Orbital- and millennial-scale Asian winter monsoon variability across the Pliocene-Pleistocene glacial intensification.

Intensification of northern hemisphere glaciation (iNHG), ~2.7 million years ago (Ma), led to establishment of the Pleistocene to present-day bipolar icehouse state. Here we document evolution of orbital- and millennial-scale Asian winter monsoon (AWM) variability across the iNHG using a palaeomagnetically dated centennial-resolution grain size record between 3.6 and 1.9 Ma from a previously undescribed loess-palaeosol/red clay section on the central Chinese Loess Plateau. We find that the late Pliocene-early Pleistocene AWM was characterized by combined 41-kyr and ~100-kyr cycles, in response to ice volume and atmospheric CO2 forcing. Northern hemisphere ice sheet expansion, which was accompanied by an atmospheric CO2 concentration decline, substantially increased glacial AWM intensity  and its orbitally oscillating amplitudes across the iNHG. Superposed on orbital variability, we find that millennial AWM intensity fluctuations persisted during both the warmer (higher-CO2) late Pliocene and colder (lower-CO2) early Pleistocene, in response to both external astronomical forcing and internal climate dynamics.

Evidence of economic development revealed in centennial scale sedimentary records of organic pollutants in Huguangyan Marr Lake.

Sedimentary records of polycyclic aromatic hydrocarbons (PAHs) and phthalates could reflect energy consumption and industrial production adjustment. However, there is limited knowledge about their effects on variations of PAH and phthalate compositions in the sediment core. The PAH and phthalate sedimentary records in Huguangyan Maar Lake in Guangdong, China were constructed, and random forest models were adopted to quantify the associated impact factors. Sums of sixteen PAH (∑16 PAH) and seven phthalate (∑7 PAE) concentrations in the sediment ranged from 28.8 to 1110 and 246-4290 µg/kg dry weight in 1900-2020. Proportions of 5-6 ring PAHs to the ∑16 PAHs increased from 32.0 %-40.7 % in 1900-2020 with increased coal and petroleum consumption, especially after 1980. However, those of 2-3 ring PAHs decreased from 30.7 % to 23.6 % due to the biomass substitution with natural gas. The proportions of bis (2-ethylhexyl) phthalate to the ∑7 PAEs decreased from 52.3 %-29.1 % in 1900-2020, while those of di-isobutyl phthalate increased (13.7 % to 42.3 %). The shift from traditional plasticizers to non-phthalates drove this transformation, though the primary plastic production is increasing. Our findings underscore the effectiveness of optimizing energy structures and updating chemical products in reducing organic pollution in aquatic environments.

Delayed recovery of surface water chemistry from acidification in subtropical forest region of China.

The three largest acid rain regions of current earth are located in northern and western Europe, eastern North America, and East Asia. Sulfur and nitrate concentrations in headwater streams in Europe and North America decreased as atmospheric sulfur and nitrogen deposition decreased, albeit with a considerable delay. However, how water chemistry responds to the declining sulfur and nitrogen deposition in China is unclear. The regional survey of surface water chemistry during 2010 and 2018 within the Sichuan Basin in southwestern China showed that the recovery of the surface water chemistry was delayed for at least 5 years owing to the release of previously deposited sulfur and nitrogen stored in the soil. After sulfur deposition declined from its peak value, the subregions of purplish soil with low sulfate adsorption capacity still exhibited a net sulfur release in 2010, but this release was no longer evident by 2018. The subregions with the red and yellow soils, which have a high sulfate adsorption capacity, operated as sulfur sinks during 2010 and 2018, indicating a continuous immobilization process through sulfate reduction despite a decrease in sulfur deposition. Additionally, this sulfate reduction countered the release of sulfate caused by sulfur desorption. There was a substantial nitrogen sink within the Sichuan Basin. Nitrogen leaching decreased slowly with the declined nitrogen deposition, except in regions where nitrogen deposition exceeded the critical threshold. Compared to temperate forest regions in Europe, the Sichuan Basin and its surrounding areas have experienced higher decline rates in the leaching of sulfur and nitrogen, highlighting that the subtropical forest region undergoes a faster restoration of surface water chemistry.

