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.

Maternal serum neonicotinoids during early-mid pregnancy and congenital heart diseases in offspring: An exploratory study.

Experimental evidence has indicated a correlation between in-utero exposure to neonicotinoid pesticides (NEOs) and adverse birth outcomes in mammals. However, the distribution of NEO exposure during human pregnancy, as well as its association with congenital heart diseases (CHDs), the most common birth defects, are unclear. Our purpose was to explore the distribution of and contributing factors to NEO exposure in pregnant women during early-mid pregnancy and to assess the associations between NEOs and CHDs. This nested case-control study was conducted within an ongoing prospective birth cohort study and enrolled 141 CHD singletons and their 282 individually matched controls. Six "parent" NEOs and three NEO metabolites were measured in maternal serum collected at an average gestational age of 16 weeks, using liquid chromatography-tandem mass spectrometry. Logistic regression was used to quantify the NEOs-CHDs associations and explore potential contributing factors to serum NEO levels in controls. N-desmethyl acetamiprid (N-dm-ACE) and imidacloprid (IMI) were the most frequently detected NEOs, found in 100% and 20% of maternal sera, respectively. We did not find a statistically significant association between total NEOs and overall CHDs. However, there was a trend towards a higher risk of septal defects with greater serum NEOs (ORs ranged from 1.80 to 2.36), especially nitro-containing NEOs represented by IMI. Pregnant women with lower education had elevated serum total NEOs compared to women with higher education (OR = 48.39, 95% CI: 23.48-99.72). Pregnant women were primarily exposed to N-dm-ACE and IMI during early-mid pregnancy. Gestational exposure to NEOs may be associated with an increased risk of septal defects, but the evidence is limited at present. Education is a potential contributing factor to NEO exposure in pregnant women. Larger and more precise studies with longitudinal biospecimen collection, are recommended to validate our exploratory findings.

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.

Phthalate metabolites in breast milk from mothers in Southern China: Occurrence, temporal trends, daily intake, and risk assessment.

The extensive production and use of phthalates means that these compounds are now ubiquitous in the environment and various biota, which raises concerns about potential harmful health effects. In this study, phthalate metabolites (mPAEs) were measured in breast milk (n = 100) collected from mothers of southern China between 2014 - 2022. Of the nine target mPAEs, five were detected in all of the samples, including mono-methyl phthalate (MMP), mono-ethyl phthalate (MEP), mono-isobutyl phthalate (MiBP), mono-n-butyl phthalate (MnBP), and mono-(2-ethylhexyl) phthalate (MEHP). The total levels of mPAEs in breast milk ranged from 4.76 to 51.6 ng/mL, with MiBP and MnBP being the predominant isomers (MiBP + MnBP > 48.3%). Increasing trends were observed in MMP (5.7%/year) and MEHP (7.1%/year) levels during the study period, while a decreasing trend were observed in MiBP (-6.6%/year); no clear temporal trends were found for the other metabolites and total mPAE levels. The results indicate that exposure to phthalates is still prevalent in southern China. Breastfeeding was found to contribute to estimated daily phthalate intakes of 0.383-6.95 µg/kg-bw/day, suggesting insignificant health risks to infants based on dietary exposure. However, the increasing exposure to MMP and MEHP calls for more research into the possible sources and potential risks.

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.

Organophosphate esters (OPEs) in a heavily polluted river in South China: Occurrence, spatiotemporal trends, sources, and phase distribution.

In the past decade, organophosphate esters (OPEs) undergo rapid increase in production and use. Meanwhile, owing to their additive property, OPEs exhibit liability to escape from related products and therefore ubiquity in various environments. Moreover, numerous researches verify their bioavailability and negative effects on biota and human, hence their occurrence and associated risks have caught much concern, particularly those in aquatic systems. So far, however, OPEs in water are generally investigated as a whole, their phase distribution and behavior in waterbodies are incompletely characterized. We examined 25 OPEs in water (including dissolved and particulate phases), sediment, and sediment core samples from the Lian River, which flows through the Guiyu e-waste recycling zone and Shantou specific economic zone in South China. Compared to most global waterbodies, the Lian River showed high or ultrahigh OPE levels in both water and sediments, particularly in the reaches surrounded by e-waste recycling and plastic-related industries, which were the top two greatest OPE sources. Non-industrial and agriculture-related anthropogenic activities also contributed OPEs. Sediment core data suggested that OPEs have been present in waters in Guiyu since the 1960s and showed a temporal trend consistent with the local waste-recycling business. The phase distribution of OPEs in the Lian River was significantly correlated with their hydrophobicity and solubility. Owing to their wide range of physicochemical properties, OPE congeners showed significant percentage differences in the Lian River water and sediments. Generally, OPEs in water reflect their dynamic real-time inputs, while those in sediment signify their accumulative deposition, which is another cause of their phase distribution disparities in the Lian River. The physicochemical parameters of OPEs first imposed negative and then positive influences on their dissolved phase-sediment distribution, indicating the involvement of both the adsorption of dissolved OPEs and the deposition of particle-bound OPEs.

