Contents
Introduction - Environmental Analytical Chemistry as a Tool
for Studying Chemical Processes in Marine Environments ................... 1
Introduction ............................................................................... 1
Biogeochemical Cycles ................................................................... 1
Metals and Organometallic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 2
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 4
Part I Biogeochemical Cycles ............................................................... 7
1
The Carbonate System in Marine Environments ................................. 9
1.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 9
1.2 Equilibria of Carbonate Species ....................................................... 14
1.3 Parameters of the CO2 System in Sea Water .......................................... 16
1.4 Distribution of Carbonate Species .................................................... 21
1·4·1 PC02' • • • • • • • • . . • . . • . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . • • • • • •• • •• 21
1.4.2 pH .................................................................................. 22
1.4.3 TA .. ................................................................................. 26
1.4.4 TC02 . ..............................................................................• 28
1.5 CaC0 3 Dissolution in Sea Water ....................................................... 31
1.6 Calculating the Penetration of Anthropogenic CO2 into the Oceans ............. 33
1.6.1 Time Series Method ............................................................. 33
1.6.2 Calculation by Correcting for Dissolution of CaC03
and Oxidation of Plant Material ............................................... 34
Acknowledgements ...................................................................... 37
References ................................................................................. 37
Appendix - Thermodynamic Equations for the Carbonic Acid System
in Sea Water ............................................................................... 39
Solubility of CO2 (Weiss 1974) .................................................. 39
Carbonic Acid (Millero 1995) ................................................... 39
Boric Acid (Dickson 1990b) .................................................... 39
Water (Millero 1995) ............................................................. 39
HS04 (Dickson 1990a) ........................................................... 40
HF (Dickson and Riley 1979) ................................................... 40
Solubility of CaC03 (Mucci 1983) .............................................. 40
Relationships for the Various pH Scales (Millero 1995) .................... 40