Rough-interval-based multicriteria decision analysis for remediation of 1,1-dichloroethane contaminated groundwater.

A rough-interval-based multicriteria decision analysis method (RI-MCDA) is developed for supporting the selection of remediation strategies for 1,1-dichloroethane contaminated sites. The concept of ''rough interval'' is introduced in the design framework to represent dual-uncertain parameters. Three rough-interval scenarios generated through pair-wise combining the values under three confidence levels (i.e. 68.3%, 95.4% and 99.7%) and one deterministic scenario adopted crisp numbers for parameters are introduced into the framework. The proposed method is then applied to a contaminated site in the Pudong district of Shanghai, China. Fifty remediation alternatives under four duration options (i.e. 5, 10, 15, and 20 years) and ten criteria, including daily total pumping rate, total cost and rough-interval risk information in light of uncertainty parameter (e.g. slope factor), are taken into consideration to compare different alternatives through RI-MCDA. Results indicated that the most desirable remediation strategy lied in A25 for the 5-year, A10 for the 10-year, A15 for the 15-year, and A11 for the 20-year remediation. Compared to the traditional MCDA, the proposed RI-MCDA shows the uniqueness in addressing the interaction between dual intervals of highly uncertain parameters, as well as their joint impact on the decision results, which reduces the subjectivity as much as possible.

Evaluation of substrate removal kinetics for UASB reactors treating chlorinated ethanes.

PURPOSE: Lack of focus on the treatment of wastewaters bearing potentially hazardous pollutants like 1,1,2 trichloroethane and 1,1,2,2 tetrachloroethane in anaerobic reactors has provided an impetus to undertake this study. The objective of this exercise was to quantify the behavior of upflow anaerobic sludge blanket reactors and predict their performance based on the overall organic substrate removal. METHODS: The reactors (wastewater-bearing TCA (R2), and wastewater-bearing TeCA (R3)) were operated at different hydraulic retention times (HRTs), i.e., 36, 30, 24, 18, and 12 h corresponding to food-to-mass ratios varying in the range of 0.2­0.7 mg chemical oxygen demand (COD) mg−1 volatile suspended solids day−1. The process kinetics of substrate utilization was evaluated on the basis of experimental results, by applying three mathematical models namely first order, Grau second order, and Michaelis-Menten type kinetics. RESULTS: The results showed that the lowering of HRT below 24 h resulted in reduced COD removal efficiencies and higher effluent pollutant concentrations in the reactors. The Grau second-order model was successfully applied to obtain the substrate utilization kinetics with high value of R 2 (>0.95). The Grau second-order substrate removal constant (K 2) was calculated as 1.12 and 7.53 day−1 for reactors R2 and R3, respectively. CONCLUSION: This study demonstrated the suitability of Grau second-order kinetic model over other models, for predicting the performance of reactors R2 and R3, in treating wastewaters containing chlorinated ethanes under different organic and hydraulic loading conditions.

Simultaneous counter-flow of chlorinated volatile organic compounds across the saturated-unsaturated interface region of an aquifer.

Concentrations of chlorinated volatile organic compounds (Cl-VOCs) at the saturated-unsaturated interface region (SUIR; depth of approximately 18m) of a sandy phreatic aquifer were measured in two monitoring wells located 25m apart. The concentrations of the Cl-VOCs obtained above and below the water table along a 413-day period are interpreted to depict variable, simultaneous and independent movement of trichlorothene, tetrachloroethene, 1,1-dichloroethene, cis-1,2-dichloroethene, 1,1,1-trichloroethane, chloroform and 1,1-dichloroethane vapors in opposite directions across the SUIR.

1,1,1-trichloroethane and 1,1-dichloroethane reductive dechlorination kinetics and co-contaminant effects in a Dehalobacter-containing mixed culture.