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.

Atmospheric occurrences and health risk assessment of polycyclic aromatic hydrocarbons and their derivatives in a typical coking facility and surrounding areas.

Coking facilities release large quantities of polycyclic aromatic hydrocarbons (PAHs) and their derivatives into the ambient air. Here we examined the profiles, spatial distributions, and potential sources of atmospheric PAHs and their derivatives in an industrial coking plant and its surrounding environment (gaseous and particulate). The mean concentrations of PAHs, nitrated PAHs (NPAHs), chlorinated PAHs (ClPAHs), and brominated PAHs (BrPAHs) in the air of the coking facility were 923, 23.8, 16.7 and 4.25 ng m-³, respectively, 1-2 orders of magnitude higher than those in the surrounding area and the control area. Linear regressions between contaminant concentrations and distance from the coking facility suggested that the concentrations of PAHs (r2 = 0.82, p < 0.05), NPAHs (r2 = 0.77, p < 0.01), and BrPAHs (r2 = 0.62, p < 0.01) were negatively correlated with distance. Additionally, the particle-bound fractions of PAHs and their derivatives were significantly correlated with their molecular weights (p < 0.01). Based on the calculation of the gas/particle partitioning coefficients (log KP) for PAHs and their derivatives and the corresponding subcooled liquid vapor pressures (log PL), the slope values for PAHs, NPAHs, ClPAHs, and BrPAHs ranged from -1 to -0.6, indicating that deposition of PAHs and their derivatives occurred through both adsorption and absorption. Five emissions sources were identified by positive matrix factorization (PMF), including coking emissions, oil pollution, industrial and combustion sources, secondary formation, and traffic emissions, with coking emissions accounting for more than 50% of total emissions. Furthermore, the results of the health risks assessment suggested that atmospheric PAHs and their derivatives in the coke plant and surrounding area negatively impacted human health.

Exposure to polycyclic aromatic hydrocarbons (PAHs) in outdoor air and respiratory health, inflammation and oxidative stress biomarkers: A panel study in healthy young adults.

Exposure to polycyclic aromatic hydrocarbons (PAHs) can be associated with different types of health effects. However, the systemic changes of health effects between fluctuations of PAHs exposure have not been established. In this study, urinary hydroxylated PAHs (OH-PAHs) and 12 biomarkers were determined among 36 students from the urban to the suburb in Taiyuan in 2019. The concentration of Σ12OH-PAHs in urban areas (28.2 and 21.4 µg/g Cr) was significantly higher than that in suburban area (16.8 µg/g Cr). The regression showed that hydroxy-phenanthrene (OH-Phe, 1/2/3/4/9-OH-Phe) was significantly positively correlated with lung function (PEF25 and PEF50), 8-hydroxydeoxyguanosine (8-OHdG), interleukin-8 (IL-8), and fractional exhaled nitric oxide (FeNO). Moreover, there were negative associations of 2-hydroxyfluorene (2-OH-Flu) with FVC and FEV1. 1 unit increase of 1-hydroxypyrene (1-OH-Pyr) was negatively associated with 18.8% FVC, 17.3% FEV1, and 26.4% PEF25 in the suburban location, respectively. During urban2, each unit change of 2-OH-Flu was associated with 10.9% FVC and 10.5% FEV1 decrease, which were higher than those in suburban location. 8-OHdG decreased by 32.0% with each unit increase in 3-hydroxyfluorene (3-OH-Flu) during urban2 (p < 0.05), while 1.9% in the suburban location. During the suburban period, the increase in OH-Phe was correlated with the decrease in malondialdehyde (MDA). The respiratory damage caused by PAHs in the urban disappeared after backing to the urban from the suburban area. Notably, despite the total significant liner mixed regression association of FeNO with multiple OH-PAHs, the association of FeNO with OH-PAHs was not significant during different periods except for 2-OH-Flu. Our findings suggested that short-term exposure to different concentrations of PAHs might cause changes in health effects and called for further research to investigate possible alterations between health effects and PAH exposure.

