), salinity, and nutrients. Sampling of the 34 bottles on the package took about 1.5 hours. The samples analyzed for gases were sampled first and usually drawn within an hour of the rosette reaching the deck. The deepest bottle was sampled first and bottles were sampled sequentially to the surface bottle. Care was taken to coordinate the sampling to minimize the time between the initial opening of each bottle and the completion of sample drawing. In most cases, CFCs, 3He, dissolved oxygen, and HCFC samples were collected within several minutes of the initial opening of each bottle. Oxygen, nutrient, and salinity samples were taken from all bottles. For the other parameters, not all stations or all bottles were sampled. Full profiles were typically collected at every other station for CFCs, DIC, pH, and TAlk, with partial sampling for DOC. The intermediate stations were typically only partially sampled for CFCs, DIC, pH,, TAlk. HCFC, PIC/POC. Discrete pCO2 profiles were obtained at every two degrees. 3He, DI14C, and tritium were sampled at coarser intervals. A complete listing of the samples collected is available at: http://whpo.ucsd.edu/data/CO2clivar/atlantic/a16/a16n_2003a/ index.htm To allow direct comparison, CFCs were usually drawn from the same bottles as DIC and Talk. 3He and tritium were typically drawn from the same bottles as CFCs. For casts where many parameters were sampled, water levels in some of the 12 liter bottles occasionally were very low by the time the salinity and nutrients were drawn. This was particularly true for the deepest two bottles and the shallowest two bottles that were often used for duplicate sampling for parameters with large water requirements such as DIC and TAlk. Because of the small volume (~ 3 liters) of the sample bottles on the smaller rosette, not all parameters could be drawn from these bottles. On these casts, water for DIC and Talk was collected in the same sample bottle to conserve water and some parameters (e.g. helium and tritium) were not sampled from the same bottles as the carbon parameters. A.4.2. PROBLEMS There were relatively few bottle misfires or leaking bottles on the 36 position rosette frame. Several of the release pins on the 24 position small volume rosette did not function reliably and a number of bottles did not close on these casts. Sample bottles that did not close or bottles that had obvious leaks while on deck were noted on the sample log sheets. Typically, no water samples were not drawn from leaky bottles. Notes made on the sample log sheet s concerning bottle/rosette problems are listed below: Stn Cast Bottles Problem --- ---- -------- --------------------------------------------- 1 1 2, 11 leaky air vent screw 1 1 11 not enough water for salt sample 2 1 11 leaky air vent screw 9 1 1-3 winch problem, had to re-lower package after 1- 3tripped. Did not sample these 9 1 16 stopcock pushed in 9 1 22 leaky air vent 13 1 Deck was washed with cleaning agent containing phosphate possible contamination of surface nutrient samples 21 1 light rain during sampling 23 1 4 bottom endcap did not close 25 1 6 did not close properly 26 1 rain during sampling 29 1 12 lanyard trapped under hose clamp 32 1 1-17 wire spooling problem, re-lowered after closing, did not sample these bottles 33 1 33 lanyard hang up on hose clamp 35 2 6 leaker (small rosette) 35 2 1, 9, 24 did not close 36 1 1,8,9,15 did not close (small rosette) 37 2 9,19 did not close (small rosette) 37 2 20 no water for nutrient sample 38 1 1,9,19 did not close (small package) 39 1 1,5,9 did not close (small package) 40 1 5,9 did not close (small package) 41 1 1,8,9,15 did not close (small package) 41 2 9,15 did not close (small package) 42 1 9,15 did not close (small package) Stn Cast Bottles Problem --- ---- -------- --------------------------------------------- 42 1 23 no water for salt, nutrients 50 1 25 stopcock pushed in 56 1 1-9 winch problem, had to re-lower package after 1-9 closed 58 1 1-9 winch problem, had to re-lower package after 1-5 closed 61 2 9 closed while package still moving 65 1 11 closed while package still moving 74 1 35 only enough water to partially fill salt bottle 76 1 4 bottom cap lanyard broken, possible early closure 89 1 21 stopcock pushed in 90 1 13 air vent open 93 1 12-36 lost communication with package, cast aborted 99 1 30 lanyard hang up 101 1 wire problems, replaced sheave after this station 102 2 5 did not close (small rosette) 102 2 6 leak around bottom O-ring 102 2 19 stopcock pushed in 103 1 5,8 did not close (small rosette) 103 1 19 stopcock pushed in 110 2 35 no water for nutrient 114 1 33 no water for nutrient; sampled while raining 122 2 33 no water for nutrient, salt 123 1 1 stopcock pushed in 133 1 35 not closed, lanyard hang-up 140 1 15 did not close- pylon problem 142 1 5,9,16 did not close (small rosette) 143 1 8,9,17 did not close (small rosette) 149 1 1 stopcock pushed in HYDROWIRE AND WINCH PROBLEMS: On the RB-03-04 cruise, a new hydrowire was provided on the forward CTD hydro winch. Level-wind problems were encountered on this winch early on the cruise. Because the new hydrowire was shipped to the R/V Brown already spooled on a drum, there was uncertainty if the deeper layers of wire on the drum had been spooled under tension, which is essential for proper performance. Some time was lost during the up-casts on Leg 2 due to level-wind problems and 'nesting' of the wire as it was wound onto the winch, and a small number of water samples were compromised because the CTD/rosette package had to be re-lowered at depth to correct severe level-wind and nesting problems. Water samples were not drawn from these compromised bottles. Near the end of Leg 2 and during Leg 3, the winch operators became proficient in stopping the winch as necessary during upcasts and manually adjusting the clutch/level-wind mechanism as each layer of wire was spooled on the drum. This reduced these problems significantly, but was labor intensive. The General Oceanics sheave for the hydrowire was replaced after station 101. For at least several stations prior to its replacement, the hydrowire was observed to be pulling strongly to one side and wearing a groove into the side of the sheave. On the casts immediately before 101, the sheave began to vibrate excessively. The sheave was turned 180 degrees before station 101, and another cast was attempted. On the return to deck after cast 101, hockles and birdcages were observed in the upper part of the wire. Some un-twisting of the wire strands may also have occurred at a significant distance down the wire. About 500 meters of hydrowire were cut from the spool and the wire re- terminated after this cast,. Since no equivalent replacement for this sheave was available on board, a smaller diameter sheave was substituted. Such smaller sheaves may place significantly greater stress on the hydrowire. Short circuits or wire breaks occurred in 2 of the 3 conducting wires in the hydrowire during Leg 3, leaving only 1 conducting wire (and the steel armor of the hydrowire) available for the last ~40 stations on the second leg. A failure of the last remaining conducting wire would have required an unknown amount of hydrowire to be cut off, or resorting to use of the other hydrowinch. A.4.3. BOTTLE DATA PROCESSING: Water samples collected and properties analyzed shipboard were managed centrally in a relational database run on a Linux workstation. The sample log (and any diagnostic comments) was entered into the database once sampling was completed. WOCE/CLIVAR quality flags associated with sampled properties were set to indicate that the property had been sampled, and sample container identifications were noted where appropriate (e.g., oxygen flask number). Most samples were analyzed on board with the exception of 3He, DI14C, tritium, DOC, CDOM, and PIC/POC that were sampled and preserved for shore-based analysis. Descriptions of sampling and analysis procedures, as well as the relevant statistics on data quantity and quality are included in individual sections below. The results of individual shipboard analyses were then uploaded through the website as results became available. These results included a quality code associated with each measured value and followed the coding scheme developed for the World Ocean Circulation Experiment (WOCE) Hydrographic Programme (WHP) (Joyce, 1994). Various consistency checks and detailed examination of the data continued throughout the cruise. Post cruise data processing and quality checking is discussed in the individual sections below. TRACE METAL CASTS: In addition to the 150 CTD/rosette casts, separate trace metal casts were made at along the section, nominally at 60 mile spacing. Trace metal casts were made at stations: 4,5,9,10,13,17,19,23,26,28,31,33,35,42,44,46,48,50,53,55,57,5 9,61,63,65,67,69,70,72,74,76,78,80,82,84,86,88,90,92,94,96,98, 100,102,104,106,108,110,112,114,116,118,120,122,124,126,129, 132,135,138,141,142,144,146,148 Because of possible contamination problems in sampling for iron and aluminum, these samples were collected using a special trace metal clean CTD/rosette, bottles, wire and winch system. In addition to trace metal samples, samples were collected from each bottle for the analysis of salinity and nutrients. The CTD/rosette package was deployed off the stern A-Frame using a custom built winch with ~1500 m of Kevlar coated cable provided by the trace metal investigators. Bottles were closed during the up-cast without stopping the winch, to minimize possible contamination of the samples from the rosette frame and instruments. There were a number of problems with the trace metal winch, particularly with its ability to lift the package out of the water when the bottles were full. On a number of casts, member of the scientific party and crew manually assisted in pulling on the wire to help lift the trace metal rosette package out of the water and onto the deck. A.4.4. UNDERWAY MEASUREMENTS: Near surface seawater measurements of temperature, salinity, pCO2 and ADCP measurements were made continuously along the cruise track. Copies of these data are available in digital format from the CCHDO and from the Chief Scientist. Weather observations (ship position, cloud cover and type, visibility, wind speed and direction, sea state, wave height and direction, surface water temperature, atmospheric pressure, and wet and dry bulb air temperature) were recorded manually at hourly intervals by the bridge and during each hydrocast. Copies of these data log sheets are available from the Chief Scientist. FLOAT DEPLOYMENT: Float Type Serial# Time Date (GMT) Lat Lon --------------- ------- ---- ------------ ------- ------- Carbon Explorer 2122 0042 22 June 2005 60°00'N 20°00'W Carbon Explorer 1 1822 28 June 2005 47°00'N 20°00'W Carbon Explorer 2 1829 28 June 2005 47°00'N 20°00'W Drift Buoy 39149 0027 24 July 2005 19°00'N 29°00'W Drift Buoy 39148 1409 24 July 2005 18°00'N 29°00'W Profiling Float 205 1143 26 July 2005 15°00'N 29°00'W Drift Buoy 39152 0300 27 July 2005 14°00'N 29°00'W Drift buoy 39150 1752 27 July 2005 13°00'N 29°00'W Profiling Float 202 0052 28 July 2005 12°30'N 29°00'W Drift buoy 39151 0902 28 July 2005 12°00'N 29°00'W Drift buoy 35691 0050 20 July 2005 11°00'N 29°00'W Profiling Float 188 1549 29 July 2005 10°00'N 29°00'W Profiling Float 189 0957 31 July 2005 7°30'N 27°15'W Profiling Float 175 2310 1 Aug 2005 5°00'N 26°00'W Profiling Float 209 0901 3 Aug 2005 2°40'N 25°00'W A.4.5. SAMPLES PRESERVED FOR SHORE-SIDE ANALYSIS DOC SAMPLING Principal Investigator: Dennis Hansell U. Miami, RSMAS 4600 Rickenbacker Causeway Miami, FL 33149 dhansell@rsmas.miami.edu Sampler: Stacy Brown U. Miami Seawater samples were taken directly from the Niskin Bottles into the 60 ml pre-cleaned bottles for deeper than 200 m. Samples from the up 200 m were collected by in-line filtration through a/F filter. All samples were kept in frozen before analysis. 14C SAMPLING Principal Investigator: Ann McNichol WHOI Samplers: John Bullister NOAA-PMEL Nicolas Gruber UCLA Seawater was drawn directly from the Niskin bottles into 500-ml glass bottles after about 250 ml overflow of the water. Samples were then poisoned with 100 µl saturated HgCl2 solution and sealed by greased stoppers. Bottles with samples are kept in cases for shipping back to WHOI. REFERENCE: Measuring 14C in Seawater TCO2 by Accelerator Mass Spectrometry, WHOI in WHP Operation and Methods-July, 2003. HELIUM AND TRITIUM SAMPLING Principal Investigator: Peter Schlosser Lamont-Doherty Earth Observatory Palisades NY 10964 schlosser@ldeo.columbia.edu Samplers: Brent Turrin LDEO (Leg 2) Anthony Dachille LDEO (Leg 3) Sampling of helium isotope (3He) and tritium involved separate containers for 3He and tritium. Seawater for 3He analysis was sampled into re-useable stainless steel tubes of 90-ml in volume. Tritium was sampled into 1 liter brown glass bottles. The 3He samples were taken first and care was made to rid the vessel of air bubbles by hitting them with a stick and opening and closing the two valves at each end of the tube. Tritium was sampled by rinsing the bottles twice and filling with water up to the curve at the top of the bottle to allow room to allow for thermal expansion. The He extraction was done on ship on a vacuum extraction system supplied by WHOI (W. Jenkins and D. Lott). B. CTD DATA Chief Scientists: John Bullister & Nicolas Gruber Survey Department: CST Jonathan Shannahoff Final Processing: Kristy McTaggart CTD Personnel: Regina Cesario, Elena Brambilla, Nicole Lovenduski, Kristy McTaggart B.1. ACQUISITION During this cruise, 150 stations were occupied in the North Atlantic from 63N to 5S primary along 20W at 30nm spacing, and 152 CTDOXY profiles were collected. All profiles were to within 10m of the bottom, ranging from about 200m to nearly 6000m. Three underwater package configurations were used during this cruise. The primary package was a new 36-position stainless steel frame mounted with 34 12-liter Niskin bottles, Sea-Bird carousel, load cell, altimeter, pinger, LADCP, and optical sensors. The Sea-Bird CTD sensors were a 9plus CTD s/n 315; primary TC sensors s/n 4193, 1180; secondary TC sensors s/n 1455, 354; and SBE 43 oxygen sensors s/n 315, 313, or 312. During bad weather or while testing a deteriorating winch cable, a small 24-position stainless steel frame was employed. This bad weather frame was mounted with 24 4-liter Niskin bottles, AOML- owned Sea-Bird carousel, load cell, altimeter, and pinger. The Sea-Bird CTD sensors were a 9plus CTD s/n 209; primary TC sensors s/n 1370, 1434; secondary TC sensors s/n 1460, 1177; and SBE 43 oxygen sensors s/n 313 or 312. The third configuration was comprised of the primary package with the bad weather CTD and sensors, and used after the primary CTD s/n 315 blew the power supply at station 142. Sea-Bird configuration files were named a16n_1.con, a16n_2.con, and a16n_3.con, respectively. N.B., The pre-cruise pressure calibration offset for CTD s/n 315 was amended by +1 dbar in a16n_1.con. Data were acquired at full 24 Hz resolution through a Sea-Bird 11plus deck unit and the ship's dedicated PC using Seasave software version 5.28c. Analog data were archived onto VCR tapes, although likely unrecoverable. Fortunately, no real-time data were lost. Digital backups were made to Zip disks and CDs. The discrete sample database, maintained by Frank Delahoyde at sea, totals 4824 records. The only instance of rosette misfire identified was during station 119, where two bottles closed at 1400 dbar; the following 6 bottle closures were offset by one; and no sample was collected at 600 dbar. B.2. PROCESSING The reduction of profile data began with a standard suite of processing modules using Sea-Bird Seasoft software DOS version 4.249 in the following order: DATCNV converts raw data into engineering units and creates a bottle range file. Both down and up casts were processed for scan, elapsed time(s), pressure, t0, t1, c0, c1, and oxygen voltage. Optical sensor data were carried through for casts using the primary package. MARKSCAN was used to skip over scans acquired on deck and while priming the system. ALIGNCTD aligns temperature, conductivity, and oxygen measurements in time relative to pressure to ensure that derived parameters are made using measurements from the same parcel of water. Primary conductivity is automatically advanced in the deck unit by 0.073 seconds. On the primary package, the additional alignment of primary sensor s/n 1180 was -0.040 seconds (net alignment 0.033 seconds), and the total alignment for secondary sensor s/n 354 was 0.089 seconds. On the bad weather package, the additional alignment of primary sensor s/n 1434 was - 0.010 seconds (net alignment 0.063 seconds), and the total alignment for secondary sensor s/n 1177 was 0.057 seconds. For the ending package configuration, the additional alignment of primary sensor s/n 1434 was - 0.010 seconds (net alignment 0.063 seconds), and the total alignment for secondary sensor s/n 1177 was 0.089 seconds as it was then being plumbed with the optical sensors in the primary frame. It was not necessary to align temperature or oxygen. ROSSUM averages bottle data over an 8-second interval as specified in the range file, and derives salinity, theta, sigma-theta, and oxygen (µmol/kg). WILDEDIT makes two passes through the data in 100 scan bins. The first pass flags points greater than 2 standard deviations; the second pass removes points greater than 20 standard deviations from the mean with the flagged points excluded. Data were kept within 100 of the mean (i.e. all data). FILTER applies a low pass filter to pressure with a time constant shift) the filter is first run forward through the file and then run backwards through the file. Mistakenly, a time constant of only 0.03 seconds was used for this cruise, of small consequence. CELLTM uses a recursive filter to remove conductivity cell thermal mass effects from measured conductivity. In areas with steep temperature gradients the thermal mass correction is on the order of 0.005 PSU. In other areas the correction is negligible. The value used for the thermal anomaly amplitude (alpha) was 0.03. The value used for the thermal anomaly time constant (1/beta) was 7.0. Mistakenly, the secondary sensors of either CTD were not corrected for this effect. LOOPEDIT removes scans associated with pressure slowdowns and reversals. If the CTD velocity is less than 0.25 m/s or the pressure is not greater than the previous maximum scan, the scan is omitted. BINAVG averages the data into 1 db bins. Each bin is centered on an integer pressure value, e.g. the 1 db bin averages scans where pressure is between 0.5 db and 1.5 db. There is no surface bin. DERIVE uses 1 db averaged pressure, temperature, and conductiv- ity to compute salinity, theta, sigma-theta, and dynamic height. TRANS converts the data file from binary to ASCII format. Package slowdowns and reversals owing to ship roll can move mixed water in tow to in front of the CTD sensors and create artificial density inversions and other artifacts. In addition to Seasoft module LOOPEDIT, MATLAB program deloop.m computes values of density locally referenced between every 1 dbar of pressure to compute N^2 and linearly interpolates temperature, conductivity, and oxygen voltage over those records where N^2 