Assessment of Human Exposure to Traditional and Novel Organophosphate Esters via Multiple Personal Matrices.

Herein, 16 traditional and 13 novel organophosphate esters (OPEs) in skin wipes, personal PM2.5, sputum, and nails (fingernails and toenails) and 7 OPE metabolites in urine synchronously obtained from 64 college students were analyzed. Similar compositional profiles of the OPEs were found in skin wipes and nails and in personal PM2.5 and induced sputum. Significant correlations were observed between the concentrations of high-lipophilicity low-volatility OPEs in skin wipes and nails and between the concentrations of high-volatility low-lipophilicity OPEs in personal PM2.5 and sputum. These results imply that OPEs in fingernails and toenails may mainly come from external sources rather than internal exposure, and human nails and sputum can be used as indicators of human exposure to OPEs. A comparison between the daily exposure doses of the OPEs in personal PM2.5 and sputum shows that more volatile compounds may have higher inhalation bioavailability, which should be considered to improve the accuracy of inhalation exposure assessments. According to comprehensive external and internal exposure assessment, dermal absorption may be a more dominant pathway than inhalation, and skin wipes may be the best representative environmental matrix of human exposure to OPEs.

Percutaneous Penetration of Liquid Crystal Monomers (LCMs) by In Vitro Three-Dimensional Human Skin Equivalents: Possible Mechanisms and Implications for Human Dermal Exposure Risks.

Liquid crystal monomers (LCMs) are indispensable materials in liquid crystal displays, which have been recognized as emerging persistent, bioaccumulative, and toxic organic pollutants. Occupational and nonoccupational exposure risk assessment suggested that dermal exposure is the primary exposure route for LCMs. However, the bioavailability and possible mechanisms of dermal exposure to LCMs via skin absorption and penetration remain unclear. Herein, we used EpiKutis 3D-Human Skin Equivalents (3D-HSE) to quantitatively assess the percutaneous penetration of nine LCMs, which were detected in e-waste dismantling workers' hand wipes with high detection frequencies. LCMs with higher log Kow and greater molecular weight (MW) were more difficult to penetrate through the skin. Molecular docking results showed that ABCG2 (an efflux transporter) may be responsible for percutaneous penetration of LCMs. These results suggest that passive diffusion and active efflux transport may be involved in the penetration of LCMs across the skin barrier. Furthermore, the occupational dermal exposure risks evaluated based on the dermal absorption factor suggested the underestimation of the continuous LCMs' health risks via dermal previously.

Organophosphite Antioxidants and Novel Organophosphate Esters in Dust from China: Large-Scale Distribution and Heterogeneous Phototransformation.

A large-scale survey was conducted by measuring five organophosphite antioxidants (OPAs) and three novel organophosphate esters (NOPEs) in 139 dust samples across China. The median summed concentrations of OPAs and NOPEs in outdoor dust were 33.8 ng/g (range: 0.12-53,400 ng/g) and 7990 ng/g (2390-27,600 ng/g), respectively. The dust concentrations of OPAs associated with the increasing economic development and population density from western to eastern China, whereas the NOPE concentration in Northeast China (median, 11,900 ng/g; range, 4360-16,400 ng/g) was the highest. Geographically, the distribution of NOPEs was significantly associated with annual sunshine duration and precipitation at each sampling site. Results of laboratory experiments further revealed that the simulated sunlight irradiation promoted the heterogeneous phototransformation of OPAs in dust, and this process was accelerated with the existence of reactive oxygen species and enhanced relative humidity. Importantly, during this phototransformation, the hydroxylated, hydrolyzed, dealkylated, and methylated products, e.g., bis(2,4-di-tert-butylphenyl) methyl phosphate, were identified by nontargeted analysis, part of which were estimated to be more toxic than their parent compounds. The heterogeneous phototransformation pathway of OPAs was suggested accordingly. For the first time, the large-scale distribution of OPAs and NOPEs and the phototransformation of these "new chemicals" in dust were revealed.

Nontarget Screening and Fate of Emerging Per- and Polyfluoroalkyl Substances in Wastewater Treatment Plants in Tianjin, China.

