Engineering Oxygen Vacancies in In2O3 with Enhanced Polysulfides Immobilization and Selective Catalytic Capability.

Lithium-sulfur (Li-S) battery is identified as an ideal candidate for next-generation energy storage systems in consideration of its high theoretical energy density and abundant sulfur resources. However, the shuttling behavior of soluble polysulfides (LiPSs) and their sluggish reaction kinetics severely limit the practical application of the current Li-S battery. In this work, a series of In2O3 nanocubes with different oxygen vacancy concentrations are designed and prepared via a facile self-template method. The introduced oxygen vacancy on In2O3 can effectively rearrange the charge distribution and enhance sulfiphilic property. Moreover, the In2O3 with high oxygen vacancy concentration (H-In2O3) can slightly slow down the solid-liquid conversion process and significantly accelerate the liquid-solid conversion process, thus reducing the accumulation of LiPSs in electrolyte and inhibiting the shuttle effect. Contributed by the unique selective catalytic capability, the prepared H-In2O3 exhibits excellent electrochemical performance when used as sulfur host. For instance, a high reversible capacity of 609 mAh g-1 is obtained with only 0.044% capacity decay per cycle over 1000 cycles at 1.0 C. This work presents a typical example for designing advanced sulfur hosts, which is crucial for the commercialization of Li-S battery.

Calculated cancer risks for polycyclic aromatic hydrocarbon mixtures in mainstream smoke of cigarettes sold in China.

China is the world's largest consumer of cigarettes. However, the potential cancer risk posed by polycyclic aromatic hydrocarbons (PAHs) in mainstream cigarette smoke, especially species other than benzo[a]pyrene (BaP) remains unclear. In this study, we collected yield data on multiple PAH species from a variety of cigarettes in the China market and calculated their smoking-related incremental lifetime cancer risk (ILCR) values. The computed ILCRs of the total PAHs (ILCRΣPAHs) for ≥95% of the brands were one order of magnitude higher than the acceptable level. ILCRBaP accounted for only 5.0%-37.7% of ILCRΣPAHs among brands, indicating that using single analyte BaP to represent ΣPAHs would significantly underestimate ILCRΣPAHs. No clear trend of changes in ILCRΣPAHs was found for Chinese cigarettes over multiple years, suggesting that smoking cessation is still the best option to minimize the cancer risk of PAHs. The comparison study showed that rarely reported PAHs from Chinese cigarettes can contribute over half of ILCRΣPAHs for several American cigarettes, highlighting the imperativeness to improve the diversity of analytes for Chinese cigarettes. Adults would need to inhale the air-borne PAHs with a BaP equivalent concentration of at least 53.1 ng/m3 to reach the ILCR value comparable to that obtained from smoking.

Sorption in soils and bioaccumulation potential of 2,2'-DiBBPA.

2,2'-Dibromobisphenol A (2,2'-DiBBPA) is frequently detected in the environment. However, the mobility of 2,2'-DiBBPA in the soil environment is poorly understood. The present study examined the effects of soil components such as the NaClO-resistant fraction, dithionite-citrate-bicarbonate -demineralized fraction, humin fraction, black carbon, DOC-removed fraction, exogenous dissolved organic carbon and heavy metal cations on the adsorption of 2,2'-DiBBPA on several types of agricultural soils. The adsorption isotherms on soils and soil components were well fitted to the linear isotherm equation. 2,2'-DiBBPA sorption onto soils was dominated by soil organic matter content (SOM) and affected by exogenous dissolved organic carbon. Linear regression relationships between adsorption capacity (Kd) and soil characteristics were evaluated to predict partitioning of 2,2'-DiBBPA. Black carbon played a predominant role in the adsorption of 2,2'-DiBBPA. Heavy metal ions significantly inhibited the adsorptive behavior of 2,2'-DiBBPA under alkaline conditions. Semiempirical linear relationships were observed between biota-sediment accumulation factors (1.18-2.47)/logarithm of bioconcentration factors (BCFs, 2.49-2.52) of 2,2'-DiBBPA in lugworms and Kd. These results allow for the prediction of the bioaccumulation of 2,2'-DiBBPA in other soils. Furthermore, values of log BCF > 1.0 indicate the preferential bioaccumulation of 2,2'-DiBBPA in biota. These data are of significance for understanding the migration of 2,2'-DiBBPA in agricultural soils and bioaccumulation in organisms.

