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Redfield first reported a carbon: nitrogen (C:N) ratio of approximately 6.6 in marine phytoplankton. However, recent studies show that phytoplankton C:N ratio has a large range (marine: 6.5-9.9; freshwater: 7.8-10.5) and is species-specific.These studies pose a great challenge to phytoplankton stoichiometric homeostasis, which traditionally refers to their ability to maintain relatively stable elemental composition with the variation in external nutrient availability. The underlying mechanisms of the interaction between phytoplankton stoichiometric homeostasis and nutrient availability need further clarification. Therefore, in the field seven reservoirs in Tianjin, North China, were investigated to understand their phytoplankton C:N ratios and the influencing factors, and in the laboratory, Chlamydomonas reinhardtii, as a model organism, was used to investigate its C and N metabolism and relevant physiological parameters under different C and N availability. Transcriptome sequencing, nano-scale secondary ion mass spectrometry, and C stable isotope analysis were used to understand cellular C-N metabolism at the molecular level, cellular C-N compartmentation, and C utilization strategy, respectively, in the culture experiment. The main aim of this study was to understand how C-N availability affects the C:N ratio of freshwater phytoplankton at the molecular level.The results indicated that CO2 limitation had no significant effect on the phytoplankton C:N ratio in either scene, whereas limitation of dissolved inorganic N induced the ratio to be a 35% higher in the field and a 138% higher in the laboratory, respectively. Under CO2 limitation, algal CO2-concentrating mechanisms were operated to ensure a C supply, and coupled C-N molecular regulation remained the cellular C:N ratio stable. Under nitrate limitation, differentially expressed gene-regulated intensities increase enormously, and their increasing proportion was comparable to that of the algal C:N ratio; cellular metabolism was reorganized to form a “subhealthy” C-N stoichiometric state with high C:N ratios. In addition, the N transport system had a specific role under CO2 and nitrate limitations. This study implies that algal stoichiometric homeostasis depends on the involved limitation element and will help to deepen the understanding of C-N stoichiometric homeostasis in freshwater phytoplankton.

The generation of reactive oxygen species (ROS) mediated by minerals and/or microorganisms plays a vital but underappreciated role in affecting carbon and nutrient cycles at soil-water interfaces. It is currently unknown which interactions between microbial communities and iron (Fe) minerals produce hydroxyl radical (HO

Anthropogenic input of sulfate (SO

Coastal wetlands are an important source of methane emissions, and understanding the mechanisms that control methane emissions from coastal wetlands is of great significance to global warming. Anaerobic oxidation of methane driven by sulfate is an important process to prevent methane emissions from coastal wetlands. The effects of environmental changes on this process and the function of the sulfate-methane transition zone (SMTZ) are poorly understood. In this study, spatiotemporal variations in pore-water geochemistry (concentrations of SO

Rainwater dissolved organic matter (DOM) plays an important role in the biogeochemical cycle and evolution of organic matter in the land-atmosphere interface. To better understand their sources and molecular composition in the atmosphere, rainwater samples were collected at six different locations along the Yangtze River Basin. Based on the application of a combined approach including excitation-emission matrix (EEM) fluorescence and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), various sources (terrestrial, anthropogenic, and autochthonous sources) of rainwater DOM were revealed. Results show that the derivatives of biogenic volatile organic compounds were widely distributed and contributed to rainwater DOM along the Yangtze River Basin. In the up-river city Batang, rainwater DOM was affected by the long-range atmospheric transport due to the Indian summer monsoon. Lijiang, a city on the southeastern edge of Tibetan plateau, was related to strong local biomass burning. The industrial cities of Panzhihua and Luzhou showed large differences in organic composition due to distinct industrial types. Fuling, a district in Chongqing Municipality, was significantly contributed by aged organics from biomass burning. While rainwater DOM in Shanghai, a coastal megacity, contained a high fraction of sea spray organics. Further, more than 70% of rainwater DOM molecules are associated with 36 typical transformation mechanisms during rainwater-scavenging processes, e.g., oxidation reactions, dealkylation and decarboxylation. Our study demonstrates that local natural and anthropogenic emissions and climatic conditions strongly shaped the chemodiversity and possible precursor-product pairs of rainwater DOM along the Yangtze River Basin, which helps to better understand the biogeochemical cycles of organic matter in a large-scale watershed under the influence of human activities.

