Insight into the local source of polybrominated diphenyl ethers in the developing Tibetan Plateau: The composition and transport around the Lhasa landfill.

In the background region of the Tibetan Plateau (TP), the rapid urbanization probably results in the massive generation of persistent organic pollutants (POPs), which lacks monitoring and evaluation. Since landfill could serve as an important sink of the locally used POPs, the analysis of POPs in the Tibetan landfill area might help us to understand the source composition and their transport in the TP. In this study, the concentration variations of polybrominated diphenyl ethers (PBDEs) in five soil profiles and seven surficial sediments around the largest Tibetan landfill were investigated. The total concentrations of PBDEs ranged from 128 to 1219 ng/kg in soils, and from 447 to 7295 ng/kg in sediments. The dominance of nona- and deca-BDEs possibly indicated the wide usage of deca-BDE as flame retardant in the TP. The vertical and spatial distribution patterns of PBDEs within soils plausibly revealed their main transport pathways by atmospheric dispersion and leachate seepage from landfill. Based on principal components analysis and multiple linear regression, these two pathways were estimated to account for 61% and 39% of the total concentrations, respectively. Additionally, the spatial and vertical distributions of octa-to deca-BDEs within soils were significantly influenced by soil particle size. Although the PBDEs inventory in the study area was comparatively low, the rapid urbanization in the TP might dramatically accelerate the PBDE emissions in the future. This study firstly introduced the presence of local PBDEs in the TP, and the inventory already influenced the surrounding environment. Once involved in the regional cycle of the TP, the local source of PBDEs from waste might significantly serve to raise background level resulting otherwise primarily from long-range atmospheric transport.

Organochlorine pesticides in the sedimentary core of the southern Tibetan Plateau: The missing pieces induced by lateral remobilization.

The sedimentary core in remote alpine lakes has been recognized as an ideal proxy to reconstruct the emission and air deposition histories of persistent organic pollutants (POPs). Nevertheless, POPs formerly stored in a catchment might also contribute to the variation in the lake sediment by lateral remobilization. In this study, to reveal the relative importance of lateral remobilization, we measured the vertical profiles and isomeric ratios of dichlorodiphenyltrichloroethanes (DDTs), hexachlorocyclohexanes (HCHs) and endosulfan in a dated sedimentary core collected from Lake Yamzho Yumco in the southern Tibetan Plateau. In addition to the flux peaks in the 1970s corresponding to the heavy atmospheric deposition of DDTs and HCHs, these pollutants' fluxes displayed rebounds in the flood periods, with characteristic low ratios of DDT/DDE (α-/ß-HCH). This might indicate a massive remobilization of "weathered" pesticides from catchment soil to the lake because of strong hydro-dynamics. Moreover, the relative contribution of lateral remobilization to the lake sediment in the past decades was recognized through the correlation between DDT/DDE (α-/ß-HCH) ratios and ∑DDT (∑HCH) fluxes. The results showed that the lateral remobilization contributed to 20-42% of the total fluxes. This study discriminated the air deposition from the contribution of lateral remobilization, which improves current understanding of the vertical POPs profiles in the sedimentary core.

High-resolution sedimentary records of some organochlorine pesticides in Yamzho Yumco Lake of the Tibetan Plateau: Concentration and composition.

Sediment cores from lakes have been used to reconstruct the historic deposition of persistent organic pollutants (POPs), especially in remote alpine areas. To reconstruct the deposition history of organochlorine pesticides (OCPs) in the Tibetan Plateau (TP), two sediment cores from Yamzho Yumco Lake were drilled and dated with high-resolution, from which 23 OCPs were analyzed in greater detail. Regarding several legacy compounds, concentration peaks in the cores were observed in the 1970s, corresponding to the heavy usage of these compounds around the world. In addition, another peak was found at the end of the 1990s, which was explained as the addition of OCPs released from melting glaciers or the cryosphere due to global warming. Furthermore, it was found that the transformation or degradation of OCPs after deposition in the lake was limited by comparing the values of isomeric ratios at different times, such as (DDD+DDE)/∑DDTs, o,p'-DDT/p,p'-DDT and ß-HCH/∑HCHs. Such results ensure that the detected OCPs in the lake sediments really reflect their characteristics at the time of deposition. On the other hand, weak environmental self-purification of the OCPs made them last longer in the TP than in other regions. Reasonably, the fragile ecological environment of the TP would be threatened not only by legacy POPs that remain in the sediments and soils but also by POPs released from melting glaciers or the cryosphere in the next few decades under the influence of global warming. Our research provides an insight into the influence of global warming and glacial melting on the environment of the TP, and further work to gain a better understanding of the environmental processes of POPs in the TP is ongoing.

