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Phosphorus (P) availability in soils controls critical functions and properties of terrestrial ecosystems. Vertical distribution patterns of P concentration and speciation in soil profiles provide historical records of how pedogenic processes redistribute and transform P and thus change its availability in soils, which, however, remain poorly understood. We determined the patterns in three forest soil profiles of contrasting climate, using fine sampling intervals, P K-edge X-ray absorption near edge (XANES) spectroscopy and chemical extractions. The major features of the patterns persist under the contrasting climate. The total P concentration decreases from A to B horizons, reaches a minimum in the B horizons, and then increases towards the upper C horizons, but with little variations with depth in the lower C horizons. Both calcium-bound inorganic P (Ca–Pi) and organic P (Po) decrease and Fe- and Al-bound Pi [(Fe + Al)–Pi] increases in proportion downward in the A horizons because dust inputs and accumulation of organic matter both decline with increasing depth. Ca–Pi is negligible and (Fe + Al)–Pi is dominant in the B horizons due to strong weathering. There is a strong downward increase in Ca–Pi proportion and decrease in (Fe + Al)–Pi proportion from the lower B to the upper C horizons. New Ca–Pi seems to form in the upper C horizons where downward leaching Ca2+ and phosphate accumulate due to the low water permeability of the soils. In the lower C horizons, Ca–Pi increases and (Fe + Al)–Pi decreases with increasing depth due to decreasing chemical weathering. Regarding P bioavailability, the proportion of occluded P (Pocc) shows an increasing and decreasing trend with increasing depth, being the highest in the B horizons; however, there are no consistent trends for non-occluded P (Pn-occ). While the P vertical patterns can be understood by considering the relative importance of different pedogenic processes, climate affects the intensities of these processes and thus the details of the patterns. When depth-integrated, warmer/wetter climate results in decreases in the proportions of both Ca–Pi and Pn-occ but increases in the P loss and the proportions of Po, (Fe + Al)–Pi, and Pocc. Regardless of soil depth and climate, the Pi speciation, i.e., the relative proportions of Ca–Pi and (Fe + Al)–Pi over total Pi, correlates well with soil pH and weathering degree (Chemical Index of Alteration, CIA), and the Po concentration correlates with pedogenic Fe and Al and organic carbon concentration. The correlations suggest that the Pi speciation is primarily controlled by soil geochemistry/mineralogy, and the Po concentration by both soil geochemistry/mineralogy and biological activities. Pocc correlates with CIA, and thus is mainly controlled by soil mineralogy; but Pn-occ correlates weakly with soil properties, probably due to its susceptibility to combined influences of dust inputs, leaching, biological activities, and adsorption on minerals. The above quantitative relationships may help predict P speciation and availability in diverse soils. We further show that soil profiles, and climate and CIA gradients are useful tools for studying P transformations, particularly for the Pi pool, during pedogenesis. This study provides an integration and synthesis of controls of climatic and edaphic variables on P dynamics in forest soils.

Snow serves as a vital scavenging mechanism to gas-phase and particle-phase organic nitrogen substances in the atmosphere, providing a significant link between land-atmosphere flux of nitrogen in the surface-earth system. Here, we used optical instruments (UV-vis and excitation-emission matrix fluorescence) and a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) to elucidate the molecular composition and potential precursors of snow samples collected simultaneously at four megacities in North China. The elemental O/N ratio (≥3), together with the preference in the negative ionization mode, indicates that the one and two nitrogen atom-containing organics (CHON1 and CHON2) in snow were largely in the oxidized form (as organic nitrates, -ONO2). This study assumed that scavenging of particle-phase and gas-phase organic nitrates might be significant sources of CHON in precipitation. A gas-phase oxidation process and a particle-phase hydrolysis process, at a molecular level, were used to trace the potential precursors of CHON. Results show that more than half of the snow CHON molecules may be related to the oxidized and hydrolyzed processes of atmospheric organics. Potential formation processes of atmospheric organics on a molecular level provide a new concept to better understand the sources and scavenging mechanisms of organic nitrogen species in the atmosphere.

This study investigated the effects of different elevated CO2 concentrations [ambient CO2 concentration (CK), CK plus 40 μmol mol-1 (T1), CK plus 200 μmol mol-1 (T2)] on photosynthetic characteristics and growth of rice (Oryza sativa L.) and winter wheat (Triticum aestivum L.). The results showed that T2 treatment decreased the net photosynthetic rate and leaf nitrogen content (LNC) but increased the light-saturated net photosynthetic rate of rice. Additionally, T2 treatment increased biomass accumulation and yield in both rice and winter wheat to some extent. T1 treatment, however, had little effect on photosynthetic parameters, LNC, biomass, and yield during the rice and winter wheat growing seasons. The above results suggest that the photosynthesis and growth responses of rice and winter wheat to different CO2 concentrations differed, in general, the increase of CO2 concentrations influenced more photosynthetic performance and growth of C3 plants than lower CO2 concentrations.

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Nitrate (NO3−) is a key component of secondary inorganic aerosols and PM2.5. However, the contributions of nitrogen oxides (NOx) emission sources to NO3− in PM2.5 remain poorly constrained. This study measured nitrogen (N) isotopes of NO3− (hereafter as δ15N-NO3-) in PM2.5 collected at Beijing in 2014. We observed that δ15N-NO3- values in PM2.5 (−2.3‰ − 19.7‰; 7.3 ± 5.4‰ annually) were significantly higher in winter (11.9 ± 4.4‰) than in summer (2.2 ± 2.5‰). The δ15N differences between source NOx and NO3− in PM2.5 (hereafter as Δ values) were estimated by a computation module as 7.8 ± 2.2‰ − 10.4 ± 1.6‰ (8.8 ± 2.4‰). Using the Δ values and δ15N values of NOx from major fossil (coal combustion, vehicle exhausts) and non-fossil sources (biomass burning, microbial N cycle), contributions of major NOx sources to NO3− in PM2.5 were further estimated by the SIAR model. We found that seasonal variations of δ15N-NO3- values in PM2.5 of Beijing were mainly caused by those of NOx contributions from coal combustion (38 ± 10% in winter, 20 ± 9% in summer). Annually, NOx from coal combustion, vehicle exhausts, biomass burning, and microbial N cycle contributed 28 ± 12%, 29 ± 17%, 27 ± 15%, and 16 ± 7% to NO3− in PM2.5, respectively, showing actually comparable contributions between non-fossil NOx (43 ± 16%) and fossil NOx (57 ± 21%). These results are useful for planning the reduction of NOx emissions in city environments and for elucidating relationships between regional NOx emissions and atmospheric NO3− pollution or deposition.

