A multi-path chain kinetic reaction model to predict the evolution of 1,1,1-trichloroethane and its daughter products contaminant-plume in permeable reactive bio-barriers.

Permeable reactive bio-barriers (Bio-PRBs) are a new and developing technique for in situ remediation of groundwater contamination. Some remediation technologies have often been impeded by insufficient understanding of contaminant transport and transformation in the subsurface environment. Therefore, advanced knowledge in contaminant transport and reactions in Bio-PRBs will be crucial to the successful practical application of this technique. A two-dimensional reaction model C1 was developed for predicting the multi-path chain kinetic reaction of 1,1,1-trichloroethane (1,1,1-TCA) in Bio-PRBs. This study demonstrates that model C1 is able to predict the 1,1,1-TCA breakthrough time and rapidly evaluate the Bio-PRBs retardation performance. The results show that microbial growth and immobilization are the key factors that affect the retardation and remediation performance of Bio-PRBs. The free growth of microorganisms had significant negative effects on hydraulic conductivity (K) in the zero-valent iron (ZVI) region of free microorganism Bio-PRBs (FM-PRBs). The total head loss in the FM-PRB was 9.0 cm, which was significantly greater than the head loss (6.5 cm) of immobilized microorganism Bio-PRBs (IM-PRBs). Compared to ZVI-PRBs and FM-PRBs, the numerical simulation results reveal that microbial immobilization significantly improves the remediation performance of IM-PRBs by 550.9% and 32.7%, respectively. The dual effect of microorganisms leads to significant differences in the 1,1,1-TCA and daughter products (1,1-dichloroethane, 1,1-dichloroethene, chloroethane and vinyl chloride) contaminant-plume evolution between FM-PRBs and IM-PRBs. In addition, model C1 can be utilized to design standard Bio-PRBs for real site of 1,1,1-TCA contanminated groundwater. To meet the safety standard of groundwater as potable water, the width of IM-PRBs needs to be increased by 24 cm. However, in FM-PRBs, the width needs to be increased by 42 cm. Therefore, IM-PRBs save costs significantly. This work has successfully used a model to optimize Bio-PRBs and to predict 1,1,1-TCA and daughter products contaminant-plume evolution in different Bio-PRBs.

Enhanced reductive dechlorination of 1,1,1-trichloroethane using zero-valent iron-biochar-carrageenan microspheres: preparation and microcosm study.

In this study, a composite remediation material for the enhanced reductive dechlorination (ERD) of 1,1,1-trichloroethane (1,1,1-TCA) in aqueous solution was prepared. This material was comprised of biochar as the carrier and adsorbent, and carrageenan (CG) as the embedding medium to entrap the organic carbon sources and zero-valent iron (ZVI). We determined the suitable biochar dosage and organic carbon source in the composite alongside the optimal preparation conditions. Furthermore, using an anaerobic microcosm study, we discussed the performance and possible mechanisms of the composite on 1,1,1-TCA removal in aqueous solution. From this, we found that the suitable dosage of biochar in water during the preparation of composite microspheres was 0.2% (w/v). Under this condition, the biochar had a strong capacity to adsorb 1,1,1-TCA with a removal efficiency of 84.2%. Soluble starch was selected as the appropriate organic carbon source, because starch-microspheres show an excellent slow-release effect in water. The optimal preparation conditions of microspheres were identified as follows: 2% CG (w/v) colloidal solution, 6% CaCl2 (w/v) solution, and a 12-h curing time. After 25-day incubation with the composite prepared under optimized conditions, the removal efficiency of 1,1,1-TCA was 95.68%, which was 24.69% higher than that observed in the microcosm with a commercial remediation material. The scanning electron microscopy (SEM) images show that the amounts of ZVI and soluble starch inside the microsphere decreased obviously, while the biochar amount remained about the same. This indicates that 1,1,1-TCA in aqueous solution was mainly removed via soluble starch-enhanced biotic reductive dechlorination and ZVI-enhanced abiotic reductive dechlorination. The changes in microbial community structure demonstrate that the composite stimulated the activities of functional anaerobic bacteria, in particular, regarding dechlorination and fermentation abilities in the microcosm, therefore enhancing the anaerobic biodegradation of 1,1,1-TCA. This study suggests that the composite, entrapping biochar, ZVI, and organic carbon source in CG microspheres can significantly enhance the reductive dechlorination of 1,1,1-TCA in aqueous solution. We anticipate this novel remediation material could be successfully applied to the in situ ERD remediation of natural groundwater mainly contaminated with 1,1,1-TCA.