Exotic plant invasion is an urgent issue occurring in the biosphere, which can be stimulated by environmental nitrogen (N) loading. However, the allocation and assimilation of soil N sources between leaves and roots remain unclear for plants in invaded ecosystems, which hampers the understanding of mechanisms behind the expansion of invasive plants and the co-existence of native plants. This work established a new framework to use N concentrations and isotopes of soils, roots, and leaves to quantitatively decipher intra-plant N allocation and assimilation among plant species under no invasion and under the invasion of Chromolaena odorata and Ageratina adenophora in a tropical ecosystem of SW China. We found that the assimilation of N derived from both soil ammonium (NH4+) and nitrate (NO3-) were higher in leaves than in roots for invasive plants, leading to higher leaf N levels than native plants. Compared with the same species under no invasion, most native plants under invasion showed higher N concentrations and NH4+ assimilations in both leaves and roots, and increases in leaf N were higher than in root N for native plants under invasion. These results inform that preferential N allocation, dominated by NH4+-derived N, to leaves over roots as an important N-use strategy for plant invasion and co-existence in the studied tropical ecosystem.

This study investigates the concentrations and δ15N values of NH4+ in PM2.5 at three heights (8, 120, and 260 m) on a 325 m tower in urban Beijing. NH4+ concentrations were lower during the Parade ...

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.

Hydropower plays an important role in the supply of renewable energy, but it also exerts a great influence on the river continuum. Understanding nutrient cycling and microbial community succession in hydropower reservoirs is key to weighing hydroelectric pros and cons. However, the underlying control mechanisms are still not well known, especially with respect to the impacts of hydrological conditions. Based on a comprehensive survey of hydropower reservoirs along the Wujiang River in SW China and an integration of published data, we found that reservoir physicochemical and biological stratifications and planktonic microbial community assembly were synergistically evolving, and reservoir hydraulic load (i.e., mean water depth per unit retention time) was a key factor controlling the strength of stratifications, CO

To better understand the origins and photochemical processing (aging) of organic aerosols (OA), we studied fine aerosols (PM

Calcium is a critical element in the global carbon cycle due to its role in carbon sequestration via silicate weathering and carbonate formation. Here we apply calcium (δ

Sulfur (S) dynamics in soils formed from granite remain poorly understood despite its importance as an essential plant macronutrient and component of soil organic matter. We used stable S isotope ratios to trace the sources and biogeochemical processes of S in four forest soil profiles developed on granite under contrasting climate conditions. The soil S is derived mainly from decomposing litter; no significant geogenic contribution to its content is noted as a result of the low S concentration of the granite (~ 5 μg/g). Colder/drier climate results in high organic S retention at the surface due to weak mineralization of organic S. Although warmer/wetter climate increases the S mineralization and leaching loss, SO42− adsorption is an important S retention process in the subsurface. The vertical distribution of S isotope compositions in the soil profiles across the four sites indicates (i) a downward increase in δ34S values in the upper profiles due to continuous mineralization of organic S with an occasional decrease in δ34S values in the subsurface due to dissimilatory sulfate reduction (DSR), (ii) constantly high δ34S values in the middle profiles due to the low water permeability, and (iii) a downward decrease in δ34S values in the low profiles due to increased contribution of bedrock with depth. Regardless of the variation in soil depth and climate, the total S concentration is proportional to the pedogenic Fe/Al minerals, suggesting the important role of secondary Fe/Al minerals in retaining S in soils. This study provides an integration and synthesis of controls of climatic and edaphic variables on S dynamics in forest soil profiles developed on granite.

Since the industrial revolution, it has been assumed that fossil-fuel combustions dominate increasing nitrogen oxide (NOx) emissions. However, it remains uncertain to the actual contribution of the non-fossil fuel NOx to total NOx emissions. Natural N isotopes of NO3− in precipitation (δ15Nw-NO3−) have been widely employed for tracing atmospheric NOx sources. Here, we compiled global δ15Nw-NO3− observations to evaluate the relative importance of fossil and non-fossil fuel NOx emissions. We found that regional differences in human activities directly influenced spatial-temporal patterns of δ15Nw-NO3− variations. Further, isotope mass-balance and bottom-up calculations suggest that the non-fossil fuel NOx accounts for 55 ± 7% of total NOx emissions, reaching up to 21.6 ± 16.6Mt yr−1 in East Asia, 7.4 ± 5.5Mt yr−1 in Europe, and 21.8 ± 18.5Mt yr−1 in North America, respectively. These results reveal the importance of non-fossil fuel NOx emissions and provide direct evidence for making strategies on mitigating atmospheric NOx pollution., This study investigates in the importance of non-fossil fuel NOx emissions in the surface-earth-nitrogen cycle. The study shows how changes of regional human activities directly influence δ15N signatures of deposited NOx to terrestrial environments and that emissions have largely been underestimated.

