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Exploration of the exposure of preconception couples to per- and polyfluoroalkyl substances (PFAS), as well as the most important influencing factors, promotes the understanding of the joint effects of parental exposure on reproductive health. In the present study, a total of 938 preconception couples recruited through the Shanghai Birth Cohort were investigated for the variations of PFAS exposure and contributing factors within and between couples. While linear perfluorooctanoic acid (n-PFOA, median 20.4 ng/mL) and linear perfluorooctanesulfonic acid (n-PFOS, 12.1 ng/mL) remained dominant in plasma, emerging PFAS, particularly 6:2 chlorinated polyfluorinated ether sulfonate (10.5 ng/mL), 6:2 polyfluoroalkyl phosphate diester (0.41 ng/mL), and branched PFOS or PFOA isomers, were also frequently detected. Although individual PFAS were generally correlated within couples, gender differences significantly existed in the concentrations of most individual PFAS and isomer profiles of PFOS and PFOA. Men generally exhibited higher plasma concentrations than their partners, likely reflecting gender-specific elimination pathway and kinetics. Couple-based PFAS exposure also varied greatly. After adjustment for individual factors, several household factors, including annual household income, dwelling floor type, drinking water source, and living near farmlands, were found to be associated with couple-based PFAS exposure. Our study constitutes one of the few studies addressing couple-based exposure to PFAS and lays a solid ground for further assessment of the impacts of parental exposure on reproductive health.

The substituted p-phenylenediamines (PPDs) represent a suite of effective antioxidants broadly applied in rubber industries. However, knowledge of their environmental occurrences and fate remains e...

Elucidation of the chemical components of airborne fine particulate matter (PM2.5) facilitates the characterization of atmospheric contamination sources and associated human exposure risks. In the present study, we employed a high-throughput analytical approach to investigate the abundance and distribution of 163 plastic additives in ambient PM2.5 collected from 94 different sites across the Pearl River Delta region, China. These chemicals are from six categories, including organophosphate esters (OPEs), phthalate esters (PAEs), PAE replacements, bisphenol analogues, UV stabilizers, and antioxidants. Ninety-three of them exhibited a detection frequency greater than 50% in PM2.5, while the combined concentrations of target plastic additives ranged from 610 to 49,400 μg/g (median: 3500 μg/g) across sites. By category, concentrations of PAEs (median: 2710 μg/g) were one to three orders of magnitude greater than those of other groups, followed by PAE replacements (540 μg/g) and OPEs (76.2 μg/g). Chemical-dependent exposure risks to PM2.5-bound plastic additives were characterized via the estimated daily intake and hazard quotient (HQ) approaches, which resulted in two different risk prioritization systems. Although the HQ approach suggested no or very low health concerns when considering individual chemicals, the complexity of co-concurrent chemicals in PM2.5 raises the concern on potential health risks from exposure to airborne particles and a cocktail of chemical components.

Organophosphate esters (OPEs) represent an important group of industrial additives with broad applications. However, their occurrences and fate in the atmospheric environment have not been sufficiently investigated. Our study focused on four novel OPEs, including tris(2,4-di-tert-butylphenyl) phosphate (AO168 = O), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphate, triisodecyl phosphate, and trisnonylphenol phosphate, and characterized their organophosphite antioxidant (OPA) precursors and selected transformation products, in airborne fine particles from South China. House dust from South China was also studied for comparison. Among these four OPEs, exceedingly high concentrations were determined for AO168 = O (i.e., median: 25 500 ng/g in PM2.5, 52 900 ng/g in PM1.0, and 10 700 ng/g in indoor dust), reaching 1 order of magnitude greater than those of traditional OPEs. Their OPA precursors were not detectable in airborne particles but hypothesized as one of the sources for airborne OPEs. In addition, potential transformation products of AO168 = O, including bis(2,4-di-tert-butylphenyl) phosphate (B2,4DtBPP) and 2,4-di-tert-butylphenol (2,4DtBP), also exhibited broad distributions. The levels of 2,4DtBP even surpassed those of AO168 = O in particles. The links between OPAs, OPEs, and other transformation products indicate the complexity of OPE-related chemicals in atmospheric environments. These links should be taken into consideration for a better characterization of OPEs' environmental and health risks.