Chemical weathering in glacial catchment acting as a net carbon source.

Over geological time scales, continental silicate weathering is considered as a critical carbon sink that regulates long-term climate feedback. By contrast, recent studies indicate that sulfide oxidation during weathering can be as a potential carbon source. However, whether chemical weathering in glacial conditions characterized by extreme erosion is a net carbon sink or source remains elusive. Here, we present the seasonal carbon cycle processes in a typical glacier catchment, via high-resolution (weekly) river water sampling during the whole 2017 in the Laohugou river, northeastern Tibetan Plateau. Our seasonal result shows that the release of CO2 by sulfide oxidation during the monsoon period can be much faster than CO2 consumption through weathering of silicate rocks, with maximum of ∼26 times. Extending to global glacial basins, we observed a consistent pattern that inorganic carbon releases in alpine glaciers are faster than atmospheric CO2 consumption. We propose that weathering in global glacial environment acts as a significant carbon source, and thus affects climate feedback.

Two-century sediment records of atmospheric mercury variations in North China and their relations with regional and global emissions.

Sedimentary mercury (Hg) records from remote areas are significant for revealing historical variations of regional Hg and understanding the influence of regional and global Hg emissions. In this study, sediment cores were retrieved from two subalpine lakes in Shanxi Province in North China and employed to reconstruct atmospheric Hg variations over the last two centuries. The two records show similar anthropogenic Hg fluxes and evolution trends, corresponding with that they were affected mainly by regional atmospheric Hg deposition. Before ~1950, the records show negligible Hg pollution signals. Atmospheric Hg in the region had increased rapidly since the 1950s, lagged more than a half-century compared to the global Hg. This indicates that they were seldom affected by Hg emissions dominated by Europe and North America after the industrial revolution. The Hg increases since the 1950s in the two records corresponded well with rapid industrial developments in and around Shanxi Province after the founding of the China, implying the dominant contribution of domestic Hg emissions. By comparing other Hg records, we find that widespread increases in atmospheric Hg in China likely occurred post ~1950. This study rouses to re-examine historical variations in atmospheric Hg at various settings, which is significant to understanding global Hg cycling in the industrial era.

Li isotopic seasonality in a small catchment at the northeastern Tibetan Plateau: Roles of hydrology and temperature dependency.

Silicate weathering is critical to sustain our habitable planet. Lithium (Li) isotopes enable us to investigate the nature of silicate weathering. A number of riverine Li isotope (δ7Lirw) investigations have been made from polar to equatorial terrains, but there remains no consensus about the controlling mechanisms of both weathering and δ7Lirw. Here we investigated δ7Lirw response to climate by collecting weekly river water samples in a small catchment (the Buha River within the Lake Qinghai basin) on the northeastern Tibetan Plateau, with stable tectonic, lithology, and topography. In the hydrology year of 2007 of the Buha River, we find that during the dry seasons, δ7Lirw ratios show temperature dependency typically, when the groundwater fed the river. During the monsoon seasons, δ7Lirw were obviously lower than the temperature dependency predicted values, when abundant rock dissolved and thereby fresh Li release into rivers. We propose that the hydrology and temperature dependency together play important roles in regulating δ7Lirw ratios in such an alpine small catchment. The mechanism is that long residence time facilitates the equilibrium chemical and Li isotopic fractionation during the dry seasons, so a temperature dependency of δ7Lirw is achieved. In contrast, rapid erosion and weathering contribution of fresh rock-like δ7Li to river water would significantly decrease δ7Lirw ratios during the monsoon seasons. This hypothesis can better interpret previously reported data of seasonal δ7Lirw variation, as a superposition between temperature dependency and hydrology regulation on silicates weathering in the small catchments besides tectonics.

Sediment records of global and regional Hg emissions to the atmosphere in North China over the last three centuries.

