Arsenic, iron and sulfur co-diagenesis in lake sediments

Profiles of porewater pH and dissolved As, Fe, Mn, sulfate, total sulfide (Sigma S-11), total zero-valent sulfur (Sigma S-0), organic carbon and major ion concentrations, as well as those of solid As, acid-volatile sulfide (AVS), total S. Fe, Mn, Al, organic C, Pb-210 and Cs-137 were determined in the sediment of four lakes spanning a range of redox and geochemical conditions. An inverse modeling approach, based on a one-dimensional transport-reaction equation assuming steady-state, was applied to the porewater As profiles and used to constrain the net rates of reactions involving As (R-net(As)). The model defines depth intervals where As is either released to (positive R-net(As)) or removed from (negative R-net(As)) the porewaters. At two of the sites, whose bottom water were oxygenated at sampling time, a production zone (R-net(As) = 12 x 10(-18) mol cm(-3) s(-1)-71 X 10(-18) mol cm(-3) s(-1)) is inferred a few cm below the sediment-water interface, coincident with sharp porewater As and Fe peaks that indicate an intense coupled recycling of As and Fe. This process is confirmed by solid As and Fe maxima just below the sediment surface. In these two lakes a zone of As consumption (R-net(As) = -5 x 10(-18) mol cm(-3) s(-1) to -53 x 10(-18) mol cm(-3) s(-1)), attributed to the slow adsorption of As to authigenic Fe oxyhydroxides, occurs just above the production zone. A second-order rate constant k(ads)(As) of 0.12 +/- 0.03 cm(3) mol(-1) s(-1) is estimated for this adsorption reaction. Such features in the porewater and solid profiles were absent from the two other lakes that develop a seasonally anoxic hypolimnion. Thermodynamic calculations indicate that the porewaters of the four lakes, when sulfidic (i.e., Sigma S-11 >= 0.1 mu M), were undersaturated with respect to all known solid As sulfides; the calculation also predicts the presence of As-V oxythioanions in the sulfidic waters, as suggested by a recent study. In the sulfidic waters, the removal of As (R-net(As) = -1 X 10(-18) mol cm(-3) s(-1) to -23 x 10(-18) mol cm(-3) s(-1)) consistently occurred when saturation, with respect to FeS(,), was reached and when Asv oxythioanionswere predicted to be significant components of total dissolved As. This finding has potential implications for As transport in other anoxic waters and should be tested in a wider variety of natural environments. Crown copyright (C) 2009 Published by Elsevier Ltd. All rights reserved.