• Journal of Korean Society of Environmental Engineers
• /
• v.27 no.3
• /
• pp.253-261
• /
• 2005

Catalytic wet oxidation of ppm levels of trichloroethylene (TCE) in water has been conducted using $TiO_2$-supported cobalt oxides at a given temperature and weight hourly space velocity. 5% $CoO_x/TiO_2$ might be the most promising catalyst for the wet oxidation at $36^{\circ}C$ although it exhibited a transient behavior in time on-stream activity. Not only could the bare support be inactive for the wet decomposition reaction, but no TCE removal also occurred by the process of adsorption on $TiO_2$ surface. The catalytic activity was independent of all particle sizes used, thereby representing no mass transfer limitation in intraparticle diffusion. Characterization of the $CoO_x$ catalyst by acquiring XPS spectra of both fresh and used Co surfaces gave different surface spectral features of each $CoO_x$. Co $2p_{3/2}$ binding energy of Co species exposed predominantly onto the outermost surface of the fresh catalyst appeared at 781.3 eV, which is very similar to the chemical states of $CoTiO_x$ such as $Co_2TiO_4$ and $CoTiO_3$. The spent catalyst possessed a 780.3 eV main peak with a satellite structure at 795.8 eV. Based on XPS spectra of reference Co compound, the TCE-exposed Co surfaces could be assigned to be in the form of mainly $Co_3O_4$. XRD measurements indicated that the phase structure of Co species in 5% $CoO_x/TiO_2$ catalyst even before reaction is quite comparable to the diffraction lines of external $Co_3O_4$ standard. A model structure of $CoO_x$ present on titania surfaces would be $Co_3O_4$, encapsulated in thin-film $CoTiO_x$ species consisting of $Co_2TiO_4$ and $CoTiO_3$, which may be active for the decomposition of TCE in a flow of water.

• Journal of Environmental Health Sciences
• /
• v.40 no.2
• /
• pp.114-126
• /
• 2014

Objectives: We aimed to develop a measurement method of five metabolites of trichloroethylene (TCE) in a concurrent biological sample, e.g., trichloroacetic acid (TCA), dichloroacetic acid (DCA), S-(1,2-dichlorovinyl) glutathione (DCVG), S-(1,2-dichlorovinyl)-L-cysteine (DCVC), and N-Acetyl-S-(1,2-dichlorovinyl)-L-cysteine (NAcDCVC) and to validate the method before application to pharmacokinetic study. Methods: TCE metabolites were simultaneously analyzed using high performance liquid chromatography coupled with electrospray ionization mass spectrometry (HPLC-ESI-MS/MS) with as little as 50 ${\mu}L$ of serum and urine. DCA, TCA and NAcDCVC were extracted with diethyl ether, while DCVC and DCVG were extracted by solid phase extraction. This method was validated according to the guidelines for bioanalytical method validation of the Korean National Institute of Toxicological Research. Then, we determined the five metabolites in five strains of mice at 24 hr after exposure to 1 g TCE /kg body weight. Results: The limits of detection for the five metabolites in biological samples ranged from 0.001 to 0.076 nmol/mL, which is comparable to or better than those previously reported. Most calibration curves showed good linearity ($R^2=0.99$), and between-batch variation was less than 20% expressing acceptable robustness and reproducibility. Using this method, we found TCA and DCA were detected in all test mice at 24 hr after the oral administration while NAcDCVC and DCVC were detected in some strains, which showed strain-dependent metabolism of TCE. Conclusions: The present method could provide robust and accurate measurements of major key metabolites of TCE in biological media, which allowed concurrent analysis of TCE metabolism for limited amounts of biospecimens.

• Environmental Engineering Research
• /
• v.25 no.2
• /
• pp.197-204
• /
• 2020

A number of different nanoscale zero-valent iron (nZVI) materials have been prepared and compared depending on the desired properties for the particular application, but different physicochemical properties of this prepared nZVI make it difficult to universally compare and standardize them to the same scale. In this study, we aimed to demonstrate a simple microplate-based colorimetric assay using 4-chlorophenol as an indicator with respect to the remediation of real treatment targets, such as trichloroethylene (TCE), 1,1,1-trichloroethane (TCA), and atrazine. Effect of nickel contents on 4-chlorophenol reduction was successfully investigated by the miniaturized colorimetric assay. In the same manner, the effect of nickel contents on dehalogenation of TCE, TCA, and atrazine was investigated and the pseudo-first-order kinetic constants were compared with the results for 4-chlorophenol. The similar pattern could be observed between 4-chlorophenol reduction obtained by colorimetric assay and TCE, TCA, atrazine reduction obtained by a traditional chromatographic method. The reaction kinetics does not match perfectly, but the degree of reaction can be estimated. Therefore, the colorimetric assay can be a useful and simple screening tool to determine nZVI reactivity toward halogenated organics before it is applied to a particular remediation site.