The emerging source of polycyclic aromatic hydrocarbons from mining in the Tibetan Plateau: Distributions and contributions in background soils.

The Tibetan Plateau (TP) serves as the background for persistent organic pollutants around the world. In addition to outside sources, local sources greatly contribute to the environment of the TP in recent decades. Mining activity could serve as an emerging source of polycyclic aromatic hydrocarbons (PAHs), although this issue has been neglected in the TP until now. To investigate the distributions and contributions of PAHs transported from mining activity, forty-one surface soil samples along six sampling directions were collected at a regular distance from the Jiama mining area (JMA) of the TP at altitudes between 3726 and 4863m. The total concentration of 16 PAHs was 52.34±22.58ng/g. The result of the source identification suggested that mining activity represented the primary source for heavy molecular weight (HMW) PAHs in soils, while light molecular weight (LMW) and middle molecular weight (MMW) PAHs were contributed by multiple sources. For HMW PAHs, the concentrations and proportions decreased logarithmically with transport distance from the JMA. Furthermore, the transport distance of HMW PAHs was found to be affected by the prevailing wind direction. In addition to transport from the source area, the distributions of LMW and MMW PAHs were also influenced by the altitude. In the impact area of Jiama mining activity, the soil mass inventory was estimated to be 6.4±0.8tons for HMW PAHs. In future decades, HMW PAHs emitted from Jiama mining activity are projected to exceed 5% of the annual local emission in the TP. Our study evidenced that Tibetan mining activity serves as an important emerging source of PAHs, which would be transported within the TP and threaten the fragile ecosystem of the TP.

Evidence for persistent organic pollutants released from melting glacier in the central Tibetan Plateau, China.

Glacier alluvial deposits record persistent organic pollutants (POPs) not only derived from the atmospheric deposition but also from the release of glacial melting. The evidence for melting glacier in the Tibetan Plateau (TP) as a secondary source of pollutants is introduced through investigating the concentration of organochlorine pesticides (OCPs) in four deposited profiles collected at the edge of the Changwengluozha glacier. Two concentration peaks were observed for dichlorodiphenyltrichloroethanes (DDTs) and hexachlorocyclohexanes (HCHs) in the past century. The first peak was observed in the 1970s, corresponding with the heavy usage of HCHs and DDTs in the surrounding countries and regions. The second one was in 2000 when the production and usage of DDTs and HCHs were strictly limited, which possibly indicated a significant release from melting glacier. This result was further supported by the enantiomeric fraction values for α-HCH and o,p'-DDT. On the other hand, the dramatic increase of polycyclic aromatic hydrocarbons (PAHs) from atmospheric deposition, which was associated with the socioeconomic development in Tibet, shaded the release of PAHs from melting glacier. This study reveals not only the air deposition history of legacy POPs but also a substantial release of OCPs from glacier to the adjacent environment. Our research supports the hypothesis that the melting glacier in the TP represents a secondary source of OCPs, which is consistent with the findings in the Alps glaciers.

One century of air deposition of hydrocarbons recorded in travertine in North Tibetan Plateau, China: Sources and evolution.

The characteristic distribution patterns of hydrocarbons have been used for fingerprinting to identify their sources. The historical air depositions of hydrocarbons recorded in natural media help to understand the evolution of the air environment. Travertine is a natural acceptor of air deposition that settles on the ground layer by layer. To reconstruct the historical air environment of hydrocarbons in the North Tibetan Plateau (NTP), a unique background region, twenty-seven travertine samples were collected systematically from a travertine column according to its precipitated year. For each sample, the precipitated year was dated while n-alkanes and polycyclic aromatic hydrocarbons (PAHs) were determined. Based on source identification, the air environment of hydrocarbons in the past century was studied for the region of NTP. Before World War II, the anthropogenic sources of hydrocarbons showed little influence on the air environment. During World War II and China's War of Liberation, hydrocarbons increased significantly, mainly from the use of fossil fuels. Between 1954 and 1963, hydrocarbons in the air decreased significantly because the sources of petroleum combustion decreased. From the mid-1960s through the end of the 1990s, air hydrocarbons, which mainly originated from biomass burning, increased gradually because agriculture and animal husbandry were developing steadily in Tibet and China. From the late 1990s, hydrocarbons in the atmosphere increased rapidly due to the rapid increase of tourism activities, which might increase hydrocarbon emissions from traffic. The reconstruction of the historical air hydrocarbons in NTP clearly reflects the evolution of the region and global development.

