Assessment of interactions between elemental carbon and metals in black carbon: Hydroxyl radical generation and glutathione depletion.

Elemental carbon (EC) and metals are two important parts of atmospheric black carbon (BC). However, little information is available regarding the interaction between them and its impacts on the reactive oxygen species (ROS) formation and physiological antioxidants depletion. In this study, we chose six most frequently detected metals (Cu(Ⅱ), Fe(Ⅲ), Mn(Ⅱ), Cr(Ⅲ), Pb(Ⅱ) and Zn(Ⅱ)) in BC and examined their interactions with EC in the ROS generation and glutathione (GSH) oxidation. Results showed that only Cu(Ⅱ) and EC synergically promoted the GSH oxidation and hydroxyl radical (•OH) generation. Other five metals had negligible effects on the GSH oxidation regardless of the presence or absence of EC. The synergistic interaction between Cu(Ⅱ) and EC could be attributed to the superior electrical conductivity of EC. In the process, EC transferred electrons from the adjacent GSH to Cu(Ⅱ) through its graphitic carbon framework to yield Cu(Ⅰ) and GSH radical. Cu(Ⅰ) further reacted with dioxygen to generate •OH, which eventually led to the oxidation of GSH. Our results revealed a new driving force inducing the ROS formation and GSH depletion as well as provided novel insights into the risk assessment of BC.

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.

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.

Brominated flame retardants in atmospheric fine particles in the Beijing-Tianjin-Hebei region, China: Spatial and temporal distribution and human exposure assessment.

Atmospheric fine particle (PM2.5) samples were collected over a whole year (April 2016 - March 2017) across five sampling locations in the Beijing-Tianjin-Hebei (BTH) region, to investigate the occurrence of novel brominated flame retardants (NBFRs) and polybrominated diphenyl ethers (PBDEs). The concentrations of ∑9NBFRs were in the range of 0.63-104 pg/m3 (15.6 ±â€¯16.8 pg/m3) in atmospheric PM2.5, while the levels of ∑9PBDEs (excluding BDE-209) ranged from 0.05 to 19.1 pg/m3 (2.9 ±â€¯3.8 pg/m3) and BDE-209 concentrations ranged from 0.88 to 138 pg/m3 (22 ±â€¯28 pg/m3). Relatively higher levels of NBFRs and PBDEs were found at urban sampling sites in Beijing City and Shijiazhuang City. Decabromodiphenylethane (DBDPE) and BDE-209 were the dominant compounds with the relative abundances of 72% in ∑9NBFRs and 90% in ∑10PBDEs, respectively. Generally, the levels of most target BFRs in summer were lower than those in other seasons. However, there were no notable seasonal differences in levels of DBDPE and BDE-209 in atmospheric PM2.5 samples across the BTH region. Significant and positive correlations were found between the concentrations of BFRs and PM2.5. Daily human exposure via inhalation revealed that children have a higher probability of suffering from the adverse effects of BFRs than that of adults. In addition, residents living near sampling locations across the BTH region may suffer high exposure risks to BDE-209 and NBFRs.

Sedimentary records of polycyclic aromatic hydrocarbons (PAHs) in remote lakes across the Tibetan Plateau.

Sediment cores from five lakes across the Tibetan Plateau were used as natural archives to study the time trends of polycyclic aromatic hydrocarbons (PAHs). The depositional flux of PAHs generally showed an increasing trend from the deeper layers towards the upper layer sediments. The fluxes of PAHs were low with little variability before the 1950s, and then gradually increased to the late 1980s, with a faster increasing rate after the 1990s. This temporal pattern is clearly different compared with those remote lakes across the European mountains when PAHs started to decrease during the period 1960s-1980s. The difference of the temporal trend was attributed to differences in the economic development stages and energy structure between these regions. PAHs are dominated by the lighter 2&3-ring homologues with the averaged percentage over 87%, while it is notable that the percentage of heavier 4-6 ring PAHs generally increased in recent years, which suggests the contribution of local high-temperature combustion sources becoming more predominant.

[Vertical distribution pattern and ecological risk assessment of heavy metals in a sediment core from Pumoyum Co, Tibet].

