[Determination of six halogenated solvent residues in olive oil by headspace gas chromatography].

The residual amount of halogenated solvents in olive oil is an important indicator of its quality. The National Olive Oil Quality Standard GB/T 23347-2021 states that the residual amount of individual halogenated solvents in olive oil should be ≤0.1 mg/kg and that the total residual amount of halogenated solvents should be ≤0.2 mg/kg. COI/T.20/Doc. No. 8-1990, which was published by the International Olive Council, describes the standard method used for the determination of halogenated solvents in olive oil. Unfortunately, this method is cumbersome, has poor repeatability and low automation, and is unsuitable for the detection and analysis of residual halogenated solvents in large quantities of olive oil. At present, no national standard method for determining residual halogenated solvents in olive oil is available in China. Thus, developing simple, efficient, accurate, and stable methods for the determination of residual halogenated solvents in olive oil is imperative. In this paper, a method based on automatic headspace gas chromatography was established for the determination of residual halogenated solvents, namely, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, dibromochloromethane, tetrachloroethylene, and bromoform, in olive oil. The samples were processed as follows. After mixing, 2.00 g (accurate to 0.01 g) of the olive oil sample was added into a 20 mL headspace injection bottle and immediately sealed for headspace gas chromatography analysis. Blank virgin olive oil was used to prepare a standard working solution and the external standard method for quantification. The solvents used in the preparation of halogenated solvent standard intermediates were investigated and methanol was selected as a replacement for N,N-dimethylacetamide to prepare a halogenated solvent standard intermediate owing to its safety. The effects of different injection times (1, 2, 3, 4, 5, 6 s), equilibration temperatures (60, 70, 80, 90, 100, 110, 120 ℃), and equilibration times (4, 5, 8, 10, 20, 30, 40 min) of the headspace sampler on the detection of the residual amounts of the six halogenated solvents were investigated. The optimal injection time and equilibration temperature were 3 s and 90 ℃, respectively. The method demonstrated good analytical performance for the six halogenated solvents when the equilibration time was 30 min. A methodological study was conducted on the optimized method, and the results showed that the six halogenated solvents exhibited good linear relationships in the range of 0.002-0.200 mg/kg, with correlation coefficients of ≥0.9991. The limits of detection (LODs) and quantification (LOQs) of 1,1,1-trichloroethane and bromoform were 0.0006 and 0.002 mg/kg, respectively. The LODs and LOQs of chloroform, carbon tetrachloride, dibromochloromethane, and tetrachloroethylene were 0.0003 and 0.001 mg/kg, respectively. The average recoveries under different spiked levels were 85.53%-115.93%, and the relative standard deviations (n=6) were 1.11%-8.48%. The established method was used to analyze 13 olive oil samples available in the market. Although no halogenated solvents were detected in these samples, a limited number of samples does not represent all olive oils. Hence, monitoring residual halogenated solvents in olive oil remains necessary for its safe consumption. The LOQs of the method for the six halogenated solvents were significantly lower than that of the COI/T.20/Doc. No. 8-1990 standard method (0.02 mg/kg). In addition, the developed method can be conducted under short operation times with high precision and degree of automation as well as good accuracy. Thus, the proposed method is suitable for the determination and analysis of the residues of the six halogenated solvents in large batches of olive oil samples.

Machine learning-driven identification of air toxic combinations associated with asthma symptoms among elementary school children in Spokane, Washington, USA.

