Environmentally Relevant Concentrations of Tetrabromobisphenol A Exposure Impends Neurovascular Formation through Perturbing Mitochondrial Metabolism in Zebrafish Embryos and Human Primary Endothelial Cells.

Tetrabromobisphenol A (TBBPA), the most extensively utilized brominated flame retardant, has raised growing concerns regarding its environmental and health risks. Neurovascular formation is essential for metabolically supporting neuronal networks. However, previous studies primarily concerned the neuronal injuries of TBBPA, its impact on the neurovascularture, and molecular mechanism, which are yet to be elucidated. In this study, 5, 30, 100, 300 µg/L of TBBPA were administered to Tg (fli1a: eGFP) zebrafish larvae at 2-72 h postfertilization (hpf). The findings revealed that TBBPA impaired cerebral and ocular angiogenesis in zebrafish. Metabolomics analysis showed that TBBPA-treated neuroendothelial cells exhibited disruption of the TCA cycle and the Warburg effect pathway. TBBPA induced a significant reduction in glycolysis and mitochondrial ATP production rates, accompanied by mitochondrial fragmentation and an increase in mitochondrial reactive oxygen species (mitoROS) production in neuroendothelial cells. The supplementation of alpha-ketoglutaric acid, a key metabolite of the TCA cycle, mitigated TBBPA-induced mitochondrial damage, reduced mitoROS production, and restored angiogenesis in zebrafish larvae. Our results suggested that TBBPA exposure impeded neurovascular injury via mitochondrial metabolic perturbation mediated by mitoROS signaling, providing novel insight into the neurovascular toxicity and mode of action of TBBPA.

Atmospheric VOCs in an industrial coking facility and the surrounding area: Characteristics, spatial distribution and source apportionment.

Industrial coking facilities are an important emission source for volatile organic compounds (VOCs). This study analyzed the atmospheric VOC characteristics within an industrial coking facility and its surrounding environment. Average concentrations of total VOCs (TVOCs) in the surrounding residential activity areas (R1 and R2), the coking facility (CF) and the control area (CA) were determined to be 138.5, 47.8, 550.0, and 15.0 µg/m3, respectively. The cold drum process and coking and quenching areas within the coking facility were identified as the main polluting processes. The spatial variation in VOCs composition was analyzed, showing that VOCs in the coking facility and surrounding areas were mainly dominated by aromatic compounds such as BTX (benzene, toluene, and xylenes) and naphthalene, with concentrations being negatively correlated with the distance from the coking facility (p < 0.01). The sources of VOCs in different functional areas across the monitoring area were analyzed, finding that coking emissions accounted for 73.5%, 33.3% and 27.7% of TVOCs in CF, R1 and R2, respectively. These results demonstrated that coking emissions had a significant impact on VOC concentrations in the areas surrounding coking facility. This study evaluates the spatial variation in exposure to VOCs, providing important information for the influence of VOCs concentration posed by coking facility to surrounding residents and the development of strategies for VOC abatement.

Nontarget Screening of Novel Urinary Biomarkers for Occupational Exposure to Toxic Chemicals from Coking Industry Using HPLC-QTOF-MS.

High-resolution mass spectrometry is an advanced technique for comprehensive screening of toxic chemicals. In this study, urine samples were collected from both an occupationally exposed population at a coking site and normal inhabitants to identify novel urinary biomarkers for occupational exposure to coking contaminants. A coking-site-appropriate analytical method was developed for unknown chemical screening. Through nontarget screening, 515 differential features were identified, and finally, 32 differential compounds were confirmed as candidates for the current study, including 13 polycyclic aromatic hydrocarbon (PAH) metabolites. Besides monohydroxy-PAHs (such as 1-&2-naphthol, 2-&9-hydroxyfluorene, 2-&4-phenanthrol, and 1-&2-hydroxypyrene), many other PAH metabolites including dihydroxy metabolites, PAH oxide, and sulfate conjugate were detected, suggesting that the quantification based solely on monohydroxy-PAHs significantly underestimated the human exposure to PAHs. Furthermore, several novel compounds were recognized that could be considered as biomarkers for the exposure to coking contaminants, including quinolin-2-ol (1.10 ± 0.44 ng/mL), naphthylmethanols (11.4 ± 5.47 ng/mL), N-hydroxy-1-aminonaphthalene (0.78 ± 0.43 ng/mL), hydroxydibenzofurans (17.4 ± 7.85 ng/mL), hydroxyanthraquinone (0.13 ± 0.053 ng/mL), and hydroxybiphenyl (2.70 ± 1.03 ng/mL). Despite their lower levels compared with hydroxy-PAHs (95.1 ± 30.8 ng/mL), their severe toxicities should not be overlooked. The study provides a nontarget screening approach to identify chemicals in human urine, which is crucial for accurately assessing the health risks of toxic chemicals in the coking industry.

