Homologue Composition of Technical Chlorinated Paraffins Used in Several Countries over the Last 50 Years─SCCPs Are Still Out There.

Chlorinated paraffins (CPs) are widely produced chemicals, with certain CP subgroups facing global restrictions due to their environmental dispersion, persistence, bioaccumulation, and toxicity. To evaluate the effectiveness of these international restrictions, we assessed the homologue group contribution and the mass fraction of short-chain CPs (SCCPs: C10-C13), medium-chain CPs (MCCPs: C14-C17), and long-chain CPs (LCCPs: ≥C18) in 36 technical CP mixtures used worldwide over the last 50 years. Using low-resolution mass spectrometry (LC-ESI-MS/MS), we quantified 74 CP homologue groups (C10Cl4-C20Cl10). Additionally, high-resolution mass spectrometry (LC-ESI-QTOF-MS) screening was employed to identify unresolved CP contents, covering 375 CP homologue groups (C6Cl4-C30Cl30). Overall, 1 sample was mainly composed of

A review on management practices, environmental impacts, and human exposure risks related to electrical and electronic waste in Vietnam: findings from case studies in informal e-waste recycling areas.

Electrical and electronic waste (e-waste) has become a global concern, especially in developing countries. In this review, we conducted a literature survey of e-waste management practices, processing activities, and adverse effects in Vietnam, an emerging country in Southeast Asia, by gathering data from peer-reviewed articles published between 2009 and 2021. This is the first review paper to comprehensively discuss management and research aspects regarding e-waste in an Asian developing country. Due to the lack of an effective management and recycling system, a certain portion of Vietnamese e-waste has been processed by informal sectors without appropriate recycling and pollution control technology, resulting in localized contamination and human exposure to toxic chemicals. Primitive processing activities, such as manual dismantling, open burning, and plastic recycling, have been identified as important contributors to the environmental emission and human exposure to toxic elements (notably As, Mn, Ni, Pb, Zn) and organic pollutants like flame retardants, PAHs, PCBs, and dioxin-related compounds. Informal e-waste processing from these small-scale workshops can release pollutants at similar levels compared to large-scale facilities in developed countries. This fact suggests an urgent need to develop management best practices for e-waste in Vietnam as well as other emerging and developing countries, in order to increase recycling efficiency and minimize their adverse impacts on environmental and human health.

Emission of Dioxin-like Compounds and Flame Retardants from Commercial Facilities Handling Deca-BDE and Their Downstream Sewage Treatment Plants.

Commercial mixtures of decabromodiphenyl ether (deca-BDE), a brominated flame retardant, contain not only polybrominated diphenyl ethers (PBDEs, mainly BDE-209) as the main component but also dioxin-like compounds (DLCs) such as polybrominated dibenzofurans (PBDFs). Deca-BDE handling facilities (DHFs) and sewage treatment plants receiving effluent from DHFs are point sources of DLC and flame retardant (FR) pollution. Here, we examined their emission in Japan. For DHF effluents, DLCs detected by the dioxin-responsive chemically activated luciferase expression (DR-CALUX) assay were 1.3-890 pg TCDD-EQ/L (median 46 pg TCDD-EQ/L), while PBDEs and other FRs were <2.0-110,000 ng/L (610 ng/L) and 150-4,800,000 ng/L (41,000 ng/L). Risk quotients based on predicted no-effect concentrations suggested that DLCs, decabromodiphenyl ethane (DBDPE), tris(2,3-dibromopropyl) isocyanurate (TDBP-TAZTO), and bisphenol A bis(diphenyl phosphate) (BPA-BDPP) present significant risks for aquatic organisms. The concentrations of PBDFs, which are impurities in deca-BDE, were expected to decrease with the inclusion of deca-BDE in the Stockholm Convention list of persistent organic pollutants (May 2017). However, DLCs other than PBDFs and alternative FRs such as DBDPE, TDBP-TAZTO, and BPA-BDPP are likely still discharged. Additional findings indicate that strong (e.g., DLCs, DBDPE, and BPA-BDPP), but not weak (e.g., TDBP-TAZTO), hydrophobic compounds are sufficiently removed by current wastewater treatment processes in Japan.

The strength in numbers: comprehensive characterization of house dust using complementary mass spectrometric techniques.