Accurately quantifying the budget of carbon sources and sinks in hydropower reservoirs is important for evaluating the cleanliness of hydroelectricity. However, current research on carbon emissions from reservoirs has rarely taken into account the organic carbon (OC) buried in sediment. Only greenhouse gas emissions from the water-air interface at reservoirs have been examined, which would result in an overestimation of the greenhouse effect of reservoirs. In November 2017, this study investigated the distribution of sediment in the Hongfeng Reservoir (HFR) in southwest China, a typical large hydropower reservoir, by using an underwater seismology monitoring system. We estimated the flux of OC into sediment using the results of a sediment survey and a dataset compiled from references. Our results show that, the HFR retained 200,715 t of OC in the sediment since its impounding after dam construction to the sampling year of 2017, when the average burial flux was 3,521 t-C a−1 (106 g C a−1) and the modern burial flux was 5,449 t-C a−1. After excluding the exogenous OC, the modern valid carbon sink of the sediment was 4,632 t per year. Under the current state of the reservoir, taking the modern valid carbon sink value, the carbon emissions from the reservoirs surface, and the discharge water from the dam into consideration, the net carbon sink of the HFR is found to be 1,098.9 t-C a−1. If the hydroelectricity generated by the reservoir is converted to a carbon sink, then the total net carbon sink becomes 12,972.9 t-C a−1. This work argues that both reservoir sediment and hydroelectricity are important carbon sinks and both should be included in assessments of the greenhouse effects of reservoirs.

Accurate determination of lithium (Li)isotopic composition in natural geological samples is the basis for Li isotope geochemical studies. In this study, a method contained preparation of geological materials (water and rock) and accurate determination of Li isotopic composition was set up. The separation of Li from water and rock samples was implemented by a single column containing 1.5 mL of Bio-Rad AG 50W-X12 (200–400 mesh) resin, with 0.40 M HCl and 1.0 M HCl as eluents. Only 8.5 and 14 mL of eluents were used to separate Li from water and rock samples with this method, respectively. Blank signal of the operation procedure was (2.4 ± 0.1) mV, which was almost same as the 2.3 mV of the 2% HNO3 signal used in this study. Experimental results showed that Li isotopic fractionation during leaching process was significant and deviation of δ7Li values in these samples with incompletely recovered Li reached up to 50‰. Lithium isotopic ratios were determined by multi-collector ICP-MS (Nu Plasma II) using the sample standard bracketing (SSB) method. L-SVEC standard with similar Li concentration to samples (about 80 ng mL−1) was used in this study. The external precision (2σ) of this technique, determined by repeated measurement of pure Li standard solutions and seawater was

Total carbon content of the atmospheric suspended particulate matters consisted of as high as 89-93% organic carbon (OC) in Ulaanbaatar aerosol without showing seasonal variation. However, limited aerosol measurements have been conducted on these OC rich aerosols particularly for high molecular weight constituents. In order to address the gap above, abundance of high molecular weight humic-like substances (HULIS) in total suspended particulates (TSP) from Ulaanbaatar atmospheric aerosol were determined for the first time. HULIS molecular structure was characterised for different seasons using carbon content and UV absorbance measurements coupled with solid phase extraction methods. Although, HULIS contributions to water soluble organic fraction of the winter and summer aerosols were similar HULIS carbon concentration was higher in winter samples (9-37 mg·L-1) than in summer (2-6 mg·L-1). Consequently quantity of aromatic moieties and degree of aromaticity varied between seasons.

The terrestrial biogeochemical silicon (Si) cycle may significantly influence the stabilization of soil organic carbon (SOC), and thus plays an important role in regulating the global carbon (C) balance and climate change. Processes involved in Si-enhanced SOC stability at a decadal or centennial scale include protection of SOC through amorphous Si and interactions of Si-iron and Si-aluminum. Strategic manipulation of the Si cycle in terrestrial ecosystems offers a new opportunity to enhance soil C sequestration. Rock powder amendment, establishment of Si-rich plant buffer strips and innovative management practices that return Si-rich biomass materials to soil can be implemented as strategies to enhance soil C sequestration through regulating the terrestrial Si cycle. However, quantifying (i) the contribution of different processes to the enhancement of soil dissolved Si and secondary Si minerals, (ii) the relative importance of different SOC stabilization mechanisms, and (iii) the potential and cost of different measures has not been attempted.

The feedbacks of climate variability on CO2 consumption fluxes and carbon dynamics are thought to play an important role in moderating the global carbon cycle. High-frequency sampling campaigns and analyses were conducted in this study to investigate temporal variations of river water chemistry and the impacts of climate variability on CO2 consumption fluxes and carbon dynamics for the Xijiang River, Southwest China. Physical processes modify biogeochemical processes, so major ions display different responses to changing discharge. The annual CO2 consumption rate is (6.8 +/- 0.2) x 10(6) ton/year by carbonate weathering and (2.4 +/- 0.3) x 10(6) ton/year by silicate weathering. The annual CO2 consumption flux is much higher than most world rivers, and strong CO2 consumption capacities are observed in catchments in Southwest China. Lower negative delta C-13(DIC) values are found in the high-flow season which corresponds with high temperatures compared to those in the low-flow season. High discharge will accelerate material transport, and high temperatures will increase primary production in the catchment, both of which can be responsible for the shift of delta C-13(DIC) values in the high-flow season. Increased mineral weathering and biological carbon influx in the catchment are the main factors controlling carbon dynamics. Overall, these findings highlight the sensitivity of CO2 consumption fluxes and carbon dynamics in response to climate variability in the riverine systems. Plain Language Summary There are feedbacks between climate variability and CO2 consumption fluxes by chemical weathering and carbon dynamics. Significant temporal variations of major ions and delta C-13(DIC) are observed in the Xijiang River. Multiple biogeochemical processes occur under various hydrological conditions, shifting major ions concentrations, and delta C-13(DIC). The annual CO2 consumption rate is (6.8 +/- 0.2) x 10(6) ton/year by carbonate weathering and (2.4 +/- 0.3) x 10(6) ton/year by silicate weathering. The annual CO2 consumption rates in the Xijiang River only account for a small fraction in the global CO2 consumption rates; the CO2 consumption capacity is much higher than the global average, while much lower than its source tributaries (Beipan and Nanpan Rivers). Slow subsurface flow paths with longer transit times switch to rapid near-surface flow paths with shorter transit times, as discharge increases. High temperatures increase reaction rates, and high discharge rates remove transport limitation, both of which would accelerate the chemical weathering rates. In the high-flow season, high discharge accompanying with high temperatures, large amounts of delta C-13-depleted biological carbon, flushes into the river, affecting the carbon dynamics.

