Occurrence and human exposure assessment of organophosphate esters in atmospheric PM2.5 in the Beijing-Tianjin-Hebei region, China.

Organophosphate esters (OPEs) in atmospheric fine particles (PM2.5) were comprehensively investigated in the Beijing-Tianjin-Hebei (BTH) region from April 2016 to March 2017. The concentrations of Σ8OPEs in all the five sampling sites ranged from 90 to 8291 pg/m3 (mean 1148 ± 1239 pg/m3; median 756 pg/m3). The highest level (median 1067 pg/m3) was found at one of the urban sites in Beijing, followed by Tianjin (746 pg/m3) and Shijiazhuang (724 pg/m3). Tris(2-chloroethyl) phosphate (TCEP) and tri[(2R)-1-chloro-2-propyl] phosphate (TCPP) were the dominant compounds across the five sampling locations. Generally, the concentrations of chlorinated OPEs were relatively higher in summer than in winter (p < 0.05), but no significant seasonal difference was discovered for non-chlorinated individual OPEs. The concentrations of tri-n-butyl phosphate (TBP), TCEP, TCPP and triphenyl phosphate (TPP) were positively correlated with the meteorological parameters (i.e. temperature and relative humidity) (p < 0.05), indicating an evident influence of meteorological condition on OPE distribution. We observed a negative correlation (p < 0.05) between octanol-air partition coefficients (logKoa) and the ratio of PM2.5-bound OPE concentrations to total suspended particulates-bound OPE concentrations, suggesting that physicochemical properties affect the particle-size distribution of OPEs. Furthermore, the median value of cancer hazard quotients (HQs) of TCEP was higher than TBP and tris(2-ethylhexyl) phosphate (TEHP). The health risk assessment showed that HQ values for children were ~1.6 times higher than those for adults. Relatively higher health risk induced by PM2.5-bound OPEs via inhalation was found during severe hazy days than in clear days.

Seasonal variation and human exposure assessment of legacy and novel brominated flame retardants in PM2.5 in different microenvironments in Beijing, China.

Indoor exposure to legacy and novel brominated flame retardants (NBFRs) may cause potential risks to human health. Studies on seasonal variations of indoor PM2.5-bound BFRs are scant. This study comprehensively investigated the seasonal variations of PM2.5-bound polybrominated diphenyl ethers (PBDEs) and NBFRs in various indoor environments (i.e. activity room, dormitory, home and office) and outdoor PM2.5 in Beijing, China over one year. The levels of PBDE (226 ±â€¯108 pg m-3) were higher than that of NBFRs (27.0 ±â€¯16.0 pg m-3) in all indoor environments. Decabromodiphenyl ether (BDE-209) and decabromodiphenyl ethane (DBDPE) were the most abundant BFRs. Office showed the highest mean concentrations of Σ15PBDEs (251 ±â€¯125 pg m-3) and Σ9NBFRs (33.0 ±â€¯18.0 pg m-3), which may be related to the higher number density of indoor materials. The concentrations of Σ9NBFRs and Σ15PBDE in indoor PM2.5 were found to be significantly higher than those in the corresponding outdoor PM2.5 (p < 0.05). Two to twenty-fold seasonal variations were observed for levels of PM2.5-bound BFRs during one year, and indoor concentrations increased slightly during the central-heating period (November 2016-March 2017). Seasonal variations of BFRs could be affected by temperature, relative humidity and concentrations of particle matters. The PM2.5-bound BFRs concentrations in PM2.5 were negatively correlated with temperature and relative humidity, while positively correlated with PM2.5 concentrations (p < 0.05). Atmospheric haze pollution could possibly contribute to higher levels of indoor PM2.5-bound BFRs. Human daily intake of BFRs via PM2.5 inhalation showed seasonal differences, and the highest exposure risk occurred in winter. Toddlers were assessed to be more vulnerable to indoor PM2.5-bound BFRs in all seasons. This study provided the first-hand measurements of seasonal concentrations and human exposure to PM2.5-bound BFRs in different indoor scenarios in Beijing.

Brominated flame retardants in atmospheric fine particles in the Beijing-Tianjin-Hebei region, China: Spatial and temporal distribution and human exposure assessment.