6:2 polyfluoroalkyl phosphate diester (6:2 diPAP) has been demonstrated to disrupt reproductive endocrine functions using experimental studies. However, evidence from humans is not available yet. This cross-sectional study aims to assess the relationship between 6:2 diPAP exposure and the testicular function among adult men. A total of 902 men seeking preconception care were included. Plasma 6:2 diPAP concentrations were determined, while the testicular function was assessed via semen quality and reproductive hormones in serum. The association was assessed by multiple linear regression. Stratified analyses by age and body mass index (BMI) were conducted to assess the potential effect modification by these two variables. Regression analyses revealed that 6:2 diPAP exposure was significantly inversely associated with androgens [i.e., total testosterone (TT) and free androgen index (FAI)], markers of testosterone production potential [i.e., TT/luteinizing hormone (LH) and FAI/LH], estradiol, and insulin-like factor 3, a biomarker of Leydig cell function. These associations were robust in sensitivity analyses. However, age and BMI did not modify these associations, and no association was observed between 6:2 diPAP and semen quality. Our study suggests that exposure to 6:2 diPAP may inhibit androgen synthesis and impair Leydig cell function in adult men.

The exposure of preconception women to per- and polyfluoroalkyl substances (PFASs) could negatively affect her reproductive health. However, chemical-specific determinants for pre-conceptional exposure to PFASs, particularly the emerging ones, remain poorly understood. In the present study, it was found that the total PFAS concentration ranged from 8.9 to 440.3 ng/mL (median: 49.6 ng/mL) in 1060 preconception women. The PFAS exposure profile was dominated by PFOA (16.8 ng/mL), followed by PFOS (13.3 ng/mL), 6:2 Cl-PFESA (8.9 ng/mL), PFDA (2.4 ng/mL), PFNA (2.1 ng/mL), and others. The pre-conceptional exposure to the selected PFASs was significantly associated, in a chemical-specific pattern, with multiple demographic characteristics and the consumption frequency of different types of food. In particular, the exposure to 6:2 Cl-PFESA was associated with age, parity, alcohol drinking, educational level, household income, and the consumption frequency of red meat, marine and freshwater fish, shellfish, and shrimp. However, our analysis revealed that the investigated sociodemographic and diet variables only explained a relatively small proportion (1.3%-18.7%) of PFAS concentration variations, raising the need of exploring additional factors critical to pre-conceptional PFAS exposure. Overall, the identification of chemical-specific determinants would greatly facilitate the understanding of the link between pre-conceptional exposure and health outcomes, and the mitigation of human exposure to PFAS, particularly the emerging ones.

In this study, we investigated the distribution of brominated and organophosphate flame retardants (BFRs and OPFRs) in the paired gaseous and nine size-segregated particulate samples collected from 8 typical indoor compartments and monthly outdoor in Xinxiang, China, respectively. For the indoor environments, total concentrations of FRs (Σ

In the present study we determined the concentrations and compositions of a suite of isopropylated and tert-butylated triarylphosphate ester (ITP and TBPP) isomers in house dust from the city of Guangzhou located in South China and the city of Carbondale in Midwestern United States. These two groups of organophosphate esters (OPE) are structurally analogous to triphenyl phosphate (TPHP), but have rarely been investigated for environmental occurrences and human exposure risks. The majority of target ITP and TBPP isomers were 100% detected in house dust from the two locations. Median concentrations of ΣITPs (including all ITP isomers) and ΣTBPPs (including all TBPP isomers) were 63.4 ng/g (range: 16.0–500 ng/g) and 35.4 ng/g (8.1–198 ng/g) in South China house dust, respectively, compared with 476 ng/g (140–1610 ng/g) for ΣITPs and 81.3 ng/g (35.2–800 ng/g) for ΣTBPPs in Midwestern U.S. dust. The profiles of ITP or TBPP isomers were similar between the two locations and were dominated by 2-isopropylphenyl diphenyl phosphate (2IPPDPP) and 4-tert-butylphenyl diphenyl phosphate (4tBPDPP), respectively. Although the levels of ΣITPs and ΣTBPPs were generally one order of magnitude lower than those of TPHP in the same dust samples, the broad occurrences of most of these isomers in house dust from the two locations likely suggest their wide applications in household consumer products. Estimated intakes of ΣITPs and ΣTBPPs via dust ingestion were generally three orders of magnitude lower than the reference dose proposed for TPHP. However, these emerging OPE chemicals merit continuous environmental surveillance, given their possible applications as specific commercial mixtures or as components/impurities in other flame retardant/plasticizer mixtures.

Despite phthalate monoesters (mono-PAEs) being commonly recognized as metabolic products of phthalate diesters (di-PAEs), investigations on their environmental occurrences, particularly in indoor environments, remain limited. The present study demonstrated the presence mono-PAEs, along with a variety of di-PAEs, in house dust collected from 83 South China families. Among 15 target mono-PAEs, monobutyl phthalate (median concentration, 21.54 μg/g) dominated over other mono-PAEs in indoor dust, followed by monoethylhexyl phthalate (9.44 μg/g), monoisobutyl phthalate (5.14 μg/g), monomethyl phthalate (MMP; 2.05 μg/g), and several others. The total concentrations of detectable mono-PAEs (median, 45.40 μg/g) constituted an average of 6.7 ± 3.7% of the total concentrations of their parent diesters in the same dust. Molar concentration ratios of mono-PAEs to their respective di-PAEs varied greatly among chemicals (median, 0.001-3.1), with the highest ratios determined for the MMP/dimethyl phthalate and mono-/diisopropyl phthalate pairs (i.e., 3.1 and 1.5, respectively). In addition, no significant associations were observed between dust-associated mono- or di-PAEs and urinary mono-PAEs detected in both children (n = 48) and adult participants (n = 41). We hypothesized that mono-PAEs in dust could originate from different sources (e.g., impurities in di-PAE formulas, degradation from di-PAEs, and direct application as commercial additives), while the relative importance of various origins could differ between chemicals. Our findings demonstrate broad occurrences of mono-PAEs in indoor environments, but future studies are needed to better elucidate their sources, fate in indoor and outdoor environments, and potential human health risks.

