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Abstract Soil biogenic components are subject to continuous sequestration, and export from soils into the surrounding air and water environments. However, the processes involving the stability or lability of their mineral states remain still unclear. To assess these issues, we have measured various biogenic components in a number of agricultural, forest, grassland, and deep soils, as well as desert sands from Inner Mongolia, both in the solid state and liquid extracts. The contents of soil organic carbon (SOC) and soil total nitrogen (STN) were higher in soils than in sands, whilst those of soil total sulfur (STS) and inorganic carbon were higher in sands and deeper soils. The significant positive correlations found between STS and SOC, and STN, and their significant negative correlations with pH and δ13C-SOC in all soils suggest a pH-dependent sequestration of C, N, and S. The decreased stability of organo-mineral complexes at acidic pH, resulting from the acidification of humic substance (HS) functionalities, leads to a higher availability of nutrients that facilitates the sequestration of soil organic matter (SOM). Conversely, an increase in pH enhances the stability of organo-mineral complexes by promoting negatively charged HS functionalities, which reduces the availability of nutrients and the sequestration of SOM. The δ13C-SOC enrichment in desert sands (-17.63 to -7.10‰) and its depleted values in soils (-24.9 to -18.8‰) suggest the occurrence of C sequestration in desert, via uptake of enriched atmospheric CO2 (-8.4‰). The fluorescence spectra of humic substance components and their molecular weights in sands were typically different from those of soils. The predominant relatively low molecular weight (MW) ( 25 − 15 kDa) of water-extracted (labile state: LS) components of all soils suggest, respectively, their involvement in organo-mineral complexes and for export into the surrounding environment. The quantities of LS and CS soil components differ significantly on dependence of soil characteristics, implying their corresponding lability or stability in soils. These findings will provide useful input for the management of the corresponding soil/sand ecosystems.

Abstract Soil extractable nitrate, ammonium, and organic nitrogen (N) are essential N sources supporting primary productivity and regulating species composition of terrestrial plants. However, it remains unclear how plants utilize these N sources and how surface-earth environments regulate plant N utilization. Here, we establish a framework to analyze observational data of natural N isotopes in plants and soils globally, we quantify fractional contributions of soil nitrate (f NO3-), ammonium (f NH4+), and organic N (f EON) to plant-used N in soils. We find that mean annual temperature (MAT), not mean annual precipitation or atmospheric N deposition, regulates global variations of f NO3-, f NH4+, and f EON. The f NO3- increases with MAT, reaching 46% at 28.5 °C. The f NH4+ also increases with MAT, achieving a maximum of 46% at 14.4 °C, showing a decline as temperatures further increase. Meanwhile, the f EON gradually decreases with MAT, stabilizing at about 20% when the MAT exceeds 15 °C. These results clarify global plant N-use patterns and reveal temperature rather than human N loading as a key regulator, which should be considered in evaluating influences of global changes on terrestrial ecosystems.

Abstract Climate changes are known to have been a key regulator of the biodiversity in Earth's history. However, the dry‐humid degrees and alternating patterns throughout the Phanerozoic remain largely unconstrained. In this study, we report high contents (2.4 ± 3.8 mg N kg−1) and 17O anomalies (11.0 ± 7.4‰) of nitrate (NO3−) in the early Cambrian black shale from South China, likely caused by atmospheric NO3− intrusion under dry climates that followed tectonic uplift. By developing new methods to quantify aridity indices (AI, 0.06 ± 0.08) in combination with observational data with paleoclimate models, we reconstructed the historical AI variations. Our analyses revealed three significant dry‐to‐humid transitions which include Cambrian‐Ordovician to Silurian‐Permian, Permian‐Triassic boundary to middle Triassic‐early Jurassic, and Jurassic‐Paleogene to Neogene. This study quantitatively unlocked the Phanerozoic climate changes in South China, offering important evidence for understanding the co‐evolution of ecological and climatic systems in Earth's history.

