Abstract
BackgroundWe studied the annual variability of the concentration and isotopic composition of main sulfur species and sulfide oxidation intermediates in the water column of monomictic fresh-water Lake Kinneret. Sulfate concentrations in the lake are <1 mM and similar to concentrations that are proposed to have existed in the Paleoproterozoic ocean. The main goal of this research was to explore biogeochemical constrains of sulfur cycling in the modern low-sulfate fresh-water lake and to identify which processes may be responsible for the isotopic composition of sulfur species in the Precambrian sedimentary rocks.ResultsAt the deepest point of the lake, the sulfate inventory decreases by more than 20% between March and December due to microbial sulfate reduction leading to the buildup of hydrogen sulfide. During the initial stages of stratification, sulfur isotope fractionation between sulfate and hydrogen sulfide is low (11.6 ‰) and sulfur oxyanions (e.g. thiosulfate and sulfite) are the main products of the incomplete oxidation of hydrogen sulfide. During the stratification and at the beginning of the lake mixing (July–December), the inventory of hydrogen sulfide as well as of sulfide oxidation intermediates in the water column increases and is accompanied by an increase in sulfur isotope fractionation to 30 ± 4 ‰ in October. During the period of erosion of the chemocline, zero-valent sulfur prevails over sulfur oxyanions. In the terminal period of the mixing of the water column (January), the concentration of hydrogen sulfide decreases, the inventory of sulfide oxidation intermediates increases, and sulfur isotope fractionation decreases to 20 ± 2 ‰.ConclusionsSulfide oxidation intermediates are present in the water column of Lake Kinneret at all stages of stratification with significant increase during the mixing of the water column. Hydrogen sulfide inventory in the water column increases from March to December, and sharply decreases during the lake mixis in January. Sulfur isotope fractionation between sulfate and hydrogen sulfide as well as concentrations of sulfide oxidation intermediates can be explained either by microbial sulfate reduction alone or by microbial sulfate reduction combined with microbial disproportionation of sulfide oxidation intermediates. Our study of sulfur cycle in Lake Kinneret may be useful for understanding the range of biogeochemical processes in low sulfate oceans over Earth history.
Highlights
In oxygen-depleted aquatic systems, sulfate is usually the most abundant water soluble electron acceptor for2(CH2O) + SO42− → H2S + 2HCO3− (1)Knossow et al Geochem Trans (2015) 16:7In various aquatic and sedimentary systems a significant part of sulfide produced during microbial sulfate reduction can be re-oxidized either microbially or abiotically [11], rather than buried as pyrite
During the LK2 sampling (Figure 2c), which represents the initial stage of stratification, conductivity profile was characterized by a gradual increase with depth down to 30.5 m followed by a slight decrease below the chemocline
Hydrogen sulfide concentrations in the hypolimnion reached in December about 45% of the sulfate concentration measured during the mixis of the lake (Figure 4) and decreased back to
Summary
In various aquatic and sedimentary systems a significant part of sulfide produced during microbial sulfate reduction can be re-oxidized either microbially or abiotically [11], rather than buried as pyrite. In euphotic oxic ocean waters, significant fraction of inorganic iodine is found in the form of iodide, which is thermodynamically unstable [26]. In anoxic hydrogen sulfide rich waters iodide is the only detectable inorganic iodine species [26, 34] due to the fast reduction of iodate to iodide by hydrogen sulfide. We studied the annual variability of the concentration and isotopic composition of main sulfur species and sulfide oxidation intermediates in the water column of monomictic fresh-water Lake Kinneret. The main goal of this research was to explore biogeochemical constrains of sulfur cycling in the modern low-sulfate fresh-water lake and to identify which processes may be responsible for the isotopic composition of sulfur species in the Precambrian sedimentary rocks
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