Atmospheric fine particle (PM2.5) samples were collected over a whole year (April 2016 - March 2017) across five sampling locations in the Beijing-Tianjin-Hebei (BTH) region, to investigate the occurrence of novel brominated flame retardants (NBFRs) and polybrominated diphenyl ethers (PBDEs). The concentrations of ∑9NBFRs were in the range of 0.63-104 pg/m3 (15.6 ±â€¯16.8 pg/m3) in atmospheric PM2.5, while the levels of ∑9PBDEs (excluding BDE-209) ranged from 0.05 to 19.1 pg/m3 (2.9 ±â€¯3.8 pg/m3) and BDE-209 concentrations ranged from 0.88 to 138 pg/m3 (22 ±â€¯28 pg/m3). Relatively higher levels of NBFRs and PBDEs were found at urban sampling sites in Beijing City and Shijiazhuang City. Decabromodiphenylethane (DBDPE) and BDE-209 were the dominant compounds with the relative abundances of 72% in ∑9NBFRs and 90% in ∑10PBDEs, respectively. Generally, the levels of most target BFRs in summer were lower than those in other seasons. However, there were no notable seasonal differences in levels of DBDPE and BDE-209 in atmospheric PM2.5 samples across the BTH region. Significant and positive correlations were found between the concentrations of BFRs and PM2.5. Daily human exposure via inhalation revealed that children have a higher probability of suffering from the adverse effects of BFRs than that of adults. In addition, residents living near sampling locations across the BTH region may suffer high exposure risks to BDE-209 and NBFRs.

Distribution, seasonal variation and inhalation risks of polychlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated biphenyls and polybrominated diphenyl ethers in the atmosphere of Beijing, China.

Spatial distribution, seasonal variation and potential inhalation risks of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were investigated in the atmosphere of Beijing, using passive air samplers equipped with polyurethane foam disks. Concentrations of ΣPCDD/Fs, ΣPCBs and ΣPBDEs ranged from 8.4 to 179 fg WHO2005-TEQ/m3, 38.6-139 and 1.5-176 pg/m3, respectively. PCDFs showed higher air concentrations than those of PCDDs, indicating the influence of industrial activities and other combustion processes. The non-Aroclor congener, PCB-11, was detected in air (12.3-99.4 pg/m3) and dominated the PCB congener profiles (61.7-71.5% to ∑PCBs). The congener patterns of PBDEs showed signatures from both penta-BDE and octa-BDE products. Levels of PCDD/Fs, PCBs and PBDEs at the industrial and residential sites were higher than those at rural site, indicating human activities in urban area as potential sources. Higher air concentrations of PCDD/Fs, PCBs and PBDEs were observed in summer, which could be associated with atmospheric deposition process, re-volatilization from soil surface and volatilization from use of technical products, respectively. Results of inhalation exposure and cancer risk showed that atmospheric PCDD/Fs, dioxin-like PCBs and PBDEs did not cause high risks to the local residents of Beijing. This study provides further aid in evaluating emission sources, influencing factors and potential inhalation risks of the persistent organic pollutants to human health in mega-cities of China.

Rubber Antioxidants and Their Transformation Products: Environmental Occurrence and Potential Impact.

Antioxidants are prevalently used during rubber production to improve rubber performance, delay aging, and extend service life. However, recent studies have revealed that their transformation products (TPs) could adversely affect environmental organisms and even lead to environmental events, which led to great public concern about environmental occurrence and potential impacts of rubber antioxidants and their TPs. In this review, we first summarize the category and application of rubber antioxidants in the world, and then demonstrate the formation mechanism of their TPs in the environment, emphasizing their influence on the ozone oxidative degradation. The potential toxic effects of antioxidants and their TPs are further reviewed to improve understanding of their biological health impact and environmental risks. Finally, the environmental occurrences of antioxidants and their TPs are summarized and their environmental impacts are demonstrated based on the recent studies. Due to the currently limited understanding on the toxic and biological effects of these compounds, further studies are required in order to better assess various TPs of these antioxidants and their environmental impact. To our knowledge, this is the first review on antioxidants and their TPs in the environment, which may elevate the environmental risk awareness of rubber products and their TPs in the near future.

Ecotoxicology of persistent organic pollutants in birds.

