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1.
Chemosphere ; 254: 126842, 2020 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-32957273

RESUMEN

Diffusion, sorption-desorption, and biodegradation influence chlorinated solvent storage in, and release (mass flux) from, low-permeability media. Although bioenhanced dissolution of non-aqueous phase liquids has been well-documented, less attention has been directed towards biologically-mediated enhanced diffusion from low-permeability media. This process was investigated using a heterogeneous aquifer cell, packed with 20-30 mesh Ottawa sand and lenses of varying permeability (1.0 × 10-12-1.2 × 10-11 m2) and organic carbon (OC) content (<0.1%-2%), underlain by trichloroethene (TCE)-saturated clay. Initial contaminant loading was attained by flushing with 0.5 mM TCE. Total chlorinated ethenes removal by hydraulic flushing was then compared for abiotic and bioaugmented systems (KB-1® SIREM; Guelph, ON). A numerical model incorporating coupled diffusion and (de)sorption facilitated quantification of bio-enhanced TCE release from low-permeability lenses, which ranged from 6% to 53%. Although Dehalococcoides mccartyi (Dhc) 16S rRNA genes were uniformly distributed throughout the porous media, strain-specific distribution, as indicated by the reductive dehalogenase (RDase) genes vcrA, bvcA, and tceA, was influenced by physical and chemical heterogeneity. Cells harboring the bvcA gene comprised 44% of the total RDase genes in the lower clay layer and media surrounding high OC lenses, but only 2% of RDase genes at other locations. Conversely, cells harboring the vcrA gene comprised 50% of RDase genes in low-permeability media compared with 85% at other locations. These results demonstrate the influence of microbial processes on back diffusion, which was most evident in regions with pronounced contrasts in permeability and OC content. Bioenhanced mass transfer and changes in the relative abundance of Dhc strains are likely to impact bioremediation performance in heterogeneous systems.


Asunto(s)
Chloroflexi/metabolismo , Contaminantes Químicos del Agua/aislamiento & purificación , Adsorción , Biodegradación Ambiental , ADN Bacteriano/genética , Dehalococcoides , Difusión , Agua Subterránea , Dinámica Poblacional , Porosidad , ARN Ribosómico 16S/análisis , ARN Ribosómico 16S/genética , Tricloroetileno/aislamiento & purificación , Tricloroetileno/metabolismo , Contaminantes Químicos del Agua/metabolismo
2.
Chemosphere ; 247: 125806, 2020 May.
Artículo en Inglés | MEDLINE | ID: mdl-32069707

RESUMEN

This study evaluated the biological removal of trichloroethylene (TCE) by Rhodococcus opacus using airlift bioreactor under continuous operation mode. The effect of inlet TCE concentration in the range 0.12-2.34 g m-3 on TCE removal has studied for 55 days. During the continuous bioreactor operation, a maximum of 96% TCE removal was obtained for low inlet TCE concentration, whereas the highest elimination capacity was 151.2 g m-3 h-1 for the TCE loading rate of 175.0 g m-3 h-1. The carbon dioxide (CO2) concentration profile from the airlift bioreactor revealed that the degraded TCE has primarily converted to CO2 with a fraction of organic carbon utilized for bacterial growth. The artificial neural network (ANN) based model was able to successfully predict the performance of the bioreactor system using the Levenberg-Marquardt (LM) back propagation algorithm, and optimized biological topology is 3:12:1. The prediction accuracy of the model was high as the experimental data were in good agreement (R2 = 0.9923) with the ANN predicted data. Overall, from the bioreactor experiments and its ANN modeling, the potential strength of R. opacus in TCE biodegradation is proved.


Asunto(s)
Biodegradación Ambiental , Reactores Biológicos , Redes Neurales de la Computación , Rhodococcus/metabolismo , Tricloroetileno/aislamiento & purificación , Algoritmos , Dióxido de Carbono/metabolismo , Tricloroetileno/metabolismo
3.
Environ Sci Pollut Res Int ; 26(25): 26276-26285, 2019 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-31286373

RESUMEN

Tricholorethylene (TCE) has been recognized as second common organic pollutant found in groundwater in Taiwan. Several advanced oxidation processes (AOPs) have been applied for TCE removal and photocatalytic is one of promising AOP techniques. In this study, LaFeO3 is successfully synthesized via sol-gel method and investigated for its photocatalytic oxidation rate toward TCE in water. Experimental results indicate that 95% removal efficiency of TCE can be achieved in aqueous solution with LaFeO3 (2 g/L) as photocatalyst within 1 h of Xenon lamp illumination. Additionally, the influences of initial TCE concentration, light intensity, photocatalyst loading, and pH value on the TCE removal efficiency are evaluated as well. The highest energy efficiency obtained in this study is 10.8 mg TCE/kWh and the value is higher than those reported in previous studies. Besides, removal mechanisms have been identified and the results indicate that the overall removal efficiency reaches 82%, with adsorption and photolysis accounting for 20% and 39%, respectively.