Wastewater treatment plants (WWTPs) are typical point sources of per- and polyfluoroalkyl substances (PFAS) released into the environment. The suspect and nontarget screening based on gas chromatography or liquid chromatography-high resolution mass spectrometry were performed on atmosphere, wastewater, and sludge samples collected from two WWTPs in Tianjin to discover emerging PFAS and their fate in this study. A total of 40 PFAS (14 neutral and 26 ionic) and 64 PFAS were identified in the atmosphere and wastewater/sludge, respectively, among which 5 short-chain perfluoroalkyl sulfonamide derivatives, 4 ionic PFAS, and 15 aqueous film-forming foam-related cationic or zwitterionic PFAS have rarely or never been reported in WWTPs in China. Active air sampling is more conducive to the enrichment of emerging PFAS, while passive sampling is inclined to leave out some ultrashort-chain PFAS or unstable transformation intermediates. Moreover, most precursors and intermediates could be enriched in the atmosphere at night, while the PFAS associated with aerosols with high water content or particles enter the atmosphere easily during the day. Although most emerging PFAS could not be eliminated efficiently in conventional treatment units, deep bed filtration and advanced oxidation processes could partly remove some emerging precursors.

Degradation of Perfluorooctanoic Acid by Chlorine Radical Triggered Electrochemical Oxidation System.

Electrochemical oxidation (EO) has been shown to have the unique ability to degrade perfluorooctanoic acid (PFOA), although the radical chemistry involved in this degradation is unclear, particularly in the presence of chloride ions (Cl-). In this study, reaction kinetics, free radical quenching, electron spin resonance, and radical probes were used to examine the roles of ·OH and reactive chlorine species (RCS, including Cl·, Cl2•-, and ClO·) in the EO of PFOA. Using EO in the presence of NaCl, PFOA degradation rates of 89.4%-94.9% and defluorination rates of 38.7%-44.1% were achieved after 480 min with PFOA concentrations ranging from 2.4 to 240 µM. The degradation occurred via the synergistic effect of ·OH and Cl· rather than through direct anodic oxidation. The degradation products and density functional theory (DFT) calculations revealed that Cl· triggered the first step of the reaction, thus the initial direct electron transfer was not the rate-limiting step of PFOA degradation. The change in Gibbs free energy of the reaction caused by Cl· was 65.57 kJ mol-1, which was more than two times lower than that triggered by ·OH. However, ·OH was involved in the subsequent degradation of PFOA. The synergistic effect of Cl· and ·OH in PFOA degradation is demonstrated for the first time in this study, which is promising for the development of electrochemical technology to remove perfluorinated alkyl substances from the environment.

In situ self-sacrificial synthesis of polypyrrole/biochar composites for efficiently removing short- and long-chain perfluoroalkyl acid from contaminated water.

Efficient removal of perfluoroalkyl acids (PFAAs), especially short-chain ones, from contaminated water is of great challenge and is urgently called for so as to safeguard the ecosystem and human health. Herein, polypyrrole (PPy) functionalized biochar (BC) composites were innovatively synthesized by an in situ self-sacrificial approach to allow efficient capture of PFAAs with different chain lengths. Compared with conventional PPy-based composites synthesized by direct polymerization using FeCl3 as an oxidizing agent, PPy/BC composites were fabricated utilizing freshly generated Fe3+ as an oxidizing agent from self-sacrificial Fe3O4 for pyrrole monomers in situ polymerizing on BC. As a result, with the support of BC and gradual release of Fe3+, PPy overcame its tendency to aggregate and became uniformly dispersed on BC, and meanwhile, PPy could well tailor the surface chemistry of BC to endow its positively charged surface. Consequently, the composites exhibited strong sorption capacities of 3.89 and 1.53 mmol/g for short-chain perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS), 2.55 and 1.22 mmol/g for long-chain perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), respectively, which were superior to those of pristine BC, commercial activated carbon, and anion exchange resins reported. Additionally, they could effectively remove 17 different classes of per- and polyfluoroalkyl substances (PFAS) (removal >95%) from actual PFAS-contaminated water, and the spent sorbent could be well regenerated and reused at least 5 times. An integrated analysis indicated that such an outstanding PFAA sorption performance on PPy/BC composites could be mainly attributed to surface adsorption enhanced by electrostatic attractions (anion exchange interaction) with the traditional hydrophobic interaction and pore filling of less contribution, particularly for short-chain analogues. These results are expected to inform the design of BC with greater ability to remove PFAS from water and the new sorbent could help water facilities comply with PFAS regulations.