Effects of pH value and calcium hardness on the removal of 1,1,1-trichloroethane by immobilized nanoscale zero-valent iron on silica based supports.

Immobilizing nanoscale zero-valent iron (NZVI) particles on silica-based supports is an effective way to overcome the NZVI aggregation. The pH value and calcium hardness can change the aggregation kinetics and alter the stability of the suspensions of NZVI-silica based materials, thus change the reactivity of these NZVI-silica based materials to remove chlorinated aliphatic hydrocarbons (CAHs). The removal of CAHs by these NZVI-silica based materials includes adsorption by silica based supports and degradation by NZVI particles. Using 1,1,1-TCA and mesoporous hydrated silica (mHS) as model chlorinated aliphatic hydrocarbon (CAH) and silica based support, the effects of pH value and Ca2+ concentration on both the adsorption and adsorption-degradation processes of CAHs by NZVI-silica based materials were studied. The structural and textural features, suspension stability, particle size distribution, and Zeta potential of the materials under various conditions were characterized by different techniques. Both decreasing initial pH value and increasing Ca2+ concentration can reduce the Zeta potential of mHS and lead to the aggregation of mHS particles, thus inhibiting the removal of 1,1,1-TCA via adsorption by mHS through decreasing the number of sites for adsorption. Low initial pH value can accelerate the corrosion of NZVI core and remove the passivation layer, thus promoting the removal of 1,1,1-TCA via adsorption-degradation by NZVI@mHS. Ca2+ can decrease the sites for adsorption and form precipitates which can block mesoporous channels, thus hinder the 1,1,1-TCA removal via adsorption-degradation by NZVI@mHS.

Effects of biological clogging on 1,1,1-TCA and its intermediates distribution and fate in heterogeneous saturated bio-augmented permeable reactive barriers.

Biological clogging in porous media was an important concern in the design of bio-augmented permeable reactive barriers (Bio-PRBs) that were used to remediate groundwater with dense non-aqueous phase liquids (DNAPLs). Here, we used laboratory sandbox experiments to develop and calibrate reactive transport models (C1 and C2) simulating 1,1,1-trichloroethane (1,1,1-TCA) change in heterogeneous saturated porous media. The routine (1,1,1-TCA chain kinetic reactions) and subroutine (the relationship between hydraulic conductivity (K) and time (t)) were included in the model computer code. The simulation results suggested that the model C1 had the applicability for simulating contaminant transport and fate in bio-augmented flow field. By using the model C1 which was suitable for constant K condition, the performance of different types of Bio-PRBs was evaluated, and the regularity of contaminants chain kinetic reactions in different heterogeneous saturated porous media was obtained. The results demonstrated that Bio-PRBs in immobilized microorganism (IM) protocol were more superior to Bio-PRBs in free microorganism (FM) protocol. In addition, by using the model C2 (updated model C1) which was suitable for decreasing K condition, the different and optimized regularity of contaminants transport and transformation was obtained. The results showed that microbial growth which further decreased K was beneficial to preventing the transport of contaminants and accelerating the transformation of contaminants. However, the negative effects of biological clogging on hydraulic conductivity and relative hydraulic conductivity ratio in FM Bio-PRBs were significantly stronger than that in IM Bio-PRBs. Deploying IM Bio-PRBs for groundwater remediation would be much more efficient and meet the design criteria. The research work had guiding significance to engineering and provided consultation for designing and optimizing Bio-PRBs system. To make the design and optimization of Bio-PRBs system convenient, it was very essential to choose the suitable mathematical model (C1 or C2).

Spectroscopic methods for aqueous cyclodextrin inclusion complex binding measurement for 1,4-dioxane, chlorinated co-contaminants, and ozone.

