Search

Toxic solvents used in the fabrication of perovskite films are a non-ignorable obstacle for the commercialization of perovskite solar cells (PSCs). CsPbBr3 based solar cells have attracted increasing attention due to their high stability in ambient air. Usually, a traditional sequential deposition route is employed to fabricate CsPbBr3 films, in which toxic DMF and methanol are separately used to dissolve PbBr2 and CsBr. In order to eliminate the solvent toxicity during the fabrication of CsPbBr3 films, we develop an anomalous sequential deposition route to prepare CsPbBr3 films. In this new route, a green solvent system composed of water with the addition of appropriate ethanol and ethylene glycol (EG) is developed to prepare the CsBr solution, and a green solvent, triethyl phosphate (TEP), is used to prepare the PbBr2 solution. Different from those obtained by the traditional sequential deposition route, CsBr films are firstly prepared from their solution, then reacted with PbBr2 through a dynamic spin-coating process, and subsequently transformed to CsPbBr3 films via annealing treatment. As a result, solar cells based on the device configuration of FTO/TiO2/CsPbBr3/carbon exhibit a power conversion efficiency of 6.86%, which is comparable to that of the PSCs prepared through the traditional sequential deposition route using toxic solvents. This work provides an environment-friendly route to prepare CsPbBr3 perovskite solar cells without efficiency loss.

CsPbBr3 films have attractive applications in resistive switching memory, light-emitting diodes, photodetectors, and especially in perovskite solar cells (PSCs) because of their high stability and ease of fabrication under open air conditions. However, toxic solvents are usually employed to prepare CsPbBr3 films in these devices and pose potential threats to the health of manufacturers and the environment. Here, we develop a novel approach to achieve environment-friendly production of high quality CsPbBr3 films using water-soluble precursors of Pb(NO3)2 and CsBr in combination with phenethylammonium bromide (PEABr). In this approach, only green solvents of water and 2-propanol (IPA) are used to prepare CsPbBr3 films. After integrating into a solar cell with a typical configuration of FTO/TiO2/CsPbBr3/carbon, the best solar cell exhibits a power conversion efficiency (PCE) of 6.25% and has excellent stability in open air. This work not only provides a new approach to prepare high quality CsPbBr3 films, but also addresses the solvent toxicity during the fabrication of CsPbBr3 films, which makes it have extensive applications toward environment-friendly production of various CsPbBr3-based optoelectronic devices.

Glacierized mountain environments can preserve and release mercury (Hg) and play an important role in regional Hg biogeochemical cycling. However, the behavior of Hg in glacierized mountain environments and its environmental risks remain poorly constrained. In this research, glacier meltwater, runoff and wetland water were sampled in Zhadang-Qugaqie basin (ZQB), a typical glacierized mountain environment in the inland Tibetan Plateau, to investigate Hg distribution and its relevance to environmental risks. The total mercury (THg) concentrations ranged from 0.82 to 6.98ng·L-1, and non-parametric pairwise multiple comparisons of the THg concentrations among the three different water samples showed that the THg concentrations were comparable. The total methylmercury (TMeHg) concentrations ranged from 0.041 to 0.115ng·L-1, and non-parametric pairwise multiple comparisons of the TMeHg concentrations showed a significant difference. Both the THg and MeHg concentrations of water samples from the ZQB were comparable to those of other remote areas, indicating that Hg concentrations in the ZQB watershed are equivalent to the global background level. Particulate Hg was the predominant form of Hg in all runoff samples, and was significantly correlated with the total suspended particle (TSP) and not correlated with the dissolved organic carbon (DOC) concentration. The distribution of mercury in the wetland water differed from that of the other water samples. THg exhibited a significant correlation with DOC as well as TMeHg, whereas neither THg nor TMeHg was associated with TSP. Based on the above findings and the results from previous work, we propose a conceptual model illustrating the four Hg distribution zones in glacierized environments. We highlight that wetlands may enhance the potential hazards of Hg released from melting glaciers, making them a vital zone for investigating the environmental effects of Hg in glacierized environments and beyond.

