This study provides a twenty-two-year record of in situ degradation of chlorinated organic compounds by a granular iron permeable reactive barrier (PRB). Groundwater concentrations of trichloroethene (TCE) entering the PRB were as high as 10670 μg/L. Treatment efficiency ranged from 81 to >99%, and TCE concentrations from <1 μg/L to 165 μg/L were detected within and hydraulically down-gradient of the PRB. After 18 years, effluent TCE concentrations were above the maximum contaminant level (MCL) along segments of the PRB exhibiting upward trending influent TCE. Degradation products included cis-dichloroethene ( cis-DCE), vinyl chloride (VC), ethene, ethane, >C4 compounds, and possibly CO2(aq) and methane. Abiotic patterns of TCE degradation were indicated by compound-specific stable isotope data and the distribution of degradation products. δ13C values of methane within and down-gradient of the PRB varied widely from -94‰ to -16‰; these values cover most of the isotopic range encountered in natural methanogenic systems. Methanogenesis is a sink for inorganic carbon in zerovalent iron PRBs that competes with carbonate mineralization, and this process is important for understanding pore-space clogging and longevity of iron-based PRBs. The carbon isotope signatures of methane and inorganic carbon were consistent with open-system behavior and 22% molar conversion of CO2(aq) to methane.