Per- and poly-fluorinated substances (PFASs) are known to have the potential of binding to certain proteins. Protein binding is important to the understanding of cellular toxicities, biotransformation pathways, and the fate of selected PFASs. In this work, we provide a systematic review of major approaches to characterizing PFAS-protein binding, including the techniques based on separation, calorimetry, spectroscopy, mass spectrometry, surface plasmon resonance, molecular docking, and surfactant nature of PFASs. These approaches enable qualitative and/or quantitative characterization of binding parameters, such as the binding affinity constant and binding stoichiometry. For each approach, we review its principles and evaluate inherent strengths and limitations. In addition, the main methodologies for the identification of binding sites and target proteins are reviewed. Through the integrated review and identification of knowledge gaps and challenges, our work will guide the selection of methodologies for better characterizations of the mechanisms, kinetics, and adverse effects of PFAS-protein binding.

Despite numerous studies on the contamination of organophosphate triesters (tri-OPEs) in indoor environments, organophosphate diesters (di-OPEs) have rarely been investigated. The present study aimed to investigate whether di-OPEs coexist with tri-OPEs in house dust collected from Guangzhou ( n = 30), South China and the city of Carbondale ( n = 17) located in the Midwestern United States (U.S.). Median concentrations of bis(2-butoxyethyl) phosphate (BBOEP), bis(1-chloro-2-propyl) phosphate (BCIPP), bis(1,3-dichloro-2-propyl) phosphate (BDCIPP), bis(2-ethylhexyl) phosphate (BEHP), bis(2-methylphenyl phosphate) (BMPP), and diphenyl phosphate (DPHP) were determined to be 15.9, < LOQ, 33.6, 654, 9.5, and 605 ng/g in South China house dust, and 1580, 90.6, 234, 867, 4.0, and 6500 ng/g in Midwestern U.S. dust, respectively. The total concentrations of di-OPEs (referred to ΣdiOPEs) constituted an average of 22.9% and 21.3% of the total concentrations of tri-OPEs in dust from these two locations, respectively. Median concentration ratios of DPHP and BEHP to their respective tri-OPEs (i.e., TPHP and TEHP) were determined to be 1.1 and 1.0 in South China dust and 3.7 and 1.4 in Midwestern U.S. dust, respectively, indicating possible commercial applications for these two di-OPEs. Correlative analyses reveal chemical- and region-specific relationships between di-OPEs and their respective tri-OPEs, suggesting that the relative importance of different sources (e.g., direct commercial use, impurity in tri-OPE formulas, and tri-OPE degradation) could vary for different di-OPEs. Our findings demonstrate wide occurrences of di-OPEs in an indoor environment from the studied locations and raise concerns on human exposure to dust associated di-OPEs. Future studies are needed to explore more possible di-OPEs in indoor environments and elucidate their sources, human exposure pathways, and toxicokinetics.

Following the restriction of bisphenol A (BPA) in certain products, a number of bisphenol analogues (BPs) have been used as BPA replacements in different applications, raising environmental and health concerns. The present study determined a total of 13 bisphenol analogues in house dust and children urine from South China families (n = 46). Among all BPs, BPA, bisphenol S (BPS) and bisphenol F (BPF) were frequently detected in house dust, with concentrations ranging from 0.54 to 26.2 μg/g (median: 2.60 μg/g), 0.07-11.5 μg/g (median: 0.32 μg/g) and 0.02-2.4 μg/g (median: 0.29 μg/g), respectively. BPA (median: 2.43 ng/mL) was also the dominant BP in children urine samples, accounting for 75.2 ± 27.4% of the total concentrations of urinary BPs, followed by BPS (0.23 ng/mL), whereas BPF was only detected in less than 30% of urine samples. Children's daily intake of bisphenols through dust ingestion and total daily intakes were estimated based on the dust and urine concentrations, respectively. The estimated intake of BPA, BPS and BPF via house dust ingestion accounted for 9%, 12% and 38% of the total intakes predicted based on urinary concentrations, respectively, and exhibited very low exposure risks.