Oxidative potential of solvent-extractable organic matter of ambient total suspended particulate in Bangkok, Thailand.

Oxidative stress is a key mechanism by which ambient particulate matter induces adverse health effects. Most studies have focused on the oxidative potential (OP) of water-soluble constituents, while there has been limited work on the OP of solvent-extractable organic matter (EOM OP). In this study, the EOM OP of ambient total suspended particulate (TSP) from Bangkok, Thailand, was determined using the dithiothreitol (DTT) assay. Positive matrix factorization (PMF), combined with chemical analysis of molecular markers, was employed to apportion the contributions of various emission sources to EOM OP. The volume-normalized OP initially increased with organic carbon (OC) concentration and plateaued gradually, while the mass-normalized OP fitted well with OC concentration using a power function. Fossil fuel combustion (62%) and plastic waste burning (23%) were the major contributors to EOM OP, while biomass burning demonstrated only a limited contribution. EOM OP correlated well with each group of polycyclic aromatic hydrocarbons (PAHs), suggesting that secondary formation of quinones associated with fossil fuel combustion and plastic waste burning could be an important pathway of TSP toxicity. This study underscores the importance of considering different emission sources when evaluating potential health impacts and the implementation of air pollution regulations.

Polycyclic aromatic hydrocarbon exposure, oxidative potential in dust, and their relationships to oxidative stress in human body: A case study in the indoor environment of Guangzhou, South China.

A comparative study of internal and external exposure is a good method to comprehensively understand human exposure to environmental contaminants that may trigger oxidative stress in human body. Information is limited regarding the influences of reactive oxygen species (ROS) on human health from the environment. In addition, data on the contribution of polycyclic aromatic hydrocarbons (PAHs) from indoor environments, especially air, to total human exposure are still insufficient. The present study measured PAHs in paired indoor dust (n = 101), gas (polyurethane foams, n = 100), and particle samples (quartz fiber filters, n = 100) and their hydroxy metabolites (OH-PAHs) in 205 urine samples from 101 families in Guangzhou, South China. The oxidative potential (OP) in dust samples was quantified with a dithiothreitol (DTT) assay to reflect the oxidizability of ROSs, and explore the relationship between environmental ROSs and oxidative stress in humans (using urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG) as a biomarker). The estimated daily intakes (EDIs) of Σ16PAH via air inhalation were much higher than those from gas dermal contact, dust dermal contact, and dust ingestion (mean: 19.5 > 4.27 > 3.75 > 1.60 ng/kg_bw/day). Generally, approximately 16% of naphthalene, 28% of fluorene, 9% of phenanthrene, and 3% of pyrene were derived from indoor environments for all residents when compared with the total PAH exposure amount from all sources. Significantly positive relationships were found between OH-PAHs and 8-OHdG (coefficients ß: 0.129-0.366, p < 0.05) checked by linear mixed effect models, and males seemed to be more susceptible than females to the DNA oxidative damage related to PAH exposure. The mean OP value in dust was 7.14 ± 6.68 pmol/(min·µg). Individual PAHs in dust gradually intensified the oxidizability of dust particles as their molecular weight increased. A potential but not significant dose-relationship was found between dusty OP and urinary 8-OHdG. Further work should determine the impact of chemical profiles on OP in different environmental media and continuously explore the potential to use OP as a useful indicator to reflect the total oxidizability of several groups of environmental pollutants.

[Ozone Pollution Trend in the Pearl River Delta Region During 2006-2019].

