Technical, Environmental, and Economic Analysis Comparing Low-Carbon Industrial Process Heat Options in U.S. Poly(vinyl chloride) and Ethylene Manufacturing Facilities.

Electrification and clean hydrogen are promising low-carbon options for decarbonizing industrial process heat, which is an essential target for reducing sector-wide emissions. However, industrial processes with heat demand vary significantly across industries in terms of temperature requirements, capacities, and equipment, making it challenging to determine applications for low-carbon technologies that are technically and economically feasible. In this analysis, we develop a framework for evaluating life cycle emissions, water use, and cost impacts of electric and clean hydrogen process heat technologies and apply it in several case studies for plastics and petrochemical manufacturing industries in the United States. Our results show that industrial heat pumps could reduce emissions by 12-17% in a typical poly(vinyl chloride) (PVC) facility in certain locations currently, compared to conventional natural gas combustion, and that other electric technologies in PVC and ethylene production could reduce emissions by nearly 90% with a sufficiently decarbonized electric grid. Life cycle water use increases significantly in all low-carbon technology cases. The levelized cost of heat of viable low-carbon technologies ranges from 15 to 100% higher than conventional heating systems, primarily due to energy costs. We discuss results in the context of relevant policies that could be useful to manufacturing facilities and policymakers for aiding the transition to low-carbon process heat technologies.

A novel soluble di-iron monooxygenase from the soil bacterium Solimonas soli.

Soluble di-iron monooxygenase (SDIMO) enzymes enable insertion of oxygen into diverse substrates and play significant roles in biogeochemistry, bioremediation and biocatalysis. An unusual SDIMO was detected in an earlier study in the genome of the soil organism Solimonas soli, but was not characterized. Here, we show that the S. soli SDIMO is part of a new clade, which we define as 'Group 7'; these share a conserved gene organization with alkene monooxygenases but have only low amino acid identity. The S. soli genes (named zmoABCD) could be functionally expressed in Pseudomonas putida KT2440 but not in Escherichia coli TOP10. The recombinants made epoxides from C2 C8 alkenes, preferring small linear alkenes (e.g. propene), but also epoxidating branched, carboxylated and chlorinated substrates. Enzymatic epoxidation of acrylic acid was observed for the first time. ZmoABCD oxidised the organochlorine pollutants vinyl chloride (VC) and cis-1,2-dichloroethene (cDCE), with the release of inorganic chloride from VC but not cDCE. The original host bacterium S. soli could not grow on any alkenes tested but grew well on phenol and n-octane. Further work is needed to link ZmoABCD and the other Group 7 SDIMOs to specific physiological and ecological roles.

Integrated Advanced Molecular Tools Predict In Situ cVOC Degradation Rates: Field Demonstration.

Chlorinated volatile organic compound (cVOC) degradation rate constants are crucial information for site management. Conventional approaches generate rate estimates from the monitoring and modeling of cVOC concentrations. This requires time series data collected along the flow path of the plume. The estimates of rate constants are often plagued by confounding issues, making predictions cumbersome and unreliable. Laboratory data suggest that targeted quantitative analysis of Dehalococcoides mccartyi (Dhc) biomarker genes (qPCR) and proteins (qProt) can be directly correlated with reductive dechlorination activity. To assess the potential of qPCR and qProt measurements to predict rates, we collected data from cVOC-contaminated aquifers. At the benchmark study site, the rate constant for degradation of cis-dichloroethene (cDCE) extracted from monitoring data was 11.0 ± 3.4 yr-1, and the rate constant predicted from the abundance of TceA peptides was 6.9 yr-1. The rate constant for degradation of vinyl chloride (VC) from monitoring data was 8.4 ± 5.7 yr-1, and the rate constant predicted from the abundance of TceA peptides was 5.2 yr-1. At the other study sites, the rate constants for cDCE degradation predicted from qPCR and qProt measurements agreed within a factor of 4. Under the right circumstances, qPCR and qProt measurements can be useful to rapidly predict rates of cDCE and VC biodegradation, providing a major advance in effective site management.

