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To better understand the origins and seasonality of atmospheric aerosols in North China, we collected fine aerosols (PM2.5) at an urban site (Nankai District, ND) and a suburban site (Haihe Education Park, HEP) in Tianjin from July 2018 to July 2019. The PM2.5 was studied for carbonaceous, nitrogenous and ionic components and stable carbon and nitrogen isotope ratios of total carbon (δ13CTC) and nitrogen (δ15NTN). On average, the mass concentrations of PM2.5, organic carbon (OC), elemental carbon (EC) and water-soluble OC (WSOC) were higher in winter than in summer at both ND and HEP. SO42-, NO3- and NH4+ were the dominant ions, and their sum accounted for 89 % of the total ionic mass at ND and 87 % at HEP. NO3- and NH4+ peaked in winter and were at their minimum in summer, whereas SO42- was higher in summer than in all the other seasons at HEP and was comparable among the seasons, although it peaked in winter at ND. δ13CTC and δ15NTN were −26.5 ‰ to −21.9 ‰ and +1.01 ‰ to +22.8 ‰ at ND and −25.5 ‰ to −22.8 ‰ and +4.91 ‰ to +18.6 ‰ at HEP. Based on seasonal variations in the measured parameters, we found that coal and biomass combustion emissions are the dominant sources of PM2.5 in autumn and winter, while terrestrial and/or marine biological emissions are important in spring and summer in the Tianjin region, North China. In addition, our results implied that the secondary formation pathways of secondary organic aerosols in autumn/winter were different from those in spring/summer; i.e., they might be driven by NO3 radicals in the former period.

This work is dedicated to improving the efficient purification, collection, and clumped isotope analysis method for natural methane with a wide range of concentrations.

Nitrogen dynamics at ecosystem levels profoundly impact the Earth’s surface system due to their environmental and ecological significance. Exploring the sources and transformation of nitrogen in various Critical Zones is vital to understanding biogeochemical cycles and sustainable development. This study summarized nitrogen characteristics in soil profiles and nitrogen dynamics in diverse terrestrial ecosystems based on data from typical Critical Zones of China. The results indicated that nitrogen accumulates in the deep soils of cropland ecosystems due to intensive fertilizer applications, which potentially harms soil functions and water quality. Therefore, it is necessary and meaningful to take adequate measures to alleviate nitrogen accumulation in deep soils. Additionally, surplus nitrogen transported into groundwater and riverine systems from soil has emerged as an important issue for environmental management. There are serious nitrogen pollution issues in many river water and groundwater areas, which could be addressed by reducing the fast leaching and considerable nitrogen accumulation in the vadose zone. Systematic and long-term observational studies are needed to achieve the ultimate goal of ecological conservation and high-quality development. Therefore, future research should consider monitoring and evaluating ecosystems based on the long-term Critical Zone Observatories networks to advance appropriate environmental management strategies that adapt to nature’s rules and strengthen the ecosystem service function for sustainable development.

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.

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.

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.

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.

Atmospheric ammonia (NH3) and ammonium (NH4+) can substantially influence air quality, ecosystems, and climate. NH3 volatilization from fertilizers and wastes (v-NH3) has long been assumed to be the primary NH3 source, but the contribution of combustion-related NH3 (c-NH3, mainly fossil fuels and biomass burning) remains unconstrained. Here, we collated nitrogen isotopes of atmospheric NH3 and NH4+ and established a robust method to differentiate v-NH3 and c-NH3. We found that the relative contribution of the c-NH3 in the total NH3 emissions reached up to 40 ± 21% (6.6 ± 3.4 Tg N yr−1), 49 ± 16% (2.8 ± 0.9 Tg N yr−1), and 44 ± 19% (2.8 ± 1.3 Tg N yr−1) in East Asia, North America, and Europe, respectively, though its fractions and amounts in these regions generally decreased over the past decades. Given its importance, c-NH3 emission should be considered in making emission inventories, dispersion modeling, mitigation strategies, budgeting deposition fluxes, and evaluating the ecological effects of atmospheric NH3 loading.