Asunto(s)
Óxidos/química , Tricloroetileno/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación , Purificación del Agua/métodos , Adsorción , Agua Subterránea/química , Concentración de Iones de Hidrógeno , Oxidación-Reducción , Procesos Fotoquímicos , Fotólisis , Purificación del Agua/instrumentación
4.
Chemosphere ; 229: 515-524, 2019 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-31100622

RESUMEN

In this study, adsorption kinetics of phenanthrene (PNT) and trichloroethylene (TCE) by a graphene nanosheet (GNS), a graphene oxide nanosheet (GO), a single-walled carbon nanotube (SWCNT), a multi-walled carbon nanotube (MWCNT), and two coal based activated carbons (ACs) (F400 and HD3000) were examined in distilled and deionized water (DDW) and under natural organic matter (NOM) preloading conditions. The results showed the times needed for the adsorption of PNT and TCE to reach apparent equilibrium (i.e., ≤3% change per day) followed the order of GO ≥ MWCNT > GNS > SWCNT ∼ HD3000∼F400 and SWCNT > GNS ∼ HD3000 > F400 ∼ MWCNT > GO, respectively. The pseudo second order model successfully represented kinetics data for three classes of carbonaceous adsorbents. The Weber-Morris intraparticle diffusion model indicated three steps adsorption process for PNT and two step adsorption for TCE. In addition, the times needed to reach apparent equilibrium for the adsorption of PNT and TCE in the presence of hydrophobic (HPO) and hydrophilic (HPI) NOM solutions increased for all adsorbents (except for GO). In general, both NOM showed similar impacts on the adsorption rates of PNT and TCE. Aggregation of both GNS and CNTs rapidly occurred during initial couple hours of contact time during preloading, and spiking both PNT and TCE further increased their aggregation.


Asunto(s)
Carbón Orgánico/química , Grafito/química , Nanotubos de Carbono/química , Contaminantes Químicos del Agua/aislamiento & purificación , Purificación del Agua/métodos , Adsorción , Carbón Mineral , Interacciones Hidrofóbicas e Hidrofílicas , Cinética , Fenantrenos/aislamiento & purificación , Tricloroetileno/aislamiento & purificación
5.
Environ Geochem Health ; 41(4): 1637-1646, 2019 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-28780675

RESUMEN

Peat moss-derived biochars were produced at the pyrolytic temperatures of 300, 500, and 700 °C and were tested for evaluating the removal efficiency of volatile organic compounds (VOCs) from waters. As the pyrolytic temperature increases, the carbon contents were increased from 66 to 84%, and the contents of hydrogen and oxygen were decreased from 4 to 1% and from 19 to 4%, respectively. The surface areas of the biochars were 2 m2 g-1 at the pyrolysis temperature of 300 °C and were increased to 200 and 300 m2 g-1 at 500 and 700 °C, respectively. Results of FTIR analysis showed that functional groups such as hydroxyl, nitro, and carboxyl groups were observed in the biochar produced at 300 °C; however, the functional groups were removed in the biochars produced at higher temperatures. Sorption kinetics and equilibrium experiments were conducted with selected six VOCs of benzene (BZN), toluene (TOL), ethylbenzene (EBZ), p-xylene (pXYL), trichloroethylene (TCE), and tetrachloroethylene (PCE), which are the most common VOCs found in contaminated groundwater of South Korea. Sorption equilibrium was attained in 6 h with the constants of first order kinetic rate of 0.5 h-1 for the VOCs tested. Freundlich isotherm well described the adsorption of VOCs to the biochars. Biochar produced at 500 °C showed the highest sorption capacity for all VOCs with an average Kf of 7692 (±2265), although biochars produced at 300 °C (Kf = 3146 ± 629) and 700 °C (Kf = 2776 ± 2693) showed the similar sorption capacity. The biochars produced at 500 °C can be an excellent remover of VOCs in contaminated groundwater.


