Transformation Of TCE Research Articles

Surface carbon influences on the reductive transformation of TCE in the presence of granular iron

To gain insight into the processes of transformations in zero-valent iron systems, electrolytic iron (EI) has been used as a surrogate for the commercial products actually used in barriers. This substitution facilitates mechanistic studies, but may not be fully representative of all the relevant processes at work in groundwater remediation. To address this concern, the kinetic iron model (KIM) was used to investigate sorption and reactivity differences between EI and Connelly brand GI, using TCE as a probe compound. It was observed that retardation factors (Rapp) for GI varied non-linearly with influent concentrations to the columns (Co), and declined significantly as GI aged. In contrast, Rapp values for EI were small and insensitive to Co, and changed minimally with iron aging. Moreover, although declines in the rate constants (k) and increases in the sorption coefficients were observed for both iron types, they were most pronounced in the case of EI. SEM scans of the EI surface before and after aging (90 days) established the appearance of carbon on the older surface. This work provides evidence that iron with a higher surface carbon content outperforms pure iron, suggesting that the carbon is actively involved in promoting TCE reduction.

Degradation of TCE by TEOS Coated nZVI in the Presence of Cu(II) for Groundwater Remediation

The removal of TCE by nanofer zero valent iron (nanofer ZVI) coated with tetraethyl orthosilicate (TEOS) in the presence of Cu(II) at different environmental conditions was studied. The kinetics of TCE degradation by nanofer ZVI was determined. At a dosage of 10 mg of nanofer ZVI, almost 63% of TCE was removed, when Cu(II) and TCE were present. It contrasts with 42% degradation of TCE in the absence of Cu(II). SEM/EDS images indicated that Cu(II) is reduced to form Cu0 and Cu2O. These formations are considered to be responsible for enhancing TCE degradation. Direct reduction involves hydrogenolysis and β‐elimination in the transformation of TCE, while indirect reduction involves atomic hydrogen and no direct electron transfer from the metal to reactants. The reduction of activation energy was also noted indicating that the rate limiting step for TCE degradation in the presence of Cu(II) is surface chemical reaction rather than diffusion. Most of iron present in nanofer ZVI get dissolved causing the generation of localized positive charge regions and form metal chlorides. Local accumulation of hydrochloric acid inside the pits regenerates new reactive surfaces to serve as sources of continuous electron generation. No significant effect of TCE was noticed for Cu(II) sequestration.

3D-CSIA: Carbon, Chlorine, and Hydrogen Isotope Fractionation in Transformation of TCE to Ethene by a Dehalococcoides Culture

Carbon (C), chlorine (Cl), and hydrogen (H) isotope effects were determined during dechlorination of TCE to ethene by a mixed Dehalococcoides (Dhc) culture. The C isotope effects for the dechlorination steps were consistent with data published in the past for reductive dechlorination (RD) by Dhc. The Cl effects (combined with an inverse H effect in TCE) suggested that dechlorination proceeded through nucleophilic reactions with cobalamin rather than by an electron transfer mechanism. Depletions of (37)Cl in daughter compounds, resulting from fractionation at positions away from the dechlorination center (secondary isotope effects), further support the nucleophilic dechlorination mechanism. Determination of C and Cl isotope ratios of the reactants and products in the reductive dechlorination chain offers a potential tool for differentiation of Dhc activity from alternative transformation mechanisms (e.g., aerobic degradation and reductive dechlorination proceeding via outer sphere mechanisms), in studies of in situ attenuation of chlorinated ethenes. Hydrogenation of the reaction products (DCE, VC, and ethene) showed a major preference for the (1)H isotope. Detection of depleted dechlorination products could provide a line of evidence in discrimination between alternative sources of TCE (e.g., evolution from DNAPL sources or from conversion of PCE).

Electrochemically induced dual reactive barriers for transformation of TCE and mixture of contaminants in groundwater.

