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Size-resolved gas-particle partitioning of semi-volatile organic compounds (SVOCs) can affect their environmental behaviors and health effects, which has not been widely studied in comparing with the gas-total suspended particle partitioning. Herein, the size-resolved gas-particle partitioning quotient (KPi) of polycyclic aromatic hydrocarbons (PAHs) in a large temperature range (-20.6 â„ƒ ∼ 29.4 â„ƒ) was firstly comprehensively studied. The log KPi values of PAHs related to fine particles were significantly higher than those related to coarse particles. When the logarithm of subcooled liquid-vapor pressure (log PL0) ∈ [-7, -1), the regression slopes of log KPi vs log PL0 related to the particle size > 1.0 µm were shallower than those with the particle size range of 0.10-1.0 µm, which indicated the influence of particle size on KPi. Among the three previous prediction equations of gas-particle partitioning quotient, the empirical equation based on the ambient temperature matched better with the measured log KPi. Therefore, a new prediction equation including ambient temperature and particle size as the two major parameters was established. For most particle size ranges, the new equation showed better prediction performance than the three previous equations. In summary, this study provided new insights for the size-resolved gas-particle partitioning mechanism and quotient.

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Environmentally persistent free radicals (EPFRs) can pose exposure risks by inducing the generation of reactive oxygen species. As a new class of pollutants, EPFRs have been frequently detected in atmospheric particulate matters. In this study, the seasonal variations and sources of EPFRs in a severe cold region in Northeastern China were comprehensively investigated, especially for the high pollution events. The geomean concentration of EPFRs in the total suspended particle was 6.58 × 1013 spins/m3 and the mean level in winter was one order of magnitude higher than summer and autumn. The correlation network analysis showed that EPFRs had significantly positive correlation with carbon component, K+ and PAHs, indicating that EPFRs were primarily emitted from combustion and pyrolysis process. The source appointment by the Positive Matrix Factorization (PMF) model indicated that the dominant sources in the heating season were coal combustion (48.4%), vehicle emission (23.1%) and biomass burning (19.4%), while the top three sources in the non-heating season were others (41.4%), coal combustion (23.7%) and vehicle emissions (21.2%). It was found that the high EPFRs in cold season can be ascribed to the extensive use of fossil fuel for heating demand; while the high EPFRs occurred in early spring were caused by the large-scale opening combustion of biomass. In summary, this study provided important basic information for better understanding the pollution characteristics of EPFRs, which suggested that the implementation of energy transformation and straw utilization was benefit for the control of EPFRs in severe cold region.

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Polycyclic aromatic hydrocarbons (PAHs) have the capability for solar radiation absorption related to climate forcing. Herein, pollution characteristics and absorption spectra of size-resolved PAHs in atmospheric particles in a cold megacity were comprehensively investigated. The mean concentrations of Σ18PAHs in all the 11 particle size ranges were 3.95 ± 4.77 × 104 pg/m3 and 2.17 ± 1.54 × 103 pg/m3 in heating period (HP) and non-heating period (NHP), respectively. Except for most PAHs with 2 and 3 benzene rings in NHP, most other PAHs showed a unimodal distribution pattern with the peak at 0.56-1.0 µm in both periods, which was caused by PAH emission sources. The PAH-related climate forcing was mainly caused by the solar radiation absorptions at ∼325 (∼330) nm and ∼365 nm. In general, the absorption intensities were higher in HP than NHP. The absorption intensity in the particle size range of 0.56-1.0 µm was the highest, and benzo[e]pyrene was the dominant contributor. In colder periods in HP, higher PAH concentrations caused more intensive PAH-related climate forcing. This study provided new insights for pollution characteristics and absorption spectra of size-resolved PAHs in atmospheric particles, which will be useful for better understanding PAH-related climate forcing.

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Few simultaneous studies of organochlorine pesticides (OCPs) in the atmosphere have been conducted across Southeast and Northeast China, and no data on the gas/particle (G/P) partitioning behaviors of several current-use OCPs are available. In this study, a one-year synchronous monitoring program was conducted for OCPs in Chinese atmosphere spanning 30° latitude and 60 °C temperature. A total of 111 pairs of gas and particle samples were collected from Mohe and Harbin in Northeast China and from Shenzhen in Southeast China. The detection frequency for 66.7 % of the OCPs exceeded 80 %, indicating their prevalence in the atmosphere. The concentrations of individual OCPs spanned six orders of magnitude, indicating different pollution levels. Highest levels of hexachlorobenzene were observed at all sites. Banned OCPs were found predominantly in secondary distribution patterns, whereas current-use OCPs were dominated by primary distribution patterns. In Harbin and Mohe, the concentrations of OCPs were highest in summer, followed by autumn and winter. No obvious seasonal variation was observed in Shenzhen associated with different cultivation types. At all three sites, OCPs were predominantly found in the gas phase, and higher percentages of particle-phase OCPs were observed in Harbin and Mohe than in Shenzhen. In this study, G/P partitioning models were used to study the G/P partitioning mechanism of OCPs. The Li-Ma-Yang model provided the most accurate prediction of the G/P partitioning behavior of OCPs with high molecular weights and low vapor pressures, particularly at low temperatures. However, OCPs with lower molecular weights and higher vapor pressures were predominantly in the equilibrium state, for which the Junge-Pankow model was suitable. This systematic cross-scale study provides new insights into pollution, G/P partitioning, and the environmental behavior of OCPs in the atmosphere.