Untargeted analysis of a composite house dust sample has been performed as part of a collaborative effort to evaluate the progress in the field of suspect and nontarget screening and build an extensive database of organic indoor environment contaminants. Twenty-one participants reported results that were curated by the organizers of the collaborative trial. In total, nearly 2350 compounds were identified (18%) or tentatively identified (25% at confidence level 2 and 58% at confidence level 3), making the collaborative trial a success. However, a relatively small share (37%) of all compounds were reported by more than one participant, which shows that there is plenty of room for improvement in the field of suspect and nontarget screening. An even a smaller share (5%) of the total number of compounds were detected using both liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS). Thus, the two MS techniques are highly complementary. Most of the compounds were detected using LC with electrospray ionization (ESI) MS and comprehensive 2D GC (GC×GC) with atmospheric pressure chemical ionization (APCI) and electron ionization (EI), respectively. Collectively, the three techniques accounted for more than 75% of the reported compounds. Glycols, pharmaceuticals, pesticides, and various biogenic compounds dominated among the compounds reported by LC-MS participants, while hydrocarbons, hydrocarbon derivatives, and chlorinated paraffins and chlorinated biphenyls were primarily reported by GC-MS participants. Plastics additives, flavor and fragrances, and personal care products were reported by both LC-MS and GC-MS participants. It was concluded that the use of multiple analytical techniques was required for a comprehensive characterization of house dust contaminants. Further, several recommendations are given for improved suspect and nontarget screening of house dust and other indoor environment samples, including the use of open-source data processing tools. One of the tools allowed provisional identification of almost 500 compounds that had not been reported by participants.

Early-life exposure to Tris(1,3-dichloroisopropyl) phosphate induces dose-dependent suppression of sexual behavior in male rats.

Exposure to endocrine-disrupting chemicals may adversely affect animals, particularly during development. Tris(1,3-dichloroisopropyl) phosphate (TDCIPP) is an organophosphate with anti-androgen function in vitro that is present in indoor dust at relatively high concentrations. In male rats, androgens are necessary for the development of reproductive organs, as well as the endocrine and central nervous systems. However, we currently do not know the exact effects of TDCIPP exposure through suckling on subsequent reproductive behavior in males. Here, we show that TDCIPP exposure (25-250 mg kg-1 via oral administration over 28 consecutive days post-birth) suppressed male sexual behavior and reduced testes size. These changes were dose-dependent and appeared first in adults rather than in juveniles. These results demonstrate that TDCIPP exposure led to normal body growth and appearance in juveniles, but disrupted the endocrine system and physiology in adults. Therefore, assays should be performed using adult animals to ensure accuracy, and to confirm the influence of chemical substances given during early mammalian life.

Compositional Analysis of Commercial Oligomeric Organophosphorus Flame Retardants Used as Alternatives for PBDEs: Concentrations and Potential Environmental Emissions of Oligomers and Impurities.

Four commercial oligomeric organophosphorus flame retardants (o-PFRs) were characterized using a refractive index detector and atmospheric pressure photoionization (APPI)-quadrupole time-of-flight mass spectrometry (QTOF-MS) compatible with gel permeation chromatography (GPC). Commercial o-PFRs consisted of approximately 90% or more oligomers and several impurities. Triphenyl phosphate (TPHP), tris(dimethylphenyl) phosphate (TDMPP), tris(2-chloroisopropyl) phosphate (TCIPP), and some new impurities were identified as byproducts of some manufacturing process of commercial o-PFRs for the first time. The concentrations of TPHP, TDMPP, and TCIPP were more than 1 weight %, whereas those of new impurities might be approximately 1 weight % by comparison among their abundances acquired through GPC-APPI-QTOF-MS analysis. Based on their vapor pressure and water solubility estimations, the potential environmental emissions of low molecular weight impurities were expected to be higher than those of oligomers. The presence and environmental emissions of low molecular weight impurities might be regarded as risk factors along with commercial o-PFRs.

Impact of tightening environmental regulations against long-chain perfluoroalkyl acids on composition of durable water repellents containing side-chain fluorinated polymers.