Recalcitrant organic contaminants, such as 1,4-dioxane, typically require advanced oxidation process (AOP) oxidants, such as ozone (O3), for their complete mineralization during water treatment. Unfortunately, the use of AOPs can be limited by these oxidants' relatively high reactivities and short half-lives. These drawbacks can be minimized by partial encapsulation of the oxidants within a cyclodextrin cavity to form inclusion complexes. We determined the inclusion complexes of O3 and three common co-contaminants (trichloroethene, 1,1,1-trichloroethane, and 1,4-dioxane) as guest compounds within hydroxypropyl-ß-cyclodextrin. Both direct (ultraviolet or UV) and competitive (fluorescence changes with 6-p-toluidine-2-naphthalenesulfonic acid as the probe) methods were used, which gave comparable results for the inclusion constants of these species. Impacts of changing pH and NaCl concentrations were also assessed. Binding constants increased with pH and with ionic strength, which was attributed to variations in guest compound solubility. The results illustrate the versatility of cyclodextrins for inclusion complexation with various types of compounds, binding measurement methods are applicable to a wide range of applications, and have implications for both extraction of contaminants and delivery of reagents for treatment of contaminants in wastewater or contaminated groundwater.

Enhanced reductive de-chlorination of a solvent contaminated aquifer through addition and apparent fermentation of cyclodextrin.

In a field study, aqueous cyclodextrin (CD) was investigated for its ability to extract chlorinated volatile organic compounds (cVOC), such as trichloroethylene (TCE), 1,1,1-trichloroethane (TCA), and dichloroethene (DCE) through in-situ flushing of a sandy aquifer. After cessation of aquifer flushing, a plume of CD was left. Changes in CD, cVOC, and inorganic terminal electron acceptors (TEAs) (DO, nitrate, sulfate, iron) were monitored in four rounds of wellwater sampling (20, 210, 342, and 425days after cessation of active pumping). Post-CD flushing VOC levels rebounded (850% for TCE, 190% for TCA, and 53% for DCE) between the first two sampling rounds, apparently due to rate-limited desorption from aquifer media and dissolution from remaining NAPL. However, substantial reduction in the mass of TCE (6.3 to 0.11mol: 98%) and TCA (2.8 to 0.73mol: 74%) in groundwater was observed between 210 and 425days. DCE should primarily be produced from the degradation of TCE and is expected to subsequently degrade to chloroethene. Since DCE levels decreased only slightly (0.23 to 0.17mol: 26%), its degradation rate should be similar to that produced from the decaying TCE. Cyclodextrin was monitored starting from day 210. The mass of residual CD (as measured by Total Organic Carbon) decreased from 150mol (day 210) to 66 (day 425) (56% decrease). The naturally anaerobic zone within the aquifer where residual CD mass decreased coincided with a loss of other major potential TEAs: nitrate (97% loss), sulfate (31%) and iron (31%). In other studies, TCE and 1,1,1-TCA have been found to be more energetically favorable TEAs than sulfate and iron and their degradation via reductive dechlorination has been found to be enhanced by the fermentation of carbohydrates. Such processes can explain these observations, but more investigation is needed to evaluate whether residual levels of CD can facilitate the anaerobic degradation of chlorinated VOCs.

Surfactant-enhanced bioremediation of DDTs and PAHs in contaminated farmland soil.

Field-scale bioremediation of dichlorodiphenyl trichloroethanes (DDTs) and polycyclic aromatic hydrocarbons (PAHs) contaminated farmland soil from the Shenyang North New Area of China was studied using the bacteria Arthrobacter globiformis. The additive effects of different concentrations of biosurfactant rhamnolipids (RLs) and anionic-nonionic mixed surfactant (SDBS-Tween 80) were evaluated. DDT and PAH removal rates by A. globiformis after 150 days of remediation were 52.1% and 21.9%, respectively. At the optimum RL concentration of 5 mg kg-1, DDTs and PAHs had removal rates of 64.3% and 35.6%, respectively, at 150 days. This was 60.7% and 29.3% higher than the control; 36.9% and 19.8% higher than soil with RL-5 alone; and 12.2% and 13.8% higher than the A. globiformis treatment alone. RL-5 can enhance soil enzyme activity and A. globiformis reproduction during the DDT and PAH biodegradation processes. This study illustrates a highly efficient, low-cost in situ soil bioremediation technology that could have practical utility.