Abstract The active Himalayan-Tibetan orogen, where India underthrusts into Asia, is an important geological source of carbon dioxide (CO2) emission into Earth’s atmosphere. However, the extent to which Indian underthrusting could stimulate the mobilization of deeply-sourced carbon and its subsequent emission remains unknown. Here, we use a combination of field observations coupled with in-situ CO2 flux measurements and helium and carbon isotopic data, to study the controls on CO2 origins and fluxes in a 400-kilometre-long rift transecting northern Himalaya and southern Tibet. High diffuse CO2 fluxes sustained by pure crustal fluids are confined to rift segments in the northern Himalaya, while toward southern Tibet, CO2 fluxes become lower but mantle fluid inputs are identified. Such rift-related CO2 degassing profile suggests metamorphic decarbonation and release of carbon-bearing fluids enhanced by the underthrusting Indian lower crust, agreeing well with Himalayan metamorphism and orogen-parallel lithospheric extension. Deep CO2 fluxes from extensional tectonics in northern Himalaya and southern Tibet, primarily of crustal origins, are comparable to mantle CO2 fluxes from global mid-ocean ridges. Our findings demonstrate that geophysical and geo-tectonic responses to continental underthrusting could facilitate massive crustal carbon mobilization and emission, making active collisional orogens globally important carbon sources.

Dissolved organic matter (DOM) is closely linked to human activities in drainage basins and plays a crucial role in maintaining ecosystem functioning and reflecting environmental quality. However, the impacts of climate and anthropogenic-induced changes on DOM in riverine systems under increasingly warming conditions still need to be better understood, particularly at large regional scales. To address this knowledge gap, we analyzed a dataset containing 386 published measurements for nine major Chinese river systems, examining dissolved organic carbon (DOC) concentrations and optical properties of chromophoric DOM (CDOM) under diverse environmental conditions, including mean air temperature, precipitation, surface solar radiation, population density, and land use. Our findings indicate that riverine DOC concentrations are significantly higher in northern China (at ∼46.8%) than in the south. This disparity is primarily due to the high input of soil erosion-induced DOM from drying-affected lands (57.0%), farmland (49.1%), and forests in the north. The high temperate and strong hydrological conditions would lead to DOM degradation easily in the riverine system in the south of China. Our study highlights that various climatic and anthropogenic factors, such as agriculture, vegetation coverage, soil erosion, surface solar radiation, and precipitation, individually or in combination, can affect DOM dynamics in river systems. Therefore, considering alterations in DOM dynamics resulting from climate and environmental changes is crucial for carbon-neutral policies and sustainable river ecosystem assessments.

Abstract The Karakoram fault (KKF) is an important strike‐slip boundary for accommodating deformation following the India‐Asia collision. However, whether the deformation is confined to the crust or whether it extends into the mantle remains highly debated. Here, we show that the KKF is overwhelmingly dominated by crustal degassing related to a 4He‐ and CO2‐rich fluid reservoir (for example, He contents up to ∼1.0–1.6 vol.%; 3He/4He = 0.027 ± 0.013 RA (1σ, n = 47); CO2/N2 up to 3.7–57.8). Crustal‐scale active deformation driven by strike‐slip faulting could mobilize 4He and CO2 from the fault zone rocks, which subsequently accumulate in the hydrothermal system. The KKF may have limited fluid connections to the mantle, and if any, the accumulated crustal fluids would efficiently dilute the uprising mantle fluids. In both cases, crustal deformation is evidently the first‐order response to strike‐slip faulting.

Abstract Background Planktonic bacteria and archaea play a key role in river nutrient biogeochemical cycling; however, their respective community assembly and how to maintain their diversity are not well known in dammed rivers. Therefore, a seasonal survey of planktonic bacterial and archaeal community compositions and related environmental factors was conducted in 16 cascade reservoirs and corresponding river waters on the Wujiang River and the Pearl River in southwest China to understand the above mechanisms. Results Deterministic processes dominated bacterial and archaeal community assembly. The structural equation models showed that water temperature can directly or indirectly affect the microbial diversity. Interestingly, planktonic bacterial diversity increased with increasing water temperature, while archaea showed the opposite trend; the overall diversity of bacteria and archaea was no significant changes with changeable water temperature. Abundant microbes had a stronger distance–decay relationship than middle and rare ones, and the relationship was stronger in winter and spring than in summer and autumn. Conclusions Planktonic bacteria and archaea in dammed rivers had different biogeographic distributions, and water temperature was a key controlling factor. The different responses of planktonic bacterial and archaeal diversity to water temperature could be due to their different phylogenetic diversity. This ultimately maintained the stability of total microbial community diversity. This study reveals the different responses of planktonic bacteria and archaea to water temperature and perfects the theoretical framework for planktonic microbial biogeography in dammed rivers.