Background Previous epidemiological studies on the relationship between per- and polyfluoroalkyl substances (PFAS) exposure and male reproductive hormones were mainly limited to a few legacy PFAS and ignored the possible mixture effects. Objectives To assess the associations of PFAS mixture, branched isomers and emerging alternatives of PFAS with male reproductive hormones. Methods A total of 902 men (mean age: 31.3 years) were recruited in this cross-sectional study. We quantified 24 targeted PFAS, including 7 branched PFOS isomers, 2 branched PFOA isomers and 2 components of F-53B, in blood plasma. Five reproductive hormones, including total testosterone (TT), estradiol (E2), follicular stimulating hormone (FSH), luteinizing hormone (LH) and insulin like factor 3 (INSL3), and sex hormone binding globulin (SHBG) were measured in serum. Associations were first assessed by confounder-adjusted multiple linear regression while correcting for multiple comparisons. Bayesian kernel machine regression (BKMR) and adaptive elastic net (AENET) were further used to assess mixture effects and the adjusted exposure response (ER) relationship of individual PFAS. Results After adjusting for confounders, we found that PFAS mixture was significantly and inversely associated with E2 and E2/TT, with perfluoro-n-undecanoic acid (PFuDA) being the major contributor. Although the associations between PFAS mixture and other hormones were non-significant, certain individual PFAS presented significant associations. Notably, perfluoro-n-tridecanoic acid (PFTrDA) and perfluoro-n-dodecanoic acid (PFDoA) were found to be significantly and inversely associated with INSL3, a unique indicator of Leydig cells function. Meanwhile, significant positive associations were found between perfluorobutane sulfonic acid (PFBS) and FSH and between PFuDA and LH. But the associations with branched isomers or F-53B were sporadic and inconsistent. Conclusions Our findings provided the evidence that PFAS mixture may reduce E2 level, and certain PFAS (i.e., PFTrDA and PFDoA) may have negative effects on Leydig cells function among young men. Additional studies are much needed to confirm our results and elucidate potential mechanisms.

Multiple studies have examined the relationship between PFAS and semen quality, but none has explored the associations of PFAS mixture that includes emerging alternatives and branched isomers.22 PFAS, including 10 linear legacy PFAS, 7 branched isomers, 3 short chain alternatives and 2 components of F53B [e.g., 6:2 chlorinated polyfluorinated ether sulfonate (Cl-PFESA)] were quantified in blood plasma among 740 healthy men. Five semen quality parameters (i.e., volume, count, concentration, total motility and progressive rate) were assessed. Multiple linear regression and three multiple pollutant models (i.e., adaptive elastic net regression, quantile based g-computation, and XGBoost method) were used to assess the associations of individual PFAS and PFAS mixture with semen quality and the potential interactive effects among congeners.After adjusting for selected confounders, perfluorobutane sulfonate (PFBS) and perfluorohexane sulfonate (PFHxS) presented significant and negative associations with sperm count [βIn the current cross-sectional study, we found that two emerging PFAS replacements (i.e., 6:2 Cl-PFESA and PFBS) and PFHxS exposure were associated with reduced semen concentration, total sperm count and motility in men. Meanwhile, significant positive associations between PFHpS and sperm count and concentration were also observed. But there were no consistent associations between PFAS mixture, branched isomers and semen quality.

Previous animal and human studies suggest potential links between maternal exposure to per- and polyfluoroalkyl substances (PFASs) and adverse birth outcomes. As spontaneous preterm birth (SPB) represents a major cause of infant mortality and precursor to future morbidity, we conducted a prospective nested case-control study in Shanxi Province, China to investigate the association between prenatal PFAS exposure and SPB risk, as well as the associations with biomarkers of oxidative stress and systemic inflammation. Among 4229 women enrolled during 2009-2013, 144 SPB cases and 375 controls were included in this study. Seventeen PFASs, as well as monocyte chemoattractant protein-1 (MCP-1), interleukin-8 (IL-8), and heme oxygenase-1 (HO-1), were measured in maternal plasma or serum collected during 4th-22nd gestational weeks. Perfluorooctanoic acid (PFOA), perfluorooctane sulfonate (PFOS), and its alternative chlorinated polyfluoroether sulfonic acid (6:2 Cl-PFESA) were detected in more than 90% samples with a median concentration of 0.79, 1.79, and 0.34 ng/mL, respectively. The analyses revealed no significant associations between plasma PFASs and the SPB risk after adjusting for potential confounders. However, concentrations of PFOS and 6:2 Cl-PFESA were both significantly and positively associated with MCP-1 levels, while PFOA was inversely associated with IL-8. Our findings suggested that maternal exposure to the determined low levels of PFAS did not induce an elevated risk of SPB, but the exposure may disturb potential biochemical pathways of inflammation. The latter has important implications for possible birth outcome effects and developmental effects in fetuses and newborns, which warrants close attention.

