measurements of surface ocean carbon dioxide partial
TRANSCRIPT
Final Technical Report
Measurements of Surface Ocean Carbon Dioxide
Partial Pressure During WOCE
U. S. Department of Energy
Grant Number DE-FG03-90ER60981
1 June 1990 —31 May 1998
R. F. WeissScripps Institution of OceanographyUniversity of California, San Diego
La .TolIa,CaIifomia 92093-0220
DISCLAIMER
This report was prepared as an account of work sponsoredby an agency bfthe United States Government. Neitherthe United States Government nor any agency thereof, norany of their employees, make any warranty, express orimplied, or assumes any legal liability or responsibility forthe accuracy, completeness, or usefulness of anyinformation, apparatus, product, or process disclosed, orrepresents that its use would not infringe privately ownedrights. Reference herein to any specific commercialproduct, process, or service by trade name, trademark,manufacturer, or otherwise does not necessarily constituteor imply its endorsement, recommendation, or favoring bythe United States Government or any agency thereof. Theviews and opinions of authors expressed herein do notnecessarily state or reflect those of the United StatesGovernment or any agency thereof.
DISCLAIMER
Portions of this document may be illegiblein electronic image products. Images areproduced from the best available originaldocument.
Final Technical Report
All of the technical goals of the World Ocean Circulation Experiment (WOCE)field program which were supported under the Department of Energy research grant“Measurements of Surface Ocean Carbon Dioxide Partial Pressure During WOCE”(DE-FG03-90ER60981) have been met. This has included the measurement of the par-tial pressures of carbon dioxide (C02) and nitrous oxide (NzO) in both the surfaceocean and the atmosphere on 24 separate shipboard expedition legs of the WOCEHydrographic Programme. These measurements were made in the Pacific, Indian andAtlantic Oceans over a six-and-a-half year period, and over a distance of nearly 200,000kilometers of ship track. The total number of measurements, including ocean measure-ments, air measurements and standard gas measurements, is about 136,000 for each gas,or about 34,000 measurements of each gas in the ocean and in the air.
This global survey effort is directed at obtaining a better understanding of the roleof the oceans in the global atmospheric budgets of two important natural and anthro-pogenic modulators of climate through the “greenhouse effect”, COZ and NZO, and animportant natural and anthropogenic modulator of the Earth’s protective ozone layerthrough catalytic processes in the stratosphere, NZO. For both of these compounds, theoceans play a major role in their global budgets. In the case of COZ, roughly half of theanthropogenic production throu:@ the combustion of fossil fuels has been absorbed bythe world’s oceans. In the case of N20, roughly a third of the natural flux to the atmo-sphere originates in the oceans. As the interpretation of the variability in the oceanicdistributions of these compounds improves, measurements such as those supported bythis research project are playing an increasingly important role in improving our under-standing of natural and anthropogenic influences on climate and ozone.
The methods used to carry out these observations have been reported previously(Weiss, 1981; Weiss et aL, 1992). Briefly, surface ocean waters are pumped from thebow of the research vessel to the shipboard laboratory, where they are equilibrated witha gas headspace that is vented to atmospheric pressure using a 2-stage “equilibrator”.Samples of this gas space, and of clean air pumped to the laboratory, are analyzed by anautomated gas chromatography. COZ is detected by flame ionization after high-tempera-ture catalytic conversion to merhane in a steam of hydrogen. NZO is detected by elec-tron capture. Unknown sample injections are alternated with injections of high- andlow-concentration gas standards. The chromatographic analysis time is 7.5 minutes.Since four gases are analyzed in sequence, a total of 48 samples of equilibrated gas andof air are measured each day. The results for both gases are calibrated against sec-ondary air standards prepared at the Scripps Institution of Oceanography by C. D. Keel-ing for C02 and by R. F. Weiss for N20. The equilibrator measurements are correctedfor slight warming by the ship’s pumping system. The results are reported for both theequilibrated gas arid the air measurements as dry gas mole fractions, XC02 and XN20.These can be converted to partial pressures, pC02 and pN20, using the ancillary mea-surements of barometric pressure and water temperature (the latter for determining thewater vapor pressure).
Improvements in the measurement technique included the use of modern analog-to-digital and computer techniques to record complete chromatogmms and ancillarydata, and enlargement of the sample size used to measure N20 from 1 cm3 to 3 cm3.
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This work also represented the first time that we have relied heavily on personnel fromother laboratories to tend the equipment at sea. After some initial difficulties, and witha heavy reliance on training and on support via satellite communication, this hasbecome a reliable way to operate the measurement program at reduced cost.