Nitrogen amended graphene catalyses fast reduction of vinyl chloride by nano zerovalent iron.

Vinyl chloride (VC) is a dominant carcinogenic residual in many aged chlorinated solvent plumes, and it remains a huge challenge to clean it up. Zerovalent iron (ZVI) is an effective reductant for many chlorinated compounds but shows low VC removal efficiency at field scale. Amendment of ZVI with a carbonaceous material may be used to both preconcentrate VC and facilitate redox reactions. In this study, nitrogen-doped graphene (NG) produced by a simple co-pyrolysis method using urea as nitrogen (N) source, was tested as a catalyst for VC reduction by nanoscale ZVI (nZVI). The extent of VC reduction to ethylene in the presence of 2 g/L of nZVI was less than 1% after 3 days, and barely improved with the addition of 4 g/L of graphene. In contrast, with amendment of nZVI with NG produced at pyrolysis temperature (PT) of 950 °C, the VC reduction extent increased more than 10-fold to 69%. The reactivity increased with NG PT increasing from 400 °C to an optimum at 950 °C, and it increased linearly with NG loadings. Interestingly, N dosage had little effect on reactivity if NG was produced at PT of 950 °C, while a positive correlation was observed for NG produced at PT of 600 °C. XPS and Raman analyses revealed that for NG produced at lower PT (<800 °C) mainly the content of pyridine-N-oxide (PNO) groups correlates with reactivity, while for NG produced at higher PT up to 950 °C, reactivity correlates mainly with N induced structural defects in graphene. The results of quenching and hydrogen yield experiments indicated that NG promote reduction of VC by storage of atomic hydrogen, thus increasing its availability for VC reduction, while likely also enabling electron transfer from nZVI to VC. Overall, these findings demonstrate effective chemical reduction of VC by a nZVI-NG composite, and they give insights into the effects of N doping on redox reactivity and hydrogen storage potential of carbonaceous materials.

Western diet unmasks transient low-level vinyl chloride-induced tumorigenesis; potential role of the (epi-)transcriptome.

BACKGROUND & AIMS: Vinyl chloride (VC) monomer is a volatile organic compound commonly used in industry. At high exposure levels, VC causes liver cancer and toxicant-associated steatohepatitis. However, lower exposure levels (i.e., sub-regulatory exposure limits) that do not directly damage the liver, enhance injury caused by Western diet (WD). It is still unknown if the long-term impact of transient low-concentration VC enhances the risk of liver cancer development. This is especially a concern given that fatty liver disease is in and of itself a risk factor for the development of liver cancer. METHODS: C57Bl/6 J mice were fed WD or control diet (CD) for 1 year. During the first 12 weeks of feeding only, mice were also exposed to VC via inhalation at sub-regulatory limit concentrations (<1 ppm) or air for 6 h/day, 5 days/week. RESULTS: Feeding WD for 1 year caused significant hepatic injury, which was exacerbated by VC. Additionally, VC increased the number of tumors which ranged from moderately to poorly differentiated hepatocellular carcinoma (HCC). Transcriptomic analysis demonstrated VC-induced changes in metabolic but also ribosomal processes. Epitranscriptomic analysis showed a VC-induced shift of the modification pattern that has been associated with metabolic disease, mitochondrial dysfunction, and cancer. CONCLUSIONS: These data indicate that VC sensitizes the liver to other stressors (e.g., WD), resulting in enhanced tumorigenesis. These data raise concerns about potential interactions between VC exposure and WD. It also emphasizes that current safety restrictions may be insufficient to account for other factors that can influence hepatotoxicity.

Vinyl chloride enhances high-fat diet-induced proteome alterations in the mouse pancreas related to metabolic dysfunction.