Air toxics are atmospheric pollutants with hazardous effects on health and the environment. Although methodological constraints have limited the number of air toxics assessed for associations with health and disease, advances in machine learning (ML) enable the assessment of a much larger set of environmental exposures. We used ML methods to conduct a retrospective study to identify combinations of 109 air toxics associated with asthma symptoms among 269 elementary school students in Spokane, Washington. Data on the frequency of asthma symptoms for these children were obtained from Spokane Public Schools. Their exposure to air toxics was estimated by using the Environmental Protection Agency's Air Toxics Screening Assessment and National Air Toxics Assessment. We defined three exposure periods: the most recent year (2019), the last three years (2017-2019), and the last five years (2014-2019). We analyzed the data using the ML-based Data-driven ExposurE Profile (DEEP) extraction method. DEEP identified 25 air toxic combinations associated with asthma symptoms in at least one exposure period. Three combinations (1,1,1-trichloroethane, 2-nitropropane, and 2,4,6-trichlorophenol) were significantly associated with asthma symptoms in all three exposure periods. Four air toxics (1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, BIS (2-ethylhexyl) phthalate (DEHP), and 2,4-dinitrophenol) were associated only in combination with other toxics, and would not have been identified by traditional statistical methods. The application of DEEP also identified a vulnerable subpopulation of children who were exposed to 13 of the 25 significant combinations in at least one exposure period. On average, these children experienced the largest number of asthma symptoms in our sample. By providing evidence on air toxic combinations associated with childhood asthma, our findings may contribute to the regulation of these toxics to improve children's respiratory health.

A magnetic molecularly imprinted polymer based on an eco-friendly deep eutectic solvent for the selective recognition of dichlorodiphenyl trichloroethane and its degradation products in fruits and vegetables.

A new magnetic molecularly imprinted polymer was successfully synthesized using a ternary deep eutectic solvent derived from caffeic acid-choline chloride-formic acid as a functional monomer, thymol-menthol deep eutectic solvent as a template, ethylene glycol dimethacrylate as a cross-linker, potassium peroxodisulfate as an initiator, and aqueous ethanol solution (90% (v/v)) as a porogen. The synthesized material was characterized and applied for magnetic solid-phase extraction of dichlorodiphenyl trichloroethane and its degradation products. Optimization of the extraction condition was carried out using the central composite design and response surface methodology. The good analytical performance of magnetic solid phase extraction/gas chromatography‒mass spectrometry using the proposed adsorbent shows a wide linear range of 0.07-500 ng g-1 with R2 greater than 0.992. Low detection limits and quantitation limits were observed in the ranges of 0.01-2.00 ng g-1 and 0.07-2.50 ng g-1, respectively. The precisions shown in terms of relative standard deviations were lower than 7.0% for intraday (n=5) and 8.6% for interday (n=5 × 3) experiments. The proposed method was applied for preconcentration and determination of dichlorodiphenyl trichloroethane and its degradation products in fruit and vegetable samples. The satisfactory recoveries of the real samples at three spiked concentrations were obtained in the range of 79.1%-110.9% with RSDs lower than 7.5%. The findings highlight the importance of developing efficient sorbents for the enrichment of persistent organic pollutants in food matrices.

Spatio-temporal distribution of organochlorine pesticides in agricultural soils of southeast China during 2014-2019.

Organochlorine pesticides (OCPs) are organic pollutants that are persistent and undegradable in the environment. To investigate their residual concentrations, spatial and temporal distributions, and the relationship with the crops planted, 12 individual OCPs in 687 soil samples from Jiangsu, Zhejiang and Jiangxi provinces of southeast China were examined. The detection frequencies of OCPs in the studied areas were 1.89%-64.9%. The concentrations of dichloro-diphenyl-trichloroethanes (DDTs), hexachlorocyclohexanes (HCHs), and endosulfans ranged from 0.01 to 5659 µg/kg, 0.03-3.58 µg/kg, and 0.05-3235 µg/kg, respectively. Jiangsu was mainly contaminated by p,p'-DDT, p,p'-DDD and endosulfan sulfate, Zhejiang was more polluted by OCPs except δ-HCH, and Jiangxi was more vulnerable to the contamination of OCPs except o,p'-DDE. The partial least-squares discrimination analysis (PLS-DA) model with RX2 36.3-36.8% revealed that compounds with similar chemical properties tended to appear in the same year and month. All crop lands were polluted by DDTs and Endosulfans. The highest concentrations of DDTs and Endosulfans were found in citrus and vegetable fields, respectively. This study offers new insight into the layout and partitioning of OCPs in agricultural land and into insecticide management on public health and ecological safety.

