[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.

Oxidative stress and pro-inflammatory cytokines following perchloroethylene exposure in young female dry-cleaning workers.

BACKGROUND: The involvement of Perchloroethylene (PCE) in the development of autoimmune diseases has been reported. However, few studies investigated immunotoxicity in PCE-exposed workers. OBJECTIVE: To study changes in the oxidative stress and cytokine profile of young female dry-cleaning workers exposed to PCE. METHODS: Thirty-eight exposed workers and 38 unexposed controls were recruited. All the participants were young nonsmoker females. Individual interviews were conducted by a physician. Blood samples were collected and hematological tests were performed by an automated Coulter Counter. Plasma PCE levels were determined using gas chromatography/flame ionization detection. Plasma total antioxidant capacity (TAC), Catalase (CAT), Superoxide dismutase (SOD), and Malondialdehyde (MDA) levels were measured using the colorimetric method. The levels of plasma cytokines interleukin-1ß (IL-1ß), IL-2, IL-4, IL-6, IL-8, tumor necrosis factor-α (TNF-α) and interferon-γ (IFN-γ) were measured by commercially kits. RESULTS: The levels of plasma PCE averaged 561±96 ng/ml in the exposed group compared with 1.3±0.5 ng/ml in the controls. The hematological tests failed to find abnormalities in the exposed workers. Exposed workers presented significantly increased plasma levels of MDA, SOD and CAT. There were no significant differences between the two groups for level of plasma TAC. Significantly increased plasma IL-1ß and TNF-α and decreased IL-2 and IL-8 levels were seen in the exposed workers. There were no significant differences between the two groups for IL-4, IL-6, and IFN-γ. CONCLUSION: PCE exposure resulted in changed cytokine profile in dry-cleaning workers, suggesting the potential immunotoxicity of PCE at low exposure levels.

Occupational exposures and cancer risk in commercial laundry and dry cleaning industries: a scoping review.

BACKGROUND: The laundry and dry cleaning industries are critical for maintaining cleanliness and hygiene in our daily lives. However, they have also been identified as sources of hazardous chemical exposure for workers, leading to potentially severe health implications. Despite mounting evidence that solvents like perchloroethylene and trichloroethylene are carcinogenic, they remain commonly used in the industry. Additionally, while alternative solvents are increasingly being utilized in response to indications of adverse health and environmental effects, there remains a significant gap in our understanding of the potential risks associated with exposure to these new agents. METHODS: This study aims to identify gaps in the literature concerning worker exposure to contemporary toxic chemicals in the laundry and dry cleaning industry and their associated carcinogenic risks. A scoping review of peer-reviewed publications from 2012 to 2022 was conducted to achieve this objective, focusing on studies that detailed chemical exposures, sampling methods, and workers within the laundry and dry cleaning sector. RESULTS: In this scoping review, 12 relevant papers were assessed. A majority (66%) examined perchloroethylene exposure, with one notable finding revealing that biomarkers from dry cleaners had significant micronuclei frequency and DNA damage, even when exposed to PCE at levels below occupational exposure limits. Similarly, another study supported these results, finding an increase in early DNA damage among exposed workers. Separate studies on TCE and benzene presented varied exposure levels and health risks, raising concern due to their IARC Group 1 carcinogen classification. Information on alternative solvents was limited, highlighting gaps in health outcome data, exposure guidelines, and carcinogenic classifications. CONCLUSION: Research on health outcomes, specifically carcinogenicity from solvent exposure in dry cleaning, is limited, with 66% of studies not monitoring health implications, particularly for emerging solvents. Further, findings indicated potential DNA damage from perchloroethylene, even below set occupational limits, emphasizing the need to reevaluate safety limits. As alternative solvents like butylal and high-flashpoint hydrocarbons become more prevalent, investigations into the effects of their exposure are necessary to safeguard workers' health. This scoping review is registered with the Open Science Framework, registration DOI: https://doi.org/10.17605/OSF.IO/Q8FR3 .

[Study on formulation of standard limits for trichloroethylene and tetrachloroethylene in "Standards for indoor air quality（GB/T 18883-2022）" in China].

