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Sulfur speciation in the upper Black Sea sediments

Yücel, Mustafa
Konovalov, Sergey K.
Moore, Tommy S.
Janzen, Christopher P.
Luther, George W.
We report solid phase sulfur speciation of six cores from sediments underlying oxic, suboxic and anoxic-sulfidic waters of the Black Sea. Our dataset includes the five sulfur species [pyrite-sulfur, acid volatile sulfides (AVS), zerovalent sulfur (S(0)), organic polysulfides (RS(x)), humic sulfur] together with reactive iron and manganese, as quantified by dithionite extraction, and total organic carbon. Pyrite - sulfur was the major phase in all cores [200-400 mu mol (g dry wt)(-1)] except for the suboxic core. However, zerovalent sulfur and humic sulfur also reached very significant levels: up to about 109 and 80 mu mol (g dry wt)(-1), respectively. Humic sulfur enrichment was observed in the surface fluff layers of the eastern central basin sediments where Unit-1 type depositional conditions prevail. Elemental sulfur accumulated as a result of porewater sulfide oxidation by reactive iron oxides in turbidities from the anoxic basin margin and western central basin sediments. The accumulation of elemental sulfur to a level close to that of pyrite-S in any part of central Black Sea sediments has never been reported before and our finding indicates deep basin turbidites prevent the build-up of dissolved sulfide in the sediment. This process also contributes to diagenetic pyrite formation whereas in the non-turbiditic parts of the deep basin water column formed (syngenetic) pyrite dominates the sulfur inventory. In slope sediments under suboxic waters, organic sulfur (humic sulfur + organic polysulfides) account for 33-42% of total solid phase S, indicating that the suboxic conditions favor organosulfur formation. Our study shows that the interactions between depositional patterns (Unit 1 vs. turbidite), redox state of overlying waters (oxic-suboxic-sulfidic) and organic matter content determine sulfur speciation and enable the accumulation of elemental sulfur and organic sulfur species close to a level of pyrite-S.