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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 (Y TDS , 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 (Y DOC , 222.86 kg C km -2 ) was mostly derived during the wet season (98.19 %) under the hydrological driving force. The difference in annual Y DOC between this karst catchment and other regions can be well explained by annual water yield (Y water , 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 Y water . 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The exchange and transformation of dissolved organic matter (DOM) at the sediment-water interface are crucial factors in regulating watershed biogeochemistry, with the molecular composition of DOM serving as a pivotal determinant in elucidating this process. High-resolution mass spectrometry (HRMS) is an effective tool for resolving the composition of DOM. By analyzing the compositional characteristics of DOM at the sediment-water interface under three different salinities at the same latitude region in northern China, the findings indicate certain variations in component characteristics of DOM between low-salinity inland waters and high-salinity seawaters, with the former exhibiting greater molecular diversity and higher molecular weights, whereas the latter displayed a higher saturation and bioavailability. Notably, the presence of more CHOS substances in the low-salinity inland waters underscores the transformation of the DOM influenced by terrestrial inputs and anthropogenic activities. Conversely, the presence of more CHO and CHNO substances in high-salinity seawater underscores the microbial effects. The chemical transformation process from overlying water to pore water to sediments was characterized by methylation, hydrogenation, decarboxylation, and reduction, as determined by calculating the relations between the H/C and O/C ratios of different compound types. These findings indicate that HRMS can yield more refined results in revealing the process of DOM at the sediment-water interface under different environments, which provides a more reliable basis for a deeper understanding of the source-sink mechanism of sediment organic matter.

Nitrate dynamics within a catchment are critical to the earth's system process, yet the intricate details of its transport and transformation at high resolutions remain elusive. Hydrological effects on nitrate dynamics in particular have not been thoroughly assessed previously and this knowledge gap hampers our understanding and effective management of nitrogen cycling in watersheds. Here, machine learning (ML) models were employed to reconstruct the annual variation trend in nitrate dynamics and isotopes within a typical karst catchment. Random forest model demonstrates promising potential in predicting nitrate concentration and its isotopes, surpassing other ML models (including Long Short-term Memory, Convolutional Neural Network, and Support Vector Machine) in performance. The ML-modeled NO 3 - -N concentrations, δ 15 N-NO 3 - , and δ 18 O-NO 3 - values were in close agreement with field data (NSE values of 0.95, 0.80, and 0.53, respectively), which are notably challenging to achieve for process models. During the transition from dry to wet period, approximately 23.0 % of the annual precipitation (∼269.1 mm) was identified as the threshold for triggering a rapid response in the wet period. The modeled nitrate isotope values were significantly supported by the field data, suggesting seasonal variations of nitrogen sources, with precipitation as the primary driving force for fertilizer sources. Mixing of multiple sources appeared to be the main control of the transport and transformation of nitrate during the rising limb in the wet period, whereas process control (denitrification) took precedence during the falling limb, and the fate of nitrate was controlled by biogeochemical processes during the dry period., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The water quality in the drinking water reservoir directly affects people's quality of life and health. When external pollution input is effectively controlled, endogenous release is considered the main cause of water quality deterioration. As the major nitrogen (N) and phosphorus (P) sources in reservoirs, sediment plays a vital role in affecting the water quality. To understand the spatial and temporal variation of N and P in the sediment, this study analyzed the current characteristics and cumulative effects of a semi-humid reservoir, Yuqiao Reservoir, in North China. The N and P concentrations in the reservoir sediment were decreased along the flow direction, while the minimum values were recorded at the central sediment profile. External input and algal deposition were the main factors leading to higher sediment concentrations in the east (Re-E) and west (Re-W) areas of reservoir sediment profiles. According to the long-term datasets, the peaks of both sediment total nitrogen content and deposition rate were observed in the 2010s, which has increased about three times and six times than in the1990s, respectively. Therefore, the increase in phosphorus concentration may be the main reason for eutrophication in water in recent years. The mineralization of organic matter has a significant promoting effect on releasing N and P from sediments, which will intensify eutrophication in water dominated by P and bring huge challenges to water environment management. This study highlights that the current imbalance in N and P inputs into reservoirs and the endogenous P release from sediment will have a significant impact on water quality., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Carbon dioxide (CO 2 ) production and emissions from inland waters play considerable roles in global atmospheric CO 2 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 