Assessing ammonium pollution and mitigation measures through a modified watershed non-point source model.

Watershed water quality modeling is a valuable tool for managing ammonium (NH4+) pollution. However, simulating NH4+ pollution presents unique challenges due to the inherent instability of NH4+ in natural environment. This study modified the widely-used Soil and Water Assessment Tool (SWAT) model to simulate non-point source (NPS) NH4+ processes, specifically incorporating the simulation of land-to-water NH4+ delivery. The Jiulong River Watershed (JRW) is the study area, a coastal watershed in Southeast China with substantial sewage discharge, livestock farming, and fertilizer application. The results demonstrate that the modified model can effectively simulate the NPS NH4+ processes. It is recommended to use multiple sets of observations to calibrate NH4+ simulation to enhance model reliability. Despite constituting a minor proportion (5.6 %), point source inputs significantly contribute to NH4+ load at watershed outlet (32.4∼51.9 %), while NPS inputs contribute 15.3∼17.3 % of NH4+ loads. NH4+ primarily enters water through surface runoff and lateral flow, with negligible leaching. Average NH4+ land-to-water delivery rate is about 2.35 to 2.90 kg N/ha/a. High delivery rates mainly occur at agricultural areas. Notably, proposed NH4+ mitigation measures, including urban sewage treatment enhancement, livestock manure management improvement, and fertilizer application reduction, demonstrate potential to collectively reduce the NH4+ load at watershed outlet by 1/4 to 1/3 and significantly enhance water quality standard compliance frequency. Insights gained from modeling experience in the JRW offer valuable implications for NH4+ modeling and management in regions with similar climates and significant anthropogenic nitrogen inputs.

Storm-induced nitrogen transport via surface runoff, interflow and groundwater in a pomelo agricultural watershed, southeast China.

The storm-induced export of nitrogen (N) from agricultural watersheds significantly impacts aquatic ecosystems, yet the mechanisms of source supply and transport behind N species remain unclear. Here, we investigated the hydrological factors influencing the timing and magnitude of river N species export in a Chinese pomelo agricultural watershed. We conducted continuous observations of watershed hydrology, N species, and their isotopic ratios along a soil-groundwater-river continuum during two storm events in 2018-2019. We found the export flux of river NO3-N covers ∼80% of the total N flux during storms, and the rest for other N species. Our results further revealed distinct pathways and timing of N transport among different N species, especially between ammonium N (NH4-N) and nitrate N (NO3-N). NH4-N in stormflow predominantly originates from sewage and soil leachate, rapidly transported via surface runoff and interflow. Orchard fertilization (contributed 41-56% based on SIAR analysis) was the major source of river NO3-N, which underwent initial dilution via surface runoff and subsequently became enriched through delayed discharge of soil leachate and groundwater. The variations in timing and magnitude of N transport between storms can be explained by antecedent conditions such as precipitation, soil N pools, and storm size. These findings emphasize the hydrological controls on N export from agricultural watersheds, and highlight the variations in source supply and transport pathways among different N species. The insights gained from this study hold significance for managing agricultural pollution and restoring impaired aquatic systems.

Prioritizing ecological restoration in hydrologically sensitive areas to improve groundwater quality.

Greening is the optimal way to mitigate climate change and water quality degradation caused by agricultural expansion and rapid urbanization. However, the ideal sites to plant trees or grass to achieve a win-win solution between the environment and the economy remain unknown. Here, we performed a nationwide survey on groundwater nutrients (nitrate nitrogen, ammonia nitrogen, dissolved reactive phosphorus) and heavy metals (vanadium, chromium, manganese, iron, cobalt, nickel, copper, arsenic, strontium, molybdenum, cadmium, and lead) in China, and combined it with the global/national soil property database and machine learning (random forest) methods to explore the linkages between land use within hydrologically sensitive areas (HSAs) and groundwater quality from the perspective of hydrological connectivity. We found that HSAs occupy approximately 20 % of the total land area and are hotspots for transferring nutrients and heavy metals from the land surface to the saturated zone. In particular, the proportion of natural lands within HSAs significantly contributes 8.0 % of the variability in groundwater nutrients and heavy metals in China (p < 0.01), which is equivalent to their contribution (8.8 %) at the regional scale (radius = 4 km, area = 50 km2). Increasing the proportion of natural lands within HSAs improves groundwater quality, as indicated by the significant reduction in the concentrations of nitrate nitrogen, manganese, arsenic, strontium, and molybdenum (p < 0.05). These new findings suggest that prioritizing ecological restoration in HSAs is conducive to achieving the harmony between the environment (improving groundwater quality) and economy (reducing investment in area management).