Humic-like substances (HULIS) are major components of light-absorbing brown carbon that play an important role in Earth's radiative balance. However, their concentration, optical properties, and sources are least understood over Tibetan Plateau (TP). In this study, the analysis of total suspended particulate (TSP) samples from central of TP (i.e., Nam Co) reveal that atmospheric HULIS are more abundant in summer than that in winter without obvious diurnal variations. The light absorption ability of HULIS in winter is 2-3 times higher than that in summer. In winter, HULIS are mainly derived from biomass burning emissions in South Asia by long-range transport. In contrast, the oxidation of anthropogenic and biogenic precursors from northeast part of India and southeast of TP are major sources of HULIS in summer.

The concentrations, depositions and optical properties of precipitation DOC at three remote stations (Nam Co, Lulang and Everest) were investigated in the Himalayas and Tibetan Plateau (HTP). The results showed that their volume-weighted mean DOC concentrations were 1.05±1.01mgCL-1, 0.83±0.85mgCL-1 and 0.86±0.91mgCL-1, respectively, close to those of other remote areas in the world and lower than those of typical polluted urban cities. Combined with precipitation amounts, the DOC depositions at these three stations were calculated to be 0.34±0.32gCm-2yr-1, 0.84±0.86gCm-2yr-1 and 0.16±0.17gCm-2yr-1, respectively. The annual DOC deposition in the HTP was approximately 0.94±0.87TgC, the highest and lowest values appeared in the southeastern and northwestern plateau, respectively. The sources of DOC in the precipitation at these three stations were remarkably different, indicating large spatial heterogeneity in the sources of precipitation DOC over the HTP. Nam Co presented combustion sources from South Asia and local residents, Lulang showed biomass combustion source from South Asia, and Everest was mainly influenced by local mineral dust. The values of the MACDOC at 365nm were 0.48±0.47m2g-1, 0.25±0.15m2g-1, and 0.64±0.49m2g-1, respectively, for the precipitation at the three stations. All of these values were significantly lower than those of corresponding near-surface aerosol samples because precipitation DOC contains more secondary organic aerosol with low light absorption abilities. Additionally, this phenomenon was also observed in seriously polluted urban areas, implying it is universal in the atmosphere. Because precipitation DOC contains information for both particle-bound and gaseous components from the near surface up to the altitude of clouds where precipitation occurs, the MACDOC of precipitation is more representative than that of near-surface aerosols for a given region.

Equivalent black carbon (eBC) mass concentrations were measured by an aethalometer (AE-31) in the Nam Co, central Tibet from 2010 to 2014. Different from previous filter-sampling studies (Ming et al., J Environ Sci 22(11):1748–1756, 2010; Zhao et al., Environ Sci Pollut Res 20:5827–5838, 2013), the first high-resolution online eBC measurement conducted in central Tibet is reported here, allowing to discuss the diurnal variations as well as seasonal variabilities of eBC. Average daily eBC concentration was 74 ± 50 ng/m3, reflecting a global background level. Meteorological conditions influenced eBC concentrations largely at seasonal scale, which are higher in February–May but lower in June–January. The highest eBC concentrations (greater than 210 ng/m3) were more associated with the W and WSW winds smaller than 6 m/s. The diurnal variations of eBC showed plateaus from 10:00 to 15:00 with seasonal variations, associated with local anthropogenic activities, such as indigenous Tibetan burning animal waste and tourism traffic. The PBLHs showed a co-variance with eBC concentrations, implicating close sources. The aerosol optical depths derived from the MODIS data over the Nam Co Observatory Station (NCOS)-included sub-area (30° N–40° N, 90° E–100° E) showed significant relationship with eBC concentrations. This suggests that nearby or short-distance sources other than long-distance transported pollutants could be important contributors to eBC concentrations at the NCOS, different from the conclusions suggested by previous studies.