Asunto(s)
Carbón Orgánico/química , Sphagnopsida/química , Compuestos Orgánicos Volátiles/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación , Adsorción , Carbono/análisis , Agua Subterránea/química , Hidrógeno/análisis , Cinética , Oxígeno/análisis , Pirólisis , República de Corea , Temperatura , Tricloroetileno/química , Tricloroetileno/aislamiento & purificación , Compuestos Orgánicos Volátiles/química , Contaminantes Químicos del Agua/química , Purificación del Agua
6.
Chemosphere ; 203: 34-43, 2018 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-29605747

RESUMEN

Biochar is increasingly deemed a potential sorbent for contaminants in soil and water remediation. We tested three biochars from different feedstocks (cattle manure, grain husk, and wood chips) produced at relatively low pyrolysis temperature (450 °C), for their sorption behavior towards trichloroethylene (TCE) and tetrachloroethylene (PCE) in single- and bi-solute systems. In single-solute experiments, all biochars show stronger sorption for TCE (about 50% based on solubility-normalized Freundlich coefficients). The lower sorption of PCE is attributed to steric effects, e.g. size exclusion in small micropores and specific interactions. Plant-derived, carbon-rich biochars with high specific surface area and microporosity predominantly sorb via pore-filling, as also observed in activated carbon. Biochar produced from manure, with higher ash content and polarity, and smaller total pore volume (PVtot), shows significant contribution of partitioning. These findings also apply to bi-solute systems. TCE and PCE show different competition behavior depending on biochar properties. Plant-based biochars are pore-filling-dominated and show strong competition. However, competition behavior in microporous biochars depends on the concentration range. Manure biochar with high polarity and low PVtot shows significant partitioning and therefore less competition. Compared to the plant-based chars competition in manure biochar is not concentration-dependent. These results indicate that biochars with a large fraction of non-carbonized phase facilitate non-competitive sorption and might be a valuable sorbent in mixed contaminant systems.


Asunto(s)
Carbón Orgánico/química , Grano Comestible/química , Hidrocarburos Clorados/química , Estiércol , Tricloroetileno/química , Madera/química , Adsorción , Animales , Bovinos , Tricloroetileno/aislamiento & purificación
7.
Environ Sci Pollut Res Int ; 25(8): 7157-7169, 2018 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-26233743

RESUMEN

For in situ groundwater remediation, polyelectrolyte-modified nanoscale zerovalent iron particles (NZVIs) have to be delivered into the subsurface, where they degrade pollutants such as trichloroethylene (TCE). The effect of groundwater organic and ionic solutes on TCE dechlorination using polyelectrolyte-modified NZVIs is unexplored, but is required for an effective remediation design. This study evaluates the TCE dechlorination rate and reaction by-products using poly(aspartate) (PAP)-modified and bare NZVIs in groundwater samples from actual TCE-contaminated sites in Florida, South Carolina, and Michigan. The effects of groundwater solutes on short- and intermediate-term dechlorination rates were evaluated. An adsorbed PAP layer on the NZVIs appeared to limit the adverse effect of groundwater solutes on the TCE dechlorination rate in the first TCE dechlorination cycle (short-term effect). Presumably, the pre-adsorption of PAP "trains" and the Donnan potential in the adsorbed PAP layer prevented groundwater solutes from further blocking NZVI reactive sites, which appeared to substantially decrease the TCE dechlorination rate of bare NZVIs. In the second and third TCE dechlorination cycles (intermediate-term effect), TCE dechlorination rates using PAP-modified NZVIs increased substantially (~100 and 200%, respectively, from the rate of the first spike). The desorption of PAP from the surface of NZVIs over time due to salt-induced desorption is hypothesized to restore NZVI reactivity with TCE. This study suggests that NZVI surface modification with small, charged macromolecules, such as PAP, helps to restore NZVI reactivity due to gradual PAP desorption in groundwater.


Asunto(s)
Ácido Aspártico/química , Agua Subterránea/química , Hierro/química , Nanopartículas del Metal/química , Tricloroetileno/química , Contaminantes Químicos del Agua/química , Purificación del Agua/métodos , Adsorción , Halogenación , Tricloroetileno/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación
8.
J Environ Manage ; 206: 817-825, 2018 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-29197807