Alterations in physiological processes in pancreas have been associated with various metabolic dysfunctions and can result from environmental exposures, such as chemicals and diet. It was reported that environmental vinyl chloride (VC) exposure, a common industrial organochlorine and environmental pollutant, significantly exacerbated metabolic-related phenotypes in mice fed concurrently with high-fat diet (HFD) but not low-fat diet (LFD). However, little is known about the role of the pancreas in this interplay, especially at a proteomic level. The present study was undertaken to examine the protein responses to VC exposure in pancreas tissues of C57BL/6J mice fed LFD or HFD, with focus on the investigation of protein expression and/or phosphorylation levels of key protein biomarkers of carbohydrate, lipid, and energy metabolism, oxidative stress and detoxification, insulin secretion and regulation, cell growth, development, and communication, immunological responses and inflammation, and biomarkers of pancreatic diseases and cancers. We found that the protein alterations may indicate diet-mediated susceptibility in mouse pancreas induced by HFD to concurrent exposure of low levels of inhaled VC. These proteome biomarkers may lead to a better understanding of pancreas-mediated adaptive or adverse response and susceptibility to metabolic disease.

[Improvement of protective facilities in vinyl chloride units on liver injury status of occupational exposed group].

OBJECTIVE: To comprehensively evaluate the effectiveness of improvement of protective facilities in a vinyl chloride monomer(VCM) on promotion toward health status of occupational exposed group and safety production at poly-vinyl chloride(PVC) by comparing the liver function indicators and inspection result before and after the improvement, and to analyze the possible influential factors. METHODS: The information collection concerning facilities improvement in 2013 and 2016, identification toward critical controlling points, data or detection result from occupational on-site survey and physical examination were originated in July 2020, and 227 VCM exposed workers and 179 others without chemical reagents exposure history from production factory with calcium carbide process in Tianjin City were selected as objects. The effectiveness toward improvement of protective facilities in critical controlling points that occupational exposed workers usually involve in were evaluated through comparison toward VCM concentration result, thiodiglycolic acid(TDGA) content in urine, indicators on liver function and biochemistry and liver ultrasound. At the mean time, both binary Logistic regression analysis was used to screen the possible factors that contributed to abnormal symptoms and single dependent variable general linear regression model was used to find out the mutual interaction among influential factors. RESULTS: Prior to improvement on protective facilities, the C_(TWA)of VCM exposed by all 8 positions in G had exceeded 1 to 2 folds of occupational exposure limit(OEL=10 mg/m~3) and the position of synthetic operator and field sampling man were ones exposed to 1, 2-DCE with the range from 50% to 1 OEL, others hazard factors were found to meet relative OELs. Next, the content of TDGA in urine of exposed group was found to correlate strongly to the average concentration of VCM(r=0.79, P<0.05), and result of TDGA content, alanine aminotransferase(ALT), γ-glutamyl transpeptidase(GGT) and abnormal rate toward liver ultrasound test in exposed group were much higher than ones in control group with significant differences(P<0.05 or P<0.001). By contrast, after the improvement, the exposure level toward all identified hazard factors were declined to meet OEL levels with significant differences in TDGA content, and result of ALT, GGT and abnormal rates toward symptoms in liver ultrasound test such as liver calcification with thickened liver echo, peripheral fibrosis of the liver, multiple hepatic cysts were markedly lower than ones before improvement and still were higher than ones in control group(P<0.05 or P<0.001). Further, parameters of gender, length of employment, weekly contact time, VCM exposed level, TDGA content were all important contributing factors to abnormal symptoms in liver ultrasound test before and after improvement on protective facilities(P<0.05 or P<0.001), in which a significant interaction effect between gender and length of employment(F=4.028, P=0.044), weekly contact time and TDGA content(F=2.183, P=0.046) in urine were found in contribution analysis to abnormal symptoms in liver ultrasound test(P<0.05). CONCLUSION: The improvement measure carried out in VCM facilities by this PVC production factories with calcium carbide process effectively reduced the ambient concentration of hazard factors mainly led by VCM, but workers might still be at risk of liver injury even under VCM exposure at relative lower level, which may referred to factors of long weekly contact time, long length of employment and high fat diet.