Dynamics and geochemical responses of dissolved metals (Mn and Cu) in a subtropical estuary, China.

The research delved into the occurrence and dynamics of dissolved metals, specifically manganese (Mn) and copper (Cu), within the Jiulong River Estuary, South China, a medium-sized subtropical estuary. Our findings unveiled a nuanced seasonal and spatial variability of dissolved metals throughout the entire estuarine system. Notably, dissolved Mn concentrations peaked (~ 3.5 µM) in the upper estuary, diminishing sharply along the salinity gradient, with a modest rise in the middle estuary and outer Xiamen Bay. In the upper estuary, heightened concentrations of dissolved Mn occurred in spring due to augmented terrestrial particle inputs, followed by suboxically reductive releases; conversely, concentrations were low in summer, attributed to dilution from increased freshwater discharges and particle scavenging. In contrast, dissolved Cu exhibited differently, with elevated concentrations (29.2-37.5 nM) in the upper and middle estuaries, driven by reductive dissolution of Mn particles and chloride-induced ion exchanges, respectively. Concurrently, heightened inputs of nutrients and metals correlated with elevated phytoplankton productivity (indicated by chlorophyll a) in the upper and outer estuary regions. Our analysis underscored the sensitivity of dissolved metals to environmental parameters, including temperature, pH, and dissolved oxygen. The integration of compiled historical data underscored the dynamic nature of dissolved metals, particularly Cu, in response to geochemical processes.The elevated ion levels indicated intensified ion releases from particles and sediments, attributable to increased anthropogenic perturbation and climatic changes (e. g. ocean warming).

Carbonate chemistry and carbon sequestration driven by inorganic carbon outwelling from mangroves and saltmarshes.

Mangroves and saltmarshes are biogeochemical hotspots storing carbon in sediments and in the ocean following lateral carbon export (outwelling). Coastal seawater pH is modified by both uptake of anthropogenic carbon dioxide and natural biogeochemical processes, e.g., wetland inputs. Here, we investigate how mangroves and saltmarshes influence coastal carbonate chemistry and quantify the contribution of alkalinity and dissolved inorganic carbon (DIC) outwelling to blue carbon budgets. Observations from 45 mangroves and 16 saltmarshes worldwide revealed that >70% of intertidal wetlands export more DIC than alkalinity, potentially decreasing the pH of coastal waters. Porewater-derived DIC outwelling (81 ± 47 mmol m-2 d-1 in mangroves and 57 ± 104 mmol m-2 d-1 in saltmarshes) was the major term in blue carbon budgets. However, substantial amounts of fixed carbon remain unaccounted for. Concurrently, alkalinity outwelling was similar or higher than sediment carbon burial and is therefore a significant but often overlooked carbon sequestration mechanism.

Pollution abatement reducing the river N2O emissions although it is partially offset by a warming climate: Insights from an urbanized watershed study.

Global nitrogen (N) pollution has resulted in increased river nitrous oxide (N2O) emissions, which contribute to climate change. However, little is known about how pollution abatement conversely reduces river N2O production in a warming climate. Here, field observations and microcosmic experiments were conducted in a coastal urbanized watershed (S.E. China) to explore the interactive effect of changing nitrate and temperature on river sediment denitrification (DNF) and N2O production. The results showed that urban river reaches (UR) with higher organic carbon content and denitrifying gene abundance in sediments have a greater DNF rate, nitrate removal efficiency (NRE), and N2O concentration than agricultural river reaches (AR). Microcosmic incubation suggested that the DNF rate and associated N2O production decreased under low nitrate addition, wherein the NRE increased. The scenario simulation illustrated a nonlinear response of N2O production to nitrate removal (i.e., ΔN2O/ΔNO3-N) from both UR and AR sediments at a given temperature, and the DNF rate and N2O production increased with increasing temperature. An increase in temperature by 1 degree Celsius would offset 18.75% of the N2O reduction by nitrate removal via DNF. These findings implied that watershed pollution abatement undoubtedly contributes to the reduction in global river N2O emissions although it is partially offset by extra N2O production caused by global warming.

