A. Cruise Narrative: AR01 A.1. Highlights WHP Cruise Summary Information WOCE section designation AR01 Expedition designation (EXPOCODE) 31RBOACES24N_2 Chief Scientist(s) and their affiliation Kitack Lee AOML/CIMAS* Dates 1998.JAN.23 - 1998.FEB.24 Ship Ronald H. Brown Ports of call Las Palmas, Canary Islands to Miami, Florida Number of stations 130 27.965° Geographic boundaries of the stations -79.937 E -13.37 24.4913° Floats and drifters deployed none Moorings deployed or recovered none * Chief Scientist Atlantic Oceanographic and Meteorological Laboratory Cooperative Institute for Marine and Atmospheric Studies 4301 Rickenbacker Cwy Miami, FL 33149-1098 ABSTRACTED FROM NOAA DATA REPORT 0AR AOML-41 Atlantic Oceanographic and Meteorological Laboratory Miami, Florida June 2001 NOAA: National Oceanic and Atmospheric Administration Ocean and Atmospheric Research Laboratories NOTICE Mention of a commercial company, or product does not constitute 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. ELECTRONIC ACCESS TO DATA LISTED IN THIS REPORT The data presented in this report is available on the World Wide Web (WWW) at the following sites: Bottle and CTD data: http://www.aoml.noaa.gov/ocd/oaces/24n98.html UWpCO2 data: http://www.aoml.noaa.gov/ocd/oaces/1998data.html ADCP data: http://ilikai.soest.hawaii.edu/sadcp/woce.html LADCP data: http://www.nodc.noaa.gov/General/NODC-About/NODC- overview.html#services For further information regarding the data sets contact: Ms. Betty E. Huss Data Manager, OACES/GCC at: U.S. Dept. of Commerce NOAA/AOML/OCD 4301 Rickenbacker Causeway Miami, Florida 33149-1026 Phone: (305) 361-4395 Email: huss@aoml.noaa.gov LIST OF PARTICIPANTS Leg 1: Function Name Institution Chief Scientist Gregg Thomas AOML pCO2 Dana Greeley PMEL Total Alkalinity Mary Roche UM M-AERI Jennifer Hanafin UM M-AERI Erica Key UM Leg 2: Function Name Institution --------------------------------------------------- Chief Scientist Kitack Lee AOML/CIMAS Co-Chief Scientist David Bitterman AOML CTD Christiane Fleurant AOML/CIMAS CTD/ET Douglas Anderson AOML CTD Kristene McTaggart PMEL Salinity Gregg Thomas AOML Oxygen/ET Robert Roddy AOML Oxygen George Berberian AOML LADCP Ryan Smith AOML/CIMAS LADCP Richard Sikorski UM LADCP Deanna Spindler UM DIC Marilyn Roberts PMEL DIC Esa Peltola AOML/CIMAS pCO2 Dana Greeley PMEL pCO2 Hua Chen AOML CFC David Wisegarver PMEL CFC Fredrick Menzia PMEL Nutrients Calvin Mordy PMEL/JISAO Nutrients Charles Fisher AOML Total Alkalinity Cindy Moore UM Total Alkalinity Xiaorong Zhu UM pH Jason Joliff UM pH Xuewn Liu UM TOC/TN, and TP Rachel Parsons BBSR TOC/TN, and TP Amy Richie BBSR 13C/12C Tania Westby UW The Chief Survey Technician aboard the R/V RONALD BROWN for the cruise was Jonathan Shannahoff. Institutional Abbreviations: Abbr. Institution Address ---------------------------------------------------------------- AOML Atlantic Oceanographic and 4301 Rickenbacker Cwy Meteorological Laboratory Miami, FL 33149-1098 BBSR Bermuda Biological Station St. Georges, GE-01 for Research Bermuda PMEL Pacific Marine Environmental 7600 Sand Point Way NE Laboratory Seattle, WA 98115-0070 UM University of Miami Rosenstiel School of Marine and Atmospheric Science 4600 Rickenbacker Cwy Miami, FL 33149-1098 CIMAS Cooperative Institute for Marine & Atmospheric Studies UW University of Washington Box 357940 Seattle, WA 98195-7940 JISAO Joint Institute for Study of the Atmosphere and Ocean CONTENTS A. Cruise Narrative A.1. Highlights A.2. Cruise Summary A.3. INTRODUCTION. A.4. DESCRIPTION OF STUDY AREA. B. DATA COLLECTION AND ANALYTICAL METHODS. B.1. HYDROGRAPHIC METHODS B.1.1. CTD AND HYDROGRAPHIC OPERATIONS B.1.2. NUTRIENT ANALYSIS METHODS B.2. CARBON PARAMETERS B.2.1. TOTAL DISSOLVED INORGANIC CARBON (DIC) B.2.2. FUGACITY OF CO2 (fCO2). B.2.3. TOTAL ALKALINITY (TA) B.2.4. pH B.2.5. TOTAL ORGANIC CARBON, TOTAL NITROGEN AND TOTAL PHOSPHORUS B.2.6. 13 C/12 C OF DISSOLVED INORGANIC CARBON B.2.7. CHLOROFLUOROCARBONS (CFC) B.3. UNDERWAY MEASUREMENT METHODS. C.3.1. UNDERWAY fCO2. D. ACKNOWLEDGMENTS E. REFERENCES. FIGURES 1. Cruise track for the Atlantic Ocean AR01 cruise in January and February 1998. 2. All parameters measured vs. depth. 3. The results of the CRM measurements 4. The results of the DIC duplicates during the course of the cruise. TABLES 1. Station locations 2. Results of the certified reference material, CRM 3. Dissolved inorganic carbon duplicates 4. Replicate pCO2 analyses 5. Correction factors applied to raw data based upon carbonate parameters for Certified Reference Materials. 6. Replicate dissolved CFC-11 and CFC-12 analyses 7. Replicate dissolved CFC-113 and CCl4 analyses 8. CFC air measurements 9. CFC air values (interpolated to station locations) A.2. Cruise Summary CHEMICAL AND HYDROGRAPHIC MEASUREMENTS ON A CLIMATE AND GLOBAL CHANGE CRUISE ALONG 24° N IN THE ATLANTIC OCEAN WOCE SECTION AR01 DURING JANUARY-FEBRUARY, 1998 E. Peltola, K. Lee, R. Wanninkhof R. Feely, M. Roberts, D. Greeley, M. Baringer, G. Johnson, J. Bullister, C. Mordy, J.-Z. Zhang, P. Quay, F. Millero, D. Hansell, and P. Minnett ABSTRACT This document contains data and metadata from a zonal cruise along nominally 24.5 °N in the Atlantic Ocean from Las Palmas, Canary Islands in Spain to Miami, Florida. The cruise took place from January 23 to February 24, 1998 aboard the NOAA Ship RONALD H. BROWN under auspices of the National Oceanic and Atmospheric Administration (NOAA). This report presents the analytical and quality control procedures performed during the cruise and bottle data from the cruise. The research was sponsored by the NOAA Climate and Global Change Program under: (i) The Ocean- Atmosphere Carbon Exchange Study (OACES); and (ii) the World Ocean Circulation Experiment (WOCE) repeat hydrography program. Samples were taken from up to 36 depths at 130 stations. The data presented in this report includes the analyses of water samples for: salinity, nutrients, total dissolved inorganic carbon dioxide (DIC), fugacity of carbon dioxide (fCO2), total alkalinity (TA), pH, total organic carbon (TOC), total nitrogen (TN), total phosphorus (TP), chlorofluorocarbons, and stable carbon isotopic ratio of DIC ( 13 C/ 12 C). Basic hydrographic parameters, pressure, CTD salinity, temperature and the calculated potential temperature, and potential density are included as well. List of Principal Investigators Project Name Institution ----------------------------------------------------------- CTD/O2, LADCP, ADCP, Molly Baringer AOML Salinity, Oxygen CTD/O2 Gregory Johnson PMEL pCO2 Richard Wanninkhof AOML Total CO2 Richard Feely PMEL Chlorofluorocarbons (CFCs) John Bullister PMEL Nutrients Calvin Mordy PMEL/JISAO Nutrients Jia-Zhong Zhang NOAA/CIMAS 13C/12C Paul Quay UW Total Alkalinity, pH Frank Millero UM TOC, TN, and TP Dennis Hansell BBSR M-AERI Peter Minnett UM A.3. INTRODUCTION Since the world's oceans have a large capacity to sequester heat and carbon dioxide it is imperative that the oceans are studied in a comprehensive fashion to elucidate changes in the Earth's climate. An overall goal of the research is to observe and model the ocean sufficiently well to understand quantitatively how the ocean effects present climate, and how the ocean might change under a changing atmosphere. Thus, a long-term objective is to provide reliable predictions of climate change and associated regional implications on time scales ranging from seasons to centuries. Current predictions are uncertain, in part, because of poor understanding of source and sink patterns of greenhouse gases like carbon dioxide and the role of the ocean in mitigating or changing the timing of regional patterns associated with warmer climate. This cruise was designed to support research sponsored by the National Oceanic and Atmospheric Administration (NOAA) Climate and Global Change Program under: (i) the Ocean-Atmosphere Carbon Exchange Study (OACES); and (ii) the World Ocean Circulation Experiment (WOCE) repeat hydrography program. The second leg of the cruise was conducted aboard the NOAA Ship RONALD H. BROWN from January 23 to February 24, 1998. The OACES objective of the cruise was to determine the fluxes of CO2 in the North Atlantic during the winter. A baseline of total carbon inventory in this region was established such that the uptake rate of atmospheric CO2 can be determined in future cruises. The objective of the WOCE (repeat) hydrography component was to understand the general circulation of the global ocean well enough to be able to model its present state and predict its evolution. The data presented in this report includes: hydrography, nutrients, total dissolved inorganic carbon dioxide (DIC), fugacity/partial pressure of carbon dioxide (fCO2/pCO2)* , total alkalinity (TA), pH, total organic carbon (TOC), total nitrogen (TN), total phosphorus (TP), chlorofluorocarbons, and stable carbon isotopic ratio of DIC ( 13 C/ 12 C). Detailed information of the CTD operations can be found in NOAA Data Report, ERL PMEL-68 (McTaggart et al, 1999). * The fCO2 takes into account the non-ideality of CO2 gas and is the thermodynamic quantity mostly used in calculations. It is approximately 0.4 to 0.6 % lower than the corresponding pCO2. In this report we used the terms interchangeably. However, all reported values are fugacity values. A.4. DESCRIPTION OF STUDY AREA A total of 130 full water column CTD stations were occupied, complete with water samples analyzed for salinity, oxygen and chlorofluorocarbon (CFC) content. A large amount of high quality measurements of all the carbonate parameters including underway surface water pCO2 and nutrients were also made. The majority of the data were collected along 24.5 o N from 23.5 o W to 69 o W. Completing the transatlantic section were data collected along a NE-SW dogleg off the coast of Africa, and along a second, short, zonal section along 26.5 o N off the coast of Abaco Island from 69 o W to 77 o W, jogging north along 27 o N in the Straits of Florida to 80 o W. The cruise track and station locations are presented in Figure 1 and Table 1. The leg 1 followed this same trackline in the opposite direction, deploying XBTs to sample the temperature in the upper 750 m, and collecting underway pCO2. B. DATA COLLECTION AND ANALYTICAL METHODS One hundred and thirty CTD (Conductivity-Temperature- Depth) hydrographic stations were occupied to collect discrete water samples and hydrographic data. A CTD/Rosette unit with a Seabird-911 CTD instrument equipped with 36, specially designed 10-L samples bottles was utilized for these casts. These bottles have the same outer dimensions as standard Niskin bottles, but are modified to reduce chlorofluorocarbon sample contamination. Water samples were collected for salinity, oxygen, nutrients, chlorofluorocarbons, 13 C/ 12 C, as well as carbon related parameters including total dissolved inorganic CO2 (DIC), discrete fugacity of CO2 (fCO2), total alkalinity (TA), pH, total organic carbon (TOC), total nitrogen (TN), and total phosphorus (TP) on all casts during the cruise using these modified ioNiskinls style bottles. In the data tables the missing values are assigned a value of -9.0. The WOCE quality control flags have been listed in Appendix A. All the parameters plotted versus depth are shown in Figure 2. Detailed information on individual data collection, and analysis procedures may be found in the following method sections. B.1. HYDROGRAPHIC METHODS B.1.1. CTD AND HYDROGRAPHIC OPERATIONS Description of Measurement Techniques and Calibrations CTD AND IN SITU O2 Depth profiles were obtained