CO 2 emissions. Here, we investigated the spatiotemporal patterns of partial pressure of CO 2 (pCO 2 ) and CO 2 fluxes (FCO 2 ) in typical urban inland waters in Tianjin, China. Our observation indicated that pCO 2 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 pCO 2 and FCO 2 emphasized that the water environmental conditions and anthropogenic activities jointly adjusted primary productivity and biological respiration of inland waters. Meanwhile, statistically positive correlations between pCO 2 /FCO 2 and NH 4 + -N/NO 3 - -N (p < 0.05) suggested that nitrogen biogeochemical processes, especially the nitrification, played a dominant role in CO 2 emissions attributing to the water acidification that stimulated CO 2 production and emissions. Except for slight CO 2 sinks in waters with low organic contents, the total CO 2 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 CO 2 emissions from urban inland waters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The water-level fluctuations zones (WLFZs) are crucial transitional interfaces within river-reservoir systems, serving as hotspots for N 2 O emission. However, the comprehension of response patterns and mechanisms governing N 2 O emission under hydrological fluctuation remains limited, especially in karstic canyon reservoirs, which introduces significant uncertainty to N 2 O 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 N 2 O flux pattern and elucidate the underlying mechanism. Our results showed that nutrient distribution and N 2 O flux pattern differed significantly between two zones, with the highest N 2 O 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 N 2 O 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 N 2 O fluxes across all sites, while NO 3 - and SOC facilitated N 2 O emissions in T1-T2 and T4-T5, respectively. It was evident that N 2 O 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 N 2 O 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 N 2 O emission, particularly under the influence of anthropogenic activities and high WFPS gradient., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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 R 2 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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Excessive levels of NO 3 - can result in multiple eco-environmental issues due to potential toxicity, especially in coastal areas. Accurate source tracing is crucial for effective pollutant control and policy development. Bayesian models have been widely employed to trace NO 3 - sources, while limited studies have utilized optimized Bayesian models for NO 3 - tracing in the coastal rivers. The Bohai Rim is highly susceptible to ecological disturbances, particularly N pollution, and has emerged as a critical area. Therefore, identification the N fate and understanding their sources contribution is urgent for pollution mitigation efforts. In addition, understanding the influenced key driven factors to source dynamic in the past ten years is also implication to environmental management. In this study, water samples were collected from 36 major river estuaries that drain into the Bohai Sea of North China. The main transformation processes were analyzed and quantified the sources of NO 3 - using a Bayesian stable isotope mixing model (MixSIAR) with isotopic approach (δ 15 N-NO 3 - and δ 18 O-NO 3 - ). The overall isotopic composition of δ 15 N-NO 3 - and δ 18 O-NO 3 - in estuary waters ranged from -0.8-19.3‰ (9.3 ± 4.6‰) and from -7.1-10.5‰ (5.0 ± 4.3‰), respectively. The main sources of nitrate in most river estuaries were manure & sewage, and chemical fertilizer, while weak denitrification and mixed processes were observed in Bohai Rim region. A temporal decrease in the nitrogen load entering the Bohai Sea indicates an improvement in water quality in recent years. By incorporating informative priors and utilizing the calculated coefficients, the accuracy of sourcing results was significantly improved. This study highlighted the optimized MixSIAR model enhanced its accuracy for sourcing analysis and providing valuable insights for policy formulation. Future efforts should focus on improving management strategies to reduce nitrogen into the bay., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Nitrate contamination in aquatic systems is a widespread problem across the world. The isotopic composition (δ 15 N, δ 18 O) of nitrate and their isotope effect ( 15 ε, 18 ε) can facilitate the identification of the source and transformation of nitrate. Although previous researches claimed the isotope fractionations may change the original δ 15 N/δ 18 O values and further bias identification of nitrate sources, isotope effect was often ignored due to its complexity. To fill the gap between the understanding and application, it is crucial to develop a deep understanding of isotopic fractionation based on available evidence. In this regard, this study summarized the available methods to determine isotope effects, thereby systematically comparing the magnitude of isotope effects ( 15 ε and 18 ε) in nitrification, denitrification and anammox. We found that the enzymatic reaction plays the key role in isotope fractionations, which is significantly affected by the difference in the affinity, substrate channel properties and redox potential of active site. Due to the overlapping of microbial processes and accumulation of uncertainties, the significant isotope effects at small scales inevitably decrease in large-scale ecosystems. However, the proportionality of N and O isotope fractionation (δ 18 O/δ 15 N; 18 ε/ 15 ε) associated with nitrate reduction generally follows enzyme-specific proportionalities (i.e., Nar, 0.95; Nap, 0.57; eukNR, 0.98) in aquatic ecosystems, providing enzyme-specific constant factors for the identification of nitrate transformation. With these results, this study finally discussed feasible source portioning methods when considering the isotope effect and aimed to improve the accuracy in nitrate source identification., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