is less than or equal to -1e-5 per s^2. MATLAB program calctd_1k.m or calctd_2k.m or calctd_3k.m applies final calibrations to temperature and conductivity, and computes salinity and calibrated oxygen. Program cnv_eps1.f and cnv_eps2.f computes ITS-90 temperature, theta, sigma-t, sigma-theta, and dynamic height; creates WOCE quality flags, and converts the ASCII data files into NetCDF format for PMEL's database. Program wocelst_ox.F converts the NetCDF files into WOCE format for submission to the WHPO, and creates WOCE .SUM files, one for each leg of the cruise. B.3. SALINITIES Primary TC data were selected from the primary package. These data were used to calibrate stations 1-34, 43-101, and 104-141. Secondary TC data were selected from the bad weather package. These data were used to calibrate stations 35-42, 102-103, and 142-150. Note that stations 144-150 used bad weather CTD s/n 209 in the primary package. Samples were collected by the CTD watchstander. A duplicate sample was collected from the deepest bottle. Salinity analysis was performed by Greg Johnson on leg 1, and Dave Wisegarver on leg 2. Analysis was done on the ship's autosalinometer using Ocean Scientific ACI2000 interface and IAPSO standard seawater batch P143 dated February 2003. The bath temperature was set to 24C. The ambient room temperature should be within 1 degree of the bath temperature, preferably cooler. Samples were left to equilibrate in the Autosal lab space for a minimum of 8 hours before analysis. The Autosal was standardized once a day. Sample salinities used to calibrate CTD conductivity sensors were obtained from the Data Manager at sea. However, salinity data were re-evaluated post-cruise and a linear drift correction between standardizations was applied. The final data set was produced at PMEL in December 2003. B.4. OXYGENS SBE 43 oxygen sensor s/n 315 was used on the primary package for stations 1-60. It had a noticeable trend from the onset but it wasn't confirmed until sample oxygens were reviewed. Sensor s/n 315 was swapped out for sensor s/n 313 prior to station 61. Sea-Bird has suggested that this membrane could've been frozen or torn before the cruise. SBE 43 oxygen sensor s/n 313 was used first on the bad weather package for stations 35-42 before going on the primary package prior to station 61. Starting at station 94, s/n 313 was not responding well to the new oxygen minimum below the thermocline. It was swapped out for sensor s/n 312 prior to station 122. SBE 43 oxygen sensor s/n 312 was used first on the bad weather package for stations 102-103. It was moved to the primary package prior to station 122 and used for the remainder of the cruise. Sample oxygens used to calibrate these sensors were obtained from the Data Manager at sea. However, oxygen data were re-evaluated post-cruise and the final data set was produced at AOML in September 2004. B.5. BOTTLE DATA Seasoft module ROSSUM created a bottle data file for each cast. These files were appended using program sbecal1k.f for primary sensor data or sbecal2k.f for secondary sensor data. Program addsalk3.f matched sample salinities to CTD salinities by station/sample number. MATLAB calibration programs were used to determine best fit groupings. The final results were a second order polynomial fit for stations 1-100 using the primary sensor pair; a third order polynomial fit for stations 101-141 using the primary sensor pair; a linear fit for stations 35-42 and stations 102-103 using the secondary sensor pair; and a linear fit with a station dependent slope for stations 142-150 using the secondary sensor pair. [sta,slope,bias,newbotco,newctdco]=calcos2(stat,cond,pres,botc,2.8,1,100); number of points used 2427 total number of points 2815 % of points used in fit 86.22 fit standard deviation 0.001952 fit bias 0.0015337094 min fit slope 0.99993324 max fit slope 0.99997466 [sta,slope,bias,newbotco,newctdco]=calcos3(stat,cond,pres,botc,2.8,101,141); number of points used 1039 total number of points 1312 % of points used in fit 79.19 fit standard deviation 0.0018 fit bias -0.004654759 min fit slope 1.000081 max fit slope 1.0001403 [sta,slope,bias,newbotco,newctdco]=calcos0(stat,cond,pres,botc,2.8,35,42); number of points used 184 total number of points 202 % of points used in fit 91.09 fit standard deviation 0.001569 fit bias 0.00067359131 min fit slope 1.0000342 max fit slope 1.0000342 [sta,slope,bias,newbotco,newctdco]=calcos0(stat,cond,pres,botc,2.8,102,103); number of points used 42 total number of points 44 % of points used in fit 95.45 fit standard deviation 0.00243 fit bias -0.0086599793 min fit slope 1.0003549 max fit slope 1.0003549 [sta,slope,bias,newbotco,newctdco]=calcos1(stat,cond,pres,botc,2.8,142,150); number of points used 232 total number of points 279 % of points used in fit 83.15 fit standard deviation 0.001669 fit bias -0.0027190403 min fit slope 1.0000403 max fit slope 1.0000991 Program addoxyk3.f matched sample oxygens to CTD oxygens by station/sample number. Because of sensor hysteresis, MATLAB programs matched upcast oxygens to downcast oxygens by sigma-2. Coefficients were determined using run_oxygen_cal_1.m and saved in final.mat. Temperature viscous and drift corrections, conductivity coefficients, and oxygen coefficients were applied to the bottle data file using calclo_k.m. Quality flags for sample salinities were determined using MATLAB program sflag.m. Of the 4676 sample salinities, 0.6% were flagged as bad and 1% were flagged as questionable. Final CTD bottle data, a16n_allo.flg, were given to John Bullister to incorporate into the master data file. For PMEL's database, individual bottle files for each cast were created in NetCDF format using clb_epso.f. C. BOTTLE SAMPLING: C.1. Inorganic Nutrients (Phosphate, Nitrate, Nitrite and Silicate) Samplers and Analysts: Leg 1 Calvin Mordy David Wisegarver Leg 2 Charlie Fischer Jia-Zhong Zhang Data Reduction: Calvin Mordy EQUIPMENT AND TECHNIQUES Concentrations of dissolved nitrite (NO2-), nitrate (NO3-), phosphate (PO43-) and silicic acid (H4SiO4) were measured using an automated continuous flow analyzer with a segmented flow and colorimetric detection. The four-channel autoanalyzer was customized using components from various systems. The major components were an Alpkem 301 sampler, one 24 channel Ismatek peristaltic pump and three ThermoSeparation monochrometers (for silicic acid, nitrate, and nitrite), one Technicon AAII pump and detector (for phosphate), and custom software for digitally logging and processing the chromatographs. Glass coils and tubing from the Technicon Autoanalyzer II were used for analysis of phosphate, and micro-coils from Alpkem were used for the other three analyses. Pump tubes were changed 4 times during the expedition, although some of the tubes were changed more frequently as part of troubleshooting. CHEMISTRY NITRITE Nitrite was determined by diazotizing with sulfanilamide and coupling with N-1 naphthyl ethylenediamine dihydrochloride to form an azo dye. The color produced is measured at 540 nm (Zhang et al., 1997a). Samples for nitrate analysis were passed through a cadmium column, which reduced nitrate to nitrite. Total nitrite, mostly from reduction of nitrate with a small amount of nitrite present in the original samples, was then determined as described above. Nitrate concentrations in seawater samples were calculated by difference. PHOSPHATE Phosphate in the samples was determined by reacting with molybdenum (VI) in an acidic medium to form a phosphomolybdate complex. This complex was subsequently reduced with hydrazine at a temperature of 55°C to form phosphomolybdenum blue (Zhang et al., 2001). An AAII detector with an 880 nm filter was used to measure the absorbance during the cruise. SILICIC ACID Silicic acid was analyzed by reacting with molybdate in acidic solution to form ß-molybdosilicic acid. The ß-molybdosilicic acid was then reduced by ascorbic acid to form molybdenum blue (Zhang et al., 1997b). The absorbance of the molybdenum blue was measured at 660 nm. SAMPLING AND STANDARDS Nutrient protocols closely followed the methods of Gordon et al. (1993). Samples were drawn in 40 ml HDPE Boston Round sample bottles that had been stored in 10% HCl and rinsed 4-5 times with sample before filling. Samples were usually analyzed 2-3 hours after sampling. A replicate was always drawn from the deep bottle for analysis with samples from the subsequent station for comparison. All samples were brought to room temperature prior to analysis. A separate analytical run was conducted at each station (except for the most shallow stations). The sequence of a typical analytical run for a station was 1) blanks, 2) working standards, 3) the working standard from the previous station, 4) deep water from the previous station, 5) samples analyzed from deep to surface, 6) replicate analysis of the four deepest samples and problem samples (if any), 7) working standards, and 8) blanks. The blanks were deionized water, and the standards were simply a "zero" standard of Low Nutrient Seawater (LNSW), and a high standard of spiked LNSW. Linearity of the autoanalyzer was checked every ten days, and corrections for non- linearity were applied to the phosphate data. The high standard was made from the addition of 1 ml of primary nitrite standard and 20 ml of a secondary mixed standard (containing silicic acid, nitrate, and phosphate) in 500 ml of Low Nutrient Sea Water using pre-calibrated Eppendorf pipettes and volumetric flasks. Dry standards were pre-weighed at PMEL, and dissolved to prepare primary standards at sea. Silicic acid (Na2SiF6, >98%) and nitrate (KNO3, 99.99%) were from Aldrich, phosphate (KH2PO4, 99.99%) and nitrite (NaNO2, 98.2%) were from Baker. The secondary mixed standard was prepared by additions of the nitrate and phosphate primary standards to the silicic acid primary standard in deionized water. After each run, the electronic chromatograph was scrutinized to ensure proper selection of individual peak heights. The peak height data was inserted into Microsoft Excel worksheets and the concentrations were calculated after factoring the baseline drift, carryover corrections, refractive index, and standard drift. Quality control plots were maintained of the baseline, matrix, carryover, standard factor, old standard, and station-to-station variability of the deep water replicate. Nutrient concentrations were reported to the shipboard data manager in micromole per liter. Measurements were made in a temperature-controlled bioanalytical laboratory (20 ± 2°C), and the laboratory temperature during analysis was reported to facilitate unit conversion to a micromole per kg basis. PROBLEMS During the cruise, several detectors had to be replaced. During the first 25 stations, the data acquisition system was not working, and the peaks were read from chart recorders. After installation of Lachat Cd Column at Station 84, the NO3 carryover correction immediately increased from about 1% to 3%, followed by a steady increase to about 6% at Station 135, and then an exponential increase to about 14% at Station 150. Carryover corrections were substantial for samples collected in the nutricline, and corrections for stations 149 and 150 were closely examined. The first of the deep water replicates analyzed at the end of the run always had the largest carryover correction. This "dummy" deep sample (bottle 1) was used to wash out the previous low nutrient surface sample before analysis of bottles 2, 3 and 4. The carryover correction for the dummies from Stations 149 and 150 were ~4 µM, and this brought the concentrations to within 0.2 µM of the initial bottle 1 measurement. Although substantial, this suggests that the correction was appropriate and the error in the correction was minimal. Samples of greatest concern were at the base of the mixed layer (i.e. Sta. 149, bottle 31) where carryover corrections of 1.0 and 0.8 (stations 149 and 150 respectively) were applied to give concentrations of 0.0 and 0.1 µM - the same as observed for the upper 3 bottles. (Stations were measured deep to shallow; therefore, samples at the top of the nutricline have the largest relative carryover correction.) A check of the bottle temperature and salinity data suggests that these samples were indeed from the upper mixed layer. Another problem was a dramatic (~30%) drop in the nitrite standard factor from Station 84 to Station 111. The standard factor immediately recovered after making a new nitrite primary standard. The nitrite standard has been known to decay with time, especially if not stored in the refrigerator. The standard concentration of nitrite was recalculated for these stations based on comparisons of the decaying standard factors with standard factors from Stations 25-83 and 112-150. NUMBER OF SAMPLES, REPLICATES AND PRECISION A replicate sample was almost always drawn from the deepest bottle, and most replicate analyses were conducted on the four deepest bottles. A few replicate analyses were conducted for samples in the upper water. The precision of phosphate, silicic acid and nitrate was within 1% of full scale. | | Silicic | | | Phosphate | Acid | Nitrate | Nitrite |-----------|----------|----------|------- # of Samples | 5368 | 5369 | 5369 | 5369 # of Replicates | 499 | 500 | 490 | n/a AVG Standard | 0.006 | 0.064 | 0.062 | n/a Deviation (µM)| | | | % Deviation | 0.5% | 0.5% | 0.3% | n/a REFERENCES Gordon, L. I., Jennings Jr., J.C., Ross, A.A. and Krest, J.M. (1993) A suggested protocol for continuous 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, vol. 3: The Observational Programme, Section 3.2: WOCE Hydrographic Programme, Part 3.1.3: WHP Operations and Methods. WHP Office Report WHPO 91-1; WOCE Report No. 68/91. November, 1994, Revision 1, Woods Hole, Mass., USA, 52 loose-leaf pages. Zhang, J-Z., P. B. Ortner and C. Fischer, (1997a) Determination of nitrite and nitrate in estuarine and coastal waters by gas segmented continuous flow colorimetric analysis. EPA's manual " Methods for the determination of Chemical Substances in Marine and Estuarine Environmental Matrices - 2nd Edition". EPA/600/R-97/072, September 1997. Zhang, J-Z., and G. A. Berberian, (1997b) Determination of dissolved silicate in estuarine and coastal waters by gas segmented continuous flow colorimetric analysis. EPA's manual " Methods for the determination of Chemical Substances in Marine and Estuarine Environmental Matrices - 2nd Edition". EPA/600/R-97/072, September 1997. Zhang, J-Z., C. Fischer and P. B. Ortner, (2001) Continuous flow analysis of phosphate in natural waters using hydrazine as a reductant, International Journal of Environmental Analytical Chemistry, 80(1): 61-73. C.2. CHLOROFLUOROCARBON (CFC) MEASUREMENTS Principal Investigators: John L. Bullister, NOAA-PMEL John.L.Bullister@noaa.gov Mark J. Warner, University of Washington mwarner@ocean.washington.edu Samplers and Analysts: Mark J. Warner, University of Washington Eric Wisegarver, University of Washington esw@u.washington.edu Samples for the analysis of dissolved CFC-11, CFC-12 and CFC-113 were drawn from ~2,421 of the ~4,923 water samples collected during the expedition. Specially-designed 12-liter 'Bullister' sample bottles were used on the cruise to reduce CFC contamination. These bottles have the same outer diameter 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 provided with standard Niskin bottles. When taken, water samples for CFC analysis were the first samples drawn from the 12-liter bottles. Care was taken to coordinate the sampling of CFCs with other samples to minimize the time between the initial opening of each bottle and the completion of sample drawing. In most cases, dissolved oxygen, 3He, and HCFC 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 12-liter bottles into 100 ml precision glass syringes equipped with two- way metal stopcocks. The syringes were immersed in a holding tank of clean surface seawater until analyzed. For air sampling, a ~100 m length of 3/8" OD Dekaron tubing was run from the main laboratory to the bow of the ship. A flow of air was drawn through this line into the main laboratory using an Air Cadet pump. The air was compressed in the pump, with the downstream pressure held at ~1.5 atm. Using a backpressure regulator. A tee allowed a flow (100 cc min-1) of the compressed air to be directed to the gas sample valves of the CFC analytical system, while the bulk flow of the air (>7000 cc min- 1) was vented through the backpressure regulator. Air samples were only analyzed when the relative wind direction was within 60° of the bow of the ship to reduce the possibility of shipboard contamination. The pump was run continuously to insure that the air inlet lines and pump were thoroughly flushed. Analysis of ~ 190 bow air samples was performed along the cruise track. At each location, replicate measurements were made to increase the precision. Concentrations of CFC-11 and CFC-12 in air samples, seawater, and gas standards were measured by shipboard electron capture gas chromatography (EC-GC) using techniques modified from those described by Bullister and Weiss (1988). For seawater analyses, water was transferred from a glass syringe to a fixed volume chamber (~30 ml). The contents of the chamber were then injected into a glass-sparging chamber. The dissolved gases 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 ml min-1. Water vapor was removed from the purge gas during passage through an 18 cm long, 3/8" diameter glass tube packed with the desiccant magnesium perchlorate. The sample gases were concentrated on a cold-trap consisting of a 1/8" OD stainless steel tube with a ~10 cm section packed tightly with Porapak N (60-80 mesh), held at ~ -20°C in a cryogenic bath. After 4 minutes of purging, the trap was isolated, and the trap was heated electrically to ~100°C. The sample gases held in the trap were then injected onto a precolumn (~25 cm of 1/8" O.D. stainless steel tubing packed with 80-100 mesh Porasil C, held at 70°C) for the initial separation of CFC-12, CFC-11, and CFC-113 from later eluting compounds. After these CFCs had passed from the pre-column into the main analytical column (~183 cm of 1/8" OD stainless steel tubing packed with Carbograph 1AC, 80-100 mesh, held at 70°C) of the GC (a Shimadzu Mini-2 gas chromatograph with ECD) The analytical system was calibrated frequently, using a 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 used. Multiple injections of these loop volumes could be made to allow the system to be calibrated over a relatively wide range of 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 or blank samples was ~11 minutes. Concentrations of the CFCs in air, seawater samples, and gas standards are reported relative to the SIO98 calibration scale (Cunnold et. Al., 2000). 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 per kilogram seawater (pmol kg-1). 