ABSTRACT
Many bacteria perform extracellular electron transfer (EET), whereby electrons are transferred from the cell to an extracellular terminal electron acceptor. This electron acceptor can be an electrode and electrons can be delivered indirectly via a redox-active mediator molecule. Here, we present a protocol to study mediated EET in Lactiplantibacillus plantarum, a probiotic lactic acid bacterium widely used in the food industry, using a bioelectrochemical system. We detail how to assemble a three-electrode, two-chambered bioelectrochemical system and provide guidance on characterizing EET in the presence of a soluble mediator using chronoamperometry and cyclic voltammetry techniques. We use representative data from 1,4-dihydroxy-2-naphthoic acid (DHNA)-mediated EET experiments with L. plantarum to demonstrate data analysis and interpretation. The techniques described in this protocol can open new opportunities for electro-fermentation and bioelectrocatalysis. Recent applications of this electrochemical technique with L. plantarum demonstrated an acceleration of metabolic flux towards producing fermentation end-products, which are critical flavor components in food fermentation. As such, this system has the potential to be further developed to alter flavors in food production or produce valuable chemicals.
Subject(s)
Electrochemical Techniques , Electrodes , Electron Transport , Electrochemical Techniques/methods , Electrochemical Techniques/instrumentation , Lactobacillus plantarum/metabolismABSTRACT
Climate change and human interference, notably nutrient input, affect the water quality. Nitrogen (N) and phosphorus (P) are pivotal in managing eutrophication. This study investigated the effects of water dynamics and chemical constituents on water quality in Hongfeng Lake, a typical weakly stratified reservoir suffering from algae blooms in Southwest China, using the Environmental Fluid Dynamics Code. Leveraging climate, hydrological, and water quality data, we constructed, calibrated, and validated the temperature-hydrodynamics-water quality-sediment model. Various scenarios were analyzed, including wind speed, air temperature, solar radiation, rainfall, water discharge, N and P external input, and internal release. The findings revealed that no rain and warming increased trophic state index (TSI) and chlorophyll-a (Chl-a) concentration, and no solar radiation initially elevated nitrate concentration, followed by an increase in ammonium concentration. Besides, no solar radiation and changes in rainfall significantly increased total phosphate concentration. The management scenarios of N and P reduction, halving tributary, and mainstream flow scenarios improved water quality and reduced eutrophication. The wind speed under the N and P reduced scenarios showed that a doubling in wind led to increased concentrations of the particulate organic matter, Chl-a, and dissolved oxygen, alongside decreased ammonium and nitrate, while TSI exhibited minimal change. However, 5- and 10-times wind speed scenarios amplified TSI in shallow water, potentially due to a substantial rise in internal nutrient release. The degradation trend observed in drinking water quality amid climate change (warming and flooding) raises concerns regarding health-related risks. These simulations provided the quantified influence of climate change and environmental management strategies on water quality in the weakly stratified reservoir, notably highlighting the looming threat of exacerbated eutrophication due to warming, necessitating more stringent N and P reduction measures compared to current practices.
ABSTRACT
This study conducted a comprehensive analysis of trace element concentrations in the Upper Indus River Basin (UIRB), a glacier-fed region in the Western Himalayas (WH), aiming to discern their environmental and anthropogenic sources and implications. Despite limited prior data, 69 samples were collected in 2019 from diverse sources within the UIRB, including mainstream, tributaries, and groundwater, to assess trace element concentrations. Enrichment factor (EF) results and comparisons with regional and global averages suggest that rising levels of Zn, Cd, and As may pose safety concerns for drinking water quality. Advanced multivariate statistical techniques such as principal component analysis (PCA), absolute principal component scores (APCS-MLR), Monte Carlo simulation (MCS), etc were applied to estimate the associated human health hazards and also identified key sources of trace elements. The 95th percentile of the MCS results indicates that the estimated total cancer risk for children is significantly greater than (>1000 times) the USEPA's acceptable risk threshold of 1.0 × 10-6. The results classified most of the trace elements into two distinct groups: Group A (Li, Rb, Sr, U, Cs, V, Ni, TI, Sb, Mo, Ge), linked to geogenic sources, showed lower concentrations in the lower-middle river reaches, including tributaries and downstream regions. Group B (Pb, Nb, Cr, Zn, Be, Al, Th, Ga, Cu, Co), influenced by both geogenic and anthropogenic activities, exhibited higher concentrations near urban centers and midstream areas, aligning with increased municipal waste and agricultural activities. Furthermore, APCS-MLR source apportionment indicated that trace elements originated from natural geogenic processes, including rock-water interactions and mineral dissolution, as well as anthropogenic activities. These findings underscore the need for targeted measures to mitigate anthropogenic impacts and safeguard water resources for communities along the IRB and WH.