There are clear indoor air pollution sources of trichloroethylene and tetrachloroethylene. A large number of epidemiological evidence has confirmed their carcinogenic toxicity and non-carcinogenic toxicity. Several countries and international organizations have paid attention to indoor air trichloroethylene and tetrachloroethylene. It has been also assessed that there should be certain potential health risk of indoor air trichloroethylene and tetrachloroethylene in China. Based on the latest research results of health risk assessment of indoor air trichloroethylene and tetrachloroethylene, the "Standards for indoor air quality (GB/T 18883-2022)" added trichloroethylene and tetrachloroethylene as indicators. The index limit of trichloroethylene is 6 µg/m3 for an 8-hour average concentration. The index limit of tetrachloroethylene is 120 µg/m3 for an 8-hour average concentration. The technical contents related to the determination of the standard limits of trichloroethylene and tetrachloroethylene in indoor air were analyzed and discussed, including the sources, the exposure, the health effects, the determination of the limit values, and the recommendations for standard implementation. It also proposed recommendations for the implementation of"Standards for indoor air quality (GB/T 18883-2022)".

The effect of sand fractional wettability on SDBS-enhanced PCE immiscible mobilization in porous media.

Fractional wettability is common in the dense non-aqueous phase liquids (DNAPL) contaminated sites. However, it is still unclear how fractional wettability affects surfactant-enhanced DNAPL immiscible mobilization in saturated porous media. The macro-contact angle of the fractional wettability media was measured. The results of column experiments showed that the entrapped tetrachloroethene (PCE) saturations after sodium dodecyl benzene sulfonate (SDBS) flooding were lower in the media where NAPL-wet sand was present compared with those in water-wet media. In the media which contained 25% octadecyltrichlorosilane (OTS)-treated sand, the entrapped PCE saturations decreased to the minimum, and the decrease was much larger in fine sand media. The SDBS-enhanced PCE recoveries were jointly affected by fractional wettability, particle size, and interfacial tension (IFT). When NAPL-wet sand was present and SDBS concentration was just 0.125 g⋅L-1, the SDBS-enhanced PCE recoveries increased significantly. As the SDBS concentration continues to increase to 0.5 g⋅L-1, they only increased slightly. In the fine sand media, the SDBS-enhanced PCE recoveries were higher, and they increased more obviously with the increase of NAPL-wet sand fractions. The influence weight of fractional wettability on SDBS-enhanced PCE recoveries was the largest (47.09%) under the experimental conditions. These findings indicate that it is important to consider fractional wettability characteristics when establishing a DNAPL immiscible mobilization strategy, because it is not sufficient to consider only IFT reduction, especially in media with finer pore structures.

Volatile organic compounds in water matrices: Recent progress, challenges, and perspective.

Volatile organic compounds (VOCs) are a group of organic compounds that have a molecular structure containing carbon and their chemical properties allow them to be easily converted to steam and gas and remain for a long period of time and have diverse effects on the environment. The purpose of this study is determination of the concentration of VOCs such as alachlor, anthracene, benzene, bromoform, chloroform, heptachlor, isophorone, tetrachloroethylene, γ -chlordane, toluene, etc. in water matrices. The results showed that among studies conducted on VOCs, the concentration of tetrachloroethylene, m,p-xylene, and toluene were at the top in water matrices, and the lowest average concentrations were found in chloroform, anthracene, and butyl benzyl phthalate. In terms of VOC concentrations in water matrices, China was the most polluted country. Moreover, the data analysis indicated that China was the only country with carcinogenic risk. A Monte-Carlo simulation showed that although the averages obtained were comparable to the acceptable limits, for heptachlor, the maximum carcinogenic risk is achieved at a level that is slightly over the limit, only 25% from the population being exposed.

Expanding the calibration range of compound-specific chlorine isotope analysis by the preparation of a 37 Cl-enriched tetrachloroethylene.

