Bench-scale
experiments were performed on natural sediments to
assess abiotic dechlorination of trichloroethene (TCE) under both
aerobic and anaerobic conditions. In the absence of oxygen (<26
μM), TCE dechlorination proceeded via a reductive pathway generating
acetylene and/or ethene. Reductive dechlorination rate constants up
to 3.1 × 10–5 d–1 were measured,
after scaling to in situ solid:water ratios. In the
presence of oxygen greater than 120 μM, TCE dechlorination proceeded
via an oxidative pathway generating formic/glyoxylic and glycolic/acetic
acids, and oxidative dechlorination rate constants (again scaled to in situ conditions) up to 7.4 × 10–3 d–1 were measured. These rates correspond to half-lives
of 60 and 0.25 years for abiotic TCE dechlorination under anaerobic
and aerobic conditions, respectively, indicating the potentially large
impact of aerobic TCE oxidation in the field. For both reductive and
oxidative TCE dechlorination pathways, measured first-order rate constants
increased with increasing ferrous iron content, suggesting the role
of iron oxidation. Hydroxyl radical formation was measured and increased
with increasing oxygen and ferrous iron content. Rate constants associated
with TCE oxidation products increased with increasing hydroxyl radical
generation rates, and were zero in the presence of a hydroxyl radical
scavenger, suggesting that oxidative TCE dechlorination is a hydroxyl
radical driven process.