Tightening of environmental regulations against long-chain perfluoroalkyl acids (PFAAs) since the 2000s may have led to significant increases in the occurrence of short-chain PFAAs in the environment. Understanding the impact of the regulations on composition of durable water repellents (DWRs) is imperative to guide implementation of pragmatic actions during their use and end-of-life treatment. Substantial decreases in the frequencies of detection and concentrations of long-chain PFAAs and long-chain PFAA-precursors, and substantial increases in those of short-chain PFAAs and short-chain PFAA-precursors, have been observed in the impurities and hydrolysis products of side-chain fluorinated polymers (SCFPs). Comparison of profiles among the DWRs containing fluorinated ingredients in 2011 indicated that DWRs containing C8F17- and C10F21-SCFPs were the dominant products and accounted for 90 % of the samples, whereas DWRs containing C4F9- and C6F13-SCFPs were the dominant products and accounted for 70 % of the samples collected in 2021. Tightening of the regulations have caused decreasing applications of long-chain SCFPs and increasing use of short-chain SCFPs in DWRs containing fluorinated ingredients. The ingredients of one DWR were changed from PFAS-free alternatives to short-chain SCFPs, whereas those of another DWR were changed from short-chain SCFPs to PFAS-free alternatives. The presence of unexplained extractable organic fluorine has been observed in DWRs containing fluorinated ingredients, which may be difficult to be hydrolyzed and form known compounds. A historical series of DWRs available from before and after the tightening of regulations and a multifaceted analytical technique consisting of combustion ion chromatographic and mass spectrometric approaches combined with two extraction techniques involving ultrasonic treatment and alkaline hydrolysis revealed the impact of tightening regulations on composition of DWRs.

Bioaccessibility of halogenated flame retardants and organophosphate esters in settled dust: Influences of specific dust matrices from informal e-waste and end-of-life vehicle processing areas in Vietnam.

Bioaccessibility of halogenated flame retardants (HFRs) and organophosphorus esters (OPEs) is necessarily investigated to provide more accurate risk assessment and information about absorption behavior of these pollutants. In this study, total and bioaccessible concentrations of HFRs (including legacy and alternative substances) and OPEs were determined in settled dust samples collected from Vietnamese e-waste and end-of-life vehicle (ELV) processing areas. Concentrations of both HFRs and OPEs were significantly higher in the e-waste dust than ELV dust. Bioavailability of HFRs and OPEs in dust was determined by using an in vitro assay with human-simulated digestive fluids, dialysis membrane, and Tenax® TA sorptive sink. Bioaccessibility of HFRs was markedly lower than that of OPEs, which could be largely due to higher hydrophobicity of HFRs compared to OPEs. Bioaccessibility of almost hydrophobic compounds were markedly lower in the e-waste dust (containing micronized plastic debris) than in the ELV dust (containing oily materials), suggesting the influence of specific dust matrices on pollutant bioaccessibility. Although the daily uptake doses of selected HFRs and OPEs from dust were markedly higher in the e-waste sites compared to the ELV sites, the direct exposure risk was not significant. Our results suggest that bioaccessibility can partly explain the differences between dust and uptake profiles, which may relate to accumulation profiles of HFRs and OPEs in human samples.

Identification and quantification of additive-derived chemicals in beached micro-mesoplastics and macroplastics.

Although marine plastic debris are expected to retain various chemical additives, little is known about the additives that are retained. We conducted a screening analysis of additives in 261 macroplastic and micro-mesoplastic debris from two beaches. We detected 52 chemicals-antioxidants, phthalates, ultraviolet stabilizers, hindered amine light stabilizers, and flame retardants-and quantified the concentrations of 15 of them. Comparison of the concentrations of Irgafos 168, an antioxidant stabilizer, among sample categories indicated that leaching had occurred from micro-mesoplastics. Differences in diffusion rates between polymer types may explain faster leaching from polyethylene than polypropylene. The significant amounts of Irgafos 168 retained in even micro-mesoplastics indicated the importance of plastics as a vector of additives. This study provides fundamental data needed to assess the risks to organisms from exposure to plastic additives and to understand the effect of stabilizers on the aging behavior of marine plastics.

Estrogenic, androgenic, and glucocorticoid activities and major causative compounds in river waters from three Asian countries.