with a Seabird 911 plus CTD, deck unit, and rosette pylon. The CTD included dual temperature sensors, dual conductivity sensors, two Beckman oxygen sensors, one Paroscientific pressure transducer, and two pumps to decrease the response time. Thirty-six 10-l "Niskin" bottles were mounted on the frame, along with the CTD, pinger, Lowered Acoustic Doppler Current Profiler (LADCP), and LADCP external battery pack. The bottles were specially designed to reduce chlorofluorocarbon contamination. These bottles have the same outer dimensions as standard 10-l "Niskin" bottles, but use a modified end-cap design to minimize the contact of the water sample with the end-cap O-rings after closing. The O-rings used in these water sample bottles were vacuum-baked prior to the first station. Stainless steel springs covered with a nylon powder coat were substituted for the internal elastic tubing standardly used to close "Niskin" bottles. Seabird software was used to acquire, plot, and process the CTD data on PC's. Raw data were stored on VHS tapes, PC hard drives, and SyQuest drives. Typically each cast sampled to within 10 meters of the sea floor as indicated by the pinger signal. The CTD/O2 data were processed and calibrated following Seabird recommendations (CTD Data Acquisition Software and Technical Notes, Sea- Bird Electronics, Inc., 1808 - 136th Place NE, Bellevue, Washington 98005). Exceptional items are noted below. Details can be found in NOAA Data Report, ERL PMEL-68 (McTaggart et al, 1999). Pre- and post-cruise pressure, temperature, and conductivity sensor calibrations were performed at Sea-Bird Electronics, Inc. in Bellevue, Washington. Secondary sensor pair T1075 and C1347 were selected for final data reduction for all stations. The oxygen sensor was calibrated by using the pre- and post-cruise laboratory calibration. Secondary oxygen data from sensor s/n 353 was retained for stations 1-32 and 34; primary oxygen data from sensor s/n 381 was retained for stations 33 and 35-130. Post-cruise calibrations were applied to CTD data associated with bottle data using the PMEL program CALBOT. WOCE quality flags were appended to bottle data records using the PMEL program FLAG. Quality flags were determined by plotting the absolute value of sample residuals versus pressure and selecting a cutoff value for bad flags. Values which were 2.8 standard deviations from the mean were considered bad. Of the 4313 sample salinities, 0.4% were flagged as bad and 3.6% were flagged as questionable. Of the 4130 sample oxygens, 1.2% were flagged as bad and 4.9% were flagged as questionable. MEASUREMENT OF CURRENTS A hull-mounted RD Instruments 150 kHz narrowband acoustic Doppler current profiler (ADCP) operated continuously during the cruise. Velocity data, averaged in earth coordinates using gyrocompass heading, were logged in three-minute (approximately 180 pings) ensembles using RDI Data Acquisition Software (DAS) version 2.48. Vertical bin size was 8 meters. The center of the first bin was located at 16 meters. Range varied from 200 to 400 meters, depending primarily on sea state. A user exit program (UE4, provided by Eric Firing, U. Hawaii) was used to interface navigation and heading equipment. Position was logged at the beginning and end of each ensemble from a Trimble Centurion P-code GPS receiver (estimated position accuracy of 5 - 10 meters). Mean gyrocompass corrections for each ensemble were recorded from an Ashtech 3DF GPS attitude determination system; 3DF array orientation was calibrated using P- code GPS and ADCP bottom track comparison. These data are used in post- processing to calculate mean ship velocity to reference ensemble means, and to compensate for dynamic gyrocompass errors. Estimated errors for an ensemble are 1-2 cm/s for relative velocity and 3-4 cm/s for ship speed errors due to position inaccuracy; errors induced by heading inaccuracies are reduced to less than 1 cm/s using GPS heading data. This total error of 4-6 cm/s over a three minute ensemble is reduced further by averaging during postprocessing; the fifteen minute averages commonly used represent an average over five kilometers at cruising speed, and should be accurate to 1-3 cm/s. The ADCP data will be available through internet address: http://ilikai.soest.hawaii.edu/sadcp/woce.html On-station velocity profiles were obtained using a RDI 150 kHz Narrowband ADCP (Lowered or LADCP) mounted looking downward from the CTD frame. This technique measures and records velocity shear profiles extending 150 to 350 meters below the instrument approximately once per second. In postprocessing, the individual shear profiles are averaged by depth to produce a full-depth shear profile, which is integrated to estimate the depth dependent (baroclinic) component of the velocity field. The depth- independent (barotropic) component of velocity can be recovered if positions at the start and end of the cast are known; positions were logged on this cruise using a Trimble Centurion P-code GPS receiver, accurate to 5 - 10 meters. Readers are advised to refer to Fischer and Visbeck (1993) for a full explanation of methods and standard processing procedures. The LADCP data will be available through internet address http://www.nodc.noaa.gov/General/NODC-About/NODC- overview.html#services SALINITY ANALYSES A Guildline 8400B autosal was used for the salinity analysis with batch P125 standard water. The autosal room was maintained at 22 °C, and the autosal was set at 24 °C. A total of 4380 samples were measured and 37 of them were rejected. OXYGEN TECHNIQUE An automatic titration system was used for the oxygen analysis with the Carpenter modification of the Winkler method using a photometric determined endpoint. Reagents for the Carpenter method titration were mixed by the AOML/OCD Group of George Berberian as specified in Friederich's MBARI Technical Report #91-6 (Friederich et al, 1991). Apparent oxygen utilization (AOU) is defined as O2 measured- O2 sat., where O2 sat. is the saturation value at potential temperature and salinity of the sample determined according to Weiss (1970). A total of 4310 samples were measured and 52 of them were rejected. B.1.2. NUTRIENT ANALYSIS METHODS SAMPLING AND ANALYTICAL METHODS Nutrient samples were collected from 10-L "Niskin" bottles in acid washed 25-ml linear polyethylene bottles after three complete seawater rinses and analyzed within 1 hour of sample collection. Measurements were made in a temperature- controlled laboratory (20 ± 2 ºC). Concentrations of nitrite (NO2 - ), nitrate (NO3 - ), phosphate (PO4 3- ) and silicic acid (H4SiO4) were determined using an Alpkem Flow Solution Auto-Analyzer aboard the ship. The following analytical methods were employed: NITRATE AND 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 home made cadmium column (Zhang et al., 2000), which reduced nitrate to nitrite and the resulting nitrite concentration was then determined as described above. Nitrate concentrations were determined from the difference of nitrate + nitrite and nitrite. PHOSPHATE: Phosphate in the samples was determined by reacting with molybdenum (VI) and antimony (III) in an acidic medium to form an antimonyphosphomolybdate complex at room temperature. This complex was subsequently reduced with ascorbic acid to form a blue complex and the absorbance was measured at 710 nm (Grasshoff et al. ,1983). A total of 4306 samples were measured and 1248 of them were rejected. SILICIC ACID: Silicic acid in the sample was analyzed by reacting the aliquote with molybdate in a acidic solution to form € -molybdosilicic acid . The € -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. CALIBRATION AND STANDARDS: Stock standard solutions were prepared by dissolving high purity standard materials (KNO3 , NaNO2 , KH2PO4 and Na2SiF6 ) in deionized water. Working standards were freshly made at each station by diluting the stock solutions in low nutrient seawater. The low nutrient seawater used for the preparation of working standards, determination of blank, and wash between samples was filtered seawater obtained from the surface of the Gulf Stream. Standardizations were performed prior to each sample run with working standard solutions. Two or three replicate samples were collected from the "Niskin" bottle sampled at deepest depth at each cast. The relative standard deviation from the results of these replicate samples were used to estimate the overall precision obtained by the sampling and analytical procedures. The precisions of these samples were 0.04 µmol/kg for nitrate, 0.01 µmol/kg for phosphate and 0.1 µmol/kg for silicic acid. B.2. CARBON PARAMETERS B.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 (PMEL-1 and PMEL-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 at BNL (Wilke, 1993). The CO2 gas volumes bracketed the amount of CO2 extracted from the water samples for the two PMEL systems. All DIC values were corrected for dilution by 0.2 ml of HgCl2 used for sample preservation. The total water volume was 540 ml. The correction factor used for dilution was 1.00037. The instruments were calibrated at the beginning, middle, and end of each coulometer cell solution with a set of the gas loop injections. 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. Certified Reference Materials (CRMs), consisting of poisoned, filtered, and UV irradiated seawater supplied by Dr. A. Dickson of Scripps Institution of Oceanography (SIO), were run on each cell. The results were close to the values determined manometrically by Dr. Charles D. Keeling at SIO as shown below. The CRM results have been presented in Figure 3 and Table 2. The overall accuracy and precision for the CRMs on both instruments combined was -0.1 +/-2.1 (n=125). DIC data reported for this cruise have been corrected to the Batch 40 CRM value by adding the difference between the certified value and the mean shipboard CRM value (certified value - shipboard analyses) on a per instrument/per leg basis. Av. value of CRMs run on PMEL-1: 1987.3±2.0 µmol/kg (n = 59) Av. value of CRMs run on PMEL-2: 1984.6±1.2 µmol/kg (n = 66) Manometric value was 1985.8±0.7 µmol/kg (n = 10) [SIO reference material batch #40] Samples were drawn from the "Niskin" bottles into cleaned, precombusted 500-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 both the surface and 1000 m "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 water replicate in the middle of the cell after about 12 mg of C were titrated. The first one of the 1000 m replicates was run at the end of the cell after about 25 mg of C were titrated, while the second one of the 1000 replicate samples was run using a new coulometer cell solution. No systematic difference between the replicates was observed. As example, the 1000m replicate samples run on both PMEL1 and PMEL2 combined had a standard deviation of 1.3 µmol/kg for 32 sets of duplicates, and the results of the surface replicates yielded a standard deviation of 0.9 µmol/kg for 98 sets of duplicates. The deviation is very similar to that observed for the CRMs and suggest no strong dependency of results with amount of carbon titrated for a particular cell. The results of the duplicate samples have been presented in Figure 4 and Table 3. CALCULATIONS Calculation of the amount of CO2 injected was according to the Department of Energy (DOE) CO2 handbook [DOE, 1994]. The gas loops yielded a calibration factor for the instrument defined as: calculated moles of CO2 injected from gas loop Cal. f actor = -------------------------------------------------------- (1) actual moles of CO2 injected