Abstract The driving forces, kill and recovery mechanisms for the end-Permian mass extinction (EPME), the largest Phanerozoic biological crisis, are under debate. Sedimentary records of mercury enrichment and mercury isotopes have suggested the impact of volcanism on the EPME, yet the causes of mercury enrichment and isotope variations remain controversial. Here, we model mercury isotope variations across the EPME to quantitatively assess the effects of volcanism, terrestrial erosion and photic zone euxinia (PZE, toxic, sulfide-rich conditions). Our numerical model shows that while large-scale volcanism remains the main driver of widespread mercury enrichment, the negative shifts of Δ199Hg isotope signature across the EPME cannot be fully explained by volcanism or terrestrial erosion as proposed before, but require additional fractionation by marine mercury photoreduction under enhanced PZE conditions. Thus our model provides further evidence for widespread and prolonged PZE as a key kill mechanism for both the EPME and the impeded recovery afterward.

Abstract Ferric ions can bind strongly with dissolved organic matter (DOM), including humic acids (HA), fulvic acids (FA), and protein-like substances, whereas isolation of Fe-DOM precipitates (Fe-DOMP) and their biochemical characteristics remain unclear. In this work FeCl3 was used to isolate DOM components from various sources, including river, lake, soil, cow dung, and standard tryptophan and tyrosine, through precipitation at pH 7.5–8.5. The Fe-DOMP contribute to total DOM by approximately 38.6–93.8% of FA, 76.2% of HA and 25.0–30.4% of tryptophan and tyrosine, whilst fluorescence spectra allowed to monitor/discriminate the various DOM fractions in the samples. The relative intensity of the main infrared peaks such as 3406‒3383 cm−1 (aromatic OH), 1689‒1635 cm−1 (‒COOH), 1523–1504 cm−1 (amide) and 1176–1033 cm−1 (‒S=O) show either to decline or disappear in Fe‒DOMP. These results suggest the occurrence of Fe bonds with various functional groups of DOM, indicating the formation of π–d electron bonding systems of different strengths in Fe‒DOMP. The novel method used for isolation of Fe-DOMP shows promising in opening a new frontier both at laboratory and industrial purposes. Furthermore, results obtained may provide a better understanding of metal–organic complexes involved in the regulation of the long-term stabilization/sequestration of DOM in soils and waters.

By integrating nitrogen isotope systematics of ammonia emissions and transformations in the atmosphere, this study quantified the combustion-related ammonia emission and uncovered its importance for mitigating strategies of ammonia pollution.

Organic nitrogen (ON) is an important participant in the Earth’s N cycle. Previous studies have shown that penguin feces add an abundance of nutrients including N to the soil, significantly changing the eco-environment in ice-free areas in Antarctica. To explore the molecular transformation of ON in penguin guano-affected soil, we collected guano-free weathered soil, modern guano-affected soil from penguin colonies, ancient guano-affected soil from abandoned penguin colonies, and penguin feces from the Ross Sea region, Antarctica, and Fourier transform ion cyclotron mass spectrometry (FT-ICR MS) was used to investigate the chemical composition of water-extractable ON. By comparing the molecular compositions of ON among different samples, we found that the number of ON compounds (>4,000) in weathered soil is minimal, while carboxylic-rich alicyclic-like molecules (CRAM-like) are dominant. Penguin feces adds ON into the soil with > 10,000 CHON, CHONS and CHN compounds, including CRAM-like, lipid-like, aliphatic/ peptide-like molecules and amines in the guano-affected soil. After the input of penguin feces, macromolecules continue to degrade, and other ON compounds tend to be oxidized into relatively stable CRAM-like molecules, this is an important transformation process of ON in guano-affected soils. We conclude the roles of various forms of ON in the N cycle are complex and diverse. Combined with previous studies, ON eventually turns into inorganic N and is lost from the soil. The lost N ultimately returns to the ocean and the food web, thus completing the N cycle. Our study preliminarily reveals the molecular transformation of ON in penguin guano-affected soil and is important for understanding the N cycle in Antarctica.