Estrogen, androgen, and glucocorticoid receptors (ER, AR, and GR) agonist activities in river water samples from Chennai and Bangalore (India), Jakarta (Indonesia), and Hanoi (Vietnam) were evaluated using a panel of chemical-activated luciferase gene expression (CALUX) assays and were detected mainly in the dissolved phase. The ER agonist activity levels were 0.011-55 ng estradiol (E2)-equivalent/l, higher than the proposed effect-based trigger (EBT) value of 0.5 ng/l in most of the samples. The AR agonist activity levels were < 2.1-110 ng dihydrotestosterone (DHT)-equivalent/l, and all levels above the limit of quantification exceeded the EBT value of 3.4 ng/l. GR agonist activities were detected in only Bangalore and Hanoi samples at dexamethasone (Dex)-equivalent levels of < 16-150 ng/l and exceeded the EBT value of 100 ng/l in only two Bangalore samples. Major compounds contributing to the ER, AR, and GR agonist activities were identified for water samples from Bangalore and Hanoi, which had substantially higher activities in all assays, by using a combination of fractionation, CALUX measurement, and non-target and target chemical analysis. The results for pooled samples showed that the major ER agonists were the endogenous estrogens E2 and estriol, and the major GR agonists were the synthetic glucocorticoids Dex and clobetasol propionate. The only AR agonist identified in major androgenic water extract fractions was DHT, but several unidentified compounds with the same molecular formulae as endogenous androgens were also found.

Short- and medium-chain chlorinated paraffins in polyvinyl chloride consumer goods available in the Japanese market.

Chlorinated paraffins (CPs), including short-chain CPs (SCCPs) and medium-chain CPs (MCCPs), are hazardous chemical additives widely applied as plasticizers and flame retardants in polymers, mainly in polyvinyl chloride (PVC). In 2017, SCCPs were listed under the Stockholm Convention on Persistent Organic Pollutants (POPs). MCCPs were proposed for listing as POPs in 2021. SCCPs are also restricted under the Basel Convention, with two tentative low POP content (LPC) limits (100 and 10,000 mg kg-1) for SCCPs in waste. As a signatory Party of both conventions, Japan must ensure their implementation and manage SCCP wastes in environmentally sound ways. Therefore, we aimed to assess the occurrence of SCCPs and MCCPs in PVC consumer goods (n = 87) available in the Japanese market. CPs were detected in 48% of the samples. Regarding positive samples, children's products and toys (1.3-120,000 mg kg-1) were more impacted by SCCPs whereas electrical and electronic cables (1.2-59,000 mg kg-1) and house interior products (3.5-550 mg kg-1) were more impacted by MCCPs. Fourteen and four samples exceeded the LPC limit of 100 and 10,000 mg kg-1 for SCCPs, respectively. Most products were impacted by CP contents (<1 % w/w) considerably below those reported as intentional CP uses in PVC. However, 11 samples with total CP contents ranging from 1.3% to 15 % (w/w) might have been impacted by intentional CP use as secondary plasticizer in PVC. Most of the impacted consumer goods available in the Japanese market were manufactured overseas, highlighting that only restricting POPs nationally is not enough for thorough implementation of the Basel and Stockholm Conventions. Therefore, imported PVC consumer goods, PVC waste and PVC recycling streams need to be monitored as relevant potential sources of SCCPs worldwide, even where the national industry strictly follows the restriction of such chemicals.

Recycling plastics containing decabromodiphenyl ether into new consumer products including children's toys purchased in Japan and seventeen other countries.

Polybrominated diphenyl ethers (PBDEs) are flame retardants widely used to manufacture several commercial plastic products. The major homologue in commercial PBDE mixtures are listed in the Stockholm Convention on Persistent Organic Pollutants and are scheduled for global elimination. Hence, to understand more about unintentional contamination of plastic recycling stream by restricted PBDEs, we examined 540 small plastic consumer products (1139 components after dismantling), including children's toys, purchased in 18 countries (mainly Japan) between 2015 and 2019. Handheld X-ray fluorescence analysis revealed that 219 plastic components (19% of the total samples) contained bromine at a concentration of ≥30 mg kg-1. Chemical analysis of these bromine-positive components revealed that 109 pieces (9.6% of the total), mainly those made of black-colored plastic, contained PBDEs at concentrations ranging between 35 and 10,000 mg kg-1, with the maximum contribution from decabromodiphenyl ether (decaBDE). These PBDE concentrations were insufficient to impart flame retardancy, suggesting that the recycled plastic used to manufacture these consumer products probably originated from electronic waste, the manufacture of which was the primary use of commercial decaBDE mixtures. PBDEs were also found in secondary raw plastic materials and their final products obtained in India in 2019, demonstrating that plastics containing decaBDE end up in products where they serve no functional purpose. To contribute to the circular economy, the recycling of plastic waste in end-of-life products should be promoted. However, urgent action is needed to prevent plastic additives of concern, including PBDEs, from entering new products used in daily lives, particularly those used by children.