The present study investigated the occurrence of 20 organophosphate esters (OPEs) in house dust from 51 South China homes and the risks of human exposure to OPEs via two pathways: dust ingestion and hand-to-mouth contact. In addition to several traditional OPEs, five out of six novel OPEs, including bisphenol A bis(deiphenyl phosphate) (BPA-BDPP), t-butylphenyl diphenyl phosphate (BPDPP), cresyl diphenyl phosphate (CDP), isodecyl diphenyl phosphate (IDDPP), and resorcinol-bis(diphenyl)phosphate (RDP), were frequently detected in house dust (median concentration: 59.7-531 ng/g). Eight of the 20 target OPEs were frequently detected in hand wipes collected from adults and children ( n = 51 and 31, respectively), which in combination (referred to as Σ8OPEs) had a median mass of 76.9 and 58.9 ng, respectively. Increasing dust concentrations of Σ8OPEs or three individual substances among these eight OPEs, including tris(1-chloro-2-propyl) phosphate (TCIPP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), and triphenyl phosphate (TPHP), were strongly associated with their levels in children's hand wipes ( p < 0.05 in all cases). By contrast, in adults' hand wipes only TPHP exhibited a marginally significant association with dust concentrations ( p = 0.04). Levels of Σ8OPEs in hand wipes from children, but not adults, were inversely influenced by hand washing frequency ( p = 0.002), while indoor temperature was inversely associated with hand wipe levels of Σ8OPEs from both children and adults ( p = 0.01 and 0.002, respectively). Exposure estimation suggests that hand-to-mouth contact represents another important pathway in addition to dust ingestion and that children are subjected to higher OPE exposure than adults.

One of the major goals of the Stockholm Convention on Persistent Organic Pollutants is to continuously reduce the releases of unintentional persistent organic pollutants (POPs) such as polychlorinated dibenzo-para-dioxins and dibenzofurans (PCDD/PCDF) or polychlorinated biphenyls (PCB) from anthropogenic sources. Until now, most efforts have focused on the releases of PCDD/PCDF and to a lesser extent on unintentionally generated PCB, and therefore, release inventories reported as toxic equivalents (TEQ) do not include the twelve dioxin-like PCB (dl-PCB). In order to facilitate the development of national release inventories for the total TEQ - consisting of PCDD, PCDF and PCB - this study collected and summarized published emission factors (EFs) of unintentional dl-PCB or calculated them from measured data for the sources listed in the UNEP Toolkit. In total, 286 EFs for dl-PCB were found (or could be calculated) whereby 233 described release to air, 23 EFs addressed to residue, 25 EFs to product; and only 5 EFs addressed releases to land. Taking into account performance criteria such as the facility type and scale or abatement technologies, the EFs were grouped and assigned to the source categories and/or classes used in the UNEP Toolkit. With these newly added data and EFs of dl-PCB, the already existing EFs in the Toolkit can be improved and amended. In addition, a statistically significant correlation between the EFAir of dl-PCB proposed in this study and EFAir of PCDD/PCDF recommended in the Toolkit was observed.

Hexachlorobenzene (HCB) and pentachlorobenzene (PeCBz) have been listed as unintentional POPs in the annex of the Stockholm Convention and thus, attracted attention by government and researchers. Since the intentional production and use has ceased in most countries, the unintentional releases to the environment have increased. This study gathered 206 and 78 emission factors (EFs) of unintentional HCB and PeCBz from scientific publications and governmental reports, respectively. Most of the EFs referred to the release vector “air” (EFAir) and to a less extent to “product” (EFProduct). EFs were proposed for different source categories/classes used in the Toolkit according to the technologies that released the HCB or PeCBz. Overall, lowest and highest EFAir for HCB were found in the metallurgical industry range from 1 μg/t in well controlled plants (coke, iron and steel) up to 40,000 μg/t (secondary zinc). EFs for PeCBz were in similar order of magnitude. Due to lack of data, EFs to water, land or residue cannot be proposed. Using linear regression and statistical analysis such as Pearson correlation, we found strongest correlation of EFAir between HCB and PeCBz (R2 = 0.79, P

Photodegradation has been demonstrated as one of the important environmental factors affecting the fate of contaminants such as brominated flame retardants (BFRs). However, a number of emerging BFRs, particularly those with high bromine substitution, have rarely been investigated for their photodegradation kinetics. Our study evaluated photodegradation of two highly brominated FRs, 1,3,5-tris-(2,3-dibromopropyl)-1,3,5-triazine-2,4,6-trione (TDBP-TAZTO) and decabromodiphenyl ethane (DBDPE), under various conditions. The results indicated that the degradation kinetics was affected by UV irradiation wavelength, intensity, solvent type, as well as the structural characteristics. TDBP-TAZTO exhibited degradation half-lives (t1/2) of 23.5-6931 min under various UV irradiation conditions and 91.2 days under natural sunlight. Its degradation was much slower than that of DBDPE which exhibited t1/2 of 0.8-101.9 min under UV and 41.3 min under natural sunlight. A variety of degradation products were detected as a result of different breakdown pathways. This indicated that photodegradation could substantially influence the fate of these highly brominated FRs, resulting in a cocktail of degradation products as environmentally occurring contaminants. This could also complicate the evaluation of the ecological risks of these target flame retardants, given that degradation products generally possess physicochemical properties and biological effects different from their parent chemicals.

