Abstract: In-situ chemical oxidation (ISCO) has been widely
used for source zone remediation of Dense Nonaqueous Phase
Liquids (DNAPLs) in subsurface environments. DNAPL source
zones for karst aquifers are generally located in epikarst where the
DNAPL mass is trapped either in karst soil or at the regolith contact
with carbonate bedrock. This study aims to investigate the
performance of oxidation of residual trichloroethylene found in such
environments by potassium permanganate. Batch and flow cell
experiments were conducted to determine the kinetics and the mass
removal rate of TCE. pH change, Cl production, TCE and MnO4
destruction were monitored routinely during experiments. Nonreactive
tracer tests were also conducted prior and after the oxidation
process to determine the influence of oxidation on flow conditions.
The results show that oxidant consumption rate of the calcareous
epikarst soil was significant and the oxidant demand was determined
to be 20 g KMnO4/kg soil. Oxidation rate of residual TCE (1.26x10-3
s-1) was faster than the oxidant consumption rate of the soil (2.54 -
2.92x10-4 s-1) at only high oxidant concentrations (> 40 mM
KMnO4). Half life of TCE oxidation ranged from 7.9 to 10.7 min.
Although highly significant fraction of residual TCE mass in the
system was destroyed by permanganate oxidation, TCE
concentration in the effluent remained above its MCL. Flow
interruption tests indicate that efficiency of ISCO was limited by the
rate of TCE dissolution and the rate-limited desorption of TCE. The
residence time and the initial concentration of the oxidant in the
source zone also controlled the efficiency of ISCO in epikarst.
Abstract: Palladium-catalyzed hydrodechlorination is a
promising alternative for the treatment of environmentally relevant
water bodies, such as groundwater, contaminated with chlorinated
organic compounds (COCs). In the aqueous phase
hydrodechlorination of COCs, Pd-based catalysts were found to have
a very high catalytic activity. However, the full utilization of the
catalyst-s potential is impeded by the sensitivity of the catalyst to
poisoning and deactivation induced by reduced sulfur compounds
(e.g. sulfides). Several regenerants have been tested before to recover
the performance of sulfide-fouled Pd catalyst. But these only
delivered partial success with respect to re-establishment of the
catalyst activity. In this study, the deactivation behaviour of
Pd/Al2O3 in the presence of sulfide was investigated. Subsequent to
total deactivation the catalyst was regenerated in the aqueous phase
using potassium permanganate. Under neutral pH condition,
oxidative regeneration with permanganate delivered a slow recovery
of catalyst activity. However, changing the pH of the bulk solution to
acidic resulted in the complete recovery of catalyst activity within a
regeneration time of about half an hour. These findings suggest the
superiority of permanganate as regenerant in re-activating Pd/Al2O3
by oxidizing Pd-bound sulfide.