Changes in source contributions to the oxidative potential of PM2.5 in urban Xiamen, China.

The toxicity of PM2.5 does not necessarily change synchronously with its mass concentration. In this study, the chemical composition (carbonaceous species, water-soluble ions, and metals) and oxidative potential (dithiothreitol assay, DTT) of PM2.5 were investigated in 2017/2018 and 2022 in Xiamen, China. The decrease rate of volume-normalized DTT (DTTv) (38%) was lower than that of PM2.5 (55%) between the two sampling periods. However, the mass-normalized DTT (DTTm) increased by 44%. Clear seasonal patterns with higher levels in winter were found for PM2.5, most chemical constituents and DTTv but not for DTTm. The large decrease in DTT activity (84%-92%) after the addition of EDTA suggested that water-soluble metals were the main contributors to DTT in Xiamen. The increased gap between the reconstructed and measured DTTv and the stronger correlations between the reconstructed/measured DTT ratio and carbonaceous species in 2022 were observed. The decrease rates of the hazard index (32.5%) and lifetime cancer risk (9.1%) differed from those of PM2.5 and DTTv due to their different main contributors. The PMF-MLR model showed that the contributions (nmol/(min·m3)) of vehicle emission, coal + biomass burning, ship emission and secondary aerosol to DTTv in 2022 decreased by 63.0%, 65.2%, 66.5%, and 22.2%, respectively, compared to those in 2017/2018, which was consistent with the emission reduction of vehicle exhaust and coal consumption, the adoption of low-sulfur fuel oil used on board ships and the reduced production of WSOC. However, the contributions of dust + sea salt and industrial emission increased.

Size-segregated characteristics of water-soluble oxidative potential in urban Xiamen: Potential driving factors and implications for human health.

Oxidative potential (OP), defined as the ability of particulate matter (PM) to generate reactive oxygen species (ROS), has been considered as a potential health-related metric for PM. Particles with different sizes have different OP and deposition efficiencies in the respiratory tract and pose different health risks. In this study, size-segregated PM samples were collected at a coastal urban site in Xiamen, a port city in southeastern China, between August 2020 and September 2021. The water-soluble constituents, including inorganic ions, elements and organic carbon, were determined. Total volume-normalized OP based on the dithiothreitol assay was highest in spring (0.241 ± 0.033 nmol min-1 m-3) and lowest in summer (0.073 ± 0.006 nmol min-1 m-3). OP had a biomodal distribution with peaks at 0.25-0.44 µm and 1.0-1.4 µm in spring, summer, and winter and a unimodal pattern with peak at 0.25-0.44 µm in fall, which were different from the patterns of redox-active species. Variations in the seasonality of fine and coarse mode OP and their correlations with water-soluble constituents showed that the size distribution patterns of OP could be attributed to the combined effects of the size distributions of transition metals and redox-active organics and the interactions between them which varied with emissions, meteorological conditions and atmospheric processes. Respiratory tract deposition model indicated that the deposited OP and the toxic elements accounted for 47.9 % and 36.8 % of their measured concentrations, respectively. The highest OP doses and the excess lifetime carcinogenic risk (ELCR) were found in the head airway (>70 %). However, the size distributions of OP deposition and ELCR in the respiratory tract were different, with 63.9 % and 49.4 % of deposited ELCR and OP, respectively, coming from PM2.5. Therefore, attention must be paid to coarse particles from non-exhaust emissions and road dust resuspension.

[Characterization and Health Risk Assessment of Heavy Metals in PM2.5 in Xiamen Port].

PM2.5 samples at Haitian and Songyu container terminals in Xiamen Port were collected in summer and autumn/winter in 2020 and analyzed for 20 elements to investigate their temporal-spatial distribution features, sources, and health risk. The results showed that the levels of PM2.5 were relatively low and did not show significant spatial and diurnal differences. Ca and Si were the main crustal elements, and Zn and Mn were the main heavy metals in PM2.5. Compared with GB 3095-2012 guidelines, Cr(Ⅵ) was in the range of 27.4-28.6 times above the standard. Under the influence of monsoon and port throughput, the concentrations of some elements in summer were higher than those in autumn/winter. Significant diurnal variations were observed for Cu, Zn, SO2, and NO2 but not for V and Ni. Industrial sources were identified as the primary contributor (55.2%-59.4%), followed by traffic (28.7%-31.3%), ship emissions (7.1%-7.7%), and sea salt plus construction dust (4.8%-5.8%). The results of health risk assessment showed that heavy metals in PM2.5in Xiamen Port had potential carcinogenic risk (ECR>1(10-5) to people living near the port, and Cr(Ⅵ), V, and As together accounted for 97.3%-97.5% of the total risks; however, the non-carcinogenic risk was negligible (HI<1), and the major contributors were V, Mn, Ni, and As (89.6%-91.2%). The relative contributions of each contributor to ECR was in the order of traffic (47.2%-49.4%)>industrial (23.8%-24.2%)>ship emissions (16.9%-20.8%)>sea salt plus construction dust (5.7%-12.1%), and the relative contribution to HI was in the order of traffic (38.7%-42.3%)>industrial (24.5%-28.2%)>ship emissions (24.1%-27.2%)>sea salt plus construction dust (5.4%-9.6%).

Solubility of aerosol minor and trace elements in Xiamen Island, Southeast China: Size distribution, health risk and dry deposition.