ABSTRACT
Dissolved organic carbon (DOC) and discharge are often tightly coupled, though these relationships in karst environments remain poorly constrained. In this study, DOC dynamics over 13 hydrological events, alongside monthly monitoring over an entire hydrological year were monitored in a small karst catchment, SW China. The concurrent analyses of power-law model and hysteresis patterns reveal that DOC behavior is generally transport-limited due to flushing effects of increased discharge but highly variable at both intra- and inter-event scales. The initial discharge at event onset and discharge-weighted mean concentration of DOC ([DOC]DW) of individual events can explain 37.7 % and 19.9 % of the variance of DOC behavior among events, respectively. The sustained dry-cold antecedent conditions make DOC hysteresis behavior during the earliest event complex and different from subsequent events. At event scale, the variability in DOC export is primarily controlled by [DOC]DW (explaining 64.3 %) and the yield of total dissolved solutes (YTDS, explaining 30.4 %), reflecting the impacts of variable hydrological connectivity and intense soil-water-rock interactions in this karst catchment. On an annual scale, DOC yield (YDOC, 222.86 kg C km-2) was mostly derived during the wet season (98.19 %) under the hydrological driving force. The difference in annual YDOC between this karst catchment and other regions can be well explained by annual water yield (Ywater, explaining 24.2 %) and [DOC] (explaining 35.4 %), whereas the variance in DOC export efficiency among catchments is almost exclusively controlled by [DOC] alone, independent of drainage area and annual Ywater. This study highlights the necessity of high-frequency sampling for modeling carbon biogeochemical processes and the particularity of the earliest hydrological events occurred after a long cold-dry period in karst catchments. Under the changing climate, whether DOC dynamics in karst catchments will present source-limited patterns during more extreme hydrological events merits further study.
ABSTRACT
The bioavailable diverse dissolved organic matter (DOM) present in glacial meltwater significantly contributes to downstream carbon cycling in mountainous regions. However, the comprehension of molecular-level characteristics of riverine DOM, from tributary to downstream and their fate in glacier-fed desert rivers remains limited. Herein, we employed spectroscopic and high-resolution mass spectrometry techniques to study both optical and molecular-level characteristics of DOM in the Tarim River catchment, northwest China. The results revealed that the DOC values in the downstream were higher than those in the tributaries, yet they remained comparable to those found in other glacier-fed streams worldwide. Five distinct components were identified using EEM-PARAFAC analysis in both tributary and downstream samples. The dominance of three protein-like components in tributary samples, contrasting with a higher presence of humic-like components in downstream samples, which implied that the dilution and alterations of the glacier DOM signature and overprinting with terrestrial-derived DOM. Molecular composition revealed that thousands of compounds with higher molecular weight and increased aromaticity were transformed, generated and introduced from terrestrial inputs during downstream transportation. The twofold rise in polycyclic aromatic and polyphenolic compounds observed downstream compared to tributaries indicated a greater influx of terrestrial organic matter introduced into the downstream during water transportation. The study suggests that the glacier-sourced DOM experienced minimal photodegradations, with limited influence from human activities, while also being shaped by terrestrial inputs during its transit in the alpine-arid region. This unique scenario offers valuable insights into comprehending the fate of DOM originating from glacial meltwater in arid mountainous regions.