Mantle degassing transect across different tectonic units within a plate convergent setting has been well documented for oceanic convergent margins by systematic changes in geochemistry (e.g., 3He/4He, δ13C, and CO2/3He) of hydrothermal gases. However, little is known about spatial variations in volatile geochemistry across a continental convergent margin. In this study, we identify a mantle degassing transect in the southeastern Tibetan Plateau using He-CO2 systematics of hydrothermal gases, which extends from India-Asia continental convergent margin to intra-continent extensional region. δ13C-CO2 (−11.8‰ to −3.1‰) and CO2/3He (1.7 × 108 to 7.1 × 1011) values of hydrothermal gases show large variations that are consistent with modification by secondary physico-chemical processes, such as multi-component mixing, hydrothermal degassing, and calcite precipitation. Three levels of He degassing can be recognized based on 3He/4He dataset (0.01–5.87 RA) of the hydrothermal gas samples and their distances to volcanic centers. A magmatic level He degassing (35–74% mantle He) is found near active and/or Quaternary volcanoes fed by mantle-derived magmas. With increasing distance to volcanic centers, the outgassed magmatic volatiles are gradually diluted by crustal components (e.g., radiogenic 4He), defining a transitional level He degassing (13–33% mantle He). The 3He/4He values (8.16–8.48 RA) of olivine phenocrysts indicate a MORB (mid-ocean ridge basalts)-type mantle source for the magmatic and transitional levels of He degassing that are localized in Quaternary volcanic fields. In contrast, a background level He degassing (

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.

A large number of gases are releasing from the medium-high temperature geothermal fields distributed along the large-scale strike-slip fault zones in the southeastern margin of the Tibetan Plateau. In this study, 11 hot spring water and the associated bubbling gas samples were collected along the Xianshuihe-Anninghe fault zones (XSH-ANHFZ) and analyzed for chemical and isotopic compositions. The $${\delta ^{18}}{{\rm{O}}_{{{\rm{H}}_2}{\rm{O}}}}$$ and $$\delta {{\rm{D}}_{{{\rm{H}}_2}{\rm{O}}}}$$ values indicate that hot spring waters are predominantly meteoric origin recharged from different altitudes. Most water samples are significantly enriched in Na+ and HCO3− due to the dissolution of regional evaporites, carbonates and Na-silicates. 3He/4He ratios of the gas samples are 0.025–2.73 times the atmospheric value. The 3He/4He ratios are high in the Kangding region where the dense faults are distributed, and gradually decrease with increasing distance from Kangding towards both sides along the Xianshuihe fault zones (XSHFZ). Hydrothermal fluids have dissolved inorganic carbon (DIC) concentrations from 2 to 42 mmol L−1, δ13CDIC from −6.9‰ to 1.3‰, $${\delta ^{13}}{{\rm{C}}_{{\rm{C}}{{\rm{O}}_2}}}$$ from −7.2‰ to −3.6‰ and Δ14C from −997‰ to −909‰. Combining regional geochemical and geological information, the CO2 sources can be attributed to deep-sourced CO2 from mantle and metamorphism of marine carbonate, and shallow-sourced CO2 from the dissolution of marine carbonate and biogenic CO2. The mass balance model shows that 11±6% of the DIC is sourced from the dissolution of shallow carbonate minerals, 9±8% formed by pyrolysis of sedimentary organic matter, 80±9% derived from deep metamorphic origin and mantle-derived CO2. Among them, the deep-sourced CO2 in Anninghe fault zones (ANHFZ) is merely metamorphic carbon, whereas ca. 12% and ca. 88% of the deep-sourced CO2 in the XSHFZ are derived from the mantle and metamorphic carbon, respectively. The average deep-sourced CO2 flux in the Kangding geothermal field is estimated to be 160 t a−1. If all the hot springs in various fault zones in the southeastern margin of the Tibetan Plateau are taken into account, the regional deep-sourced CO2 flux would reach ca. 105 t a−1. These results show that the deep-sourced CO2 released from non-volcanic areas might account for a considerable proportion of the total amount of global deep-sourced carbon degassing, which should be paid more attention to.

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.

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.

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.

Landscape evolution is modulated by the regional tectonic uplift, climate change, and river dynamics. However, how to distinguish these mechanisms through the research of surface exhumation and fluvial incision remains controversial. In this study, cosmogenic 10Be, 26Al, and 21Ne concentrations in quartz from cave deposits, modern river sediments, and bedrocks were measured to constrain the applicability of cosmogenic 21Ne and discuss Quaternary landscape evolution history in the Guizhou Plateau, southeast China. Using the 26Al-10Be and 21Ne-10Be pairs to distinguish the cosmogenic 21Ne concentration from the excess 21Ne, we found that the nucleogenic 21Ne produced by the U and Th decay in quartz is significant in the samples although there is the possibility of inherited cosmogenic 21Ne. Combining with previous studies, we suggest that the precise approach for applying the cosmogenic 21Ne could be reached by (1) estimating the contribution from nucleogenic 21Ne, (2) avoiding samples with complex burial histories to exclude inherited cosmogenic 21Ne, and (3) combining the 10Be-26Al-21Ne nuclides method for the Quaternary samples. In addition, both pre-burial basin denudation rates and burial ages derived from the 26Al-10Be pair were used to determine the different timescale surface denudation rate and fluvial incision rate in relation to previous work. The consistency of the different timescales pre-burial basin denudation rate, 36Cl surface denudation rate, and modern basin denudation rate indicates that the landscape-scale surface denudation has been likely stabilized since the Quaternary in the Guizhou Plateau area. The slightly higher river incision rates than the local surface denudation rate show that the river dynamics may not have reached a steady-state due to the regional tectonic uplift in the Guizhou Plateau.