The concentration of CO2 ([CO2]) in the samples were determined according to: (Counts - Blank * Run Time) * K µmol/count [CO2] = Cal factor *. ------------------------------------------------- (2) pipette volume * density of sample where "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 pipette volume was determined by taking aliquots at known temperature of distilled water from the volumes prior to, during, and after the cruise. The weights with the appropriate densities were used to determine the volume of the syringes and pipette. Calculation of pipette volumes, density, and final CO2 concentration were performed according to procedures outlined in the DOE CO2 handbook (DOE, 1994). B.2.2. FUGACITY OF CO2 (fCO2) GAS CHROMATOGRAPHIC (GC) METHOD A total of 1463 discrete fCO2 samples from 130 stations were taken and analyzed on the cruise using an analysis system based on gas chromatography (Neill et al., 1997). Sampling from the "Niskin" bottles occurred immediately after O2 samples were drawn. Samples were drawn into 120 ml Pyrex septum bottles after rinsing the bottles several times. On the final fill water was drawn into the bottom of the bottle and overflowed at least one half volume. A Teflon lined septum was crimp sealed on the bottle ensuring that no headspace was present. Prior to analysis 5-ml water was withdrawn and replaced with a headspace of known CO2 concentration that was expected to closely match that of the water. The remaining water and headspace were equilibrated by rotating the bottles for at least 40 minutes in a constant temperature bath at 20 °C. The fCO2 of the headspace was measured in a flame ionization detector (FID) after quantitative conversion of the CO2 to methane. The analyses were referenced against a series of six gas standards with the following mole fractions: 198.09, 348.16, 977.79, 508.35, 1479.46, 717.4. The standards, which were run after each dozen samples, bracketed most of the concentrations measured in the water column. The precision of the fCO2 measurements was estimated at 0.86% of the signal based on 89 replicate samples (see Table 4). The fCO2 measurements had a data gap mid- cruise because of a catastrophic instrument failure caused by water being injected onto the column and catalyst. Good, full water column, coverage was obtained at the Eastern and Western side of the basin. The surface water measurements showed that the water undersaturated for most of the transect except at the boundaries. The undersaturation reaches its greatest value of -45 to - 50 µatm between 60 and 75 °E. The fCO2 in the deep water showed a strong trend with lower concentrations in the West due to better ventilation of the Western half of the basin. B.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 plexiglass water-jacketed cells were similar to those used by Bradshaw et al. (1988), except that a larger volume (200 ml) was used to increase the precision. The cells had fill and drain valves with zero dead- volume to increase the reproducibility of the cell volume. The HCl solutions used throughout the cruise were made, standardized, and stored in 500-ml glass bottles in the laboratory for use at sea. The 0.2489 M HCl solutions (Batch 9601) were prepared by dilution of concentrated HCl in 0.45 M NaCl to yield an ionic strength equivalent to that of average seawater (0.7 M). The acid was independently standardized using a coulometric technique (Taylor and Smith, 1959; Marinenko and Taylor, 1968) by the University of Miami and by Dr. Dickson 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 40 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 (see Table 5) (Millero et al, 2000). Carbonate parameters of surface waters indicate the occurrence of upwelling near the African coast. The surface carbonate parameters are consistent with those collected during the WOCE (World Ocean Circulation Experiment) 1992 cruise that sampled stations along the same latitude (24 o N). Both studies yield values for normalized TA (TA*35/S) of 2291±6 µmol kg -1 . The values of TA for the deep water are in good agreement (± 3.8 µmol/kg). Crossover comparison with OACES 1993 study also showed good agreement (±3 µmol/kg in TA). The pH is on average 0.004 higher than those made on the 1993 cruise. Kitack Lee from AOML/OCD calculated total alkalinity (TA) from spectroscopic pH (25 o C) and coulometric total dissolved inorganic carbon (DIC) using the carbonic acid dissociation constants of Mehrbach et al. (1973) as refit by Dickson and Millero (1987). A value of 1.2 µmol kg -1 has been subtracted from calculated TA values because calculated values are 1.2 µmol kg -1 higher than measured values. B.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 25°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 Kodak m-cresol purple sodium salt (C21H17O5Na) in MilliQ water. The absorbance ratio of the concentrated indicator solution (RI = 578A/434A) was 0.95. All absorbance ratio measurements were obtained in the thermostatted (25.0±0.05°C) cell compartments of HP 8453 UV-visible Diode Array Spectrophotometers. Measurements of pH were taken at 25°C on the total hydrogen ion concentration ([H+]T) scale, in mol/kg solution, and converted to seawater scale ([H+]sw). The overall precision of the pH measurements obtained from the duplicate samples was ±0.0006. A total of 1997 samples were measured and 24 of them were rejected. B.2.5. TOTAL ORGANIC CARBON, TOTAL NITROGEN AND TOTAL PHOSPHORUS TOTAL ORGANIC CARBON ANALYSES TOC samples were analyzed by a high-temperature combustion (HTC) method using custom made instruments. Samples were analyzed with a furnace divided into two temperature zones (Hansell and Peltzer, 1998; Carlson et al., 1999). Ultra high purity O2 flowed through the instrument at 175 ml/min. Samples were acidified (10 µl of 85% H3PO4 per 10 ml of sample) and sparged with CO2 free oxygen for at least 10 minutes to remove inorganic carbon. One hundred µl of sample was injected manually through a septumless port into the quartz combustion tube packed with Pt gauze (Aldrich), 7% Pt on alumina catalyst (Shimadzu), Sulfix (Wako Pure Chemical Industries, Inc.) and CuO wire (Leeman Labs). The Pt gauze and Pt beads were heated to 800°C in the upper zone while the remaining packing material was heated to 600°C in the lower zone. The resulting CO2 flowed through two water traps and a final copper halide trap then detected with a LiCor 6252 CO2 analyzer. The signal was integrated with chromatographic software (Dynamax Macintegrator I version 1.3; Rainin Inst.). Extensive conditioning of the combustion tube was essential to minimize the machine blank. The system blank (<10 µM) was assessed daily with ampoulated low carbon waters (LCW). The system response was standardized daily with a four point calibration curve of glucose solution in LCW. Deep Sargasso Sea water (>2000 m), which had been acidified and ampoulated, served as a daily reference material. Analyzing low carbon water and reference deep seawater several times a day allowed us to assess the system stability from run-to-run and day-to-day, ensuring confidence in our analysis. Both the low carbon and the deep Sargasso Sea references waters are part of an international certified reference material program for marine DOC measurement, run by the laboratory of Dr. Hansell. As such, the TOC analyses from the 24°N line are referenced to the international community of DOC laboratories using the CRM(tm)s. TOTAL NITROGEN ANALYSES Concentrations of TN (total nitrogen, or the sum or organic and inorganic N) were determined by high temperature combustion and detection of the nitric oxide produced. Samples had been collected into 60 ml polyethylene bottles for frozen storage until analysis in the shore laboratory. In the high temperature system, a €ls quartz combustion tube was held at 900 °C in the upper zone and 800-900 °C in the lower zone of a 2-zone Thermcraft tube furnace. The combustion tube has a 12 cm head space, 2-3 screens of pure Pt (52 mesh), an 8 cm bed of 7% Pt on alumina (Shimadzu, Inc.), and a 10 cm bed of quartz beads. 100 µl injections of seawater were made into the combustion tube by syringe through a septum. The carrier gas (UHP oxygen) flowed at a rate of 200 ml/min. Recovery of known standards (glycine, urea, EDTA, etc.) was >90%. Detection of NO was done with an Antek Model 7020 chemiluminescence detector. Oxygen flow through the ozone generator was 28 ml/min. Standardization was performed daily with potassium nitrate in Milli-Q water. Q water was used as the system blank, and it was assumed to have zero N content. The system blank was normally <1 µM. Low nutrient sea water, collected at the surface of the Sargasso Sea, was used as a reference material for daily use. The coefficient of variation in low nutrient surface water (4-5 µM TN) was 3-4%, while in deep water (>20 µM TN) it was 1%. Data acquisition was performed on a Dynamax Macintegrator I version 1.3, produced by Rainin Instruments. TOTAL PHOSPHORUS ANALYSES Concentrations of TP (total phosphorus; organic plus inorganic P) were determined by UV photo-oxidation. Samples had been stored frozen in 60 ml polyethylene bottles until shore based analysis. A 6 ml aliquot was removed from each sample bottle and placed in a 20 ml fused quartz tube equipped with a Pyrex ground stopper (Quartz Scientific, Inc.). One hundred µl of 30% hydrogen peroxide was added to each tube and placed in a homemade irradiation unit (2 hours). The irradiation unit contained a 1200 W UV lamp (Hanovia) protected by a quartz jacket. A 2-tiered aluminum tube holder (40 tubes total) fitted around the lamp and held the samples 7 cm from the lamp. A fan placed at the bottom of the unit blew air across the samples for cooling. A hinged aluminum cylinder, open at the top and bottom, was fitted around the samples to keep stray UV light from leaving the system. This entire unit was placed in a fume hood, the front of which was covered with a black curtain while in use (again to collect stray UV light). After irradiation, aliquots of the samples that had not been oxidized, and the photo- oxidized aliquots, were analyzed for phosphate using a colorimetric method on a Technicon Autoanalyzer II (Knap et al. 1997). Daily calibration was achieved from 4 point calibration curves using KH2PO4. Low nutrient seawater (Sargasso Sea surface water) was always processed with the samples as a daily quality control measure. Coefficients of variation for the measurement was X and X% for shallow and deep water samples. B.2.6. 