High arsenic groundwater generally coexists with elevated Fe2+ concentrations (mg L−1 levels) under reducing conditions, but an explanation for the extremely high arsenic (up to ∼2690) concentrations at very low Fe2+ (i.e., μg L−1 levels) in groundwater of Datong Basin remains elusive. Field groundwater investigation and laboratory microcosm experiments were implemented in this study. The field groundwater was characterized by weakly alkaline (pH 7.69 to 8.34) and reducing conditions (Eh −221.7 to −31.9 mV) and arsenic concentration averages at 697 μg L−1. Acinetobacter (5.9–51.3%), Desulfosporosinus (4.6–30.2%), Brevundimonas (3.9–19%) and Pseudomonas (3.2–14.6%) were identified as the dominant genera in the bacterial communities. Bacterially mediated arsenate reduction, Fe(III) reduction, and sulfate reduction are processes occurring (or having previously occurred) in the groundwater. Results from incubation experiment (27 d) revealed that nitrate, arsenate, and Fe(III)/sulfate reduced sequentially with time under anoxic conditions, while Fe(III) and sulfate reduction processes had no obvious differences, occurring almost simultaneously. Moreover, low Fe2+ concentrations were attributed to initially high pH conditions, which relatively retarded Fe(III) reduction. In addition, arsenic behavior in relation to groundwater redox conditions, matrices, and solution chemistry were elaborated. Bacterial arsenate reduction process proceeded before Fe(III) and sulfate reduction in the incubation experiment, and the total arsenic concentration (dominated by arsenite) gradually increased from ∼7 to 115 μg L−1 as arsenate was reduced. Accordingly, bacterially mediated reductive desorption of arsenate is identified as the main process controlling arsenic mobility, while Fe(III) reduction coupled with sulfate reduction are secondary processes that have also contributed to arsenic enrichment in the study site. Overall, this study provide important insights into the mechanism controlling arsenic mobility under weakly alkaline and reducing conditions, and furnishes that arsenate reduction by bacteria play a major role leading to high accumulation of desorbed arsenite in groundwater.

The δ15N of nitrate (NO3−) and particulate organic nitrogen (PON) was used to study the sources and fate of nitrogen in the impounded Maotiao River, southwest China. During months when the reservoi...

To understand the origins, secondary formation and seasonality of carbonaceous aerosols in North China, we collected PM2.5 samples on day- and night-time bases in summer and winter 2016 from a typical metropolis, Tianjin, and studied their carbonaceous components and stable carbon isotope ratios of total carbon (δ13CTC). PM2.5 ranged from 21.2 μg m−3 to 74.8 μg m−3 in summer and 25.3–816 μg m−3 in winter. On average, organic carbon (OC) elemental carbon (EC) and water-soluble OC were found to be higher (3–5 times) in winter than that in summer. Secondary organic carbon that estimated by EC-tracer method was enhanced by a factor of 7 in winter compared to that in summer. δ13CTC showed a small enrichment of 13C (average −25.41 ± 0.34‰) in summer compared to that (−24.42 ± 0.44‰) in winter. Linear relations and mass ratios of selected carbonaceous components and δ13CTC imply that the carbonaceous aerosols in Tianjin were mainly derived from biomass burning emissions and photochemical processing in summer. In winter, coal combustion emissions and in situ secondary formation of organics, including water-insoluble OC (WIOC), were dominant. This study warrants a need to understand the formation mechanisms of WIOC in the urban atmosphere and thus to reconcile the atmospheric models.

Rivers play an important role in global water and carbon cycling, but there are still large uncertainties concerning evaporation and aquatic photosynthesis. Here we combined measurements of water chemistry, isotopic compositions (i.e., δ D w , δ 18 O w , δ 13 C DIC and ▵ 14 C DIC ) and geographic characteristics (i.e., river width) to elucidate in-stream hydrological and biogeochemical processes across rivers in Hainan Island, China. The results showed that dissolved inorganic carbon (DIC) in river waters was largely of modern origin, with about 95% from contemporary biogenic sources based on an isotopic mass balance of ▵ 14 C DIC . Significant evaporation and aquatic primary production co-occurred in these tropical rivers with large amounts of water and DIC being rapidly turned over in the water column, altering the water cycle and the carbon balance. High rates of evaporation and aquatic primary production were observed in the headwater segments, with narrow river width but broad available reactive surface area at the air-water interface. The asymmetric aquatic photosynthesis at different river segments caused the spatial heterogeneities of dissolved solutes. The results suggest that the available reactive area at the water-air interface is responsible for synchronous water loss and dissolved carbon evolution in flat tropical rivers. This study provides evidence that intense evaporation and aquatic photosynthesis mainly occurred in headwater segments, which has implications for understanding global carbon cycling.

To constrain sources of anthropogenic nitrogen (N) deposition is critical for effective reduction of reactive N emissions and better evaluation of N deposition effects. This study measured δ15N signatures of nitrate (NO3−), ammonium (NH4+) and total dissolved N (TDN) in precipitation at Guiyang, southwestern China and estimated contributions of dominant N sources using a Bayesian isotope mixing model. For NO3−, the contribution of non-fossil N oxides (NOx, mainly from biomass burning (24 ± 12%) and microbial N cycle (26 ± 5%)) equals that of fossil NOx, to which vehicle exhausts (31 ± 19%) contributed more than coal combustion (19 ± 9%). For NH4+, ammonia (NH3) from volatilization sources (mainly animal wastes (22 ± 12%) and fertilizers (22 ± 10%)) contributed less than NH3 from combustion sources (mainly biomass burning (17 ± 8%), vehicle exhausts (19 ± 11%) and coal combustions (19 ± 12%)). Dissolved organic N (DON) accounted for 41% in precipitation TDN deposition during the study period. Precipitation DON had higher δ15N values in cooler months (13.1‰) than in warmer months (−7.0‰), indicating the dominance of primary and secondary ON sources, respectively. These results newly underscored the importance of non-fossil NOx, fossil NH3 and organic N in precipitation N inputs of urban environments.

Carbon stable isotope techniques were extensively employed to trace the dynamics of soil organic carbon (SOC) across a land-use change involving a shift to vegetation with different photosynthetic pathways. Based on the isotopic mass balance equation, relative contributions of new versus old SOC, and SOC turnover rate in corn fields were evaluated world-wide. However, most previous research had not analyzed corn debris left in the field, instead using an average corn plant δ 13C value or a measured value to calculate the proportion of corn-derived SOC, either of which could bias results. This paper carried out a detailed analysis of isotopic fractionation in corn plants and deduced the maximum possible bias of SOC dynamics study. The results show approximately 3‰ isotopic fractionation from top to bottom of the corn leaf. The 13C enrichment sequence in corn plant was tassel > stalk or cob > root > leaves. Individual parts accounting for the total dry mass of corn returned distinct values. Consequently, the average δ 13C value of corn does not represent the actual isotopic composition of corn debris. Furthermore, we deduced that the greater the fractionation in corn plant, the greater the possible bias. To alleviate bias of SOC dynamics study, we suggest two measures: analyze isotopic compositions and proportions of each part of the corn and determine which parts of the corn plant are left in the field and incorporated into SOC.

