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Currently, there is a lack of systematic knowledge concerning carbon (C) biogeochemical cycles in impounded rivers. In this study, we investigated different C species and related environmental factors from July 2007 to June 2008 and from May 2011 to May 2012 in the impounded Wujiang River, SW China to understand the influence of dam construction on the riverine C cycle. The results showed that average concentrations of dissolved CO2, dissolved inorganic C (DIC), dissolved organic C, and particulate organic C (POC) were 81.73 μmol/L, 2283.55 μmol/L, 158.11 μmol/L, and 37.54 μmol/L, respectively. Meanwhile, δ13CDIC ranged from − 10.07‰ to − 4.92‰ with an average of − 8.33‰, while δ13CPOC ranged from − 35.30‰ to − 22.28‰ with an average of − 29.20‰. Thermal and chemical stratifications developed seasonally and exerted a significant influence on the C cycle of the released water. The C species and related δ13C showed remarkable heterogeneity in time and space. Evidence from δ13C demonstrated that the C system in this river was primarily influenced by carbonate weathering, whereas in the reservoir, it was primarily controlled by algal activity. The coefficients of variance for different C species in the reservoir and released water were higher than those in the river. Our study indicated that biological activity became a key controlling factor for the C biogeochemical cycle and accelerated it after damming, especially in the warm seasons. The results of this study have important implications for understanding the C cycle in elongated and deep reservoirs.

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.

Land use and land cover (LULC) products derived from remote sensing data are fundamental to the earth's surface ecological environment studies. Various LULC products have different data sources with large uncertainties and varying spatio-temporal resolutions. In this study, our objectives are to understand the accuracy of the current LULC products at the coastal area of Tianjin city. We conducted accuracy verification and comparative analysis of the LULC datasets available from different sources, MCD12Q1, CGLS-LC100, FROM_GLC, GLC_FCS30 and GlobeLand30 for the years of 2010, 2015, 2017 and 2020, at varying spatial resolutions 500–100–30–10 m. Using land cover dataset for these years, we conducted time-series analysis of land cover changes and driving factors. Results showed that GLC_FCS30-2020 has the highest classification accuracy (72.57%), followed by GlobeLand30-2020 (72.23%) and GlobeLand30-2010 (70.10%). The classification accuracy is related to the spatial resolution of original data source and the classification system. The verification accuracies of all products are found to be lower than their official announcements. Additionally, the accuracy comparison among different land types indicated that the classification accuracy of agricultural land, impervious surface, and water bodies is high, while that of forest, grassland, and shrubs is low. According to the spatio-temporal pattern analysis of land cover changes in Tianjin during 2010–2020, the area of agricultural land is slowly decreasing, and construction land is increasing, and the increase results mainly from the conversion of agricultural land and grassland. The rapid population growth, economic development and policy guidance are the main driving factors.

Understanding of the binding characteristics of wetland dissolved organic matter (DOM) and different metals is important for the quantitative assessment of the environmental behavior of metals in wetlands. In this study, different types of spectroscopy including ultraviolet-visible absorption, Fourier transform infrared, and fluorescence spectroscopy was used to investigate the binding characteristics of Fe3+, Cu2+, Cr3+, Cd2+, and Zn2+ with DOM from wetland water. Differential absorption spectra identified binding sites for these five metals in this wetland DOM at 210 nm, 280 nm, 335 nm, and > 400 nm regions. The low binding capacity of DOM in this wetland with Cd and Zn indicated that the toxicity and environmental effects of these metals in this wetland warrant further study. The calculated △EEM combined with fluorescence regional integration (FRI) analysis clearly revealed that Fe and Cu preferred to bind with humic-like DOM while Cd and Zn preferred to bind with protein-like DOM in this wetland. △EEM successfully demonstrated the characteristics of DOM complexing with different metals and could be a compelling tool in evaluating metal-DOM interactions. In addition, 2D-FTIR-COS identified the binding sites and the dynamic processes of binding at the functional group level. Metals preferentially bind with the C O, C O functional group, and then binds to the O H functional group. This study revealed that different DOM components will facilitate the migration of different metals in the environment and provided new slights into an improved understanding of migration and transformation of metals in aquatic environments.

Extensional rift systems provide important pathways for the release of large amounts of deeply-sourced CO2 into the atmosphere. Continental rifting zones (e.g., East African rift) are thus invoked to be important for understanding the links between CO2 outgassing and global climate change associated with continental breakup. However, deeply-sourced CO2 emissions from extensional rift systems in continental collision zones remain poorly understood. Here, we focus on hydrothermal CO2 emissions from the southern segment of the Yadong-Gulu rift (YGR), the largest extensional rift in southern Tibetan Plateau, aiming at delineating rift-related CO2 emissions from the India-Asia continental collision zone. In-situ measurements of diffuse soil CO2 emissions indicate that average soil CO2 fluxes from the Kangbu, Mengzha, and Chaduo hydrothermal fields are 40, 700, and 255 g m−2 d−1, respectively. Combined with average soil CO2 fluxes (20–437 g m−2 d−1) from central and northern YGR, we speculate a relatively steady-state CO2 degassing pattern for the entire rift. The magnitude of soil CO2 fluxes of the YGR is higher than that of representative areas of the East African rift system. Evidence from 3He/4He reveals a pure crustal origin for CO2-bearing fluids in southern YGR, while the involvement of mantle CO2 is recognized in the central and northern rift segments. We suggest that metamorphic decarbonation of crustal rocks at variable depths is the primary cause for CO2 origin in southern YGR, which differs from the magma‑carbonate interaction model of central and northern YGR. Ternary mixing calculation based on He-CO2 systematics of hydrothermal gases indicates dominant contributions from carbonate rocks to total carbon inventory, with mantle CO2 contributions absent in southern YGR but discernible in northern YGR. The characteristic high proportions of crustal CO2 (>90%) distinguish the YGR from extensional rifts fed primarily by mantle CO2 in continental rifting zones. Our results reveal a crustal-scale carbon cycle in accretionary wedge of the India-Asia continental collision zone, together with magmatic front setting of the central and northern YGR, outlining a transect of the rift-related CO2 emissions across continental collision zones. This would contribute to better understanding the role of continental assembly in deeply-sourced CO2 emissions and global carbon budget.