RATIONALE: The recent development of reliable GC/qMS methods for δ37 Cl compound-specific stable isotope analysis (CSIA) paves the way for dual carbon-chlorine isotope analysis of chlorinated ethenes and thus allows deeper insights into underlying transformation processes/mechanisms. A two-point calibration is indispensable for the precise and correct conversion of raw data to the international δ37 ClSMOC scale. The currently available calibration standards for tetrachloroethylene (PCE) span only a very narrow range from -2.52‰ (EIL2) to +0.29‰ (EIL1), which is considerably smaller than observed δ37 Cl isotope enrichment in (bio-)transformation studies (up to 12‰). METHODS: We describe the preparation and evaluation of a new 37 Cl-enriched PCE standard to avoid bias in δ37 Cl CSIA arising from extrapolation beyond the calibration range. The preparation comprised: (i) partial PCE reduction by zero-valent zinc in a system of PCE, ethanol (initial volume ratio 3/5) and trace amounts of water followed by (ii) liquid-liquid extraction and (iii) a subsequent fractional distillation to purify the 37 Cl-enriched PCE. RESULTS: The obtained PCE (PCEenriched ) showed a purity of 98.8% (mole fraction) and a δ37 ClSMOC value of +10.8 ± 0.5‰. The evaluation of an experimental dataset with and without extrapolation showed no significant variation. CONCLUSIONS: The new PCE standard (PCEenriched ) expands the calibration range to 13.3‰ (previously 2.8‰) and thus prevents potential bias introduced by extrapolation beyond the calibration range.

Air pollution, children's academic achievement and the potential mediating role of preterm birth.

INTRODUCTION: Previous research has observed relationships between higher prenatal exposure to air pollutants and neurodevelopmental and academic outcomes later in childhood. Identifying intermediate outcomes mediating this relationship would inform prevention and intervention efforts. We aimed to investigate if previously observed associations between prenatal exposure to common urban air pollutants, diesel and perchloroethylene, and performance on third grade standardized tests were mediated through increased risk of preterm birth. METHODS: Data from the 1994-1998 birth cohorts within the New York City Longitudinal Study of Early Development were included in this analysis. Exposure was determined by linking the mother's residence at the time of delivery to the U.S. EPA's 1996 National Air Toxic Assessment of estimated ambient concentrations of diesel and perchloroethylene. Children's third grade standardized math and language tests were used as the markers for academic achievement. Missing data on covariates were imputed, while participants with missing information on gestational age and test scores were excluded. Linear regression models and causal mediation analysis were used to examine potential mediation by preterm birth. RESULTS: In total, 187,723 and 196,122 participants were included in language and math analyses, respectively. Children with exposure to the fourth quartile of diesel or perchloroethylene had approximately 0.03 (95%CI: 0.02, 0.04) lower math z-scores when compared to individuals with exposure in the first quartile, although there was no consistent decreasing trend in math z-scores over increasing quartiles of diesel or perchloroethylene. We did not find evidence of mediation by preterm birth or exposure-mediator interaction in our models. CONCLUSION: We did not find evidence that observed relationships between exposure to common urban air pollutants and test z-scores in childhood were mediated through an increased risk of preterm birth. This suggests other pathways between early exposure to air pollution and neurodevelopment should be investigated with causal mediation approaches.

Physisorption of trichloroethylene and tetrachloroethylene on novel zeta arsenene nanotubes - A first-principles study.

The structural stability of novel ζ-arsenene nanotubes (ζ-AsNT) is studied based on the density functional theory framework and is used as a base material for the detection of trichloroethylene and tetrachloroethylene vapours. The formation energy of ζ-AsNT is found to be -4.321 eV/atom and the energy band gap is 0.304 eV. Besides, the changes in the electronic properties of ζ-AsNT are explored with regard to the projected density of states, charge transfer, and electron density difference. The bandgap energy decreases for hollow site orientation to 0.205 and 0.204 eV for trichloroethylene and tetrachloroethylene vapours and increases for the valley and top site orientations. The adsorption energies were maximum for the valley site orientation of target molecules onto ζ-AsNT (01.165 and -1.513 eV for trichloroethylene and tetrachloroethylene, respectively). Moreover, the target vapours trichloroethylene and tetrachloroethylene are physisorbed on ζ-AsNT enabling the recycling of base substrate for continuous operation. The average energy gap changes vary from 18 to 32.9% depending on adsorption sites. The variation in the average energy gap owing to adsorption of trichloroethylene and tetrachloroethylene indicates the chemo-sensing nature of ζ-AsNT. The current report lays the inroads in the development of a new sensing element for the detection of chloroethylene molecules.

