Gas-phase trichloroethylene removal by Rhodococcus opacus using an airlift bioreactor and its modeling by artificial neural network.

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.

Effect of carboxylic acids on the properties of zerovalent iron toward adsorption and degradation of trichloroethylene.

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.

Phase Transfer of Palladized Nanoscale Zerovalent Iron for Environmental Remediation of Trichloroethene.

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.

Characterization of trichloroethylene adsorption onto waste biocover soil in the presence of landfill gas.

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.

Acclimation of aerobic-activated sludge degrading benzene derivatives and co-metabolic degradation activities of trichloroethylene by benzene derivative-grown aerobic sludge.

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.

Iron nanoparticles coated with amphiphilic polysiloxane graft copolymers: dispersibility and contaminant treatability.

Amphiphilic polysiloxane graft copolymers (APGCs) were used as a delivery vehicle for nanoscale zerovalent iron (NZVI). The APGCs were designed to enable adsorption onto NZVI surfaces via carboxylic acid anchoring groups and polyethylene glycol (PEG) grafts were used to provide dispersibility in water. Degradation studies were conducted with trichloroethylene (TCE) as the model contaminant. TCE degradation rate with APGC-coated NZVI (CNZVI) was determined to be higher as compared to bare NZVI. The surface normalized degradation rate constants, k(SA) (Lm(2-) h(-1)), for TCE removal by CNZVI and bare NZVI ranged from 0.008 to 0.0760 to 007-0.016, respectively. Shelf life studies conducted over 12 months to access colloidal stability and 6 months to access TCE degradation indicated that colloidal stability and chemical reactivity of CNZVI remained more or less unchanged. The sedimentation characteristics of CNZVI under different ionic strength conditions (0-10 mM) did not change significantly. The steric nature of particle stabilization is expected to improve aquifer injection efficiency of the coated NZVI for groundwater remediation.

Rapid reductive dechlorination of trichloroethene in contaminated ground water using biostimulation agent, BD-1, formulated from canola oil.

A case study of the bioremediation of groundwater contaminated with trichloroethene (TCE) was conducted using the biostimulation agent, BD-1. TCE levels were monitored by gas chromatography-mass spectroscopy. Total organic carbon (TOC) and volatile fatty acids (VFAs) were analyzed to investigate the environmental fate of BD-1. The effects of BD-1 on microbial activity were investigated using 16S rRNA gene-based quantitative polymerase chain reaction (qPCR) analysis. The biodegradation of BD-1 was accompanied by a reduction in TCE, and the initially high TOC levels decreased rapidly as BD-1 was transformed into VFAs. qPCR analysis showed that the genus Dehalobacter became progressively dominant through the experiment. These results suggested that BD-1 might dechlorinate TCE by activating dechlorinating bacteria.

Coupling of zero valent iron and biobarriers for remediation of trichloroethylene in groundwater.

This study attempted to construct a three series barrier system to treat high concentrations of trichloroethylene (TCE; 500 mg/L) in synthetic groundwater. The system consisted of three reactive barriers using iron fillings as an iron-based barrier in the first column, sugarcane bagasse mixed with anaerobic sludge as an anaerobic barrier in the second column, and a biofilm coated on oxygen carbon inducer releasing material as an aerobic barrier in the third column. In order to evaluate the extent of removal of TCE and its metabolites in the aquifer down gradient of the barrier system, a fourth column filled with sand was applied. Residence time of the system was investigated by a bromide tracer test. The results showed that residence time in the column system of the control set and experimental set were 23.62 and 29.99 days, respectively. The efficiency of the three series barrier system in removing TCE was approximately 84% in which the removal efficiency of TCE by the iron filling barrier, anaerobic barrier and aerobic barrier were 42%, 16% and 25%, respectively, cis-Dichloroethylene (cis-DCE), vinyl chloride (VC), ethylene and chloride ions were observed as metabolites following TCE degradation. The presence of chloride ions in the effluent from the column system indicated the degradation of TCE. However, cis-DCE and VC were not fully degraded by the proposed barrier system which suggested that another remediation technology after the barrier treatment such as air sparging and adsorption by activated carbon should be conducted.