Age at menarche and chemical exposure: per- and polyfluoroalkyl substances (PFAS), dichloro-diphenyl-trichloroethane (DDT), dichloro-diphenyl-dichloroethylene (DDE), and polychlorinated biphenyls (PCBs).

CONTEXT: Humans are now exposed to a multitude of chemicals throughout the life course, some of which may affect growth and development owing to their endocrine-like activity. OBJECTIVE: To assess the relationship of suspect toxicants to maturation, specifically to age at menarche. METHODS: We conducted two systematic reviews of age at menarche and PFOA, PFOS, PCBs and DDE/DDT based on publications indexed by pubmed. RESULTS: 16 unique reports were identified. Most studies of PFOA and PFOS reported either no association or delays in the age at menarche; only one reported an earlier age. Studies of DDT and DDE were more mixed. Reports on PCBs varied by PCB congener group with an equal number of them reporting delays and no association but one an acceleration. Sources of variation in results include the timing of exposure assessment (prenatal vs. postnatal), level of the toxicant, and sample size. No obvious pattern to the variation in results could be tied to those sources of variation. CONCLUSION: The absence of consistent evidence from multiple reports of earlier age at menarche suggests that these toxicants may not be responsible for accelerated sexual maturation in girls. However, human populations naturally vary in the variety and levels of exposure, making the comparison of studies difficult. Further, studies vary in methodology, complicating aggregation of results and generalisations.

[Method for the determination of tetrachloromethane, trichloroethane, 1,1,2-trichloroethane, and tetrachloroethene in the air at workplaces]. / Metoda oznaczania tetrachlorometanu, trichloroetenu, 1,1,2-trichloroetanu i tetrachloroetenu w powietrzu na stanowiskach pracy.

BACKGROUND: Chemical substances from the halogenated aliphatic hydrocarbons group are used in industry, e.g., as intermediates in syntheses, auxiliaries, solvents in degreasing processes, and laboratory tests. Due to their harmful effects on human health and the environment, their use is often banned or limited to certain industrial uses only. MATERIAL AND METHODS: A sorbent tube containing 2 layers (100/50 mg) of coconut shell charcoal was used as a sampler for air sampling. Gas chromatography-mass spectrometry technique and the use of HP-5MS column (30 m × 0.25 mm × 0.25 µm), an oven temperature ramp program from 40°C to 250°C and selected ion monitoring mode were chosen for the determination. RESULTS: The established chromatographic conditions enable the simultaneous determination of tetrachloromethane, trichlorethane, 1,1,2-trichloroethane and tetrachloroethene in the concentration range 2-100 µg/ml. The average desorption coefficients obtained were: 0.97 for tetrachloromethane, 0.96 for trichloroethene, 0.96 for 1,1,2-trichloroethane and 0.96 for tetrachloroethene. CONCLUSIONS: The calculation of the substance concentration in the analyzed air requires the determination of the amount of substances trapped by the sorbent tube, the desorption coefficient and the air sample volume. Adequate dilution of the extract makes it possible to determine tetrachloromethane, trichloroethene, 1,1,2-trichloroethane and tetrachloroethene in ranges corresponding to 0.1-2 times the maximum admissible concentrations in the workplace air. This article discusses the issues occupational safety and health, which are the subject matter of health sciences and environmental engineering research. Med Pr. 2023;74(1):53-62.

National temporal trend for organophosphate pesticide DDT exposure and associations with chronic kidney disease using age-adapted eGFR model.