13C/12C OF DISSOLVED INORGANIC CARBON SHIPBOARD SAMPLE COLLECTION METHODS Samples were collected in pre-washed and baked (450 ºC) 500 ml ground glass- stoppered bottles using the following method. A length of Tygon tubing was attached to the "Niskin" bottle or seawater line and flushed for a few seconds. The end of the tubing was then placed at the bottom of the upright sample bottle and the bottle was filled, then overflowed with an amount equal to its volume if "Niskin" water volume permitted, otherwise with at least half its volume. Flow was stopped as the Tygon tubing was removed from the top of the bottle to avoid any splashing in the top. Using a syringe or turkey baster, 10 to 20 ml were withdrawn off the top of the sample to lower the water level to approximately 1 ml below the neck of the bottle, avoiding backwash of water from the turkey baster into the sample. The ground glass joint of the bottle was wiped dry with Kimwipes. Then 100 µl of a saturated HgCl2 solution (per 250 ml of seawater) was injected beneath the surface of the sample using an Eppendorf pipet. The ground- glass stopper, which had been pre-greased with Apiezon M grease, was then inserted straight into the bottle without twisting. If any air streaks in the grease seal were visible, the stopper was removed, cleaned, and regreased, and the bottle was resealed. Clips (if required for the bottle neck-type) were placed on the necks of the bottles, and two heavy rubber bands were placed around the stopper and bottle to prevent leakage. The sample bottle was then inverted a couple of times to mix the HgCl2 throughout the sample. LABORATORY METHODS CO2 is extracted from the DIC seawater sample using a modification of the helium stripping technique described by Kroopnick (1974) as described in Quay et al (1992). The stripper is comprised of a glass tube with a stainless steel fitting and silicone-greased glass stopcock at the bottom (which connects to the He line), a glass frit which the He passes through, and a stainless steel fitting containing a 3-layer silicone rubber septum at the top. Approximately 1 ml phosphoric acid is injected into the stripper and bubbled with He for 10 minutes. The gas is then evacuated out of the stripper and the stripper is weighed. Then 80 to 125 ml of the sample is drawn into the stripper and it is weighed again to calculate the weight of water analyzed. A stainless steel needle pierces the septum and connects the stripper to the extraction line, which has been evacuated and filled with helium. The sample is stripped with 99.997% pure He at a flow rate of 200 ml/min for 20 minutes. Water is trapped out in two glass traps submerged in Dewars containing a slush mixture of dry ice and isopropanol at -70ºC. CO2 is collected at -196ºC in glass loop traps submerged in liquid N2. The € 13 C is then measured on a Finnigan MAT 251 mass spectrometer. The efficiency of the extraction method is 100 ± 0.5 percent based on gravimetrically prepared Na2CO3 standards. The precision of the 13 C/ 12 C analysis is ± 0.02 0 /00 based on a replicate analysis of standards and seawater samples. B.2.7. CHLOROFLUOROCARBONS (CFC) As described above specially designed 10-l water sample bottles were used on the cruise to reduce CFC contamination. Samples for the analysis of dissolved CFC-11, CFC-12 and CFC-113 were drawn from approximately 1700 of the 4300 water samples collected during the expedition. Samples for carbon tetrachloride (CCl4 or CFC-10) analysis were drawn from approximately 430 samples. When taken, water samples for CFC analysis were usually the first samples drawn from the 10-l bottles. Care was taken to co- ordinate 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, fCO2, total CO2, alkalinity and pH samples were collected within several minutes of the initial opening of each bottle. To minimize contact with air, the CFC samples were drawn directly through the stopcocks of the 10-l bottles into 100-ml precision glass syringes equipped with 2- way metal stopcocks. The syringes were immersed in a holding tank of clean surface seawater until analyzed. To reduce the possibility of contamination from high levels of CFCs frequently present in the air inside research vessels, the CFC extraction/analysis system and syringe holding tank were housed in a modified 20' laboratory van on the aft deck of the ship. For air sampling, a 100 meter length of 3/8" OD Dekaron tubing was run from the CFC lab van to the bow of the ship. A flow of air was drawn through this line into the CFC van using an Air Cadet pump. The air was compressed in the pump, with the downstream pressure held at 1.5 atm using a back-pressure regulator. A tee allowed a flow (100 cc min -1 ) of the compressed air to be directed to the gas sample valves, while the bulk flow of the air (>7 l min -1 ) was vented through the back pressure regulator. Air samples were only analyzed when the relative wind direction was within 60 degrees of the bow of the ship to reduce the possibility of shipboard contamination. The Air Cadet pump was run for at least 60 minutes prior to analyzing each batch of air samples to insure that the air inlet lines and pump were thoroughly flushed Concentrations of CFC-11, CFC- 12 and CFC-113 in air samples, seawater and gas standards on the cruise were measured by shipboard electron capture gas chromatography (EC-GC), using techniques similar to those described by Bullister and Weiss (1988). For seawater analyses, a 30-ml aliquot of seawater from the glass syringe was transferred into the glass sparging chamber. The dissolved CFCs in the seawater sample were extracted by passing a supply of CFC-free purge gas through the sparging chamber for a period of 4 minutes at 70 cc min -1 . Water vapor was removed from the purge gas during passage through an 18 cm long x 3/8 inch diameter glass tube packed with the desiccant magnesium perchlorate. The sample gases were concentrated on a cold-trap consisting of a 1/8 inch OD stainless steel tube with an about 7 cm section packed tightly with Porapak N (60-80 mesh). To cool the trap, isopropanol cooled by a Neslab Cryocool refrigeration system was forced from a reservoir beneath the trap to a level above the packing with a stream of compressed nitrogen. After quickly bringing the isopropanol to the top of the trap, a low flow of nitrogen was bubbled through the bath to reduce gradients and maintained a temperature of -20 o C. After 4 minutes of purging the seawater sample, the sparging chamber was closed and the trap was held open for an additional 1 minute to allow nitrous oxide (N20) to pass through the trap and thereby minimize its interference with CFC-12. The trap was isolated, the cold isopropanol in the bath was drained, and the trap was heated electrically to 125 o C. The sample gases held in the trap were then injected onto a precolumn (30 cm of 1/8 inch O.D. stainless steel tubing packed with 80- 100 mesh Porasil C, held at 90 o C), for the initial separation of the CFCs and other rapidly eluting gases from the more slowly eluting compounds. The CFCs then passed into the main analytical column (about 183 cm of 1/8 inch OD stainless steel tubing packed with Carbograph 1AC, 80-100 mesh, held at 90 o C) for final separation, and into the EC detector for quantification. The analysis of carbon tetrachloride was made on a separate, but nearly identical apparatus to the electron capture-gas chromatography system used in the analysis of CFC- 11, CFC-12 and CFC-113 (Bullister and Weiss, 1988). Samples were drawn in the same type of syringes used for the CFC analysis. In the CCl4 system, the sample injection port was flushed with 30-40 ml of sample before injecting sample into a calibrated loop (about 30 ml). After filling, an additional 30 ml of water was pushed through the loop and allowed to overflow. For analysis, a valve was switched and the water sample held in the loop was pushed into the stripper with the same CCl4 free nitrogen that was used to strip the sample. The gases removed from the sample were dried while passing through an ~18 cm x 3/8 inch OD tube of magnesium perchlorate and concentrated on a trap packed with four inches of Porapak N and held at -30 °C during trapping. At the conclusion of stripping, the trap was heated electrically and the contents swept onto the precolumn (0.53mm I. D. x 30 meters, DB624 capillary column, 45 °C)) with clean nitrogen. The desired gases passed on to the main analytical column (0.53mm I. D. x 30 meters, DB624 capillary column, 45 °C), before the precolumn vented the later peaks. All other aspects of the analysis were the same as the CFC analysis. Both of the analytical systems were 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 present in the CFC analytical system, while four calibrated sample loops were used in the CCl4 system. 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 a seawater, air, standard or blank sample was 12 minutes on the CFC system and 20 minutes on the CCl4 system. Concentrations of the CFC's and CCl4 in air, seawater samples and gas standards are reported relative to the SIO93 calibration scale (Cunnold, et. al., 1994). 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 and CCl4 concentrations are given in units of picomoles per kg seawater (pmol kg -1 ). CFC and CCl4 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 33790 for CFC-11, CFC-12 and CFC-113; PMEL cylinder 33780 for CCl4) into the analytical instrument. The concentrations of CFC-11 and CFC-12 in this working standard were calibrated before and after the cruise versus a primary standard (36743) (Bullister, 1984). No measurable drift in the concentrations of CFC-11 and CFC-12 in the working standard could be detected during this interval. Full range calibration curves were run at intervals of 3 days during the cruise. Single injections of a fixed volume of standard gas at one atmosphere were run much more18 frequently (at intervals of 1 to 2 hours) to monitor short term changes in detector sensitivity. Extremely low (<0.01 pmol kg -1 ) CFC concentrations were measured in deep water (>3000 meters) in the Eastern Basin of the North Atlantic between 25 ºW and 45 ºW along this section. Based on the median of CFC concentration measurements in the deep water of this region, which is believed to be nearly CFC-free, blank corrections of 0.003 to 0.015 pmol kg -1 for CFC-11, 0.006 to 0.007 pmol kg -1 for CFC-12 and 0.006 to 0.011 pmol kg -1 for CFC-113 have been applied to the data set. If the measured CFC concentration for a sample is very low, subtracting a blank can result in a very small negative number reported (see Figure 2). No blank corrections were required for the CCl4 data. On this expedition, we estimate precision (1 standard deviation) of 1% or 0.005 pmol kg -1 (whichever is greater) for dissolved CFC-11, 2% or 0.005 pmol kg -1 (whichever is greater) for dissolved CFC-12 measurements (see listing of replicate samples given in Table 6), 4.4% or 0.002 pmol kg -1 for CFC-113 and 1.4% or 0.006 pmol kg -1 for CCl4 (Table 7). The results of the CFC air measurements are reported in Tables 8 and 9. A number of water samples had clearly anomalous concentrations relative to adjacent samples for one or more of the trace gases. These anomalous samples appeared to occur more or less randomly during the cruise, and were not clearly associated with other features in the water column (e.g. elevated oxygen concentrations, salinity or temperature features, etc.). This suggests that the high values were due to individual, isolated low- level CFC contamination events. Measured concentrations for these samples are included in this report, but are given a quality flag of either 3 (questionable measurement) or 4 (bad measurement). A total of 4 analyses of CFC-11, 8 analyses of CFC-12, 3 analyses of CFC-113 and 2 analyses of CCl4 were assigned a flag of 3. A total of 9 analyses of CFC- 11, 8 analyses of CFC-12, 18 analyses of CFC-113 and 4 analyses of CCl4 were assigned a value of 4. B.3. UNDERWAY MEASUREMENT METHODS B.3.1. UNDERWAY fCO2 Underway pCO 2 system version 2.5 (analogous to those described in Ho et al. 1997, and Feely et al. 1998) was used to determine the pCO 2 of surface water and overlaying air on a continuous basis (Keeling 1965, Wanninkhof and Thoning 1993). When in operation, seawater is drawn from the uncontaminated seawater intake from the bow intake approximately 6 meters below the water line to a 30-l shower head equilibrator located in the main laboratory, where the headspace and seawater reach equilibrium on a short time scale. At specific times during an hourly cycle, the content of the headspace is measured by an infrared CO 2 analyzer. Uncontaminated air from the marine boundary layer is drawn continuously from the bow mast to the underway pCO 2 system. At a designated time, air is analyzed by a the infrared CO 2 analyzer, otherwise the air is bled off through a vent . The CO 2 measurements are made by a Li-Cor differential, non-dispersive, infrared (NDIR) CO 2 analyzer (model 6251), and the result is based on the difference in absorption of infrared (IR) radiation passing through two gas cells. The reference cell is continuously flushed with a gas of known CO 2 concentration using the lowest concentration of three reference gas standards. During the hourly cycle the sample cell is flushed with one of three reference gas standards, marine boundary layer air, or headspace gas from the equilibrator. The data may be downloaded via WWW site:@ http://www.aoml.noaa.gov/ocd/oaces/1998data.html 3. 