DCE Degradation Research Articles

Photocatalytic Degradation of Chlorinated Hydrocarbons: The By-Product of the Petrochemical Industry Using Ag-Cu/Graphite Bimetallic Carbon Nitride

In this study, the author improved and modified g-C3N4 by doping it with the metals Ag and Cu, which changed the photochemical properties of g-C3N4, narrowed the band gap, and improved the photocatalytic performance regarding quantum efficiency. Organic hydrocarbons such as 1,2-dichloroethane (DCE) are very stable prepared materials produced as intermediates to obtain polyvinyl chloride, and the prepared photo-catalyst is an innovative method for extreme decomposition of chlorinated hydrocarbons. However, some significant results were obtained using different analysis techniques. X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR) showed that the addition of Ag and Cu-NPS partially altered the structure of pure graphitic carbon nitride (g-C3N4-Pure). Scanning electron microscopy (TEM) analysis revealed that the morphological features of Ag-Cu/g-C3N4 contain quantum dots of Ag and Cu nanoparticles in addition to 2d-g-C3N4. The better separation of the photo-generated charge carriers is attributed to better photoactivity in the case of 0.3 g Ag-Cu/g-C3N4 with a reaction time of less than 30 min. Furthermore, the Ag-Cu/g-C3N4 recycling experiment showed that the catalyst remained stable after three stages of the pyrolysis experimental cycle. Another clear indicator of DCE degradation is the measurement using the titration of the Cl ions released by the decomposition.

Transition metal doping effect and high catalytic activity of CeO2–TiO2 for chlorinated VOCs degradation

A series of transition metals (Fe, Co, Ni, Cu, Cr and Mn)-doped CeO2–TiO2 catalysts were prepared by the sol–gel method and applied for the catalytic removal of 1,2-dichloroethane (DCE) as a model for chlorinated VOCs (CVOCs). The various characterization methods including X-ray diffraction (XRD), N2 adsorption–desorption, UV-Raman, NH3 temperature-programmed desorption (NH3-TPD) and H2 temperature-programmed reduction (H2-TPR) were utilized to investigate the physicochemical properties of the catalysts. The results show that doping Fe, Co, Ni or Mn can obviously promote the activity of CeO2–TiO2 mixed oxides for DCE degradation, which is related to their improved texture properties, acid sites (especially for strong acidity) and low-temperature reducibility. Particularly, CeTi–Fe doped with moderate Fe exhibits excellent activity for 1,2-dichloroethane (DCE) degradation, giving a T90% value as low as 250 °C. More importantly, only trace chlorinated byproducts were produced during the low-temperature degradation of various CVOCs (dichloromethane (DCM), trichloroethylene (TCE) and chlorobenzene (CB)) over CeTi–Fe1/9 catalyst with high durability.

Pt-support interaction and nanoparticle size effect in Pt/CeO2–TiO2 catalysts for low temperature VOCs removal

A series of Pt/CeO2–TiO2 catalysts (0.5 wt% Pt) with size-controllable Pt nanoparticles were prepared by a modified ethylene glycol reduction method and the Pt particle size effect of Pt/CeO2–TiO2 catalysts on benzene and 1,2-dichloroethane (DCE) degradation was investigated. It reveals that the metal-support interaction of PtOx species and CeO2–TiO2 mixed oxides is enhanced by the reduced Pt particle sizes. The formation of more Pt2+ species and stronger redox properties at low-temperature resulted by the enhanced metal-support interaction of Pt/CeO2–TiO2 catalysts both greatly promotes the deep oxidation for benzene and C2H3Cl byproduct during DCE degradation at low temperature. Pt/CeTi-11 with the smallest average Pt particle size (1.53 nm) exhibits the highest activity among all the catalysts for benzene degradation, with T90% of only 152 °C (1000 ppm, GHSV = 15,000 h−1). However, more acidic sites (especially the strong acid) were formed on the Pt/CeO2–TiO2 catalysts with bigger Pt nanoparticle (>2.95 nm), contributing to activate and convert DCE to C2H3Cl. More importantly, Pt/CeO2–TiO2 catalysts are extremely stable in DCE degradation reaction, and have been scarcely influenced by the presence of benzene and water in the feed gases.