Microbial mat extracellular polymeric substances (EPS) and their fate and transformation in natural waters are unidentified under diurnal condition. EPS from highly saline arid origins were characterised and exposed to natural sunlight conditions to identify its physico-chemical changes over 72 h. Fourier Transform Infrared Spectroscopy (FTIR) and potentiometric titration analyses confirmed the presence of −COOH and –OH functional groups in raw EPS. In addition, size exclusion chromatography (SEC) confirmed the presence of two proteins-sized molecules in the original EPS which were found to degrade upon sunlight exposure. The excitation-emission matrix (EEM) and parallel factor (EEM-PARAFAC) identified two fluorescent components: A combined humic-like and protein-like component, and an individual tyrosine-like component. FTIR in irradiated samples confirmed degradation of EPS by showing presence of the −CH 3 group at 1377 cm −1 . Two proteins-sized molecules identified in SEC were degraded, thereby causing to significant changes in the pH and redox potential (Eh). Correspondingly, three fluorescent components were identified in irradiated samples using EEM-PARAFAC modelling and found to change in their fluorescence intensities upon sunlight exposure. It is therefore suggested that photochemical processes are important for sequential transformation of EPS into various organic substances in surface waters.

Terrestrial lipid biomarkers are one of the key tracers in the studies of atmospheric aerosols. Here, we investigated such organic compounds in marine aerosols collected at Chichijima Island, the western North Pacific for two 4-year periods: 1990–1993 and 2006–2009. A homologous series of lipid biomarkers including C18–C37 n-alkanes, C9–C34 fatty acids, and C14–C35 fatty alcohols were determined by gas chromatography/mass spectrometry (GC/MS). The atmospheric levels of these tracers increased from 1990–1993 to 2006–2009. Their seasonal trends were clearly characterized by winter–spring maxima and summer–fall minima. The relative abundance of the high-molecular-weight (HMW) n-alkanes (C25–C37) and n-alcohols (C20–C35) in total HMW lipids peaked in winter and winter/fall, respectively, whereas those of HMW fatty acids (C20–C34) peaked in summer. Air-mass backward trajectory analyses suggest that the Asian continent, Southeast Asia including tropical regions, and the Central Pacific are the main source regions. The seasonal shift and distribution of the carbon preference index and average chain length for the HMW lipids were controlled by the changes in climatic factors and source regions. The higher abundance of terrestrial lipids during 2006–2009 than 1990–1993 indicates a higher emission from terrestrial plantation in the 2000s than in the early 1990s in upwind regions of East Asia. Furthermore, HMW lipid compounds exhibited much stronger positive correlations with levoglucosan, a biomass-burning tracer, during 2006–2009 than 1990–1993, suggesting that biomass-burning emissions contributed more significantly in this century.

Silicon (Si) is beneficial for rice health and production by alleviating various biotic and abiotic stresses. However, the continual export of grain off-farm may result in Si deficiency for rice plants. The current levels of plant available Si (PASi) in rice paddies in China remain unclear, as do the factors that control PASi content in these soils. We conducted a nationwide sampling campaign across the paddy fields of China between 2016 and 2019, and used calcium chloride extractable Si (Si-CaCl2) and buffered acetate extractable Si (Si-NaAc, pH = 4) to quantify PASi. We show that Si-CaCl2 pool was mainly influenced by mean annual temperature (MAT), soil salinity, soil organic carbon (SOC), mean annual precipitation (MAP), and soil pH, suggesting both pedological and biological control mechanisms. However, the Si-NaAc pool was influenced most by soil pH, MAT and MAP, implying pedological control. Compared to data from the 1990s, the Si-NaAc content decreased by 14.1% on a national scale with an annual decline rate of 0.54%. Based on our investigation, at least 65% of China’s paddy fields are deficient in PASi, which is an increase in area of ~15% over the last 20 years. The principal regions where PASi deficiency was recorded are mainly located in southern China, with the levels of Si deficiency lowering as the paddy fields are located further north. The continual off-site removal of PASi from rice grain and straw will need to be addressed through the use of Si-fertilizers, including organic amendments, to maintain a productive and sustainable rice industry in China.

The release of biospheric organic matter (OM) stored in the humus-rich black soils of Northeast China is highly susceptible to permafrost thaw and agriculturally induced erosion processes, and plays a disproportionate role in the global carbon cycle. However, the perturbations of global change and anthropogenic activities on riverine export of particulate organic carbon (POC) in the high-latitude agricultural areas remain poorly constrained. In the present study, this knowledge gap was filled by identifying the provenances of particulate organic matter (POM) and the erosional flux of POC from the rivers draining Northeast China. The elemental (POC%, PON% and C/N ratio) and isotopic (δ13C and δ15N) compositions of POM in suspended particulate matter (SPM) from the rivers in Northeast China (the Songhua River (SRB) and Liao River basins (LRB)) were analyzed. The results showed that during the wet season, the δ13C and δ15N values of POM in SPM were −25.8 ± 1.2‰ and 6.6 ± 2.2‰ respectively. Elemental and isotopic characteristics of the SPM samples and potential sources indicated that the sources of POM differed significantly among different sampling periods and sites. During the wet season, Soil OM was the primary POM contributor. Compared to the SRB, autochthonous OM made relatively larger contributions to POM in the LRB. During the dry season, for the SPM samples mainly from the LRB, the δ13C and δ15N values of POM were −22.7 ± 4.3‰ and 3.1 ± 2.4% respectively, suggesting that effluent detritus was the predominant source. The flux and yield of SPM revealed the seasonal and spatial variations of physical erosion rate that controls POC export. Seasonally, up to 61% of the annual SPM load and 58% of the annual POC flux of the SRB occurred in May and August due to thawing processes and increasing precipitation. Spatially, the lower reaches of the SRB had the highest SPM yield and contributed more than half of the annual SPM load of the SRB, likely attributable to the high intensity of agricultural activities. Globally, the POC% in SPM and POC yield of the SRB were larger than a series of the world's largest rivers under a given SPM condition, suggesting the high sensitivity of terrestrial OM export to erosion. These findings highlight the perturbation and mobilization of terrestrial OM in Northeast China under intensive agricultural activities and ongoing global climate change.

