Vinyl Chloride Removal Research Articles

Nitrogen amended graphene catalyses fast reduction of vinyl chloride by nano zerovalent iron

Vinyl chloride (VC) is a dominant carcinogenic residual in many aged chlorinated solvent plumes, and it remains a huge challenge to clean it up. Zerovalent iron (ZVI) is an effective reductant for many chlorinated compounds but shows low VC removal efficiency at field scale. Amendment of ZVI with a carbonaceous material may be used to both preconcentrate VC and facilitate redox reactions. In this study, nitrogen-doped graphene (NG) produced by a simple co-pyrolysis method using urea as nitrogen (N) source, was tested as a catalyst for VC reduction by nanoscale ZVI (nZVI). The extent of VC reduction to ethylene in the presence of 2 g/L of nZVI was less than 1% after 3 days, and barely improved with the addition of 4 g/L of graphene. In contrast, with amendment of nZVI with NG produced at pyrolysis temperature (PT) of 950 °C, the VC reduction extent increased more than 10-fold to 69%. The reactivity increased with NG PT increasing from 400 °C to an optimum at 950 °C, and it increased linearly with NG loadings. Interestingly, N dosage had little effect on reactivity if NG was produced at PT of 950 °C, while a positive correlation was observed for NG produced at PT of 600 °C. XPS and Raman analyses revealed that for NG produced at lower PT (<800 °C) mainly the content of pyridine-N-oxide (PNO) groups correlates with reactivity, while for NG produced at higher PT up to 950 °C, reactivity correlates mainly with N induced structural defects in graphene. The results of quenching and hydrogen yield experiments indicated that NG promote reduction of VC by storage of atomic hydrogen, thus increasing its availability for VC reduction, while likely also enabling electron transfer from nZVI to VC. Overall, these findings demonstrate effective chemical reduction of VC by a nZVI-NG composite, and they give insights into the effects of N doping on redox reactivity and hydrogen storage potential of carbonaceous materials.

Enhanced removal of cis-1,2-dichloroethene and vinyl chloride in groundwater using ball-milled sulfur- and biochar-modified zero-valent iron: From the laboratory to the field

Sulfidated zero-valent iron (ZVI) and biochar-supported ZVI have received increasing attention for their potential to dechlorinate trichloroethylene. However, minimal data are available regarding the combined effect of sulfur and biochar ZVI on trichloroethylene byproducts. The primary aim of the current study is to determine whether sulfur- and biochar-modified ZVI (ZVI-BC-S) enhances the removal of cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC) from groundwater. Results show that biochar and sulfur facilitated the milling of ZVI-BC-S into micro- and nanoscale particles and increased FeS formation. Moreover, the rates of cDCE and VC removal by ZVI-S increased by 30.1% and 30.2%, respectively, compared to those obtained with ZVI, owing to enhanced dechlorination via β-elimination by sulfur. Meanwhile, treatment with ZVI-BC-S harnessed the benefits of biochar and sulfur to enhance the cDCE and VC removal rates by 62.0% and 67.7%, respectively. Mechanistically, biochar enhanced the corrosion of ZVI-S to increase FeS production and enhance the electron transfer, β-elimination, and hydrogenolysis involved in cDCE and VC dechlorination. The effectiveness of ZVI-BC-S was confirmed in a field demonstration, during which cDCE and VC concentrations significantly decreased within 10 days following injection. The findings of this study can help inform the rational design of ZVI for in-situ remediation of chlorinated hydrocarbons in groundwater.

Cometabolic Vinyl Chloride Degradation at Acidic pH Catalyzed by Acidophilic Methanotrophs Isolated from Alpine Peat Bogs.