Electronic-Waste-Driven Pollution of Liquid Crystal Monomers: Environmental Occurrence and Human Exposure in Recycling Industrial Parks.

Liquid crystal monomers (LCMs) in liquid crystal displays (LCDs) may be released into the environment, especially in electronic waste (e-waste) recycling industrial parks with a high pollution risk. However, little has been known about the environmental release and human exposure to LCMs until now. Herein, a total of 45 LCMs were detected in LCDs of commonly used smartphones and computers by high-resolution mass spectrometry with suspect screening analysis. Fluorinated biphenyls and their analogs were the dominant LCMs. Based on available standards of the screening results and previous studies, 55 LCMs were quantified in samples from an e-waste recycling industrial park in Central China. The LCMs were frequently detected in outdoor dust (n = 43), workshop #1 indoor dust (n = 53), and hand (n = 43) and forehead wipes (n = 43), with median concentrations of 6950 ng/g, 67,400 ng/g, 46,100 ng/m2, and 62,100 ng/m2, respectively. The median estimated daily intake values of the LCMs via dust ingestion and dermal absorption were 48.3 and 16.5 ng/kg body weight/day, respectively, indicating a high occupational exposure risk of these compounds. In addition, 16 LCMs were detected in the serum of eight elderly people (≥60 years old) with over 5 years of experience in e-waste dismantling operations, resulting in a total concentration range of 3.9-26.3 ng/mL.

Identification of Novel Organophosphate Esters in Hydroponic Lettuces (Lactuca sativa L.): Biotransformation and Acropetal Translocation.

The absorption, translocation, and biotransformation behaviors of organophosphate esters (OPEs) and diesters (OPdEs) in a hydroponic system were investigated. The lateral root was found as the main accumulation and biotransformation place of OPEs and OPdEs in lettuce. The nontarget analysis using high-resolution mass spectrometry revealed five hydroxylated metabolites and five conjugating metabolites in the OPE exposure group, among which methylation, acetylation, and palmitoyl conjugating OPEs were reported as metabolites for the first time. Particularly, methylation on phosphate can be a significant process for plant metabolism, and methyl diphenyl phosphate (MDPP) accounted for the majority of metabolites. The translocation factor values of most identified OPE metabolites are negatively associated with their predicted logarithmic octanol-water partitioning coefficient (log Kow) values (0.75-2.45), indicating that hydrophilicity is a dominant factor in the translocation of OPE metabolites in lettuce. In contrast, palmitoyl conjugation may lead to an enhanced acropetal translocation and those with log Kow values < 0 may have limited translocation potential. Additionally, OPE diesters produced from the biotransformation of OPEs in lettuce showed a higher acropetal translocation potential than those exposed directly. These results further emphasize the necessity to consider biotransformation as an utmost important factor in the accumulation and acropetal translocation potential of OPEs in plants.

Influence of Air Pollution on Inhalation and Dermal Exposure of Human to Organophosphate Flame Retardants: A Case Study During a Prolonged Haze Episode.

The health impact of haze is of great concern, but few studies have explored its influence on human inhalation and dermal exposure to trace pollutants. Size-segregated atmospheric particles ( n = 72) and forehead wipe samples ( n = 80) from undergraduates were collected in Xinxiang, China, during a prolonged haze episode and analyzed for 10 organophosphate flame retardants (OPFRs). ∑TCPP and TCEP were the most abundant OPFR substances in all samples. The arithmetic mean particle-bound and forehead OPFR concentrations under a heavy pollution condition (air quality index (AQI), 350-550) were 41.9 ng/m3 (∑8OPFRs) and 7.4 µg/m2 (∑6OPFRs), respectively, apparently greater than the values observed under a light pollution condition (AQI, 60-90) (19.5 ng/m3 and 3.9 µg/m2, respectively). Meteorological conditions played distinctive roles in affecting the OPFR occurrence in atmospheric particles (statistically significant for TCEP and ∑TCPP) and forehead wipes (excluding TPHP), implying that OPFR exposure through inhalation and dermal absorption was synchronously influenced by air quality, and OPFRs on the forehead may be mainly absorbed from the air. Inhalation contributed dominantly to the total OPFR exposure dose for humans when using the relative absorption method to assess dermal exposure, while according to the permeability coefficient method, dermal exposure was much more significant than inhalation. The results of this study indicate that OPFR exposure should attract particular concern in regions with heavy air pollution.

