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Abstract
Carbon tetrachloride (CT) and 1,2,3‑trichloropropane (TCP), two chlorinated aliphatic contaminants with contrasting reactivities, were investigated across multiple abiotic degradation pathways. Batch experiments showed that CT reduction by zero‑valent iron (Fe⁰) proceeds primarily via hydrogenolysis to chloroform, with yields strongly influenced by iron surface composition. Magnetite‑containing surfaces and nano‑Fe⁰ with a magnetite shell promoted alternative reduction pathways that reduced chloroform formation. Aging studies of nano‑Fe⁰ demonstrated rapid surface transformation to mixed‑valence iron oxides. In contrast, TCP exhibited limited reactivity under reductive conditions but degraded more effectively via oxidative pathways, particularly activated persulfate, which achieved rapid and complete dechlorination. These results highlight the importance of reaction pathway selection for effective remediation of chlorinated contaminants.