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 N 2 O 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 N 2 O 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 N 2 O 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 N 2 O emission. On the contrary, the concentrations of nitrogen (e.g., TN and NO 3 - -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 N 2 O flux (78.3 μmol/m 2 /h) in the rainfall event period was much larger than that in the non-rainfall period (1.63 μmol/m 2 /h). The frequency dam regulation resulted in the water level fluctuation, which could enhance wet-dry alternation and simulated N 2 O 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 N 2 O emission, especially during high-intensity rainfall events, which cannot be ignored in the context of annual N 2 O release., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Karst groundwater provides drinking water for a quarter of Earth's population. However, in intensive agricultural regions worldwide, karst water is commonly polluted by nitrate (NO 3 - ), particularly in the valley depression areas with well hydrological connectivity. The valley depression aquifers are particularly vulnerable to anthropogenic pollution because their pipes and sinkholes respond quickly to rainfall events and anthropogenic inputs. Identifying nitrate sources and transport paths in the valley depression areas is key to understanding the nitrogen cycle and effectively preventing and controlling NO 3 - pollution. This study collected high-resolution samples at four sites including one surface stream-SS, two sinkholes-SH and reservoir-Re, during the wet season in the headwater sub-catchment. The chemical component concentrations and stable isotopes (δ 15 N-NO 3 - and δ 18 O-NO 3 - ) were analyzed. The stable isotope analysis model in R language (SIAR) was used to quantitatively analyze the contribution rate of NO 3 - sources. The results showed that the down section site (Re) has the highest [NO 3 - -N], followed by SH and the lowest SS. The sources calculation of SIAR demonstrated that, during the non-rainfall period, soil organic nitrogen was the primary source of the down section site, followed by fertilizer and the upper reaches sinkholes. During the rainfall period, fertilizer was the primary source of the down section site, followed by soil organic nitrogen and from upper reaches sinkholes. Rainfall events accelerated fertilizer-leaching into the groundwater. Slight denitrification may have occurred at the sampling sites but the assimilation of Re and SH could not occur. In conclusion, agricultural activities were still the primary influencing factor of [NO 3 - -N] in the study area. Therefore, the focus of NO 3 - prevention and control in the valley depression areas should consider the methods and timing of fertilization and the spatial distribution of sinkholes. To reduce nitrogen flux in the valley depression area, effective management policy should consider, e.g., prolongation of water residence time by wetland, and blocking nitrogen loss paths by sinkholes., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Karst terrain seasonal monsoonal rainfall is often associated with high concentrations of nitrate-N in streams draining agricultural land. Such high concentrations can pose problems for environmental and human health. However, the relationship between rainfall events that mobilize nitrate and resulting nitrate export remains poorly understood in karst terrain. To better understand the processes that drive nitrate dynamics during rainfall events, the characteristics of individual rainfall events were analyzed using sensor technology. Thirty-eight rainfall events were separated from the high-frequency dataset spanning 19 months at a karst spring site. The results revealed that nitrate-discharge (N-Q) hysteresis in 79% of rainfall events showed anticlockwise hysteresis loop patterns, indicating nitrate export from long distances within short event periods. Karstic hydrological connectivity and source availability were considered two major determining factors of N-Q hysteresis. Gradual increase in hydrological connectivity during intensive rainfall period accelerated nitrate transportation by karst aquifer systems. Four principal components (PCs, including antecedent conditions PC1&3 and rainfall characteristics PC2&4 explained 82% of the cumulative variance contribution to the rainfall events. Multiple linear regression of four PCs explained more than 50% of the variation of nitrate loading and amplitude during rainfall events, but poorly described nitrate concentrations and hydro-chemistry parameters, which may be influenced by other factors, e.g., nitrate transformation, fertilization time and water-rock interaction. Although variation of N concentration during event flow is evident, accounting for antecedent conditions and rainfall factors can help to predict rainfall event N loading during rainfall events. Pollution of the karstic catchment occurred by a flush of nitrate input following rainfall events; antecedent and rainfall conditions are therefore important factors to consider for the water quality management. Reducing source availability during the wet season may facilitate to reduction of nitrogen loading in similar karst areas., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Due to the excessive exploitation of traditional energy sources, the attention paid to water energy has increased in recent years. As an important means to effectively utilize water