Carbon-climate feedback is sensitive in the Qinghai-Tibet Plateau. A series of temporal measurements from Jinsha River and Yalong River, in conjunction with flow information, were used to study the carbon dynamics and predict future carbon fluxes under ongoing climate change. DIC and DOC concentrations showed considerable temporal variations, with low DIC and high DOC concentrations in the high-flow season, and vice versa. DIC and DOC concentrations had negative and positive relationships with runoff changes, respectively, showing the hydro-biogeochemical controls on carbon dynamics. With the increase of runoff, the accelerated chemical weathering and the high carbonate buffering capacity should be responsible for the chemostatic behaviors of DIC. Meanwhile, warm weather would enhance organic carbon degradation, and also thicken the active layer of permafrost in the source area, both of which would produce DOC. In addition, organic carbon degradation in the high-flow season would produce DIC with 13C-depleted values. δ13CDIC also had significant temporal variations, synchronous with runoff changes (i.e., light values under high runoff conditions), supporting that biological carbon plays an important role in carbon dynamics during the warm season. Based on the clear positive correlations between carbon fluxes and runoff, we predicted that the sensitivities of DOC fluxes to temperature changes are 12.2%/°C and 8.3%/°C for the Jinsha River and Yalong River, respectively. The sensitivities of DIC fluxes to temperature changes are much lower, which are 5.5%/°C and 6.1%/°C for the Jinsha River and Yalong River, respectively. This study sheds lights on the alpine riverine carbon cycling based on runoff-shifting concentration-isotope (q-C-I) relationships in the Qinghai-Tibet Plateau, which has implications on the understanding of climate forcing on carbon fluxes in alpine areas.

Carbon dioxide (CO2) emissions from aquatic surface to the atmosphere has been recognized as a significant factor contributing to the global carbon budget and environmental change. The influence of river damming on the CO2emissions from reservoirs remains poorly constrained. This is hypothetically due to the change of hydraulic retention time (HRT) and thermal stratification intensity of reservoirs (related to the normal water level, NWL). To test this hypothesis, we quantified CO2fluxes and related parameters in eight karst reservoirs on the Wujiang River, Southwest China. Our results showed that there was a significant difference in the values ofpCO2(mean = 3205.7μatm, SD = 2183.4μatm) andδ13CCO2(mean = −18.9‰, SD = 1.6‰) in the cascade reservoirs, suggesting that multiple processes regulate CO2production. Moreover, the calculated CO2fluxes showed obvious spatiotemporal variations, ranging from −9.0 to 2269.3 mmol m−2d−1, with an average of 260.1 mmol m−2d−1. Interestingly, the CO2flux andδ13CCO2from reservoirs of this study and other reservoirs around the world had an exponential function with the reservoir effect index (Ri, HRT/NWL), suggesting the viability of our hypothesis on reservoir CO2emission. This empirical function will help to estimate CO2emissions from global reservoirs and provide theoretical support for reservoir regulation to mitigate carbon emission.

High levels of dissolved arsenic (As) have been reported in many rivers running though the Tibetan Plateau (TP), the “Water Tower of Asia”. However, the source, spatiotemporal variations, and geochemical behavior of dissolved As in these rivers remain poorly understood. In this study, hot spring, river water, and suspended particulate material samples collected from the Yarlung Tsangpo River (YTR) (upper reaches of the Brahmaputra River) system in 2017 and 2018 were analyzed. Spatial results shown that the upper reaches of YTR (Zone I) have comparatively high levels of dissolved As ([As]dissolved: mean 31.7 μg/L; 4.7–81.6 μg/L; n = 16), while the tributaries of the lower reaches (Zone II) have relatively low levels (mean 0.54 μg/L; 0.11–1.3 μg/L; n = 7). Seasonal results shown that the high [As]dissolved (6.1–22.4 μg/L) were found in September to June and low [As]dissolved (1.4–3.7 μg/L) were observed in July to August. Geothermal water is suspected as the main source of the elevated As levels in YTR due to the extremely high [As]dissolved in hot springs (1.13–9.76 mg/L) and abundance of geothermal systems throughout TP. However, the seasonal results suggested that weathering of As-containing rocks and minerals is also a key factor affecting the [As]dissolved in the river water in July to August (wet-season). Natural attenuation of As in main channel is dominated by dilution process due to the lower As concentrations in tributaries, but mostly occurred by both dilution and adsorption (or co-precipitation) processes in tributaries. This work highlights that the weathering process may have an important contribution to the dissolved As in the river waters in wet-season, and the geochemical behavior of As is largely transported conservatively in the main channel and relative non-conservatively in the tributaries in YTR system.

Air pollution by particulate matter is a serious problem in Beijing. Strict pollution control measures have been carried out in Beijing prior to and during the 2015 China Victory Day Parade in order to improve air quality. This distinct event provides an excellent opportunity for investigating the impact of such measures on the chemical properties of particulate matter with an aerodynamic diameter ≤2.5 μm (PM 2.5 ). The water-soluble ions as well as sulfur and oxygen isotopes of sulfate in PM 2.5 collected between August 19 and September 18, 2015 (n = 31) were analyzed in order to trace the sources and formation processes of PM 2.5 in Beijing. The results exhibit a decrease in concentration of water-soluble ions in PM 2.5 including aerosol sulfate. In contrast, the mean values of δ 34 S sulfate (4.7 ± 0.8‰ vs. 5.0 ± 2.0‰) and δ 18 O sulfate (18.3 ± 2.3‰ vs. 17.2 ± 6.0) in PM 2.5 during the air pollution control period and the non-source control period exhibit no significant differences, which suggests that despite a reduction in concentration, the sulfate source remains identical for the two periods. It is inferred that the decrease in concentration of sulfate in PM 2.5 mainly results from variations in air mass transport. Notably, the air mass during the pollution control period originated mainly from north and northeast and changed to southerly directions thereafter. The sulfur and oxygen isotopes of the sulfate point to coal combustion as the major source of sulfate in PM 2.5 from the Beijing area.

Application of bioleaching process for metal recovery from electronic waste has received an increasing attention in recent years. In this work, a column bioleaching of copper from waste printed circuit boards (WPCBs) by Acidithiobacillus ferrooxidans has been investigated. After column bioleaching for 28d, the copper recovery reached at 94.8% from the starting materials contained 24.8% copper. Additionally, the concentration of Fe(3+) concentration varied significantly during bioleaching, which inevitably will influence the Cu oxidation, thus bioleaching process. Thus the variation in Fe(3+) concentration should be taken into consideration in the conventional kinetic models of bioleaching process. Experimental results show that the rate of copper dissolution is controlled by external diffusion rather than internal one because of the iron hydrolysis and formation of jarosite precipitates at the surface of the material. The kinetics of column bioleaching WPCBs remains unchanged because the size and morphology of precipitates are unaffected by maintaining the pH of solution at 2.25 level. In bioleaching process, the formation of jarosite precipitate can be prevented by adding dilute sulfuric acid and maintaining an acidic condition of the leaching medium. In such way, the Fe(2)(+)-Fe(3+) cycle process can kept going and create a favorable condition for Cu bioleaching. Our experimental results show that column Cu bioleaching from WPCBs by A. ferrooxidans is promising.