Influence of humidity and of the electric and magnetic microwave radiation fields on the remediation of TCE-contaminated natural sandy soils.

The influence of moisture content (15% w/w) on the remediation (vaporization) of trichloroethylene (TCE) present in natural sands, chosen as a TCE-polluted model system for soils, was investigated with regard to applied microwave power levels, the depth of the sand sample, and the dielectric factors. The heating process occurring in the sand samples arises through the microwave conduction loss heating and dielectric loss heating mechanisms. The characteristic relevance of the electric and magnetic microwave radiation fields to the heating mechanisms was also examined. Heating by the magnetic microwave radiation field was considerable when magnetite was added to the dry and wet sand samples as the microwave absorber. Optimal microwave conditions are reported for a single-mode microwave applicator. Near-quantitative elimination of the TCE contaminant was achieved for sandy soils within a very short time.

Demonstration of combined zero-valent iron and electrical resistance heating for in situ trichloroethene remediation.

The effectiveness of in situ treatment using zero-valent iron (ZVI) for nonaqueous phase or significant sediment-associated contaminant mass can be limited by relatively low rates of mass transfer to bring contaminants in contact with the reactive media. For a field test in a trichloroethene (TCE) source area, combining moderate-temperature subsurface electrical resistance heating with in situ ZVI treatment was shown to accelerate TCE treatment by a factor of about 4 based on organic daughter products and a factor about 8 based on chloride concentrations. A mass-discharge-based analysis was used to evaluate reaction, dissolution, and volatilization processes at ambient groundwater temperature (~10 °C) and as temperature was increased up to about 50 °C. Increased reaction and contaminant dissolution were observed with increased temperature, but vapor- or aqueous-phase migration of TCE out of the treatment zone was minimal during the test because reactions maintained low aqueous-phase TCE concentrations.

Aerobic treatment of N-nitrosodimethylamine in a propane-fed membrane bioreactor.

N-Nitrosodimethylamine (NDMA) is a suspected human carcinogen that has recently been detected in wastewater, groundwater and drinking water. Treatment of this compound to low part-per-trillion (ng/L) concentrations is required to mitigate cancer risk. Current treatment generally entails UV irradiation, which while effective, is also expensive. The objective of this research was to explore potential bioremediation strategies as alternatives for treating NDMA to ng/L concentrations. Batch studies revealed that the propanotroph Rhodococcus ruber ENV425 was capable of metabolizing NDMA from 8 µg/L to <2 ng/L after growth on propane, and that the strain produced metabolites that do not pose a significant risk at the concentrations generated (Fournier et al., 2009). A laboratory-scale membrane bioreactor (MBR) was subsequently constructed to evaluate the potential for long-term ex situ treatment of NDMA. The MBR was seeded with ENV425 and received propane as the primary growth substrate and oxygen as an electron acceptor. At an average influent NDMA concentration of 7.4 µg/L and a 28.5 h hydraulic residence time, the reactor effluent concentration was 3.0 ± 2.3 ng/L (>99.95% removal) over more than 70 days of operation. The addition of trichloroethene (TCE) to the reactor resulted in a significant increase in effluent NDMA concentrations, most likely due to cell toxicity from TCE-epoxide produced during its cometabolic oxidation by ENV425. The data suggest that an MBR system can be a viable treatment option for NDMA in groundwater provided that high concentrations of TCE are not present.

The effect of carbon type on arsenic and trichloroethylene removal capabilities of iron (hydr)oxide nanoparticle-impregnated granulated activated carbons.

