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1.
Sci Total Environ ; 940: 173708, 2024 Jun 01.
Article in English | MEDLINE | ID: mdl-38830421

ABSTRACT

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 degrade into 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.

2.
Sci Total Environ ; 926: 172045, 2024 May 20.
Article in English | MEDLINE | ID: mdl-38554968

ABSTRACT

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.


Subject(s)
Air Pollution, Indoor , Electronic Waste , Environmental Pollutants , Flame Retardants , Humans , Dust/analysis , Environmental Monitoring/methods , Flame Retardants/analysis , Vietnam , Electronic Waste/analysis , Air Pollution, Indoor/analysis , Organophosphates/analysis , Esters/analysis , China
3.
Environ Sci Technol ; 57(35): 13136-13147, 2023 09 05.
Article in English | MEDLINE | ID: mdl-37607020

ABSTRACT

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

Subject(s)
Paraffin , Tandem Mass Spectrometry , Chromatography, Liquid
4.
Mar Pollut Bull ; 186: 114438, 2023 Jan.
Article in English | MEDLINE | ID: mdl-36473243

ABSTRACT

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.


Subject(s)
Microplastics , Water Pollutants, Chemical , Water Pollutants, Chemical/analysis , Environmental Monitoring , Plastics/analysis , Antioxidants/analysis
5.
Environ Sci Pollut Res Int ; 30(8): 20765-20774, 2023 Feb.
Article in English | MEDLINE | ID: mdl-36255587

ABSTRACT

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.


Subject(s)
Glucocorticoids , Water Pollutants, Chemical , Androgens/analysis , Biological Assay/methods , Estrogens/analysis , Estrone/analysis , Glucocorticoids/analysis , India , Rivers/chemistry , Water/analysis , Water Pollutants, Chemical/analysis , Indonesia , Vietnam
6.
Environ Geochem Health ; 45(6): 2705-2728, 2023 Jun.
Article in English | MEDLINE | ID: mdl-36194303

ABSTRACT

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.


Subject(s)
Electronic Waste , Environmental Pollutants , Polychlorinated Biphenyls , Humans , Electronic Waste/analysis , Vietnam , Environmental Pollutants/toxicity , Environmental Pollutants/analysis , Polychlorinated Biphenyls/analysis , Recycling , Environment , Environmental Monitoring
7.
Sci Total Environ ; 853: 158669, 2022 Dec 20.
Article in English | MEDLINE | ID: mdl-36108870

ABSTRACT

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.


Subject(s)
Electronic Waste , Flame Retardants , Child , Humans , Flame Retardants/analysis , Electronic Waste/analysis , Silicones , Vietnam , Environmental Monitoring , Halogenated Diphenyl Ethers/analysis , Recycling , Dust/analysis , Organophosphates/analysis
8.
Sci Total Environ ; 849: 157762, 2022 Nov 25.
Article in English | MEDLINE | ID: mdl-35926616

ABSTRACT

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.


Subject(s)
Environmental Pollutants , Flame Retardants , Hydrocarbons, Chlorinated , Child , China , Environmental Monitoring , Hazardous Substances , Humans , Hydrocarbons, Chlorinated/analysis , Japan , Paraffin/analysis , Persistent Organic Pollutants , Plasticizers , Polyvinyl Chloride
9.
Environ Pollut ; 310: 119809, 2022 Oct 01.
Article in English | MEDLINE | ID: mdl-35931384

ABSTRACT

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.


Subject(s)
Electronic Waste , Flame Retardants , Humans , Dust , Environmental Monitoring , Esters , Halogenated Diphenyl Ethers , Organophosphates , Risk Assessment , Vietnam
10.
Environ Pollut ; 303: 119114, 2022 Jun 15.
Article in English | MEDLINE | ID: mdl-35276247

ABSTRACT

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.


Subject(s)
Water Pollutants, Chemical , Water Purification , Environmental Monitoring , Environmental Pollution , Microplastics , Plastics , Recycling , Wastewater , Water Pollutants, Chemical/analysis
11.
Chemosphere ; 289: 133179, 2022 Feb.
Article in English | MEDLINE | ID: mdl-34875294

ABSTRACT

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.