Considering the explosive growth of the list of persistent organic pollutants (POPs), the scientific community is combatting increasing challenges to protect humans and wildlife from the potentially negative consequences of POPs. Herein, we characterize the main aspects and progress in the ecotoxicology of POPs in avian species since 2000. The majority of previous efforts has revealed the global occurrence of high levels of various POPs in birds. Laboratory research and epidemiological studies imply that POPs exert a broad-spectrum of side-effects on birds by interfering with their endocrine, immune and neural system, reproduction, and development, and growth. However, inconsistent results suggest that the potential effects of POP exposure on the physiological parameters in birds are multifactorial, involving a multitude of biological processes, species-specific differences, gender, age and types of compounds. Great progress has been achieved in identifying the species-specific sensitivity to dioxin-like compounds, which is attributed to different amino acid residues in the ligand-binding domain of the aryl hydrocarbon receptor. Besides the conventional concentration additivity, several studies have suggested that different classes of POPs possibly act synergistically or antagonistically based on their concentration. However, ecotoxicology information is still recorded in a scattered and inadequate manner, including lack of enough avian species, limited number of POPs investigated, and insufficient geographical representation, and thus our understanding of the effects of POPs on birds remains rudimentary, although mechanistic understanding of their mode of action is progressing. Particularly, research on what happens to wild bird populations and their ecosystems under POP stress is still unavailable. Thus, our aim is to predict and trace the effects POPs at different biological organization levels, especially from the molecular, cellular and individual levels to the population, community and ecosystem levels because of the limited and scattered information, as mentioned above.

Novel brominated flame retardants in West Antarctic atmosphere (2011-2018): Temporal trends, sources and chiral signature.

Novel brominated flame retardants (NBFRs) were comprehensively investigated in both gaseous and particle phase samples collected using a high-volume active air sampler (HV-AAS) at the Chinese Great Wall Station in King George Island, West Antarctica from 2011 to 2018. The concentrations of ∑12NBFRs ranged from 0.27 to 3.0 pg m-3, with a mean value of 1.1 ± 0.50 pg m-3 and the levels showed a slightly increasing trend over the eight years. Decabromodiphenyl ethane (DBDPE) was the predominant NBFR with a relative contribution of 50% on average. Most of the studied NBFRs tended to distribute in gaseous phase with an average ratio of 72 ± 16% while NBFRs with higher log KOA values had higher proportions in particle phase. The gas/particle partitioning models were employed to evaluate the environmental behavior of NBFRs. Compared to the equilibrium-state-based model, the steady-state-based model performed much better to predict the gas/particle partitioning of NBFRs in the West Antarctic atmosphere. Additionally, no temperature dependence was found for NBFRs except rac-(1R,2R,5R,6R)-1,2,5,6-tetrabromocyclooctane (ß-TBCO). The annual mean concentrations of ∑12NBFRs showed a significantly negative correlation with the frequency of east-southeast (ESE, 112.5°) wind and calm wind (~0 m s-1) (p < 0.05), and a significantly positive correlation with the frequency of wind from northwest interval (west to north-northwest, 270° to 337.5°) (p < 0.05), suggesting a significant effect of air mass from the ocean area. Furthermore, the chiral signature of NBFRs showed commonly non-racemic residue in the atmosphere. The enantiomer fractions (EF) of rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethly)cyclohexane (α-TBECH) and ß-TBCO were 0.115-0.962 and 0.281-0.795, revealing secondary sources of NBFRs, e.g., seawater-air exchange and/or non-racemic residue in the source regions. As far as we know, this is one of very few studies on NBFRs in the Antarctic atmosphere.

Spatial and temporal distribution of organophosphate esters in the atmosphere of the Beijing-Tianjin-Hebei region, China.

High volume air samples were collected from April 2016 to March 2017 at five locations across the Beijing-Tianjin-Hebei (BTH) region, to investigate the atmospheric occurrence of organophosphate esters (OPEs). The mean atmospheric concentrations of ∑8OPEs (gas and particle phases) varied from 531 ±â€¯393 pg/m3 to 2180 ±â€¯1490 pg/m3 with the highest level observed at the urban sampling site in Tianjin City. ∑8OPEs were predominated by the chlorinated OPEs (TCEP, TCPP, and TDCIPP), which accounted for 60% ±â€¯16% of the OPE concentrations across the BTH region. Generally, higher levels of gaseous OPEs were found in summer, while higher levels of particle-bound OPEs were observed in winter. The concentrations of gaseous OPEs were positively and significantly correlated with local temperatures (p < 0.05) and relative humidity (p < 0.01), while significantly positive correlations were found between concentrations of particle-bound OPEs and total suspended particulates (TSP) (p < 0.01). These findings confirmed that temperatures, relative humidity and levels of TSP are the main drivers for OPE distributions in different seasons and areas. Gas/particle partitioning of OPEs was also investigated based on the absorption-partitioning model (octanol-air partitioning coefficient (Koa) -based model) and Junge-Pankow adsorption-partitioning model (J-P model). Koa-based model generally showed a better performance in comparison with the measured results. The assessment of inhalation exposure risks indicated that relatively higher exposure risks were found in the urban areas, in particular, in Tianjin City (a median value of the estimated daily intake (EDI) of 106 pg/kg body weight/day), suggesting that more attention should be drawn to OPE distributions in the heavily industrialized megacities.

