Factors Controlling Sulfide Geochemistry in Sub-tropical Estuarine and Bay Sediments |
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| Authors: | John W Morse Heather Thomson David W Finneran |
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| Institution: | (1) Department of Oceanography, Texas A&M University, College Station, TX 77843, USA |
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| Abstract: | The primary factors that control the concentration of total reduced (inorganic) sulfide in coastal sediments are believed
to be the availability of reactive iron, dissolved sulfate and metabolizable organic carbon. We selected nine sites in shallow
(<3 m), close to sub-tropical, estuaries and bays along the central Texas coast that represented a range in sediment grain
size (a proxy for reactive iron), salinity (a proxy for dissolved sulfate), and total organic carbon (a proxy for metabolizable
organic carbon). Based on these parameters a prediction was made of which factor was likely to control total reduced sulfide
at each site and what the relative total reduced sulfide concentration was likely to be. To test the prediction, the sediments
were analyzed for total reduced sulfide, acid volatile sulfide, and citrate dithionate-extractable, HCl-extractable and total
Fe in the solid phase. Using solid-state gold–mercury amalgam microelectrodes and voltammetry, we determined pore water depth
profiles of Fe(II) and ΣH2S and presence or absence of FeS(aq). At five of the nine sites the calculated degree of sufildization of citrate dithionite-reactive-iron was close to or greater
than 1 indicating that rapidly reactive iron was probably the limiting factor for iron sulfide mineral formation. At one site
(salinity = 0.9) dissolved Fe(II) was high, ΣH2S was undetectable and the total reduced sulfide concentration was low indicating sulfate limitation. At the last three sites
a low degree of sulfidization and modest total reduced (inorganic) sulfide concentrations appeared to be the result of a limited
supply of metabolizable organic carbon. Fe(II)–S(-II) clusters (FeS(aq)) were undetectable in 10 out of 12 bay sediment profiles where ΣH2S was close to or below detection limits, but was observed in all other porewater profiles. Acid volatile sulfide, but not
total reduced sulfide, was well correlated with total organic carbon and ranged from being undetectable in some cores to representing
a major portion of total reduced sulfide in other cores. Although predicted controls on total reduced sulfide were good for
very low salinity water or sandy sediments, they were only right about half the time for the other sediments. The likely reasons
for the wrong predictions are the poor correlation of total organic carbon with grain size and differing fractions of metabolizable
organic carbon in different sedimentary environments. Differences in sediment accumulation rates may also play a role, but
these are difficult to determine in this region where hurricanes often resuspend and move sediments. This study demonstrates
the need to examine more complex and often difficult to determine parameters in anoxic “normal marine” sediments if we are
to understand what controls the concentration and distribution of sulfides. |
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| Keywords: | Sulfide Acid volatile sulfides Iron Estuary Sediments Diagenesis |
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