Silicone emulsion-enhanced recovery of chlorinated solvents: batch and column studies

Batch and column experiments were conducted to investigate the feasibility of flushing with silicone oil emulsion for the removal of chlorinated solvents, including trichloroethylene (TCE), perchloroethylene (PCE) and 1,2-dichlorobenzene (DCB). In the batch experiments, solubilization potentials of emulsion and effects of surfactants as additives were examined. The emulsion prepared with 2% (v/v) silicone oil could solubilize 90.7% of 10,000 ppm TCE, 97.3% of 4000 ppm PCE and 99.7% of 7,800 ppm DCB. Results of one-dimensional column studies indicated that aqueous solubility and sorption of contaminants determined the flushing efficiency. The addition of surfactants below their critical micelle concentration (CMC) did not affect the removal of chlorinated solvents in batch and column experiments. The results of this study show that flushing with oil-based emulsion can be applied to treat the chlorinated solvents.     

Reactivity of Fe(II)/cement systems in dechlorinating chlorinated ethylenes

Ferrous iron (Fe(II)) in combination with Portland cement is effective in reductively dechlorinating chlorinated organics and can be used to achieve immobilization and degradation of contaminants simultaneously. Reactivities of chlorinated ethylenes (perchloroethylene (PCE), trichloroethylene (TCE), 1,1-dichloroethylene (1,1-DCE), vinyl chloride (VC)) in Fe(II)/cement systems were characterized using batch slurry reactors. Reduction kinetics of the chlorinated ethylenes were sufficiently fast to be utilized for the proposed treatment scheme, and were described by a pseudo-first-order rate law. The order of reactivity of the chlorinated ethylenes was TCE>1,1-DCE>PCE>VC. Reduction of TCE and PCE mainly yielded acetylene, implying that the transformation of the two compounds occurred principally via reductive beta-elimination pathways. Transformation of 1,1-DCE and VC gave rise to primarily ethylene, implying that major degradation pathways were a reductive alpha-elimination for the former and a hydrogenolysis for the latter. The reactivity of the Fe(II)/cement systems in dechlorinating TCE was proportional to Fe(II) dose when the Fe(II)/cement mass ratio varied between 5.6 and 22.3%. The Fe(II)/cement systems with a higher Fe(II) loading were less extensively affected by pH in reductive reactions for TCE than in the previous experiments with PCE or chlorinated methanes. Amendment of Fe(II)/cement systems with Fe(III) addition was found effective in increasing the reactivity in the previous study, but the current findings indicated that the extent to which the reaction rate increased by the amendment might be dependent on the source of the cement and/or the compounds tested.     

Oxidation of chlorinated ethenes by potassium permanganate: a kinetics study

The kinetics of oxidation of perchloroethylene (PCE), trichloroethylene (TCE), three isomers of dichloroethylene (DCE) and vinyl chloride (VC) by potassium permanganate (KMnO(4)) were studied in phosphate-buffered solutions of pH 7 and ionic strength approximately 0.05 M and under isothermal, completely mixed and zero headspace conditions. Experimental results have shown that the reaction appears to be second order overall and first order individually with respect to both KMnO(4) and all chlorinated ethenes (CEs), except VC. The degradation of VC by KMnO(4) is a two-consecutive-step process. The second step, being the rate-limiting step, is of first order in VC and has an activation energy (E(a)) of 7.9+/-1 kcal mol(-1). The second order rate constants at 20 degrees C are 0.035+/-0.004 M(-1) s(-1) (PCE), 0.80+/-0.12 M(-1) s(-1) (TCE), 1.52+/-0.05 M(-1) s(-1) (cis-DCE), 2.1+/-0.2 M(-1) s(-1) (1,1-DCE) and 48.6+/-0.9 M(-1) s(-1) (trans-DCE). The E(a) and entropy (DeltaS(*)) of the reaction between KMnO(4) and CEs (except VC) are in the range of 5.8-9.3 kcal mol(-1) and -33 to -36 kcal mol(-1) K(-1), respectively. Moreover, KMnO(4) is able to completely dechlorinate CEs, and the increase in acidity of the solution due to CE oxidation by KMnO(4) is directly proportional to the number of chlorine atoms in CEs.     