Subject(s)
Ice Cover , Rivers , China , Rivers/chemistry , Ice Cover/chemistry , Environmental Monitoring/methods , Organic Chemicals/analysis , Water Pollutants, Chemical/analysis , Humic Substances/analysis , Mass Spectrometry , Desert ClimateABSTRACT
Floods in global large rivers modulate the transport of dissolved organic carbon (DOC) and estuarine hydrological characteristics significantly. This study investigated the impact of a severe flood on the sources and age of DOC in the Yangtze River Estuary (YRE) in 2020. Comparing the flood period in 2020 to the non-flood period in 2017, we found that the flood enhanced the transport of young DOC to the East China Sea (ECS), resulting in significantly enriched Δ14C-DOC values. During the flood period, the proportion of modern terrestrial organic carbon (OC) was significantly higher compared to the non-flood period. Conversely, the proportion of pre-aged sediment OC was significantly lower during the flood period. The high turbidity associated with the flood facilitated rapid transformation and mineralization of sedimentary and fresh terrestrial OC, modifying the sources of DOC. The flux of modern terrestrial OC transported to the ECS during the flood period was 1.58 times higher than that of the non-flood period. These findings suggest that floods can modulate the sources and decrease the age of DOC, potentially leading to increased greenhouse gas emissions. Further research is needed to understand the long-term impacts of floods on DOC dynamics in global estuaries.
Subject(s)
Carbon , Estuaries , Floods , Rivers , China , Rivers/chemistry , Carbon/analysis , Environmental Monitoring , Geologic Sediments/analysis , Geologic Sediments/chemistry , Water Pollutants, Chemical/analysisABSTRACT
Carbon dioxide (CO2) production and emissions from inland waters play considerable roles in global atmospheric CO2 sources, while there are still uncertainties regarding notable nutrient inputs and anthropogenic activities. Urban inland waters, with frequently anthropogenic modifications and severely nitrogen loadings, were hotspots for CO2 emissions. Here, we investigated the spatiotemporal patterns of partial pressure of CO2 (pCO2) and CO2 fluxes (FCO2) in typical urban inland waters in Tianjin, China. Our observation indicated that pCO2 values were oversaturated in highly polluted waters, particularly in sewage rivers and urban rivers, exhibiting approximately 9 times higher than the atmosphere equilibrium concentration during sampling campaigns. Obviously, the spatiotemporal distributions of pCO2 and FCO2 emphasized that the water environmental conditions and anthropogenic activities jointly adjusted primary productivity and biological respiration of inland waters. Meanwhile, statistically positive correlations between pCO2/FCO2 and NH4+-N/NO3--N (p < 0.05) suggested that nitrogen biogeochemical processes, especially the nitrification, played a dominant role in CO2 emissions attributing to the water acidification that stimulated CO2 production and emissions. Except for slight CO2 sinks in waters with low organic contents, the total CO2 emissions from the urban surface waters of Tianjin were remarkable (286.8 Gg yr-1). The results emphasized that the reductions of nitrogen loadings, sewage draining waters, and agricultural pollution could alleviate CO2 emissions from urban inland waters.