Subject(s)
Electronic Waste , Flame Retardants , Child , Electronic Waste/analysis , Environmental Monitoring , Flame Retardants/analysis , Halogenated Diphenyl Ethers/analysis , Humans , Japan , Plastics , Recycling
12.
Chemosphere ; 281: 130909, 2021 Oct.
Article in English | MEDLINE | ID: mdl-34289607

ABSTRACT

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.


Subject(s)
Hydrocarbons, Chlorinated , Paraffin , Carbon , China , Environmental Monitoring , Hydrocarbons, Chlorinated/analysis , Paraffin/analysis , Vapor Pressure
13.
Sci Total Environ ; 791: 148233, 2021 Oct 15.
Article in English | MEDLINE | ID: mdl-34126480

ABSTRACT

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.


Subject(s)
Flame Retardants , Humans , Manufacturing and Industrial Facilities , Sewage , Textiles , Triazines
14.
Chemosphere ; 277: 130301, 2021 Aug.
Article in English | MEDLINE | ID: mdl-33794427

ABSTRACT

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.


Subject(s)
Flame Retardants , Halogenated Diphenyl Ethers , Electrons , Flame Retardants/analysis , Gas Chromatography-Mass Spectrometry , Halogenated Diphenyl Ethers/analysis , Hydrocarbons, Brominated , Mass Spectrometry , Plastics
15.
Chemosphere ; 276: 130085, 2021 Aug.
Article in English | MEDLINE | ID: mdl-33690031

ABSTRACT

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.


Subject(s)
Benzofurans , Dioxins , Benzofurans/analysis , Dibenzofurans/analysis , Dibenzofurans, Polychlorinated , Dioxins/analysis , Humans , Manufacturing and Industrial Facilities , Wastewater
16.
Article in English | MEDLINE | ID: mdl-33530429

ABSTRACT

This study investigates the presence of Stockholm Convention listed short-chain chlorinated paraffins (SCCPs) and their replacement medium-chain chlorinated paraffins (MCCPs) counterparts in polyvinyl chloride and rubber consumer products and toys purchased on the Belgian market in 2019. SCCPs were detected in 27/28 samples at concentrations ranging from

Subject(s)
Hydrocarbons, Chlorinated , Paraffin , Belgium , China , Environmental Monitoring , Hydrocarbons, Chlorinated/analysis , Paraffin/analysis , Polyvinyl Chloride , Rubber
17.
Sci Rep ; 11(1): 4426, 2021 02 24.
Article in English | MEDLINE | ID: mdl-33627839

ABSTRACT

Chlorinated Paraffins (CPs) are high volume production chemicals and have been found in various organisms including humans and in environmental samples from remote regions. It is thus of great importance to understand the physical-chemical properties of CPs. In this study, gas chromatographic (GC) retention indexes (RIs) of 25 CP congeners were measured on various polar and nonpolar columns to investigate the relationships between the molecular structure and the partition properties. Retention measurements show that analytical standards of individual CPs often contain several stereoisomers. RI values show that chlorination pattern have a large influence on the polarity of CPs. Single Cl substitutions (-CHCl-, -CH2Cl) generally increase polarity of CPs. However, many consecutive -CHCl- units (e.g., 1,2,3,4,5,6-C11Cl6) increase polarity less than expected from the total number of -CHCl- units. Polyparameter linear free energy relationship descriptors show that polarity difference between CP congeners can be explained by the H-bond donating properties of CPs. RI values of CP congeners were predicted using the quantum chemically based prediction tool COSMOthermX. Predicted RI values correlate well with the experimental data (R2, 0.975-0.995), indicating that COSMOthermX can be used to accurately predict the retention of CP congeners on GC columns.

18.
Environ Sci Technol ; 55(4): 2324-2335, 2021 02 16.
Article in English | MEDLINE | ID: mdl-33440927

ABSTRACT

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.