Mechanical recycling of plastic waste as a point source of microplastic pollution.

Plastic pollution has become one of the most pressing environmental issues. Recycling is a potential means of reducing plastic pollution in the environment. However, plastic fragments are still likely released to the aquatic environment during mechanical recycling processes. Here, we examined the plastic inputs and effluent outputs of three mechanical recycling facilities in Vietnam dealing with electronic, bottle, and household plastic waste, and we found that large quantities of microplastics (plastics <5 mm in length) are generated and released to the aquatic environment during mechanical recycling without proper treatment. Comparisons with literature data for microplastics in wastewater treatment plant effluents and surface water indicated that mechanical recycling of plastic waste is likely a major point source of microplastics pollution. Although there is a mismatch between the size of the microplastics examined in the present study and the predicted no-effect concentration reported, it is still possible that microplastics generated at facilities pose risks to the aquatic environment because there might be many plastic particulates smaller than 315 µm, as suggested by our obtained size distributions. With mechanical recycling likely to increase as we move to a circular plastics economy, greater microplastics emissions can be expected. It is therefore an urgent need to fully understand not only the scale of microplastic generation and release from plastic mechanical recycling but also the environmental risk posed by microplastics in the aquatic environment.

Comprehensive characterization of halogenated flame retardants and organophosphate esters in settled dust from informal e-waste and end-of-life vehicle processing sites in Vietnam: Occurrence, source estimation, and risk assessment.

Information about the co-occurrence of halogenated flame retardants (HFRs) and organophosphate esters (OPEs) in the environment of informal waste processing areas is still limited, especially in emerging and developing countries. In this study, OPEs and HFRs including polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), and chlorinated flame retardants (CFRs) were determined in settled dust from Vietnamese e-waste recycling (WR) and vehicle processing (VP) workshops. Pollutant concentrations decreased in the order: OPEs (median 1500; range 230-410,000 ng/g) ≈ PBDEs (1200; 58-250,000) > NBFRs (140; not detected - 250,000) > CFRs (13; 0.39-2200). HFR and OPE levels in the WR workshops for e-waste and obsolete plastic were significantly higher than in the VP workshops. Decabromodiphenyl ether and decabromodiphenyl ethane are major HFRs, accounting for 60 ± 26% and 25 ± 29% of total HFRs, respectively. Triphenyl phosphate, tris(2-chloroisopropyl) phosphate, and tris(1,3-dichloroisopropyl) phosphate dominated the OPE profiles, accounting for 30 ± 25%, 25 ± 16%, and 24 ± 18% of total OPEs, respectively. The OPE profiles differed between WR and VP dust samples, implying different usage patterns of these substances in polymer materials for electric/electronic appliance and automotive industries. Human health risk related to dust-bound HFRs and OPEs in the study areas was low.

Silicone wristband- and handwipe-based assessment of exposure to flame retardants for informal electronic-waste and end-of-life-vehicle recycling workers and their children in Vietnam.

Measuring personal exposure to flame retardants (FRs) is crucial for assessing and controlling human health risks posed by FRs during the recycling of electronic waste (e-waste) and end-of-life vehicles (ELVs). Here, we examined the use of handwipes and silicone wristbands to measure personal FR exposure for e-waste and ELV recycling workers and their children in Vietnam. On the handwipes from the e-waste recycling workers, the predominant five FRs detected were TBBPA (median concentration: 3700 ng/wipe), BDE-209 (1700 ng/wipe), TPHP (500 ng/wipe), DBDPE (410 ng/wipe), and BPA-BDPP (360 ng/wipe). On the handwipes from ELV recycling workers, TPHP (60 ng/wipe), IPPDPP (47 ng/wipe), BIPPPP/DIPPDPP (33 ng/wipe), BDE-209 (26 ng/wipe), and TCIPP (23 ng/wipe) were detected as the five predominant FRs. On the wristbands from the e-waste recycling workers, the five predominant FRs detected were TBBPA (median concentration: 340 ng/g), BDE-209 (330 ng/g), DBDPE (65 ng/g), TPHP (50 ng/g), and TMPP (34 ng/g). On the wristbands from the ELV recycling workers, TPHP (34 ng/g), IPPDPP (18 ng/g), TCIPP (14 ng/g), TDMPP (13 ng/g), BIPPPP/DIPPDPP (9.3 ng/g) and TMPP (9.3 ng/g) were detected as the predominant FRs. The data obtained with the wristbands were comparable to those obtained with the handwipes. Similar FR profiles were found in between the workers and their children. The profiles indicate that the informal e-waste and ELV recycling caused FR exposure not only for workers but also for their children who live in the workshops. By using the handwipe and wristband sampling approaches, we determined types and concentrations of FRs to which the workers and their children were dominantly exposed. Silicone wristband- and handwipe-based assessment is expected to be effective means of measuring personal FR exposure for the informal e-waste and ELV recycling workers and their children.