Exploring the source, transformation pathways, and the fate of natural organic matter (NOM) is critical to understanding the regional/global carbon cycle and carbon budget. The dissolved fraction of NOM, i.e., dissolved organic matter (DOM), is a complex mixture resulting from the transformation of plant, animal and microbial matter and plays a crucial role in many biogeochemical processes at the land-ocean-atmosphere interfaces. The advance of Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) makes the detailed characterization of DOM at the molecular level possible. On the other hand, elucidation of complex DOM sample also presents significant analytical challenges, and these challenges also act as a driving force for the instrumentation and methodology development on FT-ICR MS. This review article has been written to aid those working in biogeochemistry, environmental and atmospheric chemistry, and related areas which investigate elemental cycles and DOM transformations. First, the fundamental theory, historical perspective, and recent advances in the field have been introduced. The detailed molecular characterization of environmental and geological samples continues to present significant analytical challenges, and it also has become a driving force for the development of the instrumentation and experimental methods. These achievements in DOM analysis have had an impact upon the fields of environmental science, geochemistry, and analytical chemistry. Next, varieties of applications of FT-ICR MS have also been described, followed by our view of the future of this technique in earth science research. We believe that this review covers the essential pairing of FT-ICR MS and collectively offers environmental and geochemical scientists a substantial resource for their research. Graphical abstract

Nitrogen oxides (NOx, the sum of nitric oxide (NO) and N dioxide (NO2)) emissions and deposition have increased markedly over the past several decades, resulting in many adverse outcomes in both terrestrial and oceanic environments. However, because the microbial NOx emissions have been substantially underestimated on the land and unconstrained in the ocean, the global microbial NOx emissions and their importance relative to the known fossil-fuel NOx emissions remain unclear. Here we complied data on stable N isotopes of nitrate in atmospheric particulates over the land and ocean to ground-truth estimates of NOx emissions worldwide. By considering the N isotope effect of NOx transformations to particulate nitrate combined with dominant NOx emissions in the land (coal combustion, oil combustion, biomass burning and microbial N cycle) and ocean (oil combustion, microbial N cycle), we demonstrated that microbial NOx emissions account for 24 ± 4%, 58 ± 3% and 31 ± 12% in the land, ocean and global environment, respectively. Corresponding amounts of microbial NOx emissions in the land (13.6 ± 4.7 Tg N yr−1), ocean (8.8 ± 1.5 Tg N yr−1) and globe (22.5 ± 4.7 Tg N yr−1) are about 0.5, 1.4 and 0.6 times on average those of fossil-fuel NOx emissions in these sectors. Our findings provide empirical constraints on model predictions, revealing significant contributions of the microbial N cycle to regional NOx emissions into the atmospheric system, which is critical information for mitigating strategies, budgeting N deposition and evaluating the effects of atmospheric NOx loading on the world.