Abstract Planktonic bacteria and archaea play a key role in maintaining ecological functions in aquatic ecosystems; however, their biogeographic patterns and underlying mechanisms have not been well known in coastal wetlands including multiple types and at a large space scale. Therefore, planktonic bacteria and archaea and related environmental factors were investigated in twenty-one wetlands along China’s coast to understand the above concerns. The results indicated that planktonic bacteria had different biogeographic pattern from planktonic archaea, and both patterns were not dependent on the wetland's types. Deterministic selection shapes the former’s community structure, whereas stochastic processes regulate the latter’s, being consistent with the fact that planktonic archaea have a larger niche breadth than planktonic bacteria. Planktonic bacteria and archaea co-occur, and their co-occurrence rather than salinity is more important in shaping their community structure although salinity is found to be a main environmental deterministic factor in the coastal wetland waters. This study highlights the role of planktonic bacteria-archaea co-occurrence on their biogeographic patterns, and thus provides a new insight into studying underlying mechanisms of microbial biogeography in coastal wetlands.

Phytoplankton cell size is well known as an essential functional trait, but its control factors are still unclear. Considering light provides the necessary energy for phytoplankton survival, we hypothesized that photosynthetic light energy utilization could influence phytoplankton cell size control. Several scenarios were conducted to understand the relationship between Fv/Fm and cell size for phytoplankton interspecies, and metatranscriptome in the field and transcriptome in the laboratory were used to understand relevant molecular mechanisms. The results indicated that there was a universal significant positive relationship between Fv/Fm and cell volume in general. The molecular evidence demonstrated that light utilization by phytoplankton regulates their cell size by harmonizing the generation and allocation of chemical energy and fixed carbon in the cell. Phytoplankton cell size would cease to enlarge once the increased light energy conversion and subsequent fixed carbon could no longer satisfy the increasing demand of size enlargement. This unity of energy and matter in shaping phytoplankton size results in cell size being an important functional trait. This study is the first to discover the above molecular mechanisms and is helpful to deepen the understanding on the cell size control of phytoplankton.

Planktonic microorganisms play an important role in maintaining the ecological functions in aquatic ecosystems, but how their structure and function interrelate and respond to environmental changes is still not very clear. Damming interrupts the river continuum and alters river nutrient biogeochemical cycling and biological succession. Considering that river damming decreases the irregular hydrological fluctuation, we hypothesized that it can enhance the ecological functional stability (EFS) of planktonic microorganisms. Therefore, the community composition of planktonic bacteria and archaea, functional genes related to carbon, nitrogen, sulfur, and phosphorus cycling, and relevant environmental factors of four cascade reservoirs in the Pearl River, Southern China, were investigated to understand the impact of damming on microbial community structure and function and verify the above hypothesis. Here, the ratio of function to taxa (F:T) based on Euclidean distance matrix analysis was first proposed to characterize the microbial EFS; the smaller the ratio, the more stable the ecological functions. The results showed that the reservoirs created by river damming had seasonal thermal and chemical stratifications with an increasing hydraulic retention time, which significantly changed the microbial structure and function. The river microbial F:T was significantly higher than that of the reservoirs, indicating that river damming enhances the EFS of the planktonic microorganisms. Structural equation modeling demonstrated that water temperature was an important factor influencing the relationship between the microbial structure and function and thus affected their EFS. In addition, reservoir hydraulic load was found a main factor regulating the seasonal difference in microbial EFS among the reservoirs. This study will help to deepen the understanding of the relationship between microbial structure and function and provide a theoretical basis of assessing the ecological function change after the construction of river damming.

Microbial diversity, together with carbon function, plays a key role in driving the wetland carbon cycle; however, the composition, driving factors of carbon-functional genes and the relationship with microbial community have not been well characterized in coastal wetlands. To understand these concerns, microbes, carbon-functional genes, and related environmental factors were investigated in twenty wetlands along China’s coast. The results indicate that carbon-functional gene composition is dominated by archaeal rather than bacterial community and that Nanoarchaeaeota is the dominant archaeal phylum associated with carbon cycling in anoxic sediments. Compared with microbes, carbon-functional composition was more stable because they showed the highest Shannon diversity and archaeal functional redundancy. Deterministic processes dominated microbial community, and stochastic processes were more important for carbon-functional genes. Labile Fe governed archaeal and carbon-functional composition by coupling with nitrogen and carbon biogeochemical cycles, while bacterial community was affected by NH4-N and SOC/SON. This study highlights the predominant contributions of archaea to carbon-functional genes and to the stability of carbon-functional composition, thus providing new insights into the microbial dominance of the carbon cycle and the evaluation of carbon function in coastal wetlands.