Subject(s)
Carbon Dioxide , Nitrogen , Carbon Dioxide/analysis , Nitrogen/analysis , Environmental Monitoring , China , Rivers/chemistryABSTRACT
High-elevation mountains have experienced disproportionately rapid warming, yet the effect of warming on the lateral export of terrestrial carbon to rivers remains poorly explored and understood in these regions. Here, we present a long-term data set of dissolved inorganic carbon (DIC) and a more detailed, short-term data set of DIC, δ13CDIC, and organic carbon from two major rivers of the Qinghai-Tibetan Plateau, the Jinsha River (JSR) and the Yalong River (YLR). In the higher-elevation JSR with â¼51% continuous permafrost coverage, warming (>3 °C) and increasing precipitation coincided with substantially increased DIC concentrations by 35% and fluxes by 110%. In the lower-elevation YLR with â¼14% continuous permafrost, such increases did not occur despite a comparable extent of warming. Riverine concentrations of dissolved and particulate organic carbon increased with discharge (mobilization) in both rivers. In the JSR, DIC concentrations transitioned from dilution (decreasing concentration with discharge) in earlier, colder years to chemostasis (relatively constant concentration) in later, warmer years. This changing pattern, together with lighter δ13CDIC under high discharge, suggests that permafrost thawing boosts DIC production and export via enhancing soil respiration and weathering. These findings reveal the predominant role of warming in altering carbon lateral export by escalating concentrations and fluxes and modifying export patterns.
ABSTRACT
The water-level fluctuations zones (WLFZs) are crucial transitional interfaces within river-reservoir systems, serving as hotspots for N2O emission. However, the comprehension of response patterns and mechanisms governing N2O emission under hydrological fluctuation remains limited, especially in karstic canyon reservoirs, which introduces significant uncertainty to N2O flux assessments. Soil samples were collected from the WLFZs of the Hongjiadu (HJD) Reservoir along the water flow direction from transition zone (T1 and T2) to lacustrine zone (T3, T4 and T5) at three elevations for each site. These soil columns were used to conduct simulation experiments under various water-filled pore space gradients (WFPSs) to investigate the potential N2O flux pattern and elucidate the underlying mechanism. Our results showed that nutrient distribution and N2O flux pattern differed significantly between two zones, with the highest N2O fluxes in the transition zone sites and lacustrine zone sites were found at 75 % and 95 % WFPS, respectively. Soil nutrient loss in lower elevation areas is influenced by prolonged impoundment durations. The higher N2O fluxes in the lacustrine zone can be attributed to increased nutrient levels resulting from anthropogenic activities. Furthermore, correlation analysis revealed that soil bulk density significantly impacted N2O fluxes across all sites, while NO3-and SOC facilitated N2O emissions in T1-T2 and T4-T5, respectively. It was evident that N2O production primarily contributed to nitrification in the transition zone and was constrained by the mineralization process, whereas denitrification dominated in the lacustrine zone. Notably, the annual N2O efflux from WLFZs accounted for 27 % of that from the water-air interface in HJD Reservoir, indicating a considerably lower contribution than anticipated. Nevertheless, this study highlights the significance of WLFZs as a vital potential source of N2O emission, particularly under the influence of anthropogenic activities and high WFPS gradient.
ABSTRACT
Agricultural ditches are significant methane (CH4) sources since substantial nutrient inputs stimulate CH4 production and emission. However, few studies have quantified the role of diffusion and ebullition pathways in total CH4 emission from agricultural ditches. This study measured the spatiotemporal variations of diffusive and ebullitive CH4 fluxes from a multi-level ditch system in a typical temperate agriculture area, and assessed their contributions to the total CH4 emission. Results illustrated that the mean annual CH4 flux in the ditch system reached 1475.1 mg m-2 d-1, among which 1376.7 mg m-2 d-1 was emitted via diffusion and 98.5 mg m-2 d-1 via ebullition. Both diffusive and ebullitive fluxes varied significantly across different types of ditches and seasons, with diffusion dominating CH4 emission in middle-size ditches and ebullition dominating in large-size ditches. Diffusion was primarily driven by large nutrient inputs from adjacent farmlands, while hydrological factors like water temperature and depth controlled ebullition. Overall, CH4 emission accounted for 86 % of the global warming potential across the ditch system, with 81 % attributed to diffusion and 5 % to ebullition. This study highlights the importance of agricultural ditches as hotspots for CH4 emissions, particularly the dominant role of the diffusion pathway.