Based on the monitoring data of the Guangdong-Hong Kong-Macao Pearl River Delta Regional (PRD) Air Quality Monitoring Network from 2006 to 2019, the ozone trend in RRD was analyzed using the Mann-Kendall test method, Sen's slope method, and the Pettitt change point test. The results show that:① the average ozone concentration in the PRD has increased significantly from 2006 to 2019 (P<0.05), with an average growth rate of 0.80 µg·(m3·a)-1. After 2016, the rate of ozone increase has accelerated. ② The average annual ozone concentration in the central PRD increased significantly, while in the peripheral areas of the PRD, this is not obvious. Ozone increases significantly in summer but not in other seasons.③ From 2006 to 2019, the concentration of NO2 in the central PRD decreased remarkably, so the titration effect weakened and resulted in an increase in the ozone concentration. The concentration of NO2 in the marginal areas of the PRD has little change, so the ozone concentration in these areas has little change. ④ With the changes of VOCs and NO2 concentrations, the chemical sensitivity of O3 production in the PRD is changing. The VOC-limited regimes are continuously decreasing, and the mixed NOx-VOC-limited regimes and NOx-limited regimes are increasing. In order to deal with regional ozone pollution, the cooperative control of VOCs and NOx needs to strengthen.

PCDD/Fs in paired hair and serum of workers from a municipal solid waste incinerator plant in South China: Concentrations, correlations, and source identification.

Human hair has been widely used to evaluate the exposure to drugs and organic pollutants. However, reports on the relationship between polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzo-p-furans (PCDFs) in hair and the body burden of PCDD/Fs are limited. In this study, the association between PCDD/Fs in paired hair and serum samples from workers was examined in a municipal solid waste incinerator (MSWI) plant in South China. Fly ash and flue gas from the MSWI plant were also analyzed to determine the source apportionment of PCDD/Fs in the hair. The median international toxic equivalents (I-TEQs) of ΣPCDD/F in serum and hair were 28.0 pg TEQ/g (lipid weight) and 0.30 pg TEQ/g (dry weight), respectively. The indicator congener of PCDD/Fs for the TEQ levels was 2,3,4,7,8-pentachlorodibenzofuran (PeCDF) in both hair and serum, the concentrations of which both exhibited significant and strong linear dependence on the total TEQ levels (p < 0.01, R2 = 0.966 and R2 = 0.670, respectively). Significant positive correlations were found in the 1,2,3,6,7,8-hexachlorodibenzo-p-dioxin (HxCDD) and octachlorodibenzo-p-dioxin (OCDD) levels between the hair and serum samples (p < 0.05). Flue gas (which is an external source) was identified as the primary source of PCDD/Fs in human hair. Blood and flue gas were accountable for, on average, 37% and 61% of the PCDD/Fs in hair, respectively.

Levels and sources of PBDEs and PCBs in human nails from e-waste, urban, and rural areas in South China.

Human nails have been increasingly used as a biomarker for human exposure to persistent organic pollutants (POPs). In the present study, the fingernails of e-waste-dismantling workers from Longtang town, Qingyuan city, rural residents from Shijiao town, Qingyuan city, and urban residents from Guangzhou city, respectively, were collected from South China to monitor the human burdens of polybrominated diphenyl ether (PBDEs) and polychlorinated biphenyl (PCBs). The median concentrations of in the nails of the e-waste-dismantling workers, and urban and rural residents were 412, 129, and 82.1 ng g-1, respectively, and the median concentrations of were 108, 8.4, and 22.1 ng g-1, respectively. The levels of PCBs and PBDEs in the nails of e-waste-dismantling workers were significantly higher as compared to those for urban and rural residents (p < 0.05), implying the continuous and greater exposure to these chemicals in the e-waste recycling areas. BDE 209 (92-98%) was the major congener of PBDEs and CB 52 (26-51%) was the main congener of PCB in nail samples. However, no significant gender difference was observed for PBDE and PCB levels in nails from all three investigated areas, and no significant correlation was found between their levels and the age of the participants. The enantiomer fractions (EFs) of CBs 95 and 132 indicated that the external sources (e.g. dust and/or air) were the primary sources for CBs 95 and 132 in human nails from the e-waste area, while the contribution from the internal sources (e.g. serum) could be in a small percentage. The results of this study indicate that human nails can be used as a proper indicator of human exposure to PCBs and PBDEs, and further studies are needed by a comprehensive investigation of the relationships between the PCB and PBDE levels in the nails and serum and/or other internal tissues.