Whilst certain environmental organochlorine pesticide exposure may still pose significant burden, the associations between dichloro-diphenyl-trichloroethane (DDT) and chronic kidney disease (CKD) remain disputable notwithstanding the potentially inaccurate disease definition between age groups. National DDT exposure burden atlas was depicted from 92,061 participants by measuring their serum concentrations of DDT congeners and major metabolite in the US from 1999 to 2016. Temporal analyses of these toxicant exposure suggested that although serum DDT concentrations exhibited recent decline, the detection rates remain up to 99.8% every year, posing great concern for exposure risk. A total of 3,039 US adults were further included from these participants demonstrating the weighted CKD prevalence of 40.2% using the new age-adapted CKD-EPI40 model compared to 28.0% using the current CKD-EPI method. After adjustment for covariates, logistic regression model results showed individual metabolites and total DDT burden were positively, yet monotonically, associated with risk of CKD incidence (P-trend for all < 0.05), particularly among adults 40 years of age and older. Much heightened renal disease risk was also observed with high DDT exposure (OR, 1.55; 95 % CI, 1.11-2.15) in those who were hypertensive (P for heterogeneity < 0.001) but not with diabetes. The current high DDT exposure risk combined with elevated probability for CKD incidence call for health concerns and management for the environmentally persistent pollutants.

Impact of Environmental Risk Factors on Mitochondrial Dysfunction, Neuroinflammation, Protein Misfolding, and Oxidative Stress in the Etiopathogenesis of Parkinson's Disease.

As a prevalent progressive neurodegenerative disorder, Parkinson's disease (PD) is characterized by the neuropathological hallmark of the loss of nigrostriatal dopaminergic (DAergic) innervation and the appearance of Lewy bodies with aggregated α-synuclein. Although several familial forms of PD have been reported to be associated with several gene variants, most cases in nature are sporadic, triggered by a complex interplay of genetic and environmental risk factors. Numerous epidemiological studies during the past two decades have shown positive associations between PD and several environmental factors, including exposure to neurotoxic pesticides/herbicides and heavy metals as well as traumatic brain injury. Other environmental factors that have been implicated as potential risk factors for PD include industrial chemicals, wood pulp mills, farming, well-water consumption, and rural residence. In this review, we summarize the environmental toxicology of PD with the focus on the elaboration of chemical toxicity and the underlying pathogenic mechanisms associated with exposure to several neurotoxic chemicals, specifically 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP), rotenone, paraquat (PQ), dichloro-diphenyl-trichloroethane (DDT), dieldrin, manganese (Mn), and vanadium (V). Our overview of the current findings from cellular, animal, and human studies of PD provides information for possible intervention strategies aimed at halting the initiation and exacerbation of environmentally linked PD.

Phyto-Fenton remediation of a dichloro-diphenyl-trichloroethane contaminated site in Ha Tinh Province, Vietnam.

A field trial was conducted at a site in Cam Binh commune, Ha Tinh province, Vietnam, highly contaminated with organo-pesticides. The phyto-Fenton process was applied to remove pesticide residues in soils. In addition to magnetite (Fe3O4) materials added to the soils, fertilizers and elicitors for oxidative burst were also added in the different experimental treatments. Dichloro-diphenyl-trichloroethane (DDT) and isomers were removed in all experimental lots. The removal efficiency was highest in lot B1, a site where only iron materials were added. The removal efficiency and the final content of DDTs in B1 were 98.4% and 0.009 mg kg-1, respectively. In the presence of elicitors, the conversion of DDT to dichloro-diphenyl-dichloroethylene was more favorable. Analysis of soil properties indicated that the phyto-Fenton process can occur at neutral soil pH, and when there are only small changes in soil organic carbon content and cation exchange capacities. Shifts in the composition of the microbial communities were observed. Further studies on the interactions between materials added to soil, plants, and the soil microbiome are needed to understand the mechanism of action of the phyto-Fenton process during soil remediation.

Geobacter sp. Strain IAE Dihaloeliminates 1,1,2-Trichloroethane and 1,2-Dichloroethane.