ABSTRACT
Carbon capture and storage (CCS) of CO2 is a key technology for substantially mitigating global greenhouse gas emissions. Determining the biogeochemical processes in host rocks after CO2 injection informs the viability of carbon storage as a long-term sink for CO2, the complexity of reservoir CH4 cycling, as well as the direct and indirect environmental impacts of this strategy. The doubly substituted ('clumped') isotopologues of methane (13CH3D and 12CH2D2) provide novel insights into methane origins and post-generation processing. Here, we report the chemical compositions of hydrocarbons (C1/C2+ molecular ratios), and methane bulk and clumped isotopes (δ13C, δD, Δ13CH3D and Δ12CH2D2) of a CO2 enhanced coal bed methane recovery (CO2-ECBM) area in Qinshui basin, China and is an analogue for carbon capture and storage. The clumped isotopologue compositions observed in the study area are generally consistent with a range of temperatures spanning 73 to 193 °C. The range in apparent temperature and correlations among clumped and bulk isotopic indices are best explained by mixing between a high maturity thermogenic methane (high in δ13C and δD, with a clumped isotope composition equilibrated near â¼249 °C) and biogenic methane formed or processed in the reservoir (low in δ13C and δD, with a clumped isotope composition equilibrated near 16-27 °C). We hypothesize that the biogenic endmember may result from slow methanogenesis and/or anaerobic oxidation of methane (AOM). This study demonstrates that the potential of methane clumped isotope approach to identify in situ microbial metabolic processes and their association with carbon cycling in CO2-ECBM area, improving our understanding of biogeochemical mechanisms in analogous geological reservoirs.
ABSTRACT
Pharmaceuticals and personal care products (PPCPs) are emerging contaminants that have raised urgent environmental issues. The dissolved organic matter (DOM) plays a pivotal role on PPCPs' migration and transformation. To obtain a comprehensive understanding of the occurrence and distribution of PPCPs, a seasonal sampling focused on the riverine system in coastal zone, Tianjin, Bohai Rim was conducted. The distribution and transformation of thirty-three PPCPs and their interaction with DOM were investigated, and their sources and ecological risks were further evaluated. The total concentration of PPCPs ranges from 0.01 to 197.20 µg/L, and such value is affected by regional temperature, DOM and land use types. PPCPs migration at soil-water interface is controlled by temperature, sunlight, water flow and DOM. PPCPs have a high affinity to the protein-like DOM, while the humus-like DOM plays a negative influence and facilitates PPCPs' degradation. It is also found that protein-like DOM can represent point source pollution, while humus-like substances indicate non-point source (NPS) emission. Specific PPCPs can be used as markers to trace the source of domestic discharge. Additionally, daily use PPCPs such as ketoprofen, caffeine and iopromide are estimated to be the main risk substances, and their ecological risk varies on space, season and river hydraulic condition.
Subject(s)
Cosmetics , Water Pollutants, Chemical , Seasons , Dissolved Organic Matter , Environmental Monitoring , Water Pollutants, Chemical/analysis , Cosmetics/analysis , China , Water , Soil , Rivers , Pharmaceutical PreparationsABSTRACT
Accurate prediction of dissolved oxygen (DO) dynamics is crucial for understanding the influence of environmental factors on the stability of aquatic ecosystem. However, limited research has been conducted to determine the optimal frequency of water quality monitoring that ensures continuous assessment of water health while minimizing costs. To address these challenges, the present study developed a hybrid stochastic hydrological model (i.e., ARIMA-GARCH hybrid model) and machine learning (ML) models. The objective of this study is to identify the best-performing model and establish the optimal monitoring frequency. Results revealed that high-frequency DO monitoring data exhibit greater variability compared to low-frequency data. Moreover, the ARIMA-GARCH model demonstrates promising potential in predicting DO concentrations for low-frequency monitoring data, surpassing ML models in performance. Furthermore, increasing the monitoring frequency significantly improves the prediction accuracy of models, regardless of whether point (with lower R2 values of 0.64 and 0.51 for daily detection than these of every 15 min (0.96 and 0.99) at CHQ and LHT, respectively) or interval predictions (with RIW higher values of 2.00 and 1.55 for daily detection higher than these of 0.02 and 0.16 in every 15 min at CHQ and LHT, respectively) are considered. Additionally, a 4 hourly monitoring frequency was found to be optimal for water quality assessment using each model. These findings identify the superior performing of the ARIMA-GARCH model and highlight the crucial role of monitoring frequency in enhancing DO prediction and improving model performance.