The production of fluorescent dissolved organic matter (FDOM) by phytoplankton and its subsequent degradation, both of which occur constantly under diurnal-day time sunlight and by night time dark-microbial respiration processes in the upper layer of surface waters, influence markedly several biogeochemical processes and functions in aquatic environments and can be feasibly related to global warming (GW). In this work sunlight-mediated high-temperature was shown to accelerate the production of FDOM, but also its complete disappearance over a 24-h diurnal period in July at the highest air and water temperatures (respectively, 41.1 and 33.5 °C), differently from lower temperature months. Extracellular polymeric substances (EPS), an early-state DOM, were produced by phytoplankton in July in the early morning (6:00–9:00), then they were degraded into four FDOM components over midday (10:00–15:00), which was followed by simultaneous production and almost complete degradation of FDOM with reformation of EPS during the night (2:00–6:00). Such transformations occurred simultaneously with the fluctuating production of nutrients, dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and the two isotopes (δ15N and δ18O) of NO3−. It was estimated that complete degradation of FDOM in July was associated with mineralization of approximately 15% of the initial DOC, which showed a nighttime minimum (00:00) in comparison to a maximum at 13:00. FDOM identified by excitation-emission matrix spectroscopy combined with parallel factor analysis consisted of EPS, autochthonous humic-like substances (AHLS) of C- and M-types, a combined form of C- and M-types of AHLS, protein-like substances (PLS), newly-released PLS, tryptophan-like substances, tyrosine-like substances (TYLS), a combined form of TYLS and phenylalanine-like substances (PALS), and their degradation products. Finally, stepwise degradation and production processes are synthesized in a pathway for FDOM components production and their subsequent transformation under different diurnal temperature conditions, which provided a broader paradigm for future impacts on GW-mediated DOM dynamics in lake water.

Carbon (C) cycling and phytoplankton community succession are very important for hydropower reservoir ecosystems; however, whether the former controls the latter or the reverse is still debated. To understand this process, we investigated phytoplankton species compositions, stable C isotope compositions of dissolved inorganic C and particulate organic C (δ13C-DIC and δ13C-POC), and related environmental factors in seven hydropower reservoirs on the Wujiang River, Southwest China. A total of 36 algal genera from seven phyla were identified, and phytoplankton community exhibited obvious temporal and spatial difference. The δ13C-DIC (from -9.96 to -3.73‰) and δ13C-POC (from -33.44 to -21.17‰) co-varied with the algal species succession and increased markedly during the shift of dominant species from Bacillariophyta to Pyrrophyta or Cyanophyta. In addition, the strong C fixation in the euphotic layer resulted in great δ13C-DIC and CO2 stratification in the reservoir profile. Statistical analyses and C isotope evidence demonstrate that an increase in water temperature triggers phytoplankton community succession, and that CO2 availability is a key to drive the succession direction, and in turn, C cycling is enhanced when phytoplankton are dominated by Pyrrophyta or Cyanophyta in hydropower reservoirs. This study confirms that C cycling and phytoplankton community succession interact with each other and evolve synchronously, and will be helpful to systematically evaluate the environmental consequences of river damming.Keywords: Carbon biogeochemical cycling; Phytoplankton community succession; Stable carbon isotope; Reservoir effect; Wujiang River.

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.

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.

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.

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.

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.

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.

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.

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

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.

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.

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.

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.