In order to assess the impact of the monsoonal climate on denudation, physical erosion, and chemical weathering processes, we measured cosmogenic nuclides 10Be, 26Al and immobile element Zr in five granitic regolith profiles across Northeast to South China. The 10Be and 26Al concentrations are 2.98 × 104–25.20 × 104 atoms g−1 and 2.18 × 105–16.62 × 105 atoms g−1, respectively. Compiling previous depth profile data from Leymon and Beacon Heights, we find that the 26Al/10Be ratios systematically increase or decrease with the depth. Our numerical model shows that muons contributions can produce higher 26Al/10Be ratios (greater than 6.75) in both steady-state and non-steady state scenarios, which can result in underestimated burial age (initial 26Al/10Be ratio) and exaggerated denudation rates (due to non-negligible production from muons) for the application of dual-nuclide in Earth Science. The denudation rates, chemical weathering rates and physical erosion rates derived from cosmogenic nuclides and Zr are 28–45, 9–31 and 6–22 m Ma−1, respectively. Chemical weathering rates, excluding the JLN profile, comprise a large proportion of the denudation rates (greater than 50%). Despite the wide range of mean annual precipitation (MAP) and mean annual temperature (MAT), the denudation rates vary without an apparent gradient from northeast to south. However, the physical erosion and chemical weathering results show good relationships with climate, suggesting the limitation type changed from kinetic-limited in the north, to supply-limited in the south. Chemical weathering indices (chemical index of alteration, CIA and weathering intensity factor, WIF) also indicate that the extent of chemical weathering strengthens from northeast to south and increases with chemical weathering rates, but decreases with physical erosion rates.

Particulate inorganic carbon (PIC) is one of the most important components of carbon cycle in hydropower reservoirs. However, the processes of production, migration, and transformation of PIC in hydropower reservoirs are still unclear. As such, we investigated the concentration and carbon isotope composition of PIC and dissolved inorganic carbon and related environmental parameters of hydropower reservoirs on the Wujiang River, Southwest China, to understand these processes. The observed δ13C datasets demonstrated that the river PIC is derived from exogenous carbonate weathering and endogenous carbonate precipitation, whereas the reservoir PIC is dominated by authigenic PIC driven by phytoplankton. The reservoir PIC concentration and δ13CPIC showed seasonal stratification in the water profile, the extent of which depends on surface photosynthesis and bottom respiration. The influence of phytoplankton on the production and transformation of PIC was different among the reservoirs with different ages and trophic levels, and the δ13C technique can reveal these processes very well. This study improves the comprehensive understanding of carbon cycling in hydropower reservoirs and environmental effects of river damming.

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.

The present study seeks to evaluate the application of the 238U-234U-230Th radioactive disequilibrium methodology for the determination of the regolith production rates in thick weathering profiles marked by long histories, encountered under various climate regimes, but still very little studied by these techniques. For this purpose, 238U-234U-230Th disequilibria have been analyzed in the top 11 m of a lateritic profile developed on a granitic bedrock in south China (Longnan, Jiangxi Province) under a subtropical climate. The results demonstrate that in such a weathering profile the determination of weathering rates from the analysis of U-series nuclides in bulk rock samples cannot be recovered by applying in one step to the entire alteration profile the modeling approach classically used to interpret the U-series nuclides, i.e. the “gain and loss” model. The modeling has to be made on subsections of relatively small size (

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.

The distribution and anomalies of rare earth elements (REEs) of granitic regolith were studied in Inner Mongolia and Hainan Island, China. One profile showed slight REE enrichment of an upper layer and no obvious light REE/heavy REE (LREE/HREE) fractionation (LaN/YbN of 0.9). The second profile was significantly enriched in REEs and enriched in LREEs in the upper portion (LaN/YbN > 1.8). Eu, Ce, and Gd anomalies of the two profiles are different. Slightly negative Eu, Ce, and Gd anomalies in NMG-3-1 indicate slow dissolution of primary minerals and little secondary products; in contrast, a positive Eu anomaly in HN-2 suggests the vegetation cycle may contribute to soil. The Ce anomaly of HN-2 reflects oxidation of Ce and coprecipitation by Fe- and Mn-oxides and organic matter. Correlation between Ce and Gd anomalies in HN-2 suggests Ce and Gd are both influenced by redox-reduction.

Rare earth elements (REEs) can record geologic and geochemical processes. We studied two granitic regolith profiles from different climatic zones in eastern Tibetan Plateau and found that (1) ΣREEs ranged from 119.65 to 275.33 mg/kg in profile ND and 5.11–474.55 mg/kg in profile GTC, with average values of 205.79 and 161 mg/kg, respectively. ΣREEs was higher in accumulation horizon and semi-regolith; (2) Influenced by climate, the fractionation of light and heavy REEs (LREEs and HREEs) varied during weathering. The ratio of LREEs/HREEs in pedosphere was higher than semi-regolith in tropical profile; (3) A negative Eu anomaly in both profiles was the result of bedrock weathering. A positive Ce anomaly was observed in all layers of profile ND, and only in the upper 100 cm of profile GTC. This indicates that redox conditions along the regolith profile varied considerably with climate. (4) Normalized by chondrite, LREEs accumulated much more than HREEs; REE distribution curves were right-leaning with a V-type Eu anomaly in both profiles.

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.

This study investigated the impact of topography and vegetation on distribution of rare earth elements (REEs) in calcareous soils using methods of single extraction and mass balance calculation. The purposes of the study were to set a basis for further research on the biogeochemical REE cycle and to provide references for soil–water conservation and REE-containing fertilizer amendments. The results show a generally flat Post-Archean Average Australian Shale—normalized REE pattern for the studied calcareous soils. REE enrichment varied widely. The proportion of acid-soluble phases of heavy REEs was higher than that of light REEs. From top to bottom of the studied hills, dominant REE sources transitioned from limestone in-situ weathering to input from REE-containing phases (e.g., clay minerals, amorphous iron, REE-containing fluids). Our results indicate that the REE content of calcareous soils is mainly controlled by slope aspect, while the enrichment degree of REEs is related to geomorphological position and vegetation type. Furthermore, the proportion of acid-soluble phases of REEs is mainly controlled by geomorphological position.

