Transformation of reactive iron minerals in a permeable reactive barrier (biowall) used to treat TCE in groundwater

Iron and sulfur reducing conditions generally develop in permeable reactive barrier systems (PRB) constructed to treat contaminated groundwater. These conditions allow formation of FeS mineral phases. FeS readily degrades TCE, but a transformation of FeS to FeS2 could dramatically slow the rate of TCE degradation in the PRB. This study uses acid volatile sulfide (AVS) and chromium reducible sulfur (CRS) as probes for FeS and FeS2 to investigate iron sulfide formation and transformation in a column study and PRB field study dealing with TCE degradation. Solid phase iron speciation shows that most of the iron is reduced and sulfur partitioning measurements show that AVS and CRS coexist in all samples, with the conversion of AVS to CRS being most significant in locations with potential oxidants available. In the column study, 54% of FeS was transformed to FeS2 after 2.4 years. In the field scale PRB, 43% was transformed after 5.2 years. Microscopy reveals FeS, Fe3S4 and FeS2 formation in the column system; however,only pyrite formation was confirmed by X-ray diffraction. The polysulfide pathway is most likely the primary mechanism of FeS transformation in the system, with S-0 as an intermediate species formed through H2S oxidation.