A combination of microbial flocculant (MBF) and ferric trichloride (FeCl3) was applied to aggregate and harvest algae. The orthogonal experiment was designed to optimize conditions of flocculation. Mechanism of flocculation was observed through determining the zeta potential and observing the morphology of algal floc using stereo and scanning electron microscope. The results showed that the optimum combination of flocuulants was 0.175 g of FeCl3 with 10 mL MBF per liter, which exhibited the highest flocculation efficacy (95.12%) and lowest chemical oxygen demand (10.44 mg/L). The flocculation mechanism was charge neutralization, where the MBF first adhered and coated algae. Due to its high affinity to iron-hydroxy ions and long-chain molecules, the MBF attracted positively charged hydroxyl irons generated by FeCl3 hydrolysis and interacted with the iron-hydroxy ions to form a larger floc by bridging. The coat made of MBF formed a thin film which protected algae from being destroyed, and trapped th...

This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ 34 S SO4 with the median value of 10.3‰ ( n = 4) and 7.9‰ to 15.6‰ for δ 18 O SO4 with the median value of 14.3‰ ( n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ 34 S SO4 and δ 18 O SO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II 1 ) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ 34 S SO4 and δ 18 O SO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II 2 ) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ 34 S SO4 and δ 18 O SO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II 3 ) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ 34 S SO4 and δ 18 O SO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ 34 S SO4 = 10–35‰ and δ 18 O SO4 = 7–20‰), soil sulfate (δ 34 S SO4 = 5.9‰ and δ 18 O SO4 = 5.8‰) and sewage water (δ 34 S SO4 = 10.0‰ and δ 18 O SO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II 3 ), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ 34 S SO4 and δ 18 O SO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers.

Enhanced ammonia (NH3) emissions and deposition caused negative effects on air quality and ecosystems. Precipitation is an efficient pathway to remove NH3 and particulate ammonium (p-NH4+) from the atmosphere into ecosystems. However, precipitation scavenging of p-NH4+ in chemical transport models has often considered fine p-NH4+, with inadequate constraints on NH3 and coarse p-NH4+. Based on distinct δ15N values between NH3 and NH4+ in PM2.5 (particulate matters with aerodynamic diameters ≤ 2.5 μm) or TSP (total suspended particulates), this paper interpreted intra-event variations of precipitation NH4+ concentrations and δ15N values (δ15N-NH4+ values) at Guiyang (Xiao et al., 2015). Generally decreased NH4+ concentrations across rain events reflected decreasing scavenging of NH3 and p-NH4+. Using a Bayesian isotope mixing model, we found that differing contributions between 15N-depleted NH3 and 15N-enriched p-NH4+ were responsible for the three-stage variations of intra-event δ15N-NH4+ values. The decreases of δ15N-NH4+ values across the first and third stages indicated more decreases in scavenging p-NH4+ than NH3, while the increases of δ15N-NH4+ values across the second stage were resulted primarily from more increases in scavenging p-NH4+ (particularly fine p-NH4+) than NH3. These results stressed influences of differing scavenging between NH3 and p-NH4+ on precipitation δ15N-NH4+ values, which should be considered in modeling precipitation scavenging of atmospheric p-NH4+.

Radiocarbon (14C) has been measured in single tree ring samples collected from the southwest of the Fukushima Dai-ichi Nuclear Power Plant. Our data indicate south-westwards dispersion of radiocarbon and the highest 14C activity observed so far in the local environment during the 2011 accident. The abnormally high 14C activity in the late wood of 2011 ring may imply an unknown source of radiocarbon nearby after the accident. The influence of 14C shrank from 30 km during normal reactor operation to 14 km for the accident in the northwest of FDNPP, but remains unclear in the southwest.

Sediment pore waters were examined in four Chinese lakes (Bosten, Qinghai, Chenghai and Dianchi) to characterise the sources of dissolved organic matter (DOM) and their microbial changes in the sediment depth profiles. Parallel factor (PARAFAC) modelling on the sample fluorescence spectra confirmed that the pore water DOM was mostly composed of two components with a mixture of both allochthonous and autochthonous fulvic acid-like substances in three lakes, except Lake Dianchi, and protein-like components in Lake Bosten. However, DOM in Lake Dianchi was composed of three components, including a fulvic acid-like, and two unidentified components, which could originate from mixed sources of either sewerage-impacted allochthonous or autochthonous organic matter (OM). Dissolved organic carbon (DOC) concentrations were typically high (583–7410 μM C) and fluctuated and increased vertically in the depth profile. The fluorescence intensity of the fulvic acid-like substance and absorbance at 254 nm increased vertically in the sediment pore waters of three lakes. A significant relationship between DOC and the fluorescence intensity of the fulvic acid-like component in the sediment pore waters of three lakes, except Lake Dianchi, suggested that the fulvic acid-like component could significantly contribute to total DOM and could originate via complex microbial processes in early diagenesis on OM (ca. phytoplankton, terrestrial plant material) in these lakes. Pore water DOM components could therefore be a useful indicator to assess the DOM sources of the lake sediment during sedimentation over the past several decades, which have been heavily affected by ambient terrestrial vegetation and human activities.