Understanding where nitrate is mobilized from and under what conditions is required to reduce nitrate loss and protect water quality. Low frequency sampling may inadequately capture hydrological and biogeochemical processes that will influence nitrate behavior. We used high-frequency isotope sampling and in-situ nitrate sensing to explore nitrate export and transformation in a karst critical zone. Nitrate was mobilised during light rainfall, and transferred from soil layers to the karst matrix, where some nitrate was retained and denitrified. Nitrate isotopic composition changed rapidly during the rising limb of events and slowly during the falling limb. The main nitrate source was synthetic fertiliser (up to 80% during event flow), transported by conduit flow following high rainfall events, and this contribution increased significantly as discharge increased. Soil organic nitrogen contribution remained constant indicating at baseflow this is the primary source. Isotope source appointment of nitrate export revealed that synthetic fertilizer accounted for more than half of the total nitrate export, which is double that of the secondary source (soil organic nitrogen), providing valuable information to inform catchment management to reduce nitrate losses and fluvial loading. Careful land management and fertilizer use are necessary to avoid nitrate pollution in the karst agroecosystem, for example by timing fertilizer applications to allow for plant uptake of nitrate before rainfall can flush it from the soils into the karst and ultimately into catchment drainage.

n-Alkanes and fatty acids are important molecular markers for the source apportionment of organic matter in the atmosphere. Traditional approaches to date have mostly relied upon the source-specific differences in their molecular distributions and carbon preference index. Alternatively, we demonstrate here the use of stable carbon and radiocarbon isotopic composition (δ 13C and Δ14C, respectively) of n-alkanes and n-fatty acids in aerosols from two urban receptor sites (Beijing and Tianjin) in Northeast China to assess their sources in autumn. The Δ14C n -alkanes of C19–C24 and C26–C32 even-carbon homologs (−851 to −708‰) indicate their dominance from fossil fuel combustion. In contrast, the Δ14C of most abundant palmitic acid (C16:0) and stearic acid (C18:0) suggest a larger contribution from nonfossil sources (~91%–94%), mainly due to inputs from cooking, biomass burning and microorganisms. Compared with lower Δ14C of C27 and C31 n-alkanes (−449‰), C29 n-alkane (−241‰) and C20–C30 n-fatty acids (−263‰) showed more contemporary likely due to significant contribution from plant litter and biomass burning that contain more fresh biogenic material. Fossil character of C27–C31 n-alkanes (40%) and C20–C30 n-fatty acids (30%) could be from soil resuspension and/or loess deposits in upwind regions through long-range atmospheric transport., Environmental Research Letters, 15 (7), ISSN:1748-9326, ISSN:1748-9318

The effect of dams on dissolved inorganic carbon (DIC) transport and riverine ecosystems is unclear in karst cascade reservoirs. Here, we analyzed water samples from a karst river system with seven cascade reservoirs along the Wujiang River, southwestern China, during one hydrological year. From upstream to downstream, the average concentration of DIC increased from 2.2 to 2.6 mmol/L and its carbon isotope composition (δ13CDIC) decreased from −8.0 to −10‰. Meanwhile, the air temperature (Ta) increased from 20.3 °C to 26.7 °C and 10 °C to 13.7 °C in the warm and cold seasons, respectively. The results suggest that a cascade of dams has a stronger effect on DIC dynamics and retention than a single dam. The good correlation between Ta/HRT (hydraulic retention time) and Δ[DIC] as well as Δ[δ13CDIC] mean that Ta and HRT affected the magnitude of the damming effect by altering changes in concentration of DIC and δ13CDIC in the reservoir compared to the inflowing water. In particular, daily regulated reservoirs with short retention times acted more like river corridors and had a smaller effect on carbon dynamics, so modulating retention time might be used reduce the effect of dams on the riverine ecosystem.

Experiments involving boron incorporation into brucite (Mg(OH)2) from magnesium-free artificial seawater with pH values ranging from 9.5 to 13.0 were carried out to better understand the incorporation behavior of boron into brucite and the influence of it on Mg/Ca-SST proxy and δ11B-pH proxy. The results show that both the concentration of boron in deposited brucite ([B]d) and its boron partition coefficient (Kd) between deposited brucite and final seawater are controlled by the pH of the solution. The incorporation capacity of boron into brucite is almost the same as that into corals, but much stronger than that into oxides and clay minerals. The isotopic compositions of boron in deposited brucite (δ11Bd) are higher than those in the associated artificial seawater (δ11Bisw) with fractionation factors ranging between 1.0177 and 1.0569, resulting from the preferential incorporation of B(OH)3 into brucite. Both boron adsorptions onto brucite and the precipitation reaction of H3BO3 with brucite exist during deposition of brucite from artificial seawater. The simultaneous occurrence of both processes determines the boron concentration and isotopic fractionation of brucite. The isotopic fractionation behaviors and mechanisms of boron incorporated into brucite are different from those into corals. The existence of brucite in corals can affect the δ11B and Mg/Ca in corals and influences the Mg/Ca-SST proxy and δ11B-pH proxy negatively. The relationship between δ11B and Mg/Ca in corals can be used to judge the existence of brucite in corals, which should provide a reliable method for better use of δ11B and Mg/Ca in corals to reconstruct paleo-marine environment.

It is generally difficult to measure atmospheric gaseous ammonia concentration and to identify its sources by isotopic technique due to the isotopic fractionation after it enters the atmosphere. In this study, Rayleigh model was successfully used to quantify atmospheric concentration and isotopic composition of gaseous ammonia based on sampling of 20 rain events from October 1st, 2008 to September 30, 2009 in Guiyang, southwest China. The estimated gaseous ammonia concentration was 25.7 ± 36.3 μg/m 3 and estimated isotopic composition was − 16.8 ± 4.9‰ in Guiyang. The study also showed that estimated enrichment factor was + 10.4 ± 4.3‰, inferring that large nitrogen isotopic fractionation occurred during exchange reactions in most of the rain events. The atmospheric ammonium deposition was further estimated to be 38.1 kg/ha/year. However, there is no validation for the approach from an actual gas phase NH 3 measurement to examine the model in this study.

Biological dissimilatory reduction of selenite (SeO32−) to elemental selenium (Se0) is common, but the mineral formation and the biogenic process remain uncertain. In this study, we examined the Se0 formation during the selenite bioreduction by Bacillus licheniformis SeRB-1 through transmission electron microscope (TEM), energy-dispersive spectrometry (EDS) and X-ray absorption fine structure (XAFS) techniques. Results showed that the reduction process occurred mostly during the exponential phase and early stationary phase, whilst the elemental selenium was produced in these periods. From the TEM images and polyacrylamide gel electropheresis, it is known that the Se0 granule formation is a biologically-induced type, and the cell envelopes are the main biomineralization positions, and particles may go through a process from nucleation to crystallization, under the control of microbes. In fact, the minerals are spherical nanoparticles, occurring as a microcrystal or amorphous form. It is vital to recognize which kinds of proteins and/or polysaccharides act as a template to direct nanoparticle nucleation and growth? This should focus for further studies. This study may shed light on the process of formation of Se(0) nanosphere.