Remediation of toxic chlorinated ethenes via microbial reductive dechlorination can lead to ethene formation; however, the process stalls in acidic groundwater, leading to the accumulation of carcinogenic vinyl chloride (VC). This study explored the feasibility of cometabolic VC degradation by moderately acidophilic methanotrophs. Two novel isolates, Methylomonas sp. strain JS1 and Methylocystis sp. strain MJC1, were obtained from distinct alpine peat bogs located in South Korea. Both isolates cometabolized VC with CH4 as the primary substrate under oxic conditions at pH at or below 5.5. VC cometabolism in axenic cultures occurred in the presence (10 μM) or absence (<0.01 μM) of copper, suggesting that VC removal had little dependence on copper availability, which regulates expression and activity of soluble and particulate methane monooxygenases in methanotrophs. The model neutrophilic methanotroph Methylosinus trichosporium strain OB3b also grew and cometabolized VC at pH 5.0 regardless of copper availability. Bioaugmentation of acidic peat soil slurries with methanotroph isolates demonstrated enhanced VC degradation and VC consumption below the maximum concentration level of 2 μg L-1. Community profiling of the microcosms suggested species-specific differences, indicating that robust bioaugmentation with methanotroph cultures requires further research.

Examining aerobic degradation of chloroethenes mixture in consortium composed of Comamonas testosteroni RF2 and Mycobacterium aurum L1

An environmental isolate Comamonas testosteroni RF2 has been previously described to cometabolize trichloroethene (TCE), 1,2-cis-dichloroethene (cDCE), 1,2-trans-dichloroethene (tDCE), and 1,1-dichloroethene (1,1DCE) when grown on phenol and lactate sodium. In this study, three vinyl chloride (VC) degrading strains, Mycobacterium aurum L1, Pseudomonas putida PS, and Rhodococcus ruber Sm-1 were used to form consortia with the strain RF2 in terms to achieve the removal of VC along with above-mentioned chloroethenes. Degradation assays were performed for a binary mixture of cDCE and VC as well as for a mixture of TCE, all DCEs and VC. The consortium composed of C. testosteroni RF2 and M. aurum L1 showed to be the most efficient towards the removal of cDCE (6.01 mg L−1) in the binary mixture with VC (10 mg L−1) and was capable of efficiently removing chloroethenes in the mixture sample at the initial concentrations of 116 μg L−1 for TCE, 662 μg L−1 for cDCE, 42 μg L−1 for tDCE, 16 μg L−1 for 1,1DCE, and 7 mg L−1 for VC with a removal efficiency of nearly 100% for all of the compounds. Although complete removal of VC took a significantly longer time than the removal of other chloroethenes, the consortium composed of C. testosteroni RF2 and M. aurum L1 displayed strong bioremediation potential for aquifers with downstream contamination characterized by the presence of less chlorinated ethenes.

Aerobic Vinyl Chloride Metabolism in Groundwater Microcosms by Methanotrophic and Etheneotrophic Bacteria.

Vinyl chloride (VC) is a carcinogen generated in groundwater by reductive dechlorination of chloroethenes. Under aerobic conditions, etheneotrophs oxidize ethene and VC, while VC-assimilators can use VC as their sole source of carbon and energy. Methanotrophs utilize only methane but can oxidize ethene to epoxyethane and VC to chlorooxirane. Microcosms were constructed with groundwater from the Carver site in MA containing these three native microbial types. Methane, ethene, and VC were added to the microcosms singly or as mixtures. In the absence of VC, ethene degraded faster when methane was also present. We hypothesized that methanotroph oxidation of ethene to epoxyethane competed with their use of methane, and that epoxyethane stimulated the activity of starved etheneotrophs by inducing the enzyme alkene monooxygenase. We then developed separate enrichment cultures of Carver methanotrophs and etheneotrophs, and demonstrated that Carver methanotrophs can oxidize ethene to epoxyethane, and that starved Carver etheneotrophs exhibit significantly reduced lag time for ethene utilization when epoxyethane is added. In our groundwater microcosm tests, when all three substrates were present, the rate of VC removal was faster than with either methane or ethene alone, consistent with the idea that methanotrophs stimulate etheneotroph destruction of VC.