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 working standard (PMEL cylinder 34603) into the analytical instrument. The response of the detector to the range of moles of CFC passing through the detector remained relatively constant during the cruise. Full-range calibration curves were run at intervals of 14 days during the cruise. These were supplemented with occasional injections of multiple aliquots of the standard gas at more frequent time intervals. Single injections of a fixed volume of standard gas at one atmosphere were run much more frequently (at intervals of ~90 minutes) to monitor short-term changes in detector sensitivity. The efficiency of the purging process was evaluated periodically by re- stripping high concentration surface water samples and comparing the residual concentrations to initial values. These re-strip values were approximately 0.8% for CFC-11, 0.2% for CFC-12 and 0.0% for CFC-113. Corrections for the efficiency were applied to the final data set. On this expedition, based on the analysis of ~100 duplicate samples, we estimate precisions (1 standard deviation) of 1% or 0.004 pmol kg-1 (whichever is greater) for dissolved CFC-11, 1% or 0.004 pmol kg-1 for CFC-12 measurements and 2% or 0.009 pmol kg-1 for CFC-113 A small number of water samples had anomalously high CFC concentrations relative to adjacent samples. These samples occurred sporadically during the cruise and were not clearly associated with other features in the water column (e.g., anomalous dissolved oxygen, salinity, or temperature features). This suggests that these samples were probably contaminated with CFCs during the sampling or analysis processes. Measured concentrations for these anomalous samples are included in the preliminary data, but are given a quality flag value of either 3 (questionable measurement) or 4 (bad measurement). A quality flag of 5 was assigned to samples which were drawn from the rosette but never analyzed due to a variety of reasons (e.g., leaking stopcock, plunger jammed in syringe barrel). A total of 35 analyses of CFC-11, 24 analyses of CFC-12 and 5 analyses of CFC-113 were assigned a quality flag of 3. A total of 16 analyses of CFC-11, 13 analyses of CFC-12 and 17 analysis of CFC-113 , were assigned a quality flag of 4. REFERENCES Bullister, J.L., and R.F. Weiss, 1988: Determination of CC13F and CC12F2 seawater and air. Deep-Sea Res., v. 25, pp. 839-853. 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, 2000: A history of chemically and radiatively important gases in air deduced from ALE/GAGE/ AGAGE. J. Geophys. Res., v. 105, pp. 17,751-17,792. A16N_2003a AIR MEASUREMENTS DATE TIME CFC-11 CFC-12 CFC-113 YYYYMMDD HHMM (ppt) (ppt) (ppt) -------- ---- ------ ------ ------- 20030619 0829 254.0 534.2 79.4 20030619 0841 254.1 533.1 78.9 20030619 0853 253.3 532.7 78.9 20030619 0905 253.1 532.4 78.8 20030619 0917 252.7 532.6 78.8 20030619 1825 252.2 527.4 78.6 20030619 1837 251.5 528.9 77.9 20030619 1849 252.6 528.6 78.3 20030619 1901 252.5 528.2 78.3 20030619 1913 251.4 528.3 78.6 20030620 0121 251.8 526.8 78.9 20030620 0133 251.6 527.0 77.2 20030620 0145 250.8 525.6 79.0 20030620 0157 251.1 527.4 78.3 20030620 0209 251.2 527.3 78.5 20030620 1458 250.1 514.4 76.2 20030620 1510 250.7 514.6 76.3 20030620 1522 250.4 513.2 75.7 20030623 0730 251.8 511.6 75.0 20030623 0742 250.2 511.8 75.1 20030623 0754 252.1 512.2 75.9 20030623 0806 250.2 511.0 75.9 20030626 0352 253.1 540.7 81.8 20030626 0404 253.8 541.0 81.5 20030626 0416 253.4 539.9 80.8 20030626 0428 253.9 539.7 81.5 20030627 0456 253.1 541.7 80.2 20030627 0508 252.8 541.8 80.4 20030627 0520 252.2 541.0 79.8 20030627 0532 252.3 540.8 80.4 20030628 0702 251.7 541.1 80.7 20030628 0714 252.5 539.9 81.4 20030628 0726 250.8 539.0 81.2 20030628 0738 251.7 540.7 81.4 20030629 0026 251.5 540.4 81.3 20030629 0038 249.8 540.9 82.6 20030629 0050 250.0 540.0 79.8 20030629 0102 252.3 543.0 80.3 20030629 1000 251.0 545.6 82.5 20030629 1012 252.4 542.6 82.2 20030629 1024 252.9 542.9 81.1 20030629 1036 252.9 547.1 81.5 20030629 1048 252.7 543.1 80.9 20030630 0007 251.9 543.2 80.5 20030630 0019 253.1 543.9 80.9 A16N_2003a AIR MEASUREMENTS (Continued) DATE TIME CFC-11 CFC-12 CFC-113 YYYYMMDD HHMM (ppt) (ppt) (ppt) -------- ---- ------ ------ ------- 20030630 0031 252.4 540.2 81.3 20030630 0043 251.8 544.1 81.1 20030630 0055 252.9 542.3 80.0 20030630 1206 252.4 543.2 80.9 20030630 1218 251.9 541.4 80.9 20030630 1230 251.8 539.6 80.3 20030630 1242 251.9 541.7 80.4 20030702 0410 252.2 543.5 80.6 20030702 0422 252.4 544.7 81.1 20030702 0434 253.4 543.8 81.0 20030702 0446 253.5 541.9 80.5 20030703 0718 255.1 545.5 81.2 20030703 0730 254.7 546.6 81.2 20030703 0742 253.6 546.6 81.1 20030703 0754 254.4 545.9 80.7 20030703 02233 254.1 545.8 79.5 20030703 2245 253.6 545.3 80.2 20030703 2257 254.2 545.6 80.6 20030703 2309 254.5 545.1 80.4 20030703 2321 253.8 543.6 80.4 20030704 1656 253.6 544.5 80.2 20030704 1708 252.9 544.1 81.0 20030704 1720 252.8 543.7 81.0 20030704 1732 253.5 544.3 80.8 20030705 0911 253.3 543.9 80.8 20030705 0923 253.7 542.8 80.7 20030705 0935 254.0 543.5 80.4 20030705 0947 253.5 543.9 80.6 20030706 0052 254.4 542.8 80.9 20030706 0104 252.8 540.7 79.6 20030706 0116 252.3 540.8 80.2 20030706 0128 253.8 542.8 80.7 20030706 0140 253.1 540.6 80.2 20030707 0751 253.9 541.2 80.4 20030707 0803 253.9 544.1 80.4 20030707 0815 253.0 543.8 81.0 20030707 0827 253.8 542.3 80.4 20030708 1428 254.7 545.3 81.4 20030708 1440 253.3 542.0 80.7 20030708 1452 252.8 544.0 82.4 20030708 1504 253.2 541.2 80.8 20030709 2215 252.2 541.2 79.8 20030709 2227 251.5 541.5 79.3 20030709 2239 252.3 544.1 79.4 20030709 2251 251.5 543.8 80.1 A16N_2003a AIR MEASUREMENTS (Continued) DATE TIME CFC-11 CFC-12 CFC-113 YYYYMMDD HHMM (ppt) (ppt) (ppt) -------- ---- ------ ------ ------- 20030719 1020 250.8 541.0 80.3 20030719 1032 251.5 541.8 81.2 20030719 1044 253.3 540.2 80.5 20030719 1056 252.8 543.0 80.7 20030720 0053 253.2 541.6 80.3 20030720 0105 252.6 541.5 81.1 20030720 0117 251.4 542.3 80.9 20030720 0129 252.5 542.2 80.8 20030720 0141 253.1 540.6 79.8 20030721 0644 250.7 542.7 80.4 20030721 0656 251.6 543.5 80.7 20030721 0708 251.4 543.3 81.4 20030721 0720 249.9 542.3 81.0 20030721 2214 251.2 542.3 81.4 20030721 2226 251.5 540.9 80.7 20030721 2238 250.4 541.9 81.0 20030721 2250 252.2 540.8 80.6 20030721 2302 250.3 542.4 81.6 20030722 1417 252.7 541.6 80.3 20030722 1429 251.7 540.3 81.0 20030722 1441 253.3 539.6 80.4 20030722 1453 252.4 542.0 80.3 20030723 2158 250.6 541.5 81.2 20030723 2210 253.1 540.3 80.1 20030723 2222 252.5 542.7 81.7 20030723 2234 252.0 542.8 81.0 20030723 2246 253.7 541.7 81.1 20030725 0253 251.3 542.2 81.1 20030725 0305 252.0 541.8 81.7 20030725 0317 253.7 541.6 81.0 20030725 0329 252.2 541.5 81.6 20030725 0341 254.3 541.4 81.0 20030728 0715 251.1 543.8 81.0 20030728 0727 249.9 546.0 81.3 20030728 0739 250.0 545.6 81.8 20030728 0751 250.2 544.7 81.2 20030728 2248 251.6 543.5 81.7 20030728 2300 249.9 540.5 81.6 20030728 2312 250.4 540.8 81.4 20030728 2324 251.6 541.4 80.3 20030730 0229 251.4 540.2 81.1 20030730 0241 252.8 540.3 80.9 20030730 0253 250.0 541.5 81.2 20030730 0305 251.0 541.2 80.7 20030731 0017 252.7 541.2 81.0 A16N_2003a AIR MEASUREMENTS (Continued) DATE TIME CFC-11 CFC-12 CFC-113 YYYYMMDD HHMM (ppt) (ppt) (ppt) -------- ---- ------ ------ ------- 20030731 0029 250.7 541.8 82.1 20030731 0041 250.8 541.5 81.8 20030731 0053 252.0 540.3 81.5 20030731 1703 252.4 540.2 81.2 20030731 1715 251.5 540.4 81.7 20030731 1727 249.6 540.1 80.9 20030731 1739 249.2 540.2 81.3 20030731 1751 250.3 539.8 80.8 20030801 2133 249.9 540.5 81.8 20030801 2145 250.9 540.6 81.4 20030801 2157 250.1 541.2 80.0 20030801 2209 250.1 544.1 80.8 20030801 2221 250.3 539.9 81.2 20030803 0350 250.7 541.2 81.9 20030803 0402 250.7 539.1 79.9 20030803 0414 250.7 540.7 81.3 20030803 0426 251.7 540.4 80.5 20030803 1833 250.6 542.1 81.5 20030803 1845 252.1 541.9 80.4 20030803 1857 251.2 542.7 81.1 20030803 1909 252.0 539.3 80.1 20030804 1020 252.0 539.9 81.5 20030804 1032 251.7 540.9 80.9 20030804 1044 251.4 540.8 81.0 20030804 1056 252.7 541.0 80.9 20030805 0235 251.7 543.3 81.0 20030805 0247 251.2 543.1 81.6 20030805 0259 252.4 541.4 81.5 20030805 0311 250.4 541.8 81.8 20030806 1418 251.7 541.0 80.2 20030806 1442 251.2 539.9 81.7 20030806 1454 251.6 538.6 80.1 20030807 0446 249.3 539.4 80.8 20030807 0458 252.1 540.7 80.5 20030807 0510 249.5 540.1 80.6 20030807 0522 249.6 538.3 80.2 20030808 0445 252.7 541.0 80.0 20030808 0457 250.8 541.0 81.2 20030808 0509 250.6 540.7 80.3 20030808 0521 249.5 540.8 80.5 20030808 1749 250.9 541.3 81.0 20030808 1801 252.1 541.3 81.4 20030808 1813 251.6 541.1 80.1 20030808 1825 250.7 539.4 81.5 C.3. CO2 STUDIES ON A REPEAT HYDROGRAPHY CRUISE IN THE ATLANTIC OCEAN: CO2 CLIVAR SECTION A16N_2003a DURING JUNE-AUGUST, 2003 E. Peltola, R. Wanninkhof, R. Feely, R. Castle, D. Greeley, J.-Z. Zhang, F. Millero, N. Gruber, J. Bullister and T. Graham [AOML] Notice: Mention of a commercial company or product does not con- stitute an endorsement by NOAA/AOML. Use of information from this publication concerning proprietary products or the tests of such products for publicity or advertising purposes is not authorized. ABSTRACT This report presents methods, analytical and quality control procedures performed during A16N cruise, which took place from June 4 to August 11, 2003 aboard the NOAA Ship RONALD H. BROWN under auspices of the National Oceanic and Atmospheric Administration (NOAA). The first hydrographic leg (June 19-July 10) was from Reykjavik to Funchal, Madeira along the 20˚ W meridian and the second leg (July 15-August 11) continued operations from Funchal to Natal, Brazil on a track southward and ending at 6˚ S, 25˚ W. The research was the first in a decadal series of repeat hydrography sections jointly funded by NOAA-OGP and NSF-OCE as part of the CLIVAR/CO2/hydrography/tracer program. Samples were taken from up to 34 depths at 150 stations. The data presented in this report includes the analyses of water samples for: dissolved inorganic carbon (DIC), fugacity of CO2 (fCO2), Total Alkalinity (TA), pH, nitrate (NO3), nitrite (NO2), phosphate (PO4), silicate (SiO4) and dissolved oxygen (O2). C.3.1. INTRODUCTION The A16N_2003a cruise from Reykjavik, Iceland to Natal, Brazil was the first in a series of repeat hydrography cruises to measure decadal changes in circulation, heat and fresh water budgets, and carbon inventory in the ocean. The cruises repeat a sub-set of the World Ocean Circulation Experiment/World Hydrographic Program (WOCE/WHP) lines occupied in each major ocean basin in the 1990ties. The program is driven by the need to monitor the changing patterns of carbon dioxide (CO2) in the ocean and provide the necessary data to support continuing model development that will lead to improve forecasting skill for oceans and global climate. The WOCE/JGOFS survey during the 1990s has provided a full depth, baseline data set against which to measure future changes. By integrating the scientific needs of programs requiring measurement of the full water column, major synergies and cost savings are achieved. These measurements are of importance both for major research programs, such as CLIVAR and the U.S. GCRP Carbon Cycle Science Program (CCSP), and for operational activities such as GOOS and GCOS. As outlined in the program documentation one component of a global observing system for the physical climate/CO2 system should include periodic observations of hydrographic variables, CO2 system parameters and other tracers. The large-scale observation component of the CCSP has a need for systematic observations of the invasion of anthropogenic carbon in the ocean superimposed on a variable natural background. The five topic areas that the CO2/CLIVAR repeat hydrography program addresses are: A. Carbon system studies B. Heat and freshwater storage and flux studies C. Deep and shallow water mass and ventilation studies D. Calibration of autonomous sensors E. Data for model calibration Further descriptions of the repeat hydrography program can be found at: http://ushydro.ucsd.edu/ Details of the A16N_2003a cruise can be found in the cruise instructions posted at the website of PMEL: http://www.pmel.noaa.gov/CO2/a16n/ and the repeat hydrography website: http://ushydro.ucsd.edu/ The latter website also serves the full dataset from the cruise. The A16N_2003a cruise involved efforts of a dozen investigators whose names and project are listed in Table 1. The cruise was executed under leadership of Dr. John Bullister who served as chief scientist and Dr. Niki Gruber who was co-chief scientist. A full list of personnel on the cruise is given in Table 2. A list of participating institutions is in Table 3. The cruise consisted of a transit leg from Charleston to Reykjavik on which limited surface water observations were taken. Surface water pCO2 measurements for the transit and the hydrography legs can be found at www.aoml.noaa.gov/ocd/gcc. The first hydrographic leg was from Reykjavik to Funchal, Madeira along the 20° W meridian and the second leg continued operations from Funchal to Natal, Brazil on a track southward and ending at 6° S, 25° W (see Figure 1). This data report focuses on the measurement of dissolved inorganic carbon (DIC), fugacity of CO2 (fCO2), Total Alkalinity (TA), pH, nitrate (NO3), nitrite (NO2), phosphate (PO4), silicate (SiO4) and dissolved oxygen (O2). Methodology, instrumentation and standardization of these parameters improved significantly during the WOCE/JGOFS era. Notable developments include release of manuals detailing the analytical methods and operating protocols (DOE, 1994; http://cdiac.esd.ornl.gov/oceans /handbook.html). Certified Reference Materials (CRM) are now available for DIC and TA, which are run interspersed with samples to determine calibration offsets. On this cruise the TA values were adjusted accounting for the small difference between the CRMs run at sea and the certified value determined at SIO. For DIC there were problems with the gas loop calibrations attributed to inaccurate temperature sensors. The reference materials were therefore used as primary calibration for both DIC and TA.. Instrumentation improved as well in the last decade. Alkalinity measurements can be done with better precision through automation and close checks of the response of electrodes. Burettes are independently calibrated, and the preparation of titrant (hydrochloric acid) undergoes improved quality control and standardization (Millero et al., 1998). Measurement of pH is now done at extreme precision with spectrophotometric methods (Byrne and Breland, 1989). The DIC measurements are done by coulometry, a precise integrative method. During the A16_2003a cruise we utilized two single operator multi- parameter metabolic analyzers (SOMMAs) (Johnson et al., 1999) for analyses, which facilitated a sample throughput of up to 80 samples per day. The fCO2 measurements were done with an equilibration system described in Wanninkhof and Thoning, (1993). For this cruise we changed the data reduction and calculation routines. Comparison of data with a cruise along a similar transect in 1993 shows a appreciable bias between results that is detailed in the section describing the pCO2 analyses. Oxygen measurements were performed by Winkler titrations (Carpenter, 1965) with photometric endpoint detection (Friederich et al., 1984). The titrator worked well but there were issues with errors in bottle volumes and problems with pipettes used to generate standard curves. Extensive post-cruise trouble shooting and bottle volume re- determination were necessary to reduce the data. The data underwent carefully quality assurance and quality control (QA/QC) both during the cruise and post-cruise. Precision of measurements was determined from duplicate sampling and comparison of deep-water data where little variability is expected. Outliers in the data were flagged based on several methods utilizing prior knowledge of the trends and known relationships between parameters. Depth profiles for each parameter were scrutinized for outliers. When deviations were observed, it was assessed if other parameters showed deviations. Inorganic carbon system parameters were linked through physical chemical properties and by knowledge of two of the four parameters, the other two can be calculated provided silicate, phosphate, temperature and salinity of the sample are known. These so-called over-determinations or internal consistency calculations were used to assess the difference between calculated and measured values. When the difference exceeded 10 µmol kg-1 for the measured TA and the TA calculated from DIC and pH or fCO2, the three parameters were scrutinized and compared with other methods to assess if the datum should be labeled as questionable. Other techniques described in detail below include regional multi-linear regressions (MLR) between the inorganic carbon parameters and physical and chemical parameters known to correlate with them (for instance DIC = f(T, S, AOU, Si, PO4)). Again the differences between measured and calculated parameters are inspected. Finally the parameters were plotted against latitude for narrow depth intervals. Since changes along depth horizons are usually gradual, anomalies can be easily spotted and flagged. This report describes the analytical procedures, calculations, and assessment of precision for DIC, TA, fCO2, and pH. This is followed by a description of the QA/QC methods based on internal consistency of these parameters and the MLR technique. The final section describes the procedures for measurement of nutrients and oxygen, and details the issues C.3.2. DATA COLLECTION AND ANALYTICAL METHODS C.3.2.1. TOTAL DISSOLVED INORGANIC CARBON (DIC) The DIC analytical equipment was set up in a seagoing laboratory van. The analysis was done by coulometry with two analytical systems (AOML-1 and AOML-2) used simultaneously on the cruise. Each system consisted of a coulometer (UIC, Inc.) coupled with a SOMMA (Single Operator Multiparameter Metabolic Analyzer) inlet system developed by Kenneth Johnson (Johnson et al., 1985, 1987, 1993; Johnson, 1992) formerly of Brookhaven National Laboratory (BNL). In the coulometric analysis of DIC, all carbonate species are converted to CO2 (gas) by addition of excess hydrogen ion (acid) to the seawater sample, and the evolved CO2 gas is swept into the titration cell of the coulometer with compressed nitrogen, 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. 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 by Kelly Brown, CCN Consulting (Wilke, 1993). However, due to large temperature variation the calibration factors obtained from gas loop measurements were of poor quality. Instead of using an average of the small and large loop values, we used a constant value for each analyzer throughout the entire cruise. The constant calibration value used for AOML-1 was 1.00532 and for AOML-2 1.00650. The CO2 gas volumes bracketed the amount of CO2 extracted from the water samples for the two AOML systems. All DIC values were corrected for dilution by 0.2 ml of HgCl2 used for sample preservation. The total water volume of the sample bottles was 540 ml. The correction factor used for dilution was 1.00037. A correction was also applied for the offset from the Certified Reference Material (CRM) Batch 59, supplied by Dr. A. Dickson of Scripps Institution of Oceanography (SIO). This correction was applied for each cell using the CRM value obtained in the beginning of the cell. To check the stability of the coulometer and coulometer solutions, the CRMs were measured at the beginning, middle, and end of each coulometer cell solution. The coulometer cell solution was replaced after 25 mg of carbon was titrated, typically after 9-12 hours of continuous use. Sample titration times were 9-16 minutes. Samples were drawn from the "Niskin" bottles into cleaned, precombusted 540-ml Pyrex bottles using Tygon 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. 