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 Ocean Atmospheric Carbon Exchange Study (OACES) and the World Ocean Circulation Experiment (WOCE). We wish to acknowledge the OACES program managers Drs. James Todd and Lisa Dilling for supporting the field program. 4. 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. Bullister, J.L. and R.F. Weiss, 1988. Determination of CCl3F and CCl2F2 in seawater and air. Deep-Sea Research, 35 (5), 839-853. Bullister, J.L., 1984. Anthropogenic Chlorofluoromethanes as Tracers of Ocean Circulation and Mixing Processes: Measurement and Calibration Techniques and Studies in the Greenland and Norwegian Seas, Ph.D. dissertation, Univ. Calif. 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Oceanogr., 42(8), 1774-1783 Quay P.D., Tilbrook, B., and Wong, C.S., 1992. Ocean uptake of fossil fuel CO2: Carbon- 13 evidence, Science, 256, 74-79. Taylor, J.K., and Smith S.W., 1959. Precise coulometric titration of acids and bases. J. Res. Natl. Bur. Stds., 69A, 153‘159. Wanninkhof R. and Thoning K., 1993. Measurement of fugacity of CO2 in surface water using continuous and discrete sampling methods. Mar. Chem., 44, 189- 205. Weiss, R.F., 1970. The solubility of nitrogen, oxygen and argon in water and seawater. Deep-Sea Res., 17, 721-735. 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. 2 Note, the WOCE designation in the report title is incorrect. Zhang, J-Z., Fischer C., and Ortner, P. B., 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., Ortner P. B., and Fischer, C., 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 - 2 nd Edition". EPA/600/R- 97/072. Zhang, J-Z., and Berberian, G. A., 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 - 2 nd Edition". EPA/600/R- 97/072. TABLE 1. Station locations Station Cast Latitude Longitude Date (°N) (°W) --------------------------------------------- 1 1 27.917 13.370 1/24/1998 2 1 27.965 13.404 1/24/1998 3 1 27.883 13.417 1/24/1998 4 1 27.849 13.417 1/24/1998 5 1 27.799 13.816 1/24/1998 6 1 27.617 14.235 1/24/1997 7 1 27.433 14.851 1/24/1998 8 1 27.232 15.596 1/25/1998 9 1 27.032 16.115 1/25/1998 10 1 26.833 16.668 1/25/1998 11 1 26.667 17.199 1/25/1998 12 1 26.517 17.867 1/25/1998 13 1 26.498 18.335 1/26/1998 14 1 26.167 18.817 1/26/1998 15 1 25.983 19.365 1/26/1998 16 1 25.800 19.899 1/26/1998 17 1 25.617 20.433 1/26/1998 18 1 25.424 20.949 1/27/1998 19 1 25.250 21.484 1/27/1998 20 1 25.057 22.032 1/27/1998 21 1 24.783 22.800 1/28/1998 22 1 24.500 23.484 1/28/1998 23 1 24.499 24.216 1/28/1998 24 1 24.500 24.950 1/28/1998 25 1 24.500 25.683 1/28/1997 26 1 24.500 26.416 1/29/1998 27 1 24.499 27.150 1/29/1998 28 1 24.500 27.883 1/29/1998 29 1 24.499 28.617 1/30/1998 30 1 24.499 29.433 1/30/1998 31 1 24.500 30.267 1/30/1998 32 1 24.500 31.084 1/31/1998 33 1 24.500 31.916 1/31/1998 34 1 24.500 32.733 1/31/1998 35 1 24.498 33.567 2/1/1998 36 1 24.502 34.383 2/1/1998 37 1 24.500 35.217 2/1/1998 38 1 24.500 36.033 2/2/1998 39 1 24.500 36.867 2/2/1998 40 1 24.500 37.683 2/2/1998 41 1 24.500 38.513 2/2/1998 42 1 24.500 39.250 2/3/1998 43 1 24.500 39.983 2/3/1998 44 1 24.500 40.533 2/3/1998 45 1 24.500 41.083 2/4/1998 46 1 24.500 41.633 2/4/1998 47 1 24.500 42.183 2/4/1998 48 1 24.500 42.733 2/4/1998 49 1 24.500 43.284 2/4/1998 50 1 24.500 43.473 2/5/1998 TABLE 1. Station locations (continued) Station Cast Latitude Longitude Date (°N) (°W) --------------------------------------------- 51 1 24.500 44.386 2/5/1998 52 1 24.500 44.934 2/5/1998 53 1 24.500 45.484 2/5/1998 54 1 24.500 46.034 2/5/1998 55 1 24.500 46.584 2/6/1998 56 1 24.500 47.134 2/6/1998 57 1 24.501 47.684 2/6/1998 58 1 24.500 48.234 2/6/1998 59 1 24.500 48.782 2/7/1998 60 1 24.500 49.333 2/7/1998 61 1 24.491 49.883 2/7/1998 62 1 24.501 50.433 2/8/1998 63 1 24.501 50.984 2/8/1998 64 1 24.501 51.533 2/8/1998 65 1 24.500 51.149 2/9/1998 66 1 24.501 52.637 2/9/1998 67 1 24.499 53.183 2/9/1998 68 1 24.500 53.733 2/9/1998 69 1 24.499 54.467 2/10/1998 70 1 24.499 55.201 2/10/1998 71 1 24.500 55.933 2/10/1998 72 1 24.500 56.667 2/11/1998 73 1 24.500 57.400 2/11/1998 74 1 24.500 58.134 2/11/1998 75 1 24.500 58.867 2/12/1998 76 1 24.500 59.600 2/12/1998 77 1 24.500 60.332 2/12/1998 78 1 24.500 60.067 2/12/1998 79 1 24.500 61.801 2/13/1998 80 1 24.500 63.534 2/13/1998 81 1 24.499 63.264 2/13/1998 82 1 24.500 64.000 2/14/1998 83 1 24.500 64.667 2/14/1998 84 1 24.501 65.469 2/14/1998 85 1 24.500 65.200 2/15/1998 86 1 24.500 66.933 2/15/1998 87 1 24.500 67.667 2/15/1998 88 1 24.500 68.401 2/15/1998 89 1 24.500 69.133 2/16/1998 90 1 25.016 69.502 2/16/1998 91 1 25.383 69.867 2/16/1998 92 1 25.759 70.235 2/17/1998 93 1 26.141 70.615 2/17/1998 94 1 26.501 71.012 2/17/1998 95 1 26.500 71.351 2/17/1998 96 1 26.500 71.734 2/18/1998 97 1 26.501 72.100 2/18/1998 98 1 26.501 72.467 2/18/1998 99 1 26.500 72.850 2/18/1998 100 1 26.500 73.217 2/18/1998 101 1 26.500 73.583 2/19/1998 102 1 26.500 73.967 2/19/1998 103 1 26.500 74.251 2/19/1998 104 1 26.500 74.517 2/19/1998 105 1 26.500 74.800 2/19/1998 106 1 26.500 75.084 2/20/1998 107 1 26.500 75.300 2/20/1998 108 1 26.500 75.500 2/20/1998 109 1 26.500 75.701 2/20/1998 110 1 26.500 75.900 2/20/1998 111 1 26.500 76.083 2/20/1998 112 1 26.500 76.200 2/21/1998 113 1 26.483 76.300 2/21/1998 114 1 26.505 76.422 2/21/1998 115 1 26.500 76.517 2/21/1998 116 1 26.500 76.617 2/21/1998 117 1 26.500 76.683 2/22/1998 118 1 26.499 76.753 2/22/1998 119 1 26.500 76.784 2/22/1998 120 1 26.500 76.816 2/22/1998 121 1 26.520 76.901 2/22/1998 122 1 27.001 79.200 2/23/1998 123 1 27.002 79.283 2/23/1998 124 1 27.001 79.381 2/23/1998 125 1 27.038 79.481 2/23/1998 126 1 27.013 79.605 2/23/1998 127 1 27.020 79.674 2/23/1998 128 1 27.002 79.788 2/23/1998 129 1 27.006 79.857 2/23/1998 130 1 26.999 79.937 2/23/1998 TABLE 2. Results of the certified reference material, CRM (Assigned value by SIO 40 = (1985.8 ± 0.7) mmol/kg) Coulometer: PMEL-1 Date GMT Year DIC (h:min) Day (mmol/kg) --------------------------------- 24-Jan-98 16:02 24 1987.0 25-Jan-98 0:41 25 1981.2 25-Jan-98 4:47 25 1987.0 25-Jan-98 15:19 25 1986.7 26-Jan-98 4:29 26 1987.9 26-Jan-98 18:48 26 1987.3 27-Jan-98 7:36 27 1987.1 27-Jan-98 21:31 27 1987.9 28-Jan-98 9:37 28 1985.9 28-Jan-98 22:19 28 1985.6 29-Jan-98 9:02 29 1988.1 29-Jan-98 23:31 29 1986.4 30-Jan-98 22:36 30 1986.6 31-Jan-98 22:11 31 1985.8 1-Feb-98 9:06 32 1985.1 2-Feb-98 6:16 33 1986.2 2-Feb-98 21:23 33 1985.5 3-Feb-98 11:32 34 1988.3 4-Feb-98 4:54 35 1985.8 4-Feb-98 19:43 35 1988.0 5-Feb-98 7:07 36 1988.3 5-Feb-98 21:35 36 1986.7 6-Feb-98 8:47 37 1985.4 6-Feb-98 21:16 37 1986.3 7-Feb-98 7:48 38 1986.5 7-Feb-98 18:14 38 1988.1 8-Feb-98 5:50 39 1987.9 8-Feb-98 17:42 39 1990.8 8-Feb-98 18:36 39 1991.2 9-Feb-98 4:39 40 1983.6 9-Feb-98 17:46 40 1988.6 10-Feb-98 6:53 41 1985.9 10-Feb-98 22:02 41 1986.2 11-Feb-98 13:17 42 1984.9 12-Feb-98 4:52 43 1985.8 12-Feb-98 19:40 43 1985.1 13-Feb-98 9:40 44 1985.3 14-Feb-98 9:27 45 1994.2 14-Feb-98 10:25 45 1992.0 14-Feb-98 19:54 45 1988.4 15-Feb-98 4:46 46 1987.5 15-Feb-98 19:09 46 1986.8 16-Feb-98 17:09 47 1987.7 17-Feb-98 3:02 48 1988.4 17-Feb-98 12:21 48 1988.9 18-Feb-98 4:13 49 1987.5 18-Feb-98 18:30 49 1988.3 19-Feb-98 5:36 50 1989.1 19-Feb-98 14:48 50 1988.3 TABLE 2. Results of the certified reference material, CRM (Assigned value by SIO 40 = (1985.8 ± 0.7) mmol/kg) Coulometer: PMEL-1 (continued Date GMT Year DIC (h:min) Day (mmol/kg) --------------------------------- 20-Feb-98 5:01 51 1987.7 20-Feb-98 13:07 51 1988.3 21-Feb-98 0:18 52 1987.0 21-Feb-98 13:12 52 1988.1 22-Feb-98 2:59 53 1988.4 22-Feb-98 16:47 53 1987.7 23-Feb-98 3:41 54 1987.4 23-Feb-98 10:54 54 1986.1 22-Jan-98 15:02 22 1984.2 22-Jan-98 15:16 22 1983.1 24-Jan-98 1:39 24 1986.2 24-Jan-98 6:19 24 1986.5 24-Jan-98 15:19 24 1985.3 25-Jan-98 1:02 25 1985.7 25-Jan-98 12:58 25 1986.7 25-Jan-98 23:54 25 1986.6 26-Jan-98 11:18 26 1985.9 26-Jan-98 22:56 26 1985.0 27-Jan-98 11:22 27 1986.6 27-Jan-98 23:46 27 1984.7 28-Jan-98 12:28 28 1985.7 28-Jan-98 21:53 28 1984.8 29-Jan-98 8:57 29 1984.2 29-Jan-98 23:35 29 1985.1 30-Jan-98 12:19 30 1985.4 30-Jan-98 23:14 30 1983.8 31-Jan-98 11:51 31 1983.9 1-Feb-98 4:27 32 1984.1 1-Feb-98 18:18 32 1984.7 2-Feb-98 8:21 33 1985.5 3-Feb-98 1:09 3 4 1 985.5 3-Feb-98 13:40 34 1985.4 4-Feb-98 0:49 35 1984.5 4-Feb-98 13:06 35 1983.7 4-Feb-98 23:48 35 1984.6 5-Feb-98 13:50 36 1984.1 6-Feb-98 2:55 37 1984.2 6-Feb-98 16:49 37 1986.2 7-Feb-98 2:25 38 1983.6 7-Feb-98 9:08 38 1983.6 7-Feb-98 17:03 38 1984.2 8-Feb-98 3:00 39 1983.5 8-Feb-98 12:46 39 1987.5 9-Feb-98 4:50 40 1983.7 9-Feb-98 15:56 40 1985.3 10-Feb-98 7:15 41 1987.2 10-Feb-98 19:42 41 1984.3 11-Feb-98 13:58 42 1983.8 12-Feb-98 0:04 43 1983.8 12-Feb-98 19:06 43 1983.6 13-Feb-98 4:42 44 1984.4 13-Feb-98 16:36 44 1984.8 14-Feb-98 4:10 45 1983.7 14-Feb-98 13:23 45 1984.0 15-Feb-98 3:48 46 1984.6 15-Feb-98 14:02 46 1981.7 15-Feb-98 14:42 46 1982.8 16-Feb-98 0:12 47 1983.7 16-Feb-98 20:14 47 1984.1 17-Feb-98 7:55 48 1984.2 17-Feb-98 18:25 48 1982.8 18-Feb-98 2:52 49 1984.4 18-Feb-98 15:04 49 1983.8 19-Feb-98 2:04 50 1983.0 19-Feb-98 13:42 50 1985.3 19-Feb-98 21:50 50 1983.8 20-Feb-98 8:11 51 1984.3 20-Feb-98 20:36 51 1983.8 21-Feb-98 8:47 52 1986.8 21-Feb-98 18:37 52 1984.5 22-Feb-98 4:37 53 1984.1 22-Feb-98 16:08 53 1984.0 23-Feb-98 4:18 54 1985.9 TABLE 3. Dissolved inorganic carbon duplicates Station Bottle Pressure DIC Stdev # # (db) µmol/kg ------------------------------------------- 1 9 2 2119.7 0.26 3 20 2 2103.9 0.33 4 22 4 2100.8 0.47 5 7 995 2209.6 1.75 5 27 3 2105.0 0.47 6 30 3 2096.4 0.12 7 31 3 2096.4 0.95 9 32 4 2097.8 1.27 11 16 1001 2205.0 0.23 12 36 4 2098.4 0.95 13 17 1001 2212.5 0.69 13 35 4 2099.4 1.70 14 32 3 2100.1 0.98 15 17 1000 2209.1 0.82 15 36 4 2086.9 0.81 18 36 4 2100.1 1.52 19 18 1000 2212.8 0.44 19 36 5 2101.0 0.41 20 36 6 2099.1 0.06 21 19 1000 2207.9 0.16 21 36 6 2098.6 0.08 22 36 4 2096.7 0.45 23 36 5 2098.3 1.67 24 36 3 2096.2 0.18 25 36 4 2099.6 1.14 26 36 6 2098.6 0.98 30 18 1000 2200.1 1.39 31 18 1000 2200.6 1.88 32 36 6 2101.8 0.42 36 36 5 2094.6 0.13 37 20 1002 2200.4 0.40 38 36 4 2090.6 0.35 40 36 4 2087.9 0.84 41 19 999 2200.8 0.45 41 36 6 2085.0 0.76 42 36 3 2076.3 0.84 43 17 1000 2195.0 1.90 43 36 4 2080.1 0.86 46 36 4 2081.0 0.83 49 20 997 2194.9 1.15 50 36 5 2077.0 0.01 51 19 1001 2193.5 0.78 51 36 5 2073.1 0.37 53 18 1001 2197.6 1.10 55 36 5 2073.1 0.33 56 36 5 2075.5 0.07 57 36 5 2072.2 1.03 59 17 1000 2197.5 1.63 60 36 4 2075.7 0.90 61 36 4 2064.1 0.16 62 18 999 2194.8 1.41 TABLE 3. Dissolved inorganic carbon duplicates (continued Station Bottle Pressure DIC Stdev # # (db) µmol/kg ------------------------------------------- 62 36 3 2066.6 0.18 65 36 6 2065.9 0.46 67 36 5 2050.1 1.62 68 36 4 2056.2 0.03 