Chlorinated ethanes, including 1,2-dichloroethane (1,2-DCA) and 1,1,2-trichloroethane (1,1,2-TCA), are widespread groundwater contaminants. Enrichment cultures XRDCA and XRTCA derived from river sediment dihaloeliminated 1,2-DCA to ethene and 1,1,2-TCA to vinyl chloride (VC), respectively. The XRTCA culture subsequently converted VC to ethene via hydrogenolysis. Microbial community profiling demonstrated the enrichment of Geobacter 16S rRNA gene sequences in both the XRDCA and XRTCA cultures, and Dehalococcoides mccartyi (Dhc) sequences were only detected in the ethene-producing XRTCA culture. The presence of a novel Geobacter population, designated as Geobacter sp. strain IAE, was identified by the 16S rRNA gene-targeted polymerase chain reaction and Sanger sequencing. Time-resolved population dynamics attributed the dihaloelimination activity to strain IAE, which attained the growth yields of 0.93 ± 0.06 × 107 and 1.18 ± 0.14 × 107 cells per µmol Cl- released with 1,2-DCA and 1,1,2-TCA as electron acceptors, respectively. In contrast, Dhc growth only occurred during VC-to-ethene hydrogenolysis. Our findings discover a Geobacter sp. strain capable of respiring multiple chlorinated ethanes and demonstrate the involvement of a broader diversity of organohalide-respiring bacteria in the detoxification of 1,2-DCA and 1,1,2-TCA.

Using 1,1,1-Trichloroethane degradation data to understand NAPL dissolution and solute transport at real sites.

Analytical and numerical models describing the evolution of contaminant concentrations in the plume associated with the dissolution of NAPL source and degradation processes were presented in the literature. At real sites and particularly in complex aquifers like chalk, it is difficult to understand how the sources of contaminants evolve with time. 1,1,1-Trichloroethane (1,1,1-TCA) is one of the few compounds with a well-known hydrolysis constant, that can help to improve knowledge of the contaminant sources and transport rates of dissolved contaminants in groundwater by dating the spill. In this work, different scenarios that could explain the evolution of the concentrations of 1,1,1-TCA and its degradation product 1,1-Dichloroethene (1,1-DCE) at a real contaminated site were investigated by analytical and numerical modelling. The results show that (1) the peaks of concentration time series do not correspond to a single contamination event even in the case of a complex medium, (2) the multiphasic behavior of the concentration time series is dictated by the dissolution in a heterogeneous medium, and (3) the persistence of the concentrations can arise from a small residual organic phase or transport in dual domain medium.

Polyacrylic acid-b-polyptyrene covered Ni/Fe nanoparticles to remove 1,1,1-trichloroethane in water.

A new material, polyacrylic acid-b-polyptyrene (PAA-b-PS) covered Ni/Fe nanoparticles (PAA-b-PS-nZVI-Ni), was developed and evaluated for the selective dechlorination of 1,1,1-trichloroethane (1,1,1-TCA) in the presence of potential interferents. The average size of the PAA-b-PS coated Fe/Ni bimetallic nanoparticles was approximately 50 nm, which resulted from agglomeration prevention by PAA-b-PS. The removal efficiency of 1,1,1-TCA by an optimal dose with a 1.0 g/L Fe/Ni (Ni/Fe = 2 wt%) and 0.5 g/L PAA-b-PS-coated concentration was higher (87.5%) than that of bare Fe/Ni (60%). The pseudo-first-order rate constant (Kobs) of 1,1,1-TCA removal by PAA-b-PS-nZVI-Ni was 0.0142 min-1 within 240 min. Comparatively, the Kobs values of 1,1,1-TCA removal by other materials (Fe, pure bimetallic Fe/Ni, PAA-b-PS-Fe) were only 0.003, 0.0052 and 0.0103 min-1, respectively. The 1,1,1-TCA removal efficacy by PAA-b-PS-nZVI-Ni showed no obvious gap regardless of pH or various common inorganic anions (NO3-, HCO3- and SO42-) at different concentrations. However, humic acid (HA) had great influence on the degradation of 1,1,1-TCA. In conclusion, PAA-b-PS-covered Ni/Fe nanoparticles with its selectivity high effectiveness could be used as one remedial agent for the degradation of 1,1,1-TCA in water.