A novel reactive electrochemical flow system consisting of an iron anode and a porous cathode is proposed for the remediation of mixture of contaminants in groundwater. The system consists of a series of sequentially arranged electrodes, a perforated iron anode, a porous copper cathode followed by a mesh-type mixed metal oxide anode. The iron anode generates ferrous species and a chemically reducing environment, the porous cathode provides a reactive electrochemically reducing barrier, and the inert anode provides protons and oxygen to neutralize the system. The redox conditions of the electrolyte flowing through this system can be regulated by controlling the distribution of the electric current. Column experiments are conducted to evaluate the process and study the variables. The electrochemical reduction on a copper foam cathode produced an electrode-based reductive potential capable of reducing TCE and nitrate. Rational electrodes arrangement, longer residence time of electrolytes and higher surface area of the foam electrode improve the reductive transformation of TCE. More than 82.2% TCE removal efficiency is achieved for the case of low influent concentration (<7.5 mg/L) and high current (>45 mA). The ferrous species produced from the iron anode not only enhance the transformation of TCE on the cathode, but also facilitates transformation of other contaminants including dichromate, selenate and arsenite. Removal efficiencies greater than 80% are achieved for these contaminants in flowing contaminated water. The overall system, comprising the electrode-based and electrolyte-based barriers, can be engineered as a versatile and integrated remedial method for a relatively wide spectrum of contaminants and their mixtures.

Trichloroethylene cometabolic degradation by Rhodococcus sp. L4 induced with plant essential oils

Cometabolic degradation of TCE by toluene-degrading bacteria has the potential for being a cost-effective bioremediation technology. However, the application of toluene may pose environmental problems. In this study, several plant essential oils and their components were examined as alternative inducer for TCE cometabolic degradation in a toluene-degrading bacterium, Rhodococcus sp. L4. Using the initial TCE concentration of 80 microM, lemon and lemongrass oil-grown cells were capable of 20 +/- 6% and 27 +/- 8% TCE degradation, which were lower than that of toluene-grown cells (57 +/- 5%). The ability of TCE degradation increased to 36 +/- 6% when the bacterium was induced with cumin oil. The induction of TCE-degrading enzymes was suggested to be due to the presence of citral, cumin aldehyde, cumene, and limonene in these essential oils. In particular, the efficiency of cumin aldehyde and cumene as inducers for TCE cometabolic degradation was similar to toluene. TCE transformation capacities (T (c)) for these induced cells were between 9.4 and 15.1 microg of TCE mg cells(-1), which were similar to the known toluene, phenol, propane or ammonia degraders. Since these plant essential oils are abundant and considered non-toxic to humans, they may be applied to stimulate TCE degradation in the environment.

Reductive dechlorination of trichloroethylene by combining autotrophic hydrogen-bacteria and zero-valent iron particles

The objective of this study was to evaluate the dechlorination rate (from an initial concentration of 180 micromol l(-1)) and synergistic effect of combining commercial Fe(0) and autotrophic hydrogen-bacteria in the presence of hydrogen, during TCE degradation process. In the batch test, the treatment using Fe(0) in the presence of hydrogen (Fe(0)/H(2)), showed more effective dechlorination and less iron consumption than Fe(0) utilized only (Fe(0)/N(2)), meaning that catalytic degradation had promoted transformation of TCE, and the iron was protected by cathodic hydrogen. The combined use of Fe(0) and autotrophic hydrogen-bacteria was found to be more effective than did the individual exercise even though the hydrogen was insufficient during the batch test. By the analysis of XRPD, the crystal of FeS transformed by sulfate reducing bacteria (SRB) was detected on the surface of iron after the combined treatment. The synergistic impact was caused by FeS precipitates, which enhanced TCE degradation through catalytic dechlorination. Additionally, the dechlorination rate coefficient of the combined method in MFSB was 3.2-fold higher than that of iron particles individual use. Results from batch and MFSB experiments revealed that, the proposed combined method has the potential to become a cost-effective remediation technology for chlorinated-solvent contaminated site.

Reductive Dechlorination Pathways of Tetrachloroethylene and Trichloroethylene and Subsequent Transformation of Their Dechlorination Products by Mackinawite (FeS) in the Presence of Metals