Multiple lines of evidence to demonstrate vinyl chloride aerobic biodegradation in the vadose zone, and factors controlling rates

A field-based investigation was conducted at a contaminated site where the vadose zone was contaminated with a range of chlorinated hydrocarbons. The investigation consisted of groundwater and multilevel soil-gas monitoring of a range of contaminants and gases, along with isotope measurements and microbiology studies. The investigation provided multiple lines of evidence that demonstrated aerobic biodegradation of vinyl chloride (VC) was occurring in the vadose zone (i) above the on-site source zone, and (ii) above the downgradient off-site groundwater plume location. Data from both the on-site and off-site locations were consistent in showing substantially greater (an order of magnitude greater) rates of VC removal from the aerobic vadose zone compared to more recalcitrant contaminants trichloroethene (TCE) and tetrachloroethene (PCE). Soil gas VC isotope analysis showed substantial isotopic enrichment of VC (δ¹³C -5.2 to -10.9‰) compared to groundwater (δ¹³C -39.5‰) at the on-site location. Soil gas CO₂ isotope analysis at both locations showed that CO₂ was highly isotopically depleted (δ¹³C -28.8 to -33.3‰), compared to soil gas CO₂ data originating from natural sediment organic matter (δ¹³C= -14.7 to -21.3‰). The soil gas CO2 δ¹³C values were consistent with near-water table VC groundwater δ¹³C values (-36.8 to -39.5‰), suggesting CO₂ originating from aerobic biodegradation of VC. Bacteria that had functional genes (ethene monooxygenase (etnC) and epoxyalkane transferase (etnE)) involved in ethene metabolism and VC oxidation were more abundant at the source zone where oxygen co-existed with VC. The distribution of VC and oxygen vadose zone vapour plumes, together with long-term changes in soil gas CO₂ concentrations and temperature, provided information to elucidate the factors controlling aerobic biodegradation of VC in the vadose zone. Based on the overlapping VC and oxygen vadose zone vapour plumes, aerobic vapour biodegradation rates were independent of substrate (VC and/or oxygen) concentration. The high correlation (R=0.962 to 0.975) between CO₂ concentrations and temperature suggested that aerobic biodegradation of VC was controlled by bacterial activity that was regulated by the temperature within the vadose zone. When assessing a contaminated site for possible vapour intrusion into buildings, accounting for environmental conditions for aerobic biodegradation of VC in the vadose zone should improve the assessment of environmental risk of VC intrusion into buildings, enabling better identification and prioritisation of contaminated sites to be remediated.

Vinyl chloride removal from an air stream by biotrickling filter

A biofiltration process was used for degradation of vinyl chloride as a hazardous material in the air stream. Three biotrickling filters in series–parallel allowing uniform feed and moisture distribution all over the bed were used. Granular activated carbon mixed with compost was employed as carrier bed. The biological culture consisted of mixture of activated sludge from PVC wastewater treatment plant. Concurrent flow of gas and liquid was used in the bed. Results indicated that during the operation period of 110 days, the biotrickling bed was able to remove over 35% of inlet vinyl chloride. Maximum elimination capacity was calculated to be 0.56 g.m−3.hr−1. The amount of chlorine accumulated in the circulating liquid due to the degradation of vinyl chloride was measured to be equal to the vinyl chloride removed from the air stream.

Anaerobic Degradation of Vinyl Chloride in Aquifer Microcosms

The anaerobic degradation potential at a chloroethene-contaminated site was investigated by operating two anoxic column aquifer microcosms enriched in iron(III). One column was fed with vinyl chloride (VC) only (column A) and one with VC and acetate (column B). In column A, after about 600 pore volume exchanges (PVEs), VC started to disappear and reached almost zero VC recovery in the effluent after 1000 PVEs. No formation of ethene was observed. In column B, effluent VC was almost always only a fraction of influent VC. Formation of ethene was observed after 800 PVEs and started to become an important degradation product after 1550 PVEs. However, ethene was never observed in stoichiometric amounts compared with disappeared VC. The average stable isotope enrichment factor for VC disappearance in column A was determined to be -4.3‰. In column B, the isotope enrichment factor shifted from -10.7 to -18.5‰ concurrent with an increase in ethene production. Batch microcosms inoculated with column material showed similar isotope enrichment factors as the column microcosms. These results indicated that two degradation processes occurred, one in column A and two in parallel in column B with increasing importance of reductive dechlorination with time. This study suggests that in addition to reductive dechlorination, other degradation processes such as anaerobic oxidation should be taken into account when evaluating natural attenuation of VC and that isotope analysis can help to differentiate between different pathways of VC removal.

