In Vivo Exposure Pathways of Ambient Magnetite Nanoparticles Revealed by Machine Learning-Aided Single-Particle Mass Spectrometry.

Nanosized ultrafine particles (UFPs) from natural and anthropogenic sources are widespread and pose serious health risks when inhaled by humans. However, tracing the inhaled UFPs in vivo is extremely difficult, and the distribution, translocation, and metabolism of UFPs remain unclear. Here, we report a label-free, machine learning-aided single-particle inductively coupled plasma mass spectrometry (spICP-MS) approach for tracing the exposure pathways of airborne magnetite nanoparticles (MNPs), including external emission sources, and distribution and translocation in vivo using a mouse model. Our results provide quantitative analysis of different metabolic pathways in mice exposed to MNPs, revealing that the spleen serves as the primary site for MNP metabolism (84.4%), followed by the liver (11.4%). The translocation of inhaled UFPs across different organs alters their particle size. This work provides novel insights into the in vivo fate of UFPs as well as a versatile and powerful platform for nanotoxicology and risk assessment.

Preservative effects of Osmanthus fragrans flower flavonoids on fresh-cut Yuluxiang pear.

Osmanthus fragrans flower flavonoids (OFFF) possess superior antioxidant and antibacterial activities. However, scant information exists on the efficacy of these secondary metabolites as preservatives for fresh-cut fruits and vegetables. Here, OFFF were tested as a natural preservative for the first time in fresh-cut Yuluxiang pear (Pyrus bretschneideri Rehd.) to assess effects on fruit quality. OFFF-treated samples showed significant retention of firmness, titratable acid, soluble solid content, and weight. Moreover, OFFF maintained the original fruit color, inhibited the decline of total phenol, reducing power and 2,2-diphenyl-1-picrylhydrazyl radical scavenging power, and diminished polyphenol oxidase and peroxidase oxidase activities. Furthermore, OFFF treatment effectively inhibited microbial growth. OFFF-treated samples also displayed better sensory quality. Considering cost and effectiveness, the most suitable concentrations of OFFF extract for fresh-cut Yuluxiang pear preservation were 0.7 and 0.9 mg/mL. The results indicate that OFFF treatment may be a potent strategy to inhibit browning and enhance nutritional properties of fresh-cut pear fruit.

The occurrence and sources of PAHs, oxygenated PAHs (OPAHs), and nitrated PAHs (NPAHs) in soil and vegetation from the Antarctic, Arctic, and Tibetan Plateau.

Although the fate of PAHs in the three polar regions (Antarctic, Arctic, and Tibetan Plateau) has been investigated, the occurrence and contamination profiles of PAH derivatives such as oxygenated PAHs (OPAHs) and nitrated PAHs (NPAHs) remain unclear. Some of them are more toxic and can be transformed from PAHs in environment. This study explored and compared the concentrations composition profiles and potential sources of PAHs, OPAHs, and NPAHs in soil and vegetation samples from the three polar regions. The total PAH, OPAH, and NPAH concentrations were 3.55-519, n.d.-101, and n.d.-1.10 ng/g dry weight (dw), respectively. The compounds were dominated by three-ring PAHs, and the most abundant individual PAH and OPAH were phenanthrene (PHE) and 9-fluorenone (9-FO), respectively. The sources of PAHs and their derivatives were qualitatively analyzed by the diagnostic ratios and quantified using the positive matrix factorization (PMF) model. The ratios of PAH derivatives to parent PAHs (9-FO/fluorene and 9,10-anthraquinone/anthracene) were significantly higher in the Antarctic samples than in the Arctic and TP samples, implying a higher occurrence of secondary OPAH and NPAH formation in the Antarctic region. To our knowledge, this is the first comparative study that simultaneously investigated the contamination profiles of PAHs and their derivatives in the three polar regions. The findings of this study provide a scientific basis for the development of risk assessment and pollution control strategies in these fragile regions.

PM2.5-bound polyhalogenated carbazoles (PHCZs) in urban Beijing, China: Occurrence and the source implication.