Response and recovery mechanisms of river microorganisms to gradient concentrations of estrogen.

As an important ecological system on the earth, rivers have been influenced by the rapid development of urbanization, industrialization, and anthropogenic activities. Increasingly more emerging contaminants, such as estrogens, are discharged into the river environment. In this study, we conducted river water microcosmic experiments using in situ water to investigate the response mechanisms of microbial community when exposed to different concentrations of target estrogen (estrone, E1). Results showed that both exposure time and concentrations shaped the diversity of microbial community when exposed to E1. Deterministic process played a vital role in influencing microbial community over the entire sampling period. The influence of E1 on microbial community could last for a longer time even after the E1 has been degraded. The microbial community structure could not be restored to the undisturbed state by E1, even if disturbed by low concentrations of E1(1 µg/L and 10 µg/L) for a short time. Our study suggests that estrogens could cause long-term disturbance to the microbial community of river water ecosystem and provides a theoretical basis for assessing the environmental risk of estrogens in rivers.

Impacts of a subtropical storm on nitrogen functional microbes and associated cycling processes in a river-estuary continuum.

Storms, in subtropical regions such as S.E. China, cause major changes in the physical and biogeochemical fluxes of anthropogenic N species through the river-estuary continuum to the coast. Two weeks continuous observations at a sampling station (Station E) in the upper Jiulong River Estuary (S.E. China) were conducted to track the changes of physical and biogeochemical parameters together with genomic identification of nitrogen cycling microbes through a complete storm event in June 2019. In conjunction with previous N flux measurements, it was found that there was greatly increased flux of N to and through the upper estuary during the storm. During the storm, the freshwater/brackish water boundary moved downstream, and previously deposited organic rich sediment was resuspended. During baseflow, anthropogenically derived ammonium was oxidised dominantly by the marine nitrifying (AOA) microbe Nitrosopelagicus. However, during the storm, the dominant ammonia-oxidizing archaea (AOA) at Station E changed to the riverine genus (Nitrosotenuis) while the marine genus, Nitrosopumilus decreased. At the same time the dominant ammonia-oxidizing bacteria (AOB) was still the marine genus (Nitrosomanas). Estuarine nitrifiers had higher abundance, weighted entropy and diversity during the Flood, suggesting that the high NH4-N and DO during the Rising period of the Flood resulted in a bloom of nitrifiers. The changing gene abundances of nitrifiers were reflected in changes in the concentration and isotopic composition of DIN confirming active nitrification in the oxygen-rich water column. During the storm the numbers of denitrifiers (narG, nirS and nod), DNRA (nrfA) and anammox (hzsB) were found in the water column increased, and the larger fraction was associated with the <22 µm free-living fraction. However it was not possible with the data obtained to estimate what fraction of these anaerobic bacteria were active in the dominantly oxic water column.

Seasonal hydrological dynamics govern lifestyle preference of aquatic antibiotic resistome.

Antibiotic resistance genes (ARGs) are a well-known environmental concern. Yet, limited knowledge exists on the fate and transport of ARGs in deep freshwater reservoirs experiencing seasonal hydrological changes, especially in the context of particle-attached (PA) and free-living (FL) lifestyles. Here, the ARG profiles were examined using high-throughput quantitative PCR in PA and FL lifestyles during four seasons representing two hydrological phenomena (vertical mixing and thermal stratification) in the Shuikou Reservoir (SR), Southern China. The results indicated that seasonal hydrological dynamics were critical for influencing the ARGs in PA and FL and the transition of ARGs between the two lifestyles. ARG profiles both in PA and FL were likely to be shaped by horizontal gene transfer. However, they exhibited distinct responses to the physicochemical (e.g., nutrients and dissolved oxygen) changes under seasonal hydrological dynamics. The particle-association niche (PAN) index revealed 94 non-conservative ARGs (i.e., no preferences for PA and FL) and 23 and 16 conservative ARGs preferring PA and FL lifestyles, respectively. A sharp decline in conservative ARGs under stratified hydrologic suggested seasonal influence on the ARGs transition between PA and FL lifestyles. Remarkably, the conservative ARGs (in PA or FL lifestyle) were more closely related to bacterial OTUs in their preferred lifestyle than their counterparts, indicating lifestyle-dependent ARG enrichment. Altogether, these findings enhanced our understanding of the ARG lifestyles and the role of seasonal hydrological changes in governing the ARG transition between the lifestyles in a typical deep freshwater ecosystem.