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 grease, and were stored at room temperature for a maximum of 12 hours prior to analysis. Replicate seawater samples were taken from the surface, 1000 m, and bottom "Niskin" sample bottles and run at different times during the cell. The first replicate of the surface water was used at the start of the cell with fresh coulometer solution, the second surface replicate and the first one of the 1000 replicates were run in the middle of the cell after about 12 mg of C were titrated. The second one of the 1000 m replicates and the first one of the bottom replicates were run at the end of the cell after about 25 mg of C were titrated, while the second one of the bottom replicate samples was run using a new coulometer cell solution, see. No systematic difference between the replicates was observed. The trends do not suggest any systematic dependency of results with amount of carbon titrated for a particular cell. The results of the duplicate samples have been presented in Figure 2, and Table 4 and 5. Calculations Calculation of the amount of CO2 injected was according to the Department of Energy (DOE) CO2 handbook [DOE, 1994]. The concentration of CO2 ([CO2]) in the samples was determined according to: (Counts-Blank Run Time)* K µmol/count [CO2] = Cal. Factor * ------------------------------------- pipette volume * density of sample where Cal factor is the calibration factor that were fixed for this cruise because of malfunctioning of gas loops, "Counts" is the instrument reading at the end of the analysis, "Blank" is the counts/minute determined from blank runs performed at least once for each cell of the solution, "Run Time" is the length of coulometric titration (in minutes), and K is the conversion factor from counts to µmol which is dependent on the slope and intercept relation between instrument response and charge. For a unit with Ecal slope of 1 and intercept of 0, the constant is 2.0728 * 10-4. The blank values for AOML1 were in the range of 12.0-33.3 counts/min with an average value of 19.6 counts/min and a standard deviation of 6.8 counts/min. For AOML2 they were in the range of 12.0-30.0 counts/min with an average value of 21.7 counts/min and a standard deviation of 6.1 counts/min. The pipette volume was determined by taking aliquots at known temperature of distilled water from the volumes prior to the cruise. The weights with the appropriate densities were used to determine the volume of the pipettes (AOML1: 28.726 cm3 @ 19.96°C, AOML2: 22.623 cm3 @ 22.63°C). Calculation of pipette volumes, density, and final CO2 concentration were performed according to procedures outlined in the DOE CO2 handbook (DOE, 1994). C.3.2.2. FUGACITY OF CO2 (FCO2) Instrumentation The fugacity of CO2 was measured on the A16N_2003a cruise at a constant temperature of 20°C by equilibrating a 500-ml water aliquot in a volumetric flask with a closed headspace. The headspace is circulated through a non-dispersive infrared detector that measures both CO2 and H2O levels. The analytical instrumentation is detailed in Wanninkhof and Thoning (1993) and is the same as the setup used in the N.Atl-93 cruise that occupied the same cruise line in 1993 (Castle et al., 1998). The system is patterned after that of Chipman et al. (1993) with modifications as presented in Wanninkhof and Thoning (1993). In short, in the system a 500-ml water sample is equilibrated at ambient pressure with an 80-ml headspace in a thermostatted volumetric flask. The headspace is circulated through a non-dispersive infrared analyzer, NDIR, LICOR model 6262. Upon equilibration the circulation flow is stopped and 30 readings of H2O content and CO2 content in the cell are taken over a 30-second interval and averaged. The system is a dual channel system where one equilibration occurs while circulating through the NDIR and a second flask is equilibrated offline. Once the first sample is analyzed the second flask is switched in line with the NDIR and the residual air in the NDIR is equilibrated with the second flask content. The second equilibration phase through the NDIR takes less time as a large part of the headspace already is equilibrated offline. The two-channel configuration decreases the total analysis time to about 20 minutes for two samples. The system is calibrated after every eight samples with six gaseous standards traceable to the manometrically determined values of C. D. Keeling of Scripps Institute of Oceanography. The mole fractions of the standards used during the A16N2003a cruise were: Tank number mole fraction ----------- ------------- CA05989 378.7 ppm CA05980 792.5 ppm CA05984 1036.9 ppm CA05940 1533.7 ppm CA05988 593.6 ppm CA05998 205.1 ppm The standards are also used as the headspace gas for the equilibration. Since the mole fractions of the gases in the headspace prior to equilibration are known, the small perturbation of the fCO2 in the water during the equilibration process can quantitatively be accounted for. The headspace gas is selected such that it is close the anticipated water value thereby minimizing the correction. Data Reduction The calculation of the fCO2 involves several steps including the conversion of the NDIR output to an equivalent dried mole fraction of CO2, the correction for the perturbation of the fCO2 in water by equilibration, and the small adjustment from the measurement temperature to 20°C. For the reduction of the A16N_2003a fCO2 we made an important adjustment in procedures. On previous cruises, the calibration of the samples that were run at 100% water vapor pressure (@ 20°C) to the standards that are dry was done through an empirical algorithms created by running standards both wet and dry. For this cruise we relied on the internal correction from wet to dry mole fraction of CO2 provided by the LI-COR 6262. This change is based on testing by our group and other investigators that showed that the correction provided by the instrument is of high quality and subject to less uncertainty than our empirical corrections. Since this is a fundamental change in our procedures we describe the old and new routine in detail below including comparison of the results. The correction from detector output to (dry) mole fraction of CO2, XCO2 in the headspace was previously done by measuring the voltage output of the CO2 and H2O channel. An empirical algorithm between dry standards and standards saturated with water vapor at 20°C was created of the form: MVCO2(dry) = MVCO2 (wet) + A + B*MVCO2(wet) + C*(MVCO2(wet))2 Where MV is the millivolt output of the CO2 channel and MVCO2 (wet) is the milli-volt value measured for the equilibrated headspace of the sample. From this algorithm the (water saturated) headspace gas is corrected to the dry state such that the samples can be directly related to the standard. The next step is the convert the MVCO2(dry) of the sample to a XCO2 by creating a curve of MVCO2(dry) vs. XCO2 using the standards preceding and following the samples. For each sample the three standards closest to the samples are selected and a second-order polynomial was created of MVCO2 vs. XCO2 by averaging the appropriate standards preceding and following the sample. The second- order polynomial is then used to calculate the XCO2 of the sample. Following this step the fCO2 in the headspace is calculated according to: fCO2 = XCO2 (1-pH2O)*0.9966 Where pH2O is the water vapor pressure @ 20°C (= 0.0226 atm) and 0.9966 is the conversion factor from pCO2 to fCO2 @ 20°C. The next step is the correction for change in the fCO2 in the water sample due to exchange of CO2 with the headspace during equilibration. This step is accomplished by using the mass balance criteria that the total amount of carbon in the headspace and water is conserved and by using the fact that the TA remains unchanged during equilibration. The DIC of the sample (determined independently) and the headspace gas concentration prior to equilibration along with the volume of water and headspace are used to calculate the total amount of carbon in the system. From the change in headspace CO2 before versus after equilibration the change the DIC in the water can then be determined. From this change and the TA (calculated from DIC and fCO2 after equilibration), the fCO2 in the water before equilibration can then be determined. The final step is to correct the fCO2 from analysis temperature to 20°C. The water samples are always equilibrated within 0.1°C of 20°C such that this correction is less than 0.4% of the value. The correction for perturbation of the fCO2 in the water during equilibration and the temperature correction to 20°C are performed using the carbonate dissociation constants and the temperature dependence of the constants and the calculation routines described in (Peng et al., 1987) For A16N_2003a the correction from the moist gas of the sample to an equivalent dry concentration was performed utilizing the internal correction routine built into the Li-6262 analyzer. This internal algorithm has been extensively checked by others and our tests showed that the correction was robust as well. The important advantage of this internal correction is that in our previous data reductions we assumed that the algorithm between wet and dry created in laboratory tests before the cruise or after the cruise does not change appreciably over time. This has proven not always to be the case. Secondly, the water vapor level measured during the standard runs can be appreciable despite absence of water vapor in the compressed gas standards since it takes a long time for the water vapor introduced by the equilibration of the samples to be flushed from the system. Therefore we see a decreasing trend of water vapor level when the six samples are run consecutively (see Figure 3). The modified data reduction routine uses the XCO2(dry) calculated by the detector for both standards and samples. A second-order polynomial fit is created between the actual mole fraction of CO2 in the standard and the instrument value. This standardization accounts instrument drifts over time. The detector was zeroed and spanned for CO2 every day while the water vapor channel was spanned right before the first leg and before the second leg. Standardizing the water vapor channel is difficult because of the "stickiness" of the water vapor leading to lags and very slow response times. A polynomial is created for the three standards closest to the sample by averaging the pertinent standards before and after the sample. The other steps of correcting for small temperature deviations of the water bath from 20°C and correction to fCO2 prior to equilibration are identical to the procedures outlined above. The new correction routine results in small differences in values for calculated fCO2 compared to the previous data reduction routine. Table 6 shows a comparison for station 45. The values using the new reduction are systematically about 2 µatm lower than the old reduction method. The table also gives the results of two different water vapor correction algorithms. One empirical correction was established before the cruise and one determined from running wet vs. dry standards after the cruise. The results show differences in the range from 7 to 17 µatm. Quality Control During the cruise a total of 1515 Niskin samples were analyzed for fCO2, compared to 2500 DIC samples. This was because only one full-time and a part-time operator were available for the work while two full-time analysts were involved in DIC analysis. A summary of the analysis statistics is given in Table 7. The precision of the results is based on comparison of duplicate values and is estimated to be 2 µatm or 0.3% based on the results in Table 8. There is no apparent trend in imprecision with depth or absolute concentration when comparing absolute difference. The relative (%) difference is slightly higher for lower fCO2 values found near the surface. Deep-water comparison with the 1993 cruise (NAtl-93) and crossover with 1999 cruise (24N). The A16N_2003a cruise overlapped or intersected with two previous cruises that were sampled by our group. The NAtl-93 cruise (Castle et al., 1998) followed the same track and was occupied during the summer of 1993 but it was run from South to North. A 24-bottle rosette was used such that fewer depth samples were obtained and the spacing of the stations was nominal 1 degree compared to 1/2 degree spacing on the 2003 occupation. The 24N-98 cruise was run in February and intersected the A16N_2003a cruise near 24° N, 26.5° W. In the comparison we make the assumption that changes in deep water are negligible over the time period. The crossover with the 24 N cruise is shown in Figure 4. The fCO2 shows a consistent offset with the 2003 data being about 18 µatm higher than the 1998 data. For the comparison with the 1993 data we looked at the deep water offset in the deep water for stations spaced about 5 degrees apart (Figure 5). Again a systematic bias is observed with the 2003 data being higher. The magnitude of the bias however is about 10 µatm. The cause of these offsets is disconcerting and attributed to the water vapor correction. However, the exact reason or possible corrections is not readily apparent. The surface water fCO2 levels are measured with a different system in underway mode near sea surface temperature and offer an independent assessment of agreement of fCO2 values. However, the temperature correction has some uncertainties which complicate the comparison. For the comparison the fCO2(20) values are corrected to SST as determined by the thermosalinograph using the empirical correction of ∂fCO2/∂T = 0.0423°C-1 and by using the temperature dependence of the dissociation constant and using the thermodynamic equations. The results are shown in Figure 6 and show average differences of: -3.30 ± 4.9 µatm (n=76) for fCO2(UW)-fCO2(disc)Mehr and -6.66 ± 4.1 µatm (n=76) for fCO2(UW)-fCO2(disc)4.23%. In case of fCO2(UW)- fCO2(disc)Mehr, the fCO2(20) are normalized to sea surface temperature using the Mehrbach constants as refit by Dickson and Millero. For fCO2(UW)-fCO2(disc)4.23%., the fCO2(20) are normalized to SST using the empirical relationship of 0.0423°C-1. Again our temperature corrected discrete data are on average higher than the underway measurements. The differences CO2(UW)-fCO2(disc)Mehr and fCO2(UW)-fCO2(disc)4.23% are plotted against temperature in Figure 7. There is a slight trend with temperature for the adjustments using the Mehrbach constants. Also, near 20°C when the adjustment is small the comparison shows that the discrete data is systematically higher. For the range from 18 to 22°C the difference is -5.1 ± 4.9µatm (n=76) and - 6.7 ± 4.1 µatm (n=76) for fCO2(UW)-fCO2(disc)Mehr and fCO2(UW)- fCO2(disc)4.23% very similar to the average difference over the entire temperature range suggesting that the systematic offset is not attributable to the temperature correction alone. C.3.2.3. TOTAL ALKALINITY (TA) Seawater samples were drawn from the "Niskin" bottles with a 40-cm length of silicon tubing. One end of the tubing was fit over the petcock of the "Niskin" bottle and the other end was inserted into the bottom of a 500-ml Corning glass-stoppered sample bottle. The sample bottle was rinsed three times with approximately 300 ml of seawater. The sample bottle was slowly filled from the bottom. Once filled, the sample bottles were kept in a constant water bath at 25°C for half-hour before analysis. The titration system used to determine TA consisted of a Metrohm 665 Dosimat titrator and an Orion 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 constant-temperature bath. The Plexiglas 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 cm3 glass bottles in the laboratory for use at sea. The 0.23202 M HCl solutions were made from 1 M Mallinckrodt standard solutions in 0.45 M NaCl to yield an ionic strength equivalent to that of average seawater (~0.7 M). The acid was standardized using a coulometric technique by the Univ. of Miami and by Dr. Dickson of Scripps Institution of Oceanography (SIO). 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 burettes with Milli Q 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 µmol/kg in TA. The titrators were calibrated in the laboratory before the cruise. Certified standard Reference Material (CRM) Batch 59 prepared by Dr. Dickson was used at sea to monitor the performance of the titrators. All TA data have been corrected based on CRM values for each cell and each leg. (Millero et al, 2000), see Table 9. C.3.2.4. pH Seawater samples were drawn from the "Niskin" bottles with a 20-cm length of silicon tubing. One end of the tubing was fit over the petcock of the "Niskin" 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 endcaps were also rinsed and then used to seal 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. The sample cells were kept in a waterbath at 20°C for a half an hour before analysis. Seawater pH was measured using the spectrophotometric procedure (Byrne, 1987) and the indicator calibration of Clayton and Byrne (1993). The indicator was an 8.0-mM solution of m-cresol purple sodium salt (C21H17O5Na) in MilliQ water. The absorbance measurements were made using a Varian Cary 2200 spectrophotometer. The temperature was controlled to a constant temperature of 25°C with an Endocal RTE 8DD refrigerated circulating temperature bath that regulates the temperature to ± 0.01°C. The temperature was measured using a Guildline 9540 digital platinum resistance thermometer. C.3.2.5. OXYGEN Method The analytical method for dissolved oxygen in seawater during A16N_2003a cruise was based on automated Winkler titration by Williams and Jenkinson (1982) and modified by Friederich et al. (1991). Dissolved oxygen samples were withdrawn from 10-L Niskin bottles to 145-ml Pyrex brand iodine flasks (Corning 5400, Corning, New York, USA). The exact volume of each flask at room temperature had been gravimetrically calibrated with its ground glass stopper following standard procedures (DOE, 1994; WHP Operations and methods, 1991). One ml of manganese chloride reagent and one ml of alkaline iodide reagent were added to each sample in the iodine flasks and its stopper was placed in the bottle neck. The bottles were shaken vigorously for about one minute to completely fix oxygen with manganese hydroxide. In this method, dissolved oxygen in the sample reacts with manganese hydroxide to form Mn(OH)3 precipitate. Particulate Mn(OH)3 dissolve upon the acidification and resulting Mn3+ oxidize iodide to iodine in acidic solution. The liberated iodine complex with excess iodide forming I3¯ and the latter is titrated with a sodium thiosulfate solution that is standardized by a primary standard potassium iodate. The complex I3¯ has a maximum absorbance at 352 nm and change in absorbance of I3¯ at 352 nm is used to detect the end point. A custom-build automated oxygen titrator with MS DOS interfacing software was used to determine dissolved oxygen concentrations in the samples. A total of 5011 seawater samples were taken from 150 stations and analyze for dissolved