The sediment core was collected in Pumoyum Co, a lake located in southern Tibetan Plateau, in July 2008. Samples were digested using microwave equipment and analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES), to determine the content of heavy metals in the sediments. The average concentrations for Cr, Co, Ni, Cu, Zn, Cd, Pb, Mn and Fe were 26.4 µg x g(-1), 6.64 µg x g(-1), 16.2 µg x g(-1), 26.2 µg x g(-1), 50.2 µg x g(-1), 0.363 µg x g(-1), 16.8 µg x g.(-1), 0.302 mg x g(-1) and 9.84 mg x g(-1) , respectively. The concentrations of analysed metals in Pumoyum Co were slightly higher than those in Antarctic, but lower than those from Dianchi in Yunnan, Daihai in Inner Mongolia, the Great lakes in North America and Taihu in China, which were obviously affected by anthropogenic activities. Overall, these metals in sediments from Pumoyum Co represented a low concentration level. Vertical profiles of heavy metals in the sediment core kept stable without large fluctuation and the concentrations in surface slices were relatively higher. Results of principle component analysis and cluster analysis indicated that organic matter and Mn were affected by surface runoff markedly while other metals were mainly correlated to natural diagenetic weathering and atmospheric deposition. Sediment quality guideline and potential ecological risk index were introduced to assess sediment quality and both of their results indicated that the Pumoyum Co as a whole can be ranked as low potential ecological risk.

Historical reconstruction of mercury pollution across the Tibetan Plateau using lake sediments.

The Tibetan Plateau is described as the "Roof of the World" averaging over 4000 m above sea level; it is remote, isolated, and presumed to be a pristine region. In order to study the history of atmospheric mercury (Hg) pollution and its spatial variation across the Plateau, lakes were chosen from three areas forming a north to south transect. Sediment cores were taken from three sites in each area and dated using the radionuclides 210Pb and 137Cs. Analysis of the cores yielded the first comprehensive Hg reconstructions for the Plateau, showing clear Hg pollution at all sites. The first indication of Hg pollution is much earlier than the onset of the industrial revolution in Europe, but the most significant pollution increase is from the 1970s, followed by a further marked increase from the 1990s. The mean post-2000 atmospheric pollution Hg accumulation rates for the sampling sites were estimated at between 5.1 and 7.9 microg m(-2) yr(-1). The increase in Hg pollution over the last few decades is synchronous with the recent economic development in Asia (especially China and India), and pollution Hg levels continue to increase. Furthermore, contemporary sediment Hg accumulation rate data are in broad agreement with Hg deposition values derived from global models that attribute pollution to sources mainly within southeast Asia. As most of the sites are exceptionally remote and situated above the atmospheric boundary layer, these results underline the need to understand the local Hg cycle in both regional and global context.

Assessment of polychlorinated biphenyls and polybrominated diphenyl ethers in Tibetan butter.

The Tibetan plateau is considered a potential cold trap for persistent organic pollutants (POPs) and plays an important role in the global long-range transport of these compounds. This present work surveyed the concentrations of polychlorinated biphenyl (PCBs) and polybrominated diphenyl ethers (PBDEs) in Tibetan butter samples collected from different prefectures in Tibet autonomous region (TAR). summation operator(25)PCB concentrations ranged from 137 to 2518 pg g(-1) with a mean value 519 pg g(-1), which were far lower than those in the butter from other regions in the world. The highest level was found in butter from Sichuan province, which is located to the east of the Tibetan plateau and the lowest value was in samples from southeast TAR. The average concentration of summation Sigma(12)PBDE was 125 pg g(-1). The sample with highest and lowest summation Sigma(12)PBDE concentration (955 and 18.0 pg g(-1)) was from the south and southeast part of the plateau, respectively. Back trajectory model implied that the sources of these two groups of POPs were by atmospheric deposition in south, whereas the western plateau was mainly influenced by the tropical monsoon from south Asia. Air currents from Sichuan and Gansu province are further responsible for the atmospheric transport of PCBs and PBDEs to the eastern and northern side of the plateau. Local air concentrations of summation Sigma(5)PCBs predicted using air-milk transfer factor were at the lower end of published global levels.