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Health risks from exposure to contaminants are generally estimated by evaluating concentrations of the contaminants in environmental matrixes. However, accurate health risk assessment is difficult because of uncertainties regarding exposures. This study aims to utilize data on the concentrations of organophosphate flame retardants (OPFRs) in surface soil across China coupled with Monte Carlo simulations to compensate for uncertainties in exposure to evaluate the health risks associated with contamination of soil with this class of flame retardants. Results revealed that concentrations of ∑OPFRs were 0.793-406 ng/g dry weight (dw) with an average of 23.2 ng/g dw. In terms of spatial distribution, higher OPFRs concentrations were found in economically developed regions. Although the values of health risk of OPFRs in soil across China were below the threshold, the high concentrations of OPFRs in soil in some regions should attract more attentions in future. Sensitivity analysis revealed that concentrations of OPFRs in soil, skin adherence factor, and exposure duration were the most sensitive parameters in health risk assessment. In summary, the study indicated that the national scale soil measurement could provide unique information on OPFRs exposure and health risk assessment, which was useful for the management of soil in China and for better understanding of the environmental fate of OPFRs in the global perspective.

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Environmental persistent free radicals (EPFRs) have attracted more attentions recently due to their potential adverse effects to human. EPFRs in full-size range particles were comprehensively investigated in this study. The average EPFRs concentration during heating season was 3.01 × 1014 spins/m3, which was much higher than that in non-heating season (4.30 × 1013 spins/m3). The highest concentration of EPFRs presented in 0.56-1.0 µm particles during heating season, while it shifted to 5.6-10 µm particles during non-heating season. Besides, the contributions of EPFRs on PM>10 to the total concentration of EPFRs cannot be neglected, especially in the non-heating season. The International Commission on Radiological Protection model and the specific factors of the Chinese population were applied to evaluate the inhalation exposure risk of EPFRs. The results indicated that the exposure levels of EPFRs to the upper respiratory tract were much higher. The daily exposure dose of EPFRs suggested the inhalation exposure risk of 3-4 years old was higher than other age groups. In summary, these finding provided new insights for the full range particle size distribution and the inhalation exposure risk of EPFRs, which improved our understanding on the environmental fate and the health risk of EPFRs in atmosphere.

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As the result of the phase-out on polybrominated diphenyl ethers, organophosphate flame retardants (OPFRs) were widely used as substitutes in the world. Previous studies found that OPFRs were frequently detected in environmental, biological, and human samples. Considering their adverse effects, the absorption, bioaccumulation, metabolism and internal exposure processes of OPFRs attracted more attentions recently, especially for aryl-OPFR and Cl-OPFRs. In the present study, the biotransformation, metabolic kinetics and related CYP450 isoforms of typical Cl-OPFR (tris(1,3-dichloro-2-propyl) phosphate: TDCPP) and aryl-OPFR (triphenyl phosphate: TPhP) were studied in vitro by mouse liver microsomes. Metabolomic analysis revealed that TDCPP may be easier to bio-accumulate in organisms than TPhP, which can be explained by their metabolic rates and half-life values (TDCPP: t1/2 = 1.8083 h; TPhP: t1/2 = 0.1531 h). CYP2E1, CYP2D6, CYP1A2 and CYP2C19 were suggested to be the specific enzymes for the biotransformation of TDCPP via associated inhibition assay. CYP2E1 was the primary CYP450 isoform of metabolism in vitro for TPhP. These findings may provide new insights for the potential mechanism of hepatotoxicity in mammals induced by OPFRs and the detoxification process of OPFRs in hepatocytes.

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Hydroxyl free radicals (OH radicals) play the main role in atmospheric chemistry and their involving reactions are the dominant rate determining step in the formation of secondary fine particulate matter and in the removal of air pollutants from the atmosphere. In this paper, we studied the seasonal variation characteristics of OH radicals during the daytime in Lanzhou and explored the potential formation mechanism of high concentration OH radicals. We found that the OH radicals in four seasons was 2.7 × 106, 2.6 × 106, 3.1 × 106, and 2.2 × 106 cm-3, respectively. Since the rainfall was concentrated in summer, the wet deposition had a significant effect on removing OH radicals. Among the four pollutants (including ozone (O3), volatile organic compounds (VOCs), nitrogen dioxide (NO2) and fine particulate matter (PM2.5)), the variation of OH radicals were closely related to ozone concentration especially in spring and summer. In autumn, the correlation between PM2.5 and OH radicals were the closest among the observing pollutants and its formation mechanism was different conventional regeneration pathway. In Event 1, high concentration of ozone was the main source of OH radicals; under the high humidity condition, except for ozone, the multiple factors including VOCs, NO2 and PM2.5 interplayed and leaded to the Event 2.