Metal contaminations from smelting have been widely reported, however, the study on metal mobility or transfer characteristics in soil profiles after a sudden wastewater overflow is far limited. This study was undertaken to investigate distribution and potential mobility of heavy metals in soils flooded by smelting wastewater in Hechi, China. Total heavy metal/metalloid levels were measured in topsoil, profile and profile pore-water taken in-situ. Enrichment factor (EF) and nemero synthesis index (P N ) were used to detect the contribution of anthropogenic emissions to trace element fluxes and pollution levels, respectively. Soil-water partition coefficient (K d ) was used to reflect the fate and the mobility of elements. Results showed topsoil were seriously contaminated with Sb (289–3100 mg kg − 1 ), Pb (444–6388 mg kg − 1 ), Zn (294–923 mg kg − 1 ), Cu (59–192 mg kg − 1 ), Cd (12–34 mg kg − 1 ), and As (32–405 kg − 1 ), and P N values indicated this area was in severe or strongly pollution level. Higher EF values of Sb, Zn, Cd and As were found in the flooded soils, and P N in flooded area was 5 times of that in the unflooded sites, indicating wastewater flooding aggregated pollution in the low-lying area. The Sb, Pb, and Cd concentrations declined drastically with profile but dropped to constant levels below a depth of about 20 cm. In contrast, Zn and Cu in flooding soils declined first and then increased to another extreme value even at depth of 50 cm. Pore-water profiles exhibited the similar declining trends of vertical metal/metalloid distribution pattern. The K d values ranged from 10 2 –10 6 L kg − 1 , and the mobility and bioavailability of the six elements in the profiles declined in the following order: Sb > Zn > Cu > Cd > As > Pb. The relatively low K d values for some depth intervals may reflect adsorption decrease or migration increase of metal/metalloid. However, it is worth to further study and assess their potential risk to environment in longer period.

This study focuses on the chemical and Sr isotopic compositions of the dissolved load of the rivers in the Liao River basin, which is one of the principal river systems in northeast China. Water samples were collected from both the tributaries and the main channel of the Liao River, Daling River and Hun-Tai River. Chemical and isotopic analyses indicated that four major reservoirs (carbonates (+gypsum), silicates, evaporites and anthropogenic inputs) contribute to the total dissolved solutes. Other than carbonate (+gypsum) weathering, anthropogenic inputs provide the majority of the solutes in the river water. The estimated chemical weathering rates (as TDS) of silicate, carbonate (+gypsum) and evaporites are 0.28, 3.12 and 0.75 t/km2/yr for the main stream of the Liao River and 7.01, 25.0 and 2.80 t/km2/yr for the Daliao River, respectively. The associated CO2 consumption rates by silicate weathering and carbonate (+gypsum) weathering are 10.1 and 9.94 × 103 mol/km2/yr in the main stream of the Liao River and 69.0 and 80.4 × 103 mol/km2/yr in the Hun-Tai River, respectively. The Daling River basin has the highest silicate weathering rate (TDSsil, 3.84 t/km2/yr), and the Hun-Tai River has the highest carbonate weathering rate (TDScarb, 25.0 t/km2/yr). The Raoyang River, with an anthropogenic cation input fraction of up to 49%, has the lowest chemical weathering rates, which indicates that human impact is not a negligible parameter when studying the chemical weathering of these rivers. Both short-term and long-term study of riverine dissolved loads are needed to a better understanding of the chemical weathering and controlling factors.

Lignin is a highly complex, plant-derived natural biomass component, the analysis of which requires significant demands on the analytical platform. Fourier transform ion cyclotron mass spectrometry (FT-ICR MS) has been shown to be able to readily assess the complexity of lignin and lignin degradation products by assigning tens of thousands of compounds with elemental formulae. Nevertheless, many experimental and instrumental parameters introduce discrimination towards certain components, which limits the comprehensive MS analysis. As a result, a complete characterization of the lignome remains a challenge. The present study investigated a degraded lignin sample using FT-ICR MS and compared several atmospheric pressure ionization methods, e.g., electrospray ionization, atmospheric-pressure chemical ionization, and atmospheric-pressure photoionization. The results clearly show that the number of heteroatoms (e.g., N, S, P) in the sample greatly increases the chemical diversity of lignin, while at the same time also providing potentially useful biomarkers. We demonstrate here that FT-ICR MS was able to directly isolate isotopically pure single components from the ultra-complex mixture for subsequent structural analysis, without the time-consuming chromatographic separation. CAPSULE: Various ionization techniques coupled to FT-ICR MS provide a powerful tool to assess the lignome coverage.

Emission of reactive nitrogen species has a major impact on atmospheric chemistry, ecosystem and human health. The origin and formation mechanisms of wet-deposited nitrate are not well understood in Southeast Asia (SEA). In this study, we measured stable isotopes of nitrate (δ15N and δ18O) and chemical compositions of daily rainwater from May 2015 to July 2017 in Singapore. Our results showed that δ15N-NO3- and δ18O-NO3- varied seasonally with higher values during the Inter-monsoon period (April-May and October-November) than during Northeast (December-March) and Southwest monsoon (June-September). Bayesian mixing modeling, which took account of the isotope fractionation, indicated that traffic emission (47 ± 32%) and lightning (19 ± 20%) contributed the most to NO3- with increased traffic contribution (55 ± 37%) in the Northeast monsoon and lightning (24 ± 23%) during the Inter-monsoon period. Biomass burning and coal combustion, likely from transboundary transport, contributed ∼25% of nitrate in the rainwater. Monte Carlo simulation of δ18O-NO3- indicated that oxidation process by hydroxyl radical contributed 65 ± 14% of NO3-, with the rest from hydrolysis of N2O5. Wind speed had large effect on δ18O-NO3- variations in the atmosphere with more involvement of hydroxyl radical reactions when wind speed increased. Our study highlights the key role of isotopic fractionation in nitrate source apportionment, and the influence of meteorological conditions on nitrate formation processes in SEA. Ministry of Education (MOE) National Research Foundation (NRF) This work is financially supported by National Natural Science Foundation of China (Grant Nos. 41571130072 and 41861144026), National Key R&D Program of China (Grant No. 2016YFA0601002) and also the IAEA Coordinated Research Project (No. 2279/R0) as well as the National Research Foundation Singapore and the Singapore Ministry of Education under the Research Centres of Excellence initiative, which comprises Earth Observatory of Singapore contribution No.231.