RESUMEN

Zerovalent iron (ZVI) based technology has been applied to remediate contaminated groundwater and has been paid great attention as an economic alternative. But it is still remains highly challenging to remove chlorinated pollutants such as trichloroethylene (TCE) with ZVI. Low molecular weight carboxylic ligands (formic acid (FA), oxalic acid (OA), and citric acid (CA)) were chosen to study the influence on the performance of ZVI in groundwater, including the morphology of Fe surface and the Fe dissolution. The removal rate of TCE with ZVI in the presence of 30 mM carboxylic groups followed an order of FA > OA > pure water ≅ CA. FA provides protons to promote the surface corrosion and generated more magnetite on the ZVI surface, which was further responsible for a high adsorption of TCE. With the strong complexing ability of OA and CA, passive layers could form dissoluble complexes via a ligand-promoted dissolution process. However, high concentration of OA resulted in Fe oxalate reprecipitated back onto the ZVI surface then inhibited the reactivity of ZVI. The Fe-ligand complexes also have ability to transform TCE depending on their redox properties. It is expected that effectiveness of carboxylic ligands on the ZVI: those low molecular weight carboxylic ligands in groundwater and soil may enhance the reaction efficiency of ZVI by altering the surface characteristics of ZVI. Therefore, the carboxylic ligands could increase the reactivity and the longevity of ZVI.


Asunto(s)
Tricloroetileno/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación , Adsorción , Ácidos Carboxílicos , Hierro , Cinética , Tricloroetileno/química , Contaminantes Químicos del Agua/química
9.
ACS Nano ; 11(6): 5670-5679, 2017 06 27.
Artículo en Inglés | MEDLINE | ID: mdl-28582974

RESUMEN

There is tremendous interest in graphene-based membranes as protective molecular barriers or molecular sieves for separation technologies. Graphene oxide (GO) films in the dry state are known to be effective barriers for molecular transport and to expand in the presence of moisture to create enlarged intersheet gallery spaces that allow rapid water permeation. Here we explore an application for GO membranes as water-breathable barrier layers for personal protective equipment, which are designed to allow outward perspiration while protecting the wearer from chemical toxicants or biochemical agents in the local environment. A device was developed to measure permeation rates of small-molecular toxicants in the presence of counter-current water flow simulating active perspiration. The technique was applied to trichloroethylene (TCE) and benzene, which are important environmental toxicants, and ethanol as a limiting case to model very small, highly water-soluble organic molecules. Submicron GO membranes are shown to be effective TCE barriers, both in the presence and absence of simulated perspiration flux, and to outperform current barrier technologies. A molecular transport model is developed, which suggests the limited toxicant back-permeation observed occurs not by diffusion against the convective perspiration flow in hydrophobic channels, but rather through oxidized domains where hydrogen-bonding produces a near-stagnant water phase. Benzene and ethanol permeation fluxes are higher than those for TCE, likely reflecting the effects of higher water solubility and smaller minimum molecular dimension. Overall, GO films have high water breathability relative to competing technologies and are known to exclude most classes of target toxicants, including particles, bacteria, viruses, and macromolecules. The present results show good barrier performance for some very small-molecule species, but not others, with permeation being favored by high water solubility and small minimum molecular dimension.


Asunto(s)
Contaminantes Atmosféricos/aislamiento & purificación , Benceno/aislamiento & purificación , Grafito/química , Membranas Artificiales , Ropa de Protección , Tricloroetileno/aislamiento & purificación , Difusión , Gases/aislamiento & purificación , Humanos , Modelos Moleculares , Óxidos/química , Respiración , Textiles , Volatilización , Agua/química
10.
Environ Sci Technol ; 50(16): 8631-9, 2016 08 16.
Artículo en Inglés | MEDLINE | ID: mdl-27377979

RESUMEN

Palladium-doped nanoscale zerovalent iron (Pd-NZVI) has been shown to degrade environmental contaminants such as trichloroethene (TCE) to benign end-products through aqueous phase reactions. In this study we show that rhamnolipid (biosurfactant)-coated Pd-NZVI (RL-Pd-NZVI) when reacted with TCE in a 1-butanol organic phase with limited amounts of water results in 50% more TCE mass degradation per unit mass of Pd-NZVI, with a 4-fold faster degradation rate (kobs of 0.413 day(-1) in butanol organic phase versus 0.099 day(-1) in aqueous phase). RL-Pd-NZVI is preferentially suspended in water in biphasic organic liquid-water systems because of its hydrophilic nature. We demonstrate herein for the first time that their rapid phase transfer to a butanol/TCE organic phase can be achieved by adding NaCl and creating water-in-oil emulsions in the organic phase. The significant enhancement in reactivity is caused by a higher electron release (3e(-) per mole of Fe(0)) from Pd-NZVI in the butanol organic phase compared to the same reaction with TCE in the aqueous phase (2e(-) per mole of Fe(0)). XPS characterization studies of Pd-NZVI show Fe(0) oxidation to Fe(III) oxides for Pd-NZVI reacted with TCE in the butanol organic phase compared to Fe(II) oxides in the aqueous phase, which accounted for differences in the TCE reactivity extents and rates observed in the two phases.