Modeling Substrate Interactions during Aerobic Biodegradation of Mixtures of Vinyl Chloride and Ethene

Ethene (ETH) is often associated with vinyl chloride (VC) in contaminated groundwater, as it is formed along with vinyl chloride during reductive dechlorination of higher chloroethenes (e.g., perchloroethylene and trichloroethylene). In the present study the interaction between VC and ETH during their aerobic biodegradation by enrichment cultures was investigated. The cultures were able to use both compounds as growth substrates. In mixture experiments, the degradation rate of one substrate was affected by the presence of the other. A biokinetic model based on competitive inhibition described well the observed substrate interactions over a range of initial VC (0–144 μmolL−1) and ETH (0–37.5 μmolL−1) concentrations, using parameters estimated from single-substrate experiments. Notably, half-velocity coefficients could be used as competitive inhibition coefficients. This finding shows the importance of obtaining accurate measurements of half-velocity coefficients in order model competitive inhibition processes. Simulation results showed that when the initial ETH concentration was raised from 0 to 30 μmolL−1, the apparent half-velocity coefficient for VC (KVCAPP) increased by nearly three times, from 12.9 to 35.4 μmolL−1. This finding has strong environmental implications because a low half-velocity coefficient for VC is regarded as the major prerequisite for achieving efficient and complete VC degradation. Moreover, the effect of ETH on the efficiency of VC removal is strongly dependent on the KVC∕KETH ratio, consequently determination of KETH for VC-degrading microbes is important when biodegradation (or bioaugmentation) is considered for clean up of VC-contaminated sites. Additional model simulations, using the ratio of KVC to KETH for previously characterized VC- and ETH-utilizing microorganisms (values ranged from 0.06 to 1.2) showed that their ability to degrade VC in the presence of ETH may differ significantly.

Experimental and CFD analysis of photocatalytic gas phase vinyl chloride (VC) oxidation

Photocatalytic destruction of gas phase vinyl chloride (VC) was examined using experimental and computational fluid dynamics (CFD) approaches. Experimental work involved using a differential photoreactor for determining kinetics of oxidation and an annular flow photoreactor for overall removal investigations as well as comparison with CFD models. The kinetic data obtained from differential photoreactor were used to model and predict the performance of the annular photoreactor using CFD. The photocatalytic oxidation of VC followed first order kinetics for inlet concentrations up to about 0.28 g m −3 and CFD was able to predict the removal of VC in the system. Both experimental and CFD modeling showed the removal of VC in the system increased with increasing the VC loading rate. CFD analysis of the photoreactor also provided insight into the detailed concentration gradient of VC within the reactor. The modeling results indicated significant radial VC concentration gradient and non-uniform flow distributions in the annular photoreactor. This non-uniform flow distribution, in turn, resulted in short circuiting of the VC contaminated gas and may have resulted in less than optimum removal efficiency for VC in the annular reactor over the entire range of inlet VC concentrations. Overall, the information provided by CFD modeling and simulation showed to be valuable for reactor design modification and for improving the reactor performance.