We investigated the concentrations of 10 heavy metals in Potamogeton malaianus, Nymphoides peltata, Eichhornia crassipes, and Hydrilla verticillata to evaluate their potential to bioaccumulate heavy metals and related influencing factors in Taihu Lake. Enrichment factor (EF) values of Cu, Cr, Mn, Ni, Zn, Co, Pb, and V were above 2.0, indicating moderate to significant contamination in sediment. Most of Ti, V, Cr, Mn, and Ni in P. malaianus, E. crassipes, and H. verticillata and V in N. peltata were within excess/toxic level in plants, but higher than normal level. Even though no aquatic plants in this study were identified as a hyperaccumulator, relatively higher concentrations in aquatic plants were found in Taihu Lake than have been found in other previous studies. Heavy metal in submerged plants, especially in their stems, seemed to be more closely related to metals in water and sediment than those in floating-leaf plants. Ratios of metals in stem versus leaves in all plants ranged from 0.2 to 25.8, indicating various accumulation capabilities of plant organs. These findings contribute to the application of submerged aquatic plants to heavy metal removal from moderately contaminated lakes.

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.

A clear understanding of factors governing stable isotopic variations in precipitation of tropical cyclones is critical for constraining atmospheric hydrological model simulations. The temporal and spatial variations in stable isotopic compositions of precipitation during the typhoon Lekima (2019) were investigated, based on rainwater samples collected at four sampling sites along its track between August 10 and August 12, 2019. Results showed that the δ18O and δD values of rainwater samples varied from -15.5‰ to -2.9‰ and from -112.4‰ to -17.3‰, respectively. The large ranges of δ18O and δD values in rainwater from the typhoon Lekima were most likely caused by the changes in rainfall intensity and its complex interaction with local water vapor. In addition, it was observed that the δ18O and δD values gradually decreased from the outer rainbands to the inner rainbands, and their values were more depleted of heavy isotopes than those of local rain. We speculated that both the high stratiform precipitation fractions and the deep convection system may be responsible for the isotopic depletion of rainwater related with the typhoon Lekima. It reveals that the rain type fractions and the intensity of convection should be considered in the elucidation of δ18O signals in extreme precipitation events. This study also has important implications for understanding atmospheric moisture cycles in tropical cyclones.

Lithium isotope is potentially useful tracer of continental weathering. However, the factors affecting Li isotope composition in highly weathered saprolites are still largely unclear. In the present study, Li and Nd isotope compositions in saprolites developed on granite from Huizhou, southern China, were analyzed and Li isotope composition in quartz samples separated from the saprolites was determined. The Nd isotope composition of saprolites (eNd = −6.1 ± 0.4, 1σ) was almost identical to that of parent granite (eNd = −5.7), suggesting the eolian deposition in this profile is negligible. The δ7Li value in saprolites varied greatly from −7.7‰ to +14.0‰. Below a depth of 3 m, almost all saprolites were isotopically lighter than the parent granite (+1.0‰). However, above 3 m, δ7Li values were higher in saprolites (+2.2‰ to +14.0‰, average + 7.6‰) than in the parent granite and showed a significant increasing trend toward the surface. Moreover, the δ7Li value showed a negative correlation with the CIA value below 3 m, but a positive correlation above 3 m. Compared with the parent granite, quartz separates had a higher Li concentration (1.1–28.9 mg/kg, average 9.5 mg/kg) and δ7Li value (+12.1‰ to +13.9‰). As weathering progressed, the formation of secondary minerals (such as kaolinite) led to the incorporation of lighter 6Li, which may have contributed significantly to the low δ7Li value in saprolites below 3 m. However, this mechanism could not explain the relative enrichment of heavy 7Li in the upper layer saprolites. The relative enrichment of quartz may contribute significantly to the increase of δ7Li in saprolites. The direct evidence was that Li was abundant and distinctly isotopically heavier in quartz separates. Moreover, quartz content correlated positively with Li concentration (R2 = 0.90, p

The studies in this Special Issue addressed environmental and ecological issues at the karst areas in the Southwest China. The contributions from these studies indicated that some active agricultural practices that were carried out in recent years reduced environmental risk and increased economic benefits at the karst areas. The results of ecosystem service value estimates in recent years showed improvements of ecosystem and environment in karst areas of China. Local farmers and government have realized the importance of protection of environment and ecosystem than before, which might promote to seek sustainable development goal in future. These studies have delivered new knowledgement that addressed the challenges of facilitating environmental sustainability with agricultural development in the karst region of South China. Meanwhile, further research should deepen science advances to improve the resilience of soil and water resources to agricultural practices in the fragile karst ecosystem.

Hydrological conditions are a critical factor for phytoplankton ecology in hydroelectric reservoirs, and how this factor contributes to the succession of phytoplankton functional groups is still unclear. Therefore, we investigated the phytoplankton functional groups, relative water column stability, and related environmental factors in the Wujiang cascade reservoirs to understand this process. Altogether five phyla and thirteen functional groups were identified, and they showed evident variations across space and time. The B, D, P, and J groups were dominant, and the Lo and X1 groups existed only in the reservoirs. Relative water column stability rather than nutrient availability affects the succession and distribution of phytoplankton functional groups in the study area, and high relative water column stability usually increases phytoplankton biomass. This indicates that hydrologic conditions are an important factor controlling phytoplankton composition in hydroelectric reservoirs, and this study enriches the understanding of reservoir phytoplankton ecology.