Contamination characteristics of trace metals in dust from different levels of roads of a heavily air-polluted city in north China.

Concentrations of eight trace metals (TMs) in road dust (RD) (particles < 25 µm) from urban areas of Xinxiang, China, were determined by inductively coupled plasma mass spectrometry. The geometric mean concentrations of Zn, Mn, Pb, As, Cu, Cr, Ni and Cd were 489, 350, 114, 101, 60.0, 39.7, 31.6, and 5.1 mg kg-1, respectively. When compared with TM levels in background soil, the samples generally display elevated TM concentrations, except for Cr and Mn, and for Cd the enrichment value was 69.6. Spatial variations indicated TMs in RD from park path would have similar sources with main roads, collector streets and bypasses. Average daily exposure doses of the studied TMs were about three orders of magnitude higher for hand-to-mouth ingestion than dermal contact, and the exposure doses for children were 9.33 times higher than that for adults. The decreasing trend of calculated hazard indexes (HI) for the eight elements was As > Pb > Cr > Mn > Cd > Zn > Ni > Cu for both children and adults.

Unexpected Exposure Risks to Emerging Aromatic Amine Antioxidants and p-Phenylenediamine Quinones to Residents: Evidence from External and Internal Exposure as Well as Hepatotoxicity Evaluation.

Aromatic amine antioxidants (AAs), extensively used in rubber products, and their ozone-photolyzed product p-phenylenediamine quinones (PPD-Qs) were found to be pervasive in various environments and with potential ecological and health risks. The relationship between external and internal exposure to these contaminants and their exposure risks to the general population remain poorly explored. Herein, dust-handwipe-urine samples (n = 97 pairs) from families in Tianjin, China was collected for analyzing 20 AAs and 6 PPD-Qs (including self-synthesized emerging PPD-Qs). The median concentration of ∑20AAs (1310 ng/g, 354 ng/m2, and 18.5 ng/mL, respectively) and ∑6PPD-Qs (1645 ng/g, 3913 ng/m2 and 3.76 ng/mL, respectively) in dust, handwipe, and urine samples indicated a non-negligible contamination of AAs and PPD-Qs in indoor environment. Notably, emerging DPPD-Q and DNPD-Q (oxidation products of DPPD and DNPD, respectively) were prominent, accounting for >90% of PPD-Qs. The correlation analysis and estimated daily intake (EDI) assessments indicated that neither dust ingestion nor dermal exposure may be the primary source of internal exposure to AAs and PPD-Qs in the general population, and other exposure pathways (e.g., diet and inhalation) may exist. In vitro HepG2 cell experiments demonstrated that both PPD-Qs and PPDs may have potential exposure risk of hepatotoxicity.

Methods for the characterisation of dermal uptake: Progress and perspectives for organophosphate esters.

Organophosphate esters (OPEs) are a group of pollutants that are widely detected in the environment at high concentrations. They can adversely affect human health through multiple routes of exposure, including dermal uptake. Although attention has been paid to achieving an accurate and complete quantification of the dermal uptake of OPEs, existing evaluation methods and parameters have obvious weaknesses. This study reviewed two main categories of methodologies, namely the relative absorption (RA) model and the permeability coefficient (PC) model, which are widely used to assess the dermal uptake of OPEs. Although the PC model is more accurate and is increasingly used, the most important parameter in this model, the permeability coefficient (Kp), has been poorly characterised for OPEs, resulting in considerable errors in the estimation of the dermal uptake of OPEs. Thus, the detailed in vitro methods for the determination of Kp are summarised and sorted. Furthermore, the commonly used skin membranes are identified and the factors affecting Kp and corresponding mechanisms are discussed. In addition, the experimental conditions, conclusions, and available data on Kp values of the OPEs are thoroughly summarised. Finally, the corresponding knowledge gaps are proposed, and a more accurate and sophisticated experimental system and unknown Kp values for OPEs are suggested.