1,1,1-Trichloroethane (1,1,1-TCA) is a common groundwater contaminant that can be reductively dechlorinated to 1,1-dichloroethane (1,1-DCA) and monochloroethane, and can support the growth of certain dehalorespiring strains of Dehalobacter We used reductive dehalogenase cell-free extract assays (with reduced methyl viologen) and whole cell suspension dechlorination assays (with hydrogen) and a Dehalobacter-containing enrichment culture to explore the kinetics of l,1,1-TCA and 1,1-DCA reductive dechlorination in the presence of the common co-contaminants trichloroethene (TCE), cis-dichloroethene (cDCE), and vinyl chloride (VC). These chlorinated ethenes were most significant inhibitors of 1,1,1-TCA dechlorination in cell-free extracts, indicating direct effects on the reductive dehalogenase enzyme(s). The inhibition was present but less pronounced in whole cell suspension assays. None of the chlorinated ethenes inhibited 1,1-DCA dechlorination in cell-free extract assays, yet cDCE and particularly VC were inhibitors in whole cell assays, indicating an effect on Dehalobacter, but not on the dehalogenase enzyme(s). Marked differences in kinetic parameters for 1,1,1-TCA and 1,1-DCA, and an uncoupling of these two activities in cultures grown on 1,1-DCA compared to those grown on 1,1,1-TCA was strong evidence for the existence of distinct 1,1,1-TCA and 1,1-DCA reductive dehalogenase enzymes.

Misidentification of ethyl chloride in the routine GC-FID analysis for alcohol.

UNLABELLED: GC-FID is the method of choice for alcohol screening and quantitative analysis in modern forensic medical practice. Although specific enough for routine use, some results could be misleading. In the current article we present a case of sexual asphyxia with drug and volatile substance abuse. Toxicological analysis revealed the presence of methamphetamine at a concentration of 1.3 microg/mL in blood. An ethanol-like peak was detected during our routine GC-FID test for alcohol (methylethylketone IS). Subsequent GC-MS analysis identified the peak as ethyl chloride. Levels of 0.05 mg/mL in blood and 0.01 mg/mL in urine were measured. Two facts proved misleading in our case. First: very small difference of 0.027 between the ethyl chloride and ethanol peaks in relative retention times at the GC-FID chromatograms. Second: missing evidence for the use of ethyl chloride at the scene-neither cans of the substance were found, nor such information was available otherwise. CONCLUSION: there is a substantial risk for mistaking ethyl chloride for ethanol, when ethyl chloride abuse is unanticipated. In the case of slightest uncertainty a GC-MS analysis should be employed to reliably determine the actual substance.

De novo formation of chloroethyne in soil.

To date, chloroethyne in the environment has been proposed to occur as a reactive intermediate during the reductive dechlorination of tri- and tetrachloroethene with zerovalent metals. Such artificial conditions might possibly be found at organohalide-contaminated sites that are surrounded by remediation barriers made of metallic iron. In this paper, it is shown that the highly reactive chloroethyne is also a product of natural processes in soil. Soil air samples from three differentterrestrial ecosystems of Northern Germany showed significant chloroethyne concentrations, besides other naturally produced monochlorinated compounds, such as chloromethane, chloroethane and chloroethene. Measured amounts range from 5 to 540 pg chloroethyne in air purged from 1 L of soil. A possible route of chloroethyne formation in soil is discussed, where chloroethyne is probably produced as a byproduct of the oxidative halogenation of aromatic compounds in soil. A series of laboratory studies, using the redox-sensitive catechol as a discrete organic model compound, showed the formation of chloroethyne when Fe3+ and hydrogen peroxide were added to the system. We therefore propose that the natural formation of chloroethyne in soil proceeds via oxidative cleavage of a quinonic system in the presence of the ubiquitous soil component chloride.

Methyl-coenzyme M reductase of Methanobacterium thermoautotrophicum delta H catalyzes the reductive dechlorination of 1,2-dichloroethane to ethylene and chloroethane.