ABSTRACT
Dam construction significantly impacts river hydrodynamics, subsequently influencing carbon biogeochemical processes. However, the influence of hydrodynamic conditions on the migration and transformation of Dissolved Inorganic Carbon (DIC) remains uncertain. To bridge this knowledge gap, we integrated hydrochemistry, isotopic composition (δ13CDIC), and a hydrodynamic model (CE-QUAL-W2) to examine the distinctions, control mechanisms, and environmental effects of DIC biogeochemical processes in a typical large and deep reservoir (Hongjiadu Reservoir) under different hydrodynamic conditions. We evaluated hydrodynamic alterations through the Schmidt stability index and relative water column stability. The analysis disclosed that during weak hydrodynamics periods, the energy necessary for complete mixing the surface and deep water was 34 times higher (3615.32 J/m2 vs.106.86 J/m2), and stability was 13 times greater (312.96 vs. 24.69) compared to periods of strong hydrodynamics. Additionally, the spatiotemporal heterogeneity of DIC concentrations (1.4 % to -9.1 %) and δ13CDIC (-1.7 % to -19.5 %) from the dry to wet seasons reflected disparities in DIC control mechanisms under varied hydrodynamic conditions. Based on model simulations, our calculations indicate that during weak hydrodynamics periods, the enhancement of the biological carbon pump effect resulted in substantial sequestration of DIC, reaching up to 379.6 t-DIC·d-1 in the water. Conversely, during strong hydrodynamics periods, DIC retention capacity decreased by 69.2 t·d-1, resulting in reservoir CO2 emissions of 22.7 × 104 t, which were more than 7 times higher than during weak hydrodynamics periods (3.2 × 104 t). Our findings emphasize the discernible impact of hydrodynamic conditions on reservoir biogeochemical processes related to DIC. Considering the increasing construction of reservoirs globally, understanding and controlling hydrodynamic conditions are crucial for mitigating CO2 emissions and optimizing reservoir management.
Subject(s)
Carbon Dioxide , Hydrodynamics , Carbon Isotopes/analysis , Environmental Monitoring/methods , Rivers/chemistry , Water/analysis , Carbon/analysis , ChinaABSTRACT
A subset of microorganisms that perform respiration can endogenously utilize insoluble electron donors, such as Fe(II) or a cathode, in a process called extracellular electron transfer (EET). However, it is unknown whether similar endogenous EET can be performed by primarily fermentative species like lactic acid bacteria. We report for the first time electron uptake from a cathode by Lactiplantibacillus plantarum, a primarily fermentative bacteria found in the gut of mammals and in fermented foods. L. plantarum consumed electrons from a cathode and coupled this oxidation to the reduction of both an endogenous organic (pyruvate) and an exogenous inorganic electron acceptor (nitrate). This electron uptake from a cathode reroutes glucose fermentation toward lactate degradation and provides cells with a higher viability upon sugar exhaustion. Moreover, the associated genes and cofactors indicate that this activity is mechanistically different from that one employed by lactic acid bacteria to reduce an anode and to perform respiration. Our results expand our knowledge of the diversity of electroactive species and of the metabolic and bioenergetic strategies used by lactic acid bacteria.