A Synergistic Platform for Continuous Co-removal of 1,1,1-Trichloroethane, Trichloroethene, and 1,4-Dioxane via Catalytic Dechlorination Followed by Biodegradation.

Groundwater co-contaminated with 1,4-dioxane, 1,1,1-trichloroethane (TCA), and trichloroethene (TCE) is among the most urgent environmental concerns of the U.S. Department of Defense (DoD), U.S. Environmental Protection Agency (EPA), and industries related to chlorinated solvents. Inspired by the pressing need to remove all three contaminants at many sites, we tested a synergistic platform: catalytic reduction of 1,1,1-TCA and TCE to ethane in a H2-based membrane palladium-film reactor (H2-MPfR), followed by aerobic biodegradation of ethane and 1,4-dioxane in an O2-based membrane biofilm reactor (O2-MBfR). During 130 days of continuous operation, 1,1,1-TCA and TCE were 95-98% reductively dechlorinated to ethane in the H2-MPfR, and ethane served as the endogenous primary electron donor for promoting 98.5% aerobic biodegradation of 1,4-dioxane in the O2-MBfR. In addition, the small concentrations of the chlorinated intermediate from the H2-MPfR, dichloroethane (DCA) and monochloroethane (MCA), were fully biodegraded through aerobic biodegradation in the O2-MBfR. The biofilms in the O2-MBfR were enriched in phylotypes closely related to the genera Pseudonocardia known to biodegrade 1,4-dioxane.

Long-term cometabolic transformation of 1,1,1-trichloroethane and 1,4-dioxane by Rhodococcus rhodochrous ATCC 21198 grown on alcohols slowly produced by orthosilicates.

Long-term cometabolic transformation of 1,1,1-trichlorethane (1,1,1-TCA) and 1,4-dioxane (1,4-D) was achieved using slow release compounds (SRCs) as growth substrates for pure cultures of Rhodococcus rhodochrous ATCC 21198 (ATCC strain 21198). Resting cell transformation tests showed 1,4-D transformation occurred without a lag phase for cells grown on 2-butanol, while an induction period of several hours was required for 1-butanol grown cells. These observations were consistent with activity-based labeling patterns for monooxygenase hydroxylase components and specific rates of tetrahydrofuran (THF) degradation. 1,1,1-TCA and 1,4-D degradation rates for alcohol-grown cells were slower than those for cells grown on gaseous alkanes such as isobutane. Batch metabolism and degradation tests were performed, in the presence of 1,1,1-TCA and 1,4-D, with the growth of ATCC strain 21198 on alcohols produced by the hydrolysis of orthosilicates. Three orthosilicates were tested: tetrabutylorthosilicate (TBOS), tetra-s-butylorthosilicate (T2BOS), and tetraisopropoxysilane (T2POS). The measured rates of alcohol release in poisoned controls depended on the orthosilicate structure with TBOS, which produced a 1° alcohol (1-butanol), hydrolyzing more rapidly than T2POS and T2BOS, that produced the 2° alcohols 2-butanol and 2-propanol, respectively. The orthosilicates were added as light non-aqueous phase liquids (LNAPLs) with ATCC strain 21198 and formed dispersed droplets when continuously mixed. Continuous rates of oxygen (O2) consumption and carbon dioxide (CO2) production confirmed alcohol metabolism by ATCC strain 21198 was occurring. The rates of metabolism (TBOS > T2POS > T2BOS) were consistent with the rates of alcohol release via abiotic hydrolysis. 1,4-D and 1,1,1-TCA were continuously transformed in successive additions by ATCC strain 21198 over 125 days, with the rates highly correlated with the rates of metabolism. The metabolism of the alcohols was not inhibited by acetylene, while transformation of 1,4-D and 1,1,1-TCA was inhibited by this gas. As acetylene is a potent inactivator of diverse bacterial monooxygenases, these results suggest that monooxygenase activity was required for the observed cometabolic transformations but not for alcohol utilization. Alcohol concentrations in the biologically active reactors were maintained below the levels of detection, indicating they were metabolized rapidly after being produced. Much lower rates of O2 consumption were observed in the reactors containing T2BOS, which has benefits for in-situ bioremediation. The results illustrate the importance of the structure of the SRC when developing passive aerobic cometabolic treatment systems.