Analysis and risk assessment of vinyl chloride emitted from aerosol products.

The objectives of this study were to develop a novel analytical method for quantifying vinyl chloride (VC) emitted from aerosol products, to provide analytical data on VC in aerosol products, and to evaluate consumer VC exposure by aerosol products. Our quantitative method involves absorbing VC into dimethyl sulfoxide and analyzing it using headspace gas chromatography/mass spectrometry. The correlation coefficients of the VC calibration curves were ≥ 0.9994 in the range of 0.16-80 µg/mL VC standard gases, which were prepared under either nitrogen or emission gases containing dimethyl ether or liquid petroleum gas. VC concentrations in these emission gases were calculated using a VC calibration curve from standard gases prepared under nitrogen; they were within ± 10% of the actual concentrations. We analyzed 39 household aerosol products; VC concentrations of 0.095, 0.098, and 0.28 µg/L were detected in three polyvinyl chloride spray paints. Consumer VC inhalation exposure level was estimated through an exposure scenario, and the hazard quotient was confirmed to be very low when comparing the exposure level with a cancer risk level of 10-5 for inhaled VC. These results suggest that the human health risk from VC in spray paint was low.

The structure and properties of mechanochemically modified acrylonitrile butadiene rubber (NBR)/poly (vinyl chloride) (PVC) scraps and fresh NBR composites.

Vulcanized acrylonitrile-butadiene rubber (NBR)/poly (vinyl chloride) (PVC) blends are mainly served as insulation rubber-plastic materials. However, methods to reuse the waste NBR/PVC composites lack research. Here, we found that the mechanochemically modified waste NBR/PVC composites powders (WNPP) could be an alternative to fresh NBR. According to the results, the optimal replacement amount of WNPP for NBR was 20%, and the highest feasible proportion was 40%. WNPP treated by solid-state shear milling technology (S3M) would have a high degree of desulfurization, and the cross-linked chains within WNPP would be transformed into free chains. While co-vulcanizing, the sulfur agents and heat would induce the free chains of WNPP to react with the polymer chains of the NBR substrate, thereby generating dangling chains to form a robust interfacial layer. It was beneficial for the improvement of the mechanical properties of reclaimed products. And the strain of the excellent recycled sample (20C) reached 707%. Moreover, the modified WNPP in the co-vulcanized rubber represented heterogeneity because of the internal residual crosslinked network and the not-melting PVC plastic phase. Although the heterogeneity of WNPP damaged the continuity of the NBR matrix, it also brought a better hysteresis loss capability to the composite. In conclusion, this work expanded the mechanochemical application scope in recycling NBR/PVC wastes.

Mechanochemical reclaiming and thermoplastic re-processing of waste Acrylonitrile-butadiene rubber (NBR)/poly (Vinyl Chloride) (PVC) insulation materials.

Cross-linked acrylonitrile-butadiene rubber (NBR)/poly(vinyl chloride) (PVC) blends are extensively served as commercial insulation foams. However, methods to reclaim the wasted NBR/PVC composites are usually inappropriate, causing severe pollution. Herein, we reported that the waste NBR/PVC composites powders (WNPP) with high thermal stability and degree of reclaiming were prepared by solid-state shear milling technology (S3M). Furthermore, the reclaimed products via thermoplastic re-processing had excellent mechanical properties, and the optimal stress and strain were increased by 208.2 % and 269.4 %, respectively, compared with the products made from virgin scraps. Through the investigation of each sample's molecular chains and thermal properties, it was found that when the cross-linked polar rubber-plastic composites are reclaimed, the molecular chains of the rubber phase would be close to each other. The interaction among polar groups would be enhanced, which is the main contributing factor limiting the movability of the polymer chains. And the interaction between the polar rubber and plastic phases would also increase, which is beneficial for the compatibility of the two phases. Moreover, there is a phase separation between the de-crosslinked continuous phase and the residual cross-linked network region for the re-processing products.

