RESUMO
The Black Sea is the largest euxinic basin on the Earth. The anoxic zone consists of the upper part water mass stratified by density, and the lower water mass homogenized relative to density (depth >1750 m), named the Bottom Convective Layer. To assess homogeneity and possible exchange of matter across the upper and lower boundaries of the Bottom Convective Layer, new data on stable isotope composition of S, O and H were obtained. Samples were collected in August 2008 and March 2009 from two stations located in the eastern central part of the Black Sea. Distribution of δ(18)O and δD values of water for the entire water column did not vary seasonally. Appreciable differences were marked for δD value variation in the picnocline area (water depth 200-400 m) and in the BCL 5 m above the bottom that might be caused by penetration of intrusions with elevated portion of shelf modified Mediterranean Water. Observed linear relationship between δ(18)O (or δD) and salinity indicates that mixing water and salt occurs at the same time, and the deep water of the Black Sea has two end members: the high-salinity Mediterranean seawater and freshwater input. In the Bottom Convective Layer, the average δ(34)S (H2S) was -40.6 ± 0.5 and did not vary seasonally. At the bottom (depth > 2000 m), (34)S depletion down to -41.0 was observed. Our δ(34)S (SO4) data are by 2-3 higher than those measured previously for the Bottom Convective Layer. Sulfate from the aerobic zone with δ(34)S (SO4) = +21 corresponds to ocean water sulfate and that has not been subjected to sulfate reduction. Average δ(34)S (SO4) values for depths > 1250 m were found to be +23.0 ± 0.2 (1σ). Sulfur isotope composition of sulfate does not change in the Bottom Convective Layer and on its upper and lower boundaries, and does not depend on the season of observation.
RESUMO
Photolysis of (17,18)O-labeled water in the presence of molecular oxygen is accompanied by transfer of (17)O and (18)O isotopes from water to oxygen, demonstrating that photoinduced oxidation of water does occur. The reaction exhibits the following isotope effect: oxidation of H(2)(17)O is faster by 2.6% (in the Earth's magnetic field) and by 6.0% (in the field 0.5 T) than that of H(2)(18)O. The effect is supposed to arise in the two spin-selective, isotope-sorting reactions-recombination and disproportionation-in the pairs of encountering HO(2) radicals. The former is spin allowed from the singlet state; the latter occurs only in the triplet one. Nuclear spin sorting produced by these reactions proceeds in opposite directions with the dominating contribution of recombination, which provides observable (17)O/(18)O isotope fractionation in favor of magnetic isotope (17)O. Neither isotope exchange nor the reaction itself occurs in the dark.