ABSTRACT
Anthropogenic activity has caused rivers and reservoirs to become sources of nitrous oxide (N2O), which is thought to play an important role in global climate change. There are thermal and DO stratification in deep-water reservoirs with long hydraulic retention time, which change N2O production mechanism compared with shallow-water reservoirs. To promote our understanding of the relationship of N2O production in reservoirs at different depths, spatiotemporal variations in water environmental factors and N2O from cascade reservoirs of Chaishitan (CST), Longtan (LT), Yantan (YT) and Dahua (DH) reservoirs in the Zhujiang River were detected, and the LT and YT reservoirs were compared as representatives of deep-water and shallow-water reservoirs in April and July 2019. The average N2O concentrations in the LT and YT reservoirs were 22.82 ± 2.21 and 21.55 ± 1.65 nmol L-1, respectively. During spring and summer, the WT (water temperature) and DO (dissolved oxygen) concentrations in the YT reservoir were well mixed. In contrast, the LT reservoir, as a deep-water reservoir, had thermal and DO stratifications in both the shallow and middle water, especially in the summer when the solar radiation intensity was high. During summer stratification, the DO concentration in the LT reservoir showed obvious spatial variation, ranging from 1.23 to 9.84 mg L-1, while the DO concentration in the YT reservoir showed very little variation, ranging from 6.45 to 7.09 mg L-1. Structural equation modeling results showed that NH4+ was the main determinant of the N2O concentration in the YT reservoir, and DO was the most influential factor of the N2O concentration in the LT reservoir. These results suggest significant variations in the factors influencing N2O concentration among reservoirs. Additionally, the mechanisms of N2O production differ between deep-water and shallow-water reservoirs. This study highlights the spatio-temporal variations and influential factors contributing to N2O concentration. Furthermore, it discusses the production mechanisms of N2O in different types of reservoirs. These findings contribute to our understanding of N2O distribution in hydropower systems and provide valuable data for the management of hydropower facilities and research on greenhouse gas emissions.
ABSTRACT
Natural dissolved organic matter (DOM) is one of the Earth's dynamic carbon pools and a key intermediate in the global carbon cycle. Photochemical processes potentially affect DOM composition and activity in surface water. Suspended particulate matter (SPM) is the integral component of slow-moving rivers, and holds the potential for photochemical reactivity. To further investigate the influence of SPM on DOM photochemical transformation, this study conducted experiments comparing samples with and without SPM irradiated under simulated sunlight. Surface water samples from slow-moving urban rivers were collected. DOM optical characteristics and molecular features obtained by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) were investigated. Photolabile DOM was enriched in unsaturated and highly aromatic terrestrial substances. Photoproduced DOM had low aromaticity and was dominated by saturated aliphatics, protein-like substances, and carbohydrates. Study results indicated that the presence of SPM had a nonnegligible impact on the molecular traits of DOM, such as composition, molecular diversity, photolability, and bioavailability during photochemical reactions. In the environment affected by SPM, molecules containing heteroatoms exhibit higher photosensitivity. SPM promotes the photochemical transformation of a wider range of chemical types of photolabile DOM, particularly nitrogen-containing compounds. This study provides an essential insight into the more precise simulation of photochemical reactions of DOM influenced by SPM occurring in natural rivers, contributing to our understanding of the global carbon cycle from new theoretical perspectives.