This study investigates the impact of the type of virgin granular activated carbon (GAC) media used to synthesize iron (hydr)oxide nanoparticle-impregnated granular activated carbon (Fe-GAC) on its properties and its ability to remove arsenate and organic trichloroethylene (TCE) from water. Two Fe-GAC media were synthesized via a permanganate/ferrous ion synthesis method using bituminous and lignite-based virgin GAC. Data obtained from an array of characterization techniques (pore size distribution, surface charge, etc.) in correlation with batch equilibrium tests, and continuous flow modeling suggested that GAC type and pore size distribution control the iron (nanoparticle) contents, Fe-GAC synthesis mechanisms, and contaminant removal performances. Pore surface diffusion model calculations predicted that lignite Fe-GAC could remove ∼6.3 L g(-1) dry media and ∼4 L g(-1) dry media of water contaminated with 30 µg L(-1) TCE and arsenic, respectively. In contrast, the bituminous Fe-GAC could remove only ∼0.2 L/g dry media for TCE and ∼2.8 L/g dry media for As of the same contaminated water. The results show that arsenic removal capability is increased while TCE removal is decreased as a result of Fe nanoparticle impregnation. This tradeoff is related to several factors, of which changes in surface properties and pore size distributions appeared to be the most dominant.

Ten year performance evaluation of a field-scale zero-valent iron permeable reactive barrier installed to remediate trichloroethene contaminated groundwater.

The Monkstown zero-valent iron permeable reactive barrier (ZVI PRB), Europe's oldest commercially-installed ZVI PRB, had been treating trichloroethene (TCE) contaminated groundwater for about 10 years on the Nortel Network site in Northern Ireland when cores from the reactive zone were collected in December, 2006. Groundwater data from 2001-2006 indicated that TCE is still being remediated to below detection limits as the contaminated groundwater flows through the PRB. Ca and Fe carbonates, crystalline and amorphous Fe sulfides, and Fe (hydr)oxides have precipitated in the granular ZVI material in the PRB. The greatest variety of minerals is associated with a approximately 1-2 cm thick, slightly cemented crust on top (up-gradient influent entrance) of the ZVI section of the PRB and also with the discontinuous cemented ZVI material ( approximately 23 cm thick) directly below it. The greatest presence of microbial communities also occurred in the up-gradient influent portion of the PRB compared to its down-gradient effluent section, with the latter possibly due to less favorable conditions (i.e., high pH, low oxygen) for microbial growth. The ZVI filings in the down-gradient effluent section of the PRB have a projected life span of >10 years compared with ZVI filings from the continuous to discontinuous cemented up-gradient ZVI section (upper approximately 25 cm) of the PRB, which may have a life span of only approximately 2-5 more years. Supporting Information from applied, multi-tracer testing indicated that restricted groundwater flow is occurring in the upper approximately 25 cm of the ZVI section and preferential pathways have also formed in this PRB over its 10 years of operation.

Effects of nano-scale zero-valent iron particles on a mixed culture dechlorinating trichloroethylene.

Nano-scale zero-valent iron particles (NZVI) are increasingly being used to treat sites contaminated with chlorinated solvents. This study investigated the effect of NZVI on dechlorinating microorganisms that participate in the anaerobic bioremediation of such sites. NZVI can have a biostimulatory effect associated with water-derived cathodic H(2) production during its anaerobic corrosion (730+/-30 micromol H(2) was produced in 166 h in abiotic controls with 1 g/L NZVI) or an inhibitory effect upon contact with cell surfaces (assessed by transmission electron microscopy). Methanogens, which are known to compete for H(2) with dechlorinators, were significantly biostimulated by NZVI and methane production increased relative to NZVI-free controls from 58+/-5 to 275+/-2 micromol. In contrast, bacteria dechlorinating TCE were inhibited by NZVI, and the first-order degradation rate coefficient decreased from 0.115+/-0.005 h(-1) (R(2)=0.99) for controls to 0.053+/-0.003 h(-1) (R(2)=0.98) for treatments with 1 g/L NZVI. Ethene production from TCE was initially inhibited by NZVI, but after 331 h increased to levels observed for an NZVI-free system (7.6+/-0.3 micromol ethene produced in 502 h compared to 11.6+/-0.5 mmol in the NZVI-free system and 3.8+/-0.3 micromol ethene for NZVI alone). Apparently, cathodic H(2) was utilized as electron donor by dechlorinating bacteria, which recovered following the partial oxidation and presumably passivation of the NZVI. Overall, these results suggest that reductive treatment of chlorinated solvent sites with NZVI might be enhanced by the concurrent or subsequent participation of bacteria that exploit cathodic depolarization and reductive dechlorination as metabolic niches.