Boosting sensitivity of organic vapor detection with silicone block polyimide polymers

We demonstrate that silicone block polyimide polymers have an unusually high sensitivity to nonpolar organic vapors, including chlorinated organic solvent vapors. When 0.18-5.34-microm-thick films of silicone block polyimide polymers were deposited onto 10-MHz thickness shear mode (TSM) oscillators, these films were implemented to detect parts-per-billion concentrations of trichloroethylene (TCE) with a detection sensitivity of 0.5-23.5 Hz per 500 ppb of vapor. With a film thickness of 3.4 microm (91.5-kHz frequency shift upon film deposition), optimized for the minimal sensor noise of 0.04 Hz, the calculated detection limit of sensor response (S/N = 3) was 3 ppb of TCE. Detection limits for other chlorinated organic solvent vapors, such as perchloroethylene (PCE), cis-1,2-dichloroethylene (DCE), trans-1,2-DCE, 1,1-DCE, and vinyl chloride (VC) were 0.6, 6, 6, 11, and 13 ppb, respectively. Assuming only the mass-loading response when deposited onto the TSM devices, silicone block polyimide polymers have partition coefficients of over 200 000 to parts-per-billion concentrations of TCE that make them at least 100 times more sensitive than other known polymers for TCE detection. We observed that unlike conventional polyimides, water sensitivity of the new hybrid polyimides is suppressed because of the silicone soft block. Water sensitivity is comparable with the sensor response to nonpolar organic vapors. The high sensitivity and long-term stability of these sensor materials make them attractive for ultrasensitive practical sensors.     

Design and construction techniques for permeable reactive barriers.

Adequate site characterization, bench-scale column testing, and hydrogeologic modeling formed the basis for the design and construction of permeable reactive barriers for groundwater remediation at various sites, such as Dover Air Force Base, DE and Naval Air Station, Moffett Field, CA. Dissolved chlorinated solvents, such as perchloroethylene (PCE) and trichloroethylene (TCE), have been the focus at many sites because the passive nature of the reactive barrier operation makes such barriers particularly useful for treating groundwater contaminants that can persist in the aquifer for several years. A combination of conventional and innovative site characterization, design, and construction techniques were used at these sites to increase the potential cost effectiveness of field application.     

Resonance-enhanced multiphoton ionization for real-time monitoring of trichloroethylene formed by degradation of tetrachloroethylene using zero-valent zinc

Resonance-enhanced multiphoton ionization (REMPI) is investigated as a potential technique for real-time monitoring of selected volatile organochloride compounds (VOCs). In a proof-of-concept experiment, the progress of the reductive-degradation of tetrachloroethylene (PCE) to trichloroethylene (TCE) by zero-valent zinc was monitored by REMPI measurements performed in the headspace above the PCE solution. Two-photon resonant REMPI spectra of TCE and PCE were recorded over the wavelength range 305-320 nm. The concentrations of PCE and TCE in the headspace were monitored by measurement of the ionization signal with 315.64- and 310.48-nm excitation for PCE and TCE, respectively. Calibration curves yielded a linear range of more than 2 orders of magnitude for both compounds. The REMPI headspace results agreed well with the solution-phase results from gas chromatography analysis, which was used for independent verification of the progress of the reaction.     

GC/multiple collector-ICPMS method for chlorine stable isotope analysis of chlorinated aliphatic hydrocarbons

Stable isotopic characterization of chlorine in chlorinated aliphatic pollution is potentially very valuable for risk assessment and monitoring remediation or natural attenuation. The approach has been underused because of the complexity of analysis and the time it takes. We have developed a new method that eliminates sample preparation. Gas chromatography produces individually eluted sample peaks for analysis. The He carrier gas is mixed with Ar and introduced directly into the torch of a multicollector ICPMS. The MC-ICPMS is run at a high mass resolution of >/=10 000 to eliminate interference of mass 37 ArH with Cl. The standardization approach is similar to that for continuous flow stable isotope analysis in which sample and reference materials are measured successively. We have measured PCE relative to a laboratory TCE standard mixed with the sample. Solvent samples of 200 nmol to 1.3 micromol (24-165 microg of Cl) were measured. The PCE gave the same value relative to the TCE as measured by the conventional method with a precision of 0.12 per thousand (2x standard error) but poorer precision for the smaller samples.     