Hydrological connectivity affects nitrogen migration and retention in the land‒river continuum.

Land use change and excessive nitrogen (N) loading threaten the health of receiving water bodies worldwide. However, the role of hydrological connectivity in linking watershed land use, N biogeochemistry and river water quality remain unclear. In this study, we investigated 15 subwatersheds in the Jiulong River watershed (southeastern China) during a dry baseflow period in 2018, combined with 3‒year (2017-2019) nutrient monitoring in 5 subwatersheds to explore river N dynamics (dissolved nutrients, dissolved gases and functional genes) and their controlling factors at three hydrological connectivity scales, i.e., watershed, hydrologically sensitive areas (HSAs) and riparian zone. The results show that land use at HSAs (less than 20% of watershed area) and watershed scales contributed similarly to river N variation, indicating that HSAs are hotspots for transporting land N into river channels. In particular, the agricultural land was the main factor affecting river nitrate and nitrous oxide (N2O) concentrations, while the built-up land significantly affected river ammonium and nitrite. At the riparian zone scale, soils and sediments substantially influenced river N retention processes (i.e., nitrification and denitrification). Management and protection measures targeting HSAs and riparian zones are expected to efficiently reduce river N loading and improve water quality.

[Spatial and Temporal Distribution and Influencing Factors of Dissolved Trace Metals in Jiulong River Estuary and Xiamen Bay].

Trace metals play an important role in some biogeochemical processes in the marine system. The physical and hydrological conditions in estuaries and coastal seawater are complicated and significantly affected by human activities. Therefore, the biogeochemical behavior and influencing mechanism of trace metals in nearshore water have become a research hotspot. Jiulong River estuary and Xiamen Bay are located in the coastal areas of Fujian Province, which are significantly influenced by Longyan, Xiamen, and Zhangzhou City. In July 2021, November 2021, and January 2022, the trace metals chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), and cadmium (Cd) and environmental factors (water temperature, salinity, pH, dissolved oxygen (DO), suspended particulate matter (SPM), etc.) in Jiulong River estuary and Xiamen Bay were investigated. The results showed that the order of trace metal concentration average values measured in Jiulong River estuary and Xiamen Bay was Mn>Ni>Cu>Cr>Co>Cd. In July 2021, the average values of ρ(Cr), ρ(Mn), ρ(Co), ρ(Ni), ρ(Cu), and ρ(Cd) were 0.159, 47.96, 0.068, 1.56, 1.07, and 0.016 µg·L-1, respectively. In November 2021, the average values were 0.216, 8.48, 0.030, 1.70, 1.92, and 0.019 µg·L-1, respectively. The average concentrations in January 2022 were 0.281, 32.39, 0.062, 2.21, 1.54, and 0.034 µg·L-1, respectively. The concentration of dissolved metals in the estuary was higher than that in the bay area. Principal component analysis showed that the main factors affecting the concentrations of dissolved trace metals were river runoff and anthropogenic activities.

[Spatiotemporal Characteristics of Dissolved Oxygen and Control Mechanism of Hypoxia (Low Oxygen) in the Watershed-Coastal System in Fujian Province].