Reconstructing the long-term Hg history in major emission countries is important for understanding the global Hg cycle and controlling Hg pollution. In this study, the atmospheric Hg history was reconstructed over the last three centuries based on three lacustrine sediment records from southeastern Inner Mongolia in North China, and its relationship with global and regional Hg emissions was revealed. These records show little Hg pollution in the 18th and 19th centuries. This implies a limited influence of Hg emitted from Europe and North America in this region, which is confirmed by their different Hg trends during the two World Wars and the post-1970s. Atmospheric Hg in the region had increased gradually since the 1900s, primarily contributed by emissions from the former Soviet Union in Lake Dalihu (DLH) and Lake Zhagesitai (ZGST) and from the Beijing-Tianjin-Hebei region in Lake Kulunnao (KLN). In the last century, two decreases in Hg fluxes occurred in the KLN core due to the economic recession in the 1960s-1970s and reduced energy consumption and industrial production in the 1990s. In the DLH and ZGST cores, only one decrease occurred, corresponded with the dissolution of the Soviet Union in the 1990s. Although atmospheric Hg emissions in China had stabilized or even decreased in the last decade, atmospheric Hg continued to increase, particularly in KLN, because of emissions from small cities in the region. This study can help understand Hg sources and control Hg pollution in North China and supplement the understanding of the global Hg cycling.

Hydrological control of river and seawater lithium isotopes.

Seawater lithium isotopes (δ7Li) record changes over Earth history, including a ∼9‰ increase during the Cenozoic interpreted as reflecting either a change in continental silicate weathering rate or weathering feedback strength, associated with tectonic uplift. However, mechanisms controlling the dissolved δ7Li remain debated. Here we report time-series δ7Li measurements from Tibetan and Pamir rivers, and combine them with published seasonal data, covering small (<102 km2) to large rivers (>106 km2). We find seasonal changes in δ7Li across all latitudes: dry seasons consistently have higher δ7Li than wet seasons, by -0.3‰ to 16.4‰ (mean 5.0 ± 2.5‰). A globally negative correlation between δ7Li and annual runoff reflects the hydrological intensity operating in catchments, regulating water residence time and δ7Li values. This hydrological control on δ7Li is consistent across climate events back to ~445 Ma. We propose that hydrological changes result in shifts in river δ7Li and urge reconsideration of its use to examine past weathering intensity and flux, opening a new window to reconstruct hydrological conditions.

Hydrochemistry and source apportionment of boron, sulfate, and nitrate in the Fen River, a typical loess covered area in the eastern Chinese Loess Plateau.

Fen River Basin (FRB) is water-deficient and strongly influenced by human activities in the eastern Chinese Loess Plateau. The spatio-temporal variation and controlling factors of hyrochemistry and quality, sources of high boron, sulfate, and nitrate of surface waters in FRB were unclear. Major ions, δ11B, δ15N, and δ18O in surface waters in dry season and wet season of FRB were analyzed and correlation analysis (CA), principal component analysis (PCA), self-organizing map (SOM), forward model, and Bayesian isotope mixing model (MixSIAR) were used to solve above problems. Results showed that average riverine δ11B, δ15N, and δ18O of FRB was 7.8‰, 11.2‰, and 1.3‰ (1SD), respectively. Dissolved solutes ranked midstream > downstream > upstream with water type of Na +-Cl-, Ca2+-Mg2+-Cl-, and Ca2+-HCO3-, respectively. Low dissolved solutes were in forest areas while high values were in cropland and city areas. SOM analysis indicated that hydrochemistry was both influenced by natural (upstream) and pollutional input (midstream and downstream) and variation between dry season and wet season was minor. The abnormally high boron concentrations were mainly from silicate weathering (43%) and evaporites dissolution of loess (32%), urban and industrial input contributed 15% of riverine boron. High SO42- (207 ± 267 mg/L, 1SD) was mainly from sulfates. δ15N and δ18O analysis indicated that nitrification was the primary N cycling process. Further, MixSIAR showed that NO3- was mainly from municipal sewage (∼67%) and the total contribution of chemical fertilizer and soil nitrogen was ∼30% with slightly higher values in upstream and wet season. Influenced by land-use types, evaporite dissolution, and anthropogenic input, water quality below midstream was worse and strict sewage reduction policies must be developed. This study highlights the significant influence of evaporite dissolution of loess and anthropogenic input (urban and industrial input for B and sewage for NO3-) on hydrochemistry and water quality.

Global warming-induced Asian hydrological climate transition across the Miocene-Pliocene boundary.