Lithium (Li) isotopes have been shown to be fractionated significantly during chemical weathering of silicate rocks. However, previous research has mainly been focused on basalt weathering, whereas the behavior of Li isotopes during the weathering of granite remains unclear. The Li isotopic compositions in the saprolite profile developed on granite was analyzed, as well as several individual primary minerals (K-feldspar, plagioclase, quartz and biotite) in the parent granite. Lithium concentration and the isotopic compositions of the individual primary minerals appear to be heterogeneous. Biotite is rich in Li (369.4 mg/kg), but the Li concentration is very low in other minerals (1.3–11.3 mg/kg). Quartz has the highest δ7Li value (+19.9‰); other minerals contain δ7Li within a fairly narrow range (+5.8‰ to +9.0‰). The saprolite samples were mainly composed of primary minerals and were characterized by low weathering intensity (CIA = 52–60). Lithium was distinctly lost in the saprolites relative to parent granite. Meanwhile, δ7Li values of saprolites were all lower than those of parent granites (−2.0‰ to +3.9‰ vs. +7.1‰, respectively), which systematically decreased with increasing weathering intensity. The mineralogical composition and 87Sr/86Sr ratio in the saprolites suggest that the biotite was preferentially weathered below 120 cm depth in the examined profile, whereas plagioclase weathering mainly occurred above 120 cm depth. The Li released during granite weathering was characteristically different from the isotopes in the primary minerals. Lithium isotopic fractionation during granite weathering is affected by adsorption and/or incorporation of Li by secondary minerals (or clay minerals), and the release of Li from biotite. This study highlights the fact that significant Li isotope fractionation occurs during Li leaching (relatively higher 7Li/6Li ratios) from biotite in the incipient stage of granite weathering, which may help to explain the higher δ7Li values found in the dissolved load from the catchments of low weathering intensity.

Study region The impounded Wujiang River, Southwest China. Study focus Thermal stratification is an important factor shaping aquatic ecosystems in karst hydropower reservoirs. However, the underlying mechanism of thermal stratification formation is still unclear. Therefore, water temperature and related environmental factors were investigated to understand how reservoir hydraulic load (i.e., the ratio of the mean water depth to water retention time) affects thermal stratification in eight karst hydropower reservoirs on the Wujiang River. New hydrological insights for the region The reservoir surface water had a higher temperature than the inflowing and released waters. The variation in the reservoir thermal stratification showed an obvious seasonal pattern, but the extents of the thermal stratification were different among the reservoirs. The rate of water temperature change is proposed to characterize reservoir thermal stratification and is significantly negatively correlated with reservoir hydraulic load, suggesting the control of both water depth and retention time on thermal stratification. This empirical relationship will be helpful in quantitatively evaluating the hydrological effect on thermal stratification, which further affects basic environmental parameters (including pH, dissolved oxygen, and chlorophyll a) in narrow and deep karst cascade hydropower reservoirs.

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.

Rare earth elements (REEs) and major ions were determined in rainwater samples collected from Guiyang in the acid rain impacted zone of Southwest China. The concentrations of total dissolved and acid-soluble REEs in rainwater are higher than those of most of the world's cities as well as the local surface water. The dissolved REE concentrations are negatively correlated to pH in rainwater. This is consistent with acidification of rainwater resulting in increasing REE concentrations. Speciation calculations using the PHREEQC-Model predict that the free REE metal ion (i.e., Ln3 +), sulfate (LnSO4+), oxalate (LnOx+ and LnOx2−) and fluoride (LnF2 +) complexes were relatively important forms of dissolved REE. Although the contribution to rainwater acidity of oxalic acid is much lower than that of sulfuric acid, the proportion of REE-oxalate complexes is not lower than that of REE-sulfate complexes in rain waters. The rainwater is enriched in the middle REEs (MREE) compared to both the light REEs (LREE) and heavy REEs (HREE). REE-phosphate complexes, phosphatic minerals and a Fe-Mn-oxyhydroxide coating are more likely controls on the development of MREE enrichment in the rainwater. Complexation of sulfate and REE played little role in the development of MREE enrichment, even though sulfate is the most important anion in acidic rainwater. In the shale-normalized REE pattern plot, La showed a clear positive anomaly. La might have two main anthropogenic sources in rainwater. One of the important sources could be automobile emission; another main source of excess La in rainwater could be the REE fertilizer that has been widely used in the agriculture of China for approximately 30 years.

Lead (Pb) pollution in and around Ulaanbaatar is of national concern, given that the Mongolian capital is home to nearly half of the country’s entire population. By comparison, Mongolian countryside is a pristine environment because of its sparse population and low industrial activity. The concentration of Pb in urban soils (average of 39.1 mg kg–1) was twice the values found (average 18.6 mg kg–1) in background territories (i.e., Mongolian rural sites). Furthermore, Pb contamination was examined by using Pb stable isotopic composition, and covariance of Pb isotopic ratios showed two groups between rural and urban soils as pristine and disturbed sites. The 206Pb/207Pb ratio, the most prominent fingerprint for Pb pollution, was 1.163–1.185 for the urban whereas values for rural soils (1.186–1.207) were analogue to the regional Pb isotopic signatures. Local coal sources and their combustion products, one of the potential Pb pollution sources in Ulaanbaatar, have significant radiogenic properties in terms of Pb isotopic composition and revealed an average of 1.25 for 206Pb/207Pb and 19.551 for 206Pb/204Pb ratios. Thus, contributions from coal firing activity to Pb pollution lower than it was assumed, and smaller range of these values measured in urban soils may be attributed to the mixing of less radiogenic Pb as a constituent of the leaded gasolines.