Concentration and chiral signature of chlordane in soils and sediments of the Central Tibetan Plateau, China: Transformation in the surficial process.

The fraction of trans-chlordane (TC) in chlordane was used to indicate racemic degradation while the enantiomer fractions (EFs) indicated enantioselective depletion. In 44 soils of the Central Tibetan Plateau, the fractions of TC ranged from 0.368 to 0.411. The EFs ranged from 0.174 to 0.696 for TC and from 0.483 to 0.672 for cis-chlordane (CC). (-) enantiomer excess (ee) was found to be 80.0% in the soils for TC and (+) ee was 86.5% for CC. The fraction of TC changed with the clay content while the EFs changed with the soil organic carbon. Meanwhile, the fractions of TC and the EFs were determined for the surficial sediments in Yamzhog Yumco Lake, which were compared with those in the soils at its catchment area. The composition and chiral signature of chlordane did not vary between soils and sediments. Our results will help to elucidate the transformation of chlordane in soils and in surficial transport.

Polycyclic aromatic hydrocarbons in soils of the central Tibetan Plateau, China: Distribution, sources, transport and contribution in global cycling.

Forty-four soil samples were collected across the central Tibetan Plateau (CTP) at altitudes between 3711 m and 5352 m, and their polycyclic aromatic hydrocarbons (PAHs) contents were measured to be from 0.43 to 26.66 ng/g. The main sources of PAHs were identified for each of four sub-areas, and their concentrations in soils were determined to be mainly influenced by local sources. Along a 600 km sampling trajectory from Lhasa, which served as the biggest local source, the concentrations of PAHs decreased logarithmically with increasing distances from the source. Meanwhile, the fractional proportions of PAHs were observed to change logarithmically according to the transport distances. Conclusively, PAHs from local sources were transported within the CTP and dominated PAHs concentrations in the soils, but few of them were transported outside the CTP. In global cycling, the soils in the CTP mainly serve as background and a "sink" for PAHs.

Polybrominated diphenyl ethers in surface soils near the Changwengluozha Glacier of Central Tibetan Plateau, China.

Forty-two congeners of polybrominated diphenyl ethers (PBDEs) were detected for each of 27 surface-soil samples collected at an area near the Changwengluozha Glacier in the Central Tibetan Plateau (CTP), a remote background area at altitude from 5080 to 5217 m. The total concentrations of BDEs in soils ranged from 15.3 to 248.0 ng/kg, which were found to be positively correlated with the clay contents in the soil. In addition to adsorption, the clay was found to serve as a catalyst for the debromination of PBDEs in soils. Three pieces of evidence confirmed that the clay was significantly correlated with the debrominating transformation from the higher brominated congeners to the less brominated congeners. The transforming rate was found to be increased 3.5% with a 10% increase in clays. Debromination is an important way for highly brominated congeners to transform into lighter brominated congeners that are more toxic. This study first provided the direct field evidences for clays contributing to the debromination of PBDEs, and elucidated the importance of it in PBDEs' environmental fate.

Polychlorinated biphenyls in surface soils of the Central Tibetan Plateau: altitudinal and chiral signatures.

The soils in the Central Tibetan Plateau (CTP), which is a unique background region, play an important role in the fate of the global cycling of polychlorinated biphenyls (PCBs). Forty-four soil samples from across the CTP were collected at altitudes between 3711 m and 5352 m, and the concentrations of 122 PCB congeners were measured from 66.98 to 150.81 ng/kg. The concentration of PCBs was positively correlated with the sampling altitude and clay content. Furthermore, enantiomeric fractions (EFs) of CB-95, CB-136 and CB-149 in soils of CTP were first determined. A (+)-enantiomer excess was identified for CB-136 and CB-149 in all of the samples investigated. Additionally, enantiomer-specific excess was found for CB-95. The dominance of enantiomer-specific excess decreased with increased the sampling altitude and congener concentration. It is likely that the addition of enantiomeric mixtures of PCBs from the atmosphere changed the EFs in the soils according to the altitude.

Chiral signature of α-HCH and o,p'-DDT in the soil and grass of the Central Tibetan Plateau, China.