• Journal of Soil and Groundwater Environment
• /
• v.13 no.1
• /
• pp.92-100
• /
• 2008

Experimental studies were conducted to identify the active agents for reductive dechlorination of TCE in cement/Fe(II) systems focusing on cement components such as CaO, $Fe_2O_3$, and $Al_2O_3$. A hematite that was used to simulate an $Fe_2O_3$ component in cement was found to have degradation efficiencies (k = 0.641 $day^{-1}$) equivalent to that of cement/Fe(II) systems in the presence of CaO/Fe(II), only when it contained an aluminum impurity$(Al_2O_3)$. When the effect of $Al_2O_3$ content of hematite/CaO/$Al_2O_3$/Fe(II) system was tested, the mole ratio of $Al_2O_3$ to CaO affected the rate of TCE degradation with an optimum ratio around 1 : 10 that resulted in a rate constant of 0.895 $day^{-1}$. In the SEM images of hematite/CaO/$Al_2O_3$/Fe(II) systems, acicular crystals were also found that were also observed in cement/Fe(II) systems. Thus it was suspected that these crystals were reactive reductants and that they might be goethite or ettringite that are known to have acicular structures. An EDS element map analysis revealed that these crystals were not goethite crystals. A subsequent experiment that tested reactivities of compounds formed during the ettringite synthesis showed that ettringite and minerals associated with ettringite formation are not reactive reductants. These observations conclude that a mineral containing CaO and $Al_2O_3$ with a acicular structure could be a major reactive reductant of cement/Fe(II) systems.

• Applied Chemistry for Engineering
• /
• v.16 no.4
• /
• pp.533-541
• /
• 2005

Non-aqueous cleaning agents were formulated with 2,2,2-trifluoroethanol (TFEA) and hydrofluoroether (HFE), and their physical properties and cleaning abilities were examined. TFEA-based aqueous cleaning agents were also formulated with nonionic surfactants, hydrotropes and builders, and their cleaning abilities were compared. Possibilities of these cleaning agents as substitutes for CFC-113 and 1,1,1-TCE were finally evaluated. In this work, fluxes, cutting oils, greases, and fluoric oils were selected as model contaminants for cleaning experiments. These contaminants have different properties of water-solubility or hydrophilicity, and fat-solubility or lypophilicity. Cleaning abilities of TFEA-based cleaning agents were analyzed and compared through the measurement of contaminant weight changes as a function of cleaning time, and their possibilities as alternative cleaning agents were evaluated. As a result, it was shown that TFEA and HFE-based non-aqueous cleaning agents have quite a good cleaning power for fluxes and fluorine soils but low one for greases. And TFEA-based agueous cleaning agents which consisted of nonionic surfactants, hydrotrope, and builders were very effective for cleaning fluxes and greases under certain formulation conditions. Thus, it was revealed that the TFEA-based cleaning agents were very effective for cleaning specific contaminants and can be used as substitutes for CFC-113 and 1,1,1-TCE in some industrial applications.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
• /
• 2005.04a
• /
• pp.114-116
• /
• 2005

Natural attenuation has been actively studied and often selected as final clean-up process in remediation of contaminated ground-water and soil for the last decade. Accordingly, understanding of natural processes affecting the fate and transport of contaminants in the subsurface becomes important for a success of implementation of the natural remediation strategy, Contaminant advection and diffusion processes in the unsaturated zone are naturally related to environmental changes in the atmosphere. The atmospheric pressure changes affecting the transport of contaminants in the subsurface are investigated in this study. Moisture content, trichloroethylene (TCE) concentration, temperature, and pressure variations in the subsurface were measured for the July, August, November, and December 2001 at Picatinny Arsenal, New Jersey. These data were used for a one-phase flow and one-component transport model in simulating the soil-gas flow and accordingly the TCE transport in the subsurface in accordance with the atmosphere pressure variations at the surface. The soil-gas velocities during the sampling periods varied with a magnitude of $10^{-6}\;to\;10^{-7}\;m\;s^{-1}$ at land surface. The TCE advection fluxes at land surface were several orders of magnitude smaller than the TCE diffusion fluxes. A sensitivy analysis indicated that advection fluxes were more sensitive to changes in geo-environmental conditions compared to diffusion fluxes. Of all the parameters investigated in this study, moisture content has the most significant effect on TCE advection and diffusion fluxes.

• Membrane and Water Treatment
• /
• v.13 no.2
• /
• pp.85-95
• /
• 2022

Tetrachloroethylene (PCE) and trichloroethylene (TCE), critical pollutants to human health and groundwater ecosystems, are managed by groundwater quality standards (GQS) in South Korea. However, there are no GQSs for their by-products, such as cis-dichloroethylene (DCE) and vinyl chloride (VC) produced through the dechlorination process of PCE and TCE. Therefore, in this study, we monitored PCE, TCE, cis-DCE, and VC in 111 national groundwater wells for three years (2016 to 2018) to evaluate their distributions, a biological dechlorination possibility, and human risk assessment. The detection frequency of them was 30.2% for PCE, 45.1% for TCE, 43.9% for cis-DCE and 13.4% for VC. The four chlorinated compounds were commonly detected in 21 out of 111 wells. In the results of statistical analysis with 21 wells data, DO and ORP also had a negative correlation with four organic chlorinated compounds, while EC and sulfate has a positive correlation with the compounds. This indicates that the 21 wells were relatively met with suitable environments for a biological dechlorination reaction compared to the other wells. Finally, cis-DCE had a non-carcinogenic risk of 10^-1 and the carcinogenic risk of VC was 10^-6 or higher. Through this study, the distribution status of the four chlorinated compounds in groundwater in South Korea and the necessity of preparing plans to manage cis-DCE and VC were confirmed.