Thermally activated persulfate oxidation of NAPL chlorinated organic compounds: effect of soil composition on oxidant demand in different soil-persulfate systems.

This study investigates the interaction of persulfate with soil components and chlorinated volatile organic compounds (CVOCs), using thermally activated persulfate oxidation in three soil types: high sand content; high clay content; and paddy field soil. The effect of soil composition on the available oxidant demand and CVOC removal rate was evaluated. Results suggest that the treatment efficiency of CVOCs in soil can be ranked as follows: cis-1,2-dichloroethene > trichloroethylene > 1,2-dichloroethane > 1,1,1-trichloroethane. The reactions of soil components with persulfate, shown by the reduction in soil phase natural organics and mineral content, occurred in parallel with persulfate oxidation of CVOCs. Natural oxidant demand from the reaction of soil components with persulfate exerted a large relative contribution to the total oxidant demand. The main influencing factor in oxidant demand in paddy-soil-persulfate systems was natural organics, rather than mineral content as seen with sand and clay soil types exposed to the persulfate system. The competition between CVOCs and soil components for oxidation by persulfate indicates that soil composition exhibits a considerable influence on the available oxidant demand and CVOC removal efficiency. Therefore, soil composition of natural organics and mineral content is a critical factor in estimating the oxidation efficiency of in-situ remediation systems.

High-density natural luffa sponge as anaerobic microorganisms carrier for degrading 1,1,1-TCA in groundwater.

Anaerobic microorganisms were applied to degrade organic contaminants in groundwater with permeable reactive barriers (PRBs). However, anaerobic microorganisms need to select optimal immobilizing material as carrier. The potential of high-density natural luffa sponge (HDLS) (a new variety of luffa) for the immobilization and protection of anaerobic microorganisms was investigated. The HDLS has a dense structure composed of a complicated interwoven fibrous network. Therefore, the abrasion rate of HDLS (0.0068 g s-1) was the smallest among the four carriers [HDLS, ordinary natural luffa sponge (OLS), polyurethane sponge (PS), and gel carrier AQUAPOROUSGEL (APG)]. The results suggest that it also had the greatest water retention (10.26 H2O-g dry carrier-g-1) and SS retention (0.21 g dry carrier-g-1). In comparison to well-established commercialized gel carrier APG, HDLS was of much better mechanical strength, hydrophilicity and stability. Microbial-immobilized HDLS also had the best performance for the remediation of 1,1,1-TCA simulated groundwater. Analysis of the clone libraries from microorganism-immobilized HDLS showed the HDLS could protect microorganisms from the toxicity of 1,1,1-TCA and maintain the stability of microbial community diversity. The mechanism of HDLS immobilizing and protecting microorganisms was proposed as follows. The HDLS had a micron-scale honeycomb structure (30-40 µm) and an irregular ravine structure (4-20 µm), which facilitate the immobilization of anaerobic microorganisms and protect the anaerobic microorganisms.

Degradation of chlorinated organic solvents in aqueous percarbonate system using zeolite supported nano zero valent iron (Z-nZVI) composite.

Chlorinated organic solvents (COSs) are extensively detected in contaminated soil and groundwater that pose long-term threats to human life and environment. In order to degrade COSs effectively, a novel catalytic composite of natural zeolite-supported nano zero valent iron (Z-nZVI) was synthesized in this study. The performance of Z-nZVI-catalyzed sodium percarbonate (SPC) in a heterogeneous Fenton-like system was investigated for the degradation of COSs such as 1,1,1-trichloroethane (1,1,1-TCA) and trichloroethylene (TCE). The surface characteristics and morphology of the Z-nZVI composite were tested using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Total pore volume, specific surface area, and pore size of the natural zeolite and the Z-nZVI composite were measured using Brunauer-Emmett-Teller (BET) method. SEM and TEM analysis showed significant elimination of aggregation and well dispersion of iron nano particles on the framework of natural zeolite. The BET N2 measurement analysis indicated that the surface area of the Z-nZVI composite was 72.3 m(2)/g, much larger than that of the natural zeolite (0.61 m(2)/g). For the contaminant analysis, the samples were extracted with n-hexane and analyzed through gas chromatograph. The degradation of 1,1,1-TCA and TCE in the Z-nZVI-catalyzed percarbonate system were 48 and 39 % respectively, while strong augmentation was observed up to 83 and 99 %, respectively, by adding the reducing agent (RA), hydroxyl amine (NH2OH•HCl). Probe tests validated the presence of OH(●) and O2 (●-) which were responsible for 1,1,1-TCA and TCE degradation, whereas both free radicals were strengthened with the addition of RA. In conclusion, the Z-nZVI/SPC oxidation with reducing agent shows potential technique for degradation of groundwater contaminated by 1,1,1-TCA and TCE.