Coking-Produced Aromatic Compounds in Urine of Exposed and Nonexposed Populations: Exposure Levels, Source Identification, and Model-Based Health Implications.

Coking contamination in China is complex and poses potential health risks to humans. In this study, we collected urine samples from coking plant workers, nearby residents, and control individuals to analyze 25 coking-produced aromatic compounds (ACs), including metabolites of polycyclic aromatic hydrocarbons (PAHs) and their derivatives, chlorophenols, and nitrophenols. The median concentration of total ACs in urine of workers was 102 µg·g-1 creatinine, significantly higher than that in the other two groups. Hydroxy-PAHs and hydroxy hetero-PAHs were the dominant ACs. Workers directly exposed from coking industrial processes, i.e., coking, coal preparation, and chemical production processes, showed higher concentrations of hydroxy-PAHs and hydroxy hetero-PAHs (excluding 5-hydroxyisoquinoline), while those from indirect exposure workshops had higher levels of other ACs, indicating different sources in the coking plant. The AC mixture in workers demonstrated positive effects on DNA damage and lipid peroxidation with 5-hydroxyisoquinoline and 3-hydroxycarbazole playing a significant role using a quantile g-computation model. Monte Carlo simulation revealed that coking contamination elevated the carcinogenic risk for exposed workers by 5-fold compared to controls with pyrene, pentachlorophenol, and carbazole contributing the most, and workers from coking process are at the highest risk. This study enhances understanding of coking-produced AC levels and provides valuable insights into coking contamination control.

Co-exposure health risk of benzo[a]pyrene with aromatic VOCs: Monoaromatic hydrocarbons inhibit the glucuronidation of benzo[a]pyrene.

Occupational workers and residents near petrochemical industry facilities are exposed to multiple contaminants on a daily basis. However, little is known about the co-exposure effects of different pollutants based on biotransformation. The study examined benzo[a]pyrene (BaP), a representative polycyclic aromatic hydrocarbon related to the petrochemical industry, to investigate changes in toxicity and co-exposure mechanism associated with different monoaromatic hydrocarbons (MAHs). A central composite design method was used to simulate site co-exposure scenarios to reveal biotransformation of BaP when co-exposed with benzene, toluene, chlorobenzene, or nitrobenzene in microsome systems. BaP metabolism depended on MAH concentration, and association of MAH with microsome concentration/incubation time. Particularly, MAH co-exposure negatively affected BaP glucuronidation, an important phase Ⅱ detoxification process. BaP metabolite intensities decreased to 43%-80% for OH-BaP-G, and 32%-71% for diOH-BaP-G in co-exposure system with MAHs, compared with control group. Furthermore, glucuronidation was affected by competitive and time-dependent inhibition. Co-exposure significantly decreased gene expression of UGT 1A10 and BCRP/ABCG2 in HepG2 cells, which are involved in BaP detoxification through metabolism and transmembrane transportation. Therefore, human co-exposure to multiple contaminants may deteriorate toxic effects of these chemicals by disturbing metabolic pathways. This study provides a reference for assessing toxic effects and co-exposure risks of pollutants.

Associations between urinary monohydroxylated polycyclic aromatic hydrocarbons and unexplained recurrent spontaneous abortion and health risk assessment in a large case-control study in China.