oxygen concentrations. At the beginning of cruise, a test CTD cast was made by sampling 20 Niskin bottles from same depth (170 m). Analysis of these samples was listed in Table 10 and indicate a precision of 0.3 µmole/L. Throughout the cruise duplicate samples from same Niskin bottle were collected at each station to estimate the precision of overall measurement (sampling and analysis). Analyses of 300 replicate samples listed in Table 11 indicated that the precision of shipboard automated Winkler titration is 0.29 including all outliers and 0.24 µmole/L excluding the outliers. Analysis of outliers indicated that most outliers in duplicate analysis were due to errors in the volumes of oxygen bottles if it is not a problem with Niskin bottles or sampling error. The outliers in vertical profiles of oxygen were also used to identify the bottles that might have errors in volumes. Total of 33 sample bottles were recalibrated and 11 of them had volume errors greater than 0.3 ml (Table 12). This accounts about 5% of sample bottles used during the A16N cruise. The volumes of such identified questionable oxygen bottles were recalibrated after the cruise and dissolved oxygen concentrations were recalculated for those samples using correct volumes. The primary iodate standard solution was prepared from high purity reagent grade KIO3 (Mallinckrodt, USA), pre-dried in an oven at 110_C for overnight and cooled in a desiccator before weighing. The thiosulfate solution was prepared from reagent grade Na2S2O3 5H2O (Mallinckrodt, USA). During the cruise, total of 25 bottles of thiosulfate solutions (1 liter each) were consumed for oxygen analyses. Each new bottle of thiosulfate solution was first standardized by the primary standard KIO3 solution before using it for sample titration. Standardizations of the thiosulfate solutions were performed by titration of known amounts of KIO3 solution (usually 2, 4, 6, and 8 ml). Regression analysis of four titration points generates a slope (factor) and an intercept (blank) from which sample concentration are calculated. Extending KIO3 solution to 20 ml produced essentially the same calibration curve as shown in the thiosulfate bottle 21 in Table 13. Each bottle of thiosulfate usually lasts for 2 to 3 days of sample titration. The thiosulfate bottle 24 had replicate standardization. The thiosulfate bottle 19 was standardized at the beginning and the end of its life span to check its stability during storage. All the replicate analyses produced acceptable results within uncertainty of standardization as shown in Table 13. It should be pointed out that at beginning of cruise there are several standardizations with lower slopes and larger intercepts as shown in Figure 8. These were attributed to malfunction of titration system used during that period. When system is functioning properly it produced slopes within 1% of the theoretical value of 24.818 and intercepts less than ± 0.01 as shown in most part of cruise in Figure 8. At the beginning of leg 2 (from stations 72 to 79) a problematic automatic pipette was used to deliver the KIO3 standard solution for standardization of thiosulfate solution in bottle 14. An unusually high slope was observed and this pipette was not used in subsequent analyses. Shipboard and post cruise comparison indicated that there is an error in volume delivery of this automatic pipette. Dissolved oxygen concentrations from station 72 to 79 have been corrected for errors in volume delivery of iodate solution by this automatic pipette used in the standardization of thiosulfate solution. A correction factor (1.0153) was estimated based on post-cruise recalibration of the automatic pipette as shown in Table 14 and was applied to data from station 72 to 79. Since the Dosimat titrators have demonstrated high precision and accuracy (0.05 and 0.2% at delivery of 10ml solution, respectively) in volume delivery of titrants, we recommend use a Dosimat or similar positive displacement burette to quantitatively dispense the iodate standard solution in the future cruises. This procedure can improve the accuracy of shipboard oxygen analysis. ACKNOWLEDGMENTS The dedication and assistance of the officers and crew of the NOAA Ship RONALD H. BROWN is gratefully appreciated and hereby acknowledged. This research was supported by the Climate Observation and Services Panel of NOAA. We wish to acknowledge the COSP program manager Mike Johnson for supporting the field program. The CO2 CLIVAR repeat hydrography program is a joint effort between NOAA and NSF-OCE. Eric Itsweire of NSF was instrumental in forming the program. REFERENCES Bradshaw, A.L. and Brewer, P.G., 1988. High precision measurements of alkalinity and total carbon dioxide in seawater by potentiometric titration-1. Presence of unknown protolyte(s)?, Mar. Chem., 23, 69- 86. Byrne, R.H., and J.A. Breland, High precision multiwavelenth pH determinations in seawater using cresol red, Deep-Sea Research, 36, 803-810, 1989. Byrne, R. H., 1987. Standardization of standard buffers by visible spectrometry. Anal.Chem., 59, 1479-1481. Carpenter, J.H., The Chesapeake Bay Institute technique for the Winkler dissolved oxygen method, Limnol. Oceanogr., 10, 141-143, 1965. Castle, R., R. Wanninkhof, S.C. Doney, J. Bullister, L. Johns, R.A. Feely, B.E. Huss, F.J. Millero, and K. Lee, Chemical and hydrographic profiles and underway measurements from the North Atlantic during July and August of 1993, NOAA data report ERL AOML- 32, NOAA/AOML, Springfield NJ, 1998. Chipman, D.W., J. Marra, and T. Takahashi, Primary production at 47_N and 20_W in the North Atlantic Ocean: A comparison between the 14C incubation method and mixed layer carbon budget observations, Deep- Sea Research II, 40, 151-169, 1993. Clayton T. and Byrne, R.H., 1993. Calibration of m-cresol purple on the total hydrogen ion concentration scale and its application to CO2- system characteristics in seawater, Deep-Sea Research, 40, 2115- 2129. Dickson, A.G., 1981. An exact definition of total alkalinity and a procedure for the estimation of alkalinity and total CO2 from titration data, Deep-Sea Res., 28, 609-623. DOE, Handbook of methods for the analysis of the various parameters of the carbon dioxide system in sea water; version 2, edited by A.G. Dickson, and C. Goyet, DOE, 1994. Friederich, G.E., L.A. Codispoti and C. M. Sakamoto, An Easy-to- constructed Winkler titration system. Monterey Bay Aquarium Research Institute, 1991; Technical Report No. 91-6. Friederich, G.E., P. Sherman, and L.A. Codispoti, A high precision automated Winkler titration system based on a HP-85 computer, a simple colorimeter and an inexpensive electromechanial buret, Bigelow Lab. Technical Report, 42, 24 pp, 1984. Johnson, K.M., A. Körtzinger, L. Mintrop, J.C. Duinker, and D.W.R. Wallace, Coulometric total carbon dioxide analysis for marine studies: measurement and internal consistency of underway surface TCO2 concentrations, Mar. Chem, Accepted, 1999. Johnson, K.M., Wills, K.D., Butler, D.B., Johnson, W.K., and Wong C.S., 1993. Coulometric total carbon dioxide analysis for marine studies: Maximizing the performance of an automated continuous gas extraction system and coulometric detector. Mar. Chem., 44, 167-189. Johnson, K.M., 1992 Operator's manual: Single operator multiparameter metabolicanalyzer (SOMMA) for total carbon dioxide (CT) with coulometric detection. Brookhaven National Laboratory, Brookhaven, N.Y., 70 pp. Johnson, K.M., Williams, P.J., Brandstrom, L., and Sieburth J. McN., 1987. Coulometric total carbon analysis for marine studies: Automation and calibration. Mar. Chem., 21, 117-133. Johnson, K.M., King, A.E., and Sieburth, J. McN., 1985. Coulometric DIC analyses for marine studies: An introduction. Mar. Chem., 16, 61-82. Millero, F. J., Zhu, X., Liu, X., Roche, M. P., Moore, C., Jolliff, J., 2000. The pH and TA along 24˚ North in the Atlantic Ocean. Univ. of Miami Technical Report No. RSMAS-2000-03, 41 pp. Millero, F.J., et. al. Total alkalinity measurements in the Indian Ocean during the WOCE Hydrographic Program CO2 survey cruises 1994-1996, Mar. Chem., 63, 9-20, 1998. Millero F. J., Zhang, J. Z., Lee, K., and Campbell, D. M., 1993. Titration alkalinity of seawater, Marine Chemistry, 44, 153-165. Peng, T.-H., T. Takahashi, W.S. Broecker, and J. Olafsson, Seasonal variability of carbon dioxide, nutrients and oxygen in the northern North Atlantic surface water: observations and a model, Tellus, 39B, 439-458, 1987. 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. WHP Operation and methods: dissolved oxygen by C.H. Culberson, 1991. Wilke, R.J., Wallace, D.W.R., and Johnson, K.M., 1993. Water-based gravimetric method for the determination of gas loop volume. Anal. Chem. 65, 2403-2406. Williams, P.J.LeB and N.W. Jenkinson, A transportable microprocessor- controlled precise Winkler titration suitable for field station and shipboard use. Limnol. Oceangr., 1982; 27:576-584. Zhang, J-Z., C. Fischer and P. B. Ortner, (2001) Continuous flow analysis of phosphate in natural waters using hydrazine as a reductant, International Journal of Environmental Analytical Chemistry, 80(1): 61-73. Zhang, J-Z., C. Fischer and P. B. Ortner, (2000) Comparison of open tubular cadmium reactor and packed cadmium column in automated gas- segmented continuous flow nitrate analysis. International Journal of Environmental Analytical Chemistry, 76(2):99-113. Zhang, J-Z., P. B. Ortner and C. Fischer, (1997a) Determination of nitrite and nitrate in estuarine and coastal waters by gas segmented continuous flow colorimetric analysis. EPA's manual " Methods for the determination of Chemical Substances in Marine and Estuarine Environmental Matrices - 2nd Edition". EPA/600/R-97/072, September 1997. Zhang, J-Z., and G. A. Berberian, (1997b) Determination of dissolved silicate in estuarine and coastal waters by gas segmented continuous flow colorimetric analysis. EPA's manual " Methods for the determination of Chemical Substances in Marine and Estuarine Environmental Matrices - 2nd Edition". EPA/600/R-97/072, September 1997. TABLE 1: Principal Investigators PROJECT NAME INSTITUTION -------------------------- -------------------- ----------- CTD Gregory Johnson PMEL Salinity Gregory Johnson PMEL CTD/O2 Gregory Johnson PMEL Chlorofluorocarbons (CFCs) John Bullister PMEL Chlorofluorocarbons (CFCs) Mark Warner UW HCFs Shari Yvon-Lewis AOML Total CO2(DIC), pCO2 Richard Feely PMEL Total CO2(DIC), pCO2 Richard Wanninkhof AOML Nutrients Calvin Mordy PMEL Nutrients Jia-Zhong Zhang AOML Dissolved Oxygen Jia-Zhong Zhang AOML Helium/tritium Peter Schlosser LDEO Total Alkalinity Frank Millero Miami pH Frank Millero Miami Trace Metals Christopher Measures Hawaii Trace Metals William Landing FSU Aerosols William Landing FSU ADCP Eric Firing Hawaii ALACE Float deployment Breck Owens WHOI ALACE Float deployment Silvia Garzoli AOML PIC/POC Jim Bishop LBNL DOC Dennis Hansell Miami 13-C, 14-C Ann McNichol WHOI Alkyl Nitrate Eric Saltzman UCI Bathymetry Ship personnel Underway thermosalinograph Ship personnel TABLE 2: Cruise Personnel Leg Position Name Institution Country 0 1 2 ------------------ ------------------- ------------- ------- - - - Chief Scientist John Bullister PMEL US * * Co-Chief Scientist Nicolas Gruber UCLA Swiss * * Data Manager Frank Delahoyde SIO US * * Grad Student Nicole Lovenduski UCLA US * Grad Student Elena Brambilla SIO Italy * Grad Student Regina Cesario UW US * CTD Data Processor Kristene McTaggart PMEL US * * ET Douglas Anderson AOML US * ET David Bitterman AOML US * LADCP Julia Hummon UH US * * Salinity Gregory Johnson PMEL US * Salinity David Wisegarver PMEL US * O2 George Berberian AOML US * * Nutrients Jia-Zhong Zhang AOML US * Nutrients David Wisegarver PMEL US * Nutrients Charles Fischer AOML US * Nutrients Calvin Mordy UW-JISAO/PMEL US * CFC Mark Warner UW US * * CFC Eric Wisegarver PMEL US * * Helium/Tritium LDEO * * HCFC Shari Yvon-Lewis AOML * * Alkalinity & pH Xiaorong Zhu UM China * * Alkalinity & pH Taylor Graham UM US * * Alkalinity & pH Mike Trapp UM US * Alkalinity & pH Vanessa Koehler UM US * * * Alkalinity & pH William Hiscock UM US * * Alkalinity & pH David Sergio Valdes UM Mexico * Alkalinity & pH Denis Pierrot UM France * DIC1 Esa Peltola AOML US * * DIC2 Robert Castle AOML US * * pCO2 Dana Greeley PMEL US * * pCO2 Kevin Sullivan UM-CIMAS/AOML US * Trace Metal Chris Measures UH Chile * * Trace Metal Rodrigo Torres WHOI US * * * Trace Metal Matt Brown UH * Aerosol William Landing FSU US * * * Aerosol Clifton Buck FSU US * * * Aerosol Erik Kvaleberg FSU Norway * Aerosol Anthony Arguez FSU US * POC/PIC Jim Bishop LBNL US * POC Alexey Mishonov TAMU Ukraine * DOC Stacy Brown UM US * Alkyl Nitrate Elizabeth Dahl UCI CIRIMS-IR-SST Trina Litchendorf UW US * The Chief Survey Technician aboard the R/V Ronald Brown for the cruise was Jonathan Shannahoff. TABLE 3: PARTICIPATING INSTITUTIONS AOML NOAA, ATLANTIC OCEANOGRAPHIC & METEOROLOGICAL LABORATORY 4301 Rickenbacker Causeway Miami, FL 33149-1098 FSU FLORIDA STATE UNIV. DEPARTMENT OF OCEANOGRAPHY 0102 OSB, West Call Street Tallahassee, FL 32306 LBNL EO LAWRENCE BERKELEY NATIONAL LABORATORY 1 Cyclotron Road Berkeley, California 94720 LDEO THE LAMONT-DOHERTY EARTH OBSERVATORY 61 Route 9W Palisades, NY 10964-1000 PMEL NOAA, PACIFIC MARINE ENVIRONMENTAL LABORATORY 7600 Sand Point Way NE Seattle, WA 98115-0070 SIO SCRIPPS INSTITUTION OF OCEANOGRAPHY 8602 La Jolla Shores Drive La Jolla, CA. 92037 TAMU TEXAS A&M UNIV., DEPARTMENT OF OCEANOGRAPHY College Station TX 77843-3146 UCI UNIV. OF CALIFORNIA, IRVINE, EARTH SYSTEM SCIENCE Irvine, CA 92697-3100 UCLA UNIV. OF CALIFORNIA, INSTITUTE OF GEOPHYSICS AND Planetary Physics & Dept. of Atmospheric Sci 5853 Slichter Hall, Los Angeles, CA 90095-1567 UCSD UNIV. OF CALIFORNIA, SAN DIEGO 9500 Gilman Drive La Jolla, CA 92093 - 0214 UH UNIV. OF HAWAII, DEPARTMENT OF OCEANOGRAPHY, Univ. of Hawaii at Manoa 1000 Pope Rd, Marine Sci. Bldg, Honolulu, HI 96822 UM UNIV. OF MIAMI 4301 Rickenbacker Causeway, Miami, Florida 33149 UM-CIMAS UNIV. OF MIAMI/COOPERATIVE INSTITUTE FOR Marine and Atmospheric Studies 4301 Rickenbacker Causeway, Miami, Florida 33149 UW UNIV. OF WASHINGTON Box 357940, Seattle, WA 98195-7940 UW-JISAO UNIV. OF WASHINGTON/JOINT INSTITUTE FOR STUDY OF THE ATMOSPHERE AND OCEAN Box 357940, Seattle, WA 98195-7940 WHOI WOODS HOLE OCEANOGRAPHIC INSTITUTION Co-op Building, MS #16 Woods Hole, MA 02543 TABLE 4: Dissolved Inorganic Carbon Duplicate Statistics Duplicate Statistics: | BB | BM | ME | BE | DC | DI |BEBE| MM | EE |Deleted --------|--------|-------|-------|------|-------|------|----|------|------|------- Avg: | 0.8 | 1.3 | 1.2 | 1.3 | 1.4 | 0.7 | - | 1.3 | 1.0 | Stdev: | 0.80 | 0.94 | 0.57 | 1.27 | 0.86 | 0.42 | - | 1.01 | 0.30 | Number: | 94 | 39 | 13 | 8 | 56 | 3 | 0 | 6 | 3 | 64 Total: | 286 | | | | | | | | | BB The duplicate samples were measured back-to-back BM One duplicate was measured in the beginning and the other one in the end of the cell ME One duplicate was measured in the middle and the other one in the end of the cell BE One duplicate was measured in the beginning and the other one in the end of the cell DC The duplicates were run on a same instrument, but on different cells DI The duplicates were run on different instruments BEBE Both duplicates were measured in the beginning of the cell, but not back-to-back MM Both duplicates were measured in the middle of the cell, but not back-to-back EE Both duplicates were measured in the end of the cell, but not back-to-back TABLE 5: Dissolved Inorganic Carbon (DIC) Duplicates Pres DIC Stn Cast Btl (db) µmol/kg Stdev --- ---- --- ----- ------- ----- 1 1 1 200 2145.9 0.38 1 1 11 2 2099.3 1.71 2 1 1 553 2157.6 0.36 2 1 18 2 2105.8 0.86 3 1 1 1,009 2157.6 1.23 5 1 1 1,816 2161.5 0.81 5 1 8 1,000 2157.2 1.23 6 1 29 2 2085.1 1.11 7 1 29 2 2079.5 0.15 8 1 30 2 2068.8 0.52 10 1 32 2 2064.4 0.16 11 1 12 1,051 2168.3 0.72 11 1 33 3 2064.7 1.19 12 1 32 2 2062.6 0.25 13 1 33 2 2063.3 0.86 15 1 1 1,647 2161.9 0.50 15 1 27 2 2090.1 0.60 16 1 1 1,168 2172.1 0.70 17 1 21 2 2082.7 0.87 19 1 1 1,464 2159.3 1.70 21 1 26 9 2088.8 0.54 22 1 25 6 2083.1 0.17 23 1 1 1,418 2160.7 0.05 24 1 31 3 2088.7 0.04 25 1 1 2,706 2190.1 0.41 25 1 26 125 2128.7 0.03 25 1 32 2 2080.1 1.84 26 1 33 3 2090.8 0.22 27 1 1 3,812 2203.2 0.18 27 1 13 1,050 2166.7 0.80 29 1 14 1,100 2172.0 0.51 29 1 35 20 2086.3 1.75 30 1 33 2 2082.2 0.74 31 1 1 4,472 2204.0 1.60 31 1 13 1,050 2180.3 0.49 32 1 35 2 2075.3 0.98 33 1 1 4,482 2201.4 0.27 33 1 14 1,002 2177.5 0.49 34 1 33 3 2072.3 0.60 36 1 24 8 2079.6 0.34 41 1 20 1,001 2180.5 0.13 41 2 24 4 2069.7 0.50 42 1 23 25 2070.1 0.05 43 1 1 4,066 2197.4 0.75 43 1 14 1,003 2182.1 1.45 43 1 35 4 2070.2 0.25 TABLE 5: Dissolved Inorganic Carbon (DIC) Duplicates (Continued) Pres DIC Stn Cast Btl (db) µmol/kg Stdev --- ---- --- ----- ------- ----- 44 2 32 3 2067.4 0.03 45 1 1 5,240 2200.0 0.53 45 1 14 1,001 2184.3 1.73 45 1 35 3 2067.2 0.68 46 1 33 3 2067.6 2.01 47 1 1 2,458 2169.3 1.26 47 1 10 1,049 2192.6 1.47 47 1 31 3 2068.4 0.28 48 2 30 3 2070.7 0.49 49 1 1 4,775 2197.9 1.64 51 1 15 1,046 2190.3 0.05 51 1 35 3 2069.7 2.05 52 1 1 4,734 2198.0 1.72 52 1 33 4 2069.9 0.91 53 1 1 4,826 2201.0 1.04 53 1 14 900 2179.3 1.10 53 1 32 19 2066.9 0.53 54 1 35 3 2068.2 1.82 55 2 1 5,218 2200.6 0.14 55 2 17 950 2189.1 0.43 55 2 30 92 2099.1 0.25 55 2 35 4 2085.9 0.29 57 2 1 3,875 2196.1 0.64 57 2 35 4 2086.4 0.60 58 1 35 4 2092.6 2.11 59 1 15 1,051 2194.2 1.71 59 1 35 3 2090.1 1.04 60 1 33 3 2089.6 0.32 61 2 1 5,215 2201.5 0.26 61 2 17 992 2185.1 0.81 61 2 35 4 2085.9 0.67 62 1 35 3 2095.4 0.30 63 2 1 5,319 2200.1 0.71 63 2 14 1,051 2190.1 0.01 63 2 35 3 2107.4 0.93 64 1 35 4 2094.4 1.43 65 1 1 5,343 2198.8 0.36 65 1 33 3 2109.3 1.39 66 1 35 3 2105.5 0.78 67 2 1 5,252 2200.5 0.72 67 2 17 951 2190.2 1.62 67 2 35 4 2104.1 1.84 68 1 17 942 2186.7 1.25 68 1 35 3 2108.3 0.62 69 1 1 5,317 2199.7 2.33 69 1 14 1,002 2187.6 0.54 69 1 35 4 2101.5 0.27 70 1 33 3 2103.2 0.02 71 1 1 5,332 2199.4 0.99 71 1 17 951 2186.6 0.59 71 1 35 3 2103.0 0.17 72 2 1 5,332 2198.1 0.41 72 2 17 950 2188.8 0.57 TABLE 5: Dissolved Inorganic Carbon (DIC) Duplicates (Continued) Pres DIC Stn Cast Btl (db) µmol/kg Stdev --- ---- --- ----- ------- ----- 72 2 31 65 2095.3 0.92 72 2 35 3 2109.7 1.77 74 1 1 5,275 2199.4 1.87 74 1 14 1,000 2191.4 0.40 74 1 35 4 2111.0 1.54 75 1 35 3 2111.9 0.63 76 1 1 5,306 2198.7 0.80 76 1 13 1,050 2197.3 1.86 76 1 35 4 2112.4 0.05 78 2 1 5,329 2193.8 1.01 78 2 35 3 2103.6 0.05 79 1 35 3 2109.9 0.55 80 1 14 1,000 2196.4 0.57 80 1 35 3 2108.1 0.17 81 1 35 4 2096.7 0.65 82 2 1 5,491 2201.1 0.17 82 2 17 949 2195.7 0.52 82 2 35 4 2100.5 0.04 83 1 35 4 2101.6 0.36 84 1 1 5,551 2202.9 0.88 84 1 17 950 2205.3 0.90 84 1 35 4 2102.1 1.65 85 1 35 4 2097.5 1.73 86 1 35 3 2100.1 0.09 87 1 35 4 2082.8 0.56 88 2 1 5,528 2201.2 0.34 88 2 17 949 2209.3 0.59 88 2 35 4 2086.0 1.88 89 1 35 3 2083.5 0.72 90 1 1 5,125 2198.7 1.31 90 1 14 1,000 2209.0 2.12 91 1 35 3 2065.0 0.53 92 1 1 4,874 2201.0 1.05 92 1 12 1,050 2208.2 1.57 92 1 35 4 2064.0 2.10 94 2 1 4,632 2200.6 0.55 94 2 33 3 2062.8 0.29 95 1 35 4 2064.9 0.47 96 1 1 4,612 2202.5 2.00 96 1 15 950 2216.7 1.24 96 1 35 3 2055.3 0.08 97 1 33 3 2063.7 0.82 98 2 13 1,000 2211.4 0.77 98 2 33 4 2035.1 0.49 100 2 1 3,892 2203.1 0.68 100 2 12 1,050 2220.2 0.19 100 2 33 4 2048.2 0.14 101 1 35 3 2035.8 0.09 104 2 1 