Asunto(s)
Restauración y Remediación Ambiental , Hierro/química , Tricloroetileno/aislamiento & purificación , 1-Butanol , Glucolípidos/química , Nanopartículas del Metal/química , Paladio/química
11.
Environ Sci Pollut Res Int ; 22(18): 14043-9, 2015 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-25956516

RESUMEN

The simultaneous aerobic removal of a mixture of benzene, toluene, ethylbenzene, and o,m,p-xylene (BTEX); cis-dichloroethylene (cis-DCE); and trichloroethylene (TCE) from the artificially contaminated water using an indigenous bacterial isolate identified as Pseudomonas plecoglossicida immobilized on waste scrap tyres was investigated. Suspended and immobilized conditions were compared for the removal of these volatile organic compounds. For the immobilized system, toluene, benzene, and ethylbenzene were completely removed, while the highest removal efficiencies of 99.0 ± 0.1, 96.8 ± 0.3, 73.6 ± 2.5, and 61.6 ± 0.9% were obtained for o-xylene, m,p-xylene, TCE, and cis-DCE, respectively. The sorption kinetics of contaminants towards tyre surface was also evaluated, and the sorption capacity generally followed the order of toluene > benzene > m,p-xylene > o-xylene > ethylbenzene > TCE > cis-DCE. Scrap tyres showed a good capability for the simultaneous sorption and bioremoval of BTEX/cis-DCE/TCE mixture, implying a promising waste material for the removal of contaminant mixture from industrial wastewater or contaminated groundwater.


Asunto(s)
Benceno/aislamiento & purificación , Pseudomonas/metabolismo , Tolueno/aislamiento & purificación , Tricloroetileno/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación , Xilenos/aislamiento & purificación , Adsorción , Derivados del Benceno/aislamiento & purificación , Biodegradación Ambiental , Dicloruros de Etileno , Agua Subterránea/análisis , Tricloroetileno/metabolismo , Eliminación de Residuos Líquidos , Contaminantes Químicos del Agua/metabolismo , Contaminación del Agua , Purificación del Agua
12.
J Hazard Mater ; 295: 185-92, 2015 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-25909498

RESUMEN

Waste biocover soils (WBS) have been demonstrated to have great potential in mitigating trichloroethylene (TCE) emission from landfills, due to the relatively high TCE-degrading capacity. In this study, the characteristics of TCE adsorption on WBS in the presence of the major landfill gas components (i.e., CH4 and CO2) were investigated in soil microcosms. The adsorption isotherm of TCE onto WBS was fitted well with linear model within the TCE concentrations of 7000 ppmv. The adsorption capacity of TCE onto WBS was affected by temperature, soil moisture content and particle size, of which, temperature was the dominant factor. The adsorption capacity of TCE onto the experimental materials increased with the increasing organic matter content. A significantly positive correlation was observed between the adsorption capacity of TCE and the organic matter content of experimental materials that had relatively higher organic content (r = 0.988, P = 0.044). To better understand WBS application in practice, response surface methodology was developed to predict TCE adsorption capacity and emissions through WBS in different landfills in China. These results indicated that WBS had high adsorption capacity of TCE in LFG and temperature should be paid more attention to manipulate WBS to reduce TCE emissions from landfills.


Asunto(s)
Suelo/química , Tricloroetileno/aislamiento & purificación , Administración de Residuos , Adsorción , Modelos Químicos
13.
Environ Technol ; 36(1-4): 115-23, 2015.
Artículo en Inglés | MEDLINE | ID: mdl-25409590

RESUMEN

The acclimation of aerobic-activated sludge for degradation of benzene derivatives was investigated in batch experiments. Phenol, benzoic acid, toluene, aniline and chlorobenzene were concurrently added to five different bioreactors which contained the aerobic-activated sludge. After the acclimation process ended, the acclimated phenol-, benzoic acid-, toluene-, aniline- and chlorobenzene-grown aerobic-activated sludge were used to explore the co-metabolic degradation activities of trichloroethylene (TCE). Monod equation was employed to simulate the kinetics of co-metabolic degradation of TCE by benzene derivative-grown sludge. At the end of experiments, the mixed microbial communities grown under different conditions were identified. The results showed that the acclimation periods of microorganisms for different benzene derivatives varied. The maximum degradation rates of TCE for phenol-, benzoic acid-, toluene-, aniline- and chlorobenzene-grown aerobic sludge were 0.020, 0.017, 0.016, 0.0089 and 0.0047 mg g SS(-1) h(-1), respectively. The kinetic of TCE degradation in the absence of benzene derivative followed Monod equation well. Also, eight phyla were observed in the acclimated benzene derivative-grown aerobic sludge. Each of benzene derivative-grown aerobic sludge had different microbial community composition. This study can hopefully add new knowledge to the area of TCE co-metabolic by mixed microbial communities, and further the understanding on the function and applicability of aerobic-activated sludge.