To better understand the characteristics and seasonality of trace elements in fine aerosols (PM2.5) in the Tianjin region, North China, we conducted a long-term PM2.5 sampling during July 2018 to July 2019 (n = 121) at an urban location in Tianjin. We measured 28 trace elements in PM2.5 using inductively coupled plasma mass spectroscopy (ICP-MS). Zn, As, Cd, V, and Ni, which are mainly emitted from anthropogenic sources, found to be abundant followed by the elements of natural origin and of dust, respectively. Concentrations of most of the elements varied substantially from season to season, indicating the seasonal differences in emission sources. However, V, Ni, and Cr did not show any significant seasonal variation during the whole campaign, which suggested that the impact of local emissions from the industry was significant throughout the year at Tianjin. The positive matrix factorization (PMF) analysis of the data resulted six factors, representing the sources: emissions of coal combustion, industries, biomass burning, soil dust, vehicle exhaust and secondary formation, with the relative contributions of 17.3%, 12.5%, 14.3%, 18.8%, 25.3% and 11.9%, respectively. Although the annual contribution to PM2.5 from vehicle exhaust was higher, the contributions from biomass burning, secondary formation, coal combustion and the vehicle exhaust were dominated in spring, summer, autumn and winter, respectively. This study provides insights on PM2.5 seasonal characteristics and to develop a controlling strategy for air pollution in mid-latitude coastal cities, especially in northeastern Asia.

Deeply-sourced volatiles are releasing from orogenic plateau regions, providing windows to plateau growth dynamics occurring at variable depths. Here the authors show that mantle-derived volatiles reveal the involvement of mantle dynamics in southeastward growth of the Tibetan Plateau.

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.

Abstract Travel restrictions in the wake of the COVID‐19 pandemic resulted in an unprecedented decrease of 73% in global flight mileage in April–May 2020 compared to 2019. Here we examine the CALIPSO satellite observations and do not find a significant increase in ice crystal number concentrations (Ni) in cirrus clouds in the mid‐latitudes of the Northern Hemisphere, which might be expected due to an increase in homogeneous freezing when soot from aircraft emissions is reduced. Nevertheless this result is consistent with our model simulations, so do not rule out a positive forcing if reductions in aircraft emissions continue. A relatively small positive global average radiative effect of 21 mW m−2 is estimated if a decrease in aircraft traffic continues, with an average of up to 64 mW m−2 over the area where aviation is most active. We infer from this analysis that the worldwide adoption of biofuel blending in aircraft fuels that lead to smaller soot emissions could lead to a significant change in the microphysical properties of cirrus clouds but a rather small positive radiative effect.

Sauce-flavor Baijiu is one of the most complex and typical types of traditional Chinese liquor, whose trace components have an important impact on its taste and quality. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) is one of the most favorable analytical tools to reveal trace molecular components in complex samples. This study analyzed the chemical diversity of several representative sauce-flavor Baijiu using the combination of electrospray ionization (ESI) and FT-ICR MS. The results showed that ESI+ and ESI− exhibited different chemical features characteristic of trace components. Overall, sauce-flavor Baijiu was dominated by CHO class compounds, and the main specific compound types were aliphatic, highly unsaturated with low oxygen, and peptide-like compounds. The mass spectral parameters resolved by FT-ICR MS of several well-known brands were relatively similar, whereas the greatest variability was observed from an internally supplied brand. This study provides a new perspective on the mass spectrometry characteristics of trace components of sauce-flavor Baijiu and offers a theoretical foundation for further optimization of the gradients in Baijiu.

In terrestrial ecosystems, vegetation is sensitive to climate change and human activities. Its spatial-temporal changes also affect the ecological and social environment. In this paper, we considered the Beijing–Tianjin–Hebei region to study the spatio-temporal vegetation patterns. The detailed analysis of a moderate-resolution imaging spectroradiometer (MODIS) data were carried out through the Google Earth Engine (GEE) platform. Our results show a slow and tortuous upward trend in the average leaf area index (LAI) in the study region for the periods 2001–2020. Specifically, Beijing had the highest LAI value, with an average of 1.64 over twenty years, followed by Hebei (1.30) and Tianjin (1.04). Among different vegetation types, forests had the highest normalized difference vegetation index (NDVI) with the range of 0.62–0.78, followed by shrubland (0.58–0.75), grassland (0.34–0.66), and cropland (0.38–0.54) over the years. Spatially, compared to the whole study area, index value in the northwestern part of the Beijing–Tianjin–Hebei region increased greatly in many areas, such as northwest Beijing, Chengde, and Zhangjiakou, indicating a significant ecological optimization. Meanwhile, there was ecological degradation in the middle and southeast regions, from Tangshan southeastward to Handan, crossing Tianjin, Langfang, the east part of Baoding, Shijiazhuang, and the west part of Cangzhou. Air temperature and precipitation were positively and significantly correlated with net primary production (NPP) and precipitation stood out as a key driver. Additionally, an intensification of the urbanization rate will negatively impact the vegetation NPP, with the shrubland and forest being affected most relative to the cropland.

