A recent article presented geochemical and microbial evidence establishing metabolic adaptation to and in-situ reductive dechlorination of trichloroethene (TCE) in a fractured dolomite aquifer. This study was designed to further explore site conditions and microbial populations and to explain previously reported enhancement of reductive dechlorination by the addition of pulverized dolomite to laboratory microcosms. A survey of groundwater geochemical parameters (chlorinated ethenes, ethene, H2, CH4, DIC, DOC, and ??13C values for CH4, DIC, and DOC) indicated that in situ reductive dechlorination was ongoing and that an unidentified pool of organic carbon was contributing, likely via microbial respiration, to the large and relatively light onsite DIC pool. Petroleum hydrocarbons associated with the dolomite rock were analyzed by GC/MS and featured a characteristically low ??13C value. Straight chain hydrocarbons were extracted from the dolomite previously found to stimulate reductive dechlorination; these were particularly depleted in hexadecane (HD). Thus, we hypothesized that HD and related hydrocarbons might be anaerobically respired and serve both as the source of onsite DIC and support reductive dechlorination of TCE. Microcosms amended with pulverized dolomite demonstrated reductive dechlorination, whereas a combusted dolomite amendment did not. HD-amended microcosms were also inactive. Therefore, the stimulatory factor in the pulverized dolomite was heat labile, but that component was not HD. Amplified Ribosomal DNA Restriction Analysis (ARDRA) of the microbial populations in well waters indicated that a relatively low diversity, sulfur-transforming community outside the plume was shifted toward a high diversity community including Dehalococcoides ethenogenes-type microorganisms inside the zone of contamination. These observations illustrate biogeochemical intricacies of in situ reductive dechlorination reactions.