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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 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.)

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.)

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.)

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.)

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 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.)

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.)

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.)