Remediation of groundwater contaminated with DNAPLs by biodegradable oil emulsion

Emulsion-based remediation with biodegradable vegetable oils was investigated as an alternative technology for the treatment of subsurface DNAPLs (dense non-aqueous phase liquids) such as TCE (trichloroethylene) and PCE (perchloroethylene). Corn and olive oil emulsions obtained by homogenization at 8000rpm for 15min were used. The emulsion droplets prepared with corn and olive oil gave a similar size distribution (1-10microm) and almost all of initially injected oil, >90%, remained in a dispersed state. In batch experiments, 2% (v/v) oil emulsion could adsorb up to 11,000ppm of TCE or 18,000ppm of PCE without creating a free phase. Results of one-dimensional column flushing studies indicated that contaminants with high aqueous solubility could be efficiently removed by flushing with vegetable oil emulsions. Removal efficiencies exceeded 98% for TCE and PCE with both corn and olive oil emulsions. The results of this study show that flushing with biodegradable oil emulsion can be used for the remediation of groundwater contaminated by DNAPLs.     

Degradation of trichloroethylene by Fenton reaction in pyrite suspension

Degradation of trichloroethylene (TCE) by Fenton reaction in pyrite suspension was investigated in a closed batch system under various experimental conditions. TCE was oxidatively degraded by OH in the pyrite Fenton system and its degradation kinetics was significantly enhanced by the catalysis of pyrite to form OH by decomposing H(2)O(2). In contrast to an ordinary classic Fenton reaction showing a second-order kinetics, the oxidative degradation of TCE by the pyrite Fenton reaction was properly fitted by a pseudo-first-order rate law. Degradation kinetics of TCE in the pyrite Fenton reaction was significantly influenced by concentrations of pyrite and H(2)O(2) and initial suspension pH. Kinetic rate constant of TCE increased proportionally (0.0030 ± 0.0001-0.1910 ± 0.0078 min(-1)) as the pyrite concentration increased 0.21-12.82 g/L. TCE removal was more than 97%, once H(2)O(2) addition exceeded 125 mM at initial pH 3. The kinetic rate constant also increased (0.0160 ± 0.005-0.0516 ± 0.0029 min(-1)) as H(2)O(2) concentration increased 21-251 mM, however its increase showed a saturation pattern. The kinetic rate constant decreased (0.0516 ± 0.0029-0.0079 ± 0.0021 min(-1)) as initial suspension pH increased 3-11. We did not observe any significant effect of TCE concentration on the degradation kinetics of TCE in the pyrite Fenton reaction as TCE concentration increased.     

Potential use of cyclodextrins to enhance the solubility of YM466 in aqueous solution

Various solubilizing agents for YM466, a new Factor Xa inhibitor, were investigated to begin designing the aqueous formulation for subcutaneous administration. The tentative target concentration was 5 mg/mL. First, three kinds of buffer solutions (glycine-HCl, citrate, and lactate) were examined for their solubilizing effects. The dissolution rate of YM466 in lactate buffer was the fastest, as determined by visual examination at room temperature. The dissolution rate of YM466 in lactate buffer was enhanced, without degradation, by heating at 40 degrees C, and YM466 solution at a concentration of 1 mg/mL became transparent 10 min after the start of heating. The solubility of YM466 increased along with lactate concentrations ranging from 50 mM to 200 mM and reached a high of 1.3 mg/mL after increasing lactate concentration to 200 mM at 5 degrees C. The addition of cyclodextrins beta-cyclodextrin (beta-CD), 2-hydroxypropyl-beta-cyclodextrin (HP-beta-CD), and gamma-cyclodextrin (gamma-CD), but not alpha-cyclodextrin (alpha-CD), had remarkable impact on its solubility, and 7-8 mg/mL of YM466 was dissolved by the addition of HP-beta-CD or gamma-CD. These results demonstrated that YM466 was included in cyclodextrins and that the inclusion formations required a cavity size larger than alpha-CD. Based on the calculation from the linear portion of the phase solubility diagrams, apparent stability constants of alpha-CD, beta-CD, HP-beta-CD, and gamma-CD at 5 degrees C were estimated to be 2M(-1), 206M(-1), 143M(-1), and 276M(-1), respectively. Therefore, we found that gamma-CD has the largest inclusion capacity.     

