Kinetics of transformation of 1,1,1-trichloroethane by Fe(II) in cement slurries

This study examines the applicability of the iron-based degradative solidification/stabilization (DS/S-Fe(II)) process to 1,1,1-trichloroethane (1,1,1-TCA), which is one of common chlorinated aliphatic hydrocarbons (CAHs) of concern at contaminated sites. DS/S-Fe(II) combines contaminant degradation by Fe(II) and immobilization by the hydration reactions of Portland cement. The transformation of 1,1,1-TCA by Fe(II) in 10% Portland cement slurries was studied using a batch slurry reactor system. The effects of Fe(II) dose, pH, and initial concentration of 1,1,1-TCA on the kinetics of 1,1,1-TCA degradation were evaluated. Degradation of 1,1,1-TCA in cement slurries including Fe(II) was very rapid and could be described by a pseudo-first-order rate law. The half-lives for 1,1,1-TCA were measured between 0.4 and 5h when Fe(II) dose ranged from 4.9 to 39.2mM. The pseudo-first-order rate constant increased with pH to a maximum near pH 12.5. A saturation rate equation was able to predict degradation kinetics over a wide range of target organic concentrations and at higher Fe(II) doses. The major transformation product of 1,1,1-TCA in mixtures of Fe(II) and cement was 1,1-dichloroethane (1,1-DCA), which indicates that degradation occurred by a hydrogenolysis pathway. A small amount of ethane was observed. The conversion of 1,1,1-TCA to ethane was better described by a parallel reaction model than by a consecutive reaction model.     

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.     

Long-term aerobic cometabolism of a chlorinated solvent mixture by vinyl chloride-, methane- and propane-utilizing biomasses

The aerobic cometabolic biodegradation of a mixture of chlorinated aliphatic hydrocarbons (CAHs) including vinyl chloride (VC), cis- and trans-1,2-dichloroethylene (cis-DCE, trans-DCE), trichloroethylene (TCE), 1,1,2-trichloroethane (1,1,2-TCA) and 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA) was investigated at both 25 and 17 degrees C by means of bioaugmented and non-bioaugmented sediment-groundwater slurry microcosm tests. The goals of the study were (i) to study the long-term aerobic biodegradation of a CAH mixture including a high-chlorinated solvent (1,1,2,2-TeCA) generally considered non-biodegradable in aerobic conditions; (ii) to investigate the efficacy of bioaugmentation with two types of internal inocula obtained from the indigenous biomass of the studied site; (iii) to identify the CAH-degrading bacteria. VC, methane and propane were utilized as growth substrates. The non-bioaugmented microcosms were characterized, at 25 degrees C, by an average 18-day lag-time for the direct metabolism of VC (accompanied by the cometabolism of cis- and trans-DCE) and by long lag-times (36-264 days) for the onset of methane or propane utilization (associated with the cometabolism of the remaining CAHs). In the inoculated microcosms the lag-phases for the onset of growth substrate utilization and CAH cometabolism were significantly shorter (0-15 days at 25 degrees C). Biodegradation of the 6-CAH mixture was successfully continued for up to 410 days. The low-chlorinated solvents were characterized by higher depletion rates. The composition of the microbial consortium of a propane-utilizing microcosm was determined by 16s rDNA sequencing and phylotype analysis. To the best of our knowledge, this is the first study that documents the long-term aerobic biodegradation of 1,1,2,2-TeCA.     

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.     

Degradation of trichloroethylene and related compounds by <Emphasis Type="Italic">Mycobacterium</Emphasis> spp. isolated from soil

 Mycobacterium spp. strains TA5 and TA27 (ethane-utilizing bacteria), which can degrade trichloroethylene (TCE) and 1,1,1-trichloroethane (1,1,1-TCA), were isolated from soil. Both bacteria could cometabolically degrade dichloromethane, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-TCA, 1,1,2-TCA, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, 1,1-dichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, and TCE with ethane as a carbon source. They could not degrade carbon tetrachloride, freon 113, or tetrachloroethylene. The TCE degradation characteristics of strain TA27 were determined. Under a head-space gas containing 3% ethane, strain TA27 degraded more than 95% of TCE at an initial concentration of 1 mg l^–1 within 3 days. We observed good growth and TCE degradation between 25 and 35  °C. At an initial TCE concentration of 30 mg l^–1, it degraded 30% of TCE within 7 days. Although growth was inhibited for more than 50 mg l^–1 TCE at 3% ethane concentration, good growth and 50% degradation of TCE were observed at 12% ethane concentration within 14 days. High ethane concentration may mitigate the toxicity of TCE. Received: 24 January 2000 / Accepted: 10 March 2000     

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.     