Bulk chemical composition and mineralogy were examined in three soil profiles and a deeper 11-meter profile weathering on a granite ridgeline under subtropical climate conditions in south China. The weathering sequence is delineated by mineralogy and major element variations. Apatite, biotite, hornblende and plagioclase dissolve early during weathering, resulting in nearly 100% Ca and Na loss and significant Mg, Fe and P depletion at depth. The K-feldspar reaction front begins at the depth of depletion of plagioclase, leading to a loss of ~ 80% of the K at the land surface near the bottom of the ridgeline and almost 100% at the top. Dissolution of quartz and other silicates releases about 60% of Si in the profiles. Kaolinite is the dominant clay mineral and it transforms to gibbsite in the uppermost layer. The soil horizon (upper 100 cm) is the zone dominated by pedogenic processes, including active biological activity, physical erosion and influx of high concentrations of atmospheric components (especially CO2 and O2). The pedogenic processes are characterized by low pH (~ 4.54 to 5.85), high clay content (kaolinite: 6–16 wt.%; gibbsite: 2–8 wt.%) and total organic carbon content (0.13–3.93%) and intensive fracturing and dissolution of quartz and K-feldspar compared with the lower horizons. Accumulation of organic material and resistant minerals downslope is attributed to down-ridge movement of water (termed here, interflow) and weathering products in the uppermost 100 cm down the ridgeline. Using a mass balance model calculation for the catena that assumes steady-state soil thickness at all sites, the bottom profile shows the highest apparent total chemical weathering loss rate (~ 14 g m− 2 y− 1) whereas the middle position shows the highest physical erosion loss rate (~ 44 g m− 2 y− 1). SiO2 accounts for about 84% of the chemical weathering outflux from the soil horizons along the ridgeline hillslope. Chemical weathering rates at the bottom of the hillslope may be accelerated by high concentrations of organic material and by dissolution of kaolinite. This study demonstrates that mineral reaction fronts in granite become separated over depth intervals of meters and that elemental fluxes and release mechanisms vary with position along a ridgeline catena.

Ocean acidification, a complex phenomenon that lowers seawater pH, is the net outcome of several contributions. They include the dissolution of increasing atmospheric CO2 that adds up with dissolved inorganic carbon (dissolved CO2, H2CO3, HCO3−, and CO32−) generated upon mineralization of primary producers (PP) and dissolved organic matter (DOM). The aquatic processes leading to inorganic carbon are substantially affected by increased DOM and nutrients via terrestrial runoff, acidic rainfall, increased PP and algal blooms, nitrification, denitrification, sulfate reduction, global warming (GW), and by atmospheric CO2 itself through enhanced photosynthesis. They are consecutively associated with enhanced ocean acidification, hypoxia in acidified deeper seawater, pathogens, algal toxins, oxidative stress by reactive oxygen species, and thermal stress caused by longer stratification periods as an effect of GW. We discuss the mechanistic insights into the aforementioned processes and pH changes, with particular focus on processes taking place with different timescales (including the diurnal one) in surface and subsurface seawater. This review also discusses these collective influences to assess their potential detrimental effects to marine organisms, and of ecosystem processes and services. Our review of the effects operating in synergy with ocean acidification will provide a broad insight into the potential impact of acidification itself on biological processes. The foreseen danger to marine organisms by acidification is in fact expected to be amplified by several concurrent and interacting phenomena.

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.

The karst region in southwestern China is a typical region with fragile ecological environments, and the coordination of regional agricultural development and environmental protection faces enormous challenges. Based on the soil and hydrological characteristics of karst in southwestern China, this study summarized water-related environmental issues caused by agricultural activities in this karst region. Agriculture in the karst hills is more likely to cause soil and nutrient losses due to the fast hydrological flow through special karst structures with high permeability. Thus, this review emphasized the impacts of agricultural development on the riverine biogeochemical cycles of elements based on previous studies. Meanwhile, the carbon cycle is also strongly impacted by agricultural activities in this karst region due to enhanced carbonate weathering by nitric acid from the nitrification of ammonium. This weathering mechanism represents a net source of atmospheric CO2 and might impact regional and global carbon cycling in the Anthropocene. Based on the results summarized in this study, we advocate that in the future, better management of agricultural land, improvement of fertilizer use efficiency, and boosting of nutrient recycling rate should be taken into account for reducing nutrient losses and water quality deterioration. Targeted management of local agricultural practices along with guidance from scientific research results is needed to be devoted to sustainable development of agriculture and economies while protecting water environment.

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

In situ cosmogenic nuclides are widely employed to quantify topographic and geomorphic landscape evolution. However, few studies are devoted to investigating possibly unsteady denudation. In this work the denudation rates of five surface bedrock and one depth profile are measured using in situ cosmogenic 36Cl in different climate zones in China; cosmogenic 36Cl is a powerful proxy for the surface denudation processes of carbonate landscapes in different climatic gradients since carbonates are more sensitive to climate change than silicates. Compiling previous worldwide surface denudation studies in different gradients, we find that: (I) denudation rate increases systematically with mean annual precipitation (MAP) in arid climatic zones (MAP lower than ~700 mm yr−1) and is dominated by long-term climatic gradients; (II) humid climatic zone (MAP greater than ~700 mm yr−1) denudation rates are about constrained to 34.1 ± 11.7 mm kyr−1 by carbonate dissolution kinetics; and (III) denudation rate is also influenced by short-term physical erosion or abrupt erosive events. Accordingly, the reconstructed evolutionary history of the Guizhou depth profile results from either a relatively high denudation rate (55.5–4.4 +5.6 mm kyr−1) and long duration exposure (274–147 +120 ka), or an alternative a low denudation rate (0.8–0.8 +13.3 mm kyr−1) and a recent abrupt erosive event (13.0–1.6 +1.9 ka). These two possible solutions suggest that assumed long-term averaged denudation rate can conceal episodic erosion events. Given tectonic quiescence we propose that climate change might mainly control an erosive event during the last glacial termination (~14 ka), which also implies that caution should be taken when determining the denudation rate of a landscape where climate change and/or tectonic activity plays an important role.