5,534 2207.5 1.41 104 2 20 548 2240.9 0.10 104 2 35 3 2040.4 0.24 105 1 35 3 2025.6 0.54 TABLE 5: Dissolved Inorganic Carbon (DIC) Duplicates (Continued) Pres DIC Stn Cast Btl (db) µmol/kg Stdev --- ---- --- ----- ------- ----- 106 2 1 5,796 2198.2 1.94 106 2 35 4 2026.5 0.21 107 1 35 3 2013.5 0.20 108 1 1 5,798 2199.3 0.69 108 1 15 749 2238.0 1.96 108 1 35 3 2018.2 0.69 109 1 35 3 2028.2 0.04 110 2 1 6,071 2198.1 0.24 110 2 35 3 2026.0 0.03 111 1 35 3 2019.1 0.93 112 1 1 5,446 2201.7 0.23 112 1 17 950 2226.5 0.64 112 1 35 3 2004.8 1.92 113 1 35 3 1977.0 0.73 114 1 1 5,296 2205.2 0.96 114 1 14 1,001 2223.8 0.60 114 1 33 20 1978.5 0.50 116 2 1 5,162 2206.6 2.36 116 2 20 424 2226.5 0.18 116 2 35 3 1955.0 0.01 117 1 35 4 1953.3 0.52 118 2 1 4,422 2193.1 2.31 118 2 13 1,000 2224.7 0.83 118 2 33 3 1954.8 0.18 119 1 35 3 1951.9 0.11 120 1 1 4,358 2193.9 1.04 120 1 20 449 2238.3 0.26 120 1 35 4 1944.9 1.08 121 1 35 3 1948.3 0.28 122 2 1 4,577 2197.4 0.16 122 2 13 1,051 2217.4 0.93 122 2 33 10 1986.5 0.30 123 1 35 4 1987.8 1.40 124 1 1 4,088 2195.7 0.12 124 1 35 3 1987.2 0.63 125 1 35 3 1986.0 0.96 126 2 18 550 2218.4 1.62 126 2 33 10 1986.7 0.26 127 1 35 3 1989.8 0.16 128 1 1 3,803 2191.6 0.97 129 1 1 3,932 2194.4 2.15 129 1 13 999 2217.2 0.09 129 1 35 4 1987.8 2.23 130 1 35 3 1995.2 0.45 131 1 1 3,678 2191.5 1.51 132 1 1 3,358 2186.2 1.64 132 1 12 1,052 2212.8 0.68 132 1 33 3 2038.5 1.27 133 1 33 19 2042.0 0.33 134 1 35 4 2043.1 0.28 135 1 1 3,231 2185.0 1.00 135 1 12 1,000 2216.5 0.06 135 1 33 4 2044.8 0.15 TABLE 5: Dissolved Inorganic Carbon (DIC) Duplicates (Continued) Pres DIC Stn Cast Btl (db) µmol/kg Stdev --- ---- --- ----- ------- ----- 136 1 32 3 2044.9 0.02 137 1 33 3 2048.5 1.54 138 2 1 3,187 2182.0 0.95 138 2 11 1,049 2214.8 1.10 138 2 32 3 2049.6 0.21 141 1 1 5,019 2257.0 1.09 141 1 15 1,000 2216.5 0.56 141 1 35 3 2040.2 0.80 144 2 1 5,410 2257.3 0.23 144 2 14 1,050 2215.4 0.10 144 2 35 3 2037.1 0.59 146 1 17 1,000 2215.3 0.21 146 1 35 4 2024.2 2.17 148 2 1 5,807 2255.9 0.61 148 2 17 950 2215.0 1.66 148 2 35 4 2017.4 0.31 150 1 18 1,000 2214.9 0.72 150 1 35 4 2020.1 0.58 TABLE 6: Comparison of results of different water vapor correction routines Key Lat fCO2(20) fCO2(20) fCO2(20) field (N) pressure (final) (cruise) (newH2O) ----- --- -------- -------- -------- -------- 45101 43 5239.7 762.9 765.80 745.8 45102 43 4994.3 765.7 768.80 748.5 45103 43 4499.7 769.5 771.45 751.7 45104 43 3983.9 768.5 770.30 751.8 45106 43 3001.5 758.4 760.50 742.1 45108 43 2000.5 755.2 756.60 738.6 45109 43 1800.0 761.4 762.90 745.3 45111 43 1401.5 746.0 747.80 729.8 45112 43 1200.0 728.4 730.10 712.9 45114 43 1001.0 724.1 725.70 708.1 45115 43 900.3 728.7 730.40 713.2 45116 43 800.7 712.4 714.00 696.6 45117 43 699.6 712.3 713.80 696.9 45118 43 601.3 687.2 689.00 672.7 45119 43 501.0 635.2 637.20 621.3 45121 43 401.1 576.8 578.60 563.8 45123 43 299.7 556.3 557.90 543.4 45125 43 201.0 510.7 512.10 499.1 45127 43 151.0 507.8 509.00 495.7 45129 43 99.7 494.1 495.30 482.3 45130 43 79.6 486.6 487.80 474.8 45131 43 60.0 482.2 483.40 471.7 45132 43 39.5 450.7 451.80 440.2 45133 43 19.9 381.9 384.20 374.2 45135 43 3.4 374.7 375.30 365.6 fCO2(20)(final) final data reduction using the detector XCO2 (dry) output fCO2(20)(cruise) data reduction on cruise using an empirical water vapor correction fCO2(20)(new H2O) data reduction in Jan 2004 using an empirical water vapor correction that was determined post-cruise TABLE 7: Analysis statistics for fCO2(20) Total number of stations 150 Total number of stations sampled for fCO2 (full depth) 67 Total number of Niskin bottles tripped 4823 Total number of Niskin bottles sampled for fCO2 1522 Number of duplicates 140 Number of bad values 6 Number of questionable values 48 TABLE 8: Table OF pCO2 duplicate values Dif. Key (µatm) # number Depth % Dif. Ave. samps Comment ------ ------ ------ --- ----- ----- -------------------- 1101 200.1 4.4 0.7 644 2 B 1111 2 4 0.8 503.1 2 B 5108 999.7 5 0.7 718.9 2 B 9112 1199.8 4.8 0.6 781 2 B 9133 20.5 0.4 0.1 435.8 2 C 10131 19.8 0.3 0.1 409.0 4 A & B, 4 bottles 13105 2101 4.6 0.6 758 2 B 17103 799.7 4.2 0.6 749.6 2 B 18125 3.1 2.5 0.6 453.45 2 B 25106 1700.4 0 0.0 770.8 2 C 25107 1500.5 770.8 1 B, 1 dup bad 26135 2.3 3.6 0.8 453.2 2 B 28235 2.2 424.4 1 B, 1 dup bad 33102 4000.4 1.7 0.2 775.15 2 B 33135 2.5 384 1 B, 1 dup bad 41121 893.9 2.8 0.4 737.9 2 C 43105 3000.8 1.3 0.2 760.15 2 B 45103 4499.7 1.8 0.2 769.5 2 B 45125 201 0.8 0.2 510.7 2 B 45133 19.9 3.2 0.8 381.9 2 B 47103 1999.7 4.2 0.6 751.2 2 B 47113 748.8 3.5 0.5 707.85 2 B 49111 1199.7 2.2 0.3 701.3 2 B 49126 149.4 507.7 1 B, 1 dup bad 49132 20.3 3.9 1.0 371.75 2 B 51113 1457.1 0.5 0.1 750.05 2 B 51135 2.9 2.9 0.8 356.8 2 B 52133 3.6 358.9 1 B, 1 dup bad 53112 1099.9 2.5 0.3 715.4 2 B 53120 400.3 6.4 1.1 571.9 2 B 54104 4304.7 0.5 0.1 762.5 2 B 54111 1437.6 2.5 0.3 715.4 4 A & B, 2 bottles dup 54135 2.8 357.3 1 B, 1 dup bad 56133 3.2 3.3 0.9 359.7 2 B 57205 2492.3 3.3 0.4 745.0 2 B 57221 398.7 1.4 0.2 597.1 2 B 61204 4297.4 1.9 0.2 763.2 2 B 61215 1300.5 2.9 0.4 740.4 2 B 61230 100.7 1.6 0.4 409.8 2 B 63202 4999.8 1.7 0.2 765.4 2 B 63214 1050.6 1.4 0.2 725.8 2 B 65102 5001.8 2.4 0.3 765.4 2 B 65108 2000.5 3.8 0.5 735 2 B 65114 1099.3 0.6 0.1 766.9 2 B 67203 4707.3 3.4 0.4 770 2 B 67216 1100.5 1.5 0.2 729.1 2 B 67218 800 3.3 0.5 732.2 2 B 69104 4000.4 2.5 0.3 765.3 2 B 69106 2999.5 0 0.0 757.1 2 B 69112 1199.3 2.7 0.4 739.3 2 B 71107 3349.7 761.5 1 B, 1 dup bad 71110 2650.8 1.8 0.2 751 2 B 71113 1750 0 0.0 731.2 2 B 72207 3549.7 0.3 0.0 760.5 2 B 72210 2650.2 0.2 0.0 750.8 2 B 72213 1749 1 0.1 733.7 2 B 74103 4500.1 0.1 0.0 766.4 2 B TABLE 8: Table OF pCO2 duplicate values (Continued) Dif. Key (µatm) # number Depth % Dif. Ave. samps Comment ------ ------ ------ --- ----- ----- -------------------- 74107 2500.1 4.6 0.6 752.2 2 B 75135 3.2 0.9 0.3 331.3 2 B 76103 4244.4 760.2 1 B, 1 dup bad 76107 2248.6 1.9 0.3 749.4 2 B 76110 1499.2 1.2 0.2 764.5 2 B 78202 5000 3.4 0.4 765.1 2 B 78206 2998.9 0.3 0.0 755.9 2 B 80102 4150 7.1 0.9 758.3 2 B 80106 2949.8 0.3 0.0 755.1 2 B 80110 1750.6 0.8 0.1 762.8 2 B 80126 190 0.3 0.1 420.1 2 B 82203 4747.8 1.3 0.2 766.4 2 B 82207 3549 0 0.0 761.6 2 B 84102 5299.6 2 0.3 770.5 2 B 84106 3799.5 0.6 0.1 768.1 2 B 84112 1899.2 0.6 0.1 765 2 B 84116 1099.9 0.4 0.0 897.9 2 B 86101 5611.2 1.8 0.2 766.1 2 B 86105 4399.6 2.1 0.3 765.6 2 B 88204 4449.5 0.3 0.0 766.5 2 B 88206 3849 1.7 0.2 763.0 2 B 88217 949.2 1.9 0.2 1002.1 2 B 90105 3499.8 3.9 0.5 761.6 3 A & B 90115 898.3 3.3 0.3 1078.4 2 B 94203 4002 0.4 0.1 764.8 2 B 94206 2499.6 0.9 0.1 764.45 2 B 94215 799.2 1151.3 1 B, 1 dup bad 96103 4150.3 0.7 0.1 766.95 2 B 96106 3250.3 0.9 0.1 765.55 2 B 98203 3997.9 770.4 1 B, 1 dup bad 98205 2996.7 757.4 1 B, 1 dup bad 100204 2797.3 756.4 1 B, 1 dup bad 100206 2200 0.4 0.1 762.5 2 B 100214 849.5 3.7 0.3 1183.9 2 B 104205 4147.9 2.1 0.3 779.15 2 B 104207 3548.8 1.8 0.2 760.9 2 B 104213 1748.6 0.8 0.1 791.7 2 B 106206 3998.4 0.6 0.1 777 2 B 106209 2798.8 1.8 0.2 757.5 2 B 108112 1299.2 2.6 0.3 947.7 2 B 108135 2.7 2.3 0.8 285.25 2 B 110205 4400.3 1.2 0.2 777.9 2 B 110212 1899.9 1.8 0.2 763.4 2 B 110226 199.4 8.3 0.8 1048.7 2 B 112105 4148 0.4 0.1 770.6 2 B 112120 550.1 1.6 0.1 1433 2 B 112133 14.5 1.6 0.6 277.8 2 B 114103 4500.9 3.2 0.4 776.2 2 B 114110 1600.6 0 0.0 804.7 2 B 116203 4249.5 0.4 0.1 776.1 2 B 116207 2249.5 0.7 0.1 755.3 2 B 116216 749.2 2.8 0.2 1336.6 2 B 118203 3999.4 3.9 0.5 771.6 2 B TABLE 8: Table OF pCO2 duplicate values (Continued) Dif. Key (µatm) # number Depth % Dif. Ave. samps Comment ------ ------ ------ --- ----- ----- -------------------- 118211 1199.5 5 0.5 1053.1 2 B 118224 199.6 5.2 0.6 873.7 2 B 118233 3.2 0.6 0.2 252.3 2 C 118235 3.1 1.6 0.6 252.6 2 B 120103 3599.9 0.4 0.1 775 2 B 120108 2000 767.1 1 B, 1 dup bad 120129 99.3 0 0.0 596.1 2 B 122204 2999.6 0.2 0.0 769.8 2 B 122212 1149.3 2.9 0.3 1037.1 2 B 124105 2401.5 1.7 0.2 760.0 2 B 124123 300.6 2.2 0.2 1099.6 2 B 126203 3398.7 0 0.0 774.1 2 B 126208 1899.2 0 0.0 758.3 2 B 126225 185.5 3 0.4 855.2 2 B 129103 3098.8 2.7 0.4 770.75 2 B 129133 19.6 0.7 0.3 267.05 2 B 130116 747.7 0.7 0.1 1177.2 2 B 130125 184.6 5 0.6 815.6 2 B 130129 90.4 6 0.8 756.8 2 B 131113 1049.3 1 0.1 1090.7 2 A & B,1 dup bad 132103 2900.3 0.8 0.1 768.2 2 B 132115 750.7 2.5 0.2 1185.1 2 B 132130 50.4 0.4 0.1 323.4 2 B 133133 19.1 1.1 0.4 313.3 2 B 135105 1899.3 1.6 0.2 757.4 2 B 135114 799.4 0.2 0.0 1177.5 2 B 135128 79.6 1.5 0.4 419.25 2 B 138203 2599.7 2.4 0.3 765.1 2 B 138207 1599.3 0.9 0.1 780.0 2 B 138231 10 0.2 0.1 318.7 2 B 141104 3999.6 1.5 0.2 799.75 2 B 141114 1199.6 1016.4 1 B, 1 dup bad 141126 219.8 2.2 0.2 933.8 2 B 144203 4599.9 2.1 0.2 962.55 2 B 144209 1899.6 0 0.0 750.2 2 B 146103 4898.9 5.5 0.6 993.05 2 B 146110 2800 0.7 0.1 764.85 2 B 146126 199.8 0 0.0 910.2 2 B 148203 4998.7 2.3 0.2 1001.15 2 B 148220 548.4 3.8 0.3 1238.8 2 B 150133 25.7 1.1 0.4 293.15 2 B ------------------------------------------- Average 2.0 0.3 Stdev 1.7 0.3 Values were labeled questionable or bad based on the quality control procedures listed below. A = from same sample bottle B = from same Niskin C = from different Niskins sampled at same depth TABLE 9: Total Alkalinity (TA) Certified Reference Material Measurements (DIC and pH values have been calculated from TA titrations) pH (total scale) Total TA µmol/kg DIC kg/kg @ 25°C Runs --------------- ------------ ------------ ---------------- ----- LEG 1 System 1 2222.2 ± 3.6 2015.0 ± 3.7 7.891 ± 0.007 15 System 2 2224.2 ± 3.2 2017.7 ± 3.4 7.893 ± 0.007 17 LEG 2 System 1 2222.5 ± 4.5 2012.1 ± 2.4 7.895 ± 0.009 16 System 2 2222.9 ± 3.8 2016.1 ± 4.1 7.890 ± 0.009 15 Manual Sys 2217.2 ± 2.1 2013.4 ± 0.5 7.888 ± 0.006 3 BOTH LEGS System 1 2222.4 ± 3.8 2013.6 ± 3.4 7.891 ± 0.011 33 System 2 2223.6 ± 3.5 2017.0 ± 3.8 7.891 ± 0.008 30 Manual Sys 2217.2 ± 2.1 2013.4 ± 0.5 7.888 ± 0.006 3 ALL SYSTEMS 2222.7 ± 3.6 2015.2 ± 3.5 7.891 ± 0.009 66 CERTIFIED VALUES CRM Batch 59 2220.98 2007.1 7.895a 7.9674 ± 0.0005b 19 TRIS 8.0855 ± 0.0003a 19 CORRECTION FACTOR LEG 1 System 1 0.9994 0.9961 0.004 System 2 0.9980 0.9947 0.002 LEG 2 System 1 0.9988 0.9975 0.000 System 2 0.9991 0.9958 0.005 Manual Sys 1.0017 0.9969 0.007 TABLE 10: Replicate analyses of dissolved oxygen concentration from the test CTD cast Niskin Depth Stn Bottle (m) DO (µm) ---- ------ ----- ------- test 1 170 277.2 test 2 170 277.2 test 3 170 276.9 test 4 170 277.1 test 5 170 276.8 test 6 170 276.8 test 7 170 277.1 test 8 170 276.8 test 9 170 276.7 test 10 170 277.4 test 11 170 277.6 test 12 170 274.5* test 13 170 277.9 test 14 170 277.2 test 15 170 277.3 test 16 170 276.8 test 17 170 277.4 test 18 170 276.9 test 19 170 277 test 20 170 276.8 ------------------------------ Average 277.1 STDV 0.03 * Outlier in replicate analyses not included in the average and possibly due to errors in bottle volumes or sampling. TABLE 11: Replicate analyses of dissolved oxygen concentration (µmol/L) by Winkler titration from same Niskin bottle or different bottles at same depth Station Sample Replicate 1 Replicate 2 Replicate 3 Replicate 4 ------- ------ ----------- ----------- ----------- ----------- 1 1 276.1 266.8* 1 4 279.1 279.4 1 8 266.7 289.2 1 11 297.2 296.1 2 2 262.8 262.2 2 18 297.2 302.7* 297.4 4 1 287.1 161.1* 5 4 277.3 266.3* 5 25 276.2* 279.9 6 1 302.1* 288.1 6 12 245.4 245.3 7 8 250.4 249.9 7 14 269.9* 261.1 10 6 286.6 286 10 32 306.3 306.8 11 4 286.2 286.5 11 35 307.6 308.3 307.6 12 23 273.1 273.4 14 3 277.5 278 14 32 275.1 275.6 15 7 232.4 232.1 15 "27, 28" 274.3 275.6 16 2 241.1 241.6 16 24 279.8 279.9 19 4 264 264.5 19 "26, 27" 274.6 281.7* 20 4 231.1* 227.4 20 17 258 257.8 21 "25, 26" 275.5 275.1 24 7 265.7 265.1 24 25 259 259.3 25 5 284.3 284.3 25 20 241 241 25 28 263.8 264.4 26 "33, 35" 268.3 267.9 28 2 243.7 244.2 30 9 275.6 276.6 30 31 271.9 271.7 32 27 194 194.2 34 "33, 35" 269.6 270.2 40 1 270.2* 246.5 43 6 268.8 268.6 43 17 196.5 192.9 44 7 263.9 264.1 45 2 247 246.9 45 35 248.7 249.4 46 10 208.2 208.4 47 7 229.7 229.9 47 "31, 32" 247.1 247 49 33 240 239.8 TABLE 11: Replicate analyses of dissolved oxygen concentration (µmol/L) by Winkler titration from same Niskin bottle or different bottles at same depth (continued) Station Sample Replicate 1 Replicate 2 Replicate 3 Replicate 4 ------- ------ ----------- ----------- ----------- ----------- 51 15 195.5 195.9 51 32 278.3 278.6 52 11 200.4 200.1 52 32 240.2 240.4 53 "33, 35" 237.9 237.7 54 14 190.1 191.5 54 31 261.4 261.4 55 7 251.2 250.6 55 31 260 259.9 57 6 264.9 265.4 57 33 238.1 237.8 60 1 250.9 250.8 250.8 60 13 218.7 216.1 216.9 60 29 236 235.5 235.4 60 "11,5.0" 248.1 247.7 246.3 247.3 61 1 258.9 253.3* 61 2 253.1 251.7 61 5 251.7 252 252.6 61 7 252.9 253.1 62 1 250.9 251 62 3 251 250.8 62 5 250.8 250.7 62 7 251 251.5 63 8 261 260.9 261.5 63 13 190.1 190.1 190 63 17 187.9 187.6 187.9 63 24 212.6 212.8 212.5 63 29 234.3* 240 241.6 63 33 242.3 242.2 64 4 251.4 250.8 64 12 186.8 182.4* 64 30 237.6 237.8 65 1 251.1 251 65 4 251.8 251.6 65 17 170.6 170.6 66 3 251.6 251.4 66 9 247.4 246.8 66 15 181.1 181 180.8 66 28 228.2 228.8 67 7 251.2 250.8 251.1 67 20 191.6 191.5 191.6 68 1 251.6 251.8 68 3 251.6 251.9 68 7 251.3 251.5 68 16 189.5 189.7 68 25 209.5 209.4 68 33 226.2 226.1 69 1 251.1 251.3 69 3 251.5 251.3 69 5 250.9 250.6 TABLE 11: Replicate analyses of dissolved oxygen concentration (µmol/L) by Winkler titration from same Niskin bottle or different bottles at same depth (continued) Station Sample Replicate 1 Replicate 2 Replicate 3 Replicate 4 ------- ------ ----------- ----------- ----------- ----------- 69 16 180.9 181.3 69 33 229.8 229.8 70 9 246.1 245.8 70 22 213.5 213.1 70 "12,3.0" 192.2 191.3 71 1 251.6 251.9 71 5 251.4 251.6 71 18 169.8 170 71 30 242.8 242.9 72 12 246.3 246 72 28 217 217.1 73 1 246.5 246.6 73 3 246.9 246.6 73 5 245.9 246.2 73 16 161.8 162.4 73 33 213.8 213.8 74 1 246.1 246.3 74 4 247.3 247 74 17 171.6 171.6 74 21 195.4 195 74 33 214 214.1 74 35 213.6 213.8 75 1 246.4 246.4 75 5 246.9 246.6 76 1 246.6 246.7 76 4 247 246.8 76 18 182.5 182.3 77 1 247.3 246.4 77 5 246.8 247 77 23 197.8 197.4 78 4 246.4 246.8 78 10 214.2 214.4 79 1 246.3 246.8 79 5 246.1 246 79 18 154* 158.2 79 33 212.7 212.5 80 3 249.2 249.3 80 14 161.4 161.1 80 32 229.9 229.7 81 1 249.3 249.6 81 2 249.6 249.8 82 2 249.8 249.6 82 28 213 212.6 83 1 249.3 249 83 5 249.3 248.9 83 18 132.2 132.2 84 3 238.4* 249.3 84 15 181.4 181.6 85 1 248.6 249.2 85 2 248.8 249.2 TABLE 11: Replicate analyses of dissolved oxygen concentration (µmol/L) by Winkler titration from same Niskin bottle or different bottles at same depth (continued) Station Sample Replicate 1 Replicate 2 Replicate 3 Replicate 4 ------- ------ ----------- ----------- ----------- ----------- 86 1 249.7 248.8 86 5 249.2 248.8 86 19 131.2 130.8 87 1 254.6 254.2 87 19 130 130.3 88 1 254.5 254 88 16 173 172.8 89 1 253.8 253.5 89 3 252.3 253.8 89 5 252.2 251.9 89 16 133 131.7 90 2 253.3 253.8 90 18 116.2 115.7 91 1 252.9 252.4 91 18 94.70 95.20 92 1 251.9 251.8 92 2 251.7 252 92 18 110.9 110.3 92 33 215.7 215.8 94 2 249 249.3 94 14 117.9 117.5 95 1 256.4* 245.3 95 6 243.2 243.4 95 23 74.00 73.90 96 2 243.5 243.2 96 22 70.50 70.80 96 32 220.8 220.2 97 2 246.8 246.9 97 18 93.20 96* 98 2 245.9 249.2* 98 19 81.00 80.60 98 32 209 209 99 2 248.1 248 99 21 94.80 95.00 99 23 94.00 93.90 100 2 250.5 250.7 100 22 76.50 76.20 100 32 211.2 211 101 1 250.9 251.2 101 19 71.60 71.60 104 2 252 251.9 104 23 72.90 72.90 104 33 206.7 206.7 105 1 253.1 253.3 105 4 250.1 249.9 105 25 79.30 79.70 106 2 253.9 253.6 106 22 59.50 59.50 106 33 206.8 206.6 107 1 252 252.2 TABLE 11: Replicate analyses of dissolved oxygen concentration (µmol/L) by Winkler titration from same Niskin bottle or different bottles at same depth (continued) Station Sample Replicate 1 Replicate 2 Replicate 3 Replicate 4 ------- ------ ----------- ----------- ----------- ----------- 107 18 70.30 70.20 107 32 206.6 206.2 108 2 253.4 254.2 108 21 51.00 51.20 108 32 211.6 211.8 109 2 254.1 254.4 254.2 109 14 225.3 225.5 109 22 50.40 51.70 110 2 254.4 254.5 110 21 51.40 51.00 111 4 250.7 250.8 111 24 67.70 67.50 111 30 83.30 83.70 112 4 253.6 254.5 112 24 96.20 96.40 112 32 179.8 179.9 113 5 254.3 254 113 17 92.70 92.70 113 23 89.60 89.50 114 6 255.5 255.9 114 25 102.3 102.1 114 32 186.4 186.5 115 1 249 249.2 115 21 64.60 64.50 115 33 205.5 205.2 116 2 252.1 252.2 116 20 77.60 77.30 116 32 207.9 207.8 117 4 259.6 259.9 117 22 63.70 63.00 118 2 257 257.1 118 19 62.60 62.20 118 33 206.8 206.9 119 1 254.8 254.7 119 22 55.60 55.40 119 35 206.6 206.9 120 4 254.8 255.1 120 24 140 140.3 120 33 205.4 205.1 121 3 255.2 255.1 121 19 70.00 69.90 121 33 206.7 206.5 122 2 255.4 255.3 122 18 87.80 87.60 122 33 209.1 209 123 1 252 252 123 17 131.6 131.8 123 29 155.3 155.1 124 3 255.6 256 124 28 137.2 137.4 TABLE 11: Replicate analyses of dissolved oxygen concentration (µmol/L) by Winkler titration from same Niskin bottle or different bottles at same depth (continued) Station Sample Replicate 1 Replicate 2 Replicate 3 Replicate 4 ------- ------ ----------- ----------- ----------- ----------- 124 30 205.5 205.8 125 1 253 253.4 125 19 112.8 113.8 125 35 255 254.7 126 4 256.2 256.3 126 13 160.7 161 126 26 98.70 98.10 127 4 257 257.4 127 28 99.40 98.90 127 33 209.2 209.1 128 2 259.3 259.1 128 16 153.7 153.9 128 28 96.70 96.30 129 3 255 255 129 19 136.7 136.9 129 32 207.2 207.5 130 1 253.6 253.4 130 35 213.5 213.2 131 3 257.6 258 131 26 108.5 108.7 131 33 212.3 212.4 132 4 253.6 253.3 132 19 121.5 121 132 28 132.5 132.5 133 1 261.2 261 133 23 105.4 105.3 133 32 204.6 204.8 134 1 257.9 257.7 134 23 96.80 96.60 134 35 210.5 210.3 135 6 245.9 245.9 135 20 116.9 116.6 135 33 208.8 208.8 136 1 256.6 256.2 136 8 229.2 229.6 136 26 175.7 175.5 137 2 256.9 257.2 137 24 113.4 113.3 137 32 209.3 209.5 138 2 255.8 256 138 20 83.20 83.00 138 31 208.9 209.1 139 2 232.5 232.2 139 23 95.80 95.60 140 3 240.9 241.2 140 23 70.10 70.30 140 31 207.3 207.5 141 3 236.2 236.3 141 15 166.4 166.7 141 32 209.1 209.2 TABLE 11: Replicate analyses of dissolved oxygen concentration (µmol/L) by Winkler titration from same Niskin bottle or different bottles at same depth (continued) Station Sample Replicate 1 Replicate 2 Replicate 3 Replicate 4 ------- ------ ----------- ----------- ----------- ----------- 143 13 158.7 158.9 144 2 230.2 230.3 144 15 158.9 158.8 144 31 169.2 169.5 145 1 228 228.1 145 23 104.3 104.7 145 35 212.9 212.7 146 4 234.1 234.3 146 16 174.5 174.3 146 25 101.8 101.9 147 4 233.2 233.6 147 28 106.3 106.3 147 33 209.7 209.7 148 1 228.6 229.2 148 23 90.70 90.60 148 33 210.3 210 149 2 228.9 228.6 149 24 86.50 86.20 149 35 208.4 208.4 150 3 231.1 231.2 150 24 85.90 86.20 150 31 205.6 205.6 TABLE 12: After cruise recalibration of the volumes (cm3) of the oxygen bottles Old New Bottle Volume Volume Difference ------ ------- ------- ---------- 1 145.853 145.610 -0.243 2 145.200 145.209 0.009 3 145.318 149.967 4.649 4 143.917 143.908 -0.009 5 139.471 138.748 -0.723 6 145.464 145.470 0.006 7 145.443 145.441 -0.002 8 152.778 152.796 0.018 9 142.276 146.019 3.743 10 145.662 145.666 0.004 11 143.687 143.643 -0.044 12 145.292 147.003 1.711 13 142.335 142.307 -0.028 14 141.151 145.220 4.069 15 145.456 145.507 0.051 16 145.908 145.897 -0.011 17 145.645 145.644 -0.001 18 144.759 144.734 -0.025 19 142.898 142.913 0.015 20 143.300 143.310 0.010 21 146.299 141.180 -5.119 22 144.406 147.777 3.371 23 145.704 