Polycyclic aromatic hydrocarbons (PAHs) are a group of environmental endocrine disruptors with known carcinogenic, reproductive, and developmental toxicity. Important knowledge gaps remain regarding the relationship between PAH exposure and unexplained recurrent spontaneous abortion (URSA). In the present study, twelve monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) were measured in the urine of 413 URSA cases and 434 controls. The main OH-PAHs measured in this study were monohydroxy metabolites of naphthalene, followed by fluorene and phenanthrene. After the creatinine correction, the median concentration of urinary OH-PAHs in the control group (17.4 µg/g Creatinine) was higher than that in the case group (14.2 µg/g Creatinine). There was no positive relationship between PAH exposure and URSA using binary logistic regression analysis. Among 847 Chinese women of childbearing age, residential environment, type of drinking water, and education level were the influencing factors of PAH exposure. The health risk assessment showed that over 98% of women had a carcinogenic risk with carcinogenic risk values above the acceptable level (10-6). Although this large-scale case-control study did not observe an association between PAH exposure and URSA, more attention should be paid to the high carcinogenic risk due to PAH exposure in women of reproductive age.

New Insights into Human Biotransformation of BDE-209: Unique Occurrence of Metabolites of Ortho-Substituted Hydroxylated Higher Brominated Diphenyl Ethers in the Serum of e-Waste Dismantlers.

Extremely high levels of decabromodiphenyl ether (BDE-209) are frequently found in the serum of occupationally exposed groups, such as e-waste dismantlers and firefighters. However, the metabolism of BDE-209 in the human body is not adequately studied. In this study, 24 serum samples were collected from workers at a typical e-waste recycling workshop in Taizhou, Eastern China, and the occurrence and fate of these higher brominated diphenyl ethers (PBDEs) were investigated. The median concentration of the total PBDEs in the serum was 199 ng/g lipid weight (lw), ranging from 125 to 622 ng/g lw. Higher brominated octa- to deca-BDEs accounted for more than 80% of the total PBDEs. Three ortho-hydroxylated metabolites of PBDEs─6-OH-BDE196, 6-OH-BDE199, and 6'-OH-BDE206─were widely detected with a total concentration (median) of 92.7 ng/g lw. The concentrations of the three OH-PBDEs were significantly higher than their octa- and nona-PBDE homologues, even exceeding those of the total PBDEs in several samples, indicating that the formation of OH-PBDEs was a major metabolic pathway of the higher brominated PBDEs in occupationally exposed workers. An almost linear correlation between 6-OH-BDE196 and 6-OH-BDE199 (R = 0.971, P < 0.001) indicates that they might undergo a similar biotransformation pathway in the human body or may be derived from the same precursor. In addition, the occurrence of a series of penta- to hepta- ortho-substituted OH-PBDEs was preliminarily identified according to their unique "predioxin" mass spectral profiles by GC-ECNI-MS. Taken together, the tentative metabolic pathway for BDE-209 in e-waste dismantlers was proposed. The oxidative metabolism of BDE-209 was mainly observed at the ortho positions to form 6'-OH-BDE-206, which later underwent a consecutive loss of bromine atoms at the meta or para positions to generate other ortho-OH-PBDEs. Further studies are urgently needed to identify the chemical structures of these ortho-OH-PBDE metabolites, and perhaps more importantly to clarify the potentially toxic effects, along with their underlying molecular mechanisms.

Levels and health risks of urinary phthalate metabolites and the association between phthalate exposure and unexplained recurrent spontaneous abortion: a large case-control study from China.