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.

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

Abstract Upon exposure to sunlight extracellular polymeric substances (EPS) were partially transformed into transparent exopolymer particles (TEP) and unstable flocs of different sizes without the addition of any precursors. Parallel factor (PARAFAC) modelling of the sample fluorescence spectra identified humic-like and protein-like or tyrosine-like components in both untreated and irradiated EPS samples. After 58 hours of solar irradiation, humic-like substances were entirely decomposed, while the regenerated protein-like substance from EPS was the key component in the irradiated samples. Degradation and reformation of EPS occurred which was confirmed by the results of size exclusion chromatography, dissolved organic carbon, total protein and total polysaccharide analyses. Irradiated EPS was composed of –COOH or C = O (amide I band) and –NH and –CN (amide II band), while Fourier transform infrared spectroscopy (FTIR) of TEP revealed more acidic –COOH and –C–O groups, indicating typical acidic protein-like TEP. The regenerated protein-like substances could form complexes with free metals originating from degraded EPS in irradiated samples, which could be responsible for the formation of TEP/floc in the aqueous media. These results suggest that TEP/floc formation from EPS could occur by a complexation mechanism between dissolved organic matter and metals, thereby causing ionic charge neutralisation upon sunlight exposure.

Carbon dioxide (CO _2 ) 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 CO _2 emissions 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 CO _2 fluxes 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 of p CO _2 (mean = 3205.7 μ atm, SD = 2183.4 μ atm) and δ ^13 C _CO2 (mean = −18.9‰, SD = 1.6‰) in the cascade reservoirs, suggesting that multiple processes regulate CO _2 production. Moreover, the calculated CO _2 fluxes showed obvious spatiotemporal variations, ranging from −9.0 to 2269.3 mmol m ^−2 d ^−1 , with an average of 260.1 mmol m ^−2 d ^−1 . Interestingly, the CO _2 flux and δ ^13 C _CO2 from reservoirs of this study and other reservoirs around the world had an exponential function with the reservoir effect index ( R _i , HRT/NWL), suggesting the viability of our hypothesis on reservoir CO _2 emission. This empirical function will help to estimate CO _2 emissions from global reservoirs and provide theoretical support for reservoir regulation to mitigate carbon emission.

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 ^13 C and Δ ^14 C, 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 Δ ^14 C _n _-alkanes of C _19 –C _24 and C _26 –C _32 even-carbon homologs (−851 to −708‰) indicate their dominance from fossil fuel combustion. In contrast, the Δ ^14 C of most abundant palmitic acid (C _16:0 ) and stearic acid (C _18:0 ) suggest a larger contribution from nonfossil sources (∼91%–94%), mainly due to inputs from cooking, biomass burning and microorganisms. Compared with lower Δ ^14 C of C _27 and C _31 n -alkanes (−449‰), C _29 n -alkane (−241‰) and C _20 –C _30 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 C _27 –C _31 n -alkanes (40%) and C _20 –C _30 n -fatty acids (30%) could be from soil resuspension and/or loess deposits in upwind regions through long-range atmospheric transport.