Chlorinated ethene biodegradation and associated bacterial taxa in multi-polluted groundwater: Insights from biomolecular markers and stable isotope analysis

Chlorinated ethenes (CEs) are most problematic pollutants in groundwater. Dehalogenating bacteria, and in particular organohalide-respiring bacteria (OHRB), can transform PCE to ethene under anaerobic conditions, and thus contribute to bioremediation of contaminated sites. Current approaches to characterize in situ biodegradation of CEs include hydrochemical analyses, quantification of the abundance of key species (e.g. Dehalococcoides mccartyi) and dehalogenase genes (pceA, vcrA, bvcA and tceA) involved in different steps of organohalide respiration (OHR) by qPCR, and compound-specific isotope analysis (CSIA) of CEs. Here we combined these approaches with sequencing of 16S rRNA gene amplicons to consider both OHRB and bacterial taxa involved in CE transformation at a multi-contaminated site. Integrated analysis of hydrogeochemical characteristics, gene abundances and bacterial diversity shows that bacterial diversity and OHRB mainly correlated with hydrogeochemical conditions, suggesting that pollutant exposure acts as a central driver of bacterial diversity. CSIA, abundances of four reductive dehalogenase encoding genes and the prevalence of Dehalococcoides highlighted sustained PCE, DCE and VC degradation in several wells of the polluted plume. These results suggest that bacterial taxa associated with OHR play an essential role in natural attenuation of CEs, and that representatives of taxa including Dehalobacterium and Desulfosporosinus co-occur with Dehalococcoides. Overall, our study emphasizes the benefits of combining several approaches to evaluate the interplay between the dynamics of bacterial diversity in CE-polluted plumes and in situ degradation of CEs, and to contribute to a more robust assessment of natural attenuation at multi-polluted sites.

Promoting effect of Nb doping on catalytic performance for deep oxidation of 1, 2-dichloroethane over (Ce,Cr)xO2-Nb2O5 catalysts.

A series of Nb-doped (Ce,Cr)xO2-Nb2O5 mixed oxides with varying (Ce,Cr)xO2/Nb2O5 mass ratio were prepared by a co-precipitation method and evaluated for the catalytic performance of eliminating 1,2-dichloroethane (DCE). The results indicate that there exists a strong synergistic effect between acid sites and redox species in (Ce,Cr)xO2-Nb2O5 improving the catalytic activity for DCE oxidation. Appropriate Nb doping could promote the high dispersion and the interaction of metal oxides in the (Ce,Cr)xO2-Nb2O5 catalysts, resulting in the formation of more Cr6+ species with strong oxidizing ability and excellent mobility of oxygen species from bulk to surface to create more active sites for DCE deep oxidation. The (Ce,Cr)xO2-Nb2O5 catalysts with (Ce,Cr)xO2/Nb2O5 ratios of 2/1~1/2 exhibit excellent catalytic activity and durability for DCE degradation in dry air as well as benzene or water vapor, and less chlorinated byproduct is produced during the degradation of DCE.

Characterization of microbial communities in the aqueous phase of a constructed model wetland treating 1,2-dichloroethene-contaminated groundwater

The dynamics and composition of microbial communities in the aqueous phase of a model wetland supplied with cis- and trans-1,2-dichloroethenes (DCE)-contaminated groundwater was characterized. PCR-denaturing gradient gel electrophoresis analysis of water samples obtained from different parts of the wetland revealed that changes of the bacterial community structure coincided with a succession of the hydrochemical conditions in the wetland, from oxic towards anoxic conditions. During this transition phase, the appearance of vinyl chloride and ethene correlated with the presence of putative dechlorinating bacteria (Dehalococcoides spp., Geobacter spp. and Dehalobacter spp.). Additionally, a shift of the DCE isotopic composition indicated the progressive prevalence of reductive dechlorination in the wetland. Although the DCE degradation processes varied over time, biodegradation activity was maintained in the wetland system. 16S rRNA gene libraries revealed that Proteobacteria accounted for >50% of 16S rRNA genes clone libraries, whereas approximately 17% of the sequences from the wetland were related to sulphate reducers. Based on a multiple-method approach, this study illustrates the linkage between microbial community dynamics and composition, changes of hydrochemical conditions and processes of DCE degradation in a wetland system.