69 36 4 2060.2 0.25 70 18 1000 2195.2 0.91 70 36 5 2056.3 1.32 71 36 6 2046.5 0.43 72 36 4 2046.1 0.08 73 17 1000 2195.1 0.01 73 36 4 2044.4 0.23 74 36 7 2033.7 1.69 75 36 5 2041.7 0.27 76 36 6 2038.2 0.99 77 36 5 2037.6 1.61 78 36 7 2035.3 0.39 79 36 5 2035.2 0.38 80 36 6 2023.7 0.07 81 36 4 2016.1 0.76 82 36 4 2036.6 0.48 83 36 4 2041.5 0.26 84 36 6 2036.9 1.46 85 36 4 2017.7 0.16 86 17 999 2202.1 0.01 86 36 4 2018.4 0.79 87 36 5 2028.5 0.73 88 36 5 2032.7 0.72 89 17 1001 2179.8 1.17 90 16 1001 2186.1 0.71 90 36 4 2037.9 0.34 94 36 4 2034.8 0.33 95 36 4 2035.4 0.54 98 36 4 2043.1 0.89 99 36 5 2042.8 0.93 101 18 1001 2191.6 1.88 101 36 4 2042.2 0.96 102 18 999 2187.3 0.54 102 36 5 2047.7 0.18 106 36 4 2041.5 0.79 107 36 4 2041.6 0.11 110 36 4 2037.3 0.85 111 36 4 2039.0 0.06 112 18 999 2190.4 1.20 113 36 3 2040.1 1.11 114 36 4 2040.5 1.41 117 36 3 2036.4 0.49 118 15 999 2185.3 1.56 121 18 5 2023.1 0.45 122 18 4 2014.1 0.45 123 20 3 2013.4 0.81 124 21 4 2006.8 0.63 125 23 4 2007.7 0.47 126 21 3 2011.0 0.04 127 20 4 2016.7 0.16 129 11 4 2026.3 0.13 TABLE 4. Replicate pCO2 analyses STATION Bottle Latitude Longitude Depth Ave (fCO2,20C) Stdev(fCO2,20C) (°N) (°W) (m) (µatm) (µatm) ---------------------------------------------------------------------------- 2 10 28 13 149 480.1 2.05 6 30 28 14 3 361.7 5.59 7 12 27 15 849 881.1 3.11 8 17 27 16 847 803.0 5.23 8 33 27 16 3 344.1 0.14 10 32 27 17 117 392.5 6.79 13 15 26 18 1201 863.0 0.71 14 17 26 19 800 950.8 3.11 18 16 25 21 1229 827.3 0.57 19 18 25 21 1000 953.0 4.60 21 3 25 23 4499 752.0 0.64 22 26 25 23 449 691.3 1.63 23 10 24 24 2879 743.1 7.14 24 36 25 25 3 338.1 4.17 25 13 25 26 2497 733.8 4.88 27 36 24 27 4 318.4 2.83 28 18 25 28 1201 854.9 5.52 30 18 24 29 1000 872.6 11.88 30 30 24 29 248 418.4 0.28 34 5 25 33 4589 531.7 318.83 34 12 25 33 2401 741.1 2.69 34 14 25 33 2002 746.4 3.61 38 17 25 36 1250 831.4 13.65 39 12 25 37 2096 735.1 0.71 40 36 25 38 4 312.2 8.56 42 14 25 39 1999 742.9 7.78 43 8 25 40 2949 680.4 13.08 45 5 25 41 4051 706.1 5.16 45 13 25 41 2050 685.9 10.82 46 4 25 42 4000 691.8 7.99 47 5 25 42 3098 712.2 27.79 47 9 25 42 2092 676.5 7.07 48 36 25 43 7 289.9 29.63 49 5 25 43 3201 715.0 7.42 49 10 25 43 2198 698.2 2.97 50 5 25 43 3092 704.4 10.68 51 14 25 44 1500 743.3 25.24 51 34 25 44 100 253.7 0.64 52 36 25 45 7 316.9 44.90 53 8 25 45 2000 711.8 13.22 53 19 25 45 901 851.9 4.95 53 36 25 45 6 267.9 18.10 54 36 25 46 5 272.3 10.25 55 9 25 47 1999 726.2 8.13 56 36 25 47 5 283.8 1.41 57 36 25 48 5 278.4 0.71 58 20 25 48 902 844.0 15.06 58 21 25 48 802 777.8 17.96 58 22 25 48 700 689.0 20.36 58 29 25 48 276 385.5 11.74 58 36 25 48 5 262.5 18.60 59 36 25 49 4 277.7 1.84 60 36 25 49 4 278.2 25.31 61 36 24 50 4 274.1 2.40 62 36 25 50 3 274.1 2.26 64 1 25 52 5363 733.8 8.27 65 36 25 51 6 276.4 1.70 66 16 25 53 1248 809.2 5.16 67 6 24 53 3999 743.7 6.01 67 13 24 53 1951 725.5 15.77 67 20 24 53 802 784.3 0.57 67 30 24 53 248 380.8 4.81 67 36 24 53 5 261.1 10.32 68 35 25 54 3 266.5 6.23 69 19 24 54 1051 848.9 5.80 70 1 24 55 6008 798.2 5.09 70 16 24 55 1402 743.8 1.20 70 36 24 55 5 260.2 4.24 71 2 25 56 6050 794.8 4.03 72 36 25 57 4 275.5 2.05 73 12 25 57 1900 721.2 7.35 74 6 25 58 3900 730.5 4.95 75 36 25 59 5 276.2 6.43 76 36 25 60 6 272.2 0.07 77 4 25 60 4698 691.1 67.18 79 1 25 62 5891 794.9 3.68 80 36 25 64 6 263.6 3.04 81 6 24 63 3966 736.2 2.40 82 1 25 64 5862 785.8 3.11 82 16 25 64 1049 840.5 1.48 83 13 25 65 1851 708.1 4.95 84 36 25 65 6 275.6 1.56 85 13 25 65 2101 720.4 8.41 86 1 25 67 5816 792.9 4.95 86 26 25 67 400 446.3 3.96 87 2 25 68 5291 784.6 4.81 88 36 25 68 5 275.1 0.35 89 1 25 69 5736 789.8 7.92 90 4 25 70 4450 740.8 9.55 91 36 25 70 5 283.8 0.49 94 3 27 71 4840 733.1 7.78 94 30 27 71 225 374.2 5.87 95 36 27 71 4 282.4 3.61 97 11 27 72 1998 725.7 3.46 98 1 27 72 5263 762.5 5.37 99 36 27 73 5 285.4 1.84 101 36 27 74 4 294.5 0.28 102 25 27 74 349 376.2 2.19 103 36 27 74 4 297.7 1.56 107 36 27 75 4 292.8 3.32 108 1 27 76 4751 748.1 6.22 110 34 27 76 96 301.3 3.25 111 36 27 76 4 285.8 0.42 113 36 26 76 3 287.6 3.32 114 3 27 76 4100 735.0 3.11 115 36 27 77 4 289.3 1.06 116 3 27 77 4188 736.3 5.37 117 36 27 77 3 288.9 1.70 120 3 27 77 1300 765.7 9.69 121 3 27 77 351 412.4 3.75 123 20 27 79 3 282.8 5.30 124 21 27 79 4 276.3 2.19 126 21 27 80 3 278.2 1.91 127 20 27 80 4 281.4 1.48 130 6 28 80 3 304.9 2.62 TABLE 5. Correction factors applied to raw data based upon carbonate parameters for Certified Reference Materials CRM TA pH (mmol/kg) ===================================================== Batch #40 2196.4 7.91 ----------------------------------------------------- CELL TA pH (mmol/kg) ----------------------------------------------------- Measured C.F. Measured C.F. N 2193.2 ± 1.2 1.001489 7.883 ± 0.004 0.026 12 2a 2198.5 ± 1.3 0.999062 7.883 ± 0.005 0.027 19 2193.0 ± 1.3 1.001547 7.872 ± 0.004 0.039 11 12 2194.7 ± 2.7 1.000779 7.875 ± 0.006 0.035 4 18b 2200.3 ± 3.0 0.998228 7.874 ± 0.002 0.032 10 21 2198.9 ± 0.9 0.998863 7.859 ± 0.005 0.051 48 a. Three slightly different correction factors were applied to cell 2 due to the change in volume from a broken piston. b. The weighted average was used TAcorr = TAsample x C.F. (TA) pHcorr = pHsample + C.F.(pH) TABLE 6. Replicate dissolved CFC-11 and CFC-12 analyses Station Bottle CFC-11 CFC-11 CFC-12 CFC-12 (pmol/kg) Stdev (pmol/kg) Stdev --------------------------------------------------- 3 9 2.227 0.025 1.189 0.005 5 6 0.184 0.006 0.092 0.004 7 14 0.814 0.012 0.415 0.001 7 28 2.348 0.018 1.325 0.009 8 27 2.403 0.040 1.319 0.016 9 6 0.012 0.005 0.012 0.001 9 30 2.253 0.021 1.306 0.032 11 12 0.147 0.004 0.092 0.013 11 18 0.468 0.002 0.242 0.003 11 33 2.228 0.010 1.295 0.009 13 28 2.352 0.013 1.301 0.002 14 6 0.001 0.003 -9.000 -9.000 14 32 2.159 0.018 1.221 0.010 16 19 0.141 0.001 -9.000 -9.000 16 30 2.286 0.008 1.305 0.001 19 5 0.008 0.000 0.005 0.001 19 29 2.445 0.008 1.310 0.027 21 19 0.135 0.005 0.077 0.006 22 5 0.004 0.001 -0.001 0.003 22 17 0.030 0.006 0.010 0.004 22 34 2.088 0.004 1.401 0.003 24 1 0.003 0.001 0.001 0.001 24 18 0.054 0.001 0.031 0.004 24 22 0.144 0.000 0.085 0.003 24 35 2.247 0.030 1.407 0.013 26 2 -0.001 0.001 0.000 0.001 26 12 0.007 0.000 -9.000 -9.000 26 14 0.010 0.003 0.003 0.002 26 24 2.161 0.019 1.132 0.006 26 35 1.978 0.013 1.143 0.010 28 9 -0.002 0.001 -0.002 0.001 28 17 0.039 0.001 0.021 0.001 28 22 0.652 0.011 0.331 0.002 28 30 2.358 0.016 1.324 0.012 29 2 0.002 0.001 -0.004 0.006 29 23 1.609 0.001 0.827 0.001 30 1 0.000 0.000 -0.003 0.002 30 19 0.143 0.001 0.078 0.004 30 28 2.370 0.018 1.294 0.009 30 35 2.015 0.012 1.167 0.008 31 30 2.372 0.006 1.317 0.007 32 1 -0.002 0.000 -0.001 0.004 32 20 0.137 0.000 0.064 0.004 32 34 2.033 0.007 1.172 0.001 34 21 0.367 0.001 0.171 0.002 34 34 1.962 0.012 1.137 0.005 35 4 -0.001 0.000 0.004 0.001 35 18 0.055 0.001 0.025 0.001 35 33 2.310 0.026 1.316 0.008 36 2 0.001 0.001 -0.001 0.001 36 14 0.005 0.001 -0.001 0.003 36 34 1.978 0.006 1.145 0.004 37 21 0.090 0.000 0.039 0.001 37 31 2.348 0.010 1.330 0.008 38 12 0.000 0.000 -0.004 0.001 38 22 0.766 0.001 0.361 0.006 38 30 2.375 0.013 1.315 0.008 39 7 0.001 0.000 -0.004 0.002 39 24 2.049 0.008 1.064 0.001 40 1 0.003 0.001 0.002 0.001 40 22 1.307 0.016 0.641 0.004 40 28 2.361 0.001 1.297 0.004 42 4 -0.001 0.002 -0.001 0.001 42 26 2.270 0.004 1.229 0.006 42 34 2.071 0.001 1.192 0.001 44 33 2.314 0.010 1.328 0.002 46 6 -0.001 0.001 -0.001 0.004 46 20 0.567 0.001 0.275 0.001 46 32 2.266 0.034 1.288 0.016 48 1 0.003 0.001 0.003 0.001 48 3 0.001 0.000 0.003 0.004 48 20 0.138 0.002 0.067 0.004 48 31 2.253 0.014 1.277 0.021 48 34 1.908 0.008 1.098 0.000 50 1 0.001 0.000 0.001 0.001 50 20 0.920 0.003 0.466 0.002 50 30 2.310 0.064 1.269 0.062 52 14 0.123 0.000 0.067 0.001 52 23 1.566 0.004 0.810 0.002 54 4 0.023 0.001 0.016 0.005 54 16 0.109 0.001 0.057 0.002 54 28 2.306 0.015 1.262 0.013 54 34 1.937 0.007 1.106 0.011 56 23 0.801 0.008 0.426 0.001 58 1 0.015 0.001 0.016 0.003 58 14 0.117 0.001 0.067 0.006 58 23 1.506 0.017 0.781 0.011 58 32 2.278 0.021 1.290 0.006 60 2 0.010 0.001 0.012 0.004 60 16 0.245 0.007 0.136 0.006 60 26 2.298 0.028 1.244 0.011 62 2 0.012 0.001 0.007 0.001 62 14 0.098 0.000 0.056 0.001 62 28 2.316 0.004 1.291 0.008 64 18 0.168 0.003 0.091 0.003 66 1 0.019 0.001 0.014 0.001 66 20 0.524 0.004 0.276 0.002 66 30 2.336 0.001 1.308 0.004 68 33 2.090 0.002 1.182 0.001 70 1 0.026 0.002 0.021 0.000 70 20 0.211 0.001 0.114 0.001 70 22 0.748 0.001 0.386 0.002 70 32 2.308 0.006 1.283 0.001 72 21 0.334 0.004 0.180 0.005 74 5 0.033 0.001 0.018 0.001 74 16 0.355 0.003 0.184 0.003 74 32 2.286 0.000 1.284 0.001 TABLE 6. Replicate dissolved CFC-11 and CFC-12 analyses (continued) Station Bottle CFC-11 CFC-11 CFC-12 CFC-12 (pmol/kg) Stdev (pmol/kg) Stdev --------------------------------------------------- 76 34 2.105 0.001 1.193 0.005 78 2 0.031 0.002 0.023 0.001 78 16 0.219 0.003 0.122 0.001 78 27 2.338 0.000 1.295 0.005 80 28 2.327 0.001 1.284 0.006 81 8 0.073 0.001 0.039 0.003 82 6 0.062 0.001 0.029 0.000 82 13 0.219 0.001 0.115 0.003 82 21 0.952 0.003 0.488 0.000 82 32 2.334 0.001 1.306 0.000 84 5 0.151 0.001 0.080 0.001 86 5 0.121 0.001 0.068 0.001 86 14 0.793 0.009 0.390 0.001 86 30 2.295 0.004 1.265 0.005 88 17 0.712 0.005 0.352 0.006 88 31 2.221 0.009 1.223 0.004 90 7 0.150 0.000 0.081 0.001 90 20 0.708 0.002 0.364 0.004 92 14 0.216 0.006 0.113 0.003 92 16 0.302 0.000 0.159 0.001 92 26 2.207 0.003 1.188 0.000 92 32 2.222 0.003 1.248 0.004 94 5 0.324 0.003 0.165 0.001 94 15 0.770 0.002 0.381 0.001 94 26 2.312 0.003 1.261 0.006 96 6 0.410 0.001 0.206 0.000 96 28 2.319 0.023 1.288 0.016 98 6 0.614 0.004 0.298 0.001 98 18 0.321 0.002 0.167 0.003 98 26 2.321 0.004 1.270 0.007 100 16 0.997 0.006 0.486 0.004 100 25 2.251 0.125 1.227 0.093 102 15 0.990 0.004 0.486 0.002 102 24 2.197 0.066 1.196 0.042 104 3 0.508 0.003 0.248 0.006 104 29 2.303 0.000 1.263 0.003 106 18 0.269 0.001 0.142 0.000 108 16 0.972 0.004 0.476 0.001 108 26 2.321 0.011 1.271 0.003 110 3 0.515 0.005 0.253 0.000 110 32 2.284 0.017 1.294 0.010 112 18 0.331 0.001 0.167 0.001 112 30 2.074 0.004 1.190 0.004 114 2 0.524 0.178 0.259 0.078 114 13 1.245 0.007 0.609 0.001 114 24 2.370 0.019 1.328 0.010 116 8 0.610 0.122 0.301 0.061 116 16 1.190 0.001 0.585 0.004 116 26 2.192 0.002 1.198 0.013 118 10 0.862 0.368 0.420 0.180 118 12 1.164 0.008 0.568 0.001 118 22 2.265 0.001 1.238 0.001 120 16 1.655 0.371 0.867 0.204 120 20 2.224 0.117 1.248 0.040 125 10 1.673 0.001 0.891 0.001 125 22 1.715 0.004 1.005 0.001 129 7 2.069 0.008 1.180 0.007 TABLE 7. Replicate dissolved CFC-113 and CCl4 analyses Station Bottle CFC-113 CFC-113 CCl4 CCl4 (pmol/kg) Stdev (pmol/kg) Stdev ---------------------------------------------------- 3 9 0.043 0.024 -9.000 -9.000 5 6 0.002 0.006 -9.000 -9.000 7 14 0.018 0.006 -9.000 -9.000 7 28 0.178 0.008 -9.000 -9.000 8 27 0.056 0.006 -9.000 -9.000 9 6 0.000 0.000 -9.000 -9.000 9 30 0.174 0.008 -9.000 -9.000 11 12 -0.003 0.001 -9.000 -9.000 11 18 0.001 0.004 -9.000 -9.000 11 33 0.156 0.008 -9.000 -9.000 13 28 0.055 0.004 -9.000 -9.000 14 6 0.000 0.000 -9.000 -9.000 14 32 0.172 0.005 -9.000 -9.000 16 19 0.000 0.000 -9.000 -9.000 16 30 0.051 0.001 -9.000 -9.000 19 5 0.001 0.001 -9.000 -9.000 19 29 0.029 0.008 -9.000 -9.000 21 19 -0.004 0.000 -9.000 -9.000 22 5 0.001 0.001 -9.000 -9.000 22 17 -0.004 0.005 -9.000 -9.000 22 34 0.157 0.008 -9.000 -9.000 24 1 -0.002 0.001 -9.000 -9.000 24 18 -0.005 0.002 -9.000 -9.000 24 22 -0.001 0.006 -9.000 -9.000 24 35 0.163 0.007 -9.000 -9.000 26 2 -0.002 0.001 -9.000 -9.000 26 12 0.006 0.001 -9.000 -9.000 26 14 0.005 0.007 -9.000 -9.000 26 24 0.023 0.004 -9.000 -9.000 26 35 0.166 0.002 -9.000 -9.000 28 9 -0.006 0.001 -9.000 -9.000 28 17 0.001 0.002 -9.000 -9.000 28 22 0.004 0.002 -9.000 -9.000 28 30 0.059 0.004 -9.000 -9.000 29 2 -0.004 0.002 -9.000 -9.000 29 23 0.015 0.005 -9.000 -9.000 30 1 -0.003 0.004 -9.000 -9.000 30 19 -0.001 0.001 -9.000 -9.000 30 28 0.031 0.005 -9.000 -9.000 30 35 0.176 0.001 -9.000 -9.000 31 30 0.039 0.002 -9.000 -9.000 32 1 -0.005 0.001 -9.000 -9.000 32 20 -0.002 0.010 -9.000 -9.000 32 34 0.160 0.011 -9.000 -9.000 33 1 -9.000 -9.000 0.031 0.001 33 26 -9.000 -9.000 0.451 0.002 33 35 -9.000 -9.000 1.912 0.046 34 21 0.004 0.004 -9.000 -9.000 34 34 0.169 0.006 -9.000 -9.000 35 4 -0.003 0.000 -9.000 -9.000 35 18 -0.009 0.002 -9.000 -9.000 35 33 0.140 0.004 -9.000 -9.000 36 2 -0.002 0.004 -9.000 -9.000 36 3 -9.000 -9.000 0.021 0.002 36 14 -0.004 0.000 -9.000 -9.000 36 18 -9.000 -9.000 0.086 0.006 36 33 -9.000 -9.000 1.095 0.032 36 34 0.154 0.003 -9.000 -9.000 37 21 0.002 0.005 -9.000 -9.000 37 31 0.067 0.001 -9.000 -9.000 38 12 0.002 0.001 -9.000 -9.000 38 22 0.011 0.005 -9.000 -9.000 38 30 0.038 0.003 -9.000 -9.000 39 7 -0.001 0.001 -9.000 -9.000 39 10 -9.000 -9.000 0.022 0.006 39 24 0.032 0.001 -9.000 -9.000 39 29 -9.000 -9.000 0.566 0.008 40 1 -0.001 0.001 -9.000 -9.000 40 22 0.021 0.002 -9.000 -9.000 40 28 0.031 0.001 -9.000 -9.000 42 4 0.001 0.001 -9.000 -9.000 42 26 0.029 0.001 -9.000 -9.000 42 34 0.182 0.012 -9.000 -9.000 43 1 -9.000 -9.000 0.035 0.001 43 19 -9.000 -9.000 0.227 0.013 43 34 -9.000 -9.000 1.036 0.016 44 33 0.154 0.001 -9.000 -9.000 46 6 -0.001 0.001 -9.000 -9.000 46 20 0.008 0.001 -9.000 -9.000 46 32 0.091 0.006 -9.000 -9.000 47 1 -9.000 -9.000 0.028 0.001 47 31 -9.000 -9.000 0.956 0.011 48 1 0.003 0.001 -9.000 -9.000 48 3 0.002 0.002 -9.000 -9.000 48 20 0.002 0.001 -9.000 -9.000 48 31 0.112 0.008 -9.000 -9.000 48 34 0.188 0.013 -9.000 -9.000 50 20 0.009 0.001 -9.000 -9.000 50 30 0.023 0.033 -9.000 -9.000 51 1 -9.000 -9.000 0.067 0.013 51 17 -9.000 -9.000 0.230 0.009 51 26 -9.000 -9.000 0.442 0.042 52 14 0.005 0.005 -9.000 -9.000 52 23 0.017 0.004 -9.000 -9.000 54 4 0.001 0.002 -9.000 -9.000 54 16 0.005 0.001 -9.000 -9.000 54 28 0.031 0.004 -9.000 -9.000 54 34 0.182 0.025 -9.000 -9.000 56 23 0.010 0.006 -9.000 -9.000 56 27 -9.000 -9.000 0.451 0.012 58 1 0.002 0.003 -9.000 -9.000 58 14 0.008 0.002 -9.000 -9.000 58 23 0.020 0.000 -9.000 -9.000 58 32 0.081 0.003 -9.000 -9.000 60 2 0.002 0.001 -9.000 -9.000 60 5 -9.000 -9.000 0.130 0.008 60 16 0.007 0.001 -9.000 -9.000 60 26 0.035 0.003 -9.000 -9.000 60 33 -9.000 -9.000 1.077 0.017 62 2 0.006 0.001 -9.000 -9.000 62 14 0.005 0.001 -9.000 -9.000 62 28 0.035 0.001 -9.000 -9.000 64 1 -9.000 -9.000 0.127 0.006 64 2 -9.000 -9.000 0.131 0.003 64 18 0.006 0.002 -9.000 -9.000 64 33 -9.000 -9.000 0.844 0.039 66 1 0.006 0.002 -9.000 -9.000 66 20 0.008 0.002 -9.000 -9.000 66 30 0.035 0.006 -9.000 -9.000 68 1 -9.000 -9.000 0.199 0.004 68 3 -9.000 -9.000 0.190 0.001 68 33 0.162 0.008 -9.000 -9.000 TABLE 7. Replicate dissolved CFC-113 and CCl4 analyses (continued) Station Bottle CFC-113 CFC-113 CCl4 CCl4 (pmol/kg) Stdev (pmol/kg) Stdev ---------------------------------------------------- 70 1 -0.002 0.002 -9.000 -9.000 70 20 0.005 0.001 -9.000 -9.000 70 22 0.013 0.006 -9.000 -9.000 70 32 0.038 0.009 -9.000 -9.000 72 1 -9.000 -9.000 0.205 0.001 72 4 -9.000 -9.000 0.408 0.004 72 14 -9.000 -9.000 0.342 0.181 72 17 -9.000 -9.000 0.451 0.011 72 21 0.006 0.001 -9.000 -9.000 72 35 -9.000 -9.000 1.935 0.043 74 4 -9.000 -9.000 0.327 0.008 74 5 0.012 0.001 -9.000 -9.000 74 16 0.011 0.001 -9.000 -9.000 74 32 0.078 0.007 -9.000 -9.000 76 2 0.007 0.001 -9.000 -9.000 76 4 -9.000 -9.000 0.294 0.004 76 8 -9.000 -9.000 0.143 0.005 76 25 -9.000 -9.000 0.436 0.003 78 2 0.007 0.001 -9.000 -9.000 78 16 0.008 0.001 -9.000 -9.000 78 27 0.035 0.000 -9.000 -9.000 80 13 -9.000 -9.000 0.944 0.016 80 28 0.039 0.005 -9.000 -9.000 80 33 -9.000 -9.000 0.822 0.010 81 8 0.006 0.001 -9.000 -9.000 82 6 0.004 0.002 -9.000 -9.000 82 13 0.008 0.002 -9.000 -9.000 82 21 0.012 0.001 -9.000 -9.000 82 32 0.056 0.001 -9.000 -9.000 84 4 -9.000 -9.000 0.455 0.006 84 5 0.010 0.006 -9.000 -9.000 84 34 -9.000 -9.000 1.751 0.012 86 5 0.005 0.003 -9.000 -9.000 86 14 0.030 0.001 -9.000 -9.000 86 30 0.024 0.003 -9.000 -9.000 88 4 -9.000 -9.000 0.533 0.011 88 17 0.022 0.002 -9.000 -9.000 88 31 0.030 0.006 -9.000 -9.000 88 33 -9.000 -9.000 0.463 0.006 90 4 -9.000 -9.000 0.865 0.006 90 7 0.006 0.005 -9.000 -9.000 90 20 0.010 0.000 -9.000 -9.000 92 5 -9.000 -9.000 0.654 0.294 92 14 0.005 0.003 -9.000 -9.000 92 16 0.008 0.003 -9.000 -9.000 92 26 0.026 0.004 -9.000 -9.000 92 32 0.055 0.005 -9.000 -9.000 94 5 0.020 0.001 -9.000 -9.000 94 6 -9.000 -9.000 0.884 0.002 94 15 0.033 0.002 -9.000 -9.000 94 26 0.027 0.003 -9.000 -9.000 96 4 -9.000 -9.000 0.988 0.001 96 6 0.018 0.001 -9.000 -9.000 96 28 0.037 0.001 -9.000 -9.000 98 4 -9.000 -9.000 1.169 0.028 98 6 0.024 0.000 -9.000 -9.000 98 18 0.010 0.006 -9.000 -9.000 98 26 0.033 0.008 -9.000 -9.000 100 4 -9.000 -9.000 1.051 0.006 100 16 0.036 0.001 -9.000 -9.000 100 25 0.037 0.008 -9.000 -9.000 102 6 -9.000 -9.000 1.135 0.006 102 15 0.043 0.001 -9.000 -9.000 102 24 0.041 0.004 -9.000 -9.000 104 3 0.032 0.007 -9.000 -9.000 104 4 -9.000 -9.000 1.105 0.007 104 29 0.021 0.001 -9.000 -9.000 104 32 -9.000 -9.000 0.607 0.318 104 34 -9.000 -9.000 2.017 0.059 106 12 -9.000 -9.000 1.044 0.000 106 18 0.003 0.001 -9.000 -9.000 108 16 0.039 0.006 -9.000 -9.000 108 26 0.022 0.003 -9.000 -9.000 110 3 0.028 0.001 -9.000 -9.000 110 5 -9.000 -9.000 1.249 0.013 110 26 -9.000 -9.000 0.639 0.012 110 32 0.103 0.005 -9.000 -9.000 112 18 0.006 0.007 -9.000 -9.000 112 30 0.164 0.004 -9.000 -9.000 114 2 0.028 0.001 -9.000 -9.000 114 4 -9.000 -9.000 1.241 0.020 114 6 -9.000 -9.000 1.129 0.028 114 13 0.055 0.001 -9.000 -9.000 114 24 0.059 0.001 -9.000 -9.000 116 8 0.021 0.007 -9.000 -9.000 116 10 -9.000 -9.000 0.996 0.002 116 16 0.052 0.001 -9.000 -9.000 116 26 0.030 0.001 -9.000 -9.000 118 4 -9.000 -9.000 1.128 0.026 118 10 0.049 0.017 -9.000 -9.000 118 12 0.058 0.007 -9.000 -9.000 118 22 0.033 0.002 -9.000 -9.000 120 16 0.017 0.005 -9.000 -9.000 120 20 0.045 0.035 0.429 0.015 125 8 -9.000 -9.000 0.270 0.008 125 22 0.145 0.003 -9.000 -9.000 129 7 0.136 0.003 -9.000 -9.000 130 6 -9.000 -9.000 2.107 0.021 TABLE 8. CFC air measurements Date GMT Latitude Longitude CFC-11 CFC-12 CFC-113 CCl4 (hhmm) (°N) (°W) (ppt) (ppt) (ppt) (ppt) -------------------------------------------------------------------- 24-Jan-98 1840 27.433 14.850 259.836 535.550 79.192 -9.000 24-Jan-98 1851 27.433 14.851 260.321 537.726 79.103 -9.000 24-Jan-98 1902 27.433 14.851 261.361 534.915 77.644 -9.000 24-Jan-98 1913 27.433 14.851 261.377 536.906 77.760 -9.000 24-Jan-98 1924 27.424 14.891 262.772 537.277 77.314 -9.000 27-Jan-98 1946 24.909 22.448 262.927 540.885 79.736 -9.000 27-Jan-98 1956 24.876 22.532 263.902 543.954 82.513 -9.000 27-Jan-98 2006 24.871 22.547 263.581 547.197 78.311 -9.000 27-Jan-98 2026 24.840 22.632 263.681 548.454 79.922 -9.000 27-Jan-98 2036 24.834 22.646 264.611 549.683 78.559 -9.000 27-Jan-98 2046 24.834 22.646 265.075 549.246 77.953 -9.000 28-Jan-98 2106 24.500 24.961 263.434 537.866 79.534 -9.000 28-Jan-98 2116 24.501 25.026 262.535 538.353 77.246 -9.000 28-Jan-98 2126 24.503 25.062 263.367 540.686 78.619 -9.000 28-Jan-98 2146 24.504 25.080 262.361 538.433 78.813 -9.000 28-Jan-98 2156 24.503 25.182 259.377 534.339 79.203 -9.000 28-Jan-98 2206 24.503 25.199 259.908 536.414 77.986 -9.000 29-Jan-98 1239 24.500 26.755 265.207 539.051 77.299 -9.000 29-Jan-98 1309 24.499 26.869 264.325 543.569 81.042 -9.000 29-Jan-98 1319 24.501 26.932 265.751 543.250 81.041 -9.000 29-Jan-98 1329 24.501 26.966 261.947 539.318 81.010 -9.000 29-Jan-98 1339 24.500 26.983 264.225 543.042 78.873 -9.000 29-Jan-98 1420 24.500 27.146 265.708 542.256 81.572 -9.000 31-Jan-98 2100 24.500 32.733 260.684 533.662 80.721 -9.000 31-Jan-98 2110 24.500 32.733 262.469 537.215 80.101 -9.000 31-Jan-98 2120 24.500 32.733 260.907 533.539 78.561 -9.000 31-Jan-98 2150 24.500 32.750 258.837 532.814 77.423 -9.000 31-Jan-98 2200 24.500 32.784 263.848 541.865 77.622 -9.000 31-Jan-98 2210 24.500 32.801 259.333 532.263 77.621 -9.000 1-Feb-98 1413 24.502 34.383 -9.000 -9.000 -9.000 89.351 1-Feb-98 1433 24.502 34.383 -9.000 -9.000 -9.000 85.866 1-Feb-98 1453 24.502 34.383 -9.000 -9.000 -9.000 84.658 3-Feb-98 1515 24.500 39.983 262.053 536.784 79.448 -9.000 3-Feb-98 1525 24.498 39.996 262.736 536.844 78.944 -9.000 3-Feb-98 1535 24.498 40.029 261.965 536.178 78.790 -9.000 3-Feb-98 1545 24.498 40.029 261.492 536.176 79.798 -9.000 3-Feb-98 1615 24.501 40.143 262.094 539.114 77.696 -9.000 3-Feb-98 1625 24.501 40.240 261.884 539.831 78.942 -9.000 3-Feb-98 1803 24.500 40.533 -9.000 -9.000 -9.000 94.672 3-Feb-98 1823 24.500 40.533 -9.000 -9.000 -9.000 93.793 4-Feb-98 734 41.633 40.533 -9.000 -9.000 -9.000 92.265 4-Feb-98 754 41.633 40.533 -9.000 -9.000 -9.000 94.492 4-Feb-98 834 41.633 40.533 -9.000 -9.000 -9.000 91.098 4-Feb-98 854 41.633 40.533 -9.000 -9.000 -9.000 93.565 6-Feb-98 1137 24.500 47.134 -9.000 -9.000 -9.000 94.687 6-Feb-98 1157 24.500 47.134 -9.000 -9.000 -9.000 92.685 6-Feb-98 1237 24.500 47.134 -9.000 -9.000 -9.000 91.974 6-Feb-98 1257 24.500 47.134 -9.000 -9.000 -9.000 93.088 7-Feb-98 1224 24.500 49.333 262.958 538.920 79.104 -9.000 7-Feb-98 1234 24.500 49.333 261.579 540.095 80.068 -9.000 7-Feb-98 1244 24.500 49.333 261.338 538.346 79.588 -9.000 7-Feb-98 1314 24.500 49.333 265.800 540.404 81.139 -9.000 7-Feb-98 1324 24.500 49.333 262.774 539.189 79.657 -9.000 7-Feb-98 1334 24.500 49.333 262.934 539.476 79.559 -9.000 7-Feb-98 1531 24.500 49.461 258.404 531.774 78.156 -9.000 8-Feb-98 1914 24.501 51.533 261.171 537.612 80.509 -9.000 8-Feb-98 1924 24.500 51.533 262.143 538.129 79.696 -9.000 8-Feb-98 1934 24.499 51.546 265.034 538.779 80.208 -9.000 8-Feb-98 2004 24.500 51.636 262.012 536.424 80.017 -9.000 8-Feb-98 2014 24.500 51.636 261.953 537.730 79.940 -9.000 8-Feb-98 2024 24.499 51.699 263.807 538.928 79.901 -9.000 8-Feb-98 2056 24.501 51.533 -9.000 -9.000 -9.000 95.090 8-Feb-98 2116 24.501 51.533 -9.000 -9.000 -9.000 93.306 8-Feb-98 2156 24.501 51.533 -9.000 -9.000 -9.000 93.817 8-Feb-98 2216 24.501 51.533 -9.000 -9.000 -9.000 91.694 9-Feb-98 2244 24.502 53.784 261.719 537.661 81.545 -9.000 9-Feb-98 2254 24.504 53.851 262.597 539.557 80.872 -9.000 9-Feb-98 2304 24.504 53.880 261.726 537.667 79.912 -9.000 9-Feb-98 2324 24.503 53.956 264.344 541.163 80.720 -9.000 9-Feb-98 2334 24.502 53.987 262.269 536.927 80.020 -9.000 9-Feb-98 2344 24.502 53.987 262.205 536.721 80.565 -9.000 TABLE 8. CFC air measurements (continued) Date GMT Latitude Longitude CFC-11 CFC-12 CFC-113 CCl4 (hhmm) (°N) (°W) (ppt) (ppt) (ppt) (ppt) -------------------------------------------------------------------- 10-Feb-98 2032 24.500 55.933 -9.000 -9.000 -9.000 94.388 10-Feb-98 2052 24.500 55.933 -9.000 -9.000 -9.000 93.208 10-Feb-98 2112 24.500 55.933 -9.000 -9.000 -9.000 92.775 10-Feb-98 2132 24.500 55.933 -9.000 -9.000 -9.000 91.823 11-Feb-98 339 24.500 56.667 -9.000 -9.000 -9.000 94.978 11-Feb-98 359 24.500 56.667 -9.000 -9.000 -9.000 95.100 11-Feb-98 439 24.500 56.667 -9.000 -9.000 -9.000 93.361 11-Feb-98 459 24.500 56.667 -9.000 -9.000 -9.000 94.658 11-Feb-98 2204 24.500 58.134 -9.000 -9.000 -9.000 96.657 11-Feb-98 2224 24.500 58.134 -9.000 -9.000 -9.000 96.483 11-Feb-98 2244 24.500 58.134 -9.000 -9.000 -9.000 96.476 13-Feb-98 115 24.500 61.067 262.315 536.445 81.119 -9.000 13-Feb-98 125 24.500 61.067 262.475 538.298 82.255 -9.000 13-Feb-98 135 24.500 61.067 261.623 538.645 80.140 -9.000 13-Feb-98 155 24.506 61.071 261.686 538.295 79.729 -9.000 