ࡱ> 352` gjbjb "ddgBBBBBBB "  *:PPPPg i i i i i i , Rl Bi" S BBPP S S S BPBPg S V$zBBBBg S S BBS . wE FS S  0 S S S S BTOTAL 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 (Wilke et al., 1993). The instruments were calibrated at the beginning, middle, 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 standards are Certified Reference Materials (CRMs) consisting of poisoned, filtered, and UV irradiated seawater supplied by Dr. A. Dickson of Scripps Institution of Oceanography (SIO), and their accuracy is determined shoreside manometrically. On this cruise, the overall accuracy and precision for the CRMs on both instruments combined was 0.9 1.1 mol/kg respectively (n=252). DIC data reported to the database have been recalculated using CTD salinities, and were also corrected to the average Batch 65 CRM value calculated on a per instrument/per leg 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 The tube was pinched off and withdrawn, creating a 5-mL headspace, and 0.2 mL of saturated HgCl2 solution was added as a preservative.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 24 hours prior to analysis. Over 4000 samples were analyzed for discrete DIC. Due to time constraints of the DIC analyses, full profiles at every station were not possible. Full profiles were completed as often as feasible, generally every other station; on the alternate stations, the upper 1200m were sampled. Replicate samples were generally taken from the surface, oxygen minimum, and bottom depth, and were interspersed throughout the station analysis for quality assurance of the integrity of the coulometer cell solutions. No systematic differences between the replicates were observed. All replicate samples were averaged and flagged in the database following WHP protocol (QC=6). Occasional equipment problems resulted in a backlog of samples; in that case only surface samples were drawn for analysis. References: Johnson, K.M., A.E. King, and J. McN. Sieburth (1985): Coulometric DIC analyses for marine studies: An introduction. Mar. Chem., 16, 6182. 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, 117133. Johnson, K.M. (1992): Operators manual: Single operator multiparameter metabolic analyzer (SOMMA) for total carbon dioxide (CT) with coulometric detection. Brookhaven National Laboratory, Brookhaven, N.Y., 70pp. 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, 167189. Lewis, E. and D. W. R. Wallace (1998) Program developed for CO2 system calculations. Oak Ridge, Oak Ridge National Laboratory.  HYPERLINK "http://cdiac.esd.ornl.gov/oceans/" http://cdiac.esd.ornl.gov/oceans/ 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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