Distribution of phthalate metabolites, benzophenone-type ultraviolet filters, parabens, triclosan and triclocarban in paired human hair, nail and urine samples.

In this study, the distribution of nineteen ingredients of personal care product (PCPs), including seven metabolites of phthalates (mPAEs), five benzophenone-type ultraviolet filters (BPs), and seven antimicrobial agents (AAs), were investigated in paired human hair, nail and urine samples. The median concentrations of ΣmPAEs, ΣBPs and ΣAAs were 135, 2.76 and 179 ng/g in hair, 37.3, 2.95 and 297 ng/g in nails, and 345, 4.03 and 50.1 ng/mL in urine, respectively. Mono-methyl phthalate (49%), 2,4-dihydroxybenzophenone (45%) and triclosan (71%) were the most abundant mPAE, BP and AA in hair samples, respectively, and had similar abundance in nail samples. In contrast, mono-n-butyl phthalate (45%), 4-hydroxy benzophenone (29%) and methyl paraben (54%) were the predominant mPAE, BP and AA in urine samples, respectively. Significant differences in the concentrations of some target compounds were observed between male and female but inconsistent across different matrices. Moreover, most compounds with significant correlations had quite different correlation coefficients in each matrix. No significant correlations were found between hair, nail and urine samples for most of the target analytes. These results suggest these analytes have matrix-specific distribution, and it is necessary to use multiple matrices to comprehensively assess the risk of ingredients of PCPs to human health.

Internal exposure risk based on urinary metabolites of PAHs of occupation and non-occupation populations around a non-ferrous metal smelting plant.

The emission of various metals from non-ferrous metal smelting activities is well known. However, relative investigations on potential occupational exposure of organic pollutants are still limited. Herein, total of 619 human urine samples were collected from workers engaged in smelting activities and residents living near and/or far from the smelting sites, and ten mono-hydroxylated metabolites of polycyclic aromatic hydrocarbons (OH-PAHs) in human urine were determined. The median levels of Σ10OH-PAHs in smelting workers (25.6 ng/mL) were significantly higher (p < 0.01) than that of surrounding residents (9.00 ng/mL) and rural residents as the control (8.17 ng/mL), indicating an increase in occupational PAH exposure in non-ferrous metal smelting activities. The composition profiles of OH-PAH congeners were similar in three groups, in which naphthalene metabolites accounted for 76-82% of the total. The effects of smoking, drinking, gender, BMI, and occupational categories on urinary OH-PAHs were considered. The partial correlation analysis showed an insignificant effect of non-ferrous metal smelting activities on PAH exposure for surrounding residents. In the health risk assessments, almost all smelting workers had cancer risks exceeded the acceptable level of 10-6. This study provides a reference to occupational PAH exposure and reinforce the necessary of health monitoring among smelting workers.

Polybrominated diphenyl ethers and bromophenols in paired serum, hair, and urine samples of e-waste dismantlers: Insights into hair as an indicator of endogenous exposure.

Polybrominated diphenyl ethers (PBDEs) are important pollutants during dismantling activities of electronic waste (e-waste) in China due to its large production and usage. Bromophenols (BPs), which are a kind of flame retardants and diphenyl ether bond cleavage metabolites of PBDEs, are often neglected in the assessment of human exposure to e-waste. Herein, 22 PBDEs and 19 BPs were determined in paired serum, hair, and urine samples collected from workers and residents of a typical e-waste dismantling site in southern China. Both PBDE and BP congeners were more frequently detected in hair than serum and urine samples. The medians of ΣPBDEs and ΣBPs were 350 and 547 ng/g dw in hair internal (hair-In) of occupational population, respectively, which were significantly higher than non-occupational population. However, a non-significant difference was found in levels of ΣPBDEs and ΣBPs in serum and urine between occupational and non-occupational populations, suggesting that hair analysis could easily differentiate between the exposure intensities of PBDEs and BPs to populations than serum and urine analyses. Moreover, levels of BPs in hair-In were 1-2 orders of magnitude higher than those in hair external (hair-Ex), while a non-significant difference was found in the levels of PBDEs. This result indicated that BPs might have originated from endogenous contribution. Notably, as the predominant congeners, the level of 2,4,6-tribromophenol (2,4,6-TBP) in hair-In was 3-8 times higher than that of BDE-209, while level of 2,4,6-TBP in hair-Ex was 1-3 times lower than that of BDE-209. Furthermore, in vivo experiments performed on Sprague-Dawley rats following a 28-day oral treatment with BDE-209 and 2,4,6-TBP verified that endogenous accumulation of 2,4,6-TBP in hair could be attributed to the metabolism of BDE-209 and exposure to 2,4,6-TBP. In conclusion, compared with PBDEs, biomonitoring phenolic compounds or metabolites with hair could better reflect human endogenous exposure.