Effects of transition metal and sulfide on the reductive dechlorination of carbon tetrachloride and 1,1,1-trichloroethane by FeS

Reductive dechlorination of carbon tetrachloride (CT) and 1,1,1-trichloroethane (1,1,1-TCA) by FeS with transition metals (Cu(II), Co(II), and Ni(II)) and hydrosulfide was characterized in this study. The batch kinetic experiments were conducted by spiking each stock solution of CT and 1,1,1-TCA into 33 g/L of FeS suspensions with and without transition metals at pH 7.5. No significant enhancement was observed in the reductive dechlorination of target compounds by FeS with 1mM transition metals. However, except the addition of Cu(II), the reduction rate of 1,1,1-TCA increased with increasing the concentration of transition metals. The rate constants with 10mM Co(II) and Ni(II) were 0.06 and 0.11h(-1), approximately 1.3 and 3.0 times greater than those by FeS alone. The addition of 20mM HS(-) also increased the rate constants of 1,1,1-TCA by FeS by one order of magnitude. SEM analysis showed that the addition of transition metal (Ni(II)) and HS(-) caused a noticeable morphologic change of FeS surface. The transition metal added was substituted by the structural iron resulting in the decrease of iron content of FeS (52.6-46.9%). One third of the transition metal in FeS suspension existed as zero-valent form playing a catalyst role to accelerate the reaction kinetics.     

Dechlorination of trichloroethylene in aqueous solution by noble metal-modified iron

Bimetallic particles are extremely interesting in accelerating the dechlorination of chlorinated organics. Four noble metals (Pd, Pt, Ru and Au), separately deposited onto the iron surface through a spontaneous redox process, promoted the TCE dechlorination rate, and the catalytic activity of the noble metal followed the order of Pd>Ru>Pt>Au. This order was found to be dependent on the concentrations of adsorbed atomic hydrogen, indicating that the initial reaction was cathodically controlled. Little difference in the distribution of the chlorinated products for the four catalysts (cis-DCE: 51%; 1,1-DCE: 27%; trans-DCE: 15% and VC: 7%) was observed. The chlorinated by-products accumulated in both Pt/Fe and Au/Fe (10.3% and 2.5% of the transformed TCE, respectively), but did not accumulate in Pd/Fe and Ru/Fe. Ru/Fe was further examined as an economical alternative to Pd/Fe. The 1.5% Ru/Fe was found to completely degrade TCE within 80 min. Considering the expense, the yield of chlorinated products and the lifetime of a reductive material, Ru provides a potential alternative to Pd as a catalyst in practical applications.     

Results of the reactant sand-fracking pilot test and implications for the in situ remediation of chlorinated VOCs and metals in deep and fractured bedrock aquifers.