Asunto(s)
Bacterias Aerobias/fisiología , Benceno/metabolismo , Modelos Biológicos , Eliminación de Residuos/métodos , Aguas del Alcantarillado/microbiología , Tricloroetileno/metabolismo , Aclimatación/fisiología , Biodegradación Ambiental , Reactores Biológicos/microbiología , Proliferación Celular/fisiología , Simulación por Computador , Tasa de Depuración Metabólica , Consorcios Microbianos/fisiología , Tricloroetileno/aislamiento & purificación
14.
Environ Sci Process Impacts ; 16(8): 1882-8, 2014 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-24889017

RESUMEN

Stable carbon isotope fractionation through the reductive dechlorination of trichloroethylene by vitamin B12 was determined to assess the possibility of using stable carbon isotope analysis to determine the efficacy of remediation of trichloroethylene using vitamin B12. We elucidated the effects of environmental conditions, including the pH, reaction temperature, and vitamin B12 concentration, on the carbon isotope enrichment factor (ε). The ε values were relatively insensitive to the reaction temperature and vitamin B12 concentration, ranging from -15.7‰ to -16.2‰, with a mean of -15.9 ± 0.2‰, at different temperatures and vitamin B12 concentrations. Such a reproducible ε value could be particularly useful for estimating the extent of degradation in reactions in which a mass balance is difficult to achieve. However, changing the initial solution pH from 6.5 to 9.0 caused a notable change in the ε values, from -14.0‰ to -18.0‰. Reactions were investigated by calculating the apparent kinetic isotope effects for carbon, which, at 1.029-1.037, were smaller than the kinetic isotope effect values previously found for C-Cl bond cleavage. This indicates that a reaction other than the elimination of chloride may be a competitive degradation pathway. The dominant degradation pathway may be different for different initial solution pH values, and this will clearly influence carbon isotope fractionation. Therefore, if the ε value varies with reaction conditions, such as the solution pH, the calculations should take into account the actual environmental conditions that affect the rate limiting pathways.


Asunto(s)
Fraccionamiento Químico , Restauración y Remediación Ambiental , Tricloroetileno/análisis , Vitamina B 12/química , Contaminantes Químicos del Agua/análisis , Isótopos de Carbono/análisis , Isótopos de Carbono/aislamiento & purificación , Fraccionamiento Químico/métodos , Restauración y Remediación Ambiental/métodos , Halogenación , Oxidación-Reducción , Tricloroetileno/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación
15.
Chemosphere ; 107: 94-100, 2014 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-24875875

RESUMEN

Dual isotope approach has been proposed as a viable tool for characterizing and assessing in situ contaminant transformation, however, little data is currently available on its applicability to chlorinated ethenes. This study determined carbon and chlorine isotope fractionation during Fenton-like degradation of trichloroethene (TCE). Carbon and chlorine isotope enrichment factors were εC=-2.9 ± 0.3‰ and εCl=-0.9 ± 0.1‰, respectively. An observed small secondary chlorine isotope effect (AKIECl=1.001) was consistent with an initial transformation by adding hydroxyl radicals (OH) to CC bonds without cleavage of CCl bonds. The relative change in carbon and chlorine isotope ratios (Δ=Δδ(13)C/Δδ(37)Cl) was calculated to be 3.1 ± 0.2, approximately equal to the ratio of chlorine and carbon isotope enrichment factors (εC/εCl=3.2). The similarity of the Δ (or εC/εCl) values between Fenton-like degradation and microbial reductive dechlorination of TCE was observed, indicating that application of solely dual isotope approach may be limited in distinguishing the two transformation pathways.