Density-modification displacement using colloidal biliquid aphron for entrapped DNAPL contaminated aquifer remediation.

Colloidal biliquid aphron (CBLA) is a strong density modifier for dense nonaqueous phase liquids (DNAPLs). However, the underlying mechanisms responsible for density modification and displacement is not yet clear. Here, a series of batch column and sandbox experiments were conducted to achieve substantial removal and irreversible density reduction of tetrachloroethylene (PCE). The mass of PCE retained in the column and sandbox was less than 1% under suitable injection conditions, and the density of PCE in the effluent was less than that of water (fluctuated in the range of 0.74-0.96 g/cm3). The displacement process was controlled by the high viscosity ratio of CBLA to PCE (52.3). The emulsified and dissolved phase of PCE formed after reaction with CBLA, and the light nonaqueous phase liquid (LNAPL) phase formed after injecting demulsifier solution. The phase analysis played a significant role in monitoring the changes in concentration and density of PCE. The density-modification displacement technique using CBLA reduced the mass of residual PCE by a factor of 165 compared to surfactant flushing, and there was no risk of downward migration of PCE. This study contributes to a better remediation of entrapped DNAPL in contaminated aquifer.

The perchloroethylene-induced toxicity in dry cleaning workers lymphocytes through induction of oxidative stress.

Evaluation of the compounds and metabolites, and studying their side effects in the workplace is essential. This study was designed to evaluate the exposure of dry  cleaning workers to perchloroethylene (PEC), and its liver and kidney damage, and oxidative stress in B-lymphocytes isolated from the workers. Blood samples were evaluated for liver (alanine transaminase [ALT] and aspartate transaminase [AST]) and kidney (BUN and creatinine) markers. For measurement of PEC, exhaled, personal, and ambient air samples were collected and analyzed gas chromatography (GC-FID) through the NIOSH 1003 and 3704 methods. Also, the parameters of oxidative stress including the level of reactive oxygen species (ROS), glutathione (GSH), oxidized glutathione (GSSG), and lipid peroxidation (LPO) in B-lymphocytes were evaluated. The results showed that the levels of liver enzymes ALT and AST in dry cleaning workers are higher than in the control group. The personal exposure levels and exhaled air concentration of PEC in dry cleaning workers were above the recommended national occupational exposure limits (OELs) and the biological exposure index (BEI). The levels of ROS, LPO, and GSSG in B-lymphocytes from the dry cleaning workers are higher than the control group, and the levels of GSH in dry cleaning workers are lower. The results suggested that exposure of dry cleaning workers to PEC could be associated with liver damage and oxidative damage in B-lymphocytes.

Prenatal and early childhood exposure to tetrachloroethylene (PCE)-contaminated drinking water and sleep quality in adulthood: a retrospective cohort study.

BACKGROUND: Communities in Cape Cod, Massachusetts were exposed to tetrachloroethylene (PCE) through contaminated drinking water from 1969 to 1983. PCE exposure during adulthood has well-established neurotoxic effects; however, long-term impacts stemming from early life exposure, especially adverse effects on sleep quality, are not well understood. METHODS: The present analysis was based on data from the Cape Cod Health Study, a retrospective cohort study of the long-term neurotoxic impacts of early-life exposure to PCE-contaminated drinking water. Exposure to PCE-contaminated water was estimated using a validated leaching and transport model. Measures of sleep quality were obtained from self-administered questionnaires. Generalized estimating equations were used to generate risk ratios and 95% confidence intervals to estimate the association between early-life PCE exposure and sleep quality among 604 participants. RESULTS: Compared to unexposed participants, any PCE exposure during early life was associated with 1.57 times the risk of reporting breathing pauses during sleep (95% CI 0.92-2.68). Low-level exposure to PCE was associated with 1.50 times the risk of reporting sleep apnea or other sleep disorders (95% CI 0.78-2.89), while high levels of exposure had comparable risk compared to no exposure (RR = 0.94, 95% CI 0.50-1.79). Weak or no associations were observed for other sleep quality outcomes. In stratified analyses participants with mental illness and/or substance use disorder had increased risk ratios for short sleep duration associated with PCE exposure. CONCLUSION: These findings suggest that early-life exposure to PCE may be associated with a moderate increase in the risk of reporting breathing pauses during sleep in adulthood and that a history of mental illness and/or substance use disorder may exacerbate the risk of short sleep duration.