Synthesis of poly vinyl chloride/chlorinated polypropylene-active natural substance derivatives for potential packaging materials application. Tannic acid, menthol and lipoic acid.

A novel one step route for the synthesis of tannic acid, lipoic acid and menthol functionalized polyvinyl chloride, PVC, (PVC-Tann, PVC-Lip, PVC-Mnt) and chlorinated polypropylene, PP-Cl, (PP-Mnt, PP-Lip) was applied imparting antioxidative properties to the newly-formed materials. The resulting modified polymers were characterized by stress-strain mechanical measurement, 1H NMR, gel permeation chromatography (GPC) and thermogravimetric (TGA) analysis. Linseed oil, owing to its high linolenic acid content, was used to track the autoxidation process. The chloride functional groups were reacted with the hydroxyl/carboxylic acid of the natural compounds in the presence of a base. Linseed oil was poured into the natural compound functionalized PVC covered Petri dish to undergo autoxidation under white light. Each of the PVC- and PP-Cl-based polymers was active in delaying autoxidation. The PP-Mnt series and PP-Lip polymers all delayed autoxidation by 8 days over the PP-Cl precursor material. The autoxidation process was further confirmed by monitoring peroxide formation in the exposed linseed oil samples through differential scanning calorimeter (DSC) analysis.

Impact of γ-irradiation and SBR content in the compatibility of aminated (PVC/LLDPE)/ZnO for improving their AC conductivity and oil removal.

In some cases, blends containing PVC and LLDPE show low compatibility. Adding styrene-butadiene rubber to the PVC/LLDPE mixtures leads to a noticeable increase in tensile strength and compatibility of the blends. Also, an improvement in tensile strength is observed after incorporating SBR compatibilizer resulting in entirely different gamma irradiation doses. Without a compatibilizer, the mixture exhibits a distributed PVC and LLDPE phase with variable sizes and shapes; even a sizable portion of the domains resemble droplets. Styrene butadiene rubber (SBR) and gamma radiation make mixtures of (PVC/LLDPE) more compatible. The SEM study of the blends demonstrated that adding the compatibilizer resulted in finer blend morphologies with less roughness. At the same time, gamma irradiation reduced this droplet and gave a more smooth surface. Poly(vinyl chloride) (PVC) was chemically modified with four different amino compounds, including ethylene diamine (EDA), aniline (An), p-anisidine (pA) and dimethyl aniline (DMA) for improving the electric conductivity and oil removal capability of the blend polymer. All ionomers were prepared by nucleophilic substitution in a solvent/non-solvent system under mild conditions. This work novelty shows a sustainable route for producing oil adsorption materials by recycling plastic waste. After the amination process of poly(vinyl chloride) the oil adsorption was significantly enhanced.

Characteristics, sources and risk assessments of heavy metal pollution in soils of typical chlor-alkali residue storage sites in northeastern China.

In this study, thirty-four soil samples from a typical chlor-alkali slag residue storage site near the city of Qiqihar in northeastern China were collected and their arsenic, cadmium, chromium, copper, mercury, nickel, lead and zinc concentrations were determined. Sources of these heavy metals were analyzed with a positive matrix factorization model, and the health risks associated with different pollution sources were calculated. The results showed that mercury was the main heavy metal pollutant at the site (maximum concentration of 112.19 mg.kg-1) and the soil was also contaminated with arsenic, copper and lead. The sources of eight heavy metals were: mixed oil refinery wastewater and parent material (arsenic, chromium, copper and lead), vinyl chloride waste source (mercury), parent material (cadmium, nickel and zinc). The average potential ecological risk of the soil was 22344.39, with vinyl chloride waste source contributing 99.85% of this risk. The average carcinogenic risk of a mixture of oil refinery wastewater and parent material for children and adults was 9.06×10-6 and 6.36×10-6, respectively, accounting for 99.9% (children) and 99.48% (adults) of the total average carcinogenic risk. The average hazard index of vinyl chloride waste source for children and adults was 0.6 and 0.38, respectively, which accounted for 64.13% (children) and 52.34% (adults) of the total hazard index. These results provide a reference for soil pollution risk assessments at this type of site.

