╨╧рб▒с>■  *,■   )                                                                                                                                                                                                                                                                                                                                                                                                                                                ье┴й@ Ё┐╓jbjb▄б▄б Ъ ╢├╢├╓      lFFFFF R F┴ *jnnnnnnn~ А А А А А А ,ы  км nnnnnм nnjnОnn~ .n~ Lj j ^ $·╫╝FF№"j j ┴ ┴ j ╡╡j ├хTOTAL DISSOLVED INORGANIC CARBON (DIC) Dissolved Inorganic Carbon (DIC) The DIC analytical equipment was set up in a seagoing container modified for use as a shipboard laboratory. 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 Ken Johnson (Johnson et al., 1985,1987,1993; Johnson, 1992) of Brookhaven National Laboratory (BNL). In the coulometric analysis of DIC, all carbonate species are converted to CO2 (gas) by addition of excess hydrogen to the seawater sample, and the evolved CO2 gas is carried into the titration cell of the coulometer, where it reacts quantitatively with a proprietary reagent based on ethanolamine to generate hydrogen ions. These are subsequently titrated with coulometrically generated OH-. CO2 is thus measured by integrating the total change required to achieve this. The coulometers were each calibrated by injecting aliquots of pure CO2 (99.995%) by means of an 8-port valve outfitted with two sample loops. The instruments were calibrated at the beginning and end of each station with a set of the gas loop injections. Secondary standards were run throughout the cruise on each analytical system. These Certified Reference Materials (CRMs) are poisoned, filtered, and UV irradiated seawater supplied by Dr. A. Dickson of Scripps Institution of Oceanography (SIO), which have been certified in their shore-based facility to have a known concentration of DIC. Although there were numerous small equipment problems, particularly during the first third of the cruise, the overall accuracy and precision of the at-sea analyses of the CRMs on both instruments was Ц0.05▒1.01 ╡mol/kg (n=77) for both systems combined. DIC data reported to the database have been recalculated using the bottle salinities, and, although insignificant for this cruise, corrected to the Batch 61 CRM value on a per instrument basis. Samples were drawn from the Niskin-type bottles into cleaned, precombusted 500-mL Pyrex bottles using Tygon tubing. Bottles were rinsed once and filled from the bottom, overflowing half a volume, and care was taken not to entrain any bubbles. The tube was pinched off and withdrawn, creating a 5-mL headspace, and 0.2 mL of saturated HgCl2 solution was added as a preservative. The sample bottles were sealed with glass stoppers lightly covered with Apiezon-L grease, and were stored at room temperature for a maximum of 12 hours prior to analysis. Aproximately 1640 samples were analyzed for DIC; full profiles were completed on the СAТ (even numbered) stations, with replicate samples taken from the surface, oxygen minimum, and bottom Niskin-type bottles. At a minimum, replicate surface samples were taken at every СBТ (odd numbered) station, and when time permitted, additional depths were sampled. Approximately 120 replicates were collected in total. The replicate samples were run at different times during the station analysis for quality assurance of the integrity of the coulometer cell solutions. No systematic differences between the replicates were observed and the standard deviation of the differences was approximately 1.2 ╡mol/kg on both systems. References: Johnson, K.M., A.E. King, and J. McN. Sieburth (1985): Coulometric DIC analyses for marine studies: An introduction. Mar. Chem., 16, 61Ц82. Johnson, K.M., P.J. Williams, L. Brandstrom, and J. McN. Sieburth (1987): Coulometric total carbon analysis for marine studies: Automation and calibration. Mar. Chem., 21, 117Ц133. Johnson, K.M. (1992): OperatorТs manual: Single operator multiparameter metabolic analyzer (SOMMA) for total carbon dioxide (CT) with coulometric detection. Brookhaven National Laboratory, Brookhaven, N.Y., 70аpp. Johnson, K.M., K.D. Wills, D.B. Butler, W.K. Johnson, and C.S. Wong (1993): Coulometric total carbon dioxide analysis for marine studies: Maximizing the performance of an automated continuous gas extraction system and coulometric detector. Mar. Chem., 44, 167Ц189. Wilke, R.J., D.W.R. Wallace, and K.M. Johnson (1993): Water-based gravimetric method for the determination of gas loop volume. Anal. 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