Little is currently known about the trophic transfer behavior of short-chain chlorinated paraffins (SCCPs) in terrestrial ecosystems. The trophodynamics of SCCPs were investigated in a typical terrestrial food chain (plant-plateau pika-eagle) from the interior of the Tibetan Plateau with an altitude of 4730 m. Pervasive contamination by SCCPs was found in the Tibetan Plateau samples, and the average concentrations of SCCPs in soil, plant, plateau pika, eagle, and gut content of eagle samples were 81.6 ± 31.1, 173 ± 70.3, 258 ± 126, 108 ± 59.6, and 268 ± 93.9 ng/g (average ± standard deviation, dry weight, dw), respectively. The trophic magnification factor (TMF) of SCCPs was 0.37, implying the trophic dilution of SCCPs in this terrestrial food chain. The TMF values of individual congener groups were positively correlated with the values of log

In an effort to understand the biogeochemical cycling and seasonal characteristics of atmospheric Hg, a total of 80 daily sampled total suspended particulates were collected at Lhasa, the largest city of Tibet, from April 2013 to August 2014 for particulate-bound Hg (Hg P ) analysis. Daily concentrations of atmospheric Hg P ranged from 61.2 to 831 pg m −3 with an average of 224 pg m −3 , which were unexpectedly comparable to those measured in most of the Chinese metropolises. Both the daily/monthly average Hg P concentrations were slightly but not significantly higher during the non-monsoon season than during the monsoon season. Together with the fact that there was lack of significant relationship between Hg P concentration and most meteorological parameters, no significant and distinct pattern for the seasonal characteristics of atmospheric Hg P could be mainly attributed to the almost equal emission strength of two principal anthropogenic Hg sources (i.e., industrial emission sources during the non-monsoon season, and vehicular traffic and religious sources during the monsoon season). Moreover, the Hg P dry deposition rate was estimated to be 35.3 μg m −2 yr −1 by using a theoretical model, which was significantly higher than those Hg wet fluxes. The elevated deposition rate implied that dry deposition may play an important role in the biogeochemical Hg cycling over the Tibetan Plateau.

Hourly speciated measurements of atmospheric mercury made in a remote, high-altitude site in the Tibetan Plateau revealed the first field observations of the reduction of reactive mercury in the presence of sunlight in the atmosphere. Measurements were collected over four winter months on the shore of Nam Co Lake in the inland Tibetan Plateau. The data was analyzed to identify sources and atmospheric transformations of the speciated mercury compounds. The absence of local anthropogenic sources provided a unique opportunity to examine chemical transformations of mercury. An optimization algorithm was used to determine the parameters of a chemical box model that would match the measured reactive mercury concentrations. This required the presence of a photolytic reduction reaction previously observed in laboratory studies and in power plant plumes. In addition, the model estimated the role of vertical mixing in diluting reactive gaseous mercury during the day, and the role of bromine chemistry in oxidizing gaseous elemental mercury to produce reactive gaseous mercury. This work provides further evidence of the need to add the photolytic reduction reaction of oxidized mercury into atmospheric transport models in order to better simulate mercury deposition.

We combined the mercury passive sampling method and plant biomonitoring together to understand the long-term changes of atmospheric mercury concentrations on the Tibetan Plateau. Through the analysis of leaves of Androsace tapete that represent growing periods spanning the past decade, we explored the historical records of atmospheric mercury from 2006 to 2015. Mercury concentration was stable in the leaves of Androsace tapete during the period between 2006 and 2009, while a significant decrease occurred after the year of 2010. The decreasing trend is consistent with the monitoring data of the ground-based stations in other regions globally. Despite the potential uncertainties using a passive sampling method and biomonitoring technique, we suggest that Androsace tapete is a potential biomarker that could provide reliable and effective historical records of atmospheric mercury concentrations and offer new perspectives in monitoring mercury and perhaps other atmospheric pollutants in regions where long-term active monitoring was missing.