A pilot study characterizing tetrachloroethylene exposure with exhaled breath in an impacted community.

Martinsville, Indiana overlays four groundwater contamination plumes, including a U.S. Environmental Protection Agency (EPA)-designated Superfund site. The primary contaminants are tetrachloroethylene (PCE), trichloroethylene (TCE), and other volatile organic compounds (VOCs). Martinsville represents many similar communities facing the challenge of groundwater and soil contamination and vapor intrusion, where residents are often frustrated by the lack of help in understanding and addressing the problem. The objective of this study was to evaluate PCE in exhaled breath to identify and quantify exposure to PCE and to explore the extent and level of PCE exposure among community residents. We measured chlorinated VOCs in exhaled breath samples from 38 healthy individuals who lived either in a contamination area or outside any plume area. We also measured VOCs in indoor air and tap water samples collected from 10 homes. PCE was detected in all exhaled breath samples (mean: 6.6 µg/m3; range: 1.9-44 µg/m3) and tap water samples (mean: 0.74 µg/L; range: 0.39-0.92 µg/L). PCE was detected in six of nine (66%) homes with air concentrations ranging from 1.6 to 70 µg/m3, exceeding the EPA action level of 42 µg/m3. We did not detect TCE or any other chlorinated VOCs in these samples. PCE exposure occurred among individuals living on the EPA Superfund site, as well as among those living on other plume sites and those living outside any known plumes. Preventive measures should focus on identifying highly exposed groups and reducing their exposures, followed by addressing moderately elevated exposures in the community. Our results demonstrated that PCE in exhaled breath can be used as an effective tool in community engaged environmental health research to evaluate the extent and level of community exposure, increase awareness, and promote residents' participation in research and site cleanup decision-making.

Prenatal and early childhood exposure to tetrachloroethylene (PCE) and non-medical use of prescription drugs: A retrospective cohort study in Cape Cod, MA.

BACKGROUND: Between 1968 and 1983, public drinking water supplies of Cape Cod, Massachusetts were contaminated with the chlorinated solvent tetrachloroethylene (PCE). We previously found an affinity for risk-taking behaviors, including the use of illicit drugs, following prenatal and early childhood exposure to PCE. Using newly collected data, we investigated the risk of non-medical use of prescription drugs (NMUPD) following prenatal and early childhood PCE exposure. METHODS: Participants were identified from a retrospective cohort study ("Cape Cod Health Study") via cross-matching birth certificates and water system data. The original self-administered questionnaire gathered data on demographics, work and medical history, and alcohol and illicit drug use from 618 individuals (363 exposed and 255 unexposed). The follow-up survey added questions on non-medical use of prescription pain relievers, tranquilizers, stimulants and sedatives. A validated leaching and transport model was used to estimate exposure to PCE exposure in drinking water. RESULTS: There was a wide distribution of cumulative prenatal and early childhood PCE exposure levels (range: 0.04 g-3722.2 g). PCE exposed subjects had a 1.92-fold increase in risk of any non-medical use of prescription drugs [Adjusted RR: 1.92, (95% CI: 1.31, 2.83)]. Furthermore, the association followed a dose-response relationship where the risk of NMUPD was higher for those exposed to PCE levels greater than or equal the median level versus those exposed to levels less than the median [Adjusted RR: 2.05 (95% CI: 1.34, 3.15) vs. 1.83 (95% CI: 1.20, 2.79) (p-value for trend < 0.01)]. Additionally, we found moderate increases in risk by level of non-medical use (any non-medical use, non-medical use of 1 or more categories of prescription drugs, or 2+ categories) as well as by category of drug for pain relivers, stimulants and tranquilizers. CONCLUSION: We found that prenatal and early childhood exposure to PCE was associated with a moderate increase in the risk of NMUPD. Exposed subjects had dose-related increased risks of NMUPD of pain relievers, tranquilizers, and stimulants. This study has a number of limitations and is the first to report this association. Additional longitudinal studies of populations exposed to PCE during early life should be conducted to examine its long-term neurotoxic effects.