Asunto(s)
Fraccionamiento Químico/métodos , Cloro/química , Cloro/aislamiento & purificación , Contaminantes Ambientales/química , Contaminantes Ambientales/aislamiento & purificación , Peróxido de Hidrógeno/química , Hierro/química , Tricloroetileno/química , Isótopos de Carbono/química , Isótopos de Carbono/aislamiento & purificación , Cinética , Tricloroetileno/aislamiento & purificación
16.
Environ Technol ; 35(1-4): 27-35, 2014.
Artículo en Inglés | MEDLINE | ID: mdl-24600837

RESUMEN

The reactivity of different alpha-hematite (alpha-Fe203) systems for dechlorination of trichloroethylene (TCE) in the presence of Fe(II) and CaO was investigated. Initially different experiments were conducted to investigate the reactivity of pure and doped alpha-Fe203. It was found that the presence of elements such as Si, Cu, and Mn in alpha-Fe203 had a significant effect on TCE reduction potential of alpha-Fe203; however, the reduction potential was less than that of alpha-Fe203 (Bayferrox- 110 M, used in a previous study). Further studies were carried out and alpha-Fe203 was synthesized in a manner similar to that of Bayferrox-110 M. This synthetic alpha-Fe203 showed improved reactivity and was found to follow pseudo-first-order kinetics when used in TCE reduction experiments. The preliminary end products analysis showed that TCE degradation was probably via beta-elimination pathway. Detailed investigations ofa-Fe203 systems were carried out using X-ray diffraction, X-ray fluorescence, and scanning electron microscopy with energy-dispersive spectrometry. The results demonstrated that the TCE reduction capacity of alpha-Fe203 was strongly dependent on the other elements present in iron powder used to synthesize alpha-Fe203. It was suspected that these multi-elements in alpha-Fe203 helped to improve its conduction property. Current findings suggest that alpha-Fe203 not in the pure but combined with other elements could be thought as a potential system for TCE reduction.


Asunto(s)
Contaminantes Atmosféricos/química , Contaminantes Atmosféricos/aislamiento & purificación , Cloro/química , Cloro/aislamiento & purificación , Compuestos Férricos/química , Tricloroetileno/química , Tricloroetileno/aislamiento & purificación , Ensayo de Materiales , Oxidación-Reducción
17.
J Hazard Mater ; 268: 177-84, 2014 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-24491441

RESUMEN

Treating dense non-aqueous phase liquids (DNAPLs) embedded in low permeability zones (LPZs) is a particularly challenging issue for injection-based remedial treatments. Our objective was to improve the sweeping efficiency of permanganate (MnO4(-)) into LPZs to treat high concentrations of TCE. This was accomplished by conducting transport experiments that quantified the penetration of various permanganate flooding solutions into a LPZ that was spiked with non-aqueous phase (14)C-TCE. The treatments we evaluated included permanganate paired with: (i) a shear-thinning polymer (xanthan); (ii) stabilization aids that minimized MnO2 rind formation and (iii) a phase-transfer catalyst. In addition, we quantified the ability of these flooding solutions to improve TCE destruction under batch conditions by developing miniature LPZ cylinders that were spiked with (14)C-TCE. Transport experiments showed that MnO4(-) alone was inefficient in penetrating the LPZ and reacting with non-aqueous phase TCE, due to a distinct and large MnO2 rind that inhibited the TCE from further oxidant contact. By including xanthan with MnO4(-), the sweeping efficiency increased (90%) but rind formation was still evident. By including the stabilization aid, sodium hexametaphosphate (SHMP) with xanthan, permanganate penetrated 100% of the LPZ, no rind was observed, and the percentage of TCE oxidized increased. Batch experiments using LPZ cylinders allowed longer contact times between the flooding solutions and the DNAPL and results showed that SHMP+MnO4(-) improved TCE destruction by ∼16% over MnO4(-) alone (56.5% vs. 40.1%). These results support combining permanganate with SHMP or SHMP and xanthan as a means of treating high concentrations of TCE in low permeable zones.


Asunto(s)
Restauración y Remediación Ambiental/métodos , Compuestos de Manganeso/química , Óxidos/química , Suelo/química , Tricloroetileno/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación , Oxidación-Reducción , Permeabilidad , Transición de Fase , Tricloroetileno/química , Movimientos del Agua , Contaminantes Químicos del Agua/química
18.
J Hazard Mater ; 268: 92-101, 2014 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-24468531