The halogenated flame retardants (HFRs) are released into the environment and resulting a wide distribution. HFRs are entered human body by different routes and can then be accumulated and distributed. In this chapter, studies on human exposure routes (dietary intake, soil/dust ingestion or inhalation) and human body burden (blood, breast milk, hair, nail and urine) of polybrominated diphenyl ethers (PBDEs) and its metabolites, novel brominated flame retardants (NBFRs), hexabromocyclododecane, tetrabromobisphenol A, dechlorane plus (DPs), chlorinated paraffins (CPs), were summarized and discussed. Finally, knowledge gaps and research needs in future have been discussed.

Indoor environment constitutes an important source of industrial additive chemicals to human exposure. We hypothesized that the influence of residential environment on human exposure varies among different types of additive chemicals and differs between children and mothers. This study determined a suite of additive chemicals in house dust from South China dwellings (n = 47) and urine from child-mother pairs. Concentrations of phthalates (PAEs; median 601 μg/g) were 2–3 orders of magnitude greater than those of parabens (0.82 μg/g), bisphenols (3.31 μg/g), and benzophenone-related chemicals (2.69 μg/g). Urinary concentrations differed between children and mothers, but the pattern of differences varied between chemical groups. Children exhibited greater urinary levels of mono-PAEs than mothers (510 versus 395 ng/mL, p = 0.152), while the latter population exhibited greater levels of parabens and benzophenones. Regression analyses indicate a lack of association between dust and urinary levels for most chemicals, suggesting that other exposure pathways can complicate human exposure scenarios. Indeed, we estimated that the daily intake via dust ingestion only constituted 0.002–0.81% of total daily intake estimated based on urine data for mothers and 0.04–5.61% for children. Future efforts are needed to better characterize source-specific exposure for different populations.

This study was undertaken to determine levels of halogenated flame retardants (HFRs) on skin surface to provide preliminary exposure estimates from dermal absorption. Skin wipes of palms, back-of-hands, and forearms were collected from 30 participants by using gauze pads soaked in isopropyl alcohol. Eight polybrominated diphenyl ethers (PBDEs), two novel brominated FRs, and two Dechlorane Plus (DPs) isomers were determined. BDE209, Decabromodiphenylethane (DBDPE), and 1, 2-Bis (2, 4, 6-tribromophenoxy) ethane (BTBPE) were most frequently detected. BDE209 showed the highest median level (1760 ng m−2), followed by DBDPE (277 ng m−2) and anti-DP (64 ng m−2). The comparison of levels on palms and back-of-hands revealed no statistical differences, but both were significantly higher than the levels on forearms. Detections of HFRs on arms suggested that skin areas covered by clothing were exposed to these chemicals likewise. BDE209 and DPs levels from three repeated samples showed moderate to strong reliability over 3 months, while the levels of other compounds were not statistically reliable. Males had significant higher levels than females for most HFRs, while participants' age, time from last hand washing to sampling, and other behaviors contributed limitedly to the variations in levels. Daily uptakes of HFRs through dermal absorption were estimated. The estimated median total exposure from palms, back-of-hands, and forearms were 25.9, 1.6, and 7.2 ng d−1 for ∑PBDEs, ∑DPs, and ∑NBFRs, respectively, which were in the same ranges as those from diet and dust ingestion for adults in China, suggesting that dermal absorption would be an important exposure route for HFRs.