Permeable reactive barriers (PRBs), such as the Waterloo Funnel and Gate System, first implemented at Canadian Forces Borden facility in 1992, are a passive remediation technology capable of controlling the migration of, and treating contaminated groundwater in situ. Most of the PRBs installed to date have been shallow installations created by backfilling sheet-pile shored excavations with iron filing reactive media. More recently continuous trenchers [R. Puls, Installation of permeable reactive barriers using continuous trenching equipment, Proceedings of the RTDF Permeable Barriers Work Group, Virginia Beach, VA, September 1997] and Caissons [J. Vogan, Caisson installation of a pilot scale, permeable reactive barrier in situ treatment zone at the Sommersworth Landfill, NH, Presented to the RTDF Permeable Barriers Work Group, Alexandria, VA, April 1996], and vertical fracturing emplacements [G. Hocking, Vertical hydraulic fracture emplacement of permeable reactive barriers, Progress Report delivered to the Permeable Reactive Barriers Workgroup of the Remedial Technology Development Forum, Beaverton, OR, April 1998] have been used to create reactive barriers in soil. None of the prior methods are capable of adequately addressing groundwater contamination in deep and fractured bedrock aquifers. The purpose of the RSF pilot study was to install reactive media into an impacted bedrock aquifer, and to evaluate the effectiveness of in situ treatment of chlorinated volatile organic compounds (CVOCs) and metals in that type of aquifer. Three discrete fractures were identified and treated and were subjected to testing before and after treatment. Between 300 and 1700 lb. of 1 mm diameter reactive proppants were injected into each zone to facilitate treatment. Monitoring data obtained from adjacent observation wells verified that fracking fluids reached at least 42 ft from the treatment well following hydrofracturing. The concentrations of many of the CVOCs decreased up to 98% based on the results of pre- and post-RSF treatment analyses. Consistent with other research, concentrations of CVOCs were noted to decrease including trichloroethene (TCE), tetrachloroethene (PCE), 1,1,1-trichloroethane (1,1,1-TCA), 1, 1-dichloroethane (1,1-DCA), and 1,1-dichloroethene (1,1-DCE) and increases were noted in concentrations of cis-1,2-dichloroethene (cis-1,2-DCE) and chloroform suggesting that the rate of transformation of the parent compounds to these daughter products is higher than the rate of destruction of the daughter products. The RSF pilot study demonstrated that: (1) zero valent iron foam proppants have the physical and chemical properties necessary to effectively treat CVOCs and metals in groundwater when inserted under high pressures into fractured bedrock. (2) Iron foam reactive media can be placed in bedrock using high pressure hydraulic fracturing equipment and polysaccharide viscosifiers. (3) The extent of the treatment can be monitored in situ using tracers and pressure transducers. (4) Well capacity is increased by improving hydraulic conductivity through hydraulic fracturing and proppant injection. The approximate cost of all of the effort expended in the pilot study was about US$200,000. Full-scale implementations are projected to cost between US$100,000 and US$1,000,000 and would depend on site specific conditions such as the extent and level of impacted groundwater requiring treatment. This technology can potentially be implemented to create treatment zones for the passive treatment of CVOC and metal impacted groundwater in fractured rock aquifers offering a cost-effective alternative to a pump and treat forever scenario.     

Competitive immobilization of multiple component chlorinated solvents by cyclodextrin derivatives

Immobilization of chlorinated solvents with hydropropyl and methyl cyclodextrins (CDs) was observed by head-space analysis to obtain the stability constants in single and multiple component systems. In each single component system, the highest stability constant was 0.299 mM(-1) for perchloroethylene (PCE) by methyl-beta-cyclodextrin (M-beta-CD), 0.136 mM(-1) for trichloroethylene (TCE) by M-beta-CD, 0.106 mM(-1) for cis-dichloroethylene (cis-DCE) by hydropropyl-alpha-cyclodextrin, and 0.090 mM(-1) for trans-dichloroethylene (trans-DCE) by M-beta-CD. When HP-beta-CD and M-beta-CD were used, the stability constants of PCE and TCE increased and those of DCEs decreased in a multiple component system. Differences in stability constants of single and multiple component systems thus should be important parameters when cyclodextrins are applied to solubilization of multiple chlorinated solvents.     

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.     

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.     

Performance enhancement of batch aerobic digesters via addition of digested sludge

The impact of the feed sludge (FS) concentration and addition of digested sludge (DS) to an aerobic digester was evaluated with respect to its capability for removal of the total suspended solids (TSS) and volatile suspended solids (VSS). The aerobic digesters, which operated in a batch mode at constant temperature and mixing rate, were initially filled with FS to 25%, 50%, 75%, and 100% of the reactor's volume. The remaining volume of the reactor was occupied by the DS, having DS/FS ratio of 3, 1, 1/3, and 0. Analysis of the experimental data showed that in the absence of DS, TSS, and VSS destruction rates are very small; however, increasing DS/FS ratio from 1/3 to 3 results in 74-77% increase in VSS and TSS destruction, respectively. The increase of the DS/FS ratio associated with increased ratio of the measured viable biomass (Cc) to VSS concentration (Xv) suggested that DS serves as the source of viable cell mass needed for degradation of organic solids. Assuming pseudo-first-order kinetics, it was shown that while organic solid destruction rate constants (k) are inversely related to initial concentrations of sludge, their values increase with increasing DS/FS ratios.     

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.     

