Occurrence and seasonal variations of organophosphate flame retardants in air and dust from college microenvironments at Qingdao, China: Implications for student's exposure and risk assessment.

Organophosphate flame retardants (OPFRs) are widely used as alternatives to brominated flame retardants in a variety of consumer products and their consumption has continuously increased in recent years. However, their concentrations and human exposures in indoor microenvironments, particularly in a university environment, have received limited attention. In this study, the concentrations and seasonal variations of 15 OPFRs were assessed in typical microenvironments of two universities, including dormitories, offices, public microenvironments (PMEs: classroom, dining hall, gymnasium and library), and laboratories on the northern coast of China. Analysis of the OPFRs in both air and dust samples indicated widespread distribution in college campuses. The average concentration of ∑15OPFRs in the winter (12,774.4 ng/g and 5.3 ng/m3 for dust and air, respectively) was higher than in the summer (2460.4 ng/g and 4.6 ng/m3 for dust and air, respectively). The dust and air samples collected from PMEs and laboratories exhibited higher concentrations of OPFRs, followed by offices and dormitories. An equilibrium was reached between dust and air in all collected microenvironments. The daily intakes of OPFRs were significantly lower than the reference dose. Dust ingestion was the primary intake pathway in the winter, while inhalation and dust ingestion were the main intake pathways in the summer. The non-carcinogenic hazard quotients fell within the range of 10-7-10-3 in both the summer and winter, which are below the theoretical risk threshold. For the carcinogenic risk, the LCR values ranged from 10-10 to 10-8, indicating no elevated carcinogenic risk due to TnBP, TCEP, and TDCP in indoor dust and air.

Influence of oil extraction on concentration distributions, migration, secondary formation and carcinogenic risk of NPAHs and OPAHs in air and soil in an oilfield development area in China.

Oil extraction leads to environmental pollution from the oilfields and dweller activities, however, knowledge of the concentration distributions, migration, secondary formation and toxicity of nitrated/oxygenated polycyclic aromatic hydrocarbons (N/OPAHs) in oilfield regions is limited. In this research, atmospheric and soil samples in 7 different location types in an important oil industrial base in China were gathered. The ΣNPAHs and ΣOPAHs in the air ranged from 0.05 to 2.47 ng/m3 and 0.14-22.72 ng/m3, respectively, and in soil ranged from 0.22 to 17.81 ng/g and 9.69-66.86 ng/g, respectively. Both NPAHs and OPAHs in the atmosphere exhibited higher concentrations during winter. The atmospheric NPAH concentrations decreased exponentially with distance from urban area especially in the summer, revealing the impact of vehicles on the air in the Yellow River Delta area. High NPAH and OPAH concentrations were found only in soil near oil extraction facilities, indicating that the impact of oil extraction is limited to the soil near the extraction facilities. The air-soil exchanges of N/OPAHs were assessed through fugacity fraction analysis, and NPAHs were in the equilibrium-deposition state and OPAHs were in the net-deposition state in the winter. Higher incremental lifetime cancer risk (ILCR) occurred at the urban, industrial, and oilfield sites in the atmospheric samples, and the soil samples had the largest ILCR values in the oilfield sites. However, ILCR values for both air and soil did not exceed the threshold of 10-6.

Distributions of PAHs, NPAHs, OPAHs, BrPAHs, and ClPAHs in air, bulk deposition, soil, and water in the Shandong Peninsula, China: Urban-rural gradient, interface exchange, and long-range transport.

A systematic study of the movement of PAHs (Polycyclic aromatic hydrocarbons) and their derivatives through air, soil, and water is key to understanding the exchange and transport mechanisms of these pollutants in the environment and for ultimately improving environmental quality. PAHs and their derivatives, such as nitrated PAHs (NPAHs), oxygenated PAHs (OPAHs), brominated PAHs (BrPAHs) and chlorinated PAHs (ClPAHs), were analyzed in air, bulk deposition, soil, and water samples collected from urban, rural, field, and background sites on the eastern coast of China. The goal was to investigate and discuss their spatiotemporal variations, exchange fluxes, and transport potential. The concentrations of PAHs and their derivatives in the air and bulk deposition displayed distinct seasonal patterns, with higher concentrations observed during the winter and spring and lower concentrations during the summer and autumn. NPAHs exhibited the opposite trend. Significant urban-rural gradients were observed for most of the PAHs and their derivatives. According to the air-soil fugacity calculations, 2-3 ring PAHs, BrPAHs, and ClPAHs were found to volatilize from the soil into the air, while 4-7 ring PAHs, OPAHs, and NPAHs deposited from the air into the soil. The air-water fugacity of the PAHs and their derivatives indicated that surface water was an important source for the ambient atmosphere in Qingdao. The characteristic travel distances (CTDs) and persistence (Pov) for atmospheric transport were much lower than that for the water samples, which may be due to the longer half-lives of PAHs and their derivatives in water. NPAHs and ClPAHs with long transport distances and strong persistence in water could lead to a significant impact on marine pollution.