Phthalate acid esters (PAEs) are environmental endocrine disruptors that can interfere with endocrine processes and cause adverse reproductive outcomes. The link between PAE exposure and unexplained recurrent spontaneous abortion (URSA) remains unknown. In this study, nine urinary metabolites of PAEs (mPAEs) were measured in 594 URSA cases and 569 healthy controls. The measured mPAEs were ubiquitously detected and present at higher levels (median: 203 ng/mL) in the URSA cases than in the controls (median: 161 ng/mL). Multiple logistic regression analysis showed that URSA was associated with higher concentrations of mono (2-ethyl-5-hydroxyhexyl) phthalate (mEHHP), mono (2-ethylhexyl) phthalate (mEHP), and mono-ethyl phthalate (mEP) and lower concentrations of mono-isobutyl phthalate (miBP). Moreover, a quantile-based g-computation (QGC) model revealed a positive association between mPAEs mixture and URSA. The URSA cases showed significantly higher concentrations of di-(2-ethylhexyl) phthalate (DEHP) than the controls. This was consistent with the health risk assessment, which suggested that DEHP is the main contributors to potential non-carcinogenic risk. DEHP accounted for over 80% of total risk. The large case-control study results suggest that PAE exposure may increase the risk of URSA, and that policy-makers and public health experts should pay more attention to DEHP exposure.

Identifying Dermal Uptake as a Significant Pathway for Human Exposure to Typical Semivolatile Organic Compounds in an E-Waste Dismantling Site: The Relationship of Contaminant Levels in Handwipes and Urine Metabolites.

Dermal exposure to semivolatile organic compounds (SVOCs) has recently attracted widespread attention; understanding these exposures is particularly important for people whose skin is frequently exposed to different pollution surfaces. In this study, handwipes were collected from exposed occupational workers and local residents near a typical electronic waste (e-waste) dismantling area; urine samples were also sampled. The wipes were analyzed for three typical SVOCs: polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), and organophosphate flame retardants (OPFRs). The median levels of PAHs, OPFRs, and PBDEs in handwipes from e-waste dismantlers were 96.0, 183, and 238 ng, respectively. The analytes were higher in the handwipes collected from workers than those from residents, indicating that they were subjected to greater dermal exposure during primitive e-waste dismantling activities. Among the three SVOCs, the strongest correlation was found between triphenyl phosphate (TPhP) in handwipes and diphenyl phosphate (DPhP) in paired urine; the next strongest correlations were between PAHs and PBDEs and their corresponding urinary metabolites. The results showed that TPhP contributed the highest exposure to e-waste dismantlers via dermal exposure. Our research highlights the importance of dermal exposure to TPhP, which should be considered in future exposure risk assessments.

Influence of nutrients on the bioaccessibility and transepithelial transport of polybrominated diphenyl ethers measured using an in vitro method and Caco-2 cell monolayers.

Previous research has shown the absorption of polybrominated diphenyl ethers (PBDEs) in the human gastrointestinal tract, but limited attention has been given to the influence of nutrients on PBDE absorption from food matrices. We investigated the effects of nutrients (oil, starch, protein, and dietary fiber) on the absorption and transport of PBDEs in a Caco-2 cell model and bioaccessibility of PBDEs by an in vitro gastrointestinal digestion method. The results showed that the accumulation ratios of PBDE congeners in Caco-2 cells were higher in the nutrient addition groups (oil: 26.7-50.6%, starch: 27.0-58.7%, protein: 12.1-44.1%, and dietary fiber: 28.2-55.1%) than the control group (7.17-36.1%), whereas the transport ratios were lower (oil: 2.30-7.20%, starch: 1.55-9.15%, protein: 1.04-8.78%, and dietary fiber: 0.85-7.04%) than control group (3.78-11.1%). Additionally, the PBDE bioaccessibility could be increased by adding the nutrients, particularly oil and starch. This study clarified the differences in PBDE absorption in the presence of nutrients using the in vitro digestion and Caco-2 cell model. The findings showed that nutrients were an important factor that promoted PBDE absorption in the gastrointestinal tract. Therefore, it is important to focus on a novel dietary strategy of food consumption with contaminant compounds to protect human health.

Organophosphate flame retardants, tetrabromobisphenol A, and their transformation products in sediment of e-waste dismantling areas and the flame-retardant production base.