Because of frequent co-occurrence of metals with chlorinated organic pollutants, Fe(II), Co(II), Ni(II), and Hg(II) were evaluated for their impact on the dechlorination pathways of PCE and TCE and the subsequent transformation of the initial dechlorination products by FeS. PCE transforms to acetylene via beta-elimination, TCE via hydrogenolysis, and 1,1-DCE via alpha-elimination, while TCE transforms to acetylene via beta-elimination and cis-DCE and 1,1-DCE via hydrogenolysis. Acetylene subsequently transforms in FeS batches, but little transformation of cis-DCE and 1,1-DCE was observed. Branching ratio calculations indicate that the added metals decrease the reductive transformation of PCE and TCE via beta-elimination relative to hydrogenolysis, resulting in a higher production of the toxic DCE byproducts. Nonetheless, acetylene is generally the dominant product. Production of highly water-soluble compound(s) is suspected as a significant source for incomplete mass recoveries. In the transformation of PCE and TCE, the formation of unidentified product(s) is most significant in Co(II)-added FeS batches. Although nearly complete mass recoveries were observed in the other FeS batches, the subsequent transformation of acetylene would lead to the formation of unidentified product(s) over long time periods.

Nanoscale iron particles for complete reduction of chlorinated ethenes

This paper examines the potential for using laboratory synthesized nanoscale Pd/Fe bimetallic particles to reduce chlorinated ethenes. Rapid and complete dechlorination was achieved for six chlorinated ethenes: tetrachloroethene (PCE, C 2Cl 4), trichloroethene (TCE, C 2HCl 3), 1,1-dichloroethene (1,1-DCE, C 2H 2Cl 2), cis- and trans-1,2-dichloroethene (c-DCE, t-DCE, C 2H 2Cl 2), and vinyl chloride (VC, C 2H 3Cl). The chlorinated ethenes (20 mg l −1) were completely reduced within 90 min at a metal loading of 5 g l −1. Ethane was the primary product from these reactions, amount to 60–90% of the total carbon. Ethene (3–20%) was produced during the transformation of TCE, DCEs and VC. No chlorinated intermediates or final products were detected above the method detection limit (<5 μg l −1). The remarkable performance of the nanoscale particles can be attributed to: (1) High specific surface area of the nanoscale metal particles, approximately 35 m 2 g −1, tens to hundreds of times higher than commercial grade micro- or milli-scale iron particles; (2) Increased reactivity per unit metal surface area, largely due to the presence of the noble metal (Pd) on the surface. Values of the surface-area-normalized rate coefficients ( k SA) were two orders of magnitude higher than those reported in the literature for larger iron particles. Due to their small particle size and high reactivity, the nanoscale bimetallic particles may be useful in a wide array of environmental applications including subsurface injection for groundwater treatment.

Pd-catalyzed TCE dechlorination in water: effect of [H2](aq) and H2-utilizing competitive solutes on the TCE dechlorination rate and product distribution.

The aqueous-phase H2 concentration ([H2](aq)) and the presence of H2-utilizing competitive solutes affect TCE dechlorination efficiency in Pd-based in-well treatment reactors. The effect of [H2](aq) and H2-utilizing competing solutes (cis-DCE, trans-DCE, 1,1-DCE, dissolved oxygen (DO), nitrite, nitrate) on the TCE transformation rate and product distribution were evaluated using 100 mg/L of a powdered Pd-on-Al2O3 catalysts in batch reactors or 1.0 g of a 1.6-mm Pd-on-gamma-Al2O3 catalyst in column reactors. The TCE dechlorination rate constant decreased by 55% from 0.034 +/- 0.006 to 0.015 +/- 0.001 min-1 when the [H2](aq) decreased from 1000 to 100 microM and decreased sharply to 0.0007 +/- 0.0003 min-1 when the [H2](aq) decreased from 100 to 10 microM. Production of reactive chlorinated intermediates and C4-C6 radical coupling products increased with decreasing [H2](aq). At an [H2](aq) of 10 microM (P/Po = 0.01), DCE isomers and vinyl chloride accounted for as much as 9.8% of the TCE transformed at their maximum but disappeared thereafter, and C4-C6 radical coupling products accounted for as much as 18% of TCE transformed. The TCE transformation rate was unaffected by the presence of cis-DCE (202 microM), trans-DCE (89 microM), and 1,1-DCE (91 microM), indicating that these compounds do not compete with TCE for catalyst active sites. DO is twice as reactive as TCE but had no effect on TCE conversion in the column below a concentration of 370 microM (11.8 mg/L), indicating that DO and TCE will not compete for active catalyst sites at typical groundwater DO concentrations. TCE conversion in the column was reduced by as much as a factor of 10 at influent DO levels greater than 450 mM (14.3 mg/L) because the [H2](aq) fell below 100 microM due to H2 utilized in DO conversion. Nitrite reacts 2-5 times slower than TCE and reduced TCE conversion by less than 4% at a concentration of 6630 microM (305 mg/L). Nitrate was not reactive and did not effect TCE conversion at a concentration of 1290 microM (80 mg/L).