Degradation of perchloroethylene in cosolvent solutions by zero-valent iron

Remediation of sites contaminated by chlorinated organic compounds is a significant priority in the environmental field. Subsequently, the addition of cosolvent solutions for in situ flushing of contaminated source zones has been successfully field tested. However, the treatment of effluent fluids in such cleanup efforts is an often overlooked component of this technology implementation. The purpose of this research was to evaluate the effectiveness of zero-valent iron (Fe(0)) in treating perchloroethylene (PCE) in an aqueous solution, and how the presence of a cosolvent (ethanol) and modification of the iron surface altered dechlorination. The modified iron surfaces included in this study were nickel-plated iron, acid-treated iron, and untreated iron surfaces. PCE dechlorination in the presence of each of the iron surfaces displayed pseudo first-order kinetics. The highest degradation rate of PCE occurred on the nickel-plated iron surface, 5.83 x 10(-3)h(-1), followed by the acid-treated iron, 4.92 x 10(-3)h(-1), and the untreated iron, 3.34 x 10(-3)h(-1). Dechlorination on each of the surfaces decreased with increasing cosolvent fractions. It was shown that as cosolvent fractions increased, PCE adsorption decreased and resulted in a concomitant decrease in PCE degradation rates.     

Surface chemical reactivity in selected zero-valent iron samples used in groundwater remediation

Permeable iron barriers have become a popular choice as a passive, cost-effective in situ remediation technology for chlorinated solvents. However, loss of reactivity over time, due to a build up of corrosion products or other precipitates on the iron surface, is a great concern. Because first-order rate constants for trichloroethylene (TCE) degradation have differed by iron pre-treatment and sonication history, X-ray photoelectron spectroscopy (XPS) was used to explore the changes in near surface chemistry of several iron samples. Both sonicated and unsonicated filings were analyzed in unwashed and groundwater-soaked conditions. Unsonicated acid-washed iron, with the highest first-order rate constant for TCE degradation, was characterized by greater surface oxygen content and was more ionic relative to the unwashed samples. The unsonicated, unwashed sample, with the lowest rate constant, exhibited a mixture of nonstoichiometric iron oxide and oxyhydroxide species. Sonication of groundwater-soaked iron removed weakly bonded iron hydroxide species and decreased the ionic character of the surface as was observed in the unwashed samples. Thus, this type of study might provide a better understanding of the chemical reactivity of selected iron samples and design better material in remediation technology.     

Sparse polynomial chaos expansions of frequency response functions using stochastic frequency transformation

Frequency response functions (FRFs) are important for assessing the behavior of stochastic linear dynamic systems. For large systems, their evaluations are time-consuming even for a single simulation. In such cases, uncertainty quantification by crude Monte-Carlo simulation is not feasible. In this paper, we propose the use of sparse adaptive polynomial chaos expansions (PCE) as a surrogate of the full model. To overcome known limitations of PCE when applied to FRF simulation, we propose a frequency transformation strategy that maximizes the similarity between FRFs prior to the calculation of the PCE surrogate. This strategy results in lower-order PCEs for each frequency. Principal component analysis is then employed to reduce the number of random outputs. The proposed approach is applied to two case studies: a simple 2-DOF system and a 6-DOF system with 16 random inputs. The accuracy assessment of the results indicates that the proposed approach can predict single FRFs accurately. Besides, it is shown that the first two moments of the FRFs obtained by the PCE converge to the reference results faster than with the Monte-Carlo (MC) methods.     