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.

Straw return is becoming a routine practice in disposing of crop residues worldwide. However, the potential effect of such operation on the chemistry of local groundwater is not well documented. Here, shallow groundwater in an area where wheat-maize straw return is practiced was analyzed, and the seasonal changes in the nitrate concentration and the isotope compositions of NO3- and H2O were determined along two flow paths. Measured δD and δ18O in waters indicated that the groundwater was mainly recharged by atmospheric precipitation, while measured δ15N and δ18O in nitrate suggested that the sources for groundwater NO3- included urea fertilizer, soil nitrogen, and sewage/manure. Reduced NO3- concentrations coincided with an enrichment of organic matter in the groundwater of the straw return area, revealing an environmental condition that facilitates nitrate reduction, whereas increased δ15N-NO3- and δ18O-NO3- along the flow path suggested the occurrence of denitrification. Further analyses showed that, compared to the cases in the absence of straw return, as much as 80% and 90% of groundwater nitrate was removed in low and high water seasons in the straw return area, pointing to a potential positive effect of straw return to groundwater quality.

To better understand the decreases observed in pH levels downstream from the associated hydroelectric dam, the impounded Wujiang River in Southwest China was investigated. Study results indicate that the average pH decrease from upstream to downstream of the hydroelectric dam could be up to 0.47 units, and pH differences were particularly apparent during water thermal stratification. Notably, pH was controlled by [CO2]/[CO3 2−] ratios in this impounded river. The decrease in [CO2]/[CO3 2−] ratios and associated increases in pH at the surface of the reservoirs were mainly due to the prevalence of photosynthesis, while the reverse phenomenon was observed at the bottom due to respiration. The evidence from δ13CDIC clearly demonstrated these processes. The increase in phytoplankton biomass enhanced this pH decrease, while dissolved organic carbon had limited impacts on the pH variation. The decrease in pH downstream from the hydroelectric dam resulted from the development of pH stratification in the water profile and the dam operations that release bottom waters for hydropower generation. Consequently, the cascade in hydropower development could increase the risk of river acidification.

Inland waters, including rivers and lakes, are increasingly recognized as playing significant roles in the transport, mineralization and burial of organic carbon exported from land. However, in many areas, dissolved inorganic carbon (DIC) dominates the carbon export from catchments. Owing to different production processes and turnover times of organic versus inorganic carbon, CO2 emitted from rivers and lakes may have different impacts on global carbon cycling depending on its origin. Here, pCO2 and dissolved oxygen concentrations were determined, and the ratios of excess CO2 to O2 depletion (ΔCO2/ΔO2) were compared in spring water, river water and lake water in a carbonate catchment located in the southwestern plateau region of China. Results show that groundwater CO2 evasion, at 2.0 g C m−2year−1, is insignificant in terms of terrestrial carbon loss compared with soil CO2 emission. In the rivers, calcite precipitation due to oversaturation is an important mechanism for CO2 production in some seasons. In the lake, HCO3 − contributed approximately 75 % of the total carbon supply to organic matter production and calcite deposition during seasons favoring photosynthesis. The seasons which had high ΔCO2/ΔO2 are the main periods of CO2 emission from the lake, and the extra CO2 may be produced from HCO3 − titration by H+. Thus, lake CO2 evasion was controlled primarily by pH, not respiration. The spring, river, and lake waters mainly process DIC exported from the catchment, of which HCO3 − is primarily derived from carbonate weathering by soil CO2 that, with extraordinarily high ΔCO2/ΔO2, may originate from sources including organic matter decomposition, root respiration (autotrophic), and acid dissolution. Therefore, freshwater CO2 emission is a return pathway of catchment soil CO2 to the atmosphere more than that of net primary production and net ecosystem production.