Characterizing natural degradation of tetrachloroethene (PCE) using a multidisciplinary approach.

A site in mid-western Sweden contaminated with chlorinated solvents originating from a previous dry cleaning facility, was investigated using conventional groundwater analysis combined with compound-specific isotope data of carbon, microbial DNA analysis, and geoelectrical tomography techniques. We show the value of this multidisciplinary approach, as the different results supported each interpretation, and show where natural degradation occurs at the site. The zone where natural degradation occurred was identified in the transition between two geological units, where the change in hydraulic conductivity may have facilitated biofilm formation and microbial activity. This observation was confirmed by all methods and the examination of the impact of geological conditions on the biotransformation process was facilitated by the unique combination of the applied methods. There is thus significant benefit from deploying an extended array of methods for these investigations, with the potential to reduce costs involved in remediation of contaminated sediment and groundwater.

Assessing the viability of electro-absorption and photoelectro-absorption for the treatment of gaseous perchloroethylene.

This work focuses on the development of electro-absorption and photoelectro-absorption technologies to treat gases produced by a synthetic waste containing the highly volatile perchloroethylene (PCE). To do this, a packed absorption column coupled with a UV lamp and an undivided electrooxidation cell was used. Firstly, it was confirmed that the absorption in a packed column is a viable method to achieve retention of PCE into an absorbent-electrolyte liquid. It was observed that PCE does not only absorb but it was also transformed into phosgene and other by-products. Later, it was confirmed that the electro-absorption process influenced the PCE degradation, favoring the transformation of phosgene into final products. Opposite to what is expected, carbon dioxide is not the main product obtained, but carbon tetrachloride and trichloroacetic acid. Both species are also hazardous but their higher solubility in water opens possibilities for a successful and more environmental-friendly removal. The coupling with UV-irradiation has a negative impact on the degradation of phosgene. Finally, a reaction mechanism was proposed for the degradation of PCE based on the experimental observations. Results were not as expected during the planning of the experimental work but it is important to take in mind that PCE decomposition occurs in wet conditions, regardless of the applied technology, and this work is a first approach to try to solve the treatment problems associated to PCE gaseous waste flows in a realistic way.

[Examination of Analytical Methods for Methanol, Trichloroethylene, and Tetrachloroethylene to Revise the Official Methods Based on the Act on the Control of Household Products Containing Harmful Substances].

In Japan, the use of methanol, trichloroethylene, and tetrachloroethylene in aerosol household products is banned under the Act on the Control of Household Products Containing Harmful Substances. As the official analytical methods for testing for these substances have not been revised for over 35 years, several issues have been pointed out. Thus, we developed a new method to revise the official method in our previous study. In this study, validation of the proposed method for detecting the target substances was conducted using two aerosol-product samples (A and B), which contained methanol, trichloroethylene, and tetrachloroethylene. Sample A comprised regulated values of these compounds, while sample B comprised one-tenth of the regulated amounts. They also contained several volatile compounds that served as interfering substances. Subsequently, the samples were analyzed using head space/gas chromatography-mass spectrometry, and it was confirmed that the three target substances were separated from the other chemicals on chromatograms. Validation tests were conducted at seven laboratories to evaluate the proposed method using the prepared samples. In one laboratory, the recovery of trichloroethylene and tetrachloroethylene in sample B was slightly higher at 120%, while the recoveries obtained from the other tests were between 70% and 120%. Relative standard deviation at each laboratory was less than 10%. Furthermore, the relative standard deviations between the validation tests with respect to each chemical were less than 15%. Therefore, the method validated in this study was considered to be effective as a revised method for testing for methanol, trichloroethylene, and trichloroethylene in household aerosol products.

Accumulation of DNAPL waste in subsurface clayey lenses and layers.