148.320 2.616 24 141.570 152.070 10.500 25 145.085 145.109 0.024 26 145.599 145.606 0.007 27 147.751 146.772 -0.979 28 144.469 144.459 -0.010 29 147.404 147.396 -0.008 30 146.101 146.131 0.030 31 146.039 146.004 -0.035 32 145.111 145.152 0.041 33 145.501 145.501 0.000 34 146.663 146.678 0.015 35 143.309 143.347 0.038 36 147.371 147.429 0.058 37 146.290 150.489 4.199 38 140.623 144.152 3.529 39 146.959 151.425 4.466 40 144.179 144.183 0.004 41 139.747 141.192 1.445 42 143.726 150.186 6.460 43 146.369 146.369 0.000 44 142.137 142.137 0.000 45 142.478 142.478 0.000 46 143.805 143.805 0.000 47 143.494 143.500 0.006 48 145.665 142.890 -2.775 49 144.254 144.254 0.000 50 145.715 141.225 -4.490 51 147.807 147.809 0.002 52 146.055 146.055 0.000 53 143.431 143.431 0.000 54 143.347 145.342 1.995 55 144.658 144.715 0.057 56 146.009 146.032 0.023 57 142.607 144.083 1.476 58 145.371 145.372 0.001 59 144.344 144.343 -0.001 60 145.292 145.244 -0.048 61 146.185 146.159 -0.026 62 142.781 142.786 0.005 63 144.319 144.307 -0.012 64 144.039 144.042 0.003 65 145.311 149.630 4.319 66 144.080 144.153 0.073 67 143.908 143.892 -0.016 68 137.386 146.368 8.982 TABLE 12: After cruise recalibration of the volumes (cm3) of the oxygen bottles (continued) Old New Bottle Volume Volume Difference ------ ------- ------- ---------- 69 145.505 145.539 0.034 70 143.273 143.276 0.003 71 146.396 146.377 -0.019 72 145.602 145.555 -0.047 73 145.019 145.027 0.008 74 146.627 146.634 0.007 75 144.237 144.236 -0.001 76 144.935 144.856 -0.079 77 146.540 146.552 0.012 78 143.597 143.551 -0.046 79 142.704 148.421 5.717 80 146.607 145.227 -1.380 81 147.842 147.813 -0.029 82 145.624 145.493 -0.131 83 149.920 143.503 -6.417 84 149.503 142.045 -7.458 85 143.718 143.666 -0.052 86 145.641 145.552 -0.089 87 143.796 143.654 -0.142 88 140.322 140.321 -0.001 89 138.752 138.633 -0.119 90 138.785 138.658 -0.127 91 145.587 142.249 -3.338 92 144.516 142.404 -2.112 93 151.851 149.504 -2.347 94 145.714 145.720 0.006 95 149.465 149.364 -0.101 96 151.184 148.882 -2.302 97 144.609 144.592 -0.017 98 152.251 152.200 -0.051 99 144.545 144.552 0.007 100 147.346 147.187 -0.159 101 139.500 139.479 -0.021 102 149.319 149.298 -0.021 103 147.485 147.484 -0.001 104 138.295 138.310 0.015 105 139.030 139.035 0.005 106 144.610 144.606 -0.004 107 148.793 148.778 -0.015 108 146.952 146.951 -0.001 109 149.911 149.928 0.017 110 146.285 142.968 -3.317 111 149.657 141.784 -7.873 112 142.400 143.215 0.815 113 143.206 143.217 0.011 114 139.272 139.267 -0.005 115 139.648 139.631 -0.017 116 141.125 141.138 0.013 117 141.218 142.124 0.906 118 147.477 147.484 0.007 119 148.834 148.847 0.013 120 147.002 147.023 0.021 121 144.803 144.080 -0.723 122 141.945 141.949 0.004 123 143.415 143.134 -0.281 124 145.482 144.116 -1.366 125 145.685 145.706 0.021 126 144.523 144.527 0.004 127 145.756 145.780 0.024 128 140.523 140.521 -0.002 129 143.820 143.811 -0.009 130 145.730 138.828 -6.902 131 145.849 145.855 0.006 132 145.156 145.146 -0.010 133 145.696 145.673 -0.023 134 143.807 143.807 0.000 135 148.692 148.692 0.000 136 141.083 141.083 0.000 137 143.675 143.675 0.000 TABLE 12: After cruise recalibration of the volumes (cm3) of the oxygen bottles (continued) Old New Bottle Volume Volume Difference ------ ------- ------- ---------- 138 145.247 145.247 0.000 139 144.459 144.459 0.000 140 143.336 143.336 0.000 141 143.962 143.971 0.009 142 144.590 142.608 -1.982 143 145.759 145.776 0.017 144 137.683 145.339 7.656 145 145.356 145.346 -0.010 146 142.249 142.273 0.024 147 145.810 145.800 -0.010 148 144.984 144.954 -0.030 149 146.996 146.998 0.002 150 145.100 145.094 -0.006 151 142.395 142.369 -0.026 152 144.586 144.983 0.397 153 147.093 147.102 0.009 154 145.219 142.119 -3.100 155 150.067 150.055 -0.012 156 138.514 143.383 4.869 157 148.070 144.191 -3.879 158 145.740 145.788 0.048 159 143.852 143.853 0.001 160 145.975 145.999 0.024 161 144.786 144.785 -0.001 162 144.560 144.304 -0.256 163 146.144 146.096 -0.048 164 144.518 144.296 -0.222 165 144.623 144.514 -0.109 166 141.617 141.524 -0.093 167 144.192 144.162 -0.030 168 145.917 145.651 -0.266 169 145.682 145.604 -0.078 170 146.535 146.342 -0.193 171 139.221 139.144 -0.077 172 150.611 150.569 -0.042 173 145.165 145.101 -0.064 174 145.379 145.303 -0.076 175 144.814 144.744 -0.070 176 141.770 141.687 -0.083 177 143.827 143.722 -0.105 178 145.031 144.941 -0.090 179 145.668 143.528 -2.140 180 147.606 147.524 -0.082 TABLE 13: Shipboard standardization of thiosulfate solution during A16N_2003a cruise THIO STANDARD STARTING ENDING BOTTLE FILE STATION STATION INTERCEPT SLOPE REMARKS ------ -------- -------- ------- --------- ------ ----------------- 1 2 1 4 -0.004 24.743 2 6 4 8 0.1515 24.585 3 7 7 15 0.1155 23.87 4 9 16 18 0.0885 24.635 5 10 19 23 0.1117 24.312 6 11 24 29 0.05 24.96 7 15 30 37 0.143 24.495 8 16 37 46 0.1255 24.135 9 17 46 50 0.0405 24.845 10 18 51 58 0.0072 24.988 11 21 59 61 0.0042 25.075 12 22 62 65 -0.0015 25.005 13 23 66 71 -0.0025 24.87 14 24 72 79 -0.01 25.355 Digital Pipette 15 25 80 86 -0.0007 24.97 16 26 87 92 0.008 24.755 17 27 93 97 0.002 24.735 18 30 98 98 0.0045 24.92 19 30G 98 106 0.0057 24.873 19 0.001 24.89 End of the Bottle 20 31G 107 115 0.002 24.88 21 0.0096 24.719 5-20ml KIO3 21 32G 116 123 0.0043 24.747 2-16ml KIO3 22 33G 124 131 0.0056 24.757 23 35G 132 140 0.0097 24.753 24 36G 141 148 0.0063 24.682 24 0.009 24.685 Repeat 25 37G 149 150 0.007 24.697 25 38 0.007 24.678 25 39 0.0039 24.649 ------------------------------------------------------------------------- AVERAGE 0.03015 24.7421 TABLE 14: Post cruise comparison of volume delivery of a manual and the problematic automatic pipette used for stations 72-79 by standardization of KIO3 solution with same batch Na2S2O3 solution. The correction of 1.01531 was applied to all samples in this station range. AUTOMATIC MANUAL RUN FACTOR INTERCEPT R2 FACTOR INTERCEPT R2 RATIO --- --------- --------- ------ -------- --------- ------ -------- 1 25.050 -0.0023 1.0000 24.577 0.0127 1.0000 2 25.035 -0.0008 1.0000 24.690 0.0057 1.0000 3 25.017 -0.0005 1.0000 24.685 0.0040 1.0000 4 25.205 -0.0052 1.0000 24.673 0.0050 1.0000 5 25.067 0.0012 1.0000 24.687 0.0063 1.0000 6 24.990 0.0022 1.0000 24.690 0.0070 1.0000 7 25.112 -0.0030 1.0000 24.670 0.0065 1.0000 8 25.047 0.0030 1.0000 24.700 0.0060 1.0000 9 25.290 -0.0063 1.0000 24.685 0.0075 1.0000 10 24.910 0.0040 1.0000 24.658 0.0075 1.0000 11 24.861 0.0050 1.0000 24.697 0.0065 1.0000 12 24.693 0.0083 1.0000 --- --------- --------- ------ -------- --------- ------ -------- AVG 25.05309 -0.0002 24.67542 0.0069 1.015306 STD 0.120788 0.0037 0.03323 0.0022 RSD 0.5% 0.1% APPENDIX WOCE QUALITY FLAG DEFINITIONS FOR WATER BOTTLES. Flag Definition ---- -------------------------------------- 1 Bottle information unavailable 2 No problems noted 3 Leaking 4 Did not trip correctly 5 Not reported 7 Unknown problem 9 Samples not drawn from this bottle WOCE WATER QUALITY FLAG DEFINITIONS. Flag Definition ---- -------------------------------------- 1 Sample drawn but analysis not received 2 Acceptable measurement 3 Questionable measurement 4 Bad measurement 5 Not reported 6 Mean of replicate measurements 9 Sample not drawn for measurement DATA PROCESSING NOTES DATA CONTACT DATA TYPE DATA STATUS SUMMARY -------- --------- ------------- -------------------------------------------- 04/01/03 Swift CTD/BTL List of cruise parameters Here is the current parameter list for the 2003 A16N son-of-WOCE cruise. Kristin Sanborn of ODF gave me the list. She has been working with Bob Williams on preparations for the bottle data processing on that cruise. Of course some of the water samples generate many individual parameters. An asterisk after a value indicates it comes from the CTD computer. An f before a value indicates it's a flag. stnnbr castno btlnbr (bottle serial number) sampno (niskin number + castno*100) lat (decimal degrees) lon (decimal degrees) year* month* day* hour* min* second* (decimal seconds) ctdprs* ctdsal* fctdsal ctdtmp* ctdoxy* fctdoxy trans* (Bishop tranmissometer) pic* (Bishop particulate inorganic carbon) scatter* (Bishop scatter meter) sigma0* theta* cfc11 fcfc11 cfc12 fcfc12 cfc13 fcfc13 ccl4 fccl4 hcfc22 (AOML HCFC-22) fhcfc22 ch3cl (methyl chloride) fch3cl ch3br (methyl bromide) fch3br aomlcfc11 (AOML cfc-11) faomlcfc11 hcfc141b (AOML HCFC-141b) fhcfc141b ch3i (methyl iodide) fch3i aomlcfc13 (AOML cfc13) faomlcfc13 aomlccl4 (AOML ccl4) faomlccl4 tcarbn ftcarbn pco2 fpco2 nitrat fnitrat nitrit fnitrit phspht fphspht silcat fsilcat oxygen foxygen hel3 fhel3 tritum ftritum alkali falkali ph fph doc fdoc don fdon There appear to be two different CFC groups working at the same time on A16N, each apparently drawing their own samples. 08/27/03 Bullister CTD/BTL/SUM Raw shipboard prelim data available via ftp You have my permission to obtain the data from Frank and post them at the website. You should include the caveats that these data are the raw shipboard version, are still preliminary and will be updated. 09/04/03 Bullister DOC Submitted This is from John Bullister and is the project instructions document for A16N_2003a (Ron Brown). It's the closest thing that he had to cruise docs, but he's working on a preliminary post- cruise report. When he completes the work-in-progress, we should replace the new doc with the one he's working on now. 09/08/03 McTaggart CTD Submitted available on NOAA ftp site A16N preliminary CTD data files in WOCE format are ready for you on our FTP site: ftp.pmel.noaa.gov under /ctd/woce/a16n. DATA CONTACT DATA TYPE DATA STATUS SUMMARY -------- --------- ------------- -------------------------------------------- 09/08/03 Diggs CTD Data retrieved from NOAA ftp site I have received your files and am checking them over. 09/10/03 Delahoyde BTL/SUM BTL Parameters Submitted: BTLNBR CTDRAW CTDPRS CTDTMP CTDSAL CTDOXY THETA SALNTY OXYGEN SILCAT NITRAT NITRIT PHSPHT CFC-11 CFC-12 CFC113 TCO2 TALK PH PCO2 These data were provided by: PARAMETER/PROGRAM | NAME | EMAIL ADDRESS --------------------|-----------------------|----------------------------- Chief Scientist | John Bullister/PMEL | bullister@pmel.noaa.gov CTDO/S/O2/nutrients | Greg Johnson/PMEL | gjohnson@pmel.noaa.gov Nutrients | Calvin Mordy/PMEL | mordy@pmel.noaa.gov | Jia-Zhong Zhang/AOML | zhang@aoml.noaa.gov Total CO2(DIC),PCO2 | Dick Feely/PMEL | feely@pmel.noaa.gov | Rik Wanninkhof/AOML | rik.wanninkhof@noaa.gov CFC | John Bullister/PMEL | bullister@pmel.noaa.gov CFC | Mark Warner/UW | mwarner@ocean.washington.edu HCFs | Shari Yvon-Lewis/AOML | syvon@aoml.noaa.gov He/Tr | Peter Schlosser/LDEO | peters@ldeo.columbia.edu 14C/13C | Ann McNichol/WHOI | amcnichol@whoi.edu The data included in these files are preliminary, and are subject to final calibration and processing. They have made available for public access as soon as possible following their collection. Users should maintain caution in their interpretation and use. Following American Geophysical Union recommendations, the data should be cited as: "data provider(s), cruise name or cruise ID, data file name(s), CLIVAR and Carbon Hydrographic Data Office, La Jolla, CA, USA, and data file date." For further information, please contact one of the parties listed above or whpo@ucsd.edu. Users are also requested to acknowledge the NSF/NOAA-funded U.S. Repeat Hydrography Program in publications resulting from their use. A16N water property codes for WOCE ".sum" file "PROPERTIES" column: Water Water Water Water Code Property Code Property Code Property Code Property ---- -------- ---- -------- ---- -------- ---- -------- 1 Salinity 8 CFC-12 25 PCO2 101 PIC 2 O2 9 Tritium 26 PH 102 Al 3 SIO3 10 He 27 CFC-113 103 Fe 4 NO3 12 del14C 32 DON 104 AlkNO3 5 NO2 13 del13C 40 POC 105 Carbohydrates 6 PO4 23 TCO2 43 DOC 106 CDOM 7 CFC-11 24 TALK 100 HCFCs DATA CONTACT DATA TYPE DATA STATUS SUMMARY -------- --------- ------------- -------------------------------------------- 09/26/03 McTaggart CTD Submitted There is a file for you on our anonymous FTP site, ftp.pmel.noaa.gov, under /ctd/woce/a16n. It's called a16n_allo.clb and it is the preliminary calibrated discrete CTD measurements and associated sample salinities and oxygens. In generating this file, I found an error I had made in applying the preliminary calibrations to the profile data. The .ctd files now on our FTP site are correct and should be downloaded again. I apologize for this oversight. And I changed the expocode in the header to be a 13-character string instead of a 12-character string as it is on the WHPO website (e.g. suffix '_01' instead of '_1'). 09/29/03 Diggs CTD Website Updated CTD submitted and online CTD data recalibrated. Updated versions of the ctd and ctd- exchange on website. 10/03/03 Johnson CTD/BTL Defined ctd/nuts/O2 PIs For A16N please keep me (Gregory Johnson) as PI for CTD/O2 and S, but Mordy & Zhang for nutrients, and Zhang for bottle O2. 10/20/03 Diggs CTD/SUM/BTL Website Updated with Formatted files CTD, SUM, BTL available along with Exchange formatted versions on WHPO website. 10/22/03 Diggs CTD/BTL Website Updated; Citation added to files Repackaged all zip files (WOCE CTD, Exchange CTD, and WOCE Bottle w/ SUM) with new citation files per request from Talley and Swift). 10/29/03 Diggs SUM/CTD/BTL Updated archive citations Updated all citations (00_README files) embedded in each zip archive as well as the Exchange formatted bottle file. Bottle Exchange updated to reflect accurate ExpoCodes for each station from updated summary file. 10/30/03 Kappa DOC Cruise Report PDF & ASCII versions Updated • added links from TOC to text in PDF version • made a text version • added these WHPO-SIO Data Processing Notes 11/03/03 Coartney Cruise Report Website Updated; New PDF & ASCII docs online 01/30/04 Diggs CTD/BTL/SUM Website Updated; line identifiers changed Corrected all cruise line identifiers to A16N (from A16N_2003A) as per Jim Swift's request. 02/20/04 Kappa Cruise Report Updated PDF & ASCII versions made 06/11/04 Diggs CTD Website Updated; missing files added A transmission error occurred from PMEL to SIO, resulting in only 80 files being at the WHPO. Alison MacDonald from WHOI noticed the problem. I re-ftp'd the files, format checked them, convert them to Exchange, and put all of the ftp files back on the website. All checks out. DATA CONTACT DATA TYPE DATA STATUS SUMMARY -------- --------- ------------- -------------------------------------------- 10/27/04 Hansell DOC/TDN Submitted data & sampling procedures report The data disposition is: Public The file format is: Plain Text (ASCII) The archive type is: NONE - Individual File The data type(s) is: Bottle Data (hyd) • Dissolved Organic Carbon • Total Dissolved Nitrogen for A16N2003 Line • Documentation The file contains these water sample identifiers: • Cast Number (CASTNO) • Station Number (STATNO) • Bottle Number (BTLNBR) • Sample Number (SAMPNO) HANSELL, DENNIS would like the following action(s) taken on the data: • Merge Data • Place Data Online 12/10/04 Kozyr Cruise Report Submitted CO2 report I am attaching here 3 files with reports on measured carbon fields. You will have to decide what and how much information you need for cruise report. 12/10/04 Kozyr CO2 Submitted TCARBN, TALK, pH, and pCO2 I have just submitted the final TCARBN, TALK, pH, and pCO2 data for A16_2003 cruise for merging into the hydrographic data file. Could you with the new numbers. Please, let me know if you have any questions regarding the data. 12/10/04 Kozyr CO2 Submitted This is information regarding line A16N_2003 ExpoCode: 33RO200306_01 33RO200306_02 Cruise Date: 2003/06/19 - 2003/08/11 From: KOZYR, ALEX Email address: kozyra@ornl.gov Institution: CDIAC/ORNL Country: USA The file: a16n_2003_carbn_final.txt - 308958 bytes has been saved as: 20041210.063700_KOZYR_A16N_2003_a16n_2003_carbn_final.txt in the directory: 20041210.063700_KOZYR_A16N_2003 The data disposition is: Public The bottle file has the following parameters: TCARBN, TALK, PCO2, PH The file format is: WOCE Format (ASCII) The archive type is: NONE - Individual File The data type(s) is: Bottle Data (hyd) The file contains these water sample identifiers: Cast Number (CASTNO) Station Number (STATNO) Bottle Number (BTLNBR) Sample Number (SAMPNO) KOZYR, ALEX would like the following action(s) taken on the data: Merge Data Any additional notes are: This is the final bottle TCARBN, TALK, pH, and pCO2 data. I have merged these numbers from two different files I received from PMEL and AOML CO2 measurement groups. New quality flags were assigned according to QA-QC work. Please let me know if you need more information on these data. DATA CONTACT DATA TYPE DATA STATUS SUMMARY -------- --------- ------------- -------------------------------------------- 12/10/04 Anderson CO2 Website Updated OnLine Copied files submitted by A. Kozyr from INCOMING to .../a16n_2003a/original_data/20041210_KOZYR_A16N_2003. These files contain updated TCARBN, TALK, PCO2, and PH. I will merge into online file. 12/17/04 Bullister Cruise Report Submitted Final cruise report 12/29/04 Mordy NUTs Submitted by Calvin Mordy Date: Wed, 29 Dec 2004 13:44:00 -0800 (PST) From: WHPO Website To: Calvin.W.Mordy@noaa.gov, jrweir@odf.ucsd.edu, whpo@ucsd.edu Subject: WHPO DATA A16N: BOT from MORDY This is information regarding line: A16N ExpoCode: 33RO200306_01 _02 Cruise Date: 2003/06/04 - 2003/08/11 From: MORDY, CALVIN Email address: Calvin.W.Mordy@noaa.gov Institution: NOAA/PMEL Country: USA The file: A16N-Apr14nuts-submitted.xls - 1207296 bytes has been saved as: 20041229.134359_MORDY_A16N_A16N-Apr14nuts- submitted.xls in the directory: 20041229.134359_MORDY_A16N The data disposition is: Public The bottle file has the following parameters: SILCAT, NITRAT, NITRIT, PHSPHT The file format is: MS Excel (Binary) The archive type is: NONE - Individual File The data type(s) is: Bottle Data (hyd) The file contains these water sample identifiers: Cast Number (CASTNO) Station Number (STATNO) Bottle Number (BTLNBR) MORDY, CALVIN would like the following action(s) taken on the data: Merge Data Place Data Online Update Parameters Any additional notes are: Data are provided in µmole/l and µmole/kg. The lab temperature and the CTD bottle salts that were used in the unit conversion are also provided. 