The analysis of stable isotopes of sulfur (δ34S) is a useful tool for identifying sources of sulfur in soils. Concentrations and sulfur (S) isotopes of water-soluble sulfate (WSS), adsorbed sulfate (AS), residual sulfur (RS), and total sulfur (TS) in uncultivated surface soils of four Chinese provinces were systematically analyzed for identifying sources of S in the soils. Green and healthy mosses (Haplocladium microphyllum) were sampled as bioindicators. The mean WSS concentration (27.8 ± 23.4 mg kg−1) in the surface soils was lower than those of AS (101.4 ± 57.0 mg kg−1) and RS (381.5 ± 256.7 mg kg−1). The mean δ34S values of WSS and AS were very similar (about 2.0%), lower than those of RS (8.0%) and TS (6.1%). A significant linear correlation was found between the δ34S values of AS and WWS (y = 1.0002x – 0.0557, P < 0.0001), indicating that sulfate adsorption in the soils did not markedly fractionate S. All S species in the soils of Guizhou Province were characterized by the lowest δ34S values, consistent with the most 34S-depleted rainwater sulfate reported at Guiyang of Guizhou Province. The δ34S values of sulfate in mosses and rainwater previously reported were significantly linearly correlated with those of both WWS and AS in surface soils, suggesting that atmospheric S input was an important source for soil WSS and AS. However, there were no significant correlations between isotopic composition of rainwater sulfate and RS or TS. The slopes of all these significant linear correlations (soil/rainwater or soil/moss isotopic ratio) were 0.4–0.6, indicating that inorganic sulfate in the surface soils should be a result of mixing of deposited atmospheric sulfate with a more 34S-depleted sulfate component possibly from mineralization of RS.

A heavy load of nitrogenous compounds reflects nutrient loss and influences water quality in large rivers. Nitrogenous concentrations and dual isotopes of nitrate were measured to ascertain the spatial and temporal distributions of nitrate transformation in the Yellow River, the second-longest river in China. Assessment of the long-term record indicates that [NO3−–N] has increased by two-fold over the past three decades. Weekly observation of ammonium over a twelve-year period revealed high concentrations and suggests impairment of water quality, particularly since 2011. The estimated total dissolved nitrogen flux was 7.2 times higher in middle reaches than that at head waters. Anthropogenic nitrogen sources become more important in lower section of the upper reaches and middle reaches because of intensive agricultural activities and urban input. Nitrate in the lower reaches was mainly derived from transportation of upstream nitrate and point sources from cities. The spatial variation of ammonium and nitrate isotopes show that nitrification is a key process governing nitrogen transformation. Riverine biological processes could potentially be responsible for the shift of nitrate isotope signature. The first step to reducing nitrogen load and improving water quality will be containment and careful management of sources from urban input, sewage waste and irrigation runoff.

Moss nitrogen (N) concentrations and natural 15N abundance (δ15N values) have been widely employed to evaluate annual levels and major sources of atmospheric N deposition. However, different moss species and one-off sampling were often used among extant studies, it remains unclear whether moss N parameters differ with species and different samplings, which prevented more accurate assessment of N deposition via moss survey. Here concentrations, isotopic ratios of bulk carbon (C) and bulk N in natural epilithic mosses (Bryum argenteum, Eurohypnum leptothallum, Haplocladium microphyllum and Hypnum plumaeforme) were measured monthly from August 2006 to August 2007 at Guiyang, SW China. The H. plumaeforme had significantly (P < 0.05) lower bulk N concentrations and higher δ13C values than other species. Moss N concentrations were significantly (P < 0.05) lower in warmer months than in cooler months, while moss δ13C values exhibited an opposite pattern. The variance component analyses showed that different species contributed more variations of moss N concentrations and δ13C values than different samplings. Differently, δ15N values did not differ significantly between moss species, and its variance mainly reflected variations of assimilated N sources, with ammonium as the dominant contributor. These results unambiguously reveal the influence of inter-species and intra-annual variations of moss N utilization on N deposition assessment.

To better understand the mechanisms that hydrological conditions control chemical weathering and carbon dynamics in the large rivers, we investigated hydrochemistry and carbon isotopic compositions of dissolved inorganic carbon (DIC) based on high-frequency sampling in the Wujiang River draining the carbonate area in southwestern China. Concentrations of major dissolved solute do not strictly follow the dilution process with increasing discharge, and biogeochemical processes lead to variability in the concentration-discharge relationships. Temporal variations of dissolved solutes are closely related to weathering characteristics and hydrological conditions in the rainy seasons. The concentrations of dissolved carbon and the carbon isotopic compositions vary with discharge changes, suggesting that hydrological conditions and biogeochemical processes control dissolved carbon dynamics. Biological CO2 discharge and intense carbonate weathering by soil CO2 should be responsible for the carbon variability under various hydrological conditions during the high-flow season. The concentration of DICbio (DIC from biological sources) derived from a mixing model increases with increasing discharge, indicating that DICbio influx is the main driver of the chemostatic behaviors of riverine DIC in this typical karst river. The study highlights the sensitivity of chemical weathering and carbon dynamics to hydrological conditions in the riverine system.

Sulfate concentrations and sulfur isotopic compositions were measured in rainwater in Guiyang city in Southwest China between October 2008 and September 2009 to identify sulfur sources and their impacts on sulfur isotopic composition. The delta S-34 values of 1235 samples collected during this period ranged from - 12.0 to + 9.4 parts per thousand, with a volume-weighted mean of - 2.8 +/- 9.8 parts per thousand, suggesting that rainwater sulfate in Guiyang was mainly derived from SO2 produced during coal combustion. The delta S-34 values of rainwater sulfate increased from 1987 to 2009, with an increment of about + 0.16 parts per thousand per year, reflecting a gradual reduction in S-34-depleted SO2 emitted during coal combustion. Seasonal variations in delta S-34 values were pronounced, with higher values in winter than in summer. Long-distance transport of SO2 from coal burned in northern cities (which was higher than the component from southern cities), and more importantly, the aqueous oxidation of SO2 during transport affected the seasonal variation of rainwater delta S-34 values in Guiyang. Temperature-dependent aqueous oxidation of SO2 suggested that lower rainwater delta S-34 coincides with higher temperature. (C) 2014 Elsevier B.V. All rights reserved.

This study analyzed the water-soluble sulfate (SSO4) and total sulfur (ST) concentrations and their isotopic signatures (δ34SSO4 and δ34ST) in needles of Pinus massoniana Lamb collected from Guiyang (seriously affected by acid rain) and Yunnan areas (acid rain did not occur), China SW. The results indicated that the SSO4 concentrations in needles of Pinus massoniana Lamb collected from several Chinese areas were found to be significantly correlated to ambient sulfur dioxide (R2 = 0.9176, p = 0.01), showing that SSO4 concentrations in needles were more reliable to indicate atmospheric sulfur. The average δ34SSO4 (−7.2 ‰) and δ34STS (−5.1 ‰) in needles in Guiyang areas were significantly lower than those in Yunnan areas (+3.9 and +5.7 ‰, respectively), which were in accordance with the lower δ34S of coals in Guiyang areas than in Yunnan areas. The δ34SSO4 and δ34STS in needles became less positive with a distance from a plant combusted 34S-enriched coals while for another plant combusted 34S-depleted coals, more positive was observed. These results indicated that δ34SSO4 in needles was also a good indicator of atmospheric sulfur sources. A very small difference between δ34 ST and δ34 SSO4 for most needle samples suggested that little isotopic fractionation accompanies sulfur assimilation processes.