Use of dual carbon-chlorine isotope analysis to assess the degradation pathways of 1,1,1-trichloroethane in groundwater.

Compound-specific isotope analysis (CSIA) is a powerful tool to track contaminant fate in groundwater. However, the application of CSIA to chlorinated ethanes has received little attention so far. These compounds are toxic and prevalent groundwater contaminants of environmental concern. The high susceptibility of chlorinated ethanes like 1,1,1-trichloroethane (1,1,1-TCA) to be transformed via different competing pathways (biotic and abiotic) complicates the assessment of their fate in the subsurface. In this study, the use of a dual C-Cl isotope approach to identify the active degradation pathways of 1,1,1-TCA is evaluated for the first time in an aerobic aquifer impacted by 1,1,1-TCA and trichloroethylene (TCE) with concentrations of up to 20 mg/L and 3.4 mg/L, respectively. The reaction-specific dual carbon-chlorine (C-Cl) isotope trends determined in a recent laboratory study illustrated the potential of a dual isotope approach to identify contaminant degradation pathways of 1,1,1-TCA. Compared to the dual isotope slopes (Δδ(13)C/Δδ(37)Cl) previously determined in the laboratory for dehydrohalogenation/hydrolysis (DH/HY, 0.33 ± 0.04) and oxidation by persulfate (∞), the slope determined from field samples (0.6 ± 0.2, r(2) = 0.75) is closer to the one observed for DH/HY, pointing to DH/HY as the predominant degradation pathway of 1,1,1-TCA in the aquifer. The observed deviation could be explained by a minor contribution of additional degradation processes. This result, along with the little degradation of TCE determined from isotope measurements, confirmed that 1,1,1-TCA is the main source of the 1,1-dichlorethylene (1,1-DCE) detected in the aquifer with concentrations of up to 10 mg/L. This study demonstrates that a dual C-Cl isotope approach can strongly improve the qualitative and quantitative assessment of 1,1,1-TCA degradation processes in the field.

Particles and enzymes: Combining nanoscale zero valent iron and organochlorine respiring bacteria for the detoxification of chloroethane mixtures.

Nanoscale zero valent iron (nZVI) and organochlorine respiring bacteria (ORB) are two technologies used to detoxify chlorinated aliphatic hydrocarbons (CAHs). nZVI can rapidly detoxify high CAH concentrations, but is quickly oxidised and unable to degrade certain CAHs (e.g., 1,2-dichlorothane). In contrast, ORB can dechlorinate CAHs resistant to nZVI (e.g., 1,2-dichlorothane) but are inhibited by other CAHs of concern degradable by nZVI (e.g., chloroform and carbon tetrachloride). Combining the two was proposed as a unique treatment train to overcome each technology's shortcomings. In this study, this combined remedy was investigated using a mixture of 1,2-dichloroethane, degradable by ORB but not nZVI, and 1,1,2-trichloroethane, susceptible to both. Results indicated that nZVI rapidly dechlorinated 1,1,2-trichloroethane when supplied above 0.5 g/L, however ORB were inhibited and unable to dechlorinate 1,2-dichloroethane. pH increase and ionic species associated with nZVI did not significantly impact ORB, pinpointing Fe(0) particles as responsible for ORB inhibition. Below 0.05 g/L nZVI, ORB activity was stimulated. Results suggest that combining ORB and nZVI at appropriate doses can potentially treat a wider range of CAHs than each individual remedy. At field sites where nZVI was applied, it is likely that in situ nZVI concentrations were below the threshold of negative consequences.

Peroxone activated persulfate treatment of 1,4-dioxane in the presence of chlorinated solvent co-contaminants.