Chlorinated solvents like trichloroethylene (TCE) and tetrachloroethylene (PCE) are prevalent groundwater contaminants being detected more than half of the Superfund Sites. They are introduced into the subsurface due to improper disposal of hazardous wastes containing these chlorinated dense non-aqueous phase liquids (DNAPL). DNAPL wastes sink in the subsurface and form pools on clay layers. Further transport into the underlying clay layer is dominated by diffusion due to the low permeability of these soils and results in accumulation of contaminants therein overtime through diffusion. However, field evidence reported that mass storage of solvents in such zones was higher than what can be attributed to simple diffusion. To evaluate this finding, mass storage of TCE in a hypothetical aquitard after 30 years of diffusion was calculated. The diffusion coefficient reported in the field study resulted in mass storage of 137.7 g in this hypothetical aquitard whereas the mass calculated using the measured diffusion coefficient of TCE from pure solvent into water-saturated clayey soil was 25-65% of it (35.0-89.4 g). The calculated mass storage was even lower (8.2 g) if the measured diffusion coefficient of TCE from DNAPL waste into waste-contacted soil was used. So, mass of TCE accumulated through sole diffusion was not able to explain the one observed in the field. This excess mass in the field might be the mass of DNAPL entered into the cracks which were reported to form in clay layers as a result of the direct contact between water saturated clay and DNAPL waste. Mass of TCE in the cracks was calculated using reported average crack size and an assumed crack depth, and it appeared that cracks filled with DNAPL could increase the stored mass up to a minimum of 334 g which could easily account for the enhanced mass storage observed in the field.

Using routine, independent, scientific-data audits as an early-warning for potentially fraudulent toxic-site cleanup: PCE, TCE, and other VOCs at the former Naval-Ordnance Test Station, Pasadena, California.

Two of the most prevalent Superfund-site contaminants are carcinogenic solvents PCE (perchloroethylene) and TCE (trichloroethylene). Because their cleanup is difficult and costly, remediators have repeatedly falsified site-cleanup data, as Tetra Tech apparently did recently in San Francisco. Especially for difficult-to-remediate toxins, this paper hypothesizes that scientific misrepresentations occur in toxic-site assessments, before remediation even begins. To begin to test this hypothesis, the paper (1) defines scientific-data audits (assessing whether published conclusions contradict source data), (2) performs a preliminary scientific-data audit of toxic-site assessments by consultants Ninyo and Moore for developer Trammell Crow. Trammel Crow wants to build 550 apartments on an unremediated Pasadena, California site - once a premier US Navy weapons-testing/development facility. The paper (3) examines four key Ninyo-and-Moore conclusions, that removing only localized metals-hotspots will (3.1) remediate TCE/PCE; (3.2) leave low levels of them; (3.3) clean the northern half of soil, making it usable for grading, and (3.4) ensure site residents have lifetime cancer risks no greater than 1 in 3,000. The paper (4) shows that source data contradict all four conclusions. After summarizing the benefits of routine, independent, scientific-data audits (RISDA), the paper (5) argues that, if these results are generalizable, RISDA might help prevent questionable toxic-site assessments, especially those of expensive-to-remediate toxins like PCE/TCE.

Enhanced removal of tetrachloroethylene from aqueous solutions by biodegradation coupled with nZVI modified by layered double hydroxide.

Chlorinated volatile organic compounds, such as tetrachloroethylene (PCE), are the most commonly detected toxic contaminants in groundwater. In this study, the performance of PCE removal by a microbial consortium combined with nZVI modified by layered double hydroxide (nZVI-LDH) was evaluated. The enriched PCE-degrading consortium consisted of 44.49% Clostridium and other potential PCE degraders, and 0.5-2.5 mg/L PCE was completely biodegraded within 4 days. The characterization of nZVI-LDH indicated that LDH was coated on the surfaces of nZVI particles with an increased surface area. The PCE removal kinetics by nZVI-LDH was well described by a second-order model, and the removal rate constant of nZVI-LDH was 0.12 L h/mg, higher than that of native nZVI (0.02 L h/mg). Interestingly, the presence of Cu2+ improved the removal efficiency of PCE by nZVI-LDH, owing to its role as a catalyst or medium for charge transfer during reduction. Removal of PCE was enhanced by coupling the PCE-degrading consortium and nZVI-LDH. The initial removal of PCE was mainly dominated by the abiotic degradation and adsorption of nZVI-LDH, and biodegradation then played a major role in the exhaustion of nZVI-LDH. These results suggest that biodegradation coupled with nZVI-LDH has a great potential for applications in the remediation of chlorinated-solvent contaminated groundwater.