Gas phase vinyl chloride (VC) oxidation using TiO2-based photocatalysis

Photocatalytic destruction of vinyl chloride (VC) was examined in a laboratory experimental set-up and the results were compared with those obtained from trichloroethylene (TCE) photocatalysis. Granular photocatalyst used in the study consisted of silica support coated with 0.1% titanium dioxide as the main photocatalytically active ingredient. Experimental work involved passing polluted air containing VC or TCE through a UV annular reactor at varying concentrations and residence times. Ultraviolet illumination was provided by low-pressure monochromatic mercury lamps with peak intensities at either 254nm (germicidal) or 365nm (black light). The operating temperature was constant at about 30°C. UV photocatalysis provided greater than 80% VC removal at inlet concentrations of up to 60ppmv and reactor gas retention times as low as 0.6s. The overall removal capacity of the photoreactor was about 1000g VC per m3 photocatalyst per hour (gm−3h−1). Although this removal rate for VC was up to about 40% of that for TCE, this study is the first to obtain such noticeable photocatalytic destruction for VC, which is a biologically recalcitrant contaminant and its emission is a source of environmental concern.

Chlorinated Organic Compound Removal by Gas Phase Pulsed Streamer Corona Electrical Discharge with Reticulated Vitreous Carbon Electrodes

Trichloroethylene (TCE) and vinyl chloride (VC) removal by gas phase pulsed corona discharge was investigated with attention to energy efficiency and byproduct identification. Approximately 50–95% removal of TCE and vinyl chloride was observed, depending on the energy density applied to the gas. Water vapor reduced TCE removal in some experiments. Evidence was found for post-corona reactions leading to removal of vinyl chloride downstream of the plasma discharge, while significant post-corona removal of TCE was not observed. Removal efficiencies of 100–900 g/kW-hr in the case of 1000 ppm feed of TCE, and of 2–24 g/kW-hr for a 100 ppm feed of vinyl chloride were found. In the TCE experiments, the formation of dichloroacetyl chloride was observed, while an unknown byproduct was found with vinyl chloride. The addition of a platinum-rhodium coated electrode was found to reduce the post-corona removal of vinyl chloride at low energy density.

Treatment of chlorinated volatile organic compounds in upflow wetland mesocosms

Sorption, biodegradation and hydraulic parameters were determined in the laboratory for two candidate soil substrate mixtures for construction of an upflow treatment wetland for volatile organic compounds (VOCs) at a Superfund site. The major parent contaminants in the groundwater at the Superfund site were cis-1,2-dichloroethene ( cis-1,2-DCE) and 1,1,1-trichloroethane (1,1,1-TCA). The two mixtures; one a mixture of sand and peat, the other a mixture of sand, peat and Bion Soil, a product derived from agricultural wastes; were selected from ten possible mixtures based on the results of hydraulic and geotechnical testing. The sand and peat mixture had an average hydraulic conductivity of 4.95×10 −4 cm/s with a critical flow of 39.5 gpm/acre (368 l/min/ha) without fluidization of the bed. The sand, peat and Bion Soil mixture had an average hydraulic conductivity of 3.02×10 −4 cm/s with a critical flow of 36.8 gpm/acre (344 l/min/ha) without fluidization of the bed. Retardation coefficients ranged from 1 to 7.3 for target VOCs with higher coefficients observed in the mixture containing the Bion Soil. Consistently higher spatial and temporal first-order removal rate constants were observed in the sand, peat and Bion Soil mixture ( cis-1,2-DCE, 0.84±0.36/day; 1,1,1-TCA, 6.52±3.12/day) than in the sand and peat mixture ( cis-1,2-DCE, 0.37±0.13/day; 1,1,1-TCA, 1.48±0.42/day). Results from anaerobic microcosm studies confirmed that biodegradation was occurring in the columns and that the sand, peat and Bion Soil mixture had higher degradation rate than the sand and peat mixture. Vinyl chloride (VC) was identified as a ‘design’ contaminant since it is a proven carcinogen and had the lowest removal rate constant for both substrate mixtures. Effective wetland bed depths for VC removal of 900 and 210 cm will be required for peat and sand alone and sand, peat and Bion Soil mixtures, respectively.

Modeling the kinetics of vinyl chloride cometabolism by an ethane-grown Pseudomonas sp.