12/30/04 Bullister Cruise Report Submitted Oxygen Data Report The cruise we did was A16N_2003 (not p16n_2003). I forwarded Jim Swift's directive (see next message) to all the investigators on A16N_2003 last February, advising them to forward data and documentation directly to the CCHDO-WHPO. I'll send out another reminder. In addition to the carbon data and documentation, I have copies here of the revised CTD and bottle salinity data from Kristy McTaggart, revised CFC data from our group, revised oxygen data (and documen- tation) from Z. Zhang, and revised nutrient data from Calvin Mordy. I can send you these individual files as attachments to the next message. I have merged all of these revised data files into Frank Delahoyde's A16n2003 shipboard file to create a master data file in the .sea format. I can also sent this to you. Unfortunately, I am heading out tomorrow for the A16S cruise and can't do much more before I leave. I will have all the a16n2003 data with me on the cruise and should be able to answer questions by e- mail. My address should be: john.bullister.atsea@rbnems.ronbrown.omao.noaa.gov DATA CONTACT DATA TYPE DATA STATUS SUMMARY -------- --------- ------------- -------------------------------------------- 01/18/05 Anderson CO2 Website Updated, data OnLine ...File Jan. 18, 2005 a16n_2003a 33RO200306_01 Merged the carbon data (TCO2, TALK, PH, and PCO2) sent by A. Kozyr Dec. 10, 2004 re his email below into online file. Made new exchange and NetCDF files. Date: Fri, 14 Jan 2005 14:18:05 -0500 From: Alexander Kozyr Subject: A22_2003 Alkalinity data To: Sarilee Anderson Thank you very much Sarilee. Did you make a new exchange file as well? Could you check A16N_2003a files? I've sent the final carbon-related data (TCARBN (or TCO2), ALKALI, pH, and pCO2) for this section on 12/10/2004 to WHPO but did not see any changes in your files. When you merge these data, please make sure that you merge all four parameters, because from the first look it seems like TCARBN and pH are the same, but in reality we PIs changed some numbers and flags for both. 02/14/05 Kappa Cruise Report Replaced "Cruise Instructions" The bulk of this cruise report was submitted by Alex Kozyr on 12/10/04. It includes sections on: • TCARBN • Fugacity of CO2 • ALKALI • pH • Nutrients • Oxygen • Figures • Tables Both the PDF and ASCII cruise reports also contain the WHPO/CCHDO summary pages, and these Data Processing Notes. Figures are found only in the PDF version. The PDF version also has links from text to figures and tables, PDF bookmarks and PDF thumbnails. 03/10/05 McTaggart CTD Submitted Data Processing Report Attached is the CTD documentation file I gave to John Bullister along with the CTD bottle data last November. He said it was incorporated into a document with oxygens and nutrients etc. and submitted to WHPO. 03/15/05 Kappa CTD Added CTD Data Processing report 05/19/05 Locarnini CTD Data Update: oxy values corrected Please, notice that all CTD dissolved oxygen values for 33RO200306, STNNBR 018, CASTNO 1, are equal to 0.0 (Zero) and have a Quality Flag equal to 2 (Two). 06/21/05 Anderson TOC/TDN Data, Exchange, and NetCDF files online a16n_2003a 33RO200306_01 and 33RO200306_02 Merged the DOC (dissolved organic carbon) and TDN (total dissolved nitrogen) submitted by Dennis Hansell on Oct. 27, 2004. Many values of -9.00 had flag of 2 or 3, I changed the flags for values of -9.00 to 9. There was one level that was not in the online file and therefore was not merged, see below. STNNBR CASTNO SAMPNO BTLNBR DOC DOCF TDN TDNF kg/kg kg/kg 150 1 1 1 39.51 2 33.66 2 Made new exchange and NetCDF files. Sarilee Anderson DATE CONTACT DATA TYPE DATA STATUS SUMMARY -------- --------- ------------- -------------------------------------------- 08/29/05 Kozyr DOC/TDN Submitted Final Data I tried to submit some files to CCHDO through your web site, but it would not work, it would ask me to complete the form, but form was completely completed :-) and I did not know what it wanted from me. So, the attached file is the final and public DOC and TDN data measured during the A16N_2003a cruise (33RO200306_01_02). Could you please merge these data and their quality flags into the main hydrographic files. Please, let me know when the updated files will be available online. 09/06/05 Anderson DOC/TDN Data Online; No exchange file yet Merged the final DOC and TDN data submitted by Alex Kozyr (see B. Key 8/26/05 email) into the online file. No apparent problems. Was not able to make the exchange file Program needs to be modified to accept DOC and TDN. 09/22/05 Bullister Cruise Report Submitted cruise report and cfc report 09/22/05 Bullister BTL Submitted updated BTL files I was the Chief Scientist on the repeat hydrography cruise A16N_2003a (Cruise ExpoCode 33RO200306_01). I did a quick check to compare the shipboard data file from A16N_2003a to the files currently at the web site: http://whpo.ucsd.edu/data/CO2clivar/atlantic/a16/a16n_2003a/index.htm I think the bottle hydro values (ctdprs, ctdtmp, ctdsal, salnty, ctdoxy, fctdsal, fsalnty, fctdoxy), dissolved oxygen, nutrients, and CFCs have not been updated from the shipboard versions. Last year I asked the individual PI's to send their updated A16N_2003a data to the CCHDO office directly, as per Jim Swift's instructions. I also sent copies I had of the updated hydro, oxygen, nutrient and CFC data to the office some time ago I think it is important to get the updated versions of the data merged into your web site files In the next message I will attach the following files: a16n_allo.flg (revised bottle file of ctdprs, ctdtmp, ctdsal, salnty, ctdoxy, fctdsal, fsalnty, fctdoxy data, prepared by Kristy McTaggart at PMEL) A16NBottleOxygenFinal_may21_2004.xls (Excel spreadsheet of revised oxygen data, from Jia-Zhong Zhang at AOML; data are in per liter units) A16NBottleOxygenFinal_may21_2004working.txt.sent to WOCE* (ASCII version of oxygen data I extracted from above Excel spreadsheet. I changed 5 oxygen flags in this file; data are in per liter units). A16nuts-apr14.xls (Excel spreadsheet of revised nutrient data from Calvin Mordy at PMEL; data are in per liter units) A16nuts-apr14working.txt (ASCII version of revised nutrient data I extracted from above spreadsheet; data are in per liter units) a16n2003_cfc.dat (ASCII listing of revised CFC data from John Bullister; data are in per kg units) flag changes (a file describing the flag changes I applied to the master bottle data file I keep here at PMEL. These mostly change the parameter flags for samples where the fbtlnbr is 3, 4 or 9) I would be extremely grateful if you could let me know that you have received these files, if you have any questions or comments on the files, and when the data have been merged into the web site version of the A16N_2003a data set DATE CONTACT DATA TYPE DATA STATUS SUMMARY -------- --------- ------------- -------------------------------------------- 09/23/05 Locarnini CTDOXY Update Needed Please, notice that all CTD dissolved oxygen values for 33RO200306, STNNBR 018, CASTNO 1, are equal to 0.0 (Zero) and have a Quality Flag equal to 2 (Two). 09/23/05 Anderson CTDOXY Data values corrected as per Locarnini • Station 18 oxygens were all 0.0, but the Q flag was 2 • I changed the flags to 9 for all oxygens • Made new zip file with corrected sta. 18, and made a new exchange file • I was unable to make a NetCDF file at this time 09/26/05 Mordy Cruise Report Submitted nutrients report Here is a more informative version of the A16N cruise report for nutrients. 10/12/05 Kappa Cruise Report Doc Update Added new Chi Sci, PI reports: • New cruise report contains • John Bullister's cruise summary, OXY and CFC reports, • Mordy's nutrients report, • K. McTaggart's CTD report, and • NOAA/PMEL CO2 report; as well as • CCHDO data processing notes. 10/27/05 Bullister BTL Final Data Submitted Updates prelim data files, see 9/22/05 10/28/05 Bishop XMISS Data availability: 1/2006 I am responsible for the data and it's final workup. There were significant data dropouts in records during A16N. FYI, results from A16S should be available about the same time as those for A16N. I estimate completion to be approximately January 2006. We had two successive years when funding did not appear as expected (this year a 4 month gap) and all NOAA related work had to stop. 10/28/05 Anderson BTL Updating files from Bullister I am working on merging, updating the a16n_2003a line using the files the Bullister sent yesterday. 12/12/05 Smith MET Submitted Hello John, I just wanted to let you know that we received the meteorological data from your A16N cruise from the Ronald Brown's The data underwent quality control at FSU and are available as part of a larger set of Ron Brown meteorology data at: http://www.coaps.fsu.edu/RVSMDC/cgi-bin/nonwoce-ship.cgi?id=WTEC 01/19/06 Kappa Cruise Report Updated Added Chief Scientist Report Deleted redundant Oxygen Report Updated these Data Processing Notes DATE CONTACT PARAMETER EVENT SUMMARY -------- ----------------- --------- --------------- --------------------------------- 01/30/06 Jim Bishop XMISS Submitted raw data only A16N_2003 & A16S_2005 wil be completed together All I can do is work forward on this. A16N and A16S data will be completed together, after Ocean Sciences. The raw data are on line at SIO. 05/10/06 John L. Bullister CrsRpt To go online OK'd by Bullister Thanks for sending the file. I read through it and it looks OK. 05/22/06 Alexander Kozyr DOC Submitted None I submitted the DOC data from P02_2004 and A16N_2005 using CCHDO submission page. I received the A20 and A22 DOC data files from you, so I guess you have these files, but I did not see the DOC numbers for these cruises were merged at CCHDO yet. Here are attached 3 files for DOC data from P02_2004, A16N_2003, and A16S_2005 cruises. Please, let me know if you received these files OK and when are you planning to merge these data. 09/06/06 Sarilee Anderson DOC/TDN Website Updated Data OnLine; no exchange Sept. 6, 2006 Merged the final DOC and TDN data submitted by Alex Kozyr (see B.Key 8/26/05 email) into the online file. No apparent problems. Was not able to make the exchange file. Program needs to be modified to accept DOC and TDN. 11/15/06 Alexander Kozyr CO2 status summary None Here are the latest update on the Carbon Data status at CCHDO and CDIAC. A16N_2003: TCO2 - OK; TALK - OK; pCO2 - OK; pH - OK; DOC, DTN - data were not merged in CCHDO exchange file. 03/02/07 Wilford Gardner POC/PON Submitted None File: a16n1POC_submission-redo2.xls Type: Excel Status: Public Name: Gardner, Wilford D Institute: Texas A&M University Country: USA Expo:33RO2003_01 Line: A16N Date: 06/2003 Action:Merge Data,Place Data Online Notes: These are POC and PON bottle data Upload directory: /incoming_data/20070307.070610_A16N_Gardner,_Wilford_D DATE CONTACT PARAMETER EVENT SUMMARY -------- ----------------- --------- --------------- --------------------------------- 03/28/07 Alexander Kozyr PH Update Needed Do Not Use pH data for A16N_2003 have major problems and will be revised. I am going to put a note on a web that nobody should use pH numbers at this time. Could you do the same, please? I will send you new numbers as soon as I get the new file from Frank Millero. 10/04/07 Alexander Kozyr CO2/PH Submitted New params: FCO2, FCO2_TMP, PH_SWS, PH_TMP Type: Status: public Name: Kozyr, Alex Institute: CDIAC/ORNL Country: USA Expo:33RO200306_01 Line: A16N_2003a Date: 2003-06-04 Action:Merge Data, Place Online, Updated Parameters Notes:Please, replace all carbon-related parameters with these ones in the attached file. Note that PCO2 was replaced with FCO2 and extra column for FCO2_TMP, also PH was replaced with PH_SWS (pH on the sea water scale) with extra column for PH_TMP. Please, let me know when the data in this file will be merged with the master file at CCHDO. 01/02/08 Alexander Kozyr CO2 Submitted Replaces all previous CO2 data Please, replace all carbon-related parameters with these. Note that PCO2 was replaced with FCO2 and extra column for FCO2_TMP, also PH was replaced with PH_SWS (pH on the sea water scale) with extra column for PH_TMP. 08/06/08 Wilf Gardner POC/PON Submitted Revision of 7/7/08 data file Attached are two files - a revision of the file you sent and the file we sent in with the data for the bottles. In your revised file we have indicated what to do with each file. As you suspected, many of them should have been posted as cast 2. Most of the others are in-line samples (inflow) or bucket samples for which you don't have any other data. They were taken on station as indicated by the same lat-lon as the stations with which they were associated. You can add these or ignore them as you wish. The stations in question are highlighted in yellow or by a different font color in the other attached file. 07/07/08 Danie Bartolocci POC/PON Website Updated Sumbitted by Wilf Gardner Notes on Completed WOCE Bottle file: Created exchange file with no apparent errors. File named a16n_2003a_hy1.csv Following parameters were not recognized nor included in the exchange file: FCO_TMP PH_SWS PH_SWS_FLAG_W PH_TMP POC POC_FLAG_W PON PON_FLAG_W TDN TDN_FLAG_W The exchange conversion code changed FCO2 to PCO2 during conversion. This was edited back in file. Checked file with JOA, which also calls FCO2 by another parameter name, however this appears to be a JOA bug and FCO2 values appear accurate. Created netcdf files with no apparent errors. Zipped file is named a16n_2003a_nc_hyd.zip DATE CONTACT PARAMETER EVENT SUMMARY -------- ----------------- --------- --------------- --------------------------------- 07/08/08 Danie Bartolocci CO2 Website Updated Submitted by Alex Kozyr 2008.07.08 DBK Merge notes for merging Alex Kozyr's final carbon data into the a16_2003a bottle file. Data submitted by Alex on 10.05.2007. File named a16n_2003a_final_Carbon.csv contained the following parameters: FCO2,FCO2_TMP,PH_SWS_25C,PH_TMP,TALK,TALK_FLAG_W,TCO2,DOC,TDN and their associated quality flags. Instructions as per Alex's web submission entry were: Notes: Please, replace all carbon-related parameters with these ones in the attached file. Note that PCO2 was replaced with FCO2 and extra column for FCO2_TMP, also PH was replaced with PH_SWS (pH on the sea water scale) with extra column for PH_TMP. Please, let me know when the data in this file will be merged with the master file at CCHDO. MERGE NOTES: Original file was .csv and had to be converted to fixed width in order to use merge software mrgsea. mrgsea did not accept FCO2_TMP as an integer for merging. This parameter was edited to a floating point number with precision of 1 (f8.1). PH_SWS missing values of -999.0000 are larger than the woce format allows and were edited to -9.0000. All parameters merged without problems or errors. Ran wocecvt with no errors, however some parameters were unrecognized. 07/09/08 Danie Bartolocci DELC14/13 Website Updated Sumbitted by Bob Key 2008.07.09 DBK Merging notes for C14/13 into a16n_2003a bottle file. file submitted by Bob Key on 2008.06.26 called A16N.2003.CIsotopes.csv contains: DELC14,C14ERR,DELC13 and associated errors All parameters merged with no apparent errors. Checked the format of the file using woccvt. No errors were reported. Bottle file still needs PON/POC data merged. DATE CONTACT PARAMETER EVENT SUMMARY -------- ----------------- --------- --------------- --------------------------------- 07/14/08 Shari Yvon Lewis HCFC Submitted HCFC-22,HCFC142b,HCFC141b 07/14/08 Shari Yvon Lewis CH3 Submitted CH3Cl,CH3Br,CH3I 12/12/08 Chris Measures BTL Submitted Updated Fe/Al params Status: public Action: Updated Parameters Notes: These are the shorebased corrected values of the shipboard generated trace elements Fe and Al. They are in tab delimited text the output from an ODV file containing location, station, bottle cast information etc. Quality flags are assigned using the ODV mapping 0= good, 1=unknown, 4= questionable, 8= bad 08/07/09 Chris Measures Tracers Submitted AL/FE/MAN the data are public parameter names and units Station number Cast number + bottle number Aluminum (unit: nM) Flag Iron (unit: nM) Flag Manganese (unit: nM) Flag 07/31/10 Carolina Berys CH3 Website Update Available under 'Preliminary/Unprocessed' A16N_MeX_HY1.csv submitted by Shari Yvon Lewis on 2008-07-14 available under 'Preliminary/Unprocessed', unprocessed by CCHDO. 08/02/10 Carolina Berys POC/PON Website Update Available under 'Preliminary/Unprocessed' a16n1POC_submission-_149944.xls submitted by Danie Kincadeon behalf of Wilf Gardner on 2008/08/06 available under 'Preliminary/Unprocessed', unprocessed by CCHDO. POC/PON data not merged in Exchange file, these data are merged in WOCE format file. 09/21/10 Carolina Berys CDOM Website Update Available under 'as received' File a16ncdom_final.txt containing CDOM data submitted by Norm Nelson on 2005-04-20, resubmitted by email from Susan Piercy on behalf of Norm Nelson on 2010-09-21, available under 'as received', unprocessed by CCHDO. 09/21/10 Carolina Berys CDOM Submitted resubmission of text file Action: Merge Data Notes: CDOM data submitted by Norm Nelson on 2005-04-20, resubmitted by email from Susan Piercy on behalf of Norm Nelson on 2010-09-21. 08/23/11 Alex Kozyr Carbon Submitted Final data to go online I've just discovered that the CCHDO Exchange file for the a16n_2003a cruise 33RO200306, does not have PH, PH_TMP, PH_FLAG, FCO2_TMP, and TDN data. I'vesend the final carbon data file with all these data to CCHDO on 10.05.2007, according to my notes. Attached is the final a16n_2003a_final_Carbon.csv data file for your use. Please merge the data into CCHDO Exchange file. DATE CONTACT PARAMETER EVENT SUMMARY -------- ----------------- --------- --------------- --------------------------------- 08/24/11 Carolina Berys CO2 Website Updated Exchange, NetCDF files online 2011-08-24 A16N 2003 ExpoCode 33RO200306_01 WOCE to Exchange conversion notes C Berys Converted WOCE bottle file to Exchange using hyd_to_exchange.rb (J Fields) The following changes were made to the WOCE bottle file: FCO_TMP changed to FCO2TMP FCO2TMP units changed from 'ITS-90' to 'DEG C' PH_TMP units changed from 'ITS-90' to 'DEG C' NOTE: Units for PON and POC are 'UMOL/L' which does not match the value in the parameter descriptions table 'UG/KG'. All comment lines from original file copied back into new file following merge NetCDF bottle file created using exbot_to_netcdf.pl (S Diggs), files zipped NetCDF and Exchange files opened in JOA with no apparent problems Working directory: /data/co2clivar/atlantic/a16/a16n_2003a/original/20110823_carbon_cberys 11/22/11 Carolina Berys CDOM Website Updated Updated NetCDF, Exchange, WOCE files online 2011-11-22 A16N 2003 ExpoCode 33RO200306_01 merge notes - CDOM C BerysSUBMISSION a16ncdom_final.txt submitted by Norm Nelson on 2005-04-20, resubmitted by email from Susan Piercy on behalf of Norm Nelson on 2010-09-21, containing CDOM data merged into online file using merge_exchange_bot.rb (J Fields) The following parameters were added: CDOM325 CDOM325_FLAG_W CDOM340 CDOM340_FLAG_W CDOM380 CDOM380_FLAG_W CDOM412 CDOM412_FLAG_W CDOMSL CDOMSL_FLAG_W CDOMSN CDOMSN_FLAG_W The following changes were made to the submission file: added parameter mnemonics and units added cast 1 to all stations in accordance with sum file changed bottle numbers to 3 digits with leading zeros DATE CONTACT PARAMETER EVENT SUMMARY -------- ----------------- --------- --------------- --------------------------------- 11/22/11 Carolina Berys CDOM Website Updated Updated NetCDF, Exchange, WOCE files online ORIGINAL The following changes were made to the original Exchange Bottle file: DEPTH units changed from "" to "METERS" CTDRAW units changed from "" to "DBAR" NOTE: PON and PON have units "UMOL/L" which do not match the expected "UG/KG" MERGED FILE All comment lines from original file copied back in following merge NetCDF bottle file created using exbot_to_netcdf.pl (S Diggs) WOCE bottle file created using exchange_to_wocebot.rb (J Fields) Exchange and NetCDF files opened in JOA with no apparent problems Working directory: /data/co2clivar/atlantic/a16/a16n_2003a/original/2011.11.21_cdom_cberys/ 05/04/12 Jerry Kappa CrsRpt Website Updated new PDF & TXT versions online Additions/changes include: • New CFC report • New Summary/Introduction • New sections on Dissolved Organic Carbon, 14C & Helium/Tritium • Expanded Nutrients report • expanded data processing notes