1,4-dioxane is often found as a co-contaminant with chlorinated volatile organic compounds (VOCs) at solvent release sites such as landfills, solvent recycling facilities, or fire training areas. Historically, soil and groundwater samples were not routinely analyzed for 1,4-dioxane and therefore the number of known 1,4-dioxane sites is still increasing. Due to its co-occurrence with chlorinated compounds, remediation strategies are needed that simultaneously treat both 1,4-dioxane as well as chlorinated VOC co-contaminants. In this proof of concept laboratory study, the fate of 1,4-dioxane was examined during the targeted destruction of aqueous phase VOC, using a peroxone activated persulfate (PAP) chemical oxidation method. Bench-scale experiments were carried out to evaluate the treatability of 1,4-dioxane as both a single-contaminant and in the presence of trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1-TCA). Possible dependencies on oxidant concentration and reaction kinetics were studied. The oxidative destruction of 1,4-dioxane, TCE and 1,1,1-TCA in single-contaminant batch systems followed pseudo-first-order reaction kinetics and even at the most dilute oxidant concentration lasted for at least 13 days. The rate of oxidation for each contaminant increased linearly with increasing persulfate concentration over the range of oxidant concentrations tested. The rate of oxidative destruction, from most easily degraded to least, was: TCE > 1,4-dioxane > 1,1,1-TCA. Oxidation rates were up to 87% slower in a mixture of these three compounds. Although additional tests are necessary, our data suggest that PAP oxidation of 1,4-dioxane might aid in the cleanup of VOC contaminated sites.

nZVI injection into variably saturated soils: Field and modeling study.

Nano-scale zero valent iron (nZVI) has been used at a number of contaminated sites over the last decade. At most of these sites, significant decreases in contaminant concentrations have resulted from the application of nZVI. However, limited work has been completed investigating nZVI field-scale mobility. In this study, a field test was combined with numerical modeling to examine nZVI reactivity along with transport properties in variably saturated soils. The field test consisted of 142L of carboxymethyle cellulose (CMC) stabilized monometallic nZVI synthesized onsite and injected into a variably saturated zone. Periodic groundwater samples were collected from the injection well, as well as, from two monitoring wells to analyze for chlorinated solvents and other geochemistry indicators. This study showed that CMC stabilized monometallic nZVI was able to decrease tricholorethene (TCE) concentrations in groundwater by more than 99% from the historical TCE concentrations. A three dimensional, three phase, finite difference numerical simulator, (CompSim) was used to further investigate nZVI and polymer transport at the variably saturated site. The model was able to accurately predict the field observed head data without parameter fitting. In addition, the numerical simulator estimated the mass of nZVI delivered to the saturated and unsaturated zones and distinguished the nZVI phase (i.e. aqueous or attached). The simulation results showed that the injected slurry migrated radially outward from the injection well, and therefore nZVI transport was governed by injection velocity and viscosity of the injected solution. A suite of sensitivity analyses was performed to investigate the impact of different injection scenarios (e.g. different volume and injection rate) on nZVI migration. Simulation results showed that injection of a higher nZVI volume delivered more iron particles at a given distance; however, the travel distance was not proportional to the increase in volume. Moreover, simulation results showed that using a 1D transport equation to simulate nZVI migration in the subsurface may overestimate the travel distance. This is because the 1D transport equation assumes a constant velocity while pore water velocity radially decreases from the well during injection. This study suggests that on-site synthesized nZVI particles are mobile in the subsurface and that a numerical simulator can be a valuable tool for optimal design of nZVI field applications.

Destruction of 1,1,1-trichloroethane and 1,2-dichloroethane DNAPLs by catalyzed H2O2 propagations (CHP).

Catalyzed H2O2 propagations (CHP) was studied to treat 1,1,1-trichloroethane (TCA) and 1,1-dichloroethane (DCA) dense nonaqueous phase liquids (DNAPLs) and to elucidate the reactive oxygen species responsible for their destruction. A TCA DNAPL was rapidly destroyed by CHP at a rate 3.5 times greater than its maximum rate of dissolution. Using systems that generate a single reactive oxygen species, the species responsible for TCA DNAPL destruction was found to be superoxide. Both hydroxyl radical and superoxide were responsible for the destruction of the DCA DNAPL. Both compounds were destroyed at equal rates in a mixed TCA/DCA DNAPL, which suggests that the rate of treatment is limited by a surface phenomenon at the DNAPL-water interface. The optimum pH for the destruction of TCA and DCA DNAPLs was near the pKa of 4.8 for perhydroxyl radical-superoxide systems. The results of this research demonsrate that TCA and DCA DNAPLs are effectively destroyed by CHP and that superoxide generation is necessary for effective TCA DNAPL destruction, while both hydroxyl radical and superoxide are necessary for effective DCA DNAPL destruction.