Detecting vinyl chloride by phytoscreening in the shallow critical zone at sites with potential human exposure.

Chlorinated ethene (CE) contaminants are widespread in groundwater, and the occurrence of vinyl chloride (VC), among others, is a well-known issue due to its mobility, persistence, and carcinogenicity. Human exposure to VC may occur through inhalation after soil vapor intrusion into buildings at sites with shallow underground contamination. Soil vapor intrusion risk is traditionally assessed through indoor air and sub-slab sampling (direct evidence) or soil gas and groundwater surveys (indirect evidence). Phytoscreening (sampling and analysis of tree trunk matrices) was proven as a cost-effective alternative technique to indirectly detect shallow underground contamination by higher chlorinated ethenes and subsequent vapor intrusion risk. However, the technique has appeared barely capable to screen for the lower chlorinated VC, likely due to its fugacity and aerobic bio-degradability, with only one literature record to date showing successful detection in trees. We applied phytoscreening at two sites with severe CE contamination nearby residential buildings caused by illegal dumping of chlorinated pitches from petrochemical productions. The two sites show variable amounts of VC in the shallow groundwater (1e2 to 1e4 µg/L), posing potential sanitary risk issues. Former soil gas surveys did not detect VC in the vadose zone. At both sites, we sampled trunk micro-cores and trunk gas from poplar trees close to contaminated piezometers in different seasons. VC was detected in several instances, disproving the shared literature assumption of the inefficacy of phytoscreening towards this compound. Factors influencing the detectability of VC and other CEs in trees were analyzed through linear regressions. Two different conceptual models were proposed to explain the effective uptake of VC by trees at the two sites, i.e., direct uptake of contaminated groundwater at the first site and uptake of VC from an anoxic vadose zone at the second site. In planta reductive dechlorination of CEs is not expected based on current literature knowledge. Thus, the detection of VC in trunks would indicate its occurrence in the shallow underground, suggesting higher screening effectiveness of phytoscreening compared to soil gas; this has implications for indirect vapor intrusion risk assessment.

Efficient removal of nano- and micro- sized plastics using a starch-based coagulant in conjunction with polysilicic acid.

Microplastic (MP) pollution has increasingly become an enormous global challenge due to the ubiquity and uncertain environmental performance, especially for nano- and micro- sized MPs. In this work, the performance and mechanisms in coagulation of 100 nm-5.0 µm sized polystyrene particles using an etherified starch-based coagulant (St-CTA) assisted by polysilicic acid (PSA) were systematically studied on the basis of the changes in MPs removal rates under various pH levels and in the presence of different coexisting inorganic and organic substances, zeta potentials of supernatants, and floc properties. St-CTA in conjunction with PSA had a high performance in coagulation of nano- and micro- sized MPs from water with a lower optimal dose and larger and compacter flocs. Besides, the MPs removal rate can be improved in acidic and coexisting salt conditions. The efficient performance in removal of MPs by this enhanced coagulation was owing to the synergic effect, that is, the effective aggregation of MPs through the charge neutralization of St-CTA followed by the efficient netting-bridging effect of PSA. The effectiveness of this enhanced coagulation was further confirmed by removal of two other typical nano-sized MPs, such as poly(methyl methacrylate) and poly(vinyl chloride), from different water sources including tap water, river water, and sludge supernatant from a sewage treatment plant. This work provided a novel enhanced coagulation technique that can effectively remove nano- and micro- sized MPs from water.