RESUMEN

The objectives of this pilot-scale study were to (1) evaluate the effectiveness of bioremediation of trichloroethylene (TCE)-contaminated groundwater with the supplement of slow polycolloid-releasing substrate (SPRS) (contained vegetable oil, cane molasses, surfactants) under reductive dechlorinating conditions, (2) apply gene analyses to confirm the existence of TCE-dechlorinating genes, and (3) apply the real-time polymerase chain reaction (PCR) to evaluate the variations in TCE-dechlorinating bacteria (Dehalococcoides spp.). Approximately 350L of SPRS solution was supplied into an injection well (IW) and groundwater samples were collected and analyzed from IW and monitor wells periodically. Results show that the SPRS caused a rapid increase of the total organic carbon concentration (up to 5794mg/L), and reductive dechlorination of TCE was significantly enhanced. TCE dechlorination byproducts were observed and up to 99% of TCE removal (initial TCE concentration=1872µg/L) was observed after 50 days of operation. The population of Dehalococcoides spp. increased from 4.6×10(1) to 3.41×10(7)cells/L after 20 days of operation. DNA sequencing results show that there were 31 bacterial species verified, which might be related to TCE biodegradation. Results demonstrate that the microbial analysis and real-time PCR are useful tools to evaluate the effectiveness of TCE reductive dechlorination.


Asunto(s)
Chloroflexi/crecimiento & desarrollo , Coloides/química , Agua Subterránea/química , Tricloroetileno/aislamiento & purificación , Contaminantes Químicos del Agua/aislamiento & purificación , Purificación del Agua/métodos , Biodegradación Ambiental , Chloroflexi/genética , ADN Bacteriano/genética , Proyectos Piloto , ARN Ribosómico 16S/genética , Taiwán , Microbiología del Agua
19.
J Hazard Mater ; 264: 363-9, 2014 Jan 15.
Artículo en Inglés | MEDLINE | ID: mdl-24316808

RESUMEN

A two-stage waste air treatment system, consisting of hybrid bioreactors (modified bioscrubbers) and a biofilter, was used to treat waste air containing chlorinated ethenes - trichloroethylene (TCE) and tetrachloroethylene (PCE). The bioreactor was operated with loadings in the range 0.46-5.50gm(-3)h(-1) for TCE and 2.16-9.02gm(-3)h(-1) for PCE. The biofilter loadings were in the range 0.1-0.97gm(-3)h(-1) for TCE and 0.2-2.12gm(-3)h(-1) for PCE. Under low pollutant loadings, the efficiency of TCE elimination was 23-25% in the bioreactor and 54-70% in the biofilter. The efficiency of PCE elimination was 44-60% in the bioreactor and 50-75% in the biofilter. The best results for the bioreactor were observed one week after the pollutant loading was increased. However, the process did not stabilize. In the next seven days contaminant removal efficiency, enzymatic activity and biomass content were all diminished.


Asunto(s)
Filtros de Aire , Contaminantes Atmosféricos/aislamiento & purificación , Reactores Biológicos , Tetracloroetileno/aislamiento & purificación , Tricloroetileno/aislamiento & purificación
20.
Environ Sci Technol ; 48(1): 550-7, 2014.
Artículo en Inglés | MEDLINE | ID: mdl-24350777

RESUMEN

Biogenic catalysts have been studied over the last 10 years in freshwater and soil environments, but neither their formation nor their application has been explored in marine ecosystems. The objective of this study was to develop a biogenic nanopalladium-based remediation method for reducing chlorinated hydrocarbons from marine environments by employing indigenous marine bacteria. Thirty facultative aerobic marine strains were isolated from two contaminated sites, the Lagoon of Mar Chica, Morocco, and Priolo Gargallo Syracuse, Italy. Eight strains showed concurrent palladium precipitation and biohydrogen production. X-ray diffraction and thin section transmission electron microscopy analysis indicated the presence of metallic Pd nanoparticles of various sizes (5-20 nm) formed either in the cytoplasm, in the periplasmic space, or extracellularly. These biogenic catalysts were used to dechlorinate trichloroethylene in simulated marine environments. Complete dehalogenation of 20 mg L(-1) trichloroethylene was achieved within 1 h using 50 mg L(-1) biogenic nanopalladium. These biogenic nanoparticles are promising developments for future marine bioremediation applications.


Asunto(s)
Desulfovibrio desulfuricans/metabolismo , Hidrocarburos Clorados/aislamiento & purificación , Nanopartículas del Metal/química , Paladio/química , Shewanella/metabolismo , Contaminantes Químicos del Agua/aislamiento & purificación , Biodegradación Ambiental , Catálisis , Halogenación , Italia , Microscopía Electrónica de Transmisión , Paladio/aislamiento & purificación , Tamaño de la Partícula , Tricloroetileno/aislamiento & purificación , Microbiología del Agua , Difracción de Rayos X
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