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Atmospheric particulate pollution in China has attracted much public attention. Occasionally, the particle number concentration increases sharply in a short time period, which is defined as a "particulate matter explosive increase". Heavy particulate matter pollution not only reduces visibility but also has an adverse effect on human health. Hence, there is an urgent need to discover the causes of particulate matter explosive increase. During this campaign, the particle number concentration and free radicals were measured at a tall building on the campus of Lanzhou University of Technology. Additionally, we examined a series of chemicals to reproduce the observed particulate matter explosive increase in a smog chamber to determine its potential factors. Then, we analyzed the mechanism of particulate matter explosive increase in the presence of free radicals. We found that, among the potential inorganic and organic sources analyzed, a mixture of organic and SO2 in the research region had a major effect on particulate matter explosive increase. Moreover, free radical oxidation has a large effect, especially in the formation of organic particulates.

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Carbon nanofibers (CNFs) have been widely used in electrochemical energy storage devices because of their excellent conductivity, extremely large surface area and structural stability. Herein, we obtained a viscous, liquefied bio-stalk carbon via the simple chemical treatment of biomass, and mixed it with polyacrylonitrile to prepare a spinning solution. Subsequent electrospinning and high temperature activation resulted in the successful preparation of liquefied lignin-based activated carbon nanofibers. The as-prepared liquefied bio-stalk carbon nanofibers exhibited an outstanding electrochemical performance (specific capacitance of 273 F g-1 at 0.5 A g-1 current density), and a capacitance retention of 210 F g-1 even under a large current density of 10 A g-1. Besides its high specific capacitance and outstanding rate capability, the symmetrical supercapacitor cell based on the liquefied carbon-based nanofiber electrodes also exhibited an excellent cycling performance with 92.76% capacitance retention after 5000 charge-discharge cycles. This study provides a new strategy for the future development of supercapacitor electrode materials and enhances the development of biomass energy.

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An ultra-facile fabrication process for the preparation of phosphorus doped porous carbon nanofibers (P-PCNFs) through the electrospinning and heat treatment method has been studied. The materials were characterized by X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. Studies showed that fabricated P-PCNFs have unique porous fibers structures, large specific surface area (462.83 cm2 g-1), and abundant microporous and mesoporous structures. X-ray photoelectron spectroscopy analyses revealed that the contents of phosphorus and electrochemical properties in a series of P-PCNF samples can be tuned by controlling the polyphosphoric acid concentration. The electrochemical properties of the materials were evaluated using cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy. Studies showed that the specific capacitance of the fabricated P-PCNFs using the ultra-facile process reached up to 228.7 F g-1 at 0.5 A g-1 in 1 M H2SO4. Over 84.37% of the initial capacitance remains as the current density increases from 0.5 to 10 A g-1. Meanwhile, at a current density of 2 A g-1, no capacitance loss was observed in 5000 charge/discharge cycles. The highest voltage windows of sample P-PCNFs-1.0 in 1 M H2SO4 aqueous electrolyte can reach 1.4 V. These properties suggest that the fabricated P-PCNFs exhibit excellent electrochemical properties. Conclusively, the surface of carbon nanofibers can be modified by heteroatom doping or surface activation which can improve the electrochemical performance of the materials.

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Free radicals play an important role in the oxidizing power of polluted air, the development of aging-related diseases, the formation of ozone, and the production of secondary particulate matter. The high variability of peroxyl radical concentration has prevented the detection of possible trends or distributions in the concentration of free radicals. We present a new method, free radical reaction combined with liquid chromatography photodiode array detection, for identifying and quantifying peroxyl radicals in polluted air. Functionalized graphene was used for loading peroxyl radicals and reactive molecules in air sampling system, which can facilitate reaction kinetics (charge transfers) between peroxyl radicals and reaction molecules. Separation was performed with and without a preliminary exposure of the polluted air sample to reactive molecule(s) system. The integral chromatographic peak areas before and after air sampling are used to quantify the atmospheric peroxyl radicals in polluted air. The utility of the new technique was tested with measurements carried out in the field.

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Free radicals are the most important chemical intermediate or agent of the atmosphere and influenced by thousands of reactants. The free radicals determine the oxidizing power of the polluted air. Various gases present in smog or haze are oxidants and induce organ and cellular damage via generation of free radical species. At present, however, the high variability of total free radicals in polluted air has prevented the detection of possible trends or distributions in the concentration of those species. The total free radicals are a kind of contaminants with colorless, tasteless characteristics, and almost imperceptible by human body. Here we present total free radical detection and distribution characteristics, and analyze the effects of total free radicals in polluted air on human health. We find that the total free radical values can be described by not only a linear dependence on ozone at higher temperature period, but also a linear delay dependence on particulate matter at lower temperature period throughout the measurement period. The total free radical species distribution is decrease from west to east in Lanzhou, which closely related to the distribution of the air pollutants. The total free radical oxidation capacity in polluted air roughly matches the effects of tobacco smoke produced by the incomplete combustion of a controlled amount of tobacco in a smoke chamber. A relatively unsophisticated chromatographic fingerprint similarity is used for indicating preliminarily the effect of total free radicals in polluted air on human health.