Aerosol element solubility is essential to evaluate the damage to the environment and human health. In this work, the size distribution of total and soluble elements in eight particle size ranges with diameter <0.25, 0.25-0.44, 0.44-1.0, 1.0-1.4, 1.4-2.5, 2.5-10, 10-16 and >16 µm was investigated in Xiamen Island, southeast China from March 2018 to June 2020. The results showed that both total and soluble elements exhibited significant size dependence without obvious seasonal variations, and their relative contributions to PM1 mass were much lower than in particles larger than 1 µm. The correlations between some elements in soluble fraction were quite different from those in total fraction and the correlations also varied with particle size due to their different solubility. The solubility of Al, Fe, Ag and Cr was relatively low compared with other elements. Moreover, the solubility of Na, Mg, Ca, Mn and Ag was less dependent on particle size while Al, Fe and other trace elements exhibited the highest solubility in PM1 and the lowest in PM>10. Overall, the solubility of elements is primarily a function of aerosol origin and size. The carcinogenic risks of metal exposure via inhalation for children (3.31 × 10-6) and adults (4.42 × 10-6) were slightly higher than the guideline of cancer risk with >60 % from V. As for non-carcinogenic risk, the hazard index values for children and adults were 1.59 and 0.53, respectively, with Mn, V and Ni together accounting for >85 % of the risk. >85 % of the size-dependent dry deposition fluxes of the selected soluble elements over the Xiamen Bay were contributed by particles larger than 10 µm due to their high deposition velocities. The atmospheric inputs of bioavailable Fe and Cu to the sea exceeded the required amounts relative to inorganic nitrogen to meet the growth of phytoplankton.

Size distributions and health risks of particle-bound toxic elements in the southeast coastland of China.

Size-fractionated samples were collected at five coastal urban sites in Fujian Province, southeast China, in 2016 and 2017 to determine the trace elements using ICP-MS. Ca, Fe, Al, Mg, and K were the most abundant elements among the studied elements in TSP, much higher than those of heavy metals. The annual mean concentrations of Pb, As, V, Ni, Cd, and Mn were within the acceptable limits of the World Health Organization and the Ministry of Ecology and Environment of China while Cr(VI) exceeded the limits. Most elements exhibited clear seasonal patterns with maxima over the cold season and minima over the warm season. The spatial variabilities in concentrations of the measured elements were not significant except Ni and V. However, the size distribution pattern of each element was quite similar across the region. Characteristic size distributions of elements allowed identification of three main groups: (a) unimodal distribution in the coarse fraction for Ca, Al, Mg, and Ba; (b) unimodal distribution in the fine fraction for Pb, Se, As, Ag, V, Ni, Zn, and Cd; and (c) bimodal or multimodal distribution for Fe, Mn, Cr, K, and Cu. The combination of the size-fractionated concentrations, enrichment factors, correlation coefficients, and factor analysis offered the identification of mixed sources such as vehicular exhaust and wear, heavy fuel oil combustion, and resuspension of road dust. Non-carcinogenic health risks associated with inhalable exposure to airborne metals were higher than the safety threshold (hazard index > 1) across the region, suggesting non-carcinogenic health risks via inhalation. Mn, V, and Ni contributed 74-83% of the total non-carcinogenic risk. The assessment investigation of carcinogenic health risks revealed V and Cr(VI) as elements with the largest carcinogenic risks, accounting for more than 95% of the overall inhalation risk. Nevertheless, the carcinogenic risks for children and adults were between 10-6 and 10-4, within the range considered acceptable by the US EPA. In terms of the size-fractionated risk, PM2.5 contributed 43-50% and 39-44% of the total non-carcinogenic and carcinogenic risks, respectively, indicating the potential health hazard of coarse particle-bound toxic metals was not negligible.

[Uncertainty analysis of gas/particle partitioning of atmospheric polycyclic aromatic hydrocarbons].

During the period from August 10, 2010 through August 14, 2010, particle and gas phase PAHs were collected and analyzed using double filters plus PUFs (Poly Urethane Foam) sampling system, and the uncertainties of gas/particle partitioning coefficients of PAHs were investigated using the propagation of errors formulas. The results showed that low-molecular weight PAHs such as naphthalene, acenaphthylene, acenaphthene and fluorene possessed the strong breakthrough capacity with the breakthrough rates close to 50% in double PUF cartridges. The corrected K(p) values based on the sorption of PAHs to the primary filter were more than an order of magnitude higher than those without sorption correction for naphthalene, acenaphthylene and acenaphthene. The uncertainties for all the 19 PAHs ranged from 28.14% to 50.37% based on the standard error propagation formulas, with higher values for volatile and involatile PAHs and lower values for semi-volatile PAHs. The results also showed that the uncertainties of K(p) were mainly contributed from the measurements of particle (average variance contribution was 77.9%) and gas (average variance contribution was 22.0%) phase PAHs while the contributions of total suspended particle were ignorable. Thus, getting more accurate data for gaseous PAHs using an appropriate sampling system is the key to increase the accuracy of gas/particle partitioning coefficients of PAHs.

[Effect of surfactant on the volatilization of organochlorine pesticides from still artificial seawater].

The effect of sodium dodecylbenzene sulfonate (SDBS) on the volatilization of 17 organochlorine pesticides (OCPs) from still artificial seawater has been examined. The results show that SDBS at low concentration can retard the volatilization of OCPs compared to "clean" surface. The retarding influence is more pronounced for high level of SDBS than it is for low level of SDBS. A good positive correlation between the gas-seawater partition coefficients and the measured volatilization rates of OCPs is observed. Although the SDBS films present no significant, direct resistance to transfer, the films can absorb more OCPs from the above atmosphere with respect to the "clean" surface and reduce the net volatilization flux from the still artificial seawater. The effect of the film is more pronounced for volatilization of more volatile OCPs than it is for less volatile OCPs.