ࡱ> TVSa $jbjb,, (<NNxxxxxxx&&&&&4'*:':':':':':':':'r't't't't't't',%)Rw+'x:':':':':''f'xx:':''f'f'f':'x:'x:'r'f'T6xxxx:'r'f'f'xxf'.' ^W&P'f'f' '0'f'U,f'U,f'f'xdzdzDiscrete measurements (TCO2, TALK, pCO2, and pH) metadata form ( * = mandatory field) Investigator:* Name:* Rik Wanninkhof Organization: NOAA/AOML Address: 4301 Rickenbacker Causeway Miami FL 33149 Phone: 305-361-4379 Email: rik.wanninkhof@noaa.gov Dataset Info:* Dataset ID:* P16N_2006 discrete pCO2 Submission Dates:* Initial Submission: (yyyy/mm/dd): 5/5/06 Revised Submission: (yyyy/mm/dd) Cruise Info:* Experiment: CLIVAR/CO2 repeat hydrography cruises Experiment Name:* P16N_2006 Cruise: Cruise ID: (Expocode) 3250TT191 Section: (Leg) leg 1 and leg 2 Geographical Coverage:* Geographical Region: Central and North Pacific between Papeete, Tahiti and Kodiak, Alaska Bounds:* Westernmost Longitude: 153 W Enter decimal fractions of degrees: (+ = E, - = W) or Degrees, Minutes, Seconds: East West Easternmost Longitude: 150 W Enter decimal fractions of degrees: (+ = E, - = W) or Degrees, Minutes, Seconds: East West Northernmost Latitude: 56 N Enter decimal fractions of degrees: (+ = N, - = S) or Degrees, Minutes, Seconds: North South Southernmost Latitude: 17 S Enter decimal fractions of degrees: (+ = N, - = S) or Degrees, Minutes, Seconds: North South Temporal Coverage: Start Date: (yyyy/mm/dd): 2006/02/14 End Date: (yyyy/mm/dd): 2006/03/30 Ports of Call: (One per line) Papeete, Tahiti Honolulu, HI Kodiak, AL Vessel:* Vessel Name: Thomas Thompson Vessel ID: Country: Vessel Owner: Variables Info:* Variable: discrete pCO2 analyzed at constant temperature Variable Name:* PCO2_UATM@20 Description of Variable: (units) : uatm Total Variables in the Data Set: Method Description:* pCO2 Data: Analysis: pCO2 Analysis Method: Sample Volume: (mL) 500 ml Headspace Volume: 70 ml Measurement Temperature: 20 or 12 C Temperature Normalization 20 C Temperature Correction Method: See Peng et al., 1987 Variable Reported: EXPOCODE: identifier SECT_ID: identifier STNNBR; identifier CASTNO: identifier SAMPNO: identifier BTLNBR: identifier BTLNBR_FLAG_W: identifier DATE: identifier TIME_GMT: identifier LATITUDE: identifier LONGITUDE: identifier PCO2_UATM@T: pCO2 at analysis temperature (See Peng et al., 1987) pCO2temp: analysis temperature PCO2_20_UATM: pCO2 corrected to 20 C PCO2_FLAG_W: QC flag (WOCE protocol ) Gas: Standard Gas Concentrations: The cylinder serial numbers and mole fractions of CO2 with balance artificial air are: CA5998 205.1 ppm CA5989 378.7 ppm CA5988 593.6 ppm CA5980 792.5 ppm CA5984 1037.0 ppm CA5940 1533.7 ppm Frequency of Standardization: In order to maintain analytical accuracy, a set of six gas standards is run through the analyzer before and after every ten seawater samples. Field Replicate Info: Generally when samples were taken, flasks were drawn on all the Niskins including four duplicates. Two of the duplicates were analyzed at different temperatures Storage Method: Samples were drawn from Niskin bottles into 500 ml volumetric flasks using Tygon tubing with a Silicone adapter that fit over the petcock to avoid contamination of DOM samples. Bottles were rinsed while inverted and filled from the bottom, overflowing half a volume while taking care not to entrain any bubbles. About 5 ml of water was withdrawn to allow for expansion of the water as it warms and to provide space for the stopper, tubing, and frit of the analytical system. Saturated mercuric chloride solution (0.2 ml) was added as a preservative. The sample bottles were sealed with a screw cap containing a polyethylene liner. The samples were stored in coolers at room temperature generally for no more than 5 hours. Accuracy Info: (Estimate overall precision and accuracy, and why) Three types of duplicates were taken. The average difference: [ABS(sample 1-sample2)/(sample 1+sample 2) * 100], std. dev. and number for the three types are listed below: Duplicates run at 20 C: av. dif. =0.3 +- 0.23% n = 33 (one