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Soil organic carbon (SOC) in coastal wetlands, also known as "blue C," is an essential component of the global C cycles. To gain a detailed insight into blue C storage and controlling factors, we studied 142 sites across ca. 5000 km of coastal wetlands, covering temperate, subtropical, and tropical climates in China. The wetlands represented six vegetation types (Phragmites australis, mixed of P. australis and Suaeda, single Suaeda, Spartina alterniflora, mangrove [Kandelia obovata and Avicennia marina], tidal flat) and three vegetation types invaded by S. alterniflora (P. australis, K. obovata, A. marina). Our results revealed large spatial heterogeneity in SOC density of the top 1-m ranging 40-200 Mg C ha

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.

Metal stable isotopes in marine carbonates have been widely used as novel proxies for metal cycling through the geological past. Amongst these metals, copper (Cu) and zinc (Zn) have received great attention owing to their vital roles in metabolic processes. However, whether modern marine biogenic carbonates record the seawater isotope signatures of Cu (δ65Cu) and Zn (δ66Zn) and mechanisms and factors controlling isotope fractionation of these metals remain unclear, hindering applications of both isotope systems in paleoceanography. Here we present annually-resolved records of δ65Cu and δ66Zn in seven coral (Porites) cores sampled from different marine settings in the South China Sea and the Luzon Strait, western Pacific. We find that the aragonitic skeletons of corals are enriched in light Cu but heavy Zn isotopes relative to surface seawaters, with δ65Cu and δ66Zn in the range of −0.16 ± 0.06‰ to 0.40 ± 0.05‰ and 0.06 ± 0.04‰ to 0.46 ± 0.08‰ (2SD), respectively. The coral δ65Cu exhibits significant inter- and intra-colony variations, which are most likely controlled by Rayleigh-type fractionation in the calcifying fluids of corals rather than by changes in environmental factors or seawater δ65Cu. We thus suggest that δ65Cu in ancient carbonates may not be a direct record of Cu isotope compositions in coeval seawaters. In contrast, coral δ66Zn shows insignificant temporal variation, and the Zn isotope fractionation between individual corals and seawaters are relatively small and constant (0.10 ± 0.05‰, n = 33, 2SD). This limited Zn isotope fractionation is much lower than that determined during inorganic precipitation of calcite, which is likely due to pH up-regulation by the coral that changes aqueous Zn speciation, and preferential organic complexation of the heavy Zn isotopes in the calcifying fluids. Therefore, Porites corals are promising archives for tracking historical changes of surface seawater δ66Zn. Our new datasets of reef carbonates, particularly the coral δ65Cu values which are measured for the first time, could provide a better constrain on marine Cu and Zn geochemistry and their modern oceanic mass and isotope budgets.

Fungal-mediated extracellular reactive oxygen species (ROS) are essential for biogeochemical cycles of carbon, nitrogen, and contaminants in terrestrial environments. These ROS levels may be modulated by iron nanoparticles that possess intrinsic peroxidase (POD)-like activity (nanozymes). However, it remains largely undescribed how fungi modulate the POD-like activity of the iron nanoparticles with various crystallinities and crystal facets. Using well-controlled fungal-mineral cultivation experiments, here, we showed that fungi possessed a robust defect engineering strategy to modulate the POD-like activity of the attached iron minerals by decreasing the catalytic activity of poorly ordered ferrihydrite but enhancing that of well-crystallized hematite. The dynamics of POD-like activity were found to reside in molecular trade-offs between lattice oxygen and oxygen vacancies in the iron nanoparticles, which may be located in a cytoprotective fungal exoskeleton. Together, our findings unveil coupled POD-like activity and oxygen redox dynamics during fungal-mineral interactions, which increase the understanding of the catalytic mechanisms of POD-like nanozymes and microbial-mediated biogeochemical cycles of nutrient elements as well as the attenuation of contaminants in terrestrial environments.

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

Little is known about the formation processes of nitrooxy organosulfates (OSs) by nighttime chemistry. Here we characterize nitrooxy OSs at a molecular level in firework-related aerosols in urban Beijing during Chinese New Year. High-molecular-weight nitrooxy OSs with relatively low H / C and O / C ratios and high unsaturation are potentially aromatic-like nitrooxy OSs. They considerably increased during New Year's Eve, affected by the firework emissions. We find that large quantities of carboxylic-rich alicyclic molecules possibly formed by nighttime reactions. The sufficient abundance of aliphatic-like and aromatic-like nitrooxy OSs in firework-related aerosols demonstrates that anthropogenic volatile organic compounds are important precursors of urban secondary organic aerosols (SOAs). In addition, more than 98 % of those nitrooxy OSs are extremely low-volatility organic compounds that can easily partition into and consist in the particle phase and affect the volatility, hygroscopicity, and even toxicity of urban aerosols. Our study provides new insights into the formation of nitrooxy organosulfates from anthropogenic emissions through nighttime chemistry in the urban atmosphere.