Polyhalogenated carbazoles (PHCZs) are recently raising much attention due to their toxicity and ubiquitous environmental distribution. However, little knowledge is known about their ambient occurrences and the potential source. In this study, we developed an analytical method based on GC-MS/MS to simultaneously determine 11 PHCZs in PM2.5 from urban Beijing, China. The optimized method provided low method limit of quantifications (MLOQs, 1.45-7.39 fg/m3) and satisfied recoveries (73.4%-109.5%). This method was applied to analyze the PHCZs in the outdoor PM2.5 (n = 46) and fly ash (n = 6) collected from 3 kinds of surrounding incinerator plants (steel plant, medical waste incinerator and domestic waste incinerator). The levels of ∑11PHCZs in PM2.5 ranged from 0.117 to 5.54 pg/m3 (median 1.18 pg/m3). 3-chloro-9H-carbazole (3-CCZ), 3-bromo-9H-carbazole (3-BCZ), and 3,6-dichloro-9H-carbazole (36-CCZ) were the dominant compounds, accounting for 93%. 3-CCZ and 3-BCZ were significantly higher in winter due to the high PM2.5 concentration, while 36-CCZ was higher in spring, which may be related to the resuspending of surface soil. Furthermore, the levels of ∑11PHCZs in fly ash ranged from 338 to 6101 pg/g. 3-CCZ, 3-BCZ and 36-CCZ accounted for 86.0%. The congener profiles of PHCZs between fly ash and PM2.5 were highly similar, indicating that combustion process could be an important source of ambient PHCZs. To the best of our knowledge, this is the first research providing the occurrences of PHCZs in outdoor PM2.5.

Insight into the oxidation of glutathione mediated by black carbon from three typical emission sources.

Black carbon (BC) is released into the atmosphere in large quantities from different emission sources each year and poses a serious threat to human health. These BC possessed a variety of characteristics and different mediation abilities for the reactive oxygen species (ROS) generation. In this study, we collected BC (i.e., diesel BC, coal BC and wood BC) from three typica emission sources, and examined their mediation abilities to the oxidation of glutathione (GSH). Results showed that all three BC significantly promoted the GSH oxidation, and the mediation efficiencies were as follows: diesel BC > coal BC > wood BC. In comparison with the water-soluble fraction, the mediation abilities of three BC mainly came from their solid phase fractions. In the coal BC and wood BC systems, the oxidation of GSH was attributed to the catalysis of transition metals in BC. By contrast, the transition metals, phenolic -OH and persistent free radicals in diesel BC were identified as the active sites responsible for the GSH oxidation. In addition, the graphitic surface of diesel BC could synergize with these active sites to accelerate the oxidation of GSH. Under the catalysis of BC, dissolved oxygen was first reduced to ROS (O2•- and H2O2) and then caused the GSH oxidation. These findings not only help to better assess the adverse health effects of different BC, but also deepen the understanding of the reaction mechanisms.

New Insights into Unexpected Severe PM2.5 Pollution during the SARS and COVID-19 Pandemic Periods in Beijing.

During the SARS period in 2003 and COVID-19 pandemic period in 2020, unexpected severe particulate matter pollution occurred in northern China, although the anthropogenic activities and associated emissions have assumed to be reduced dramatically. This anomalistic increase in PM2.5 pollution raises a question about how source emissions impact the air quality during these pandemic periods. In this study, we investigated the stable Cu and Si isotopic compositions and typical source-specific fingerprints of PM2.5 and its sources. We show that the primary PM2.5 emissions (PM2.5 emitted directly from sources) actually had no reduction but redistribution during these pandemic periods, rather than the previous thought of being greatly reduced. This finding provided critical evidence to interpret the anomalistic PM2.5 increase during the pandemic periods in north China. Our results also suggested that both the energy structure adjustment and stringent regulations on primary emissions should be synergistically implemented in a regional scale for clean air actions in China.

Novel brominated flame retardants (NBFRs) in soil and moss in Mt. Shergyla, southeast Tibetan Plateau: Occurrence, distribution and influencing factors.

