Experimental study and steady-state simulation of biogeochemical processes in laboratory columns with aquifer material

Packed bed laboratory column experiments were performed to simulate the biogeochemical processes resulting from microbially catalyzed oxidation of organic matter. These included aerobic respiration, denitrification, and Mn(IV), Fe(III) and SO(4) reduction processes. The effects of these reactions on the aqueous- and solid-phase geochemistry of the aquifer material were closely examined. The data were used to model the development of alkalinity and pH along the column. To study the independent development of Fe(III)- and SO(4)-reducing environments, two columns were used. One of the columns (column 1) contained small enough concentrations of SO(4) in the influent to render the reduction of this species unimportant to the geochemical processes in the column.The rate of microbially catalyzed reduction of Mn(IV) changed with time as evidenced by the variations in the initial rate of Mn(II) production at the head of the column. The concentration of Mn in both columns was controlled by the solubility of rhodochrosite (MnCO(3(S))).In the column where significant SO(4) reduction took place (column 2), the concentration of dissolved Fe(II) was controlled by the solubility of FeS. In column 1, where SO(4) reduction was not important, maximum dissolved Fe(II) concentrations were controlled by the solubility of siderite (FeCO(3(S))). Comparison of solid-phase and aqueous-phase data suggests that nearly 20% of the produced Fe(II) precipitates as siderite in column 1. The solid-phase analysis also indicates that during the course of experiment, approximately 20% of the total Fe(III) hydroxides and more than 70% of the amorphous Fe(III) hydroxides were reduced by dissimilatory iron reduction.The most important sink for dissolved S(-II) produced by the enzymatic reduction of SO(4) was its direct reaction with solid-phase Fe(III) hydroxides leading initially to the formation of FeS. Compared to this pathway, precipitation as FeS did not constitute an important sink for S(-II) in column 2. In this column, the total reacted S(-II) estimated from the concentration of dissolved sulfur species was in good agreement with the produced Cr(II)-reducible sulfur in the solid phase. Solid-phase analysis of the sulfur species indicated that up to half of the originally produced FeS may have possibly transformed to FeS(2).