Spatial Distribution, Sources, Air-Soil Exchange, and Health Risks of Parent PAHs and Derivative-Alkylated PAHs in Different Functional Areas of an Oilfield Area in the Yellow River Delta, North China.

The knowledge of the spatial distribution, sources, and air-soil exchange of polycyclic aromatic compounds (PACs) in an oilfield area is essential to the development of effective control practices of PAC pollution. In this study, 48 passive air samples and 24 soil samples were collected during 2018-2019 in seven functional areas (e.g., urban, oil field, suburban, industrial, agricultural, near pump units, and background) in the Yellow River Delta (YRD) where the Shengli Oilfield is located, and 18 parent polycyclic aromatic hydrocarbons (PAHs) and five alkylated-PAHs (APAHs) were analyzed from all the air and soil samples. The ΣPAHs in the air and soil ranged from 2.26 to 135.83 ng/m3 and 33.96 to 408.94 ng/g, while the ΣAPAHs in the atmosphere and soil ranged from 0.04 to 16.31 ng/m3 and 6.39 to 211.86 ng/g, respectively. There was a downward trend of atmospheric ΣPAH concentrations with increasing the distance from the urban area, while both ΣPAH and ΣAPAH concentrations in the soil decreased with distance from the oilfield area. PMF analyses show that for atmospheric PACs, coal/biomass combustion was the main contributor in urban, suburban, and agricultural areas, while crude production and processing source contributes more in the industrial and oilfield area. For PACs in soil, densely populated areas (industrial, urban, and suburban) are more affected by traffic sources, while oilfield and near-pump unit areas are under the impact of oil spills. The fugacity fraction (ff) results indicated that the soil generally emitted low-molecular-weight PAHs and APAHs and act as a sink for high-molecular-weight PAHs. The incremental lifetime cancer risk (ILCR) of Σ(PAH+APAH) in both the air and soil, were below the threshold (≤10-6) set by the US EPA.

[Pollution Characteristics and Source Analysis of Atmospheric PM2.5-bound Polycyclic Aromatic Hydrocarbons in a Port Area].

In order to explore the pollution characteristics and potential sources of polycyclic aromatic hydrocarbons (PAHs) in the polluted air of a port area, PM2.5 samples (n=59) were collected from Qingdao Port for four seasons from August 2018 to May 2019. The seasonal variation and composition characteristics of PM2.5-bound PAHs were analyzed, the influence of meteorological factors on PAH concentrations was explored using correlation analysis, and the potential sources were analyzed using positive definite matrix factorization and potential source contribution function models. The results showed that the total mean concentration of PAHs was (8.11±12.31) ng·m-3, which was higher in autumn and winter than that in spring and summer. The seasonal molecular compositions of PAHs were similar, dominated by 4-5 ring PAHs (75.43%). Fluoranthene, benzo[e]pyrene, benzo[a]anthracene, phenanthrene, pyrene, and chrysene were the dominant species of PAHs in the study area, which are similar to the major compounds in ship exhaust. Correlation analysis showed that PAH concentrations were significantly negatively correlated with temperature and relative humidity and significantly positively correlated with atmospheric pressure and wind direction and had a poor correlation with wind speed. PMF analysis extracted six contribution factors, and the results indicated that Qingdao Port was mainly influenced by shipping emissions (28.83%), followed by vehicle emissions (20.49%), as well as crude oil volatilization (13.47%). Summer had the greatest impact on shipping emissions. The PSCF results suggested that Beijing-Tianjin-Hebei, Bohai Rim, and northern Shandong were the main source regions for long-range transport.