energy, reservoirs play an important role in drinking water, irrigation, flood control, and drought resistance. However, utilizing reservoirs often led to water quality issues resulting from the interaction of nutrients and hydrological conditions, especially due to the special structure of karst areas. Because of the change of hydrological conditions by the effect of dam construction, the dynamic of water quality will be more obvious in karst areas with a fast exchange of water and contaminants between underground and surface streams. In the present study, the change in water quality of a karst reservoir, the Muzhu Reservoir in the Houzhai Catchment, was studied. Long-term monitored datasets (1981-2002) and water quality datasets of more recent years were used to assess the effect on the water quality of reservoir expansion from the underground reservoir to the surface reservoir in a karst area. Long-term series datasets had shown that the hydro-chemistry type had been changed from HCO 3 - ·SO 4 2- -Ca 2+ ·Mg 2+ type to HCO 3 - -Ca 2+ type in the short term after the reservoir's expansion. The chemical components of water originating from a rock background reduced markedly after the reservoir's expansion, whereas the content of the anthropogenic contribution in the water decreased after the expansion, except in April and May. Isotopic characteristics showed that δ 15 N-NO 3 - and δ 18 O-NO 3 - values were positively correlated before and after the reservoir expansion, but the slope of the linear regression before the expansion was 0.34, while the slope of the linear regression before the expansion was close to 0.7. This indicated that although denitrification and assimilation may occur simultaneously after the reservoir's expansion, the role of denitrification on nitrate removal decreased, which resulted in nitrate accumulation in the karst reservoir. The results highlighted that nitrate accumulation in karst reservoirs should be monitored to decrease nitrate concentration in the future., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The pollution risks due to the soil migration of toxic metal(loid)s (TMs) are a greatly hazard to ecological environment as well as animal and human health. Previous studies have primarily focused on surface contamination while deep soil layers often contain dangerous levels of TMs. We used restored wheat and rice farmlands from aquaculture ponds as a case study to examine the ecological risk and distribution of TMs in soil profiles. The elements Cu, Zn, Cr, Cd, Hg and As were markedly enriched in the 60-180 cm soil layers of restored farmland, and their concentrations decreased in the several depths as follows: 120-180 cm > 60-120 cm > 0-60 cm. Concentrations of TMs were 9.5-128 % greater in the restored farmlands relative to farmlands not exposed to aquaculture practices. Cadmium and mercury were the most serious contaminants and increased the overall ecological risk. The subsoil of wheat farming system had the highest pollution risk versus the restored rice farmland at 60-120 cm due to elevated levels of Cu, Zn and Pb. Toxic metal(loid)s might be derived from natural sources in deep soil of conventional farmland whereas aquaculture practices were found to constitute the major contribution in the subsoil of restored farmland. Our results indicated that the TMs that were buried in deep soil layers migrated upward and were a significant pollution risk. Urgent actions should be taken to identify and alleviate the contamination sources of these deep soils in addition to the conventional leaching and migration processes of surface contaminants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The impact of rainfall on water quality may be more important in semi-arid regions, where rainfall is concentrated over a couple of months. To explore the impact of rainfall changes on water quality, e.g., nitrogen (TN) and phosphorous (TP), the diversion from Luan River to Tianjin Watershed in the northern semi-humid area was selected as the study area. TN and TP concentrations in rivers and the Yuqiao Reservoir during the three-year high-flow season (2019-2021) were analyzed. The response relationship and influencing factors among the watershed's biogeochemical process, rainfall, and water quality were clarified. The results showed that rainfall in the high flow season mainly controlled the river flow. The concentration of TN and TP in the inflow rivers is regulated by rainfall/flow, while the concentration of TN and TP in the water diversion river has different variation characteristics in the water diversion period and other periods. The lowest annual concentrations of TN and TP were observed in the normal year, while the highest annual concentration was observed in the wet year, indicating that the hydrological process drove the nutrient transport in the watershed. For the tributaries, the Li River catchment contributed a large amount of N and P to the aquatic environment. For the reservoir, the extreme TN concentrations were the same as the tributaries, while the extremes of TP concentrations decreased from the dry year to wet year, which was in contrast to the tributaries. The spatial variation of TN and TP concentrations in the reservoir showed that the concentration decreased following the flow direction from the river estuary to the reservoir outlet. Considering climate change, with the increase of rainfall in North China in the future, the TN and TP transport fluxes in the watershed may continue to increase, leading to the nitrogen and phosphorus load of the downstream reservoir. To ensure the impact of the increase of potential N and P output fluxes in the watershed on the water quality of the reservoir area, it is necessary to strengthen the effective prevention and control of non-point source pollution in the watershed.