Sonochemical degradation of chlorinated hydrocarbons using a batch and continuous flow system

The sonochemical degradation of chlorinated hydrocarbons such as 1,1,1-trichloroethane, trichloroethylene and tetrachloroethylene in aqueous solution was carried out in the batch and continuous flow systems at an ultrasonic frequency of 100kHz under an air atmosphere. In the batch experiment, the rate of degradation follows the order 1,1,1-trichloroethane>tetrachloroethylene>trichloroethylene, and the chlorinated hydrocarbon were readily degraded by ultrasonic irradiation. The experiments in the continuous flow system were performed in the range of volumetric flow rate from 7 to 30 x 10(-3)lmin(-1). The conversion of the chlorinated hydrocarbons at a steady-state of reactor depended on the volumetric flow rate. The yield of Cl(-) (as a measurement of mineralization of chlorinated hydrocarbons) was 70-90% of the chlorine atoms in the parent chlorinated hydrocarbon molecules. From the viewpoint of the scale-up process, the sonochemical degradation of trichloroethylene was simulated in a three stage reactor, and the conversion (>99%) in a third stage reactor was showed the good results that can be satisfied a desired water quality standard.     

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.     

Dechlorination of chlorinated methanes by Pd/Fe bimetallic nanoparticles

This paper examined the potential of using Pd/Fe bimetallic nanoparticles to dechlorinate chlorinated methanes including dichloromethane (DCM), chloroform (CF) and carbon tetrachloride (CT). Pd/Fe bimetallic nanoparticles were prepared by chemical precipitation method in liquid phase and characterized in terms of specific surface area (BET), size (TEM), morphology (SEM), and structural feature (XRD). With diameters on the order of 30-50 nm, the Pd/Fe bimetallic nanoparticles presented obvious activity, and were suited to efficient catalytic dechlorination of chlorinated methanes. The effects of some important reaction parameters, such as Pd loading (weight ratio of Pd to Fe), Pd/Fe addition (Pd/Fe bimetallic nanoparticles to solution ratio) and initial pH value, on dechlorination efficiency were sequentially studied. It was found that the maximum dechlorination efficiency was obtained for 0.2 wt% Pd loading. The dechlorination efficiency was observed to increase with increasing Pd/Fe addition. The optimal pH value for dechlorination reaction of chlorinated methanes was about 7. Kinetics of chlorinated methane dechlorination in the catalytic reductive system of Pd/Fe bimetallic particles were investigated. The dechlorination reaction complied with pseudo-first-order kinetics.     

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.     

Electrically induced reduction of trichloroethene in clay

Chlorinated compounds such as trichloroethene (TCE) are recalcitrant contaminants commonly detected in soil and groundwater. Contemporary remedies such as electron donor amendment tend to be less or ineffective in treating chlorinated compounds in matrix of lower permeability, such as clay. In this study, electrically induced reduction (EIR) was tested by inserting electrodes in saturated clay containing 122.49–125.43 mg TCE kg^?1. Weak electric potentials (E) of 6, 9, and 12 V m^?1 were applied, and up to 97% of TCE were depleted during the study period. Corresponding increases in chloride concentrations was observed during TCE depletion, indicating a reductive dechlorination pathway. No migration of TCE was observed between the two electrodes, neither were intermediate compounds such as dichloroethene (DCE) or vinyl chloride (VC). Results were also tested against a mathematical equation we previously established for field applications. Electrically induced reduction may offer a novel method for in situ degradation of chlorinated contaminants, especially in low-permeable media such as clay.     

Record Efficiency Stable Flexible Perovskite Solar Cell Using Effective Additive Assistant Strategy

Even though the power conversion efficiency (PCE) of rigid perovskite solar cells is increased to 22.7%, the PCE of flexible perovskite solar cells (F‐PSCs) is still lower. Here, a novel dimethyl sulfide (DS) additive is developed to effectively improve the performance of the F‐PSCs. Fourier transform infrared spectroscopy reveals that the DS additive reacts with Pb²⁺ to form a chelated intermediate, which significantly slows down the crystallization rate, leading to large grain size and good crystallinity for the resultant perovskite film. In fact, the trap density of the perovskite film prepared using the DS additive is reduced by an order of magnitude compared to the one without it, demonstrating that the additive effectively retards transformation kinetics during the thin film formation process. As a result, the PCE of the flexible devices increases to 18.40%, with good mechanical tolerance, the highest reported so far for the F‐PSCs. Meanwhile, the environmental stability of the F‐PSCs significantly enhances by 1.72 times compared to the device without the additive, likely due to the large grain size that suppresses perovskite degradation at grain boundaries. The present strategy will help guide development of high efficiency F‐PSCs for practical applications.