Mortality for Lung Cancer among PVC Baggers Employed in the Vinyl Chloride Industry.

Vinyl-chloride monomer (VCM) is classified as a known carcinogen of the liver; for lung cancer, some results suggest a potential association with polyvinyl chloride (PVC) dust. We evaluated the relationship between lung cancer mortality and exposure as PVC baggers in a cohort of workers involved in VCM production and polymerization in Porto Marghera (Venice, Italy) considering both employment status and smoking habits. The workers were studied between 1973 and 2017. A subset of them (848 over 1658) was interviewed in the 2000s to collect information about smoking habits and alcohol consumption. Missing values were imputed by the Multivariate Imputation by Chained Equations (MICE) algorithm. We calculated standardized mortality ratios (SMR) and 95% confidence intervals (95% CIs) using regional reference rates by task (never, ever, and exclusively baggers) and by smoking habits. Mortality rate ratios (MRR), adjusted for age, calendar time, time since first exposure, and smoking habits, were obtained via Poisson regression using Rubin's rule to combine results from imputed datasets calculating the fraction of information due to non-response. Lung cancer mortality was lower than the regional reference in the whole cohort (lung cancer SMR = 0.92; 95% CI 0.75-1.11). PVC baggers showed a 50% increase in lung cancer mortality compared to regional rates (SMR = 1.48; 95% CI 0.82-2.68). In the cohort analyses, a doubled risk of lung cancer mortality among PVC baggers was confirmed after adjustment for smoking and time-dependent covariates (MRR = 1.99, 95% CI 1.04-3.81). Exposure to PVC dust resulting from activity as bagger in a polymerization PVC plant was associated with an increase in lung cancer mortality risk after adjustment for smoking habits.

Novel deoxyribonucleic acid methylation perturbations in workers exposed to vinyl chloride.

To explore the epigenetic mechanism of deoxyribonucleic acid (DNA) damage induced by vinyl chloride (VC), we studied the micronuclei of peripheral blood lymphocytes in 193 subjects (92 in a VC exposure group employed in a chlorine-alkali plant; 101 in a control group employed in a power plant) and selected three pairs from the subjects (exposed and control) for whole-genome bisulfite sequencing (WGBS). The results showed that the rate of micronucleus formation in the VC exposure group was higher than that of control group (6.05 ± 3.28‰ vs. 2.01 ± 1.79‰). A total of 9534 differentially methylated regions (DMRs) were identified by WGBS, of which 4816 were hypomethylated and 4718 were hypermethylated. The Kyoto encyclopedia of genes and genomes (KEGG) pathway and gene ontology (GO) analyses showed the top three KEGG pathways were cancer , neuroactive ligand-receptor interaction, and axon guidance, and the top three GO-BP pathways enriched were multicellular organismal process, developmental process, and anatomical structure development. In the most enriched DMR pathway (pathways in cancer), we found that BCL2, TJP2, TAOK1, PFKFB3, LIPI, and LIPH were hypermethylated, and the methylation levels of BNIP1 and GRPEL2 were decreased. The methylation of differentially methylated genes (DMGs) mentioned above were verified by methylation-specific PCR (MSP) and agarose gel electrophoresis (AGE) in 50 pairs of subjects, where the coincidence rate was 60-100%. In conclusion, the epigenetic perturbations of specific DMGs (BCL2, TJP2, TAOK1, PFKFB3, LIPI, LIPH, BNIP1, and GRPEL2) may be associated with DNA damage from vinyl chloride exposure.

Generation of micro(nano)plastics and migration of plastic additives from Poly(vinyl chloride) in water under radiation-free ambient conditions.