Although numerous studies focused on nitrate source, transformation and transport of river water in karst area have been reported, it's still unclear in understanding nitrate main source and transformation in karst groundwater system and how nitrate transport from soil to water during rainfall events in karst critical zone. In order to explore the response and transport of nitrate in karst groundwater to rainfall events, different depths of well water before, during and after rainfall event were sampled, and hillslope runoff, surface runoff of different land-use types during rainfall event were sampled synchronously at a typical karst agricultural catchment in Southwest China. Results showed that fluctuations of EC, pH and DO in deep borehole well (W1) and artesian well (W2) were small, on the contrary, variations of EC and DO in shallow well (W3) were large during sampling period. The nitrate concentrations and isotopic values indicated that nitrate in karst groundwater mainly originated from chemical fertilizer (CF), and influenced by denitrification process. High intensity of denitrification was observed in deep groundwater (87%) and artesian well water (almost 100%). Extremely high dual nitrate isotope values up to 46.8 ± 1.5‰ and 24.7 ± 0.5‰ were found in the deep artesian well. The small variation of water chemistry (EC, DO and pH), nitrate concentration and dual nitrate isotope values in deep wells during sampling period suggested that newly supplied nitrogen in deep groundwater during rainfall events also comes from deep groundwater. Low nitrogen concentrations in hillslope subsurface flow and surface runoff suggests that nitrogen transport process leading to increase of water nitrogen content mainly occur in depression. Nitrogen in depression soil is mainly transported to groundwater through fissures, fractures and conduits, rather than through vertical migration processes in the soil during rainfall events., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The increase of affected river reaches by reservoirs has drastically disturbed the original hydrological conditions, and subsequently influenced the nutrient biogeochemistry in the aquatic system, particularly in the cascade reservoir system. To understand the seasonal variation of nitrogen (N) behaviors in cascade reservoirs, hydrochemistry and nitrate dual isotopes (δ 15 N-NO 3 - and δ 18 O-NO 3 - ) were conducted in a karst watershed (Wujiang River) in southwest China. The results showed that NO 3 - -N accounted for almost 90% of the total dissolved nitrogen (TDN) concentration with high average concentration 3.8 ± 0.4 mg/L among four cascade reservoirs. Higher N concentration (4.0 ± 0.8 mg/L) and larger longitudinal variation were observed in summer than in other seasons. The relationship between the variation of NO 3 - -N and dual isotopes in the profiles demonstrated that nitrification was dominated transformation, while assimilation contributed significantly in the epilimnion during spring and summer. The high dissolved oxygen concentration in the present cascade reservoirs system prevented the occurrence of N depletion processes in most of the reservoirs. Denitrification occurred in the oldest reservoir during winter with a rate ranging from 18 to 28%. The long-term record of surface water TDN concentration in reservoirs demonstrated an increase from 2.0 to 3.6 mg/L during the past two decades (~ 0.1 mg/L per year). The seasonal nitrate isotopic signature and continuously increased fertilizer application demonstrated that chemical fertilizer contribution significantly influenced NO 3 - -N concentration in the karst cascade reservoirs. The research highlighted that the notable N increase in karst cascade reservoirs could influence the aquatic health in the region and further investigations were required.

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 (δ 15 N and δ 18 O) of NO 3 - . 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., Competing Interests: Declaration of competing interest The authors declare no competing financial interest for this manuscript., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Lignin is the second most abundant natural biopolymer, which is a potential alternative to conventional fossil fuels. It is also a promising material for the recovery of valuable chemicals such as aromatic compounds as well as an important biomarker for terrestrial organic matter. Lignin is currently produced in large quantities as a by-product of chemical pulping and cellulosic ethanol processes. Consequently, analytical methods are required to assess the content of valuable chemicals contained in these complex lignin wastes. This review is devoted to the application of mass spectrometry, including data analysis strategies, for the elemental and structural elucidation of lignin products. We describe and critically evaluate how these methods have contributed to progress and trends in the utilization of lignin in chemical synthesis, materials, energy, and geochemistry.

Mass resolving power is one of the key features of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), which enables the molecular characterization of complex mixtures. Quadrupole (2ω) detection provides a significant step forward in FT-ICR MS performance, as it doubles the resolving power for a given signal acquisition time. Whether this 2ω detection technique truly substitutes for a higher magnetic field remains unknown however. In this study, a residue oil sample was characterized using both a 2ω 7 Tesla FT-ICR and a 15 Tesla FT-ICR instrument, and analytical figures of merit were systematically compared. It was shown that 2ω 7T FT-ICR MS provided comparable performance in the deep profiling of the complex oil sample, with better signal intensities and reproducibilities for absorption-mode processing. The 15T FT-ICR MS gave more precise measurements with better estimates of the sample's elemental compositions. To the best of our knowledge, this is the first published study, which thoroughly compared the performance of 2ω detection on a low magnetic field instrument with that of a high magnetic field FT-ICR-MS., Competing Interests: The authors declare no competing financial and nonfinancial interests. D.A.V. is Editor‐in‐Chief of Analytical Science Advances., (© 2020 The Authors. Analytical Science Advances published by Wiley‐VCH GmbH.)