Carbon and chlorine isotope analysis to identify abiotic degradation pathways of 1,1,1-trichloroethane.

This study investigates dual C-Cl isotope fractionation during 1,1,1-TCA transformation by heat-activated persulfate (PS), hydrolysis/dehydrohalogenation (HY/DH) and Fe(0). Compound-specific chlorine isotope analysis of 1,1,1-TCA was performed for the first time, and transformation-associated isotope fractionation ε bulk C and ε bulk Cl values were -4.0 ± 0.2‰ and no chlorine isotope fractionation with PS, -1.6 ± 0.2‰ and -4.7 ± 0.1‰ for HY/DH, -7.8 ± 0.4‰ and -5.2 ± 0.2‰ with Fe(0). Distinctly different dual isotope slopes (Δδ13C/Δδ37Cl): ∞ with PS, 0.33 ± 0.04 for HY/DH and 1.5 ± 0.1 with Fe(0) highlight the potential of this approach to identify abiotic degradation pathways of 1,1,1-TCA in the field. The trend observed with PS agreed with a C-H bond oxidation mechanism in the first reaction step. For HY/DH and Fe(0) pathways, different slopes were obtained although both pathways involve cleavage of a C-Cl bond in their initial reaction step. In contrast to the expected larger primary carbon isotope effects relative to chlorine for C-Cl bond cleavage, ε bulk C < ε bulk Cl was observed for HY/DH and in a similar range for reduction by Fe(0), suggesting the contribution of secondary chlorine isotope effects. Therefore, different magnitude of secondary chlorine isotope effects could at least be partly responsible for the distinct slopes between HY/DH and Fe(0) pathways. Following this dual isotope approach, abiotic transformation processes can unambiguously be identified and quantified.

[In-situ measurement of atmospheric methyl chloroform at the Shangdianzi GAW regional background station].

An in-situ GC-ECD monitoring system was established at the Shangdianzi GAW regional background station (SDZ) for a 2-year atmospheric methyl chloroform (CH3CCl3) measurement experiment. Robust extraction of baseline signal filter was applied to the CH3CCl3 time series to separate the background and pollution data. The yearly averaged background mixing ratios of atmospheric CH3CCl3 were (9.03 +/- 0.53) x 10(-12) mol x mol(-1) in 2009 and (7.73 +/- 0.47) x 10(-12) in 2010, and the percentages of the background data in the whole data were 61.1% in 2009 and 60.4% in 2010, respectively. The yearly background CH3CCl3 mixing ratios at SDZ were consistent with the northern hemisphere background levels observed at Mace Head and Trinidad Head stations, but lower than the results observed at sites in southern China and some Chinese cities from 2001 to 2005. During the study period, background mixing ratios trends exhibited a decreasing rate of 1.39 x 10 12(-12) a(-1). The wind direction with the maximum CH3CCl3 mixing ratio was from the southwest sector and that with the minimum ratio was from the northeast sector. The differences between the maximum and the minimum average mixing ratios in the 16 wind directions were 0.77 x 10(-12) (2009) and 0.52 x 10(-12) (2010). In the 16 different wind directions, the averaged mixing ratio of CH3CCl3 in 2010 was lower than that in 2009 by 1.03 x 10(-12) -1.68 x 10(-12).

Bio-beads with immobilized anaerobic bacteria, zero-valent iron, and active carbon for the removal of trichloroethane from groundwater.