Dissolved oxygen is a key parameter to measure water environment quality and ecosystem health. Currently, the problem of hypoxia (low oxygen) is prominent in coastal areas in China, but there is a lack of research on the spatiotemporal characteristics of dissolved oxygen and the control mechanism of hypoxia in the watershed-coastal system. Based on the data of 135 surface water (including estuaries) and 66 coastal water monitoring sites in Fujian Province from 2011 to 2020, this study analyzed the spatiotemporal variation pattern of dissolved oxygen at seasonal and interannual time scales. The data of hypoxia (10% quantile, corresponding to 67% saturation) were selected to study the characteristics and control mechanism of hypoxia in four types of water bodies (i.e., rivers, reservoirs, estuaries, and coastal waters) using mathematical statistics and a random forest model. The results showed that the dissolved oxygen saturation was the highest in the coast[(98.2±10.2)%] and the lowest in the estuary[(79.2±17.9)%]. Compared with that in the 12th Five-Year Plan (2011-2015), the frequency of hypoxia detection in rivers and reservoirs in the 13th Five-Year Plan (2016-2020) was significantly reduced, but the change in estuaries was not significant. Counting the points with hypoxia detection, the multi-year average hypoxia detection frequency of rivers and reservoirs was highest in autumn, and the frequency of estuaries was highest in summer. Hypoxia in reservoirs and estuaries was the most prominent but with different mechanisms. Specifically, hypoxia in reservoir reaches was related to summer runoff carrying large amounts of organic matter input, stratification leading to continuous oxygen depletion in the bottom water, and vertical mixing or discharge through dams in autumn, whereas hypoxia in estuaries was associated with strong pollution inputs and reductive materials. Systematic management and regionalized control mechanisms need to be established to further strengthen watershed-coastal pollution abatement to help mitigate eutrophication and hypoxia problems.

Predicting Dynamic Riverine Nitrogen Export in Unmonitored Watersheds: Leveraging Insights of AI from Data-Rich Regions.

Terrestrial export of nitrogen is a critical Earth system process, but its global dynamics remain difficult to predict at a high spatiotemporal resolution. Here, we use deep learning (DL) to model daily riverine nitrogen export in response to hydrometeorological and anthropogenic drivers. Long short-term memory (LSTM) models for the daily concentration and flux of dissolved inorganic nitrogen (DIN) were built in a coastal watershed in southeastern China with a typical subtropical monsoon climate. The DL models exhibited excellent accuracy for both DIN concentration and flux, with Nash-Sutcliffe efficiency coefficients (NSEs) up to 0.67 and 0.92, respectively, a performance unlikely to be achieved by generic process-based models with comparable data quality. The flux model ensemble, without retraining, performed well (mean NSE = 0.32-0.84) in seven distinct watersheds in Asia, Europe, and North America, and retraining with multi-watershed data further improved the lowest NSE from 0.32 to 0.68. DL interpretation confirmed that interbasin consistency of riverine nitrogen export exists across different continents, which stems from the similarities in rainfall-runoff relationships. The multi-watershed flux model projects 0.60-12.4% increases in the nitrogen export to oceans from the studied watersheds under a 20% increase in fertilizer consumption, which rises to 6.7-20.1% with a 10% increase in runoff, indicating the synergistic effect of human activities and climate change. The DL-based method represents a successful case of explainable artificial intelligence in environmental science, providing a potential shortcut to a consistent understanding of the global daily-resolution dynamics of riverine nitrogen export under the currently limited data conditions.

The spatiotemporal variations in microalgae communities in vertical waters of a subtropical reservoir.

The construction of cascade reservoirs increases eutrophication and exacerbates algal blooms and thus threatens water quality. Previous studies on the microalgae in reservoir have mainly focused on the spatio-temporal patterns of surface microalgae communities at the horizontal scale, while few studies have simultaneously considered the successions of microalgae in vertical profiles including the sediments and the effects of the nutrients release and microalgae in sediments on microalgae in upper waters. In this study, we investigated the effects of microalgae and physico-chemical parameters in waters and sediments on the successions of vertical microalgae communities in Xipi Reservoir, Southeast China. The seasonal variations in microalgae compositions decreased gradually from the surface water (the dominance of Cryptophyta and Chlorophyta in spring, Chlorophyta and Cyanophyta in summer, and relatively uniform in autumn and winter) to the sediment (the dominance of Bacillariophyta throughout the year), which was influenced by the variations of physico-chemical factors in different layers. The spatio-temporal variations in microalgae communities in waters was attributing to not only the heterogeneities of the stratification, and the physico-chemical factors such as water temperature, pH, and nutrient concentrations, especially for phosphorus in the water column, but also the combinations of phosphorus release and microalgae composition in sediments. Environmental changes would be especially problematic for microalgae groups such as Cryptophyta, Dinophyta and Chlorophyta that were sensitive to the changes of temperature and nutrients. Our results are helpful for an extensive understanding of the dynamics of microalgae communities in reservoir, and contribute to reservoir management for ensuring the safety of drinking water.

Hypolimnetic deoxygenation enhanced production and export of recalcitrant dissolved organic matter in a large stratified reservoir.