Due to the prohibition of polybrominated diphenyl ethers, organophosphate flame retardants (OPFRs) and tetrabromobisphenol A (TBBPA) have become emerging flame retardants. However, knowledge about their occurrence, especially their transformation products, is still limited. This study collected sediment samples from two rivers, i.e., Lianjiang River (located at an e-waste dismantling area) and Xiaoqing River (situated at a flame retardant production base), to investigate the occurrence, composition, and spatiality distribution of OPFRs, TBBPA, and their transformation products. Both targets were detected in the Lianjiang River in the range of 220-1.4 × 104 and 108-3.1 × 103 ng/g dw (dry weight) for OPFRs and TBBPA, and 0.11-2.35 and 4.8-414 ng/g dw for their respective transformation products, respectively. The concentrations of OPFRs and TBBPA in the Xiaoqing River ranged from 4.15 to 31.5 and 0.76-2.51 ng/g dw, respectively, and no transformation products were detected. Different compositional characteristics of OPFRs and distinct spatial distribution from mainstream and tributary observed between the two rivers are attributed to the difference in the local industries. Spatial distribution and principal component analysis indicated that e-waste dismantling activities could be a vital source of local pollution. Besides, the confluence of tributaries seemed to determine the contaminant levels in the Xiaoqing River. Also, concentration ratios and Spearman's correlation between metabolites and parent chemicals were analyzed. Low concentration ratios (3.6 ×10-4 to 0.16) indicated a low transformation degree, and Spearman's correlation analysis suggested transformation products were partly stemming from commercial products. Considering the limited study of these transformation products, more studies on their sources, transform mechanism, and toxicity are required.

New Mixed Bromine/Chlorine Transformation Products of Tetrabromobisphenol A: Synthesis and Identification in Dust Samples from an E-Waste Dismantling Site.

The large-scale production and usage of tetrabromobisphenol A (TBBPA) and its analogues have caused widespread contamination, raising concern about their potential endocrine disruption effects on both humans and ecosystems. In the present study, debromination and unknown mixed bromine/chlorine transformation products of TBBPA (X-BBPA) were screened in dust samples from an e-waste dismantling site. Five monochloro products (2-chloro-2',6,6'-TriBBPA, 2-chloro-2',6-DiBBPA, 2-chloro-2',6'-DiBBPA, 2-chloro-2'-MoBBPA, and 2-chloro-6-MoBBPA) and two dichloro products (2,2'-dichloro-6,6'-DiBBPA and 2,2'-dichloro-6-MoBBPA) were successfully synthesized and structurally identified. TBBPA and its transformation products were detected by comparison of their mass spectra and retention times with those of synthetic standards. The mean concentration of X-BBPA was 1.63 × 104 ng/g in e-waste dismantling workshop dust samples based on dry weight, which was at a similar level to TBBPA. However, it was 1 order of magnitude lower than the concentrations of the debromination congeners. Thus, both debromination and chlorine-bromine exchange may be important reactions during the thermal processing of e-waste. The results on mixed chlorinated/brominated TBBPA transformation products provided new insights into TBBPA transformation. The elevated levels of the transformation products of TBBPA suggested that these products should be targeted to avoid underestimation of possible health risks.

Derivatization gas chromatography negative chemical ionization mass spectrometry for the analysis of trace organic pollutants and their metabolites in human biological samples.

Gas chromatography negative chemical ionization mass spectrometry (GC-NCI-MS) is a preferred instrumental approach for the trace and ultra-trace analysis of various toxic organics and their metabolites in human biological fluids. Specifically, the method has played an important role in the highly sensitive and specific quantitative detection of persistent highly halogenated compounds in environmental matrices and biota during the past few decades. However, for the analysis of toxic metabolites with active hydrogen atoms, such as acids, alcohols, and phenolic compounds, from biological matrixes or organics without electronegative atoms or groups, a derivatization step is often needed prior to GC analysis. Such derivatization aims to change the properties of targets to improve their separation, increase their volatility, and enhance the sensitivity of instrumental detection. This review summarizes three derivatization strategies commonly used for GC methods, i.e., alkylation, silylation, and acylation, together with their application combined with GC-NCI-MS for the high sensitivity analysis of toxic organic metabolites in the human body. The advantages and disadvantages of each derivatization method and potential directions for future applications are discussed. Given the broad variety of applications as well as the compound-specific sensitivity for the ultra-trace analysis of target xenobiotics in human biological fluids, subsequent studies are required to develop convenient, faster derivatization procedures and reagents better suited for routine analysis. Graphical abstract.