Rainwater chemistry plays an important role in the earth-surficial ecosystem, but studies on rainwater chemical composition of karst agro-ecosystem are rare. To explore the rainwater alkalization and the provenance of components responsible for neutralization, two-years chemical monitoring of rainwater was carried out in a karst agricultural catchment in Southwest China. The main findings suggest that SO 4 2- , NO 3 - , Ca 2+ , and NH 4 + are the principal ions. All the ionic contents show distinctly seasonal variation (highest in winter) in response to variations in seasonal precipitation because the rain-scour process can efficiently remove atmospheric materials. Source identification indicates that Cl - and Na + are mainly derived from marine input whereas SO 4 2- and NO 3 - are controlled by anthropogenic emission, in particular, fixed emission sources. The source of NH 4 + is attributed to intense agricultural production, while Ca 2+ and Mg 2+ are mainly derived from calcite dissolution. The rainwater alkalization caused by the seasonal acid neutralization (via basic components, Ca 2+ and NH 4 + ) is beneficial to crop growth but also reflect agricultural overfertilization. Sulfur controlled the total wet acid deposition (68%-94%) and could be a potential agent of weathering., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Understanding where nitrate is mobilized from and under what conditions is required to reduce nitrate loss and protect water quality. Low frequency sampling may inadequately capture hydrological and biogeochemical processes that will influence nitrate behavior. We used high-frequency isotope sampling and in-situ nitrate sensing to explore nitrate export and transformation in a karst critical zone. Nitrate was mobilised during light rainfall, and transferred from soil layers to the karst matrix, where some nitrate was retained and denitrified. Nitrate isotopic composition changed rapidly during the rising limb of events and slowly during the falling limb. The main nitrate source was synthetic fertiliser (up to 80% during event flow), transported by conduit flow following high rainfall events, and this contribution increased significantly as discharge increased. Soil organic nitrogen contribution remained constant indicating at baseflow this is the primary source. Isotope source appointment of nitrate export revealed that synthetic fertilizer accounted for more than half of the total nitrate export, which is double that of the secondary source (soil organic nitrogen), providing valuable information to inform catchment management to reduce nitrate losses and fluvial loading. Careful land management and fertilizer use are necessary to avoid nitrate pollution in the karst agroecosystem, for example by timing fertilizer applications to allow for plant uptake of nitrate before rainfall can flush it from the soils into the karst and ultimately into catchment drainage., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier Ltd.)

Objective: To quantitatively evaluate the relationship between sleep duration and metabolic syndrome in adults in order to set up programs on prevention and treatment of metabolic syndrome in this population. Methods: Relevant studies were identified by systematically searching databases before October 2019. All statistical analyses were under the use of Stata 11.0. Results: A total of 656 319 participants including 150 638 cases with metabolic syndrome were involved in thes 38 articles. A U-shaped relationship between sleep duration and metabolic syndrome was noticed. For short and long sleep duration, the OR =1.11 (95% CI : 1.07-1.16) and 1.10 (95% CI : 1.03-1.18), respectively. Subgroup analyses on cross-sectional studies revealed that factors as men, aged under 60 years, being Asians or Caucasians would increase the risk of metabolic syndrome by 6%, 14%, 9%, and 24%, respectively for those with short sleep duration. Factors as aged 60 years and above, being black and with long sleep duration, would increase the risks of metabolic syndrome by 13% and 19%, respectively in women. In subgroup analyses on cohort studies, positive correlation between short sleep duration and metabolic syndrome was observed in both Asian ( RR =1.10, 95% CI : 1.07-1.13) and in Caucasians ( RR =1.56, 95% CI : 1.08-2.26) populations. Conclusions: Results of this study revealed an association between metabolic syndrome and the duration of sleep. We understand that sleep is a behavior that can be changed step by step, through adequate intervention programs, to reduce the risk of metabolic syndrome which has become an important public health issue.

Hydrochemical behavior and dissolved carbon dynamics are highly-sensitive to hydrological variations in the monsoon-influenced karstic critical zone which has high chemical weathering rates and experiences strong anthropogenic impact. Continuous high-frequency monitoring in the spring outlet of a karstic catchment in Southwestern China revealed that most hydrochemical variables changed distinctively in response to hydrologic variations, influenced by mixing of different sources and miscellaneous biogeochemical processes. Na + , K + and SO 4 2 - varied significantly with hydrology, showing weak chemostatic behavior controlled by dilution. The flushing effect and random behavior of NO 3 - and Cl - likely reflect agricultural inputs from high throughflow. Soil CO 2 in infiltrated water supports carbonate weathering, enabling DIC (dissolved inorganic carbon) and weathering products (e.g., Ca 2+ and Mg 2+ ) to maintain chemostatic behavior. Biogenic DIC exhibited a stronger chemostatic response than carbonate sources and was the foremost control in DIC behavior. Carbon exchange between DIC and DOC (dissolved organic carbon) did not significantly influence DIC concentration and δ 13 C due to very low DOC concentration. More DOC was exported by flushing from increasing discharge. Hysteretic analysis indicated that the transport processes were controlled by proximal sources mixing and diverse mobilization in various periods responding to rainstorms. NO 3 - and Cl - presented different hysteresis behavior as sourced from agricultural activities. DOC increased on the hydrograph rising limb and was controlled by a transport-limited regime. However, the hysteresis behavior of most weathering products and DIC were regulated by a process-limited regime in the karstic critical zone. Overall, biogeochemical processes, hydrogeological properties, storm intensity/magnitude and the timing of storms (antecedent conditions) are main factors influencing the response of hydrochemical variables and dissolved carbon to storm events., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier B.V. All rights reserved.)