Across the Miocene-Pliocene boundary (MPB; 5.3 million years ago, Ma), late Miocene cooling gave way to the early-to-middle Pliocene Warm Period. This transition, across which atmospheric CO2 concentrations increased to levels similar to present, holds potential for deciphering regional climate responses in Asia-currently home to more than half of the world's population- to global climate change. Here we find that CO2-induced MPB warming both increased summer monsoon moisture transport over East Asia, and enhanced aridification over large parts of Central Asia by increasing evaporation, based on integration of our ~1-2-thousand-year (kyr) resolution summer monsoon records from the Chinese Loess Plateau aeolian red clay with existing terrestrial records, land-sea correlations, and climate model simulations. Our results offer palaeoclimate-based support for 'wet-gets-wetter and dry-gets-drier' projections of future regional hydroclimate responses to sustained anthropogenic forcing. Moreover, our high-resolution monsoon records reveal a dynamic response to eccentricity modulation of solar insolation, with predominant 405-kyr and ~100-kyr periodicities between 8.1 and 3.4 Ma.

Groundwater hydrochemistry, source identification and pollution assessment in intensive industrial areas, eastern Chinese loess plateau.

Groundwater is essential for regional ecological-economic system and is an important resource of drinking water, especially in the Chinese Loess Plateau (CLP), where is a typical water-limited ecosystem. Groundwater quality deterioration will affect water security and exacerbate the water shortages. Groundwater hydrochemistry, pollution source apportionment, quality and health risks were evaluated based on analysis of major ions and selected trace elements in seasonal samples of the Fen River Basin (FRB) in the eastern CLP. Groundwaters in the FRB were mainly HCO3--Ca2+-Na+ water type with low dissolved solutes in upstream samples, high values in midstream samples and medium values in downstream samples. Solutes in upstream samples were mainly derived from carbonate weathering, while those in midstream and downstream samples came from silicate weathering, evaporites dissolution and anthropogenic sources. Self-organizing map (SOM) showed the hydrochemistry remained unchanged from dry to wet season for most sampling points. The seasonal variations of Ag, Cd, Ni, Pb, and Tl were significant due to anthropogenic input. High NO3- in upstream and downstream samples resulted primarily from sewage discharge, and high SO42- in midstream and downstream samples was from gypsum- and coal-related industries. In addition, anthropogenic input related to coal industries significantly aggravates pollution of As, Ni, Ag, Fe, and Mn. Influenced by evaporites and anthropogenic input, midstream samples had high salinity, total hardness and water quality indices (WQIs) and were unsuitable for irrigation or drinking purposes. Seasonal variation of WQI in the FRB was unsignificant except Jiaokou River sub-basin, where groundwater quality was worse in the wet season than the dry season due to coal mining. Great attention should be paid to the high non-carcinogenic risks of exposure to F, V, Mn, and Cr via dermal absorption, particularly for children. Overall, groundwater quality in the FRB was best in upstream, medium in midstream and worst in midstream based on different index. Groundwater quality is deteriorated by anthropogenic input and the sewage discharge in the FRB should be strictly controlled. Our report provides a reference for groundwater pollution evaluation and source identification in similar areas.

Spatiotemporal variations, sources, water quality and health risk assessment of trace elements in the Fen River.

As the largest river in Shanxi Province, the Fen River is the main water source for regional economic and ecological development. Water deficiency and industrialization have led to serious water pollution in the Fen River. The major and trace elements of seasonal river waters were measured to determine the spatiotemporal variations and assess the water quality as well as its controlling factors in the Fen River. Trace elements are divided into high abundance elements (B, Ba, Li, and Mn) and low abundance elements (As, Cu, Fe, Ni, Rb, Se, U, and V). The spatial variation of trace elements is obvious, with low values upstream, intermediate values downstream, and very high values midstream. The average values of the trace elements showed different seasonal variations, with high values of As, B, Ba, Mn, and Rb in the wet season, high Cu, V, and Li values in the dry season, and minor seasonal variations of Fe, Ni, Se, and U concentrations. Principal component analysis (PCA) and correlation analysis (CA) showed natural origins of Ba, Mn, Ni, and U, anthropogenic input of As, B, Cu, Li, Rb, Se, and V. According to the results of absolute principal component sore-multivariate linear regression (APCS-MLR), the major pollution sources in the Fen River basin were related to human activities. The land use type significantly influenced the concentrations of trace elements, with high values in the cropland and low values in the forest. The water quality index (WQI) values were higher in the midstream and wet season. In comparison with other rivers in the world, the pollution of the Fen River is at a moderate level. Health risk assessment showed that As, Ba, Mn, Ni, V, and Se were the potential pollutants damaging in the Fen River, especially for children. This study highlights the importance of seasonal sample analysis and can provide vital data for water quality conservation in the Fen River basin.