Spatial and temporal distribution characteristics and ozone formation potentials of volatile organic compounds from three typical functional areas in China.

BACKGROUND: Ozone is currently one of the most important air pollutants. Volatile organic compounds (VOCs) can easily react with atmospheric radicals to form ozone. In-field measurement of VOCs may help in estimating the local VOC photochemical pollution level. METHOD: This study examined the spatial and temporal distribution characteristics of VOCs during winter at three typical sites of varying classification in China; industrial (Guangzhou Economic and Technological Development District (GETDD)), urban (Guangzhou higher education mega center (HEMC)), and rural (Pingyuan county (PYC)), using Proton-Transfer-Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS). RESULTS: The concentrations of total VOCs (TVOCs) at the GETDD, HEMC and PYC sites were 352.5, 129.2 and 75.1 ppb, respectively. The dominant category of VOCs is nitrogen-containing VOCs (NVOCs, accounting for 43.3% of TVOCs) at GETDD, of which C4H11N (m/z+ = 74.10, butyl amine) was the predominant chemical species (80.5%). In contrast, oxygenated VOCs (OVOCs) were the most abundant at HEMC and PYC, accounting for 60.2% and 64.1% of the total VOCs, respectively; here, CH4O (m/z+ = 33.026, methanol) was the major compound, accounting for 40.5% of the VOCs at HEMC and 50.9% at PYC. The ratios of toluene to benzene (T/B) were calculated for different measured sites, as the ratios of T/B can reveal source resolution of aromatic VOCs. The average contributions to total ozone formation potentials (OFP) of the total measured VOCs in each area were 604.9, 315.9 and 111.7 µg/m3 at GETDD, HEMC and PYC, respectively; the highest OFP contributors of the identified VOCs were aliphatic hydrocarbons (AlHs) at GETDD, aromatic hydrocarbons (AHs) at HEMC, and OVOCs at PYC. CONCLUSIONS: OFP assessment indicated that the photochemical pollution caused by VOCs at GETDD was serious, and was also significant in the HEMC region. The dominant VOC OFP groups (AlHs and AHs) should be prioritized for control, in order to help reduce these effects.

Simultaneous determination of polybrominated diphenyl ethers, polycyclic aromatic hydrocarbons and their hydroxylated metabolites in human hair: a potential methodology to distinguish external from internal exposure.

A new method for the simultaneous detection of 20 polybrominated diphenyl ethers (PBDEs), 16 polycyclic aromatic hydrocarbons (PAHs), 4 hydroxyl PBDEs (OH-PBDEs) and 10 hydroxyl PAHs (OH-PAHs) in human hair has been developed for the first time. External target analytes from hair (hair-Ex) were ultrasonically extracted with acetone, while the internal target analytes (hair-In) were obtained with further digestion and liquid-liquid extraction of washed hair. Alkaline digestion with liquid-liquid extraction under alkaline and re-acidification combination conditions was the key procedure to successfully extract both parent and metabolic compounds from hair. Both external and internal extracts were purified with gel permeation chromatography, and the parent compounds were subsequently separated from their hydroxylated metabolites with a silica solid phase extraction column prior to instrumental analysis. GC-MS-MS, GC-MS and HPLC-MS-MS were used to analyze PAHs, PBDEs and their hydroxylated metabolites, respectively. The method showed satisfactory accuracy as well as precision, and the recoveries of PBDEs, PAHs, OH-PBDEs and OH-PAHs ranged from 62%-145%, 48%-135%, 60%-146% and 60%-88%, respectively. The developed method was validated in a pilot biomonitoring campaign. All parent analytes were approximately 100% detected in both hair-In and hair-Ex, while no OH-PBDEs were detected in hair-In and hair-Ex. All OH-PAHs were approximately 100% detected in hair-In with a mean Σ10OH-PAHs concentration of 174.7 ng per g dry weight (dw), and the concentration in hair-Ex was 18 times lower than that in hair-In with a relatively lower detection frequency. Both partial least squares discriminant analysis (PLS-DA) and Spearman correlation analysis with the concentration of analytes confirmed that the developed method performed well to distinguish the internal from external exposure to target analytes in hair.