Nitrogen isotope (δ15N) has been employed to differentiate major sources of atmospheric N. However, it remains a challenge to quantify contributions of multiple sources based on δ15N values of the N mixture in atmospheric samples. This study measured δ15N of bulk N in PM2.5 at an urban site of Beijing during a severe haze episode of 22–30 January 2013 and a background site of Qinghai, north-western China from 6 September to 15 October 2013, then applied a Bayesian isotope mixing model (SIAR, Stable Isotope Analysis in R) to analyse the N sources. At Beijing site, δ15N values of PM2.5 (−4.1‰ to +13.5‰, +2.8 ± 6.4‰) were distributed within the range of major anthropogenic sources (including NH3 and NO2 from coal combustion, vehicle exhausts and domestic wastes/sewage). At Menyuan site, δ15N values of PM2.5 (+8.0‰ to +27.9‰, +18.5 ± 5.8‰) were significantly higher than that of potential sources (including NH3 and NO2 from biomass burning, animal wastes, soil N cycle, fertilizer application and dust N). High molar ratios of $ {\text{NH}}_4^{+} $ to $ {\text{NO}}_3^{-} $ and/or $ {\text{SO}}_4^{2-} $ in PM2.5 at the background site suggested that the equilibrium of NH3 ↔ $ {\text{NH}}_4^{+} $ caused apparent 15N enrichments in ammonium. Results of the SIAR model showed that 39 and 32% of bulk N in PM2.5 of Beijing site were contributed from N emissions of coal combustion and vehicle exhausts, respectively, whereas N in PM2.5 at Menyuan site was derived mainly from N emissions of biomass burning (46%) and NH3 volatilization (34%). These results revealed that the stoichiometry between NH3 and acidic gases plays an important role in controlling the bulk δ15N signatures of PM2.5 and emissions of reactive N from coal combustion and urban transportation should be strictly controlled to advert the risk of haze episodes in Beijing.

Picophytoplankton community structure has been seasonally investigated in the cascade reservoirs along the Wujiang River from April 2006 to January 2007. Besides picoeukaryotes, two groups of picocyanobacteria have also been detected by flow cytometry. One is a phycoerythrin-rich picocyanobacteria (PE-rich Pcy), the other is a red-fluorescing cells with lacking orange fluorescence and could be a phycocyanin-rich picocyanobacteria (PC-rich Pcy). The average abundances of PC-rich Pcy, PE-rich Pcy and picoeukaryotes were 103, 104 and 102 cells mL-1, respectively. PE-rich Pcy was the dominant population but showed a reduction with eutrophication, and therefore the community structure of picophytoplankton transformed from dominant PE-rich Pcy to dominant PE-rich Pcy and PC-rich Pcy, which suggested they are excellent indicators for the change of trophic state. Picophytoplankton community structure also presented a seasonal variation, indicating the different response of each picophytoplankton group to water temperature.

In order to investigate the relationship between dissolved silicon (DSi) and bicarbonate (HCO3–), we analysed water samples from the main Changjiang channel and its main tributaries in August 2006 and, during 2007-2009, the contrasting tributaries Wujiang (WJ) – mainly dominated by carbonate weathering, and Ganjiang – mainly dominated by silicate weathering. The DSi: HCO3– ratio ranged from 0 to 0.67, which is in agreement with mixing between the weathering of carbonate or silicate. A negative correlation between DSi and HCO3– was observed and interpreted as the imprint of regional geology on water chemistry. This relationship and the DSi: HCO3– ratios illustrate the predominant role of carbonate weathering on the riverine HCO3–, even forcatchments where silicate rocks are dominant. In contrast, a cascade of dams in WJ tributary influenced the concentrations of Dsi and HCO3– and resulted in a positive correlation between DSi and HCO3–. This is because reservoirs allowed populations of diatomsto develop and diatoms stoichiometrically sequestered DSi and HCO3– causing a negative feedback regulation on the DSi: HCO3– ratio. Our study demonstrates that the relationship between DSi and HCO3–can reflect not only their geological background but also the influence of algal activity (diatom uptake) within rivers.

In order to systematically understand the mechanisms controlling the carbon stable isotope composition of phytoplankton (δ13CPHY)in freshwater ecosystems, seasonal changes in δ13CPHY and related environmental factors were determined in karst reservoirs from the Wujiang river basin, China. Substantial and systematic differences within seasons and reservoirs were observed for δ13CPHY, which ranged from -39.2‰ to -15.1‰. An increase in water temperature triggered fast growth of phytoplankton which assimilated more dissolved inorganic carbon (DIC), resulting in the increase of δ13CPHY, δ13CDIC and pH. When the concentration of dissolved carbon dioxide (CO2) was less than 10 mmol L–1, phytoplankton shifted to using HCO3– as a carbon source. This resulted in the sharp increase of δ13CPHY. The carbon stable isotope composition of phytoplankton tended to decrease with the increase of Bacillariophyta, which dominated in January and April, but tended to increase with the increase of Chlorophyta and Dinophyta, which dominated in July. Multiple regression equations suggested that the influence of biological factors such as taxonomic difference on δ13CPHY could be equal or more important than that of physical and chemical factors. Thus, the effect of taxonomic differences on δ13CPHY must be considered when explaining the δ13C of organic matter in lacustrine ecosystem.