Perfluoroalkyl acids (PFAAs) are ubiquitous in the environment. They are prone to accumulate in organisms and have raised public attention in recent decades. Feather samples have been successfully applied as nondestructive indicators for several contaminants. However, a sophisticated analytical method for determining PFAAs in feathers is still lacking. In the present study, a series of conditions, such as the use of the solid-phase extraction cartridge type and extraction/digestion methods, were optimized for the analysis of 13 PFAAs in feathers. According to the spiked recoveries, a weak-anion exchange cartridge was chosen and the methanol was selected as the extraction solvent. In the present study, an optimized pretreatment procedure combined with high-performance liquid chromatography–electrospray ionization–tandem mass spectrometric (HPLC–ESI–MS/MS) method was established for the determination of PFAAs in feathers. The recoveries and method detection limits of the PFAAs ranged from 71 to 120% and 0.16 to 0.54 ng/g, respectively. Finally, 13 PFAAs in four accipiter feather samples from Nam Co Basin, Tibetan Plateau, were analyzed, indicating that PFOS was the predominant PFAA in accipiter feathers, with an average of 4.67 ng/g, followed by the short-chain PFAAs, PFBS and PFBA, with averages of 1.91 and 1.39 ng/g, respectively. These results partly indicated the current situation of PFAA pollution in the Nam Co Basin, especially the existence of short-chain PFAAs in this region.

Precipitation samples collected at a remote high elevation site (i.e., Nam Co Station, 4730 m a.s.l.) in the southern Tibetan Plateau were analyzed for total mercury (HgT) between July 2009 and 2011, particulate-bound mercury (HgP) between July 2010 and 2011 and methylmercury (MeHg) from July through August of 2009. The volume-weighted mean (VWM) concentrations and wet deposition fluxes of HgT and MeHg in precipitation were 4.8 ng L−1 and 1.75 μg m−2 yr−1, 0.031 ng L−1 and 0.01 μg m−2 yr−1, respectively. VWM HgT concentration was approximately two times higher during the non-monsoon season than during the monsoon season, while 83% of the HgT wet deposition fluxes occurred during the monsoon season. The HgT and MeHg concentrations are comparable to the reported data for some of the most remote alpine and polar regions worldwide (e.g., Churchill), but the wet deposition fluxes of HgT and MeHg were among the lowest in the world. Analysis of Hg speciation has presented that HgP and MeHg concentrations are high, making up 71.2% and 1.82% of the HgT on average (VWM), respectively. The high HgP%, as well as a significantly positive between HgT and HgP (R2 = 0.91; n = 44; p < 0.001), confirmed that atmospheric deposition of Hg in the Tibetan Plateau was occurring in the form of HgP. A decreasing trend in HgT concentrations with increasing amount of precipitation (R2 = 0.08; N = 101; p < 0.005) was found at Nam Co Station, indicative that scavenging of HgP from the atmosphere was an important mechanism contributing Hg to precipitation. The precipitation amount, rather than HgT concentration, was found to be the governing factor affecting HgT wet deposition flux. Moreover, a comparison between measured wet deposition flux of Hg at Nam Co Station and the estimates from environmental records indicated that both snowpits and lake sediments appear to be reliable archives for estimating historical Hg accumulation rates over the Tibetan Plateau.

Ten snowpits were sampled at the Zhadang glacier during 2008 and 2011 to investigate the seasonal variations, speciation, and sources of mercury (Hg) in the southern Tibetan Plateau. In the 2008 snowpit, total Hg (Hg T ), particulate matter, most of major ions were found in higher concentrations during the non-monsoon season than in the monsoon season. Analysis of Hg speciation indicated that Hg T in the 2011 snowpits was dominated by particulate-bound Hg (Hg P ). Most of particulate matter in the 2008 snowpit was dominated by fine particulates, indicating that the influx of particulate matter and Hg P was probably occurring by long-range transportation via general atmospheric circulation. Analysis of dominant ion Ca 2+ and alkaline pH values has suggested that the long-range transported Hg P , originating from dust storm activities, may be the most important source for Hg in the Zhadang glacier snowpit during the non-monsoon season. Backward-trajectory analysis indicates the majority of the air masses arriving at the Zhandang glacier originated from the arid regions of northwestern India (e.g., Thar Desert), confirming that arid regions in central and southern Asia are likely the main sources of Hg being deposited in the Zhadang glacier snowpit. This study also suggests that ice core records from the Tibetan Plateau may be useful tools for interpreting long-term historical records of atmospheric Hg deposition, and reconstructing Hg biogeochemical cycling.