13-Feb-98 205 24.505 61.105 262.698 538.700 80.228 -9.000 13-Feb-98 215 24.505 61.105 261.676 536.758 79.115 -9.000 13-Feb-98 229 24.500 61.801 -9.000 -9.000 -9.000 93.299 13-Feb-98 249 24.500 61.801 -9.000 -9.000 -9.000 94.033 13-Feb-98 329 24.500 61.801 -9.000 -9.000 -9.000 94.533 13-Feb-98 349 24.500 61.801 -9.000 -9.000 -9.000 95.347 14-Feb-98 1944 24.500 65.468 262.707 539.047 80.631 -9.000 14-Feb-98 1954 24.500 65.467 262.465 538.199 81.209 -9.000 14-Feb-98 2004 24.501 65.467 262.275 536.354 80.125 -9.000 14-Feb-98 2024 24.500 65.467 262.132 536.824 80.285 -9.000 14-Feb-98 2034 24.501 65.467 262.028 537.808 80.243 -9.000 14-Feb-98 2044 24.501 65.467 262.004 537.114 80.121 -9.000 16-Feb-98 146 24.504 68.440 262.523 540.348 80.763 -9.000 16-Feb-98 156 24.503 68.544 263.901 539.621 81.137 -9.000 16-Feb-98 206 24.502 68.562 261.984 538.864 79.805 -9.000 16-Feb-98 226 24.498 68.666 263.276 540.683 79.877 -9.000 16-Feb-98 236 24.498 68.684 263.034 541.216 79.900 -9.000 16-Feb-98 246 24.498 68.684 263.002 541.274 80.052 -9.000 16-Feb-98 250 24.500 69.133 -9.000 -9.000 -9.000 94.950 16-Feb-98 310 24.500 69.133 -9.000 -9.000 -9.000 95.214 16-Feb-98 330 24.500 69.133 -9.000 -9.000 -9.000 93.795 19-Feb-98 25 26.500 73.216 262.293 538.847 80.539 -9.000 19-Feb-98 35 26.500 73.217 262.142 538.710 80.844 -9.000 19-Feb-98 45 26.500 73.217 261.824 539.329 80.451 -9.000 19-Feb-98 55 26.501 73.309 262.074 540.199 80.325 -9.000 19-Feb-98 110 26.500 73.583 -9.000 -9.000 -9.000 96.505 19-Feb-98 130 26.500 73.583 -9.000 -9.000 -9.000 96.064 19-Feb-98 150 26.500 73.583 -9.000 -9.000 -9.000 95.901 19-Feb-98 210 26.500 73.583 -9.000 -9.000 -9.000 94.810 20-Feb-98 1324 26.500 75.500 -9.000 -9.000 -9.000 96.687 20-Feb-98 1344 26.500 75.500 -9.000 -9.000 -9.000 95.869 20-Feb-98 1424 26.500 75.500 -9.000 -9.000 -9.000 95.886 20-Feb-98 1444 26.500 75.500 -9.000 -9.000 -9.000 95.399 20-Feb-98 2333 26.500 75.900 -9.000 -9.000 -9.000 96.398 20-Feb-98 2353 26.500 75.900 -9.000 -9.000 -9.000 95.629 21-Feb-98 1549 26.510 76.427 262.483 540.744 80.515 -9.000 21-Feb-98 1559 26.510 76.428 262.273 539.635 80.446 -9.000 21-Feb-98 1609 26.511 76.428 262.793 541.135 80.816 -9.000 21-Feb-98 1629 26.514 76.431 262.827 538.937 79.301 -9.000 21-Feb-98 1639 26.516 76.434 263.024 538.655 78.736 -9.000 21-Feb-98 1649 26.508 76.482 262.900 538.355 79.284 -9.000 22-Feb-98 108 26.500 76.617 261.254 537.878 79.587 -9.000 22-Feb-98 152 26.500 76.683 260.123 536.113 78.455 -9.000 22-Feb-98 234 26.500 76.683 -9.000 -9.000 -9.000 96.873 22-Feb-98 254 26.500 76.683 -9.000 -9.000 -9.000 96.657 23-Feb-98 237 26.111 78.494 264.570 540.167 81.155 -9.000 23-Feb-98 247 26.111 78.494 264.310 539.409 80.459 -9.000 23-Feb-98 257 26.163 78.587 262.826 539.090 79.707 -9.000 23-Feb-98 307 26.168 78.606 262.319 538.885 79.498 -9.000 23-Feb-98 337 26.171 78.731 262.246 539.018 79.676 -9.000 23-Feb-98 539 27.001 79.200 -9.000 -9.000 -9.000 93.798 23-Feb-98 559 27.001 79.200 -9.000 -9.000 -9.000 93.073 23-Feb-98 619 27.001 79.200 -9.000 -9.000 -9.000 93.724 23-Feb-98 1401 27.038 79.481 -9.000 -9.000 -9.000 97.231 23-Feb-98 1421 27.038 79.481 -9.000 -9.000 -9.000 96.196 23-Feb-98 1441 27.038 79.481 -9.000 -9.000 -9.000 95.753 24-Feb-98 250 26.999 79.937 -9.000 -9.000 -9.000 97.861 24-Feb-98 310 26.999 79.937 -9.000 -9.000 -9.000 97.393 TABLE 9. CFC air values (interpolated to station locations) Station Date Latitude Longitude CFC-11 CFC-12 CFC-113 CCl4 (°N) (°W) (ppt) (ppt) (ppt) (ppt) -------------------------------------------------------------------- 6 24-Jan-98 27.433 14.850 259.836 535.550 79.192 -9.000 7 24-Jan-98 27.433 14.851 260.321 537.726 79.103 -9.000 7 24-Jan-98 27.433 14.851 261.361 534.915 77.644 -9.000 7 24-Jan-98 27.433 14.851 261.377 536.906 77.760 -9.000 7 24-Jan-98 27.424 14.891 262.772 537.277 77.314 -9.000 20 27-Jan-98 24.909 22.448 262.927 540.885 79.736 -9.000 20 27-Jan-98 24.876 22.532 263.902 543.954 82.513 -9.000 20 27-Jan-98 24.871 22.547 263.581 547.197 78.311 -9.000 20 27-Jan-98 24.840 22.632 263.681 548.454 79.922 -9.000 20 27-Jan-98 24.834 22.646 264.611 549.683 78.559 -9.000 20 27-Jan-98 24.834 22.646 265.075 549.246 77.953 -9.000 24 28-Jan-98 24.500 24.961 263.434 537.866 79.534 -9.000 24 28-Jan-98 24.501 25.026 262.535 538.353 77.246 -9.000 24 28-Jan-98 24.503 25.062 263.367 540.686 78.619 -9.000 24 28-Jan-98 24.504 25.080 262.361 538.433 78.813 -9.000 24 28-Jan-98 24.503 25.182 259.377 534.339 79.203 -9.000 24 28-Jan-98 24.503 25.199 259.908 536.414 77.986 -9.000 26 29-Jan-98 24.500 26.755 265.207 539.051 77.299 -9.000 26 29-Jan-98 24.499 26.869 264.325 543.569 81.042 -9.000 26 29-Jan-98 24.501 26.932 265.751 543.250 81.041 -9.000 26 29-Jan-98 24.501 26.966 261.947 539.318 81.010 -9.000 26 29-Jan-98 24.500 26.983 264.225 543.042 78.873 -9.000 26 29-Jan-98 24.500 27.146 265.708 542.256 81.572 -9.000 34 31-Jan-98 24.500 32.733 260.684 533.662 80.721 -9.000 34 31-Jan-98 24.500 32.733 262.469 537.215 80.101 -9.000 34 31-Jan-98 24.500 32.733 260.907 533.539 78.561 -9.000 34 31-Jan-98 24.500 32.750 258.837 532.814 77.423 -9.000 34 31-Jan-98 24.500 32.784 263.848 541.865 77.622 -9.000 34 31-Jan-98 24.500 32.801 259.333 532.263 77.621 -9.000 36 1-Feb-98 24.502 34.383 -9.000 -9.000 -9.000 89.351 36 1-Feb-98 24.502 34.383 -9.000 -9.000 -9.000 85.866 36 1-Feb-98 24.502 34.383 -9.000 -9.000 -9.000 84.658 42 3-Feb-98 24.500 39.983 262.053 536.784 79.448 -9.000 42 3-Feb-98 24.498 39.996 262.736 536.844 78.944 -9.000 42 3-Feb-98 24.498 40.029 261.965 536.178 78.790 -9.000 42 3-Feb-98 24.498 40.029 261.492 536.176 79.798 -9.000 42 3-Feb-98 24.501 40.143 262.094 539.114 77.696 -9.000 42 3-Feb-98 24.501 40.240 261.884 539.831 78.942 -9.000 44 3-Feb-98 24.500 40.533 -9.000 -9.000 -9.000 94.672 44 3-Feb-98 24.500 40.533 -9.000 -9.000 -9.000 93.793 44 4-Feb-98 41.633 40.533 -9.000 -9.000 -9.000 92.265 44 4-Feb-98 41.633 40.533 -9.000 -9.000 -9.000 94.492 44 4-Feb-98 41.633 40.533 -9.000 -9.000 -9.000 91.098 44 4-Feb-98 41.633 40.533 -9.000 -9.000 -9.000 93.565 56 6-Feb-98 24.500 47.134 -9.000 -9.000 -9.000 94.687 56 6-Feb-98 24.500 47.134 -9.000 -9.000 -9.000 92.685 56 6-Feb-98 24.500 47.134 -9.000 -9.000 -9.000 91.974 56 6-Feb-98 24.500 47.134 -9.000 -9.000 -9.000 93.088 60 7-Feb-98 24.500 49.333 262.958 538.920 79.104 -9.000 60 7-Feb-98 24.500 49.333 261.579 540.095 80.068 -9.000 60 7-Feb-98 24.500 49.333 261.338 538.346 79.588 -9.000 60 7-Feb-98 24.500 49.333 265.800 540.404 81.139 -9.000 60 7-Feb-98 24.500 49.333 262.774 539.189 79.657 -9.000 60 7-Feb-98 24.500 49.333 262.934 539.476 79.559 -9.000 60 7-Feb-98 24.500 49.461 258.404 531.774 78.156 -9.000 64 8-Feb-98 24.501 51.533 261.171 537.612 80.509 -9.000 64 8-Feb-98 24.500 51.533 262.143 538.129 79.696 -9.000 64 8-Feb-98 24.499 51.546 265.034 538.779 80.208 -9.000 64 8-Feb-98 24.500 51.636 262.012 536.424 80.017 -9.000 64 8-Feb-98 24.500 51.636 261.953 537.730 79.940 -9.000 64 8-Feb-98 24.499 51.699 263.807 538.928 79.901 -9.000 64 8-Feb-98 24.501 51.533 -9.000 -9.000 -9.000 95.090 64 8-Feb-98 24.501 51.533 -9.000 -9.000 -9.000 93.306 64 8-Feb-98 24.501 51.533 -9.000 -9.000 -9.000 93.817 64 8-Feb-98 24.501 51.533 -9.000 -9.000 -9.000 91.694 58 9-Feb-98 24.502 53.784 261.719 537.661 81.545 -9.000 58 9-Feb-98 24.504 53.851 262.597 539.557 80.872 -9.000 58 9-Feb-98 24.504 53.880 261.726 537.667 79.912 -9.000 58 9-Feb-98 24.503 53.956 264.344 541.163 80.720 -9.000 58 9-Feb-98 24.502 53.987 262.269 536.927 80.020 -9.000 58 9-Feb-98 24.502 53.987 262.205 536.721 80.565 -9.000 71 10-Feb-98 24.500 55.933 -9.000 -9.000 -9.000 94.388 71 10-Feb-98 24.500 55.933 -9.000 -9.000 -9.000 93.208 71 10-Feb-98 24.500 55.933 -9.000 -9.000 -9.000 92.775 71 10-Feb-98 24.500 55.933 -9.000 -9.000 -9.000 91.823 72 11-Feb-98 24.500 56.667 -9.000 -9.000 -9.000 94.978 72 11-Feb-98 24.500 56.667 -9.000 -9.000 -9.000 95.100 72 11-Feb-98 24.500 56.667 -9.000 -9.000 -9.000 93.361 72 11-Feb-98 24.500 56.667 -9.000 -9.000 -9.000 94.658 74 11-Feb-98 24.500 58.134 -9.000 -9.000 -9.000 96.657 74 11-Feb-98 24.500 58.134 -9.000 -9.000 -9.000 96.483 74 11-Feb-98 24.500 58.134 -9.000 -9.000 -9.000 96.476 79 13-Feb-98 24.500 61.067 262.315 536.445 81.119 -9.000 79 13-Feb-98 24.500 61.067 262.475 538.298 82.255 -9.000 79 13-Feb-98 24.500 61.067 261.623 538.645 80.140 -9.000 79 13-Feb-98 24.506 61.071 261.686 538.295 79.729 -9.000 79 13-Feb-98 24.505 61.105 262.698 538.700 80.228 -9.000 79 13-Feb-98 24.505 61.105 261.676 536.758 79.115 -9.000 79 13-Feb-98 24.500 61.801 -9.000 -9.000 -9.000 93.299 79 13-Feb-98 24.500 61.801 -9.000 -9.000 -9.000 94.033 79 13-Feb-98 24.500 61.801 -9.000 -9.000 -9.000 94.533 79 13-Feb-98 24.500 61.801 -9.000 -9.000 -9.000 95.347 84 14-Feb-98 24.500 65.468 262.707 539.047 80.631 -9.000 84 14-Feb-98 24.500 65.467 262.465 538.199 81.209 -9.000 84 14-Feb-98 24.501 65.467 262.275 536.354 80.125 -9.000 84 14-Feb-98 24.500 65.467 262.132 536.824 80.285 -9.000 84 14-Feb-98 24.501 65.467 262.028 537.808 80.243 -9.000 84 14-Feb-98 24.501 65.467 262.004 537.114 80.121 -9.000 88 16-Feb-98 24.504 68.440 262.523 540.348 80.763 -9.000 88 16-Feb-98 24.503 68.544 263.901 539.621 81.137 -9.000 88 16-Feb-98 24.502 68.562 261.984 538.864 79.805 -9.000 88 16-Feb-98 24.498 68.666 263.276 540.683 79.877 -9.000 88 16-Feb-98 24.498 68.684 263.034 541.216 79.900 -9.000 88 16-Feb-98 24.498 68.684 263.002 541.274 80.052 -9.000 89 16-Feb-98 24.500 69.133 -9.000 -9.000 -9.000 94.950 89 16-Feb-98 24.500 69.133 -9.000 -9.000 -9.000 95.214 89 16-Feb-98 24.500 69.133 -9.000 -9.000 -9.000 93.795 100 19-Feb-98 26.500 73.216 262.293 538.847 80.539 -9.000 100 19-Feb-98 26.500 73.217 262.142 538.710 80.844 -9.000 100 19-Feb-98 26.500 73.217 261.824 539.329 80.451 -9.000 100 19-Feb-98 26.501 73.309 262.074 540.199 80.325 -9.000 101 19-Feb-98 26.500 73.583 -9.000 -9.000 -9.000 96.505 101 19-Feb-98 26.500 73.583 -9.000 -9.000 -9.000 96.064 101 19-Feb-98 26.500 73.583 -9.000 -9.000 -9.000 95.901 101 19-Feb-98 26.500 73.583 -9.000 -9.000 -9.000 94.810 108 20-Feb-98 26.500 75.500 -9.000 -9.000 -9.000 96.687 108 20-Feb-98 26.500 75.500 -9.000 -9.000 -9.000 95.869 108 20-Feb-98 26.500 75.500 -9.000 -9.000 -9.000 95.886 108 20-Feb-98 26.500 75.500 -9.000 -9.000 -9.000 95.399 110 20-Feb-98 26.500 75.900 -9.000 -9.000 -9.000 96.398 110 20-Feb-98 26.500 75.900 -9.000 -9.000 -9.000 95.629 114 21-Feb-98 26.510 76.427 262.483 540.744 80.515 -9.000 114 21-Feb-98 26.510 76.428 262.273 539.635 80.446 -9.000 114 21-Feb-98 26.511 76.428 262.793 541.135 80.816 -9.000 114 21-Feb-98 26.514 76.431 262.827 538.937 79.301 -9.000 114 21-Feb-98 26.516 76.434 263.024 538.655 78.736 -9.000 114 21-Feb-98 26.508 76.482 262.900 538.355 79.284 -9.000 116 22-Feb-98 26.500 76.617 261.254 537.878 79.587 -9.000 117 22-Feb-98 26.500 76.683 260.123 536.113 78.455 -9.000 117 22-Feb-98 26.500 76.683 -9.000 -9.000 -9.000 96.873 117 22-Feb-98 26.500 76.683 -9.000 -9.000 -9.000 96.657 122 23-Feb-98 26.111 78.494 264.570 540.167 81.155 -9.000 122 23-Feb-98 26.111 78.494 264.310 539.409 80.459 -9.000 122 23-Feb-98 26.163 78.587 262.826 539.090 79.707 -9.000 122 23-Feb-98 26.168 78.606 262.319 538.885 79.498 -9.000 122 23-Feb-98 26.171 78.731 262.246 539.018 79.676 -9.000 122 23-Feb-98 27.001 79.200 -9.000 -9.000 -9.000 93.798 122 23-Feb-98 27.001 79.200 -9.000 -9.000 -9.000 93.073 122 23-Feb-98 27.001 79.200 -9.000 -9.000 -9.000 93.724 125 23-Feb-98 27.038 79.481 -9.000 -9.000 -9.000 97.231 125 23-Feb-98 27.038 79.481 -9.000 -9.000 -9.000 96.196 125 23-Feb-98 27.038 79.481 -9.000 -9.000 -9.000 95.753 130 24-Feb-98 26.999 79.937 -9.000 -9.000 -9.000 97.861 130 24-Feb-98 26.999 79.937 -9.000 -9.000 -9.000 97.393