Aerobic Biodegradation of Chlorinated Ethenes in a Fractured Bedrock Aquifer: Quantitative Assessment by Compound-Specific Isotope Analysis (CSIA) and Reactive Transport Modeling

A model-based analysis of concentration and isotope data was carried out to assess natural attenuation of chlorinated ethenes in an aerobic fractured bedrock aquifer. Tetrachloroethene (PCE) concentrations decreased downgradient of the source, but constant delta13C signatures indicated the absence of PCE degradation. In contrast, geochemical and isotopic data demonstrated degradation of trichloroethene (TCE) and cis-1,2-dichloroethene (DCE) under the prevailing oxic conditions. Numerical modeling was employed to simulate isotopic enrichment of chlorinated ethenes and to evaluate alternative degradation pathway scenarios. Existing field information on groundwater flow, solute transport, geochemistry, and delta13C signatures of the chlorinated ethenes was integrated via reactive transport simulations. The results provided strong evidence for the occurrence of aerobic TCE and DCE degradation. The chlorinated ethene concentrations together with stable carbon isotope data allowed us to reliably constrain the assessment of the extent of biodegradation at the site and plume simulations quantitatively linked aerobic biodegradation with isotope signatures in the field. Our investigation provides the first quantitative assessment of aerobic biodegradation of chlorinated ethenes in a fractured rock aquifer based on compound specific stable isotope measurements and reactive transport modeling.

Stability and Performance of Xanthobacter autotrophicus GJ10 during 1,2-Dichloroethane Biodegradation

A nucleic acid-based approach was used to investigate the dynamics of a microbial community dominated by Xanthobacter autotrophicus GJ10 in the degradation of synthetic wastewater containing 1,2-dichloroethane (DCE). This study was performed over a 140-day period in a nonsterile continuous stirred-tank bioreactor (CSTB) subjected to different operational regimens: nutrient-limiting conditions, baseline operation, and the introduction of glucose as a cosubstrate. The microbial community was analyzed by a combination of fluorescence in situ hybridization (FISH) and denaturing gradient gel electrophoresis (DGGE). Under nutrient-limiting conditions, DCE degradation was restricted, but this did not affect the dominance of strain GJ10, determined by FISH to comprise 85% of the active population. During baseline operation, DCE degradation improved significantly to over 99.5% and then remained constant throughout the subsequent experimental period. DGGE profiles revealed a stable, complex community, while FISH indicated that strain GJ10 remained the dominant species. During the addition of glucose as a cosubstrate, DGGE profiles showed a proliferation of other species in the CSTB. The percentage of strain GJ10 dropped to 8% of the active population in just 5 days, although this did not affect the DCE biodegradation performance. The return to baseline conditions was accompanied by the reestablishment of strain GJ10 as the dominant species, suggesting that this system responds robustly to external perturbations, both at the functional biodegradation level and at the individual strain level.

Effects of oxygen and nitrogen conditions on the transformation kinetics of 1,2-dichloroethenes by Methylosinus trichosporium OB3b and its sMMOC mutant.

Transformation kinetics of trans- and cis-dichloroethylenes (DCE) by Methylosinus trichosporium OB3b wild type (WT) and PP319, a mutant that expresses soluble methane monooxygenase at copper levels up to micro 12 microM Cu (sMMOC), were determined to assess the effects of O2 level and N2-fixation on degradation capabilities. Two issues were examined: (1) the influence of O2 level and nitrogen-limitation on DCE degradation kinetics and toxicity in both organisms, and (2) the relative utility of PP319 for contaminant degradation in bioreactors. When both organisms were grown under high O2 conditions (80% saturation in air), maximum transformation rates (Vmax) and apparent first-order rate constants (Vmax/KM) were lower compared with organisms grown under low O2 conditions (10% saturation in air) regardless of nitrogen level. Further, Vmax values were near zero in nitrogen-limited WT cultures when O2 was high (as expected), whereas PP319 retained moderate Vmax levels even at high O2 levels. In general, elevated O2 conditions reduced DCE degradation rates in OB3b, although the negative effects of O2 were less in PP319 than in the WT. Given that PP319 retained moderate DCE degradation rates under most O2 and copper conditions, the mutant appears to have some utility for biodegradation applications.