[Impact of Meteorological Factors on the Ozone Pollution in Hong Kong].

Based on ozone monitoring and meteorological data from 2000 to 2015 in Hong Kong, the characteristics of ozone pollution and the influence of meteorological factors on the ozone pollution were analyzed. The results show that:① A seasonal variation of the ozone concentration in Hong Kong is notable:autumn > spring > winter > summer. Days of ozone exceeding the standard value are concentrated in summer and autumn and rarely occur in winter and spring. ② The annual mean ozone concentration of the maximum daily 8-h average (MDA8) in Hong Kong increases from 2000 to 2015, with an average growth rate of 0.77 µg·(m3·a)-1. The 90th percentile concentration of the ozone MDA8 also increases, with an average rate of 1.49 µg·(m3·a)-1. ③ Higher temperatures are necessary for ozone pollution in Hong Kong. The higher the temperature is, the more ozone pollution likely occurs. ④ In most cases, the ozone concentration is negatively correlated with the relative humidity. The higher the relative humidity is, the lower are the ozone and 90th percentile concentrations in Hong Kong. ⑤ When ozone pollution occurs in Hong Kong, prevailing winds tend to shift from northerly or easterly to westerly. In addition, with the increase of the wind speed, the average ozone concentration changes little, but the 90th percentile ozone concentration significantly decreases. ⑥ Precipitation and cloud cover are important factors affecting the ozone concentration. Weather conditions without or with little rain for many consecutive days are necessary for the occurrence of ozone pollution events. However, with the increase of the cloud cover, the average ozone and 90th percentile concentrations continue to decrease. ⑦ In the case of a total solar radiation ≤ 20 MJ·m-2 or sunshine duration ≤ 10 h, the ozone concentration is positively correlated with the solar radiation and sunshine duration. However, in the case of intense solar radiation (total solar radiation>20 MJ·m-2 or duration of sunshine>10 h), the ozone concentrations decrease with increasing solar radiation or duration because strong solar radiation often occurs in the background of sunny weather after rain. At the same time, southerly winds from the sea often prevail, making it difficult for ozone pollution to occur in Hong Kong. ⑧ Ozone excess days in Hong Kong are often accompanied by changes of a series of meteorological conditions including less rain on sunny days, stronger radiation, higher boundary layer height, lower relative humidity, smaller wind speeds, and higher temperatures. The end of the pollution process is accompanied by the opposite weather changes.

Oxidative Potential by PM2.5 in the North China Plain: Generation of Hydroxyl Radical.

Adverse health effects of ambient PM2.5 ( dp < 2.5 µm) can be associated with the production of reactive oxygen species (ROS), among which hydroxyl radical (•OH) is the most reactive. However, â€¢OH generated by PM2.5 has not been quantified and studied in the North China Plain (NCP), which has suffered from heavy air pollution in recent years. In this study, PM2.5 samples were collected at an urban site (Beijing) and a suburban site (Wangdu), extracted in a cell-free surrogate lung fluid (SLF), and •OH generated in the extracts were quantified. The results show that more •OH is produced on heavily polluted days than that on clean days (2.0 and 1.6 times higher in Beijing and Wangdu, respectively). The production of •OH per unit mass (ng/µg·PM2.5) decreases with the increase of ambient PM2.5 concentration because SO42-, NO3-, and NH4+ dominate the increased PM2.5, while these secondary inorganic components do not contribute to the generation of •OH. Trace metals (e.g., Fe, Cu, Se) and carbonaceous species (organic carbon and elemental carbon) correlate well with the •OH production, indicating that particles from combustion sources including coal combustion, vehicle exhaust, and industry contribute more to •OH generation.