Hydrodehalogenation of 1- to 3-Carbon Halogenated Organic Compounds in Water Using a Palladium Catalyst and Hydrogen Gas

Supported palladium (Pd) metal catalysts along with H{sub 2} gas show significant potential as a technology which can provide rapid, on-site destruction of halogenated groundwater contaminants. Pd catalyzes the rapid hydrodehalogenation of nine 1- to 3-carbon HOCs, resulting in little or no production of halogenated intermediates. Initial transformation rates were compared for 12 HOCs using 1 w/w% Pd-on-Al{sub 2}O{sub 3} (Pd/Al) and metallic Pd catalysts in clean, aqueous batch systems at ambient pressure and temperature. Half-lives of 4--6 min were observed for 5--100 {micro}M aqueous concentrations of PCE, TCE, cis-, trans-, 1,1-DCE, carbon tetrachloride, and 1,2-dibromo-3-chloropropane at ambient temperature and pressure with 0.22 g/L of catalyst. Using Pd/Al, TCE transformed quantitatively to ethane without formation of any detectable chlorinated intermediate compounds. This implies a direct conversion of TCE to ethane at the Pd surface. Carbon tetrachloride transformed primarily to methane and ethane and minor amounts of ethylene, propane, and propylene. Chloroform is a reactive intermediate. Formation of C2 and C3 products implies a free radical mechanism. Methylene chloride, 1,1-dichloroethane, and 1,2-dichloroethane were nonreactive. Reaction mechanisms and kinetic models are postulated for TCE, carbon tetrachloride, and chloroform transformation.

Biodegradation of High Concentrations of Tetrachloroethene in a Continuous Flow Column System

A long-term (2.5 years) study of the anaerobic biodegradation of high concentrations of perchloroethylene (PCE) was carried out in a continuously operated laboratory column filled with sand which was inoculated with biomass from an anaerobic digester. Concentrations of PCE fed to the column were increased from 12 IM to over 600 IM over 21 months, with methanol added as electron donor. Vinyl chloride (VC) was the terminal product of PCE dechlorination for the first 21 months at which point significant conversion of VC to ethylene (ETH) was detected. The onset of ETH production coincided with acetogenesis becoming the primary pathway for methanol metabolism. ETH production occurred in the column in the presence of PCE and TCE. Varying methanol:PCE molar ratios from 1.4 to 7.5 had little effect on the transformation of PCE and TCE to VC. The degradation of VC to ETH was much more sensitive, and VC accumulated when the methanol:PCE molar ratio dropped below 5.0. Withdrawal of PCE from the system for a 5 month period and maintenance of the column on methanol alone did not result in the loss of PCE degradation capability of the consortium.

Experimental evaluation of a model for cometabolism: Prediction of simultaneous degradation of trichloroethylene and methane by a methanotrophic mixed culture

A model for cometabolism is verified experimentally for a defined methanotrophic mixed culture. The model includes the effects of cell growth, endogenous cell decay, product toxicity, and competitive inhibition with the assumption that cometabolic transformation rates are enhanced by reducing power obtained from oxidation of growth substrates. A theoretical transformation yield is used to quantify the enhancement resulting from growth substrate oxidation. A systematic method for evaluating model parameters independently is described. The applicability of the model is evaluated by comparing experimental data for methanotrophic cometabolism of TCE with model predictions from independently measured model parameters. Propagation of errors is used to quantify errors in parameter estimates and in the final prediction. The model successfully predicts TCE transformation and methane utilization for a wide range of concentrations of TCE (0.5 to 9 mg/L) and methane (0.05 to 6 mg/L). (c) 1997 John Wiley & Sons, Inc. Biotechnol Bioeng 56: 492-501, 1997.

Field Evaluation of in Situ Aerobic Cometabolism of Trichloroethylene and Three Dichloroethylene Isomers Using Phenol and Toluene as the Primary Substrates

Download Hi-Res ImageDownload to MS-PowerPointCite This:Environ. Sci. Technol. 1995, 29, 6, 1628-1637