Simultaneous determination of urinary 31 metabolites of VOCs, 8-hydroxy-2'-deoxyguanosine, and trans-3'-hydroxycotinine by UPLC-MS/MS: 13C- and 15N-labeled isotoped internal standards are more effective on reduction of matrix effect.

Human beings are inevitably exposed to volatile organic compounds (VOCs) of anthropogenic emissions as they are ubiquitous atmospheric pollutants. Smoking is an important exposure route of VOCs for the general population. Health effects induced by VOC exposure raise more concerns as they are identified with carcinogenicity, genotoxicity, neurotoxicity, and reproductive toxicity. trans-3'-Hydroxycotinine (OH-Cot) is a urinary biomarker of smoking, and 8-hydroxy-2'-deoxyguanosine (8-OHDG) is a urinary biomarker of DNA oxidative damage. To develop a method for quantifying VOC exposure levels of the general population and assessing the health risks induced by VOCs from second-hand smoking, an effective, rapid, and high-throughput method for the simultaneous determination of 31 metabolites of VOCs, 8-OHDG, and OH-Cot using solid-phase extraction coupled with UPLC-MS/MS was developed and validated. Method precision and accuracy, extraction recoveries, matrix effects, and storage stabilities of most analytes met the criterion (80-120%). Extraction recoveries increased from 85.1 to 100% after adjustment by isotoped internal standards (ISs). Furthermore, 13C- and 15N-labeled ISs were more effective to reduce the influence of matrix effects on recoveries and precisions than the deuterated analogs (73.0-116% vs. 53.6-140%). This developed method was successfully applied to determine urine samples collected from children. Results showed that N-acetyl-S-(3,4-dihydrobutyl)-L-cysteine, 2,2'-thiodiacetic acid (TGA), and N-acetyl-S-(3-hydroxypropyl-1-methyl)-L-cysteine (HPMMA) were well correlated with 8-OHDG with coefficients higher than 0.82, indicating those VOCs might easily lead to DNA damage. In conclusion, our co-monitoring of metabolites of VOCs with 8-OHDG and OH-Cot in one method provides a robust analytical method, which not only suggests the potential adverse health effects induced by VOCs but also discriminates and evaluates the contribution of passive smoking in human VOC exposure. Graphical abstract.

Urinary parabens in adults from South China: Implications for human exposure and health risks.

Parabens are a kind of preservatives widely used in cosmetic and personal care products and ubiquitously detected in the environment. However, little is known on human exposure to these chemicals. Our study mainly investigated the urinary parabens in adults from South China to evaluate the cumulative risk of paraben exposure. A total of 562 urine samples were collected from adult workers for the determination of methyl paraben (MeP), ethyl paraben (EtP), propyl paraben (PrP), butyl paraben, and benzyl parabens. High detection frequencies (≥98%) were observed for MeP, EtP, and PrP with median concentrations of 8.88, 5.11, and 1.44 µg/L, respectively. Urinary parabens was 4.5-46.2 fold higher in urine of females than those in males. Urinary MeP was associated with alcohol drinking and a history of tumor, while urinary PrP was negatively associated with education levels of the subjects. There were not significant associations between urinary concentrations of parabens and body mass index, which indicated that obesity was not associated with paraben exposure. Also, parabens did not correlate with human dietary habits. Although the total estimated daily intake (TEDI) of the major compound MeP and EtP in adult workers was lower than the acceptable daily intake (ADI), the TEDI of PrP exceed the ADI for a very few subjects, especially for females and low-educated ones, suggesting potential health risks.

Polychlorinated biphenyls and their hydroxylated metabolites in the serum of e-waste dismantling workers from eastern China.