Emission of reactive nitrogen species has a major impact on atmospheric chemistry, ecosystem and human health. The origin and formation mechanisms of wet-deposited nitrate are not well understood in Southeast Asia (SEA). In this study, we measured stable isotopes of nitrate (δ 15 N and δ 18 O) and chemical compositions of daily rainwater from May 2015 to July 2017 in Singapore. Our results showed that δ 15 N-NO 3 - and δ 18 O-NO 3 - varied seasonally with higher values during the Inter-monsoon period (April-May and October-November) than during Northeast (December-March) and Southwest monsoon (June-September). Bayesian mixing modeling, which took account of the isotope fractionation, indicated that traffic emission (47 ± 32%) and lightning (19 ± 20%) contributed the most to NO 3 - with increased traffic contribution (55 ± 37%) in the Northeast monsoon and lightning (24 ± 23%) during the Inter-monsoon period. Biomass burning and coal combustion, likely from transboundary transport, contributed ∼25% of nitrate in the rainwater. Monte Carlo simulation of δ 18 O-NO 3 - indicated that oxidation process by hydroxyl radical contributed 65 ± 14% of NO 3 - , with the rest from hydrolysis of N 2 O 5 . Wind speed had large effect on δ 18 O-NO 3 - variations in the atmosphere with more involvement of hydroxyl radical reactions when wind speed increased. Our study highlights the key role of isotopic fractionation in nitrate source apportionment, and the influence of meteorological conditions on nitrate formation processes in SEA., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Nitrate is one of the primary nutrients associated with sedimentation and fuels eutrophication in reservoir systems. In this study, water samples from Bukit Merah Reservoir (BMR) were analysed using a combination of water chemistry, water stable isotopes (δ 2 H-H 2 O and δ 18 O-H 2 O) and nitrate stable isotopes (δ 15 N-NO 3 - and δ 18 O-NO 3 - ). The objective was to evaluate nitrate sources and processes in BMR, the oldest man-made reservoir in Malaysia. The δ 15 N-NO 3 - values in the river and reservoir water samples were in the range +0.4 to +14.9‰ while the values of δ 18 O-NO 3 - were between -0.01 and +39.4‰, respectively. The dual plots of δ 15 N-NO 3 - and δ 18 O-NO 3 - reflected mixing sources from atmospheric deposition (AD) input, ammonium in fertilizer/rain, soil nitrogen, and manure and sewage (MS) as the sources of nitrate in the surface water of BMR. Nitrate stable isotopes suggested that BMR undergoes processes such as nitrification and mixing. Denitrification and assimilation were not prevalent in the system. The Bayesian mixing model highlighted the dominance of MS sources in the system while AD contributed more proportion in the reservoir during both seasons than in the river. The use of δ 13 C, δ 15 N, and C:N ratios enabled the identification of terrestrial sources of the organic matter in the sediment, enhancing the understanding of sedimentation associated with nutrients previously reported in BMR. Overall, the nitrate sources and processes should be considered in decision-making in the management of the reservoir for irrigation, Arowana fish culture and domestic water supply., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Coupled nitrogen and oxygen isotopes of nitrate have proven useful in identifying nitrate sources and transformation in rivers. However, isotopic fractionation and low-resolution monitoring limit the accurate estimation of nitrate dynamics. In the present study, the spatio-temporal variations of nitrate isotopes ( 15 N and 18 O) and hydrochemical compositions (NO 3 - and Cl - ) of river water were examined to understand nitrate sources in the Xijiang River, China. High-frequency sampling campaigns and isotopic analysis were performed at the mouth of the Xijiang River to capture temporal nitrate variabilities. The overall values of δ 15 N-NO 3 - and δ 18 O-NO 3 - ranged from +4.4‰ to +14.1‰ and from -0.3‰ to +6.8‰, respectively. The results of nitrate isotopes indicated that NO 3 - mainly originated from soil organic nitrogen (SON), chemical fertilizer (CF), and manure and sewage wastes (M&S). The negative correlation of nitrate isotopic values with NO 3 - /Cl - ratios suggested the importance of denitrification in NO 3 - loss. The results of Bayesian model with incorporation of isotopic fractionation during the denitrification showed that SON and CF contributed to the most (72-73%) nitrate in the wet season; whereas approximately 58% of nitrate was derived from anthropogenic inputs (M&S and CF) in the dry season. The nitrate flux was 2.08 × 10 5  tons N yr -1 during one hydrologic year between 2013 and 2014, with 86% occurring in the wet season. Long-term fluctuations in nitrate flux indicated that nitrate export increased significantly over the past 35 years, and was significantly correlated with nitrate concentrations. The seasonal pattern of nitrate dynamics indicated the mixing of nitrified NO 3 - and denitrified