Spatial and temporal variation, source identification, and toxicity evaluation of brominated/chlorinated/nitrated/oxygenated-PAHs at a heavily industrialized area in eastern China.

Some derivatives of polycyclic aromatic hydrocarbons (PAHs) such as chlorinated and brominated PAHs (Cl/BrPAHs), nitrated and oxygenated PAHs (N/OPAHs) have attracted significant concern due to their high toxicity. Knowledge of the profiles, formation mechanisms, and potential sources of these toxic chemicals near the industrial complexes is essential for their pollution control and management. In this study, we monitored Cl/BrPAHs, N/OPAHs, and PAHs at 24 sampling sites near a heavily industrialized area (steel, chemical, and rubber plants) using passive air samplers during the heating period (7 December 2019 to 15 April 2020) and the non-heating period (2 June 2020 to 4 October 2020). The total average concentrations of 16 BrPAHs, 8 ClPAHs, 17 NPAHs, 6 OPAHs, and 18 PAHs during both sampling periods were 471 pg/m3, 229 pg/m3, 312 pg/m3, 2120 pg/m3, and 63.1 ng/m3, respectively. Except for NPAHs, BrPAHs, ClPAHs, OPAHs, and PAHs all showed higher levels during the heating period. The spatial distributions of Cl/BrPAHs, N/OPAHs, and PAHs exhibited a similar pattern, with the highest concentrations detected in the vicinity of the steel industry. Congener profiles of PAH derivatives indicated that mono-substituted low molecular weight compounds (2-3 rings) were dominant. The major formation mechanisms of halogenated PAHs were discussed by correlation analysis and relative Gibbs free energies, and direct bromination of parent PAHs could be the major formation mechanism of BrPAHs in this study. Diagnostic ratios showed that NPAHs were mainly derived from primary emissions, but the contribution of secondary formation was increased at heavily contaminated sites. The positive matrix factorization model extracted four Cl/BrPAHs, three N/OPAHs, and four PAHs factors, and the result showed that PAHs and their derivatives mainly derived from industrial and combustion sources, photochemical reactions, vehicle emissions, and crude oil volatilization, etc.

Temporal profiles, source analysis, and health risk assessments of parent polycyclic aromatic hydrocarbons (PPAHs) and their derivatives (NPAHs, OPAHs, ClPAHs, and BrPAHs) in PM2.5 and PM1.0 from the eastern coastal region of China: Urban coastal area versus coastal background area.

The eastern coastal region of China is the area with the highest emission of PAHs in China. Therefore, understanding the sources and health risk of parent polycyclic aromatic hydrocarbons (PPAHs) and their derivatives in eastern coastal cities of China is the main basis for air pollution control. In this study, we measured the concentrations of 18 parent PAHs, 17 nitrated PAHs, 7 oxygenated PAHs, 8 chlorinated PAHs, and 13 brominated PAHs in PM1.0 and PM2.5 samples collected at an urban coastal city site and a coastal background site in 2019. We analyzed the temporal distribution, molecular composition, and sources and performed health risk assessments for both winter and summer samples. The average concentration of the PPAHs and their derivatives (all 63 compounds combined) in the PM1.0 samples accounted for 75.57% of the PAHs concentration in PM2.5 samples. The average concentration of PM2.5- and PM1.0- bound PPAHs in winter was 114.70 times higher than in summer, and their derivatives was 27.51 times. Both the combined concentrations of the 18 PPAHs and the combined concentrations of the 45 derivatives were higher in the coastal city compared to the background site during the winter (1.90 and 1.48 times, respectively), but they were comparable during the summer. The positive matrix factorization analysis indicated that the compounds mainly originated from coal/biomass combustion, industrial sources, vehicle emissions, and secondary formation. In addition, the concentration-weighted trajectories model revealed that the PAHs were mainly emitted locally in Shandong Province and surrounding areas, such as Hebei Province, Henan Province, and Bohai Sea. The compounds 1-NPYR, 2+9-BrPHE, 9,10-Cl2PHE, and 1-ClPYR dominantly contributed to the derivatives of TEQ during the winter due to their high concentrations or the high TEFs of these compounds.