A number of studies have reported on the exposure of e-waste dismantling workers to significantly high concentrations of halogenated organic pollutants such as polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers. Such exposure can have adverse health effects. However, little information on the metabolites of these contaminants exists. In this study, we investigated PCBs levels and their hydroxylated metabolites (OH-PCB) in the serum of e-waste workers in Taizhou in eastern China. Our results indicate elevated PCB and OH-PCB levels in the serum of the workers, with medians of 443.7 and 133.9 ng/g lw, respectively. Tri- to hexachlorinated PCB congeners were the dominant homologue groups in all of the samples. 4-OH-CB107 was the predominant homologue among the hydroxylated metabolites, accounting for 88.9% of the total OH-PCB concentrations. While dietary sources (e.g., fish) appear to be an important route for PCB accumulation in non-occupational exposure groups, exposure via ingestion of house dust and inhalation of pollutants derived from the recycling of PCB-containing e-wastes may primarily contribute to the high body burden observed in the occupational groups. Since we found concentrations of metabolites higher than those of their parent compounds, further studies need to pay more attention to their bioaccumulation and toxicity.

Comparison of prenatal and postnatal exposure to neonicotinoids and their temporal trends in breast milk.

Although the potential effects of neonicotinoids (NEOs) in early life have received considerable attention, data on the exposure of mothers and infants to NEOs are scarce. In this study, four parent NEOs and one metabolite were widely detected in paired maternal serum (MS), umbilical cord serum (UCS) and breast milk (BM) samples, with median total NEO concentrations (ΣNEOs) of 113, 160 and 69 ng/L, respectively. Decreasing trends were observed for N-desmethyl-acetamiprid (30 %/year), acetamiprid (22 %/year) and ΣNEOs (15 %/year) in breast milk between 2014 and 2022, whereas increasing trends were seen for clothianidin (17 %/year) and thiamethoxam (30 %/year). N-desmethyl-acetamiprid was the predominant compound in all matrices. However, the contributions of N-desmethyl-acetamiprid (35 %) and thiamethoxam (36 %) in breast milk were similar in 2022. Moreover, thiamethoxam has become the predominant contributor to the estimated daily intake of ΣNEOs since 2018, with the highest contribution of 71 % in 2022, suggesting the effects of NEOs continue to evolve and more attention should be paid to the new NEOs. Notably, the correlations and ratios of NEOs between paired UCS and MS were more significant and higher than those between paired BM and MS, respectively, indicating that NEO exposure was largely affected by the prenatal period.

Exposure to polycyclic aromatic hydrocarbons (PAHs) from domestic heating and cooking combustion of different fuel types for elders in rural China.

Solid fuel combustion emitted abundant pollutants, especially polycyclic aromatic hydrocarbons (PAHs) which had significant minus impact on human health in rural China. PAHs in PM2.5 emitted from different fuels combustion and hydroxylated metabolites of PAHs (OH-PAHs) in urine samples of different fuel users were detected in this study. The indoor PAHs were higher than that in outdoors for solid fuel use households, and the concentration of PAHs in the indoor of liquefied petroleum gas (LPG) use household was not much lower than solid fuel use households. Biogas-use household produced the lowest PAHs, which significantly reduced 64-82% compared with those emitted by solid fuel combustion. The different combustion conditions influenced the gaseous PAHs in indoors between two sampling sites. The gas/particle partition indicated that PAHs tended to occur in the particle phase with increased molecular weight, and the absorption was the main mechanism. The relative higher contribution of high molecular weight PAHs (HMW-PAHs) in solid fuel use households than in clean fuel use households, induced more health risks of PAHs. The concentration of Σ10OH-PAHs in the urine samples for elders of different fuel-use households displayed the trend of coal (83.27 ng/mL) > wood (79.32 ng/mL) > LPG (51.61 ng/mL) > biogas (28.96 ng/mL), and OH-NaPs was the predominant metabolites, which accounted for more than 90% of the total concentration. The carcinogenic risk of PAHs based on internal exposure was greater than or close to 10-4, with serious carcinogenic risks. This was different with the incremental lifetime cancer risk based on the atmospheric concentrations. The exposure of PAHs from solid fuel combustion for human being especially for the elders in this region should be concerned, and more data should be done for the internal exposure of PAHs.