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

Anthropogenic input of sulfate (SO

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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.

To characterize secondary organic aerosols (SOA) over the Tianjin region, we studied the SOA tracers derived from isoprene, α/β-pinene, β-caryophyllene, and aromatics in PM2.5 collected at an urban...

Molecular compositions and stable carbon isotope ratios (δ13C) of n-alkanes and fatty acids (FA) were investigated in urban aerosols from Beijing, China. Seasonal trends for n-alkanes showed a high...

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.

Zn isotope is a useful tool for tracing biogeochemical processes as zinc plays important roles in the biogeochemistry of natural systems. However, the Zn isotope composition in the lake ecosystems has not been well characterized. In order to resolve this problem, we investigate the Zn isotope compositions of suspended particulate matter (SPM) and biological samples collected from the Aha Lake and Hongfeng Lake, and their tributaries in summer and winter, aiming to explore the potential of this novel isotope system as a proxy for biogeochemical processes in aqueous environments. Concentration of dissolved Zn ranges from 0.65 to 5.06 μg/L and 0.74 to 12.04 μg/L for Aha Lake and Hongfeng Lake, respectively, while Zn (SPM) ranges from 0.18 to 0.70 mg/g and 0.24 to 0.75 mg/g for Aha Lake and Hongfeng Lake, respectively. The Zn isotope composition in SPM from Aha Lake and its main tributaries ranges from -0.18‰ to 0.27‰ and -0.17‰ to 0.46‰, respectively, and it varies from -0.29‰ to 0.26‰ and -0.04‰ to 0.48‰, respectively in Hongfeng Lake and its main tributaries, displaying a wider range in tributaries than lakes. These results imply that Zn isotope compositions are mainly affected by tributaries inputting into Aha Lake, while adsorption process by algae is the major factor for the Zn isotope composition in Hongfeng Lake, and ZnS precipitation leads to the light Zn isotope composition of SPM in summer. These data and results provide the basic information of the Zn isotope for the lake ecosystem, and promote the application of Zn isotope in biogeochemistry.

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

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

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.

Organic aerosols (OA) that make up a large fraction (up to 90%) of the fine aerosol (PM2.5) mass have severe impact on the Earth’s climate system and can cause adverse risk to human health. Diacids and related compounds are ubiquitous in PM2.5 in different environments and accounts for a substantial fraction in OA. Because of their high water-solubility, they can influence the hygroscopic properties and capacity of cloud condensation nuclei formation activity of aerosols and thus affect the indirect radiative forcing in the atmosphere. However, their origins, secondary formation and transformations and seasonality are not fully understood yet. To better understand the seasonal characteristics, origins and photochemical processing of OA in the Tianjin region, North China, we studied the molecular distributions and seasonal variations of water-soluble diacids, oxoacids and α-dicarbonyls in PM2.5 collected at an urban and a suburban sites in Tianjin, an ideal location to study the aerosols, over a one-year period from July 2018 to June 2019. We found significant changes in concentrations and composition of diacids and related compounds from season to season at both the sites. Here, based on the results obtained together with the meteorology, oxidants (O3 and NO2) and SO2, loading and the backward air mass trajectories, we discuss the possible origins and possible secondary formation pathways of diacids and related compounds in the Tianjin region.

Little is known about the formation processes of nitrooxy-organosulfates (nitrooxy-OSs) by nighttime chemistry. Here we characterize nitrooxy-OSs at a molecular level in firework-related aerosols in urban Beijing during Chinese New Year. High-molecular-weight nitrooxy-OSs with relatively low H / C and O / C ratios and high unsaturation, which are potentially aromatic-like nitrooxy-OSs, considerably increased during the New Year’s Eve. We find that large quantities of carboxylic-rich alicyclic molecules possibly formed by nighttime reactions. The sufficient abundance of aliphatic-like and aromatic-like nitrooxy-OSs demonstrates that both anthropogenic and biogenic volatile organic compounds are essential precursors of urban secondary organic aerosols (SOA). Besides, more than 98 % of nitrooxy-OSs were extremely low-volatile organic compounds that could easily partition into and consist in the particle phase, and affected the volatility, hygroscopicity, and even toxicity of urban aerosols. Our study provides new insights into the formation of nitrooxy-organosulfates from anthropogenic emissions through nighttime chemistry in the urban atmosphere.