Orbital climate variability on the northeastern Tibetan Plateau across the Eocene-Oligocene transition.

The first major build-up of Antarctic glaciation occurred in two consecutive stages across the Eocene-Oligocene transition (EOT): the EOT-1 cooling event at ~34.1-33.9 Ma and the Oi-1 glaciation event at ~33.8-33.6 Ma. Detailed orbital-scale terrestrial environmental responses to these events remain poorly known. Here we present magnetic and geochemical climate records from the northeastern Tibetan Plateau margin that are dated precisely from ~35.5 to 31 Ma by combined magneto- and astro-chronology. These records suggest a hydroclimate transition at ~33.7 Ma from eccentricity dominated cycles to oscillations paced by a combination of eccentricity, obliquity, and precession, and confirm that major Asian aridification and cooling occurred at Oi-1. We conclude that this terrestrial orbital response transition coincided with a similar transition in the marine benthic δ18O record for global ice volume and deep-sea temperature variations. The dramatic reorganization of the Asian climate system coincident with Oi-1 was, thus, a response to coeval atmospheric CO2 decline and continental-scale Antarctic glaciation.

Spatiotemporal trends of atmospheric Pb over the last century across inland China.

Sedimentary records from remote regions contain pollutants derived dominantly from atmospheric input, and thus have the potential to trace past atmospheric pollution history. Based on seventeen sediment records from relatively remote areas of China, atmospheric Pb pollution history during the last century was studied. These records suggest only occasionally slight pollution before ~1950 and display synchronous Pb enrichment processes since the 1950s, implying the start of widespread atmospheric Pb pollution in China. This corresponded well with the beginning of socio-economic development after the establishment of the People's Republic of China. However, owing to the Chinese Cultural Revolution, a roughly unchanged atmospheric Pb status was found in the 1960-70s except on the Qinghai-Tibetan Plateau, where atmospheric Pb still increased gradually caused by long-range atmospheric transport of pollutants from southwest Asia. In ~1980-2000, atmospheric Pb experienced the greatest increase, resulting from rapid development of extensive economy after the Reform and Opening-up in 1978. After ~2000, atmospheric Pb generally stopped increase due to the phasing out of leaded gasoline, but it remained high, with the highest in Southwest China, medium in Northeast China, central North China and the Qinghai-Tibetan Plateau, and the lowest in the southeast Mongolia Plateau and West China. This study reveals spatio-temporal variations of atmospheric Pb in inland China under the influence of recent human activities, providing an important supplement for understanding global Pb pollution in the Anthropocene.

Extreme weather events recorded by daily to hourly resolution biogeochemical proxies of marine giant clam shells.

Paleoclimate research has built a framework for Earth's climate changes over the past 65 million years or even longer. However, our knowledge of weather-timescale extreme events (WEEs, also named paleoweather), which usually occur over several days or hours, under different climate regimes is almost blank because current paleoclimatic records rarely provide information with temporal resolution shorter than monthly scale. Here we show that giant clam shells (Tridacna spp.) from the tropical western Pacific have clear daily growth bands, and several 2-y-long (from January 29, 2012 to December 9, 2013) daily to hourly resolution biological and geochemical records, including daily growth rate, hourly elements/Ca ratios, and fluorescence intensity, were obtained. We found that the pulsed changes of these ultra-high-resolution proxy records clearly matched with the typical instrumental WEEs, for example, tropical cyclones during the summer-autumn and cold surges during the winter. When a tropical cyclone passes through or approaches the sampling site, the growth rate of Tridacna shell decreases abruptly due to the bad weather. Meanwhile, enhanced vertical mixing brings nutrient-enriched subsurface water to the surface, resulting in a high Fe/Ca ratio and strong fluorescence intensity (induced by phytoplankton bloom) in the shell. Our results demonstrate that Tridacna shell has the potential to be used as an ultra-high-resolution archive for paleoweather reconstructions. The fossil shells living in different geological times can be built as a Geological Weather Station network to lengthen the modern instrumental data and investigate the WEEs under various climate conditions.