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.

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.

Handwipes as indicators to assess organophosphate flame retardants exposure and thyroid hormone effects in e-waste dismantlers.

Dermal exposure is increasingly recognized as an important pathway for organic pollutant exposure. However, data on dermal exposure are limited, particularly with respect to the health effects. This study evaluated association between organophosphorus flame retardants (OPFRs) in handwipes and internal body burden on workers and adult residents in an electronic waste (e-waste) dismantling area. The impact of dermal exposure to OPFRs on thyroid hormones (THs) served as a biomarker for early effects. Triphenyl phosphate (TPhP) was the most detected compound in handwipes, with median levels of 1180, 200, and 24.0 ng in people identified as e-waste bakers, e-waste dismantlers, and adult residents. Among e-waste dismantlers, TPhP levels in handwipes were positively correlated with paired serum TPhP and urinary diphenyl phosphate (DPhP) levels. In multiple linear regression models controlling for sex, age and smoking, TPhP levels in handwipes of e-waste dismantlers were significantly negatively correlated with three THs used to evaluate thyroid function: serum reverse 3,3',5-triiodo-L-thyronine (rT3), 3,3'-diiodo-L-thyronine (3,3'-T2), and 3,5-diiodo-L-thyronine (3,5-T2). These findings suggest that handwipes can act as non-invasive exposure indicators to assess body burden of dermal exposure to TPhP and health effects on THs of e-waste dismantlers. This study highlights importance of OPFR effect on human THs through dermal exposure.

Mixed bromine/chlorine transformation products of tetrabromobisphenol A formed in the combustion of printed circuit boards: Emission characteristics and transformation pathways.

Recently, mixed bromine/chlorine transformation products of tetrabromobisphenol A (ClyBrxBPAs) were found to be possibly related to the thermal treatment processes of electronic wastes. To explore their emission characteristics and formation mechanism, printed circuit board scraps were combusted in a tube furnace, under the temperature from 25 °C to 600 °C. The emission factor of the debromination products of tetrabromobisphenol A (BrxBPAs) was the highest, whereas that of ClyBrxBPAs was the lowest. Among three phases, most of the target compounds were partitioned into the oil and particle phases, and only negligible gaseous 2-BrBPA and bisphenol A were detected. The emission rates of most compounds were fastest at 300 °C, although 2-BrBPA, 2,6-Br2BPA, and 2-Cl-6-BrBPA peaked at 350 °C. Among the chemicals in total emission, 2-BrBPA was the dominant congener in BrxBPAs, whereas 2-Cl-2',6,6'-Br3BPA, 2-Cl-2',6#-Br2BPA, and Σ2Cl1Br1BPAs shared similar proportions in ClyBrxBPAs. Meanwhile, the composition profiles at 300 °C showed that 2,2',6-Br3BPA and 2-Cl-2',6,6'-Br3BPA occupied the largest proportions in BrxBPAs and ClyBrxBPAs, respectively. To reveal the possible transformation pathways, the Gibbs free energy was calculated based on a radical substitution reaction. After "•Br" removal from tetrabromobisphenol A or other BrxBPAs, the intermediate was more easily combined with "•H" than with "•Cl." In addition, the ClyBrxBPA formation via "-•H + •Cl" by BrxBPAs is nonspontaneous, thus limiting the further generation of ClyBrxBPAs. This study not only provides ideas for the study of other mixed halogenated products, but also provides constructive suggestions for environmental source analysis by combining previous research on the occurrence of ClyBrxBPAs in various environmental matrices.

Spatial distribution, source identification, and human health risk assessment of PAHs and their derivatives in soils nearby the coke plants.

