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Discrete water column measurements of CO2 fugacity and pHT in seawater: A comparison of direct measurements and thermodynamic calculations

by: S. McElligott, R. H. Byrne, K. Lee, R. Wanninkhof, F. J. Millero, and R. A. Feely

In: MARINE CHEMISTRY, Vol. 60, Nr. 1-2 (1998) , p. 63--73.

Abstract

The NOAA Eq. Pac. CO2 system data set similar or equal to 2500 water samples has been evaluated to assess the internal consistency of measurements and calculations involving CO2 fugacity and pHT. This assessment represents the first large scale field comparison of pHT and fCO2 data. Comparisons of direct discrete CO2 fugacity fCO2 measurements with CO2 fugacity calculated from total inorganic carbon C-T, total alkalinity AT and spectrophotometric pH pHT = -logH+T indicate that a variety of improvements are needed in the parameter measurements and thermodynamic relationships used to relate fCO2, C-T, AT and pHT in seawater. CO2 fugacity calculated from C-T and pHT or AT and pHT agree with direct measurements to no better than 1%. Comparisons of measured fugacity, fCO2 measured, and CO2 fugacity calculated from C-T and pHT, fCO2 C-T, pHT, indicate that the precision of fCO2 calculations is good relative to direct measurements. In contrast, due to the extreme sensitivity of fCO2 and H+T calculations to relatively small errors in both C-T and AT, CO2 fugacity, as well as H+T, calculated from C-T and AT are very imprecise and render comparisons with direct measurements of little use. Consequently, precise calculations of fCO2 require the use of direct pHT measurements. C 1998 Elsevier Science B.V.

BibTeX record

@article{McElligott1998,
  abstract = {The NOAA Eq. Pac. CO2 system data set (similar or equal to 2500 water
	samples) has been evaluated to assess the internal consistency of
	measurements and calculations involving CO2 fugacity and pH(T). This
	assessment represents the first large scale field comparison of pH(T)
	and f(CO2) data. Comparisons of direct discrete CO2 fugacity (f(CO2))
	measurements with CO2 fugacity calculated from total inorganic carbon
	(C-T), total alkalinity (A(T)) and spectrophotometric pH (pH(T) =
	-log[H+](T)) indicate that a variety of improvements are needed in
	the parameter measurements and thermodynamic relationships used to
	relate f(CO2), C-T, A(T) and pH(T) in seawater. CO2 fugacity calculated
	from C-T and pH(T) or A(T) and pH(T) agree with direct measurements
	to no better than 1%. Comparisons of measured fugacity, f(CO2) (measured),
	and CO2 fugacity calculated from C-T and pH(T), f(CO2) (C-T, pH(T)),
	indicate that the precision of f(CO2) calculations is good relative
	to direct measurements. In contrast, due to the extreme sensitivity
	of f(CO2) and [H+](T) calculations to relatively small errors in
	both C-T and A(T), CO2 fugacity, as well as [H+](T), calculated from
	C-T and A(T) are very imprecise and render comparisons with direct
	measurements of little use. Consequently, precise calculations of
	f(CO2) require the use of direct pH(T) measurements. (C) 1998 Elsevier
	Science B.V.},
  added-at = {2009-11-03T20:21:25.000+0100},
  author = {McElligott, S. and Byrne, R. H. and Lee, K. and Wanninkhof, R. and Millero, F. J. and Feely, R. A.},
  biburl = {http://www.bibsonomy.org/bibtex/24085eae24f76aef355ccc2dd61cc968d/svance},
  citedreferences = {*UNESCO, 1991, 60 UNESCO ; CHEN HR, 1995, MEASUREMENT FUGACITY, P49 ; CLAYTON TD, 1993, DEEP-SEA RES PT I, V40, P2115 ; CLAYTON TD, 1995, DEEP-SEA RES PT II, V42, P411 ; DICKSON AG, 1987, DEEP-SEA RES, V34, P1733 ; DICKSON AG, 1994, HDB METH AN VAR PAR ; FEELY RA, 1995, DEEP SEA RES 2, V42, P365 ; GOYET C, 1989, DEEP-SEA RES, V36, P1635 ; HANSSON I, 1973, DEEP-SEA RES, V20, P461 ; LAMB MF, 1995, PMEL56 ERL NOAA ; LEE K, 1995, DEEP-SEA RES PT I, V42, P2035 ; LEE K, 1996, MAR CHEM, V55, P233 ; LEE K, 1997, IN PRESS J GEOPHYS R ; MEHRBACH C, 1973, LIMNOL OCEANOGR, V18, P897 ; MILLERO FJ, 1993, MAR CHEM, V44, P269 ; MILLERO FJ, 1995, GEOCHIM COSMOCHIM AC, V59, P661 ; MURPHY PP, 1997, UNPUB DEEP SEA RES ; ROY RN, 1993, MAR CHEM, V44, P249 ; WANNINKHOF R, 1993, MAR CHEM, V44, P189 ; WEISS RF, 1974, MAR CHEM, V2, P203},
  interhash = {4f3ce621ca274bc004879b95ea86f508},
  intrahash = {4085eae24f76aef355ccc2dd61cc968d},
  journal = {MARINE CHEMISTRY},
  keywords = {CARBONIC-ACID; CONSISTENCY; DISSOCIATION-CONSTANTS; MEASUREMENTS; PH SYSTEM},
  number = {1-2},
  owner = {svance},
  pages = {63--73},
  timestamp = {2009-11-03T20:21:25.000+0100},
  title = {Discrete water column measurements of CO2 fugacity and pH(T) in seawater: A comparison of direct measurements and thermodynamic calculations},
  volume = 60,
  year = 1998
}

Endnote record

%0 Journal Article
%1 McElligott1998
%A McElligott, S.
%A Byrne, R. H.
%A Lee, K.
%A Wanninkhof, R.
%A Millero, F. J.
%A Feely, R. A.
%D 1998
%J MARINE CHEMISTRY
%K 
%N 1-2
%P 63--73
%T Discrete water column measurements of CO2 fugacity and pH(T) in seawater: A comparison of direct measurements and thermodynamic calculations
%V 60
%X The NOAA Eq. Pac. CO2 system data set (similar or equal to 2500 water
	samples) has been evaluated to assess the internal consistency of
	measurements and calculations involving CO2 fugacity and pH(T). This
	assessment represents the first large scale field comparison of pH(T)
	and f(CO2) data. Comparisons of direct discrete CO2 fugacity (f(CO2))
	measurements with CO2 fugacity calculated from total inorganic carbon
	(C-T), total alkalinity (A(T)) and spectrophotometric pH (pH(T) =
	-log[H+](T)) indicate that a variety of improvements are needed in
	the parameter measurements and thermodynamic relationships used to
	relate f(CO2), C-T, A(T) and pH(T) in seawater. CO2 fugacity calculated
	from C-T and pH(T) or A(T) and pH(T) agree with direct measurements
	to no better than 1%. Comparisons of measured fugacity, f(CO2) (measured),
	and CO2 fugacity calculated from C-T and pH(T), f(CO2) (C-T, pH(T)),
	indicate that the precision of f(CO2) calculations is good relative
	to direct measurements. In contrast, due to the extreme sensitivity
	of f(CO2) and [H+](T) calculations to relatively small errors in
	both C-T and A(T), CO2 fugacity, as well as [H+](T), calculated from
	C-T and A(T) are very imprecise and render comparisons with direct
	measurements of little use. Consequently, precise calculations of
	f(CO2) require the use of direct pH(T) measurements. (C) 1998 Elsevier
	Science B.V.