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.

The production of fluorescent dissolved organic matter (FDOM) produced from phytoplankton and its subsequent degradation both of which occur constantly under diurnal-day time sunlight and by night time dark-microbial processes, 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, but not in lower temperature months. In July, extracellular polymeric substances (EPS), an early-state DOM, were produced from phytoplankton in early morning (06:00–09:00), then 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 night time (02:00–06:00). Such transformations occurred simultaneously with the fluctuating production of nutrients (NH4+, NO3−, NO2−, PO43− and dissolved Si), dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and the two isotopes (δ15N and δ18O) of NO3−. The FDOM components identified by fluorescence excitation-emission matrix (EEM) spectroscopy combined with parallel factor (PARAFAC) analysis consisted of EPS, autochthonous humic-like substances (AHLS) of C and M types distinctly, a combined form of C and M types of AHLS, protein-like substances (PLS), newly-released PLS, tryptophan-like substances (TLS), tyrosine-like substances (TYLS), a combined form of TYLS and phenylalanine-like substances (PALS), as well as 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.

Superoxide, produced photochemically as well as microbially, is an important reactant present in seawater and a major source of hydrogen peroxide. Superoxide decay may occur through catalyzed or uncatalyzed dismutation forming H2O2 and O2, through oxidation to O2, or through reduction into H2O2. Under definite circumstances, the redox processes that are different from dismutation could produce or consume H+, thereby altering the pH of seawater. In order to alter the pH, these processes have to involve, together with O2•, redox couples that exchange e and H+ in a ratio other than 1:1. This potential pH modification is dependent on several factors, including the extent of H+ imbalance, the rate of formation/transformation of superoxide (which reaches a steady-state concentration in seawater), and the alkalinity of seawater (which varies globally from 2.10 to 2.45 mmol L1 and buffers the pH variations). In the present study, an estimate of the possible pH changes associated with photochemically-produced superoxide in the global ocean has been provided. Among the important approximations that were required to perform the calculations, one was that it was not possible to include the microbially generated O2•, as a geographic distribution of microbial processes is not available. Unfortunately, the microbial production of O2• is comparable to or at certain times even higher than its photochemical production. Despite the above-stated and certain other limitations, it may be inferred that the tropical and equatorial oceans, because of the high O2• photoproduction rates, would be having the highest potential of undergoing pH variations (up to 0.005 pH units in ten years). Along the tropical/equatorial latitude belt, at comparable sunlight irradiance, such variations are expected to be the largest (0.005 pH units) in the Indian Ocean due to a relatively low alkalinity, in the range of 2.2–2.3 mmol L1. The lowest variations (0.003–0.004 pH units) are expected in the Atlantic Ocean, because of a relatively high alkalinity in the range of 2.3–2.4 mmol L1. The main requirement for the O2• chemistry to impact the pH of seawater significantly is that the H+-imbalance reactions should be maintained for a sufficiently long period of time. The pH effect is most probably to be operational in the river-impacted coastal areas (potential candidates are the areas affected by the following rivers: Ganges, Mekong, Irrawaddy, Zambezi, Amazon River, Orinoco, Mississippi, and Rio Grande), which are characterized by a continuous flow of redox-active organic compounds into the seawater.

Firework (FW) emission has strong impacts on air quality and public health. However, little is known about the molecular composition of FW-related airborne particulate matter (PM) especially the organic fraction. Here we describe the detailed molecular composition of Beijing PM collected before, during, and after a FW event in New Year's Eve evening in 2012. Subgroups of CHO, CHNO, and CHOS were characterized using ultrahigh resolution Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry. These subgroups comprise substantial fraction of aromatic-like compounds with low O/C ratio and high degrees of unsaturation, some of which plausibly contributed to the formation of brown carbon in Beijing PM. Moreover, we found that the number concentration of sulfur-containing compounds especially the organosulfates was increased dramatically by the FW event, whereas the number concentration of CHO and CHON doubled after the event. The co-variation of CHO, CHON, and CHOS subgroups was suggested to be associated with multiple atmospheric aging processes of aerosols including the multiphase redox chemistry driven by NOx, O3, and •OH. These findings highlight that FW emissions can lead to a sharp increase of high molecular weight compounds particularly aromatic-like substances in urban PM, which may affect the light absorption properties and adverse health effects of atmospheric aerosols.