Dietary exposure to short-chain chlorinated paraffins has increased in Beijing, China.

Short-chain chlorinated paraffins (SCCPs) persist in the environment and bioaccumulate in biota and are under review by the Stockholm Convention on persistent organic pollutants. SCCP levels were measured semiquantitatively in pooled 24 h food composite samples from Chinese (n = 10), Korean (n = 10), and Japanese (n = 40) adults in the 1990 s and 2007-2009. In Japan, SCCPs were detected in 14 of 20 pooled samples in the 1990 s and 13 of 20 pooled samples in 2009. Between these two time points, the geometric mean (GM) of the dietary intake of total SCCPs per body weight was comparable in Japan (54 ng kg-bw(-1) day(-1) in the 1990 s and 54 ng kg-bw(-1) day(-1) in the 2000s). In Beijing, SCCP levels were elevated by 2 orders of magnitude from 1993 to 2009 (GM: 620 ng kg-bw(-1) day(-1) in 2009). The 95th percentile estimate of the dietary intake was 1200 ng kg-bw(-1) day(-1) (>1% of tolerable daily intake). In Seoul, no samples in 1994 contained detectable SCCP levels and only one sample in 2007 showed trace levels of SCCPs. Preliminary evidence on the significant increase in SCCP exposure in Beijing in 2009 warrants urgent investigations to refine dietary intake estimates by targeting food types and source identification.

Investigation of novel brominated triazine-based flame retardant (TDBP-TAZTO) and its transformation products emitted from fire-retarded textile manufacturing facility and its downstream sewage treatment plant.

Investigation of transformation products from novel flame retardants emitted throughout their life cycles is crucial for understanding and predicting environmental and human health risks posed by them during the material and product life cycle. Here, to understand more about the emission of TDBP-TAZTO to the environment, we investigated the presence of novel brominated triazine-based flame retardant 1,3,5-tris-(2,3-dibromopropyl)-1,3,5-triazine-2,4,6-trione (TDBP-TAZTO) and its transformation products in the effluent from a facility manufacturing fire-retarded textiles, and in the influent, effluent, and sludge of its closest downstream sewage treatment plant. To acquire mass spectra data of the transformation products in the influent, effluent, and sludge, non-target analysis was carried out by electrospray ionization-quadrupole time-of-flight-high-resolution mass spectrometry with liquid chromatography (LC-ESI-QTOF-HRMS). Then, the HaloSeeker 2.0 software was used to filter the mass spectrometry data for signals attributable to halogenated compounds. Combination of LC-ESI-QTOF-HRMS accurate mass measurements and HaloSeeker screening allowed us to determine the most probable elemental compositions and structures of 11 transformation products from TDBP-TAZTO and to construct a possible transformation pathway that included dehydrobromination, hydroxylation, and decarbonylation reactions. Based on analysis of the absolute intensities, we found that TDBP-TAZTO and its transformation products may not be easily removed by current sewage treatment plant process. There are increasing concerns about environmental contamination by TDBP-TAZTO and its transformation products different from the one which have previously been considered to be c-decaBDE and its lower brominated congeners. However, the present data suggest that concern is also warranted over the presence of TDBP-TAZTO and its transformation products in the environment. The present data will be useful for assessing, predicting, and understanding the environmental contamination and human health risks posed by TDBP-TAZTO, and for considering appropriate measures to control the emission of TDBP-TAZTO and its transformation products during product life cycles.