ABSTRACT
The coastal zone exhibited a high population density with highly impacted by anthropogenic activities, such as river impoundment to prevent saline intrusion, which resulted in weak hydrological conditions. Rainfall events can result in dramatic changes in hydrological and nutrient transportation conditions, especially in rivers with weak hydrological conditions. However, how the nitrogen transport and N2O emissions or biogeochemistry responds to the different types of rainfall events in the weak hydrodynamics rivers is poorly understood. In this study, the hydrological, nitrogenous characteristic, as well as N2O dynamics, were studied by high-frequency water sampling during two distinct rainfall events, high-intensity with short duration (E1) and low-intensity with long duration (E2). The results displayed that the hydrologic condition in E1 with a wider range of d-excess values (from -9.50 to 32.1 ), were more dynamic than those observed in E2. The N2O concentrations (0.01-3.33 µmol/L) were higher during E1 compared to E2 (0.03-1.11 µmol/L), which indicated that high-intensity rainfall has a greater potential for N2O emission. On the contrary, the concentrations of nitrogen (e.g., TN and NO3--N) were lower during E1 compared to E2. Additionally, hysteresis was observed in both water and nitrogen components, resulting in a prolonged recovery time for pre-rainfall levels during the long-duration event. Moreover, the results showed that the higher average N2O flux (78.3 µmol/m2/h) in the rainfall event period was much larger than that in the non-rainfall period (1.63 µmol/m2/h). The frequency dam regulation resulted in the water level fluctuation, which could enhance wet-dry alternation and simulated N2O emissions. This study highlighted the characteristic of N dynamic and hydrological responses to diverse rainfall events occurrences in the coastal river. Rainfall could increase the N2O emission, especially during high-intensity rainfall events, which cannot be ignored in the context of annual N2O release.
ABSTRACT
It is generally acknowledged that riverine dissolved inorganic carbon (DIC) behaviors play a critical role in global carbon cycling and hence have an impact on climate change. However, little is known about the intricate DIC dynamics under various meteorological conditions in the alpine areas. Here, we investigated DIC biogeochemical processes in the Bailong River catchment, eastern Qinghai-Tibet Plateau (QTP), by combining measurements of major ions, stable and radioactive isotopic compositions of DIC (δ13CDIC and Δ14CDIC), and physiographic parameters in the Bailong River catchment. Statistics and stoichiometry analyses suggest that multiple biogeochemical processes could affect carbon cycling in the Bailong River catchment. The "old" DIC with low Δ14C values (-472.4 ± 127.8 , n = 3) and stoichiometry analysis of dissolved ions showed clear evidence that carbonate weathering is primarily responsible for water chemistry in the upstream (elevation >2000 m). However, upstream samples showed that δ13CDIC increased between 5 and 11 from the theoretical mixing line, concomitant with increasing pH and decreasing pCO2, suggesting that isotopic fractionation of DIC due to CO2 outgassing may be the primary cause of the increased δ13CDIC values. Additionally, the higher Δ14C values (-285.4 ± 123.5 , n = 12) in the downstream region below 2000 m suggest that allochthonous modern carbon had a great impact on DIC variations. The presence of younger DIC may have important implications for the interpretation of inorganic carbon age in downstream rivers. Our study demonstrates that physiographic conditions can regulate DIC behaviors, which can improve estimations of carbon yield and comprehension of global carbon cycle.
ABSTRACT
Methane (CH4) is a matter of environmental concern; however, global methane isotopologue data remain inadequate. This is due to the challenges posed by high-resolution testing technology and the need for larger sample volumes. Here, worldwide methane clumped isotope databases (n = 465) were compiled. We compared machine-learning (ML) models and used random forest (RF) to predict new Δ12CH2D2 distributions, which cover valuable and hard-to-replicate methane clumped isotope experimental data. Our RF model yields a reliable and continuous database including ruminants, acetoclastic methane, multiple pyrolysis, and controlled experiments. We showed the effectiveness of utilizing a new data set to quantify isotopologue fractionations in biogeochemical methane processes, as well as predicting the steady-state atmospheric methane clumped isotope composition (Δ13CH3D of +2.26 ± 0.71 and Δ12CH2D2 of +62.06 ± 4.42) with notable biological contributions. Our measured summer and winter water emitted gases (n = 6) demonstrated temperature-driven seasonal microbial community evolution determined by atmospheric clumped isotope temporal variations (Δ 13CH3D â¼ -0.91 ± 0.25 and Δ12CH2D2 â¼ +3.86 ± 0.84 ), which in turn is relevant for future models quantifying the contribution of methane sources and sinks. Predicting clumped isotopologues translates our methane geochemical understanding into quantifiable variables for modeling that can continue to improve predictions and potentially inform global greenhouse gas emissions and mitigation policy.