A batch experiment was conducted to observe the liberation of micro- and nano-sized plastic particles and plastic additive-originated organic compounds from poly(vinyl chloride) under radiation-free ambient conditions. The weathering of PVC films in deionized water resulted in isolated pockets of surface erosion. Additional ●OH from Fenton reaction enhanced PVC degradation and caused cavity erosion. The detachment of plastic fragments from the PVC film surfaces was driven by autocatalyzed oxidative degradation. Over 90% of micro-sized plastic particles were <60 µm in length. The detached plastic fragments underwent intensified weathering, which involved strong dehydrochlorination and oxidative degradation. Further fragmentation of micro-sized particles into nano-sized particles was driven by oxidative degradation with complete dehydrochlorination being achieved following formation of nanoplastics. 20 organic compounds released from the PVC films into the solutions were identified. And some of them can be clearly linked to common plastic additives. In the presence of additional ●OH, the coarser nanoplastic particles (>500 nm) tended to be rapidly disintegrated into finer plastic particles (<500 nm), while the finest fraction of nanoplastics (<100 nm) could be completely decomposed and disappeared from the filtrates. The micro(nano)plastics generated from the PVC weathering were highly irregular in shape.

The impact of vinyl chloride exposure on the health of Italian workers: an evaluation from SIREP compliance data.

The aim of the study is to investigate exposures to vinyl chloride monomer (VCM) at workplace in Italy and the related burden of diseases. Measurements data was collected from a nation-wide occupational exposure registry (SIREP, 1996-2016). Potentially exposed workers were estimated for some industrial sectors. Concurrent exposures were investigated using cluster analysis. Proportionate mortality ratios were calculated linking data to national mortality statistics (2005-2015). Overall 8,460 measurements were analyzed. Most exposures occurred in the manufacture of chemicals and plastic products. A total of 12,148 workers potentially exposed was estimated (64% male). Concurrent exposures were detected frequently (83%). An elevated proportion of deaths for liver cancer was found in male exposed workers. Although VCM is a known carcinogen for humans, there are still many exposure situations, albeit at low doses, in the chemical and plastic industries.

Biotic and abiotic reductive dechlorination of chloroethenes in aquitards.

Chlorinated solvents occur as dense nonaqueous phase liquid (DNAPL) or as solutes when dissolved in water. They are present in many pollution sites in urban and industrial areas. They are toxic, carcinogenic, and highly recalcitrant in aquifers and aquitards. In the latter case, they migrate by molecular diffusion into the matrix. When aquitards are fractured, chlorinated solvents also penetrate as a free phase through the fractures. The main objective of this study was to analyze the biogeochemical processes occurring inside the matrix surrounding fractures and in the joint-points zones. The broader implications of this objective derive from the fact that, incomplete natural degradation of contaminants in aquitards generates accumulation of daughter products. This causes steep concentration gradients and back-diffusion fluxes between aquitards and high hydraulic conductivity layers. This offers opportunities to develop remediation strategies based, for example, on the coupling of biotic and reactive abiotic processes. The main results showed: 1) Degradation occurred especially in the matrix adjacent to the orthogonal network of fractures and textural heterogeneities, where texture contrasts favored microbial development because these zones constituted ecotones. 2) A dechlorinating bacterium not belonging to the Dehalococcoides genus, namely Propionibacterium acnes, survived under the high concentrations of dissolved perchloroethene (PCE) in contact with the PCE-DNAPL and was able to degrade it to trichloroethene (TCE). Dehalococcoides genus was able to conduct PCE reductive dechlorination at least up to cis-1,2-dichloroethene (cDCE), which shows again the potential of the medium to degrade chloroethenes in aquitards. 3) Degradation of PCE in the matrix resulted from the coupling of reactive abiotic and biotic processes-in the first case, promoted by Fe2+ sorbed to iron oxides, and in the latter case, related to dechlorinating microorganisms. The dechlorination resulting from these coupling processes is slow and limited by the need for an adequate supply of electron donors.