Direct measurements and modeling of congener group specific vapor pressure for chlorinated paraffins.

Chlorinated Paraffins (CPs) are a complex group of manmade chemicals detected widely in the environment. To predict their environmental fate and effects, it is important to understand their physical-chemical properties including vapor pressure. In this study, the first direct measurements of the vapor pressure for CP congener groups (C10-16Cl4-11) are presented. Vapor pressure was measured above three industrial CP mixtures with different congener distributions between 20 and 50 °C using a gas saturation method. The measured saturated vapor pressure (P∗) decreased with increasing carbon chain length and Cl content. ΔHvap ranged between 73 and 122 kJ mol-1, consistent with data from the literature and model prediction. The experimental log P∗ at 25 °C agreed well with predictions from an empirical regression model in the literature (R2 = 0.97; RSME = 0.25) and with those predicted from the COSMO-RS-trained fragment contribution model (R2 = 0.95; RSME = 0.35). A new empirical model was calibrated with the P∗ data for 35 congener groups measured in this study. Predicted log P∗ values correlate well with field-measured gas/particle partition coefficients and may therefore be used for estimating the environmental fate and pathways of a broad range of CPs in the environment.

Simultaneous determination of polybrominated diphenyl ethers and hexabromocyclododecane in plastic waste by short-column gas-chromatography-quadrupole mass spectrometry and electron capture detector.

To avoid recycling plastic waste containing polybrominated diphenyl ethers (PBDEs) or hexabromocyclododecane (HBCD), which are listed in the Stockholm Convention on Persistent Organic Pollutants (POPs), a simple method to determine their contents at the time of waste disposal is needed. Herein, we developed a rapid analytical method using a gas chromatograph coupled with quadrupole mass spectrometry or electron capture detection to simultaneously detect PBDEs and HBCD in plastic waste. PBDEs and HBCD were ultrasonically extracted from plastic samples using toluene. The dissolved polymer matrix was then removed using n-hexane and 44% H2SO4-impregnated silica gel before analysis of the extract. A run time of less than 10 min was achieved using a custom, short GC column (5 m). The detection limits of the method were below the upper threshold of the low POP content limits defined by the Basel Convention (<1000 mg kg-1 for both PBDEs and HBCD). The accuracy of the method was confirmed by analyzing seven polymer reference materials. The determined PBDE and HBCD concentrations in most of these reference materials were within 30% of the certified values; the coefficients of variation in triplicate analysis were also within 30%. The concentrations of PBDEs and HBCD in actual plastic waste measured by this method were comparable with those obtained by more sophisticated and expensive methods, such as GC-high-resolution MS for PBDEs and liquid chromatography-tandem mass spectrometry for HBCD. Hence, the method developed herein is a less expensive alternative for identifying PBDE- and HBCD-containing wastes.

Comprehensive screening of polybromochlorodibenzo-p-dioxins, dibenzofurans as mixed halogenated compounds in wastewater samples from industrial facilities by GC×GC/ToFMS and post-data processing.

An enormous number of pollutants must be investigated to be able to understand which types threaten human health and environmental biota. In this study, we propose a workflow for screening polybromochlorodibenzo-p-dioxins and dibenzofurans (PBCDD/Fs), which are compounds that have thousands of isomers and congeners, by combining measurement of a sample without any in-laboratory-cleanup with the results of comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry and post-data processing. This process can be regarded as "in silico sample cleanup." The post-data processing stage comprises two methods in which the extracted mass spectra are matched to exact mass and isotopic ratios specified as formulae and filtering via mass deficiency. We applied this workflow to wastewater samples from industrial facilities to identify mixtures of halogenated dioxins. As a result, it was estimated that dioxins in an absolute quantity of 10-500 pg could be detected with sufficient accuracy by recovery testing of a standard mixture against sample crude extracts. Tri- to octa-halogenated dioxins were detected in 8 of 13 samples. Leachate from an industrial landfill was found to contain relatively large numbers of PBCDD/Fs, and several congeners were found in wastewater from an industrial fabric facility that handles decabromodiphenyl ether. The workflow, including the post-data processing method developed and applied in this study, has the advantage that additional identifications can be performed at any time from a single set of measurement data. This also enables the screening of substances that have thousands of homologous isomers, such as chlorinated and brominated dioxins, as well as other non-halogenated compounds.