Aromatic amine antioxidants (AAs) and p-phenylenediamines-quinones (PPD-Qs) in e-waste recycling industry park: Occupational exposure and liver X receptors (LXRs) disruption potential.

Recently, evidence of aromatic amine antioxidants (AAs) existence in the dust of the electronic waste (e-waste) dismantling area has been exposed. However, there are limited studies investigating occupational exposure and toxicity associated with AAs and their transformation products (p-phenylenediamines-quinones, i.e., PPD-Qs). In this study, 115 dust and 42 hand wipe samples collected from an e-waste recycling industrial park in central China were analyzed for 19 AAs and 6 PPD-Qs. Notably, the median concentration of ∑6PPD-Qs (1,110 ng/g and 1,970 ng/m2) was significantly higher (p < 0.05, Mann-Whitney U test) than that of ∑6PPDs (147 ng/g and 34.0 ng/m2) in dust and hand wipes. Among the detected analytes, 4-phenylaminodiphenylamine quinone (DPPD-Q) (median: 781 ng/g) and 1,4-Bis(2-naphthylamino) benzene quinone (DNPD-Q) (median: 156 ng/g), were particularly prominent, which were first detected in the e-waste dismantling area. Occupational exposure assessments and nuclear receptor interference ability, conducted through estimated daily intake (EDI) and molecular docking analysis, respectively, indicated significant occupational exposure to PPD-Qs and suggested prioritized Liver X receptors (LXRs) disruption potential of PPDs and PPD-Qs. The study provides the first evidence of considerable levels of AAs and PPD-Qs in the e-waste-related hand wipe samples and underscores the importance of assessing occupational exposure and associated toxicity effects.

Quantitative characterization of resident' exposure to typical semi-volatile organic compounds (SVOCs) around a non-ferrous metal smelting plant.

To comprehensively characterize residents' exposure to major semi-volatile organic compounds (SVOCs), samples of indoor floor wipes, size-segregated airborne particles, gaseous air, food, and paired skin wipes were simultaneously collected from residential areas around a large non-ferrous metal smelting plant as compared with the control areas, and three typical SVOCs (including polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and halogenated PAHs (HPAHs)) were determined. Comparison and correlation analysis among matrices indicated PAHs were the major contaminants emitted from metal smelting activities compared to HPAHs and PCBs, with naphthalene verified as the most important characteristic compound, and their accumulation on skin may be a comprehensive consequence of contact with floor dust and air. While patterns of human exposure pathways for the SVOCs were found to be clearly correlated to their vapor pressure, dermal absorption was the major contributor (51.1-76.3%) to total carcinogenic risk (TCR) of PAHs and HPAHs for surrounding residents, especially for low molecular weight PAHs, but dietary ingestion (98.6%) was the dominant exposure pathway to PCBs. The TCR of PAHs exceeded the acceptable level (1 × 10-4), implying smelting activities obviously elevated the health risk. This study will serve developing pertinent exposure and health risk prevention measures.

Multimedia distribution and release characteristics of emerging PFAS in wastewater treatment plants in Tianjin, China.