Application of surfactant enhanced permanganate oxidation and bidegradation of trichloroethylene in groundwater

The industrial solvent trichloroethylene (TCE) is among the most ubiquitous chlorinated solvents found in groundwater contamination. The main objectives of this study were to evaluate the feasibility of using non-ionic surfactant Simple Green™ (SG) to enhance the oxidative dechlorination of TCE by potassium permanganate (KMnO₄) employing a continuous stir batch reactor system (CSBR) and column experiments. The effect of using surfactant SG to enhance the biodegradation of TCE via aerobic cometabolism was also examined. Results from CSBR experiments revealed that combination of KMnO₄ with surfactant SG significantly enhanced contaminant removal, particularly when the surfactant SG concentrated at its CMC. TCE degradation rates ranged from 74.1% to 85.7% without addition of surfactant SG while TCE degradation rates increased to ranging from 83.8% to 96.3% with presence of 0.1 wt% SG. Furthermore, results from column experiments showed that TCE was degraded from 38.1 μM to 6.2 μM in equivalent to 83.7% of TCE oxidation during first 560 min reaction. This study has also demonstrated that the addition of surfactant SG is a feasible method to enhance bioremediation efficiency for TCE contaminated groundwater. The complete TCE degradation was detected after 75 days of incubation with both 0.01 and 0.1 wt% of surfactant SG addition. Results revealed that surfactant enhanced chemical oxidation and bioremediation technology is one of feasible approaches to clean up TCE contaminated groundwater.     

Degradation of DCE and TCE by Fe–Ni nanoparticles immobilised polysulphone matrix

The reduction of dichloroethane (DCE) and trichloroethylene (TCE) by bimetallic iron–nickel (Fe–Ni) nanoparticles has been studied in this study. The reduction mechanism involves hydrodechlorination at the iron–nickel interface. The Fe–Ni nanoparticles have been synthesised by the chemical reduction method and immobilised on to a polysulphone matrix. The as-synthesised nanoparticles and Fe–Ni immobilied polysulphone support have been characterised to establish the particle size of the nanoparticles, which are of the order of 36–41?nm, and the physical characteristics of the immobilised support. Batch experiments have been performed using gas chromatography-mass spectrometry to study the degradation of DCE and TCE. The studies have shown that the bimetallic system is quite effective in the dechlorination of DCE and TCE. Also, the stability of the nanoparticles in the matrix has been explored with respect to its suitability for use in the degradation of chlorinated hydrocarbons.     

Laboratory tests for reactive barrier design

Owing to limitations of pump-and-treat, several technologies are being investigated for groundwater treatment. One of the most promising is the treatment of contaminants through the use of reactive barriers installed in situ, especially in the case of aquifers contaminated with chlorinated solvents. This work presents results of batch and column tests with metallic iron and some chlorinated solvents (1,2-DCA, 1,1,2-TCA and TCE). Such tests provided means to evaluate the degradation rates of these compounds and their byproducts. It is concluded that the reductive dechlorination with metallic iron can have different results, depending on the type of contaminant. Some contaminants may not present any degradation, or they have a half-life time so high that the use of the reactive barrier technology may not be practical. Furthermore, the formation of chlorinated byproducts, eventually more toxic than the original contaminant and that are not degradable using this same technology, emphasises that the treatment of aquifers should be sequential.     

Degradation of phenol and TCE using suspended and chitosan-bead immobilized Pseudomonas putida

The degradability of phenol and trichloroethene (TCE) by Pseudomonas putida BCRC 14349 in both suspended culture and immobilized culture systems are investigated. Chitosan beads at a size of about 1-2mm were employed to encapsulate the P. putida cells, becoming an immobilized culture system. The phenol concentration was controlled at 100 mg/L, and that of TCE was studied from 0.2 to 20 mg/L. The pH, between 6.7 and 10, did not affect the degradation of either phenol or TCE in the suspended culture system. However, it was found to be an important factor in the immobilized culture system in which the only significant degradation was observed at pH >8. This may be linked to the surface properties of the chitosan beads and its influence on the activity of the bacteria. The transfer yield of TCE on a phenol basis was almost the same for the suspended and immobilized cultures (0.032 mg TCE/mg phenol), except that these yields occurred at different TCE concentrations. The transfer yield at a higher TCE concentration for the immobilized system suggested that the cells immobilized in carriers can be protected from harsh environmental conditions. For kinetic rate interpretation, the Monod equation was employed to describe the degradation rates of phenol, while the Haldane's equation was used for TCE degradation. Based on the kinetic parameters obtained from the two equations, the rate for the immobilized culture systems was only about 1/6 to that of the suspended culture system for phenol degradation, and was about 1/2 for TCE degradation. The slower kinetics observed for the immobilized culture systems was probably due to the slow diffusion of substrate molecules into the beads. However, compared with the suspended cultures, the immobilized cultures may tolerate a higher TCE concentration as much less inhibition was observed and the transfer yield occurred at a higher TCE concentration.     