Quantifying the impact of recovery during chromatographic purification on the accuracy of lithium isotopic determination by multi-collector inductively coupled plasma mass spectrometry.

RATIONALE: Lithium (Li) isotopes have increasingly been applied as tracers in Earth and planetary sciences and their effectiveness relies upon accurate and precise Li isotopic data. Nowadays, multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) combined with chromatographic purification is the most common strategy for obtaining Li isotopic ratios in natural samples, with a long-term internal precision better than 0.3‰ in most laboratories. However, there is a large discrepancy in the Li isotopic compositions of the same reference materials determined by MC-ICP-MS among international laboratories (e.g. ca 3.5‰ difference for measurements of homogeneous seawater), which has been attributed to insufficient recovery of Li during chromatographic purification. Despite this recognition, the exact impact of Li recovery during purification on Li isotopic determinations by MC-ICP-MS has never been quantified. METHODS: We employed a normal distribution function to model Li elution curves and quantified the Li isotopic fractionation resulting from Li recovery during chromatographic purification. Furthermore, we compared the calculated and measured relative recovery (R) with the Li isotopic ratios determined by ICP-MS to validate our theoretical calculation. RESULTS: The theoretical calculations showed that R should be higher than 99.8% in order to avoid observable Li isotopic fractionation during chromatographic purification at IEECAS. This idea is further supported by the better long-term external precisions for data with R ≥ 99.8% compared with previous values of 99.5% ≤ R < 99.8%. Our results indicated that the large differences in the reported Li isotopic ratios for homogeneous seawater among international laboratories are probably attributable to Li isotopic fractionation occurring during ion exchange chromatography. CONCLUSIONS: Our theoretical calculation via R is the first quantitative and convenient approach for monitoring Li isotopic fractionation during sample purification, ensuring that R ≥ 99.8% can avoid observable Li isotopic fractionation during purification, which will improve the accuracy of Li isotopic measurements by MC-ICP-MS and the comparability among laboratories.

Monsoonal control on a delayed response of sedimentation to the 2008 Wenchuan earthquake.

Infrequent extreme events such as large earthquakes pose hazards and have lasting impacts on landscapes and biogeochemical cycles. Sediments provide valuable records of past events, but unambiguously identifying event deposits is challenging because of nonlinear sediment transport processes and poor age control. Here, we have been able to directly track the propagation of a tectonic signal into stratigraphy using reservoir sediments from before and after the 2008 Wenchuan earthquake. Cycles in magnetic susceptibility allow us to define a precise annual chronology and identify the timing and nature of the earthquake's sedimentary record. The grain size and Rb/Sr ratio of the sediments responded immediately to the earthquake. However, the changes were muted until 2 years after the event, when intense monsoonal runoff drove accumulation of coarser grains and lower Rb/Sr sediments. The delayed response provides insight into how climatic and tectonic agents interact to control sediment transfer and depositional processes.

One-century sediment records of heavy metal pollution on the southeast Mongolian Plateau: Implications for air pollution trend in China.