Single particle mass spectral signatures from vehicle exhaust particles and the source apportionment of on-line PM2.5 by single particle aerosol mass spectrometry.

In order to accurately apportion the many distinct types of individual particles observed, it is necessary to characterize fingerprints of individual particles emitted directly from known sources. In this study, single particle mass spectral signatures from vehicle exhaust particles in a tunnel were performed. These data were used to evaluate particle signatures in a real-world PM2.5 apportionment study. The dominant chemical type originating from average positive and negative mass spectra for vehicle exhaust particles are EC species. Four distinct particle types describe the majority of particles emitted by vehicle exhaust particles in this tunnel. Each particle class is labeled according to the most significant chemical features in both average positive and negative mass spectral signatures, including ECOC, NaK, Metal and PAHs species. A single particle aerosol mass spectrometry (SPAMS) was also employed during the winter of 2013 in Guangzhou to determine both the size and chemical composition of individual atmospheric particles, with vacuum aerodynamic diameter (dva) in the size range of 0.2-2µm. A total of 487,570 particles were chemically analyzed with positive and negative ion mass spectra and a large set of single particle mass spectra was collected and analyzed in order to identify the speciation. According to the typical tracer ions from different source types and classification by the ART-2a algorithm which uses source fingerprints for apportioning ambient particles, the major sources of single particles were simulated. Coal combustion, vehicle exhaust, and secondary ion were the most abundant particle sources, contributing 28.5%, 17.8%, and 18.2%, respectively. The fraction with vehicle exhaust species particles decreased slightly with particle size in the condensation mode particles.

Characterization of PM2.5 in Guangzhou, China: uses of organic markers for supporting source apportionment.

Organic carbon (OC), elemental carbon (EC), and non-polar organic compounds including n-alkanes (n-C14-n-C40), polycyclic aromatic hydrocarbons (PAHs), phthalate esters (PAEs) and hopanes were quantified in fine particulate (PM2.5), which were collected in urban area of Guangzhou, China in winter and summer in 2012/2013. The pollutants levels were well comparable with the data obtained in previous studies in Pearl River Delta (PRD) region but much lower than most northern Chinese megacities. The contribution of EC to PM2.5 and OC/EC ratio suggest that the pollution sources were relatively consistent in GZ between the two seasons. Benzo[a]pyrene (BaP) was the most abundant PAHs, which were 4.9 and 1.0ng/m(3) on average, accounting for 10.7% and 9.1% to the total quantified PAHs in winter and summer, respectively. The total concentrations of PAEs ranged from 289.1 to 2435ng/m(3) and from 102.4 to 1437ng/m(3), respectively, in winter and summer. Di-n-butyl phthalate (DBP) was the most dominant PAEs. The ambient levels of PAEs could be partly attributed to the widespread uses of the household products, municipal garbage compressing, sewage, and external painting material on the building. Source apportionment for OC with chemical mass balance (CMB) model demonstrated coal combustion, vehicle emission, cooking, and secondary organic compounds (SOC) formation were the four major pollution sources. Both of the indices of n-alkanes and diagnostic PAHs ratios support that anthropogenic sources such as vehicle emission and coal combustion were the significant pollution sources with some extents from epicuticular waxes by terrestrial plants. The ratio of hopanes to EC proved the influences from vehicle emission, and displayed a certain degree of the air aging in the Guangzhou ambient air.

Atmospheric levels and health risk of polycyclic aromatic hydrocarbons (PAHs) bound to PM2.5 in Guangzhou, China.