Coal combustion power plant flyash materials have been reported as useful soil amendments with agronomic and environmental benefits. This paper reports the efficacy of fluidized bed combustion (FBC) and flue gas desulfurization (FGD) byproducts, when amended with dairy, swine, and broiler litter manures, in reducing phosphorus (P) solubility and potential impact on water quality. At a rate of 400 g/kg, FBC reduced water soluble P by 60% for dairy and swine and 50% for broiler litter, as compared to un-treated control samples. Byproduct FGD had little effect when amended into dairy manure, but reduced water soluble P by nearly 80% when amended into swine and broiler manure at a rate of 250 g/kg. The amount of Ca added in the amendments together with pH of the mixture is the major contributing factor in soluble P reduction. Sequential extraction results showed that the flyash treatments shifted water soluble P into mainly bicarbonate extractable P. The latter is still considered available for crop uptake but less vulnerable for environmental losses. Coal combustion byproducts, when amended into manure and used properly, can provide a useful and viable option for improving nutrient management on animal farms.

There is a growing public concern over the potential accumulation of heavy metals in agricultural soils in China owing to rapid urban and industrial development and increasing reliance on agrochemicals in the last several decades. Excessive accumulation of heavy metals in agricultural soils may not only result in environmental contamination, but elevated heavy metal uptake by crops may also affect food quality and safety. The present study is aimed at studying heavy metal concentrations of crop, paddy and natural soils in the Pearl River Delta, one of the most developed regions in China. In addition, some selected soil samples were analyzed for chemical partitioning of Co, Cu, Pb and Zn. The Pb isotopic composition of the extracted solutions was also determined. The analytical results indicated that the crop, paddy and natural soils in many sampling sites were enriched with Cd and Pb. Furthermore, heavy metal enrichment was most significant in the crop soils, which might be attributed to the use of agrochemicals. Flooding of the paddy soils and subsequent dissolution of Mn oxides may cause the loss of Cd and Co through leaching and percolation, resulting in low Cd and Co concentrations of the paddy soils. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the Fe-Mn oxide and residual fractions, while Zn was predominantly found in the residual phase. A significant percent fraction of Cu was bound in the organic/sulphide and residual phases. Based on the 206Pb/207Pb ratios of the five fractions, it was evident that some of the soils were enriched with anthropogenic Pb, such as industrial and automobile Pb. The strong associations between anthropogenic Pb and the Fe-Mn oxide and organic/sulphide phases suggested that anthropogenic Pb was relatively stable after deposition in soils.

In May 2009, snowpit samples were collected from a high-elevation glacier in the Mt. Nyainqentanglha region on the southern Tibetan Plateau. A set of elements (Al, V, Cr, Mn, Co, Ni, Cu, Zn, Cd, Hg and Pb) was analyzed to investigate the concentrations, deposition fluxes of trace elements, and the relative contributions from anthropogenic and natural sources deposited on the southern Tibetan Plateau. Concentrations of most of the trace elements in snowpit samples from the Zhadang glacier are significantly lower than those examined from central Asia (e.g., eastern Tien Shan), with higher concentrations during the non-monsoon season than during the monsoon season. The elements of Al, V, Cr, Mn, Co, and Ni display low crustal enrichment factors (EFs), while Cu, Zn, Cd, Hg, and Pb show high EF values in the snow samples, suggesting anthropogenic inputs are potentially important for these elements in the remote, high-elevation atmosphere on the southern Tibetan Plateau. Together with the fact that the concentration levels of such elements in the Mt. Nyainqentanglha region are significantly higher than those observed on the south edge of the Tibetan Plateau, our results suggest that the high-elevation atmosphere on the southern Tibetan Plateau may be more sensitive to variations in the anthropogenic emissions of atmospheric trace elements than that in the central Himalayas. Moreover, the major difference between deposition fluxes estimated in our snow samples and those recently measured at Nam Co Station for elements such as Cr and Cu may suggest that atmospheric deposition of some of trace elements reconstructed from snowpits and ice cores could be grossly underestimated on the Tibetan Plateau.