The coking industry can generate large amounts of polycyclic aromatic hydrocarbons (PAHs) and their derivatives, which may negatively impact the environment and human health. In this study, soils nearby a typical coking plant were sampled to assess the impact of coke production on the surrounding residential areas and human health. The mean concentration of PAHs and their derivatives in residential area soils nearby the coke plant was 4270 ng/g dw, which was 1 order of magnitude higher than that observed in areas far from the coke plant and approximately 4 times lower than that revealed the coke plant. In addition, the results showed that coking processing area was the most contaminant area of the coke plant (mean: 74.4 µg/g dw), where was also the main source of pollutants in residential areas. In terms of vertical soils in coking plant, the maximum levels of chemicals (mean: 205 µg/g dw) were presented at the leakage of underground pipelines, where were much higher than those in surface soils, and decreased with the increase of depth. The analysis of variance (ANOVA) results showed obvious differences in the concentrations of 6-nitrochrysene between the plant, residential areas and control areas. Meanwhile, 6-nitrochrysene had potential cancer risk (CR) for human in the coking site. Thus, 6-nitrochrysene was the most noteworthy PAH derivatives. Furthermore, the CR (mean: 5.94 × 10-5) and toxic equivalent quantities (TEQs) (mean: 14.8 µg·TEQ/g) of PAHs and their derivatives was assessed in this study. This finding suggested that PAHs and their derivatives especially those extremely toxic chemicals (Nitro-PAHs (NPAHs) and Br/Cl-PAHs (XPAHs)) might pose a potential health risk to residents nearby the coke plant. The current study provides further insights into the pollution characteristics of PAHs and their derivatives in coke plants and potential risks to the workers and surrounding residents.

Preparation of tobacco pyrolysis liquids in subcritical/supercritical ethanol and their application in the aroma enhancement of heated cigarettes.

For the aroma enhancement research of heated cigarettes, it is worth exploring whether tobacco can be pyrolyzed into pyrolysis liquids containing a large number of volatile aroma components. In this study, tobacco pyrolysis liquids were prepared in subcritical/supercritical ethanol, and their applications in the aroma enhancement of heated cigarettes were investigated. The optimal conditions of supercritical liquefaction reactions were determined by optimizing the reaction time, liquid/solid mass ratio and temperature conditions. Moreover, the effect of supercritical liquefaction conditions on volatile aroma components in tobacco pyrolysis liquids was investigated by GC-MS. The results indicated that the reaction temperature had the most significant impact on the tobacco pyrolysis reaction, and higher reaction temperature promoted the pyrolysis conversion of tobacco, resulting in enhanced tobacco conversion and a high content of volatile components in the tobacco pyrolysis liquid. The optimal reaction conditions for the preparation of tobacco pyrolysis liquid were found to be a temperature of 220°C, a liquid/solid mass ratio = 15, and a 2-h reaction time. Meanwhile, the content of ester compounds and nicotine in the tobacco pyrolysis liquid increased significantly with the increase of reaction temperature. Sub/supercritical ethanol treatment significantly destroyed the surface structure of tobacco, and the degree of tobacco depolymerization increased when temperature rised. The analysis of aroma compounds in the smoke of heated cigarettes indicated that the tobacco pyrolysis liquid could significantly increase the release of aromatic substances and has a significant aroma-enhancing effect. This article proposed and prepared tobacco pyrolysis liquid in subcritical/supercritical ethanol and explored its potential application in the aroma enhancement of heated cigarettes, offering a new route for flavor enhancement technology for this type of product.

Heterologous spatial distribution of soil polycyclic aromatic hydrocarbons and the primary influencing factors in three industrial parks.

Soil polycyclic aromatic hydrocarbons (PAHs) generated from industrial processes are highly spatially heterologous, with limited quantitative studies on their main influencing factors. The present study evaluated the soil PAHs in three types of industrial parks (a petrochemical industrial park, a brominated flame retardant manufacturing park, and an e-waste dismantling park) and their surroundings. The total concentrations of 16 PAHs in the parks were 340-2.43 × 103, 26.2-2.63 × 103, and 394-2.01 × 104 ng/g, which were significantly higher than those in the surrounding areas by 1-2 orders of magnitude, respectively. The highest soil PAH contamination was observed in the e-waste dismantling park. Nap can be considered as characteristic pollutant in the petrochemical industrial park, while Phe in the flame retardant manufacturing park and e-waste dismantling park. Low molecular weight PAHs (2-3 rings) predominated in the petrochemical industrial park (73.0%) and the surrounding area of brominated flame retardant manufacturing park (80.3%). However, high molecular weight PAHs (4-6 rings) were enriched in the other sampling sites, indicating distinct sources and determinants of soil PAHs. Source apportionment results suggested that PAHs in the parks were mainly derived from the leakage of petroleum products in the petroleum manufacturing process and pyrolysis or combustion of fossil fuels. Contrarily, the PAHs in the surrounding areas could have been derived from the historical coal combustion and traffic emissions. Source emissions, wind direction, and local topography influenced the PAH spatial distributions.

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.