[Preparation of coated iron nanoparticles for reduction of trichloroethylene].

Nanoscale alpha-Fe particles with size of about 80 nm were prepared with a microemulsion-coated method. The results demonstrated that this kind of iron particles could exist stably in the air for 7 d compared with nanoscale iron particles prepared by liquid-phase and microemulsion methods. The removal rate of trichloroethylene with an initial concentration of 10 mg x L(-1) can reach 90% in 700 h. The reduction kinetics was studied under room temperature, neutral, and anaerobic conditions. Experiments show that the reduction process of TCE by nanoscale iron particles conforms to pseudo first order reaction law. The apparent rate constant (k(obs)) is proportional to concentration of nanoscale iron particles. The k(obs), values 6.49 x 10(-40, 6.64 x 10(-4), 7.10 x 10(-4), 7.43 x 10(-4) min(-1), are corresponding to concentrations of 87.5, 175, 262.5, 350 mg x L(-1) respectively. In the reaction, nanoscale iron particles provides electrons and forms an inner film of Fe3O4, on the surface of which an outer film of Fe2O3 is formed together with water. TCE is degraded by electrons. The principal degradation products were ethene and ethane, and smaller amounts of other chlorinated degradation products were also founded.

Density functional theory studies of chloroethene adsorption on zerovalent iron.

Adsorption of perchloroethene (PCE), trichloroethene (TCE), and cis-dichloroethene (cis-DCE) on zerovalent iron is investigated using density functional theory (DFT) to evaluate hypotheses concerning the relative reactivity of these compounds on zerovalent iron. Four different chloroethene adsorption modes on the Fe(110) surface were studied using periodic DFT and the generalized gradient approximation (GGA). Of the adsorption sites examined, the atop site, where the chloroethene C==C bond straddles a surface iron atom, was the most energetically favorable site for the adsorption of all three chloroethenes. Electronic structure and property analyses provide an indication of the extent of sp2-sp3 hybridization. The strong hybridization of the pi-bonding orbital between the chloroethene C==C bond and the iron surface suggests that adsorbed chloroethenes are strongly activated on Fe(110) and are likely precursors for subsequent chloroethene dissociation on the Fe surface. When the effect of solvation is indirectly taken into account in the DFT simulations by considering the hydration energies of chloroethenes in bulkwater,the ordering ofthe adsorption energies of chloroethenes from the aqueous phase onto Fe(110) is in agreement with experimental observation (PCE > TCE > cis-DCE). Electronic properties of the adsorbed configurations of chloroethenes are also presented.

Grey-iron foundry slags as reactive media for removing trichloroethylene from groundwater.

A feasibility study was conducted using slags from six grey-iron foundries to evaluate their potential as reactive media for permeable reactive barriers (PRBs) to remove aqueous trichloroethylene (TCE) from groundwater. Batch tests indicated that the slags exhibit varying degrees of reactivity ranging from nonreactive to reactivity comparable to that obtained with commercially available granular zerovalent iron on a surface-area-normalized basis. TCE removal follows pseudo-first-order kinetics, and produces lesser-chlorinated ethene byproducts (e.g., 1,1-DCE, cis-DCE). Greater reactivity was obtained with the slags having the highest iron content and the lowest reactivity was obtained with the slag having the lowest iron content, suggesting that iron is a primary reductant in the slags. Batch tests on the two most reactive slags indicated that the rate coefficients are linearly related to surface area over the range tested, and are sensitive to initial TCE concentration. Column studies showed that reactivity is lower under flow-through conditions than anticipated based on batch tests. Calculations indicate a 2-m-thick slag PRB can degrade TCE to less than 0.005 mg/L for influent concentrations less than 2 mg/L at seepage velocities below 0.1 m/d.