Effects of migration and reproduction on the variation in persistent organic pollutant levels in Kentish Plovers from Cangzhou Wetland, China.

Migratory Birds have been considered biovectors of persistent organic pollutants (POPs) from sources to remote areas. In the present study, Kentish Plovers (Charadrius alexandrines) were collected in different periods, including immigration, breeding and emigration, to investigate the effects of migration and reproduction on POP variations in this bird species. Significant differences were found for dichlorodiphenyltrichloroethane (DDT) and hexachlorobenzene (HCB) concentrations in muscles between the immigration and emigration periods (p < 0.01 and p < 0.001, respectively), which could be attributed to the higher pesticide residues in the wintering grounds of plovers. Female plovers could excrete about 20.8-42.7% of POP load into eggs. Nevertheless, the POP levels didn't exhibit great reduction during the breeding period compared with other seasons, which suggested that the breeding status had little impact on POP levels in female plovers. The estimated mean transport masses of POPs driven by plover migration were at the milligram level (range: 0.02-7.05 mg), suggesting that the migration of plovers had limited impacts on the redistributions of POPs along their migratory routes.

Multivariate Optimization of Tenax TA-Thermal Extraction for Determining Gaseous Phase Organophosphate Esters in Air Samples.

Suitable conditions for thermal extraction of semi-volatile organic compounds have largely been arrived at by univariate optimization or based on the recommendations provided by the manufacturers of the extraction equipment. Herein, we demonstrated the multivariate optimization of Tenax TA-thermal extraction for determining organophosphate esters in the gas phase fraction of air samples. Screening and refining experiments were performed using the eighth fraction factorial and Box-Behnken designs, respectively, and satisfactory models were obtained. Subsequently, the process was optimized by Derringer's desirability function and the global desirability was 0.7299. Following optimization, the analytes were desorbed at 290 °C for 10 minutes at a helium flow of 95 mL min-1, with the transfer line set at 290 °C. The analytes were then cryofocused at 20 °C and then cryodesorbed into the chromatographic column at 295 °C for 6 minutes. Method validation exhibited high linearity coefficients (>0.99), good precision (CV < 14%) and low detection limits (0.1-0.5 ng m-3). The method was tested by pumping 0.024 m3 of real indoor environment air through Tenax TA sorbent tubes. Furthermore, with multivariate optimization, analysis time and other resources were significantly reduced, and information about experimental factor interaction effects was investigated, as compared to the univariate optimization and other traditional methods.

Temporal variations of PM2.5-bound organophosphate flame retardants in different microenvironments in Beijing, China, and implications for human exposure.

In the present study, the temporal distribution of PM2.5-bound organophosphate flame retardants (OPFRs) was comprehensively investigated in various indoor environments as well as outdoor air in Beijing, China over a one-year period. The mean concentrations of Σ9OPFRs were 22.7 ng m-3 and 1.40 ng m-3 in paired indoor and outdoor PM2.5, respectively. The concentrations of tri-n-butyl phosphate (TNBP), tris (2-chloroethyl) phosphate (TCEP) and tris (2-chloroisopropyl) phosphate (TCIPP) in indoor PM2.5 were significantly correlated with those in outdoor PM2.5. For different indoor microenvironments, mean concentrations of Σ9OPFRs were in the order of office (29.0 ±â€¯11.7 ng m-3) > home (24.0 ±â€¯9.4 ng m-3) > dormitory (19.4 ±â€¯4.9 ng m-3) > activity room (14.4 ±â€¯3.1 ng m-3). TCIPP was the most abundant compound in the indoor PM2.5, followed by TCEP. Significantly higher concentrations of OPFRs were observed in indoor environments with more furnishing, electronics or other materials (p < 0.05). Moreover, lower levels of OPFRs in indoor air were observed at well-ventilated (with higher air exchange rate) indoor sampling sites. Concentrations of Σ9OPFRs in the activity room, dormitory, homes and outdoor sites generally increased in summer and heating seasons (November 2016 to February 2017). Significant correlations (p < 0.05) were observed between temperatures and mass concentrations of OPFRs with higher vapor pressures, i.e. TNBP, TCEP and TCIPP in all indoor and outdoor samples. Seasonal differences in human exposure were observed and the highest daily exposure dose occurred in summer. Toddlers may suffer the highest exposure risk of PM2.5-bound OPFRs via inhalation among all age groups. This is one of the very few studies that have revealed the seasonal variation and human exposure of PM2.5-bound OPFRs in different microenvironments, which shed light on emission sources and fate of OPFRs and potential human exposure pathway.