Pseudomonas sp strain EA1 was isolated under aerobic conditions using ethane as the sole organic carbon and electron donor source, with an observed yield of 0.99 mg total suspended solids/mg ethane (0.85 mg volatile suspended solids / mg ethane) and a maximum specific growth rate of 0.015 d(-1). When grown on ethane, EA1 cometabolizes vinyl chloride (VC) at a maximum rate of 0.350 micromol/mg volatile suspended solids/d and with a half saturation constant of 0.62 microM VC. The rate of VC use by EA1 is twice as high when ethane is also provided, even though consumption of ethane is almost completely inhibited until VC is consumed. The presence of ethane also reduces the total amount of VC cometabolized. A model was developed that adequately describes the batch kinetics of VC cometabolism in the presence and absence of ethane, as well as ethane metabolism in the presence and absence of VC. Terms are included that increase the initial rate of VC use in the presence of ethane (according to the ratio of initial ethane concentration to the half saturation coefficient) but decrease the total amount of VC cometabolized. Parameter estimates for the model were obtained using a step-wise experimental approach, with varying initial concentrations of VC and ethane. Strain EA1 completely dechlorinates VC in the presence and absence of ethane. Measurements of soluble chemical oxygen demand indicate that approximately 50% of the VC consumed is mineralized, with the balance released as soluble, nonchlorinated products. Ethene is not used as a substrate by EA1 but it does inhibit ethane metabolism and VC cometabolism. In mixtures containing all three compounds, more VC is degraded and at a faster rate compared to VC plus ethene. The results suggest that ethane-enhanced biodegradation of VC may contribute to VC removal at the aerobic fringe of groundwater plumes undergoing reductive dechlorination.

Application of basic 3‐phase equilibrium distribution model to spray drying sorber for simultaneous removal of so2 and vinyl chloride

Simultaneous removal efficiencies of hydrophilic (SO2) and hydrophobic (vinyl chloride) gaseous pollutants are experimentally determined, and the macroscopic removal mechanism of pollutants in a spray drying sorber(SDS) is analyzed using the extended model of three phase equilibrium distribution of pollutant at high temperatures which is basically based on the different morphological conditions of adsorbent and water at varying relative humidities. For the practical simplicity, the inside of spray drying sorber is divided into three regions of ; (1) absorption, (2) transition and (3) adsorption, and the removal efficiencies of each pollutants at three different regions are observed at different experimental conditions to estimate the effects of important parameters of SDS. The two types of slurry are made of the two sorbents : 10 wt% Ca(OH)2 and 10 wt% NaOH. The result of temperature effect shows the height of absorption and transition region is decreased as the operation temperature is increased. Therefore, it resulted in the lower removal efficiency for SO2, and the higher removal efficiency for vinyl chloride in the adsorption region of SDS. The removal efficiency of SO2 with NaOH slurry is higher than with Ca(OH)2 slurry due to the hygroscopic nature of NaOH, while the removal of vinyl chloride is higher in Ca(OH)2 case. From the analysis of results using three‐phase equilibrium distribution model, the effective two‐phase partition coefficients can be obtained, and the possible extension in the application of the three‐phase equilibrium model in SDS design has been demonstrated.

Characterization of a Mycobacterium sp. and a Xanthobacter sp. for the removal of vinyl chloride and 1,2-dichloroethane from waste gases

Mycobacterium aurum L1 and Xanthobacter autotrophicus GJ10 were characterized with respect to their potential use in the biological treatment of waste gases containing vinyl chloride (VC) and 1,2-dichloroethane (DE). VC at a concentration of 125 g m −3 in the gas phase was not toxic but DE at 22 g m −3 already resulted in a decreased growth rate. Kinetic properties of washed cells were determined and chemostat cultures were run to optimize the medium for VC removal. Using a mixed culture of the two strains, simultaneous removal and mineralization of VC and DE was demonstrated. The affinity constants of growing cells found for the two substrates are, however, significantly higher than the maximal allowable concentrations of VC and DE in waste gases.

Removal of Vinyl Chloride from Gaseous Streams by Adsorption on Activated Carbon

Removal of Vinyl Chloride from Gaseous Streams by Adsorption on Activated Carbon