Historical records of heavy metals from remote areas are important for assessing temporal pollution trends of the regional atmosphere. Based on comparison analyses of heavy metals, Pb isotopes, and total carbon in sediment cores from two relatively remote lakes on the southeast Mongolian Plateau, atmospheric heavy metal pollution trends during ∼1900-2016 were reconstructed. The current anthropogenic fluxes of Zn, Cd and Pb in the region are 11.7, 0.104 and 2.44 mg m-2 yr-1, respectively, close to those in Lake Sayram in West China, but lower than most other records in China. Anthropogenic metal fluxes and 206Pb/207Pb ratios suggest that (1) before ∼1950 atmospheric metal pollution was negligible in the region; (2) since ∼1950, the pollution became detectable but was relatively slight until ∼1980, corresponded with the beginning of socio-economic development after the foundation of China in 1949 and the rapid development after the Reform and Opening-up in 1978; and (3) since ∼2000, atmospheric Pb stopped increasing because of the phasing out of leaded gasoline. Based on comparison and fitting analyses with other sediment records, a similar four-stage evolution picture of atmospheric heavy metals in China over the last century was uncovered. This study indicates rapid increase trends of atmospheric heavy metals in China since ∼1980 associated with economic development.

A validated analytical procedure for boron isotope analysis in plants by MC-ICP-MS.

Boron (B) is an essential micronutrient for plant growth. Lack of valid methods for pretreatment and measurement of δ11B in plant restrict applications of it in the biosphere. Dry ashing, one step cation exchange and micro-sublimation were combined to separate and purify boron (B) in plant tissues. The low procedure blank, high B recovery and the accurate δ11B values of the plant reference materials demonstrate that this method is suitable and valid for B pretreatment and δ11B measurement in plant samples by MC-ICP-MS. Based on this method, the δ11B in different plants (Brassica napus, Chenopodium album L, moss, lichen, and Nostoc commune) was analyzed. For Brassica napus, δ11B increased gradually from root to leaf, and then decreased to rapeseed. For the same parts, the δ11B increased from the lower parts to the higher parts. This variation may be due to the B(OH)3 transporter of NIP6;1 and the incorporation of B into the cell. The reason for lower δ11B values in shell and rapeseed compared to those in leaves presumably is to the preferred transport of borate in the phloem. The largest δ11B fractionation between leaf and root in Brassica napus and Chenopodium album L was + 24.2‰ and + 26.6‰, respectively. The large variation and fractionation of δ11B within plants indicates that δ11B is a good tracer to study the B translocation mechanisms and metabolism within plants. The δ11B in Nostoc commune, lichen, and moss showed variations of -4.1‰ to + 21.5‰, - 9.4‰ to + 7.3‰, and - 18.3‰ to + 11. 9‰, respectively. In the same site, δ11B in different plants ranked Nostoc commune>moss>lichen and δ11B in mosses growing in different environment ranked soil>tree>rock. Rain and soil available B are the main B sources for these plants. The δ11B in Nostoc commune, lichen, and moss may be a useful tracer to study the atmospheric B input. In the future, plants culture experiments under certain environments and studies from molecular level are necessary to decipher the variation of δ11B and fractionation mechanisms within plants.

Characteristics, sources, water quality and health risk assessment of trace elements in river water and well water in the Chinese Loess Plateau.

Water resources and water quality are restrictive factors in the Chinese Loess Plateau (CLP), a unique area with most severe soil erosion, fragile ecology and water shortage. River and well water samples were firstly analyzed, and multiple methods and indexes, including principal component analysis (PCA), correlation analysis (CA), sodium adsorption ratio (SAR), water quality index (WQI), hazard quotient (HQ), and hazard index (HI), were used to investigate characteristics, water quality and health risk assessment of trace elements in CLP. The average trace elements concentrations were higher than the world average with a slightly alkaline characteristic. PCA and CA showed that Al, Fe, Li, B, As, and F had natural origins from loess weathering and leaching; Cr, Pb, Cd, Cu, Ag, and Tl were mainly from anthropogenic input; Co, Ni, and Mn were dominated by both anthropogenic and natural sources. The poor river water quality was mainly related with high sodium (alkalinity) and salinity hazard. The poor well water quality samples with high WQI values, especially for As, Cr, and B, were distributed in the northwest and the Fenhe River sub-basin. The pollution level of trace elements in rivers in CLP was in medium level compared with other rivers worldwide. Arsenic pollution was the worst in well water and was the potential pollutant in river water especially for children. Arid climate together with anthropogenic input and special water characteristics (high Na, pH, and low Ca) aggravated As pollution. More work should be done to monitor the secular variation and remove As in the high As areas. The results of this study can provide the basic data for efficient water management and human health protection in CLP.