Tissue distribution and maternal transfer of persistent organic pollutants in Kentish Plovers (Charadrius alexandrines) from Cangzhou Wetland, Bohai Bay, China.

Several persistent organic pollutants, including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs), were comprehensively investigated in the egg, muscle and liver samples of Kentish Plover (Charadrius alexandrines) collected from Cangzhou Wetland in western Bohai Bay, China. DDTs were the most abundant contaminants (35.4-9853ngg-1 lipid weight, lw), followed by HCHs, PCBs, PBDEs and HCB. PCDD/Fs exhibited the lowest concentrations in all tissues (8.74-4763pgg-1 lw). PCBs and PCDD/Fs were dominated by penta- and hexa-homologs, and PBDEs mostly consisted of the signature congeners of BDE formulations, such as BDE-209, -47, -153 and -99. Significant correlations were found between the lipid-normalized concentrations in muscle and liver (r: 0.37-0.90, p<0.05) and no significant differences (p<0.05), indicating the homogenous distribution of POPs in tissue lipids at steady state. The ratios of concentrations in muscle and liver (M/L) ranged from 0.20 to 1.51, and higher ratios of M/L were found for those compounds with log Kow in the range of 6.5-7.0, suggesting the preferential accumulation of mid-halogenated compounds in muscle. Significant correlations were generally observed between the concentrations in egg and the maternal tissue (p<0.05). The concentration ratios of egg to liver (E/L) were in the range of 0.10-1.24 except for p,p'-DDT (12.7), and compounds with log Kow of 6.5-7.0 exhibited higher E/L ratios, suggesting the selective maternal transfer of mid-halogenated compounds.

Altitudinal dependence of PCBs and PBDEs in soil along the two sides of Mt. Sygera, southeastern Tibetan Plateau.

Surface soil samples were collected from Mt. Sygera in the southeast of Tibetan Plateau to investigate the altitudinal distribution of PCBs and PBDEs along the two sides of the mountain. The average concentrations of PCBs and PBDEs were 177 pg g-1 dw and 15 pg g-1 dw, respectively. The relationships between the log-transformed TOC-normalized concentrations and the altitudes showed different trends on the two sides. On the windward side, there was a positive correlation for the heavier PCBs; while on the leeward side, the concentrations increased and then decreased for PCBs and PBDEs at the altitude of 4100-4200 m, corresponding to the change in vegetation. The observed discrepancy on the two sides of the mountain demonstrated different key factors associated with precipitation and the forest canopy. Additionally, values of windward-leeward Enrichment Factors (W/L EFs) for the heavier PCB congeners (PCB-138, 153, and -180) were an order of magnitude higher in sites above 4200 m, which also suggested that vegetation played an important role in the altitudinal accumulation of POPs in soil. This is one of the very few studies that have revealed the differences in altitudinal accumulation of POPs along the two sides of a mountain.

Airborne persistent toxic substances (PTSs) in China: occurrence and its implication associated with air pollution.

In recent years, China suffered from extensive air pollution due to the rapidly expanding economic and industrial developments. Its severe impact on human health has raised great concern currently. Persistent toxic substances (PTSs), a large group of environmental pollutants, have also received much attention due to their adverse effects on both the ecosystem and public health. However, limited studies have been conducted to reveal the airborne PTSs associated with air pollution at the national scale in China. In this review, we summarized the occurrence and variation of airborne PTSs in China, especially in megacities. These PTSs included polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), halogenated flame retardants (HFRs), perfluorinated compounds (PFCs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and heavy metals. The implication of their occurrence associated with air pollution was discussed, and the emission source of these chemicals was concluded. Most reviewed studies have been conducted in east and south China with more developed economy and industry. Severe contamination of airborne PTSs generally occurred in megacities with large populations, such as Guangzhou, Shanghai and Beijing. However, the summarized results suggested that industrial production and product consumption are the major sources of most PTSs in the urban environment, while unintentional emission during anthropogenic activities is an important contributor to airborne PTSs. It is important that fine particles serve as a major carrier of most airborne PTSs, which facilitates the long-range atmospheric transport (LRAT) of PTSs, and therefore, increases the exposure risk of the human body to these pollutants. This implied that not only the concentration and chemical composition of fine particles but also the absorbed PTSs are of particular concern when air pollution occurs.