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

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

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

Tectonically active high relief areas are proposed to have a substantial impact on climate regulation throughout the Cenozoic. Here, we present lithium (Li) isotope data of the dissolved load and suspended particulate material from the basins of the Yalong River and the Jinsha River, which drain the high-relief borders of the eastern Tibetan Plateau and constitute the headwaters of the Yangtze River. Dissolved δ7Li values are relatively low and constant in the Jinsha River mainstream (+6.8‰ to +9.7‰) compared to the higher and downstream increasing values in the Yalong River mainstream (+10.8‰ to +17.5‰). Furthermore, dissolved δ7Li values in the major tributaries of the Jinsha and Yalong River are highly variable and increase downstream from +11.4‰ to +29.4‰ and from +9.0‰ to +23.6‰, respectively. Robust correlations between Li, Na, and Cl concentrations identify that evaporite dissolution in the uppermost headwaters of the Jinsha River basin controls the Li budget and riverine δ7Li values of the mainstream and has a significant impact on dissolved Li in the Yangtze River. In contrast to the Jinsha River mainstream, dissolved Li in the Yalong River mainstream and the Jinsha and Yalong River tributaries are dominantly derived from the dissolution of silicates. δ7Li variations in the Yalong River basin and the Jinsha tributaries reflect little Li uptake by clays in the upper reaches and more Li uptake by clays in the lower reaches of the river basins. SWR/D ratios (where SWR is the chemical silicate weathering rate, and D is the total denudation rate) highlight an intermediate silicate weathering intensity under a kinetically limited weathering regime for the study area. However, positive correlations between dissolved δ7Li value and silicate weathering intensity proxies (such as Si/(Nasil + K) and K/(Nasil + K)) indicate an increasing weathering intensity downstream. A positive correlation between dissolved δ7Li values and the annual precipitation and a negative one between δ7Li values and elevation indicates that larger annual precipitation under a flattening relief results in a stronger silicate weathering intensity, thus, more Li uptake in clays and higher riverine δ7Li values in the lower reaches. Compared to the lower reaches of Yangtze River basin (∼+20‰), lower dissolved δ7Li values in its headwater of this study suggest that the increase in δ7Li of seawater over the Cenozoic is influenced by weathering in floodplains that developed due to erosion of high mountains, rather than weathering of mountain belts itself. Combined with silicate weathering rates of the eastern border of the Tibetan Plateau, the highest riverine δ7Li values in its catchments come along with the highest silicate weathering rates and high CO2 consumption, suggesting that a more elevated topography may have an important role in the drawdown of CO2 during the Cenozoic.

Hydroelectric reservoirs are highly regulated ecosystems, where the understanding on bacterioplankton has been very limited so far. In view of significant changes in river hydrological conditions by dam construction, hydraulic load (i.e., the ratio of mean water depth to water retention time) was assumed to control bacterioplankton diversity in cascading hydropower reservoirs. To evaluate this hypothesis, we investigated bacterioplankton composition and diversity using high-throughput sequencing and related environmental variables in eleven reservoirs on the Wujiang River, Southwest China. Our results showed a decrease of bacterioplankton diversity index with an increase of reservoir hydraulic load. This is because hydraulic load governs dissolved oxygen variation in the water column, which is a key factor shaping bacterioplankton composition in these hydroelectric reservoirs. In contrast, bacterioplankton abundance was mainly affected by nutrient-related environmental factors. Therefore, from a hydrological perspective, hydraulic load is a decisive factor for the bacterioplankton diversity in the hydroelectric reservoirs. This study can improve the understanding of reservoir bacterial ecology, and the empirical relationship between hydraulic load and bacterioplankton diversity index will help to quantitatively evaluate ecological effects of river damming.

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

Despite the consensus that keeping global temperature rise within 1.5 °C above pre-industrial level by 2100 reduces the chance for climate change to reach the point of no return, the newest Intergovernmental Panel on Climate Change (IPCC) report warns that the existing commitment of greenhouse gas emission reduction is only enough to contain the warming to 3–4 °C by 2100. The harsh reality not only calls for speedier deployment of existing CO2 reduction technologies but demands development of more cost-efficient carbon removal strategies. Here we report an ocean alkalinity-based CO2 sequestration scheme, taking advantage of proton consumption during nitrate assimilation by marine photosynthetic microbes, and the ensuing enhancement of seawater CO2 absorption. Benchtop experiments using a native marine phytoplankton community confirmed pH elevation from ~8.2 to ~10.2 in seawater, within 3–5 days of microbial culture in nitrate-containing media. The alkaline condition was able to sustain at continued nutrient supply but reverted to normalcy (pH ~8.2–8.4) once the biomass was removed. Measurements of δ13C in the dissolved inorganic carbon revealed a significant atmospheric CO2 contribution to the carbonate alkalinity in the experimental seawater, confirming the occurrence of direct carbon dioxide capture from the air. Thermodynamic calculation shows a theoretical carbon removal rate of ~0.13 mol CO2/L seawater, if the seawater pH is allowed to decrease from 10.2 to 8.2. A cost analysis (using a standard bioreactor wastewater treatment plant as a template for CO2 trapping, and a modified moving-bed biofilm reactor for nitrate recycling) indicated that a 1 Mt CO2/year operation is able to perform at a cost of ~$40/tCO2, 2.5–5.5 times cheaper than that offered by any of the currently available direct air capture technologies, and more in line with the price of $25–30/tCO2 suggested for rapid deployment of large-scale CCS systems.