To better understand chemical weathering and controlling processes in the Yalong River of the eastern Tibetan Plateau, this study presents major ion concentrations and stable isotopes of the dissolved loads. The isotopic compositions (δ13C-DIC, δ34S and δ18O-SO4) of the dissolved loads are very useful to quantify solute sources and define the carbon budget related with chemical weathering in riverine systems. The isotopic composition of sulphate demonstrates that most of the sulphate is derived from sulphide oxidation, particularly in the upper reach of the Yalong River. The correlations between δ13C-DIC, water chemistry and isotopes of sulphate, suggest that the carbon dynamics are mainly affected by carbonate weathering by sulphuric acid and equilibration processes. Approximately 13% of the dissolved inorganic carbon in the Yalong River originates from carbonate weathering by strong acid. The CO2 consumption rates are estimated to be 2.8 × 105 mol/km2/yr and 0.9 × 105 mol/km2/yr via carbonate and silicate weathering in the Yalong River, respectively. In this study, the influence of sulphide oxidation and metamorphic CO2 on the carbon budget is estimated for the Yalong River draining the eastern Tibetan Plateau.

The adsorption of hexavalent chromium (Cr(VI)) was improved by using organic bentonite (OB) modified with iron(III) chloride. The adsorption mechanisms and characteristics of OB and organic bentonite modified by FeCl3 (FMOB) were studied by using X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy (EDS). It was found that hydroxyl-iron replaced some of the calcium and magnesium contained in the FMOB, but no significant change in its structure was shown even though the adsorption experiments proved that FMOB had a better Cr(VI) adsorption ability compared to OB. The coated material was prepared by mixing FMOB and 4A molecular sieves in a coated pot for the adsorption experiments in the test column. The relevant results showed that the adsorption of the coated material retained its high adsorption ability and maintained that ability after desorption and regeneration, which implied a potential for further application.

The contents and stable S isotope ratio (δS) values of total S, organic S, SO-S, and total reduced inorganic S (TRS) in typical limestone soil and yellow soil were analyzed in this study to examine the general distributions of S forms and their δS values in soils in karst areas of southwest China. Under a similar level of acid deposition, the vertical profiles of the S forms and their δS values differed in limesto\ne soil and yellow soil, indicating the different geochemical responses of these soils to acid deposition. The deposited SO was retained as organic S in both soils. The depletion in S of TRS relative to SO and the parallel increasing δS values of TRS and SO indicate a bacterial reduction process of sulfate in both soils. The different extents of C-bonded S mineralization and organic sulfate transport explain the different vertical profiles of total S and organic S contents in both soils. Sulfate adsorption in limestone soil was negligible because of high pH values. Sulfate adsorption in yellow soil was another important S retention process in addition to biological S retention to form organic S and TRS because of low pH values. The effect of acid deposition on yellow soil appeared more serious because of the accumulation and leaching of deposited SO, which can result in soil acidification and accelerate the loss of basic cations from yellow soil. However, compared with yellow soil, limestone soil released more S into rivers by organic S mineralization after a large decrease in annual S deposition rate.

Two strains of green microalgae C. reinhardti and C. pyrenoidosa were examined for their biosorption of Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+, and Cd2+ from aqueous multi-metal solutions. A wide range of biosorption capacities can be observed due to different strains of microalgae and different species of trace metals. This characteristic was ascribed to the distinct components and structures of algal cell walls and the different physicochemical properties of trace metals, such as atomic weight and ion density. C. pyrenoidosa showed higher uptake capacities than C. reinhardti and both of them had a preference for the uptake of cadmium over others in the trace metal solution, suggesting they can be a good biomaterial for biosorption of cadmium. Live microalgal cells displayed a more complex sorption process than dead microalgal cells because of cell assimilation.

Mosses, among all types of terrestrial vegetation, are excellent scavengers of anthropogenic nitrogen (N), but their utilization of dissolved organic N (DON) and their reliance on atmospheric N remain uncharacterized in natural environments, which obscures their roles in N cycles. Natural (15) N abundance of N sources (nitrate (NO(3)(-)), ammonium (NH(4)(+)) and DON in deposition and soil) for epilithic and terricolous mosses was analyzed at sites with different N depositions at Guiyang, China. Moss NO(3)(-) assimilation was inhibited substantially by the high supply of NH(4)(+) and DON. Therefore, contributions of NH(4)(+) and DON to moss N were partitioned using isotopic mass-balance methods. The N contributions averaged 56% and 46% from atmospheric NH(4)(+), and 44% and 17% from atmospheric DON in epilithic and terricolous mosses, respectively. In terricolous mosses, soil NH(4)(+) and soil DON accounted for 16% and 21% of bulk N, which are higher than current estimations obtained using (15) N-labeling methods. Moreover, anthropogenic NH(4)(+) deposition suppressed utilization of DON and soil N because of the preference of moss for NH(4)(+) under elevated NH(4)(+) deposition. These results underscore the dominance of, and preference for, atmospheric NH(4)(+) in moss N utilization, and highlight the importance of considering DON and soil N sources when estimating moss N sequestration and the impacts of N deposition on mosses.

This study analyzes the biotransformation of earthworms on K in potassium-bearing mineral powder (PBMP) under different PBMP recruitments. A mixture of PBMP (10% to 60% mass fraction) and decaying cow dung was used as feed for breeding the earthworms to study the potassium-releasing ability of earthworms on PBMP in soil. The mixture containing 20% and 30% PBMP resulted in good growth and propagation of the earthworms as well as higher conversion rates of potassium. Therefore, the optimum recruitments of mineral powder are 20% and 30%. The mixture of cow dung and PBMP was compared with the mixture of cow dung and corresponding proportions of quartz powder to analyze the conversion rate of earthworms on PBMP in different combinations. After the earthworms were raised with the mixture of cow dung and PBMP (8 : 2 and 7 : 3) for 30 d, the con- tents of rapidly available K and effective K were 10 824.3±35.9 and 11 688.4±16.1 mg·kg -1 as well as

In order to determine incorporation of boron species, boron isotopic fractionation, and influence of trace elements on isotopic compositions of boron in corals (δ11Bcoral), concentrations of Mg, Sr, Na, B and δ11Bcoral in growing corals from the South China Sea were measured. Relative to seawater, Sr enriched while Mg depleted in corals in the South China Sea. Although the δ11Bcoral values were different from various species and were not closely correlated with the element concentrations in corals in the South China Sea, Mg(OH)2 existed in corals can result in high δ11Bcoral. Thus, it is necessary to examine the existence of Mg(OH)2 and to choose the same species when δ11Bcoral is used in the δ11B-pH proxy. Based on the measured δ11B values of corals and coexisting seawater as well as the seawater pH in the South China Sea, a new isotopic fractionation factor a4-3 between B ( OH ) 4 - and B(OH)3 was determined to be 0.979. Besides B ( OH ) 4 - into corals, our results showed that B(OH)3 may also be incorporated into corals with variable proportions. The incorporation of B(OH)3 into corals may challenge the hypothesis of δ11Bcoral = δ11B4, resulting in increasing uncertainty to the calculated seawater pH values to the δ11B-pH proxy. We suggested that a best-fit empirical equation between δ11B of bio-carbonates and seawater pH needs to be established by the precipitation experiments of inorganic carbonates or culture experiments of corals or foraminifera.