NO 3 - between surface flow and groundwater flow under different hydrological conditions. Overall, the present study quantitatively evaluates the spatio-temporal variations in nitrate sources in a subtropical watershed, and the high-frequency monitoring gives a better estimate of nitrate exports and proportional contributions of nitrate sources., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Nitrogenous species, particularly nitrate, are some of the most significant contaminants in freshwater rivers and lakes in China, posing a significant threat to human and ecosystem health. To identify the major nitrate sources and transformation processes in a subtropical karst lake (Hongfeng, HF) in Southwest China, two sampling campaigns involving three lake profiles were conducted during the impoundment period (April) and flood period (August). Hydro-chemistry parameters, concentration of nitrogenous species, and dual isotopes of nitrate were analyzed. Nitrate was the major nitrogenous species in HF lake with higher proportion in April than August. The concentrations of NH4+, NO2- and dissolved organic nitrogen were below the detection limit in April, while NH4+ increased with depth in August, which may be a result of mineralization. Nitrification was detected during the impoundment period and from the surface to a depth of 10 m during the flood period. Denitrification was detected in the lake bottom waters during the flood period with isotopic fractionation of -10.7‰ for δ15N-NO3- and -4.7‰ for δ18O-NO3-. The Rayleigh distillation demonstrated denitrification showed spatial variation (53% and 89% of nitrate in the southern and northern region of the lake, respectively). The Bayesian modelling results suggest that organic nitrogen degradation and sediment make the largest contributions to nitrate (51% and 38% in April and 33% and 24% in August, respectively) to the lake. Tributaries contributed more nitrate in August (37%) than in April (10%). The results highlight that modified endogenous nitrogen contributed a high proportion of nitrate sources within the lake system during the two periods.

Objective: To investigate the difference of therapeutic effect of tinnitus patients with different types of hearing curve. Method: Patients with the inclusion and exclusion criteria for the treatment were studied retrospectively.Use the SPSS 20.0 Chinese version of the software to collect data and analysis.The difference was statistically significant when P <0.05. Result: A total of 164 patients were collected, and the most of the hearing curve types was high frequency hearing loss; according to the TEQ scoring and grading method, most tinnitus patients were in the middle severity; The chi-square test showed that there was no significant difference among the patients with different hearing curve types when the first visit,the severity among the groups was evenly distributed. After treatment,there was no significant difference in the effect of last visit and the follow-up between the patients with different hearing curve types. Conclusion： Unlike the sudden deafness, there was no statistically significant difference in the prognosis of tinnitus patients with different types of hearing curve. We can not choose the treatment program or even predict the curative effect according to the hearing curve type., Competing Interests: The authors of this article and the planning committee members and staff have no relevant financial relationships with commercial interests to disclose., (Copyright© by the Editorial Department of Journal of Clinical Otorhinolaryngology Head and Neck Surgery.)

A heavy load of nitrogenous compounds reflects nutrient loss and influences water quality in large rivers. Nitrogenous concentrations and dual isotopes of nitrate were measured to ascertain the spatial and temporal distributions of nitrate transformation in the Yellow River, the second-longest river in China. Assessment of the long-term record indicates that [NO 3 - -N] has increased by two-fold over the past three decades. Weekly observation of ammonium over a twelve-year period revealed high concentrations and suggests impairment of water quality, particularly since 2011. The estimated total dissolved nitrogen flux was 7.2 times higher in middle reaches than that at head waters. Anthropogenic nitrogen sources become more important in lower section of the upper reaches and middle reaches because of intensive agricultural activities and urban input. Nitrate in the lower reaches was mainly derived from transportation of upstream nitrate and point sources from cities. The spatial variation of ammonium and nitrate isotopes show that nitrification is a key process governing nitrogen transformation. Riverine biological processes could potentially be responsible for the shift of nitrate isotope signature. The first step to reducing nitrogen load and improving water quality will be containment and careful management of sources from urban input, sewage waste and irrigation runoff.