The 24 expedition legs of the US WOCE program on which underway COZ andN20 measurements were made are listed in the following tables:
WOCE Pacific Ocean Expeditions
WOCE Line
Transit
P-17C(Tunes Leg 1)
P-16WP-17S(Tunes Leg 2)
P-16C(Tunes Leg 3)
P-6C
P-6W
P-14C
P-16WP-17S(Juno Leg 9)
P-17slP-19s(Juno Leg 10)
P-19N
Dates
5/31i91-6/1/91
6/1/91 -7/1 1/91
7/17191-8/25191
9/3/91-10/1/91
5/30/92-7/6/92
7/13192-7129192
911192-9113/92
10/6/92-11/26/92
12/3/92-1122/93
2/22/93-4/13/93
Ports
San Diego-Port San Luis
Port San Luis-Papeete
Papeete-Papeete
Papeete-Honolulu
Easter Island-Auckland
Auckland-Sydney
Auckland-Suva
Papeete-Papeete
Papeete-Punta Arenas
Punta Arenas-Panama
Ship
RN Washington
RN Washington
RN Washington
WV Washington
RN Knorr
RN Knorr
RN Knorr
RN Knorr
RN Knorr
RN Knorr
Operator
F. A. Van WoyS10
K. Sullivanu. Miami
G. MathieuLDEO
D. WisegarverPMEL/NoAA
F. A. VanWoyS10
M. J. Warner
M. J. Warner
F. A. Van WoyS10
P. K. SalamehS10
K. Sullivanu. Miami
3
WOCE Indian Ocean Expeditions
WOCE Line
I-8S/I-9S
I-9N
I-8N/I-5E
I-3
I-5WA-4
I-7N
I-1
I-lo
I-2
Dates
12/01/94-1/19/95
l/24/95-3/06/95
3/lo/95-4/16/95
4/20/95-6/07/95
6/1 l/95-7/1 1/95
7115195-8/24/95
8/29/95-10/18/95
11/06/95-11/24/95
1l/28/95-
Ports Ship
WV Knorr
R/V Knorr
RN Knorr
Operator
K. HargreavesPMELINOAA
Fremantle-Fremantle
Fremantle-Colombo
K. Sullivanu. Miami
Colombo-Fremantle
R. SchottleS10
Fremantle-Mauritius
RIV Knorr F. A, Van WoyS10
K. Mailletu. Miami
Mauritius-Mauritius
R/V Knorr
RN Knorr
RIV Knorr
K. Sullivanu. Miami
Mauritius-Mattrah
Mattrah-Singapore
S. Covey
Singapore-Singapore
RN Knorr K. Sullivanu. Miami
R/V Knorr R. SchottleS10
Singapore-Mombasa1/19/96
WOCE Atlantic Ocean Expeditions
Ship OperatorWOCE Line Dates Ports
Transit 5119197- Woods Hole-5/29/97 Azores
RN Knorr F. A. Van WoyS10
RN Knorr F. A. Van WOyS10
A-24 5/29/97- Azores-7/04/97 Halifax
A-20 7/17/97- Halifax-8/10/97 Trinidad
RN Knorr C. SabinePrinceton
A-22 8/15/97- Trinidad-9/03/97 Woods Hole
R/V Knorr R. RotterPrinceton
R/V Knorr G. EischeidWHOI
AR-24 lo/05/97- Woods Hole-11/19/97 Woods Hole
4
The results from these measurements are presented graphically in the followingfigures, which show the cruise tracks and the equilibrator and atmospheric results in thesame format and with the same Gaussian smoothing procedures as were used by Weisset al. (1992). The data plots are largely self-explanatory, and provide a very consider-able improvement in the geographic coverage of pCOz and pNzO data in the vast SouthPacific and Indian Oceans, as well as providing important repeat observations in theNorth Atlantic Ocean. Beyond this simple descriptive presentation, it is the subject offuture research to interpret these results in the context of the global COZ and NZO bud-gets and the processes that control them. It is also worth noting that the data reportedhere bring the total length of ship track measurements carried out by our laboratoryusing this technique to about 529,000 kilometers over a period of 20 years.
Finally, all of these data will be reported to the Carbon Dioxide Information Anal-ysis Center (CDIAC) in the form of a data report similar to Weiss et al. (1992). Thedata are close to their final fomn, except that the detailed IMET underway position andtemperature data for the most recent WOCE North Atlantic expedition legs have yet tobe merged with our data set. With the understanding that the support for the DOE COZprogram was being terminated, we decided to use the funds that were available to us tocomplete the shipboard measurement program in the North Atlantic, rather than to com-plete the reporting of the earlier data to CDIAC and fail to complete the WOCE mea-surements. We nevertheless expect to complete this reporting requirement within twoyears of the completion of the expedition work. Until then, all the completed data areavailable directly from us over the Internet via “ftp” (Unix File Transfer Protocol).
References
Weiss, R. F. Determinations of carbon dioxide and methane by dual catalyst flame ion-ization chromatography and nitrous oxide by electron capture chromatography, J.Chromatographic Science, 19,611-616 (1981),
Weiss, R. F., F. A. Van Woy, and P. K. Salameh. Surface Water and Atmospheric Car-bon Dioxide and Nitrous Oxide Observations by Shipboard Automated Gas Chro-matography: Results j-em Expeditions between 1977 and 1990. Scripps Institu-tion of Oceanography Reference 92-11, ORNIJCDIAC-59, NDP-044. CarbonDioxide Information Analysis Center, Oak Ridge National Laboratory, OakRidge, Tennessee, 144 pp. (1992)
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