Carbon (C) and silicon (Si) biogeochemical cycles are important factors in the regulation of atmospheric CO2 concentrations and hence climate change. Theoretically, these elements are linked by chemical weathering and organism stoichiometry, but this coupling has not been investigated in freshwaters. Here we compiled data from global rivers and lakes in the United States of America and the United Kingdom, in order to characterize the stoichiometry between the biogeochemical cycles of C and Si. In rivers this coupling is confirmed by a significant relationship between HCO3−/Na+ and DSi/Na+, and DSi:HCO3− ratio can reflect the mineral source of chemical weathering. In lakes, however, these characteristic ratios of chemical weathering are altered by algal activity. The lacustrine Si:C atomic ratio is negative feedback regulation by phytoplankton, which may result in this ratio in algal assemblages similar to that in water column. And this regulation suggests lacustrine photosynthetic C fixation in this equilibrium state is quantitative and depends on the DSi concentration. These findings provide new insights into the role of freshwaters in global C and Si biogeochemical cycles.

Particulate pollution from anthropogenic and natural sources is a severe problem in China. Sulfur and oxygen isotopes of aerosol sulfate (δ34Ssulfate and δ18Osulfate) and water-soluble ions in aerosols collected from 2012 to 2014 in Beijing are being utilized to identify their sources and assess seasonal trends. The mean δ34S value of aerosol sulfate is similar to that of coal from North China, indicating that coal combustion is a significant contributor to atmospheric sulfate. The δ34Ssulfate and δ18Osulfate values are positively correlated and display an obvious seasonality (high in winter and low in summer). Although an influence of meteorological conditions to this seasonality in isotopic composition cannot be ruled out, the isotopic evidence suggests that the observed seasonality reflects temporal variations in the two main contributions to Beijing aerosol sulfate, notably biogenic sulfur emissions in the summer and the increasing coal consumption in winter. Our results clearly reveal that a reduction in the use of fossil fuels and the application of desulfurization technology will be important for effectively reducing sulfur emissions to the Beijing atmosphere.

Using isotope mixing model (IsoSource) and natural δ15N method, this study evaluated contributions of major sources to N of PM2.5 at Beijing (collected during a severe haze episode of January 22nd–30th, 2013) and a background site (Menyuan, Qinghai province; collected from September to October of 2013) of China. At Beijing, δ15N values of PM2.5 (−4.1 – +13.5 ‰; mean = +2.8 ± 6.4 ‰) distributed within the range reported for major anthropogenic sources (including NH3 and NO2 from coal combustion, vehicle exhausts and domestic wastes/sewage). However, δ15N values of PM2.5 at the background site (+8.0 – +27.9 ‰; mean = +18.5 ± 5.8 ‰) were significantly higher than that of potential sources (including NH3 and NO2 from biomass burning, animal wastes, soil N cycle, fertilizer application, and organic N of soil dust). Evidences from molecular ratios of NH4+ to NO3− and/or SO42− in PM2.5, NH3 to NO2 and/or SO2 in ambient atmosphere suggested that the equilibrium of NH3 ↔ NH4 + caused apparent 15N enrichment only in NH4 + of PM2.5 at the background site due to more abundant NH3 than SO2 and NO2. Therefore, a net 15N enrichment (33 ‰) was assumed for NH3 sources of background PM2.5 when fractional contributions were estimated by IsoSource model. Results showed that 41 %, 30 % and 14 % of N in PM2.5 of Beijing originated from coal combustion, vehicle exhausts and domestic wastes/sewage, respectively. Background PM2.5 derived N mainly from biomass burning (58 %), animal wastes (15 %) and fertilizer application (9 %). These results revealed the regulation of the stoichiometry between ammonia and acidic gases on δ15N signals in PM2.5. Emissions of NO2 from coal combustion and NH3 from urban transportation should be strictly controlled to advert the risk of haze episodes in Beijing.

Cellulose was isolated from corn stalk and modified by graft copolymerization to produce an absorbent material (AGCS-cell), which was characterized by scanning electron microscope and energy disperse spectroscopy (SEM-EDS), X-ray diffraction (XRD) and solid-state CP/MAS (13)C NMR. The results showed that AGCS-cell had better adsorption potential for cadmium ion than unmodified cellulose because of the addition of functional groups (CN and OH groups) and the lower crystallinity. The Langmuir isotherms gave the best fit to the data and gave an adsorption capacity was 21.37 mg g(-1), which was close to unpurified cellulose (AGCS) and reflected the feasibility of using AGCS-cell as an adsorbent to remove cadmium ions.

Water samples were collected for 23 different stations along a cross section profile of an estuary extending over to adjacent sea. The collected water samples were filtered and analyzed for major–minor ions and strontium isotope using the standard procedure to understand the geochemical behaviors of major and minor elements. The normalized values indicated that all riverine elements were entering to adjacent coastal sea with some significant variations at the estuary. The seawater dilution and regression lines explain about the overall patterns for seven elements. Removal processes were detected on calcium, magnesium, strontium and sulfate in the estuarine region. No significant mineral precipitation observed to release magnesium with respect to calcium. Minor variations of strontium and sulfate ions could be attributed to the presence of organic matter in the study area. Comparing seven elements with total suspended matters revealed that the total suspended matters played crucial role in either adsorption or absorption of all the elements in estuary before it reaches to coastal sea. Mixing patterns of strontium isotope showed minimal non-conservative with an evidence of active geochemical process in the estuary.

Antimony (Sb) occurs in the environment both naturally and anthropogenically. Numerous activities cause its anthropogenic accumulation and the release is mainly into the terrestrial environment. Therefore, it is crucial to investigate the fate of Sb in soils at the smelting sites where its deposition is often very high and the land needs to be cleaned up. However, little is known regarding the sorption behavior of environmentally found Sb oxidized states in the soils with different characteristics and compositions. The present study examined solubility and toxicity of Sb from the soils polluted due to the smelting operations. An inhibition of seed growth was used as an indicator of the toxic effect of Sb. Batch adsorption experiments were conducted over the pH range of 3–7 and in different equilibrium concentrations of Sb (III) as a form of the smelter release. The water soluble proportion of Sb was low (0.70–1.63%) compared to its deposition in the surface soils; however, extracted amounts caused a slightly reduced germination rate of wheat seeds with a lighter weight. Nevertheless, the soil soluble Sb concentration did not produce severe toxicity symptoms in the growth of roots and sprouts of the germinated seeds. The effects of Sb (III) and (V) forms were slightly different at the level of 5 mg·L− 1. In Sb (III) solution the smaller elongation of both sprouts and roots was observed as compared to the control samples while in Sb (V) solution only sprout lengths were shorter. Distribution coefficient (Kd) of Sb in soil water system was estimated to be 56 mL·g− 1 at pH values of 3 and 10–17 mL·g− 1 at pH of 6–7. Thus, neutral pH increases Sb mobility and its translocation to the plants that should be accounted of in agricultural production and remediation activities.