The polycyclic aromatic hydrocarbons (PAHs) in PM2.5 contribute significantly to health risk. The objectives of this study were to assess the occurrence and variation in the concentrations and sources of PM2.5-bound PAHs sampled from the atmosphere of a typical southeastern Chinese city (Guangzhou) from June 2012 to May 2013, with the potential risks being investigated. The annual average concentration of PM2.5 was 64.88µgm(-3). The annual average concentration of PAHs in PM2.5 was 33.89ngm(-3). Benzo(a)pyrene (BaP) was found to be the predominant PAH in all PM2.5 samples throughout the year, constituting approximately 8.78% of the total PAH content. The significant meteorological parameters for most of the PAHs were sunshine time, air pressure, and humidity, together representing 10.7-52.4% of the variance in atmospheric PAH concentrations. Motor-vehicle exhaust and coal combustion were probably the main sources of PAHs in PM2.5 in Guangzhou. The average inhalation cancer risk (ICR) for a lifetime of 70years was 5.98×10(-4) (ranging from 8.39×10(-5) to 1.95×10(-3)).

Mercury speciation and emission from municipal solid waste incinerators in the Pearl River Delta, South China.

The potential for Hg release during municipal solid waste incineration (MSWI) is attracting increased attention due to high volume of municipal waste being treated by incineration in China. Emission amounts have been estimated using emission factors developed for other countries. To fine tune our emission estimate total mercury (THg) and mercury speciation were measured using isokinetic sampling in eight plants, of which six used grate furnace combustor (GFC) and two circulation fluidized bed combustors (CFBCs). Results showed that average THg concentration (19.5 ± 13.6 µg/Nm) in flue gas at the facilities that used CFBC was significantly lower than that at those using GFC (51.4 ± 28.3 µg/Nm, p=0.002). Gaseous oxidized mercury (GOM), gaseous elemental mercury (GEM, Hg), and particulate mercury (Hg) represented 95.5 ± 3.8%, 4.1 ± 3.9% and 0.4 ± 0.3% in GFC, and 63.8 ± 8.6%, 33.6 ± 10.5% and 2.6 ± 1.9% in CFBC, respectively. The measured average THg emission factor for the 8 MSWI plants was 208 ± 130 mg/t in the Pearl River Delta (PRD) region, with 217 ± 158 mg/t and 188 ± 17.7 mg/t were from GFC and CFBC, respectively. Using the average emission factor the estimated total mercury emissions from MSWI were 4.67 ± 2.91 t in China, and 770 ± 65.5 kg in the PRD region in 2010. Of these, 4240 ± 210 kg, 408 ± 231 kg and 14.8 ± 14.1 kg, and 688 ± 37 kg, 78.9 ± 40.6 kg and 3.2 ± 3.0 kg were GOM, Hg, and Hg, respectively. Mercury emissions will continue to increase as the amounts of MSW being incinerated increases.

Research on flux of dry atmospheric falling dust and its characterization in a subtropical city, Guangzhou, South China.

Guangzhou is the central city in the Pearl River Delta (PRD), China, and is one of the most polluted cities in the world. To characterize the ambient falling dust pollution, two typical sampling sites: urban (Wushan) and suburban (University Town) areas in Guangzhou city were chosen for falling dust collection over 1 year at time intervals of 1 or 2 months. The flux of dry deposition was calculated. In addition, mineral composition and morphology of atmospheric falling dust were studied by X-ray diffraction, scanning electron microscopy, and microscopic observation. The results revealed that the dust flux in Guangzhou city was 3.34-3.78 g/(m(2) month) during the study period. The main minerals in the dust were quartz, illite, calcite, kaolinite, gypsum, plagioclase, dolomite, and amorphous matter. The morphological types included grained and flaky individual minerals, chain-like aggregates, spherical flying beads, and irregular aggregates, with the chain-like and spherical aggregates indicators of industrial ash. The major dusts were derived from industrial and construction activities. The gypsum present in the dust collected in winter season was not only derived from cement dust but may also have originated from the reaction of calcic material with sulfuric acids resulting from photooxidation of SO(x) and NO(x), which confirmed serious air pollution due to SO(x) and NO(x) in Guangzhou. The abatement of fossil fuel combustion emissions and construction dust will have a significant beneficial effect on dust reduction.