This study surveyed occurrences and influencing factors of organophosphorus flame retardants (PFRs) on skin surface. Skin wipe samples from palms, back-of-hands and forearms of 30 adults were collected by using gauze pads soaked in isopropyl alcohol in Beijing, China. Tris(chloropropyl) phosphate isomers (∑TCPP), tris(2-chloroethyl) phosphate (TCEP) and triphenyl phosphate (TPHP) were the most abundant compounds with detection frequencies higher than 97%. ∑TCPP showed the highest mean level (4.6 μg/m2), followed by TPHP (2.4 μg/m2) and TCEP (1.6 μg/m2). Levels on palms were slightly higher than on back-of-hands, and both were substantially higher than those on forearms. TCEP and ∑TCPP levels were strong reliable in three repeated measurements from 4 participants over a three month period (intraclass correlation of coefficient of 0.91 and 0.95, respectively), while TPHP levels were not. Washing with soap and water removed a large fraction of PFRs on hands with median reduction of 76, 72 and 67% for TCEP, ∑TCPP and TPHP, respectively. Paired dust samples, table surface wipe and hand wipe samples were collected from 17 offices (13 surface wipes and 22 hand wipes) in Beijing. Hand wipe TCEP, ∑TCPP and TPHP were neither correlated with dust samples nor with table surface wipe samples. Two methods were used for dermal exposure assessments. The estimated lower median total exposure from palms, back-of-hands and forearms by the relative absorption method were 0.6, 1.0, 0.3 ng/kg BW-d for TCEP, ∑TCPP and TPHP, respectively. These estimates were in the same range as those via dust ingestion for adults in Beijing, suggesting dermal absorption is likely a significant pathway of human PFR exposure. Keywords: Organophosphorus flame retardants, Skin wipes, Dermal absorption, Human exposure

During the investigation of dechlorane-related chemicals in North American wildlife, two unknown polychlorinated compounds (referred to as U1 and U2) were discovered. After extensive sample cleanup, structural information on U1 and U2 was characterized by gas chromatography (GC) coupled with single quadrupole mass spectrometer (MS) or GC-quadrupole time-of-flight (QToF) MS. Mass spectral evidence suggests that both U1 and U2 are structurally related to Dechlorane 603 (Dec603; C17H8Cl12), an analogue of the chlorinated flame retardant Dechlorane Plus. From the results we suspect U1 (C17H9Cl11) to be a monohydro analogue of Dec603 (i.e., one chlorine atom in Dec603 is replaced by a hydrogen atom). U1 may be formed via the degradation of Dec603's stereoisomers or present as an impurity in commercial Dec603 products. Mass spectral characterization of U2 (C17H7OCl11) suggests it is a carbonylic derivative of Dec603, likely formed via metabolic transformation of Dec603 or its photoisomer. Semiquantitative measurement revealed that U1 and U2 were present at estimated median concentrations of 49 ng/g lipid weight (lw) and 59 ng/g lw in peregrine falcon ( Falco peregrinus) eggs, from the mid-Atlantic region of the United States, and 4.6 and 3.0 ng/g lw in shortfin mako shark ( Isurus oxyrinchus) livers from the western North Atlantic Ocean, respectively. Our results demonstrate the occurrence of these two novel Dec603-related chemicals in both terrestrial and aquatic ecosystems.

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.

The present study investigated the occurrence of legacy and alternative halogenated flame retardants (FRs) in house dust (n = 51) from Guangzhou, South China and hand wipes collected from adults (n = 51) and children (n = 31). In addition to polybrominated diphenyl ether (PBDE) congeners (particularly BDE-209), several alternative FRs were also detected in >60% of dust samples, including decabromodiphenylethane (DBDPE; median: 4600 ng/g), bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEH-TEBP; 43.9 ng/g), 1,2-bis(2,4,6-tribormophenoxy)ethane (BTBPE; 9.2 ng/g), pentabromotoluene (PBT; 10.1 ng/g), and syn- and anti-dechlorane plus (DPs, 24.5 ng/g). BDE-47, BDE-209, DBDPE, BEH-TEBP, and DPs were also frequently detected on hand wipes from children (median mass: 0.1–1.1 ng) and adults (0.1–1.2 ng). Linear regression models suggest that dust concentrations of BDE-47 and DPs had significant or marginally significant associations with their masses on children's (10β = 2.82; 95% CI: 1.20, 6.64 and 10β = 5.57, 95% CI: 1.85, 16.75, respectively) and adults' hands (10β = 4.46; 95% CI: 0.92, 21.58 and 10β = 5.11; 95% CI: 1.74, 14.96, respectively), whereas no association was observed for any other FRs. Most of the investigated demographic, environmental, or behavioral factors did not significantly influence the levels of halogenated FRs on human hands. Estimation of human exposure risks via hand-to-mouth contact and dust ingestion indicates that children are subjected to elevated exposure than adults, and the relative importance of the two pathways is chemical-specific.

