Organically complexed Cu can be a significant sink of photoproduced superox
ide (O-2(-)) in seawater. Using pulse radiolysis, we examined the rate cons
tant of catalytic dismutation (k(cat)) of O-2(-) in the presence of Cu comp
lexed by strong (L-1) and weaker (L-2) organic ligands present in coastal s
eawater samples and produced by cultures of Synechococcus sp. In the coasta
l samples examined, CuL2 complexes were almost as reactive towards O-2(-) a
s inorganically complexed Cu species (k(cat) = 2.9-8.1 x 10(8) M-1 s(-1)).
Furthermore, k(cat) was invariant with added Cu (5-60 nM), implying that th
e added Cu formed a single type of Cu complex or a mixture of complexes wit
h very similar O-2(-) reactivities. Significant differences between k(cat)
values of estuarine and coastal samples were observed, suggesting an effect
of organic ligands from terrestrial sources. CuL1 complexes produced by Sy
nechococcus sp. were found to be less reactive (k(cat) < 1 x 10(8) M-1 s(-1
)). The high reactivity of CuL2 complexes decreases estimates of steady-sta
te concentrations of O-2(-) in sunlit marine waters by at least a factor of
10.