Dehalogenation of dichloroethene in a contaminated soil: fatty acids and alcohols as electron donors and an apparent requirement for tetrachloroethene.

Environmental soil contamination at an industrial site in Marion, Ohio (USA) with tetrachloroethene (perchloroethene, PCE) resulted in residual cis-1, 2-dichloroethene (DCE) contamination that had not declined after more than 15 years. Microcosm slurries containing 2.6% soil from this site were supplemented with different electron donors, i.e., individual fatty acids or alcohols. None of the microcosms supported complete DCE dechlorination, unless PCE was added to the microcosm at initiation. The addition of fresh PCE resulted in the dehalogenation of PCE to DCE in the microcosms supplemented with fatty acids having an even number of carbon atoms (acetate, butyrate, and caproate), but not in those with an odd number of carbon atoms (formate, propionate, and valerate), where negligible or no activity was detected. No significant further DCE degradation was observed in any of the microcosms supplied with fatty acids as electron donors. Microcosms supplemented with freshly added PCE bioconverted PCE to DCE and completely dehalogenated both the ex-novo and soil-supplied DCE within 60 days, but only if alcohols having an even number of carbon atoms (ethanol or butanol) were also added as electron donors. Odd-numbered alcohols either did not produce dehalogenation (as with methanol) or only dehalogenated PCE to DCE (as with propanol).

Cometabolic Degradation of TCE and DCE without Intermediate Toxicity

Trichloroethylene (TCE) and cis-1,2-dichloroethylene (DCE) cometabolic degradation by a filamentous, phenol-oxidizing enrichment from a surface-water source were investigated in batch tests. No intermediate toxicity effects were evident during TCE or DCE degradation for loadings up to 0.5 mg TCE/mg VSS or 0.26 mg DCE/mg VSS. Phenol addition up to 40 mg/L did not inhibit TCE or DCE degradation. TCE specific degradation rates ranged from 0.28 to 0.51 g TCE/g VSS-d with phenol present, versus an average endogenous rate of 0.18 g TCE/g VSS-d. DCE specific degradation rates ranged from 0.79 to 2.92 g DCE/g VSS-d with phenol present, versus 0.27 to 1.5 g DCE/g VSS-d for endogenous conditions. There was no inhibition of DCE degradation rates at concentrations as high as 83 mg/L. TCE degradation rates declined between 40 and 130 mg/L TCE. Perchloroethylene, 1,1,1-trichloroethane, and chloroform were not degraded.

Extraction and biodegradation of a toxic volatile organic compound (1,2-dichloroethane) from waste-water in a membrane bioreactor.

An extractive membrane bioreactor has been used to treat a synthetic waste-water containing a toxic volatile organic compound, 1,2-dichloroethane (DCE). Biofilms growing on the surface of the membrane tubes biodegrade DCE while avoiding direct contact between the DCE and the aerating gas. This reduces air stripping by more than an order of magnitude (from 30-35% of the DCE entering the system to less than 1%) relative to conventional aerated bioreactors. Over 99% removal of DCE from a waste-water containing 1600 mg l-1 of DCE was achieved at waste-water residence times of 0.75 h. Biodegradation was verified as the removal mechanism through measurements of CO2 and chloride ion evolution in the bioreactor. No DCE was detected in the biomedium over the operating period. The diffusion-reaction phenomena occurring in the biofilm have been described by a mathematical model, which provides calculated solutions that support the experimental results by predicting that all DCE is biodegraded within the biofilm. Experimentally, however, the rate of DCE degradation in the biofilm was found to be independent of O2 concentration, while the model predictions point to O2 being limiting.