This study aimed to investigate the exposure of three occupational populations (i.e., office worker, taxi drivers, and security guards) to flame retardants by comparing different sampling approaches (i.e., hand wipe, surface wipe, and dust). Hand wipe samples were collected from 68 participants from three populations in Beijing, China. Dust and/or surface wipes were also sampled from their respective occupational workplaces. Ten phosphorus flame retardants (PFRs), two novel brominated flame retardants (NBFRs) and eight polybrominated diphenyl ethers (PBDEs) were analyzed. BDE209, decabromodiphenylethane (DBDPE), tris(chloropropyl) phosphate isomers (∑TCPP), tris(2-chloroethyl) phosphate (TCEP) and triphenyl phosphate (TPHP) were detected in at least 95% of the samples, collectively accounting for over 90% of the total concentrations in each type of samples. Concentrations and composition profiles of flame retardants differed in hand wipes of the three populations with summed level of all target compounds (∑FRs) ranked as taxi driversoffice workerssecurity guards. Most FRs in hand wipes were significantly correlated with those in surface wipes, whereas the correlations between hand wipes and dust are weak. Estimated exposure to FRs via dust ingestion and dermal absorption for each population varied when using different types of samples for exposure assessment, suggesting the importance of sampling strategy selection. Estimation via hand wipes indicated that taxi drivers were subjected to greater exposure to PFRs among three populations, while office workers were subjected to greater BFR exposure. Our data suggest hand wipes have the potential of being standardized into a noninvasive method for evaluating human exposure to environmental contaminants across different populations.

The occurrence levels of eight polybrominated diphenyl ethers (PBDEs) and four novel brominated flame retardants (NBFRs) were determined and compared in indoor dust from different microenvironments (21 homes, 23 offices and 16 day care centers) in Beijing, China. Concentrations of ∑8PBDEs in dust were 430–17,000 ng/g, 690–8600 ng/g, and 90–2300 ng/g for homes, offices, and day care centers, respectively, and were dominated by BDE-209. Concentrations of ∑4NBFRs ranged from 310 to 17,000 ng/g, 300 to 4300 ng/g, and not detected to 500 ng/g for homes, offices, and day care centers, respectively, and were dominated by bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (BEH-TEBP) and decabromodiphenylethane (DBDPE) across microenvironments. The results showed an increasing detection and elevated concentration of NBFRs (especially BEH-TEBP), indicating that monitoring of NBFRs in dust samples should be of concern in future studies. A notable finding was that the BFR concentrations in dust samples from day care centers were generally one order of magnitude lower than those from homes and offices in the present study. This implies that previous estimates of toddler exposure via dust ingestion on data from homes may be overestimated. Concentrations of BDE-209 and ∑8PBDEs were found to be significantly higher in elevated surface dust than floor dust from day care centers. The estimates of daily intakes of BFRs via dust ingestion for Chinese adults and toddlers using Monte Carlo analysis were 2–5 orders of magnitude lower than the corresponding reference daily intakes. Keywords: Brominated flame retardants (BFRs), Floor dust, Elevated surface dust, Human exposure, Toddlers, Day care centers

To investigate halogenated flame retardant (HFR) contents in recycled plastic materials, 23 recycled plastic samples manufactured in five Chinese provinces were randomly purchased online, and the ∑12HFR concentrations of these samples (including 8 polybrominated diphenyl ethers (PBDEs, BDE 28, 47, 99, 100, 154, 153, 183 and 209), decabromodiphenylethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and 2 dechlorane plus isomers (DP, syn-DP and anti-DP)) varied from ND to 169,000 ng g−1 (mean ± SD, 46,900 ± 44,700 ng g−1). BDE 209 and DBDPE were the dominant components and their concentration ranges were from ND to 106,000 ng g−1 and ND to 81,900 ng g−1, respectively. Generally, the HFR content and plastic variety closely correlate, and the ∑HFR concentrations in the polyvinyl chloride (PVC, N = 5), polypropylene (PP, N = 9), acrylonitrile butadiene styrene (ABS, N = 5), polystyrene (PS, N = 1) and polyethylene (PE, N = 3) samples were 65,300 ± 42,400, 36,700 ± 56,000, 30,000 ± 25,200, 24,300 and 4330 ± 7500 ng g−1, respectively. The HFR abundance in plastic from Guangdong (76,000 ± 56,400 ng g−1, N = 7) and Hebei (37,500 ± 11,500 ng g−1, N = 4) was much higher than that for other provinces/cities.

Under the Stockholm Convention on Persistent Organic Pollutants (POPs), China is required not only to reduce polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) but also unintentionally produced polychlorinated biphenyls (PCB), hexachlorobenzene (HCB) and pentachlorobenzene (PeCBz). A baseline of the sources in China that generate these unintentional POPs is needed for both research and regulation purposes. In this paper, we have compiled production data of potential sources in China and assessed them in five-year intervals from 2000 to 2015. Most of these activities experienced changes from rapid growth to slow growth. Measured data for PCB, HCB and PeCBz in samples collected from potential sources in China were reviewed. Most information was associated to thermal processes with high potential of emission, including waste incineration and ferrous and non-ferrous metal production. In addition, high levels of PCB, HCB and PeCBz were found as impurities in a few chlorinated products or as by-products in solvent production, which suggested organochlorine industry might be important sources. Finally, based on the studies reviewed, recommendations for future actions in research and policy as well as a few regulatory issues in China are discussed.