Sex differences in the association of measures of sexual maturation to common toxicants: Lead, dichloro-diphenyl-trichloroethane (DDT), dichloro-diphenyl-dichloroethylene (DDE), and polychlorinated biphenyls (PCBs).

Many studies of human toxicant exposure examine the hypothesis that human sexual maturation can be affected through endocrine disruption. Within this body of literature there is significant variation in the findings. Variation may be related to the differential effects by toxicants between males and females as well as variation in sample size, toxicant levels, and the timing of exposure. We review sexual maturation outcomes between males and females when exposed to lead, dichlorodiphenyldichloroethylene (DDE), dichloro-diphenyl-trichloroethane (DDT), and polychlorinated biphenyls (PCBs) using a systematic process to gather peer-reviewed studies published from January 1994 through December 2019 on the NCBI website's PubMed search engine. The review includes 34 studies, some comprised of multiple analyses, to compare effects on sexual maturation by sex. The analysis shows that both boys and girls have delayed sexual maturation in relation to lead exposure. There are differences in the direction of effects associated with DDE/DDT and PCB exposure in boys and girls. PCBs exist as congeners of many structural forms, and that variation is considered in this review. Dioxin-like and non-dioxin-like PCBs exposure directionality differed between boys and girls as well. Future investigations into the basis of sex variation in DDE/DDT and PCB relationships to sexual maturation are warranted.

Long-Term Continuous Co-reduction of 1,1,1-Trichloroethane and Trichloroethene over Palladium Nanoparticles Spontaneously Deposited on H2-Transfer Membranes.

1,1,1-Trichloroethane (1,1,1-TCA) and trichloroethene (TCE) are common recalcitrant contaminants that coexist in groundwater. H2-induced reduction over precious-metal catalysts has proven advantageous, but its application to long-term continuous treatment has been limited due to poor H2-transfer efficiency and catalyst loss. Furthermore, catalytic reductions of aqueous 1,1,1-TCA alone or concomitant with TCE catalytic co-reductions are unstudied. Here, we investigated 1,1,1-TCA and TCE co-reduction using palladium nanoparticle (PdNP) catalysts spontaneously deposited on H2-transfer membranes that allow efficient H2 supply on demand in a bubble-free form. The catalytic activities for 1,1,1-TCA and TCE reductions reached 9.9 and 11 L/g-Pd/min, values significantly greater than that reported for other immobilized-PdNP systems. During 90 day continuous operation, removals were up to 95% for 1,1,1-TCA and 99% for TCE. The highest steady-state removal fluxes were 1.5 g/m2/day for 1,1,1-TCA and 1.7 g/m2/day for TCE. The major product was nontoxic ethane (94% selectivity). Only 4% of the originally deposited PdNPs were lost over 90 days of continuous operation. Documenting long-term continuous Pd-catalyzed dechlorination at high surface loading with minimal loss of the catalyst mass or activity, this work expands understanding of and provides a foundation for sustainable catalytic removal of co-existing chlorinated solvents.

Mosquitocidal activity of p,p'-difluoro-diphenyl-trichloroethane (DFDT).

