Organic matter mineralization and trace element post-depositional redistribution in Western Siberia thermokarst lake sediments

This study reports the very first results on high-resolution sampling of sediments and their porewaters from three thermokarst (thaw) lakes representing different stages of ecosystem development located within the Nadym-Pur interfluve of the Western Siberia plain. Up to present time, the lake sediments of this and other permafrost-affected regions remain unexplored regarding their biogeochemical behavior. The aim of this study was to (i) document the early diagenesic processes in order to assess their impact on the organic carbon stored in the underlying permafrost, and (ii) characterize the post-depositional redistribution of trace elements and their impact on the water column. The estimated organic carbon (OC) stock in thermokarst lake sediments of 14 +/- 2 kgm(-2) is low compared to that reported for peat soils from the same region and denotes intense organic matter (OM) mineralization. Mineralization of OM in the thermokarst lake sediments proceeds under anoxic conditions in all the three lakes. In the course of the lake development, a shift in mineralization pathways from nitrate and sulfate to Fe- and Mn-oxyhydroxides as the main terminal electron acceptors in the early diagenetic reactions was suggested. This shift was likely promoted by the diagenetic consumption of nitrate and sulfate and their gradual depletion in the water column due to progressively decreasing frozen peat lixiviation occurring at the lake's borders. Trace elements were mobilized from host phases (OM and Fe- and Mn-oxyhydroxides) and partly sequestered in the sediment in the form of authigenic Fe-sulfides. Arsenic and Sb cycling was also closely linked to that of OM and Fe- and Mn-oxyhydroxides. Shallow diagenetic enrichment of particulate Sb was observed in the less mature stages. As a result of authigenic sulfide precipitation, the sediments of the early stage of ecosystem development were a sink for water column Cu, Zn, Cd, Pb and Sb. In contrast, at all stages of ecosystem development, the sediments were a source of dissolved Co, Ni and As to the water column. However, the concentrations of these trace elements remained low in the bottom waters, indicating that sorption processes on Fe-bounding particles and/or large-size organo-mineral colloids could mitigate the impact of post-depositional redistribution of toxic elements on the water column.