Photocatalysis of gaseous trichloroethylene (TCE) over TiO2: the effect of oxygen and relative humidity on the generation of dichloroacetyl chloride (DCAC) and phosgene

Batch photocatalytic degradation of 80+/-2.5 ppm V trichloroethylene (TCE) was conducted to investigate the effect of the oxygen and relative humidity (RH) on the formation of the dichloroacetyl chloride (DCAC) and phosgene. Based on the simultaneous ordinary differential equations (ODEs), the reaction rate constants of TCE ((2.31+/-0.28) approximately (9.41+/-0.63)x10(-2) min(-1)) are generally larger than that of DCAC ((0.94+/-1.25) approximately (9.35+/-1.71)x10(-3) min(-1)) by approximate one order. The phenomenon indicates the degradation potential of TCE is superior to that of DCAC. DCAC appreciably delivers the same degradation behavior with TCE that means there exists an optimum RH and oxygen concentration for photocatalysis of TCE and DCAC. At the time the peak yield of DCAC appears, the conversion ratio based on the carbon atom from TCE to DCAC is within the range of 30-83% suggesting that the DCAC generation is significantly attributed to TCE degradation. Regarding the phosgene formation, the increasing oxygen amount leads to the inhibitory effect on the phosgene yield which fall within the range of 5-15%. The formation mechanism of phosgene was also inferred that the Cl atoms attacking the C-C bond of DCAC results to the generation of phosgene rather than directly from the TCE destruction.     

The effect of salinity conditions on kinetics of trichloroethylene biodegradation by toluene-oxidizing cultures

This study investigates the effect of salt (NaCl) conditions on the biodegradations of trichloroethylene (TCE) by mixed cultures enriched on toluene. Two cultures were separately cultivated in this investigation, involving culture LHTO4, cultivated with freshwater and culture HHTO4, cultivated with 3.5% (w/v) NaCl solution. Batch tests were conducted to elucidate the degradations of toluene, TCE and a mixture of toluene and TCE by cultures LHTO4 at salinities of 0, 2 and 3.5% and by HHTO4 at salinity of 3.5%. The measurements were analyzed with microbial kinetics. The results show that for culture LHTO4 in the resting cells, when the transient salinities increased from 0 to 3.5%, the maximum specific rate of TCE degradation, k(TCE), declined from 2.28 to 1.45 d(-1), and the observed TCE transformation capacity, T(c,obs), decreased from 0.060 to 0.036 mgTCE/mgVSS. In the presence of toluene, TCE degradation was more inhibited by toluene (inhibition coefficients, K(I,TOL) were 0.8, 2.2, and 0.96 mg/L for salinity 0, 2, and 3.5%, respectively) than toluene degradation was by TCE (K(I,TCE) were 14, 5.8, and 1000 mg/L for salinity 0, 2, and 3.5%, respectively). Under long-term salinity stress, the culture HHTO4 maintained its capacity to utilize toluene but lost its effectiveness in the cometabolic transformation of TCE: k(TCE) fell to 0.25 d(-1) and T(c,obs) dropped to 0.024 mgTCE/mgVSS. This work reveals that the degradation of TCE by toluene-oxidizing cultures under saline conditions can be best described by the chosen kinetic equations and experimentally estimated constants, which can thus be used to lay a foundation for the rational design of biological processes to remove TCE from saline solutions.