New insecticides are urgently needed for the control of arthropod vectors of public health diseases. As resistance to many insecticides used for the control of public health pests is ubiquitous, all available chemistries should be evaluated for their potential to effectively control both insecticide-susceptible and insecticide-resistant strains of mosquitoes. This study aimed to evaluate p-p'-difluoro-diphenyl-trichloroethane (DFDT) as a mosquito control technology and relate its activity to that of DDT. We found that topical DFDT was significantly less toxic than DDT to both pyrethroid-susceptible and pyrethroid-resistant strains of Anopheles gambiae and Aedes aegypti. Direct nervous system recording from Drosophila melanogaster CNS demonstrated that DFDT is approximately 10-times less potent than DDT at blocking nerve firing, which may explain its relatively lower toxicity. DFDT was shown to be at least 4500 times more vapor-active than DDT, with an LC50 in a vapor toxicity screening assay of 2.2 µg/cm2. Resistance to DFDT was assessed in two mosquito strains that possess target-site mutations in the voltage-gated sodium channel and upregulated metabolic activity. Resistance ratios for Akdr (An. gambiae) and Puerto Rico (Ae. aegypti) strains were 9.2 and 12.2, respectively. Overall, this study demonstrates that DFDT is unlikely to be a viable public health vector control insecticide.

Two distinct Dehalobacter strains sequentially dechlorinate 1,1,1-trichloroethane and 1,1-dichloroethane at a field site treated with granular zero valent iron and guar gum.

Chlorinated ethanes are environmental pollutants found frequently at many contaminated industrial sites. 1,1,1-Trichloroethane (1,1,1-TCA) can be dechlorinated and detoxified via abiotic transformation or biologically by the action of dechlorinating microorganisms such as Dehalobacter (Dhb). At a field site, it is challenging to distinguish abiotic vs. biotic mechanisms as both processes share common transformation products. In this study, we evaluated using the Dhb 16S rRNA gene and specific reductive dehalogenase genes as biomarkers for 1,1,1-TCA and 1,1-dichloroethane (1,1-DCA) dechlorination. We analyzed samples from laboratory groundwater microcosms and from an industrial site where a mixture of granular zero valent iron (ZVI) and guar gum was injected for 1,1,1-TCA remediation. Abiotic and biotic transformation products were monitored and the changes in dechlorinating organisms were tracked using quantitative PCR (qPCR) with primers targeting the Dhb 16S rRNA gene and two functional genes cfrA and dcrA encoding enzymes that dechlorinate 1,1,1-TCA to 1,1-DCA and 1,1-DCA to chloroethane (CA), respectively. The abundance of the cfrA- and dcrA-like genes confirmed that the two dechlorination steps were carried out by two distinct Dhb populations at the site. The biomarkers used in this study proved useful for monitoring different Dhb populations responsible for step-wise dechlorination and tracking biodegradation of 1,1,1-TCA and 1,1-DCA where both abiotic (e.g., with ZVI) and biotic processes co-occur.

Characterization of bimetallic Fe/Ni nanoparticles supported by amphiphilic block copolymer and its application in removal of 1,1,1-trichloroethane in water.

The iron and nickel bimetallic nanoparticles supported by the block copolymer polystyrene-block-poly (acrylic acid) (PS-b-PAA-nZVI-Ni) were synthesized successfully and were applied to assess the degradation of 1,1,1-trichloroethane (1,1,1-TCA) in water. An optimal dose of Ni loading was 2 wt%, while an optimal mass ratio of PS-b-PAA to Ni/Fe, i.e., 0.5:1, at which the dechlorination efficiency was a maximum. The size of PS-b-PAA-nZVI-Ni nanoparticles (average size ~ 50 nm) was three times smaller than that of nZVI-Ni due to the prevention of agglomeration of the resultant zerovalent iron nanoparticles by PS-b-PAA. In the applying aspect, the pseudo-first-order rate constant (Kobs) of 1,1,1-TCA removal by PS-b-PAA-nZVI-Ni was 0.0142 min-1 within 240 min, which was approximately five times higher than nZVI. Meanwhile, PS-b-PAA-supported nZVI-Ni nanoparticles penetrated much deeper in quartz sand columns than nZVI-Ni nanoparticles, indicating PS-b-PAA had significant influence on nZVI transport. The findings from this study suggested that PS-b-PAA-nZVI-Ni, with its high reactivity, selective screening for 1,1,1-TCA, could be one significant potential for use as remedial agent to treat chlorinated solvents in water.