Legacy and emerging PFAS in the air, wastewater, and sludge from two wastewater treatment plants (WWTPs) in Tianjin were investigated in this study. The semi-quantified nontarget PFAS accounted for up to 99 % of Æ©PFAS in the gas phase, and aqueous film-forming foam (AFFF)-related PFAS were predominant in wastewater (up to 2250 ng/L, 79 % of Æ©PFAS) and sludge (up to 4690 ng/g, 95 % of Æ©PFAS). Furthermore, field-derived air particle-gas, air-wastewater, and wastewater particle-wastewater distribution coefficients of emerging PFAS are characterized, which have rarely been reported. The emerging substitute p-perfluorous nonenoxybenzenesulfonate (OBS) and AFFF-related cationic and zwitterionic PFAS show a stronger tendency to partition into particle phase in air and wastewater than perfluorooctane sulfonic acid (PFOS). The estimated total PFAS emissions from the effluent and sludge of WWTP A were 202 kg/y and 351 kg/y, respectively. While the target PFAS only accounted for 20-33 % of the total emissions, suggesting a significant underestimation of environmental releases of the nontarget PFAS and unknown perfluoroalkyl acid precursors through the wastewater and sludge disposal. Overall, this study highlights the importance of comprehensive monitoring and understanding the behavior of legacy and emerging PFAS in wastewater systems, and fills a critical gap in our understanding of PFAS exposure.

Unraveling the contribution of melamine tableware for human internal exposure to melamine and its derivatives: Insights from crossover and biomonitoring studies.

Melamine tableware can release melamine in daily-use; however, currently there is insufficient evidence to support whether the amount released could pose human exposure risk. We therefore conducted two studies, one is 8-day randomized crossover trial involving 27 volunteers who used melamine and stainless-steel tableware in turn (n = 648) and the other is cross-sectional study including 113 college students and 200 residents (n = 313) to further provide population-based evidence. The crossover study results showed that using melamine tableware could promote urinary concentrations of melamine, cyanuric acid (CYA), and ammelide by 42.1 %, 66.9 %, and 36.2 %, respectively. In the biomonitoring survey, students who are more accessible to melamine tableware in the canteen had 1.47-fold higher median urinary concentrations of melamine-related compounds than that of common residents (393 vs 267 nmol/L, p < 0.01). Additionally, positive associations between exposure to melamine and an oxidative stress indicator, 8-oxo-7,8-dihydroguanine (ß = 1.13, 95 % CI: 0.32, 1.94), and CYA and 8-hydroxy-2'-deoxyguanosine (ß = 0.87, 95 % CI: 0.22, 1.53) were observed in students (p < 0.01), indicating long-term chronic exposure to these chemicals may induce molecular damage to nucleic acids. Our findings provide compelling evidence that frequent use of melamine tableware continues to be a potential threat to human health.

Source and bioavailability of quaternary ammonium compounds (QACs) in dust: Implications for Nationwide Exposure in China.

Quaternary ammonium compounds (QACs), widely used in various disinfectants products during the COVID-19 Pandemic, raised the concerns on their exposure and health effect. To date, the sources of QACs in indoor environments have been largely ignored. Additionally, there is no information on the nationwide human exposure assessment of QACs in China after the COVID-19. Herein, analysis of QACs in household products, including personal care (n = 27), cleaning (n = 6) and disinfection products (n = 11) from different manufacturing companies further confirmed there are extensive application of QACs in household products, raising their potential exposure to humans. QACs were frequently detected in indoor dust samples (n = 370) from 111 cities of 31 provinces/municipalities across China, with median concentration of 6778 ng/g. Benzalkyldimethylammonium compounds (BACs) and alkyltrimethylammonium compounds (ATMACs) were identified as the dominant QACs in dust samples, with the proportions of 44 % and 46 %, respectively. The in vivo bioavailability experiment (C57BL/6 male mice) showed that the relative bioavailability (RBA) of QACs through dust ingestion ranged from 5.08 % to 66.3 % and 60.3 % to 118 % in the low and high-dose group, respectively. Compared to the pre-adjustment scenario of RBA values, the exposure risk of QACs was overestimated by 2.23 - 5.14 times.

Face mask as an indicator and shield of human exposure to traditional and novel organophosphate esters.