Research on the environmental fate and behavior of novel brominated flame retardants (NBFRs) remains limited, especially in the remote alpine regions. In this study, the concentrations and distributions of NBFRs were investigated in soils and mosses collected from two slopes of Shergyla in the southeast of the Tibetan Plateau (TP), to unravel the environmental behaviors of NBFRs in this background area. The total NBFR concentrations (∑7NBFRs) ranged from 34.2 to 879 pg/g dw in soil and from 72.8 to 2505 pg/g dw in moss. ∑7NBFRs in soil samples collected in 2019 were significantly higher than those in 2012 (p < 0.05). Decabromodiphenyl ethane (DBDPE) was the predominant NBFR, accounting for 90% of ∑7NBFRs on average. The ratio of the concentrations in moss and soil showed significantly positive correlations with LogKOA except for DBDPE (p < 0.05), indicating that the role of mosses as accumulators compared to soils are more pronounced for more volatile NBFRs. In addition, the concentrations of NBFRs generally decreased with increasing altitude on the south-facing slope, whereas on the north-facing slope some NBFRs exhibited different trends, suggesting concurrent local and long-range transport sources. Normalization based on total organic carbon/lipid concentrations strengthened the correlation with altitude, implying that the altitude gradient of the mountain slope and forest cover could jointly affect the distribution of NBFRs in the TP. Furthermore, principal components analysis (PCA) with multiple linear regression analysis (MLRA) showed that the average contribution of the mountain cold trapping effect (MCTE) accounted for the major (77%) contribution and forest filter effect (FFE) has only a modest contribution to the deposition of NBFRs in soil.

COVID-19-Induced Lockdowns Indicate the Short-Term Control Effect of Air Pollutant Emission in 174 Cities in China.

The contradiction between the regional imbalance and an one-size-fits-all policy is one of the biggest challenges in current air pollution control in China. With the recent implementation of first-level public health emergency response (FLPHER) in response to the COVID-19 pandemic in China (a total of 77 041 confirmed cases by February 22, 2020), human activities were extremely decreased nationwide and almost all economic activities were suspended. Here, we show that this scenario represents an unprecedented "base period" to probe the short-term emission control effect of air pollution at a city level. We quantify the FLPHER-induced changes of NO2, SO2, PM2.5, and PM10 levels in 174 cities in China. A machine learning prediction model for air pollution is established by coupling a generalized additive model, random effects meta-analysis, and weather research and forecasting model with chemistry analysis. The short-term control effect under the current energy structure in each city is estimated by comparing the predicted and observed results during the FLPHER period. We found that the short-term emission control effect ranges within 53.0%-98.3% for all cities, and southern cities show a significantly stronger effect than northern cities (P < 0.01). Compared with megacities, small-medium cities show a similar control effect on NO2 and SO2 but a larger effect on PM2.5 and PM10.

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.

Separation and Tracing of Anthropogenic Magnetite Nanoparticles in the Urban Atmosphere.

Nanosized magnetite is a highly toxic material due to its strong ability to generate reactive oxygen species in vivo, and the presence of magnetite NPs in the brain has been linked with aging and neurodegenerative diseases such as Alzheimer's disease. Recently, magnetite pollution nanoparticles (NPs) were found to be present in the human brain, heart, and blood, which raises great concerns about the health risks of airborne magnetite NPs. Here, we report the abundant presence and chemical multifingerprints (including high-resolution structural and elemental fingerprints) of magnetite NPs in the urban atmosphere. We establish a methodology for high-efficiency retrieving and accurate quantification of airborne magnetite NPs. We report the occurrence levels (annual mean concentration 75.5 ± 33.2 ng m-3 in Beijing with clear season variations) and the pollution characteristics of airborne magnetite NPs. Based on the chemical multifingerprints of the NPs, we identify and estimate the contributions of the major emission sources for airborne magnetite NPs. We also give an assessment of human exposure risks of airborne magnetite NPs. Our findings support the identification of airborne magnetite NPs as a threat to human health.

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.

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.

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.