Quantifying the contribution of mercury (Hg) in wet deposition is important for understanding Hg biogeochemical cycling and anthropogenic sources, and verifying atmospheric models. Mercury in wet deposition was measured over the year 2010, in Lhasa the capital and largest city in Tibet. Precipitation samples were analyzed for total Hg (HgT), particulate-bound Hg (HgP), and reactive Hg (HgR). The volume-weighted mean (VWM) concentrations and wet deposition fluxes of HgT, HgP and HgR in precipitation were 24.8 ng L-1 and 8.2 μg m-2 yr-1, 19.9 ng L-1 and 7.1 μg m-2 yr-1, and 0.5 ng L-1 and 0.19 μg m-2 yr-1, respectively. Concentrations of HgT and HgP were statistically higher during the non-monsoon season than during the monsoon season, while HgR concentrations were statistically higher during the monsoon season than during the non-monsoon season. Most HgT, HgP and HgR wet deposition occurred during the monsoon season. Concentrations of HgP and HgR were 77% and 5% of the HgT on average (VWM), respectively. Concentrations of HgT and HgP were weakly negatively correlated with precipitation amount (r2 = 0.09 and 0.10; p < 0.05), indicating that below-cloud scavenging of Hg from the local atmosphere was an important mechanism contributing Hg to precipitation. High HgP%, as well as a significant positive correlation between HgT and HgP, confirms that Hg wet deposition at Lhasa was primarily occurring in the form of atmospheric HgP below-cloud scavenging. Moreover, the HgT concentration, rather than the precipitation amount, was found to be the governing factor affecting HgT wet deposition flux. A comparison among modeled wet and dry deposition fluxes, and measurements suggested that estimates of both wet and dry Hg deposition fluxes by the GEOS-Chem model were 2 to 3 times higher than the measured annual wet flux.

In snow and ice, light-absorbing particles (LAPs), such as black carbon (BC) and dust, accelerate the melting of Third Pole glaciers (TPGs). In this study, we revaluated LAP concentrations in the snow pits of TPGs (SP-TPGs), measured LAP mass absorption cross-sections (MACs), and simulated their effects on glacier darkening and melting based on the Spectral Albedo Model for Dirty Snow and a surface energy and mass balance model. The results indicated that because of their short distances to emission sources, the average BC concentrations measured in snow pits in the periphery of Third Pole were much higher than those measured in the inland Tibetan Plateau, and the average dust concentrations generally decreased from north to south. The average MACs of BC in the SP-TPGs varied from 3.1 to 7.7 m2 g−1 at 550 nm, most of the average spectral values were comparable in the visible and near-infrared bands to those calculated by Mie theory, except those in Urumqi Glacier No. 1 (UR), Syek Zapadniy Glacier (SZ), and Laohugou Glacier No.12 (LH), while the average spectral MACs of dust in the SP-TPGs were considerably smaller in magnitude than most of the variations measured in other regions. Compared with the pure snow surfaces, BC and dust played comparable roles in reducing albedo in UR, SZ, LH, and Renlongba Glacier, whereas BC was the most prominent absorber in the other glaciers. The combined effect of BC and dust accelerated melting by 30.4–345.9 mm w.e. (19.7–45.3% of the total mass balance) through surface albedo darkening (0.06–0.17) and increased radiation absorption (25.8–65.7 W m−2) within one month of the ablation season. This study provides a new data set of LAP concentrations and MACs and helps to clarify the roles of these factors in the cryospheric environment of the Third Pole.