In order to better understand the molecular composition and sources of organic aerosols in Tianjin, a coastal megacity in North China, ambient fine aerosol (PM2.5) samples were collected on a day/night basis from November to December 2016 and from May to June 2017. The organic molecular composition of PM2.5 components, including aliphatic lipids (n-alkanes, fatty acids, and fatty alcohols), sugar compounds, and photooxidation products from isoprene, monoterpene, β-caryophyllene, naphthalene, and toluene, was analysed using gas chromatography–mass spectrometry. Fatty acids, fatty alcohols, and saccharides were identified as the most abundant organic compound classes among all of the tracers detected in this study during both seasons. High concentrations of most organics at night in winter may be attributed to intensive residential activities such as house heating as well as the low nocturnal boundary layer height. Based on tracer methods, the contributions of the sum of primary and secondary organic carbon (POC and SOC respectively) to aerosol organic carbon (OC) were 24.8 % (daytime) and 27.6 % (night-time) in winter and 38.9 % (daytime) and 32.5 % (night-time) in summer. In detail, POC derived from fungal spores, plant debris, and biomass burning accounted for 2.78 %–31.6 % (12.4 %; please note that values displayed in parentheses in the following are average values) of OC during the daytime and 4.72 %–45.9 % (16.3 %) at night in winter, and 1.28 %–9.89 % (5.24 %) during the daytime and 2.08 %–47.2 % (10.6 %) at night in summer. Biomass-burning-derived OC was the predominant source of POC in this study, especially at night (16.0±6.88 % in winter and 9.62±8.73 % in summer). Biogenic SOC from isoprene, α-∕β-pinene, and β-caryophyllene exhibited obvious seasonal and diurnal patterns, contributing 2.23±1.27 % (2.30±1.35 % during the daytime and 2.18±1.19 % at night) and 8.60±4.02 % (8.98±3.67 % and 8.21±4.39 %) to OC in winter and summer respectively. Isoprene and α-∕β-pinene SOC were obviously elevated in summer, especially during the daytime, mainly due to strong photooxidation. Anthropogenic SOC from toluene and naphthalene oxidation showed higher contributions to OC in summer (21.0±18.5 %) than in winter (9.58±3.68 %). In summer, toluene SOC was the dominant contributor to aerosol OC, and biomass burning OC also accounted for a high contribution to OC, especially at night-time; this indicates that land/sea breezes also play an important role in the aerosol chemistry of the coastal city of Tianjin in North China.

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

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

Estimates of biogeochemical processes and the proportion of N2O production in the aquatic system of impoundments are important to quantify nitrogen cycling, particularly during stratification perio...

Plant nitrogen (N) use is a key component of the N cycle in terrestrial ecosystems. The supply of N to plants affects community species composition and ecosystem processes such as photosynthesis and carbon (C) accumulation. However, the availabilities and relative importance of different N forms to plants are not well understood. While nitrate (NO3−) is a major N form used by plants worldwide, it is discounted as a N source for Arctic tundra plants because of extremely low NO3− concentrations in Arctic tundra soils, undetectable soil nitrification, and plant-tissue NO3− that is typically below detection limits. Here we reexamine NO3− use by tundra plants using a sensitive denitrifier method to analyze plant-tissue NO3−. Soil-derived NO3− was detected in tundra plant tissues, and tundra plants took up soil NO3− at comparable rates to plants from relatively NO3−-rich ecosystems in other biomes. Nitrate assimilation determined by 15N enrichments of leaf NO3− relative to soil NO3− accounted for 4 to 52% (as estimated by a Bayesian isotope-mixing model) of species-specific total leaf N of Alaskan tundra plants. Our finding that in situ soil NO3− availability for tundra plants is high has important implications for Arctic ecosystems, not only in determining species compositions, but also in determining the loss of N from soils via leaching and denitrification. Plant N uptake and soil N losses can strongly influence C uptake and accumulation in tundra soils. Accordingly, this evidence of NO3− availability in tundra soils is crucial for predicting C storage in tundra., ツンドラの生態系でも硝酸イオンは大切な窒素源だった --最先端の測定技術で「見えない」硝酸イオンの重要性を検証--. 京都大学プレスリリース. 2018-03-14.

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.