Damming effects on sulfur (S) cycling remains unclear at basin scales due to the lack of basic data prior to dam construction. To explore the influence of damming on the riverine S cycle, we investigated the spatiotemporal variations of water chemistry, sulfate (SO42–) concentration, and δ34S-SO42– in January 2017 and July 2017 in the impounded Wujiang River, and the measured results in this study were compared with the data in 2002 when no dams were built in the middle and lower reaches. Results showed that SO42– was the second dominant anion and accounted for up to 30% of the total anions, and sulfuric acid played a vital role in carbonate weathering. Sulfate reducing process and organic S oxidation were markedly enhanced by seasonal thermal stratification induced by damming, particularly in summer. The seasonal differences of SO42– concentration and δ34S-SO42– in this study were not readily discernable compared to those in 2002, when the average SO42– concentration and δ34S-SO42– in winter were 31.0% and 63.3% greater than that in summer respectively. The δ34S-SO42– from upstream WJD reservoir to downstream YP reservoir in 2002 increased by 17.2% in summer; however, in this study, it drastically increased by 76.7%. The reduced seasonal variations and increased spatial differences of SO42– concentration and δ34S-SO42– reflected the damming effect of cascade dams on S cycling in river waters. Interestingly, SO42– concentration gradually decreased while the δ34S-SO42− value became positive from upstream to downstream reservoir, but both their variations inside reservoirs were homogenized to narrow ranges, which could be derived from the cumulative effects of cascade dams. After damming, the increased hydraulic retention time and water depth caused significant seasonal thermal stratification in reservoirs, which enhanced the S biogeochemical process, and this damming effect was accumulated through bottom released water. Therefore, SO42− concentration together with δ34S-SO42− could be useful indicators in assessing the damming effects of cascade dams in the river-reservoir systems.

Soil humic substances (HS) are involved in almost all biogeochemical processes and functions in soils, thus their extraction from aiming to their characterization is very important. However, many factors that influence HS extraction from soil still need further studies. The aim of this work was to assess and quantify comparatively the solubility of soil HS as a function of extraction time, various extractants, solid to liquid ratio and sequential extraction. In this work three different soils, i.e. a forest, a maize and a paddy soil, were examined to assess the solubility of soil HS based on their fluorescence (excitation-emission matrix, EEM) features and changes in nutrient (NO3−-N, PO43−-P and dissolved Si) contents using multiple extraction approaches (time-dependent, various extractants, solid to liquid ratio, and sequential extraction). Three fluorescent components, i.e. humic acids-like (HA-like), fulvic acids-like (FA-like), and protein-like fluorophores (PLF), were identified by parallel factor (PARAFAC) analysis of EEM spectra of the various soil extracts. The solubility of HS, dissolved organic carbon (DOC) and nutrients were shown to increase with extraction time, except for PLF. The FA-like fraction disappeared completely in KCl extracts of all three soils, suggesting the inefficiency of salt extraction. Conversely, HS and nutrients solubility substantially increased in alkaline extracts, and dissolved Si was correlated significantly with the fluorescent intensities of HA-like and FA-like, thus confirming the well-known typical process of alkaline dissolution of HS bound to phytolith and silicate minerals. The relative solubility of HS and nutrients was higher at lower solid to liquid ratio (1:250–1:100), whereas their maximum yields was achieved at high solid to liquid ratio (1:10) for all three soils. Sequential extraction results showed that the first water extraction step contributed 42–55% of HS, which suggested that a single extraction was insufficient to recover HS. In conclusion, water and alkaline extraction could provide, respectively, the labile and insoluble complexed HS existing in soil.

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.

Tracking of reactive nitrogen (N) sources is important for the effective mitigation of N emissions. By combining the N and oxygen (O) isotopes of atmospheric NO3−, stable isotope mixing models were recently applied to evaluate the relative contributions of major NOx sources. However, it has long been unresolved how to accurately constrain the δ15N differences between NO3− and corresponding NOx (e(NO2→NO3−) values). Here, we first incorporated the HC oxidation (NO2 → NO3−) pathway by using Δ17O values to evaluate the e(NO2→NO3−) values, performed on NO3− in PM2.5 collected during the day and at night from January 4–13, 2015 at an urban site in Beijing. We found that the Δ17O-based e values (e17O-based(NO2→NO3−)) (15.6 ± 7.4‰) differed distinctly from δ18O-based e values (e18O-based(NO2→NO3−)) (33.0 ± 9.5‰) so did not properly incorporate the isotopic effects of the HC oxidation (NO2 → NO3−) pathway. Based on the e(NO2→NO3−) values, δ15N values of NOx from coal combustion (CC), vehicle exhausts (VE), biomass burning (BB), and the microbial N cycle (MC), as well as NO3− in PM2.5, we further quantified the source contributions by using Stable Isotope Analysis in R (the SIAR model). We found that the respective fractional contributions of CC-NOx and MC-NOx were underestimated by 64% and were overestimated by 216% by using e18O-based(NO2→NO3−) values. We concluded that the new e17O-based(NO2→NO3−) values reduced uncertainties in contribution analysis and the evaluation method for atmospheric NO3− sources.

Intensive soil tillage is a significant factor in soil organic matter decline in cultivated soils. Both cultivation abandonment and foregoing tillage have been encouraged in the past 30 years to reduce greenhouse gas emissions and soil erosion. However, the dynamic processes of soil organic carbon (SOC) in areas of either continuous cultivation or abandonment remain unclear and inconsistent. Our aims were to assess and model the dynamic processes of SOC under continuous tillage and after cultivation abandonment in the black soil of Northeast China. Soil profiles were collected of cultivated or abandoned land with cultivation history of 0–100 years. An isotope mass balance equation was used to calculate the proportion of SOC derived from corn debris (C4) and from natural vegetation (C3) to deduce the dynamic process. Approximately 40% of SOC in the natural surface soil (0–10 cm) was eroded in the first 5 years of cultivation, increasing to about 75% within 40 years, before a slow recovery. C4 above 30 cm soil depth increased by 4.5%–5% or 0.11–0.12 g·kg−1 on average per year under continuous cultivation, while it decreased by approximately 0.34% annually in the surface soil after cultivation abandonment. The increase in the percentage of C4 was fitted to a linear equation with given intercepts in the upper 30 cm of soil in cultivated land. A significant relationship between the change of C4 and time was found only in the surface soil after abandonment of cultivation. These results demonstrate the loss and accumulation of corn-derived SOC in surface black soil of Northeast China under continuous tillage or cultivation abandonment.