• Economic and Environmental Geology
• /
• v.53 no.1
• /
• pp.11-21
• /
• 2020

One-dimensional analytical solutions were used for forward and back diffusion of trichloroethylene (TCE) and tetrachloroethylene (PCE) in a single system with high- and low-permeability layers. Concentration profiles in a low-permeability layer, diffusive fluxes at the interface between the high- and low-permeability layers, and contaminant persistence in the high-permeability layer due to back diffusion were simulated with a comparison of semi-infinite and finite analytical solutions. In order to validate the analytical solutions used in this study, the results of one-dimensional analytical solutions developed by Yang et al. (2015) were compared with Nash-Sutcliffe model efficiency coefficient (NSE). When compared with Yang et al. (2015), the analytical solutions used in this study showed good agreements (NSE = 0.99). When compared with semi-infinite analytical solutions, TCE and PCE concentration profiles in the low-permeability layer, the diffusive fluxes, and the contaminant tailings of the high-permeability layer were underestimated. In order to determine the appropriate analytical solutions based on the effective diffusion coefficient, the thickness of the low-permeability layer, and the diffusion time in the TCE and PCE contaminated site, a term of dimensionless diffusion length (Z_d) was used. If the Z_d is less than 0.7, the semi-infinite solutions can be used to simulate accurate concentration profiles in low-permeability layers. If the Z_d is greater than 0.7, the reliability of simulations may be improved by using the finite solutions.

• Journal of environmental and Sanitary engineering
• /
• v.23 no.2
• /
• pp.1-18
• /
• 2008

The tetrachloroethylene (PCE) dehalogenase of Clostridium bifermentans DPH-1 (a halorespiring organism) was purified, cloned, and sequenced. This enzyme is a homodimer with a molecular mass of ca. 70 kDa and exhibits dehalogenation of dichloroethylene isomers along with PCE and trichloroethylene (TCE). Broad range of substrate specificity for chlorinated aliphatic compounds (PCE, TCE, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, 1,1-dichloroethylene, 1,2-dichloropropene, and 1,1,2-trichloroethane) for this enzyme was also observed. A mixture of propyl iodide and titanium citrate caused a light-reversible inhibition of enzymatic activity suggesting the involvement of a corrinoid cofactor. A partial sequence (81 bp) of the encoding gene for PCE dehalogenase was amplified and sequenced with degenerateprimers designed from the N-terminal sequence (27 amino acid residues). Southern analysis of C. bifermentans genomic DNA using the polymerase chain reaction product as a probe revealed restriction fragment bands. A 5.0 kb ClaI fragment, harboring the relevant gene (designated pceC) was cloned (pDEHAL5) and the complete nucleotide sequence of pceC was determined. The gene showed homology mainly with microbial membrane proteins and no homology with any known dehalogenase, suggesting a distinct PCE dehalogenase. So, C. bifermentans could play some important role in the initial breakdown of PCE and other chlorinated aliphatic compounds in sites contaminated with mixtures of halogenated substances.

• Journal of Soil and Groundwater Environment
• /
• v.11 no.2
• /
• pp.68-76
• /
• 2006

Anaerobic reductive dechlorination of tetrachloroethylene (PCE) to ethylene was investigated by performing laboratory experiments using semi-continuous flow two-in-series soil columns. The columns were packed with soils obtained from TCE-contaminated site in Korea. Site ground water containing lactate (as electron donor and/or carbon source) and PCE was pumped into the soil columns. During the first operation with a period of 50 days, injected mass ratio of lactate and PCE was 620:1 and incomplete reductive dechlorination of PCE to cis-DCE was observed in the columns. However, complete dechlorination of PCE to ethylene was observed when the mass ratio increased to 5,050:1 in the second operation, suggesting that the electron donor might be limited during the first operation period. Dechlorination rate of PCE to cis-DCE was $0.62{\sim}1.94\;{\mu}mol$ PCE/L pore volume/d and $2.76\;{\mu}mol$ cis-DCE/ L pore volume/d for that for cis-DCE to ethylene, resulting that net dechlorination rate in the system was 1.43 umol PCE/L pore volume/d. During the degradation of cis-DCE to ethylene, the concentration of hydrogen in column groundwater was $22{\sim}29\;mM$ and $10{\sim}64\;mM$ for the degradation of PCE to cis-DCE. These positive results indicate that the TCE-contaminated groundwater investigated in this study could be remediated through in-situ biological anaerobic reductive dechlorination processes.