Enantiomeric fraction (EF) of organochlorine pesticides (OCPs) has been used as a signature for tracing the source and following pathways. The chiral analysis was performed for α-HCH and o,p'-DDT in paired soil and grass samples from the Central Tibetan Plateau (CTP), a unique background region. In the case of α-HCH, excess of (-) α-HCH was predominant in 83.3% of soil samples, and 80% of grass samples showed excess of (+) enantiomer. For o,p'-DDT, 90.9% of grass samples showed excess of (-) o,p'-DDT while 50% of soil samples showed excess of the (-) enantiomer. A correlation between EFs of soil and grass was not observed for either compound. The EFs of both compounds were correlated with soil concentration and with change of sampling altitude, within EFs being lower than racemic. However, these trends were not found in grass. Our study provides a database of EFs and signatures for OCPs in the CTP, one background region of the world.

Factors influencing the accumulation of organochlorine pesticides in the surface soil across the Central Tibetan Plateau, China.

Forty-four soil samples were collected across the Central Tibetan Plateau (CTP) at elevations of between 3711 and 5352 m. The scatter diagram shows that the soil concentrations of organochlorine pesticides (OCPs) were associated with the altitude of sampling site, soil clay minerals, soil organic carbon (SOC) and the fine particle fractions of soil. Pearson correction analysis and principle component analysis were used to deduce the relationship between the OCP concentrations and these factors logically. It was determined that the altitude and clays functioned as the primary factors influencing OCP accumulation, and SOC was weakly related to OCPs. The fitting equation closely matches the observations in the field while only taking the altitude and clay minerals into account. Our study found that clay minerals dominated the sorption of OCPs in soil, whereas the altitude contributed to temperature-driven condensation for the accumulation of OCPs at high altitudinal CTP.

Persistent organic pollutants in soil near the Changwengluozha glacier of the Central Tibetan Plateau, China: their sorption to clays and implication.

Twenty-seven soil samples were collected at ca. 5,000 m from the Changwengluozha glacier. In addition to soil components, the concentration of 23 organochlorine pesticides (OCPs) and 16 polycyclic aromatic hydrocarbons (PAHs) were analyzed. Clay minerals were found to play a key role in the accumulation of OCPs/PAHs in soil. The sorption ratio of chemical to clay was ordered in the OCPs and PAHs to the vapor pressure in a negatively correlated fashion. Because of the negative relationship between vapor pressure and the soil-air partition coefficients (KSA), it was understood that the higher sorption ratio responded to a higher KSA, which indicated the fate of the contaminants in soil. The soil near the Changwengluozha glacier functioned as a "sink" for OCPs in the decreasing order of 2,4'-DDT, 4,4'-DDD, HCB, δ-HCH, and α-HCH and for PAHs in an decreasing order of Pyr, Flu, Fl, Ace, and Acy.

The fractional patterns of polybrominated diphenyl ethers in the soil of the central Tibetan Plateau, China: the influence of soil components.

Sixteen soil samples were collected from the central Tibetan Plateau (CTP). The soil concentrations of polybrominated diphenyl ethers (PBDEs) in CTP were analyzed. The detected 42 congeners were divided into light, intermediate and heavy fractions. In addition to the various minerals, other soil properties were also characterized, including the content of soil organic carbon (SOC) and the particle size distribution. The clay content is positively related to the intermediate fraction of the PBDEs and negatively related to the light and heavy fractions. Similar correlations were observed for SOC and the fine-particle fraction (size < 2 µm). The coefficient of determination (r(2)) associated with a linear regression indicated that the clays were more highly correlated with the fractional pattern of the PBDEs than with the other properties, such as SOC and the fine-particle fraction. The values of r(2) between clays and three fractions of PBDEs are 0.70, 0.69 and 0.58.

Altitudinal distribution of polybrominated diphenyl ethers (PBDEs) in the soil along Central Tibetan Plateau, China.

The distribution of PBDEs in the mountains of the Central Tibetan Plateau (CTP) was determined by sampling soil along an elevation transect. The analysis of soil extracts was performed by gas chromatography and high-resolution mass spectrometry, through which 42 congeners were detected. The samples were also characterized with respect to the soil organic carbon (SOC) and mineral contents. The logarithmic concentration for three of the fractions and the ΣPBDEs increased significantly and exponentially with altitude. The slope value of the linear regression between the logarithm of the clay-normalized three fractional concentrations and the altitude is in the following order: light>intermediate