Global impoundment of river systems represents a major anthropogenic forcing to carbon cycling in reservoirs with seasonal thermal stratification. Currently, a quantitative and mechanistic understanding of how hypolimnetic deoxygenation in stratified reservoirs alters dissolved organic matter (DOM) cycling and lateral transport along the river continuum remains unresolved. Herein, we used optical and high-resolution mass spectrometric analyses to track seasonal and spatial compositional changes of DOM from a large, subtropical impounded river in southeast China. Aliphatic compounds were contributed by algal blooms to epilimnetic DOM during the spring/summer and by baseflow to the overall DOM pool during low-discharge periods. Deoxygenation-driven hypolimnetic mineralization enhanced in situ production of bio-refractory molecules and humic-like fluorescent DOM (FDOMH) by utilizing bio-labile DOM and settling biogenic particles during periods of stratification. Production efficiency of hypolimnetic FDOMH was 159-444% higher than that of the global dark ocean, and was strongly regulated by temperature and possibly substrate supply. The in situ production rate of hypolimnetic FDOMH was four to five orders-of-magnitude higher than the dark ocean, with much faster turnover rates in dark inland waters versus the dark ocean. Collectively, these findings indicate that the hypolimnion is a hotspot for microbial carbon transformations, and hence an important source and pool of refractory DOM in aquatic systems. The lateral FDOMH flux increased 10.8-32.1% due to hypolimnetic reservoir release during periods of stratification, highlighting the importance of incorporating hypolimnetic carbon transformations into models for carbon cycling of inland waters and the land-sea interface.

Assessment of water quality under various environmental features using a site-specific weighting water quality index.

In a multiregional river system, environmental features such as natural conditions and anthropogenic activities vary among regions, resulting in spatiotemporal variations in water quality. Therefore, a robust water quality assessment method (e.g., water quality index [WQI]) that considers various environmental features is essential for water resources management. This study developed a min/max autocorrelation factor analysis (MAFA) based WQI framework (MAFAWQI). The statistical procedure reduces the bias of expert opinions. The MAFAWQI characterizes impaired water quality variables as indicators and assesses appropriate weighting values of indicators at each sampling site to reflect site-specific environmental features. The MAFAWQI was successful for assessing water quality in the middle and down streams of Han River in central China with site-specific pollution features such as nitrogen and phosphorus pollution related to multiple-source in tributaries, impacts of tributaries on the main stream, and phosphorus pollution related to nonpoint-source in agricultural regions. The MAFAWQI exhibited a balanced rating of water quality compared to the strict assessment method using a single indicator and the lenient assessment method using stationary weighting values of indicators. The MAFAWQI scores indicated that the water quality in tributaries and during the spring were significantly worse than those in and during the other regions and seasons in the middle and down streams of Han River, respectively. The framework and application of the MAFAWQI may provide a new perspective for developing WQIs.

Human disturbance on phosphorus sources, processes and riverine export in a subtropical watershed.

Phosphorus (P) is a key nutrient in freshwater systems, often acting as the limiting nutrient. The dominant sources of P in the Jiulong River watershed (S.E. China) are anthropogenic. Dissolved and particulate P species were measured in the West (WJR) and North (NJR) rivers during the wet and dry seasons of 2018 and at their river outlets during a storm (June 2019). Sources of P pollution were characterized from mainly single source subcatchments (dry season). The Agriculture source (WJR) had a total P of 114.7 ± 13.1 µg P L-1, which was mainly dissolved inorganic P (DIP) from excess fertilizer washed from the fields. By contrast, the West Urban source (sewage effluent) was mainly particulate (POP) and dissolved organic P (DOP). The effect of reservoirs in the main NJR was to decrease total particulate P (TPP) and DIP and increase POP, due to increased sedimentation of particles and biological uptake. An increase in all P species was observed at the beginning of the storm, followed by a decrease on the rising hydrograph due to dilution. The final concentration of all P species was higher than baseflow, confirming that storms increase the P flux out of the watershed. P was initially washed off the fields during the storm, and during the falling hydrograph P increased due to interflow and other longer-term sources. The high DIN:DIP ratio confirmed the key importance of P inputs from human activities in substantially altering P sources and cycling, and hence the importance of science-based management to alleviate the eutrophication problem.

Measuring of time-series concentrations of nutrients in surface waters using osmotic sampler with air bubble segmentation and preservative addition.

