Redox control in arsenic accumulation with organic matter derived from a varved lacustrine deposit in the Jurassic accretionary complexes

Abstract

Oxidation states and distribution of arsenic (As) in annually laminated (varved) lacustrine deposits were analyzed with a seasonal resolution. This deposit was formed in the mid-Holocene landslide-dammed paleolake in the upper reaches of the Ane River, central Japan and the paleolake watershed consists of the Jurassic accretionary complexes (Mino-Tamba belt) including sedimentary and igneous rocks. In the outcrop, centimeter-to-decimeter-scale silty clay layers alternating with laminated layers are well developed. Bulk concentrations of As in the two layers are 77 ± 27 μg/g on average and mostly occurred in the sulfide fraction (59% ± 9%). In the laminated layers, millimeter-scale organic matter (OM)-rich and siderite-rich layers were repeated, indicating deposition during the spring and autumn mixings and the summer stratification, respectively. The OM-rich layers distinctively contain As-rich layers concentrated at the margins of the siderite layers, while they have numerous As-rich hotspots coexisting with S and amorphous OM. Synchrotron-based micro-X-ray absorption near edge structure analysis demonstrated that the As-rich layers contain FeAs^–IS, As^IIS, and As^III₂S₃ at roughly the same levels, whereas FeAs^–IS is dominant for the As in hotspots. Based on the results, it is suggested that As accumulation in the varved deposit has been controlled by seasonal changes in OM supply and fluctuation in redox potential with post-depositional degradation of OM.