value omitted) Duplicates run at 12 C: av. dif. = 0.3 +- 0.18 % n= 23 (one value omitted) Duplicates run at 12 C and 20 C* av. dif = 0.7 +- 0.75 % n= 59 (two values omitted) The omitted values were because of a problem in analysis in one of the duplicates *The duplicates run at different temperatures were normalized to 20 C and compared. Normalization was performed using the constants and procedures as outlined in Peng et al. 1987 as incorporated in the GW BASIC data reduction program. Of note is that using the constants as refit by Dickson and Millero and the salinity dependence of borate as proposed by Dickson gave an average difference of 1 %, that is, these constants yielded worse agreement in temperature normalization. Method References: (Publication(s) describing method): Wanninkhof, R., and Thoning, K., 1993, Measurement of fugacity of CO2 in surface water using continuous and discrete sampling methods: Mar. Chem., v. 44, no. 2-4, p. 189-205. Chen, H., Wanninkhof, R., Feely, R. A., and Greeley, D., 1995, Measurement of fugacity of carbon dioxide in sub-surface water: an evaluation of a method based on infrared analysis, NOAA technical report ERL AOML-85, 52 pp: NOAA/AOML, ERL AOML-85. Peng, T.-H., Takahashi, T., Broecker, W. S., and Olafsson, J., 1987, Seasonal variability of carbon dioxide, nutrients and oxygen in the northern North Atlantic surface water: observations and a model: Tellus, v. 39B, p. 439-458. Additional information: The discrete pCO2 system is patterned after the instrument described in Chipman et al. (1993) and is discussed in detail in Wanninkhof and Thoning (1993) and Chen et al. (1995). The major difference between the two systems is that Wanninkhof instrument uses a LI-COR (model 6262) non-dispersive infrared analyzer, while the Chipman instrument utilizes a gas chromatograph with a flame ionization detector. Once the samples reach the analyses temperature, a 50-ml headspace is created by displacing the water using a compressed standard gas with a CO2 mixing ratio close to the anticipated pCO2 of the water. The headspace is circulated in a closed loop through the infrared analyzer that measures CO2 and water vapor levels in the sample cell. The samples are equilibrated until the running mean of 20 consecutive 1-second readings from the analyzer differ by less than 0.1 ppm (parts per million by volume). This equilibration takes about 10 minutes. An expandable volume in the circulation loop near the flask consisting of a small, deflated balloon keeps the headspace of the flask at room pressure. In order to maintain analytical accuracy, a set of six gas standards is run through the analyzer before and after every ten seawater samples. The standards were obtained from Scott-Marin and referenced against primary standards purchased from C.D. Keeling in 1991, which are on the WMO-78 scale. The calculation of pCO2 in water from the headspace measurement involves several steps. The CO2 concentrations in the headspace are determined via a second-degree polynomial fit using the nearest three standard concentrations. Corrections for the water vapor concentration, the barometric pressure, and the changes induced in the carbonate equilibrium by the headspace-water mass transfer are made. The corrected results are reported at the analytical temperature and at a reference temperature of 20C. No instrumental problems occurred during the cruise. The relatively time-consuming analyses and the presence of only one analyst limited the spatial coverage. Sampling and analyses focused on precision and accuracy rather than high throughput. Data Set References: (Publication(s) describing data set) Citation: (How to cite this data set) Data Set Link: URL:* Label:* Link Note: (Optional instructions or remarks) ?r=Z!AJKZm   # - K U t  O e r   2 ; W c   浪hn2-hn2-OJQJhn2-hn2-6OJQJh2dhn2-OJQJh2dhn2-B*OJQJphhfwhn2-OJQJhfwhn2-6OJQJhfwhn2-56OJQJC?@Wi /Zm!)Kmgdn2-$ B n  D q  . 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