The analysis of time-series concentrations (CTS) is of great importance when investigating the biogeochemical processes of nutrients in aquatic environments. However, obtaining CTS of nutrients remains a challenge using current sampling techniques. In this study, a novel in situ sampler was constructed using reverse osmosis membrane (ROM) osmotic pumps (OP) (ROM-OP sampler), and was used to obtain the CTS of nutrients in surface waters. The sampler consisted of a sampling OP, sample storing coil, filter, bubble injection module, and preservative adding module. When deployed, the sampling OP continuously draws ambient water through the filter into the sample storing coil, while simultaneously the preservative adding module continuously delivers preservative (H2SO4 solution) into the water flow. The bubble injection module periodically injects air bubbles into the sample storing coil, to segment the sample and create time stamp indicators that allow the sample age to be defined. Upon retrieval, the sample segments in the coil are sequentially pumped out of the sample storing coil and transferred into different vials for further analysis. The sampler was applied to measure the CTS of various nutrients, including dissolved total nitrogen, dissolved total phosphorus, dissolved reactive phosphorus, and nitrate in a river over a 20 day period and in municipal sewage treatment plant effluent for a 36 h period. Results showed that the ROM-OP sampler successfully obtained CTS of nutrients, capturing nutrient variations at a high temporal resolution. This sampler is relatively low-cost (~USD 300), small in size, lightweight, robust and does not require an external power source, showing high promise as an effective and efficient tool for monitoring nutrient CTS in aquatic environments.

Tidal driven nutrient exchange between mangroves and estuary reveals a dynamic source-sink pattern.

Nitrogen (N) and phosphorus (P) are vital nutrients regulating mangrove productivity and coastal ecosystems. Understanding of the nutrient cycling and interaction between mangroves and estuary is limited. Here we show tidal-driven nutrient exchange and a dynamic source-sink pattern across the mangrove-estuary interface. Lateral nutrient fluxes were quantified based on hourly concentrations observed at a tidal creek outlet during 2016-2018 and water mass estimated by a hydrodynamic model (FVCOM). The results of nutrient fluxes suggested that mangroves always serve as a source of ammonium (NH4-N) and dissolved reactive P (DRP) to estuary, but as a strong nitrate sink (NO3-N). Dissolved organic components (DON and DOP) shifted from net efflux (source) in spring to net influx (sink) in summer, likely due to the changing balance of P input and biological and physicochemical processes. Mangroves decreased the overall loading of dissolved inorganic N (DIN), dissolved total N (DTN) and total P (TP) to the estuary. Nevertheless, the effluents (aquaculture wastewater and domestic sewage) discharged from the upstream area during ebb tide increased the export of nutrients, especially NH4-N and DRP, offsetting the role of mangrove on mitigating coastal eutrophication.

Predicting Risks of Cadmium Toxicity in Salinity-Fluctuating Estuarine Waters Using the Toxicokinetic-Toxicodynamic Model.

In estuaries, salinity fluctuates rapidly and continuously, greatly affecting the bioavailability and thus toxicity of contaminants, especially metals, causing difficulties in deriving site-specific water quality criteria. We developed a method for predicting the toxicity of the metal cadmium (Cd) in estuarine waters of any salinity fluctuation scenario. Cd bioaccumulation and toxicity were measured in an estuarine clam Potamocorbula laevis under stable salinities (salinity = 5, 15, 25) and fluctuating salinities (5-25), using the toxicokinetic-toxicodynamic (TK-TD) framework. Cd bioaccumulation decreases with increasing salinity; whereas intrinsic Cd sensitivity of organisms reaches the minimum at an intermediate salinity around 20. At each specific Cd level, interpolating TK-TD parameters measured at the stable salinities well predicts the Cd bioaccumulation and toxicity under fluctuating salinities. To extend the model for various Cd levels, the biotic ligand model (BLM) was integrated into the TK-TD framework. The BLM-based TK-TD model was successfully applied to scenarios of simulated and monitored salinity fluctuations in estuarine waters, for which the median lethal concentrations and no-effect concentrations (2.0-3.1 µg L-1) of Cd were derived. Overall, we integrated the BLM and TK-TD models and provided a useful tool for predicting metal risks and deriving criteria values for salinity-fluctuating estuarine waters.