Reductive dechlorination of 1,2-dichloroethane (1,2-DCA) to ethylene and chloroethane (CA) by crude cell extracts of Methanobacterium thermoautotrophicum delta H with H2 as the electron donor was stimulated by Mg-ATP. The heterodisulfide of coenzyme M (CoM) and 7-mercaptoheptanoylthreonine phosphate together with Mg-ATP partially inhibited ethylene production but stimulated CA production compared Mg-ATP alone. The pH optimum for the dechlorination was 6.8 (at 60 degrees C). Michaelis-Menten kinetics for initial product formation rates with different 1,2-DCA concentrations indicated the enzymatic character of the dechlorination. Apparent Kms for 1,2-DCA of 89 and 119 microM and Vmaxs of 34 and 20 pmol/min/mg of protein were estimated for ethylene and CA production, respectively. 3-Bromopropanesulfonate, a specific inhibitor for methyl-CoM reductase, completely inhibited dechlorination of 1,2-DCA. Purified methyl-CoM reductase, together with flavin adenine dinucleotide and a crude component A fraction which reduced the nickel of factor F430 in methyl-CoM reductase, converted 1,2-DCA to ethylene and CA with H2 as the electron donor. In this system, methyl-CoM reductase was also able to transform its own inhibitor 2-bromoethanesulfonate to ethylene.

Rapid gas-liquid chromatographic method for determining residues of ethephon (2-chloroethyl phosphonic acid) in tomatoes.

A rapid method is described for the determination of the growth regulator ethephon (2-chloroethyl phosphonic acid) in tomatoes. Samples are extracted with ethyl acetate. The extract is methylated, decolorized with carbon, and analyzed by gas-liquid chromatography on a column packed with 15% QF-1/10% DC-200 on Chromosorb W (HP). A flame photometric detector is used. Recoveries from tomatoes fortified with 0.1-11.0 ppm ethephon were 78-98%. The sensitivity of this method is about 0.1 ppm.

Gas-liquid chromatographic analysis of ethephon and fenoprop residues in apples and their decline before and after harvest.

Ethephon (2-chloroethylphosphonic acid) and fenoprop (2-(2,4,5-trichlorophenoxy) propionic acid) may be determined in the same apple sample. After extraction with methanol, 2 separate methylation procedures were required to quantitatively convert each compound. Ethephon was esterified with diazomethane and analyzed by a flame photometric detector in the P-mode. Fenoprop was esterified with boron trifluoride/methanol and analyzed by electron capture gas chromatography. Average recoveries were about 95% at 0.05 ppm for both compounds. The limit of detection was 0.05 ppm for ethephon and 0.01 ppm for fenoprop in a 1 g sample. The persistence of both compounds before and after harvest was studied. Ethephon and fenoprop were applied simultaneously to apple trees at the recommended concentrations of 300 and 20 ppm, respectively. Ethephon residues averaged 1.6, 0.75, and 0.4 ppm at 2 hr, 10 days, and after washing at 13 days, respectively. The corresponding fenoprop residues were 0.70, 0.025, and 0.024 ppm.

Metabolism of ethephon (2-chloroethylphosphonic acid) and related compounds in Hevea brasiliensis.

Ethephon (I) is used commercially to prolong the flow of latex from the rubber tree after tapping (Yield stimulation). The compound is applied to the bark in the region of the tapping cut and the effect on latex flow is due to the ethylene released by chemical decomposition, since gaseous ethylene itself is also a very effective stimulant. When 14C-I is applied to the bark of a young Hevea seedling, it is absorbed into the plant by processes which appear to be largely non-metabolic. Ethylene formation commences immediately at the site of application, and the gas is quickly translocated throughout the plant. Translocation of I to all parts of the plant also occurs and the accumulation of 14C in the bark above the zone of application is greater than that below. Chromatographic analysis has shown that compounds other than I remain in the plant tissue. Experiments using 14C-I have shown that detached leaves are able to convert a considerable proportion of the compound to at least twelve non-volatile acid products. One of these is a conjugate of I with an unidentified material. A major component of the products is 2-hydroxyethylphosphonic acid (II), which is itself converted to a number of compounds in leaves. The application of I to bark from mature Hevea, results in the formation of a single substance which is also a conjugate of I. Neither I nor II is effective in inducing the formation of ethylene from endogenous precursors in vegetative Hevea tissue. Ethylene is poorly metabolized by Hevea leaves and the evidence available indicates that it is unlikely that any of the compounds produced from I are metabolites of ethylene.