Iron and Sulfur Chemistry in a Stratified Lake: Evidence for Iron-Rich Sulfide Complexes |
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| Authors: | George W Luther III Brian Glazer Shufen Ma Robert Trouwborst Bradley R Shultz Gregory Druschel Charoenwan Kraiya |
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| Institution: | (1) College of Marine Studies, University of Delaware, Lewes, DE, 19958, U.S.A.;(2) Kleinschmidt Energy & Water Resource Consultants, 2 East Main Street Strasburg, PA, 17579, U.S.A. |
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| Abstract: | A four month study of a man-made lake used for hydroelectric power generation in northeastern Pennsylvania USA was conducted
to investigate seasonal anoxia and the effects of sulfide species being transported downstream of the power generation equipment.
Water column analyses show that the system is iron-rich compared to sulfide. Total Fe(II) concentrations in the hypolimnion
are typically at least twice the total sulfide levels. In situ voltammetric analyses show that free Fe(II) as Fe(H2O)6]2+ or free H2S as H2S/HS- are either not present or at trace levels and that iron-rich sulfide complexes are present. From the in situ data and total Fe(II) and H2S measurements, we infer that these iron-rich sulfide complexes may have stoichiometries such as Fe2SH3+ (or polymeric forms of this and other stoichiometries). These iron-rich sulfide complexes appear related to dissolution of
the iron-rich FeS mineral, mackinawite, because IAP calculations on data from discrete bottle samples obtained from bottom
waters are similar to the pKsp of mackinawite. Soluble iron-sulfide species are stable in the absence of O2 (both in lake waters and the pipeline) and transported several miles during power generation. However, iron-sulfide complexes
can react with O2 to oxidize sulfide and can also dissociate releasing volatile H2S when the waters containing them are exposed to the atmosphere downstream of the powerplant. Sediment analyses show that
the lake is rich in oxidized iron solids (both crystalline and amorphous). Fe concentrations in FeS solids are low (<5 μmole/grdry wt) and the pyrite concentration ranges from about equal to the solid FeS to 30 times the solid FeS concentration. The degree
of pyritization is below 0.12 indicating that pyrite formation is limited by free sulfide, which can react with the iron-rich
sulfide complexes. |
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