Herein, the trapping effectiveness of N95, filter KN95, medical surgical masks (MSMs), and disposable medical masks (DMMs) against 19 airborne traditional and novel organophosphate esters (OPEs) was evaluated. Laboratory simulations (n = 24 for each type of mask) showed that time-dependent accumulation of ∑19OPEs on the four types of masks ranged between 30.1 and 86.6 ng in 24 h, with the highest and lowest median amounts trapped by the N95 masks (53.3 ng) and DMMs (43.2 ng), respectively. The trapping efficiency of the four types of masks for ∑19OPEs decreased over time from 84 % to 39 % in 24 h, with N95 masks showing the highest median efficiency (70 %). Further, field investigations were conducted in five types of microenvironments (train, hospital, bus, supermarket, and canteen), and an analysis of 200 samples showed that ∑19OPEs were accumulated in the masks with a variable amount from 3.7 to 117 ng/mask. Consistent with the laboratory simulations, the N95 masks (29.0 ng/mask) exhibited the highest hourly median amount of trapped OPEs, followed by the KN95 masks (24.5 ng/mask), MSMSs (17.4 ng/mask), and DMMs (15.8 ng/mask). Triethyl phosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri-n-butyl phosphate (TNBP), and cresyl diphenyl phosphate (CDP) as well as 4-isopropylphenyl diphenyl phosphate (4IPPDPP) and 2,4-diisopropylphenyl diphenyl phosphate (24DIPPDPP) were the most commonly detected traditional and novel OPEs. Based on the amount of OPEs trapped on the masks, we estimated the concentration of ∑19OPEs in the train microenvironment to be the highest (222 ng/m3), which is approximately 2-5 times higher than that in the other microenvironments. The results of this study prove that masks can effectively protect humans from exposure to OPEs and act as low-cost indicators of indoor contamination.

Global patterns of human exposure to flame retardants indoors.

To fill the knowledge gaps regarding the global patterns of human exposure to flame retardants (FRs) (i.e., brominated flame retardants (BFRs) and organophosphorus flame retardants (OPFRs)), data on the levels and distributions of FRs in external and internal exposure mediums, including indoor dust, indoor air, skin wipe, serum and urine, were summarized and analysed. Comparatively, FR levels were relatively higher in developed regions in all mediums, and significant positive correlations between FR contamination and economic development level were observed in indoor dust and air. Over time, the concentration of BFRs showed a slightly decreasing trend in all mediums worldwide, whereas OPFRs represented an upward tendency in some regions (e.g., the USA and China). The occurrence levels of FRs and their metabolites in all external and internal media were generally correlated, implying a mutual indicative role among them. Dermal absorption generally contributed >60% of the total exposure of most FR monomers, and dust ingestion was dominant for several low volatile compounds, while inhalation was found to be negligible. The high-risk FR monomers (BDE-47, BDE-99 and TCIPP) identified by external exposure assessment showed similarity to the major FRs or metabolites observed in internal exposure mediums, suggesting the feasibility of using these methods to characterize human exposure and the contribution of indoor exposure to the human burden of FRs. This review highlights the significant importance of exposure assessment based on multiple mediums for future studies.

End-of-life vehicle dismantling activity emits large quantities of phthalates and their alternatives: New insights on environmental sources and co-exposure risks.

Automotive interiors have been identified as significant sources of various chemicals, yet their occupational hazards for end-of-life vehicle (ELV) dismantlers remain poorly characterized. Herein, eight classes of plasticizers, including 11 phthalates esters (PAEs) and 16 non-phthalates esters (NPAEs), were detected in dust samples from inside and outside ELV dismantling workshops. Moreover, indoor dust from ordinary households and university dormitories was compared. The indoor dust from the ELV dismantling workshops contained the highest concentrations of plasticizers (median: 594 µg/g), followed by ordinary households (296 µg/g), university dormitories (186 µg/g), and outdoor dust (157 µg/g). PAEs remained the dominant plasticizers, averaging 11.7-fold higher than their NPAE alternatives. Specifically, diisononyl phthalate and trioctyl trimellitate were notably elevated in workshop dust, being 15.5 and 4.78 times higher, respectively, than in ordinary household dust, potentially indicating their association with ELV dismantling activities. The estimated daily intake of occupational ELV dismantling workers was up to five times higher than that of the general population. Moreover, certain dominant NPAEs demonstrated nuclear receptor interference abilities comparable to typical PAEs, suggesting potential toxic effects. This study is the first to demonstrate that ELV dismantling activities contribute to the co-emission of PAEs and NPAEs, posing a substantial risk of exposure to workers, which warrants further investigation.