Subject(s)
Dioxins , Flame Retardants , Environmental Monitoring , Flame Retardants/analysis , Halogenated Diphenyl Ethers/analysis , Japan , Sewage
19.
Sci Total Environ ; 760: 143862, 2021 Mar 15.
Article in English | MEDLINE | ID: mdl-33348160

ABSTRACT

Although bioaccessibility testing is applied worldwide for appropriate chemical risk assessment, few studies have focused on the bioaccessibility of flame retardants (FRs), especially inhalation exposure. This study assessed inhalation exposure to FRs in indoor dust by workers at e-waste-dismantling workshops in northern Vietnam, by using modified simulated epithelial lung fluid (SELF) and artificial lysosomal fluid (ALF). The average mass concentrations of FRs were 130,000 ng/g for workplace dust (n = 3), 140,000 ng/g for floor dust (n = 3), and 74,000 ng/g for settled dust (n = 2), whereas the average bioaccessible concentrations of FRs were 1900, 1400, and 270 ng/g in the SELF condition and 2600, 770, and 490 ng/g in the ALF condition, respectively. Results clearly indicate that the bioaccessible concentrations of FRs are markedly lower than their mass concentrations. Tris(2-chloroethyl) phosphate (TCEP, ~19%), tris(2-chloroisopropyl) phosphate (TCIPP, ~35%), and tris(1,3-dichloroisopropyl) phosphate (TDCIPP, ~22%) showed comparably high bioaccessibility in both SELF and ALF conditions. In contrast, the bioaccessibility of tetrabromobisphenol A (TBBPA, ~20%) was high in the SELF condition, but not in the ALF condition. With regard to the test compounds' physicochemical properties, the inhalation bioaccessibility of FRs in both conditions increased as molecular weight or octanol-water partition coefficient decreased, and it decreased as water solubility decreased. Health risk assessment clearly indicated that the hazard quotient of FRs via inhalation exposure for workers in the e-waste-dismantling workshops was less than 1, suggesting that the inhalation exposure to FRs during indoor dismantling of e-waste at this site was negligible based on the current methodology of non-cancer health risk assessment used in this study.


Subject(s)
Air Pollution, Indoor , Electronic Waste , Flame Retardants , Air Pollution, Indoor/analysis , Asian People , Dust/analysis , Environmental Exposure , Flame Retardants/analysis , Halogenated Diphenyl Ethers/analysis , Humans , Organophosphates/analysis , Risk Assessment , Vietnam
20.
Environ Pollut ; 272: 115587, 2021 Mar 01.
Article in English | MEDLINE | ID: mdl-33261969

ABSTRACT

In recent years, concern about the release of anthropogenic organic micropollutants referred to as contaminants of emerging concern (CECs) has been growing. The objective of this study was to find potential CECs by means of an analytical screening method referred to as comprehensive target analysis with an automated identification and quantification system (CTA-AIQS), which uses gas and liquid chromatography combined with mass spectrometry (GC-MS and LC-QTOF-MS). We used CTA-AIQS to analyze samples from a sediment core collected in Beppu Bay, Japan. With this method, we detected 80 compounds in the samples and CTA-AIQA could work to useful tool to find CECs in environmental media. Among the detected chemicals, three PAHs (anthracene, chrysene, and fluoranthene) and tris(isopropylphenyl)phosphate (TIPPP) isomers were found to increase in concentration with decreasing sediment depth. We quantified TIPPP isomers in the samples by means of targeted analysis using LC-MS/MS for confirmation. The concentration profiles, combined with previous reports indicating persistent, bioaccumulative, and toxic properties, suggest that these chemicals can be categorized as potential CECs in marine environments.


Subject(s)
Polycyclic Aromatic Hydrocarbons , Water Pollutants, Chemical , Bays , Chromatography, Liquid , Environmental Monitoring , Japan , Polycyclic Aromatic Hydrocarbons/analysis , Tandem Mass Spectrometry , Water Pollutants, Chemical/analysis
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