Chlorinated hydrocarbons are the most common organic pollutants in groundwater systems worldwide. In this study, we developed bio-beads with immobilized anaerobic bacteria, zero-valent iron (ZVI), and activated carbon (AC) powder and evaluated their efficacy in removing 1,1,1-trichloroethane (TCA) from groundwater. Bio-beads were produced by polyvinyl alcohol, alginate, and AC powder. We found that the concentration of AC powder used significantly affected the mechanical properties of immobilized bio-beads and that 1.0 % (w/v) was the optimal concentration. The bio-beads effectively degraded TCA (160 mg L(-1)) in the anaerobic medium and could be reused up to six times. The TCA degradation rate of bio-beads was 1.5 and 2.3 times greater, respectively, than ZVI + AC treatment or microbes + AC treatment. Measuring FeS produced by microbial reactions indicated that TCA removal occurred via FeS-catalyzed dechlorination. Analysis of clonal libraries derived from bio-beads demonstrated that the dominant species in the community were Betaproteobacteria and Gammaproteobacteria, which may contribute to the long-term stability of ZVI reactivity during TCA dechlorination. This study shows that the combined use of immobilized anaerobic bacteria, ZVI, and AC in bio-beads is effective and practical for TCA dechlorination and suggests they may be applicable towards developing a groundwater treatment system for the removal of TCA.

Field assessment of guar gum stabilized microscale zerovalent iron particles for in-situ remediation of 1,1,1-trichloroethane.

A pilot injection test with guar gum stabilized microscale zerovalent iron (mZVI) particles was performed at test site V (Belgium) where different chlorinated aliphatic hydrocarbons (CAHs) were present as pollutants in the subsurface. One hundred kilograms of 56µm-diameter mZVI (~70gL(-1)) was suspended in 1.5m(3) of guar gum (~7gL(-1)) solution and injected into the test area. In order to deliver the guar gum stabilized mZVI slurry, one direct push bottom-up injection (Geoprobe) was performed with injections at 5 depths between 10.5 and 8.5m bgs. The direct push technique was preferred above others (e.g. injection at low flow rate via screened wells) because of the limited hydraulic conductivity of the aquifer, and to the large size of the mZVI particles. A final heterogeneous distribution of the mZVI in the porous medium was observed explicable by preferential flow paths created during the high pressure injection. The maximum observed delivery distance was 2.5m. A significant decrease in 1,1,1-TCA concentrations was observed in close vicinity of spots where the highest concentration of mZVI was observed. Carbon stable isotope analysis (CSIA) yielded information on the success of the abiotic degradation of 1,1,1-TCA and indicated a heterogeneous spatio-temporal pattern of degradation. Finally, the obtained results show that mZVI slurries stabilized by guar gum can be prepared at pilot scale and directly injected into low permeable aquifers, indicating a significant removal of 1,1,1-TCA.

Stable carbon isotope analysis to distinguish biotic and abiotic degradation of 1,1,1-trichloroethane in groundwater sediments.

The fate and treatability of 1,1,1-TCA by natural and enhanced reductive dechlorination was studied in laboratory microcosms. The study shows that compound-specific isotope analysis (CSIA) identified an alternative 1,1,1-TCA degradation pathway that cannot be explained by assuming biotic reductive dechlorination. In all biotic microcosms 1,1,1-TCA was degraded with no apparent increase in the biotic degradation product 1,1-DCA. 1,1,1-TCA degradation was documented by a clear enrichment in (13)C in all biotic microcosms, but not in the abiotic control, which suggests biotic or biotically mediated degradation. Biotic degradation by reductive dechlorination of 1,1-DCA to CA only occurred in bioaugmented microcosms and in donor stimulated microcosms with low initial 1,1,1-TCA or after significant decrease in 1,1,1-TCA concentration (after∼day 200). Hence, the primary degradation pathway for 1,1,1-TCA does not appear to be reductive dechlorination via 1,1-DCA. In the biotic microcosms, the degradation of 1,1,1-TCA occurred under iron and sulfate reducing conditions. Biotic reduction of iron and sulfate likely resulted in formation of FeS, which can abiotically degrade 1,1,1-TCA. Hence, abiotic degradation of 1,1,1-TCA mediated by biotic FeS formation constitute an explanation for the observed 1,1,1-TCA degradation. This is supported by a high 1,1,1-TCA (13)C enrichment factor consistent with abiotic degradation in biotic microcosms. 1,1-DCA carbon isotope field data suggest that this abiotic degradation of 1,1,1-TCA is a relevant process also at the field site.