Ligand exchange with dimethylglyoxime (DMG) and differential pulse cat
hodic stripping voltammetry (DPCSV) was applied to determine free Co(l
l) ionic concentrations [Co2+] acid Co(ll) complexation by natural org
anic ligands in freshwater. [Co2+] and the complexing parameters were
calculated on the basis of the thermodynamic equilibria between added
and natural ligands. The optimal working conditions were carefully eva
luated in synthetic solutions and in natural freshwater samples. The r
esults from samples collected at various sites from the Aare and Rhine
Rivers and the Biel and Lucerne Lakes, Switzerland, are presented. Th
e total dissolved Co concentrations are in the range of 0.5-6.5 nM, an
d [Co2+] is in the range of 0.05-0.5 nM. Organic complexes of Co are p
redominant in most samples with 80-96% of total dissolved Co. A one-li
gand model could well fit the titrations of freshwater samples with Co
(II) (using the FITEQL program). The conditional stability constants o
f the natural ligands were computed to be log K = 9.5-11.6 (pH 8.0 +/-
0.1), and the ligand concentrations were [L] = 1.4-7.6 nM. The reliab
ility and applicability of the technique and the implications of the r
esults are discussed.