Adsorption of trichloroethylene and benzene vapors onto hypercrosslinked polymeric resin.

In this research, the adsorption equilibria of trichloroethylene (TCE) and benzene vapors onto hypercrosslinked polymeric resin (NDA201) were investigated by the column adsorption method in the temperature range from 303 to 333 K and pressures up to 8 kPa for TCE, 12 kPa for benzene. The Toth and Dubinin-Astakov (D-A) equations were tested to correlate experimental isotherms, and the experimental data were found to fit well by them. The good fits and characteristic curves of D-A equation provided evidence that a pore-filling phenomenon was involved during the adsorption of TCE and benzene onto NDA-201. Moreover, thermodynamic properties such as the Henry's constant and the isosteric enthalpy of adsorption were calculated. The isosteric enthalpy curves varied with the surface loading for each adsorbate, indicating that the hypercrosslinked polymeric resin has an energetically heterogeneous surface. In addition, a simple mathematic model developed by Yoon and Nelson was applied to investigate the breakthrough behavior on a hypercrosslinked polymeric resin column at 303 K and the calculated breakthrough curves were in high agreement with corresponding experimental data.

Reductive dechlorination of trichloroethylene by combining autotrophic hydrogen-bacteria and zero-valent iron particles.

The objective of this study was to evaluate the dechlorination rate (from an initial concentration of 180 micromol l(-1)) and synergistic effect of combining commercial Fe(0) and autotrophic hydrogen-bacteria in the presence of hydrogen, during TCE degradation process. In the batch test, the treatment using Fe(0) in the presence of hydrogen (Fe(0)/H(2)), showed more effective dechlorination and less iron consumption than Fe(0) utilized only (Fe(0)/N(2)), meaning that catalytic degradation had promoted transformation of TCE, and the iron was protected by cathodic hydrogen. The combined use of Fe(0) and autotrophic hydrogen-bacteria was found to be more effective than did the individual exercise even though the hydrogen was insufficient during the batch test. By the analysis of XRPD, the crystal of FeS transformed by sulfate reducing bacteria (SRB) was detected on the surface of iron after the combined treatment. The synergistic impact was caused by FeS precipitates, which enhanced TCE degradation through catalytic dechlorination. Additionally, the dechlorination rate coefficient of the combined method in MFSB was 3.2-fold higher than that of iron particles individual use. Results from batch and MFSB experiments revealed that, the proposed combined method has the potential to become a cost-effective remediation technology for chlorinated-solvent contaminated site.

Reactivity characteristics of nanoscale zerovalent iron--silica composites for trichloroethylene remediation.

Spherical silica particles containing nanoscale zerovalent iron were synthesized through an aerosol-assisted process. These particles are effective for groundwater remediation, with the environmentally benign silica particles serving as effective carriers for nanoiron transport. Incorporation of iron into porous sub-micrometer silica particles protects ferromagnetic iron nanoparticles from aggregation and may increase their subsurface mobility. Additionally, the presence of surface silanol groups on silica particles allows control of surface properties via silanol modification using organic functional groups. Aerosolized silica particles with functional alkyl moieties, such as ethyl groups on the surface, clearly adsorb solubilized trichloroethylene (TCE) in water. These materials may therefore act as adsorbents which have coupled reactivity characteristics. The nanoscale iron/silica composite particles with controlled surface properties have the potential to be efficiently applied for in situ source depletion and in the design of permeable reactive barriers.