Microbial nitrogen nutrition links to dissolved organic matter properties in East African lakes.

East African lakes, especially soda lakes, are home habitats for massive numbers of wildlife such as flamingos, mammals, and fishes. These lakes are known for their high primary production due to local high temperatures, light intensities, and alkalinity (inorganic carbon). However, these lakes, normally within remote areas, receive low nutrient inputs. Ammonium (NH4+) recycling and/or nitrogen fixation can become the major N supply mechanisms for phytoplankton. However, the driving forces on microbial N nutrition in lakes with minimal anthropogenic disturbance remain poorly understood. Using stable isotope tracer techniques, NH4+ recycling rates were measured in 18 lakes and reservoirs in East Africa (Tanzania and Kenya) during the dry season in early 2020. Three functional genes (nifH, gdh, and ureC) relating to microbial N nutrition were also measured. The regeneration of NH4+ supported up to 71 % of the NH4+ uptake. Positive community biological NH4+ demands (CBAD) for all lakes and reservoirs indicate an obvious N demand from microbial community. Our study provides clear evidence that microbial NH4+ uptake rates linked closely to the dissolved organic matter (DOM) properties (e.g., the absorption coefficient at 254 nm, percents of total fluorescence intensity contributed by microbial humic-like and protein-like components) and that water residence time drives microbial NH4+ recycling by regulating the duration of in-lake DOM processing and influencing algal growth. Phytoplankton, especially those of Cyanophyceae, showed maximum biomass and higher NH4+ recycling rates at a certain range of water residence time (e.g., 5-8 years). However, CBAD showed a decreasing trend with longer water residence time, which may be influenced by changes in the algal community composition (e.g., % Cyanophyceae vs. % Bacillariophyceae). These results indicate that DOM dynamics and the water residence time have the potential to facilitate the understanding of microbial nitrogen supply status in East African lakes.

Global distribution and drivers of relative contributions among soil nitrogen sources to terrestrial plants.

Soil extractable nitrate, ammonium, and organic nitrogen (N) are essential N sources supporting primary productivity and regulating species composition of terrestrial plants. However, it remains unclear how plants utilize these N sources and how surface-earth environments regulate plant N utilization. Here, we establish a framework to analyze observational data of natural N isotopes in plants and soils globally, we quantify fractional contributions of soil nitrate (fNO3-), ammonium (fNH4+), and organic N (fEON) to plant-used N in soils. We find that mean annual temperature (MAT), not mean annual precipitation or atmospheric N deposition, regulates global variations of fNO3-, fNH4+, and fEON. The fNO3- increases with MAT, reaching 46% at 28.5 °C. The fNH4+ also increases with MAT, achieving a maximum of 46% at 14.4 °C, showing a decline as temperatures further increase. Meanwhile, the fEON gradually decreases with MAT, stabilizing at about 20% when the MAT exceeds 15 °C. These results clarify global plant N-use patterns and reveal temperature rather than human N loading as a key regulator, which should be considered in evaluating influences of global changes on terrestrial ecosystems.

The underestimated role of manganese in modulating the nutrient structure in a eutrophic seasonally-stratified reservoir.

Accumulation and subsequent release of nutrients have great potential to trigger algal blooms in lakes and reservoirs. We conducted high vertical resolution (2 m interval) monitoring at ∼monthly intervals over a year for hydrological parameters, Chl-a, ammonium (NH4+), nitrate (NO3-) and different species of phosphorus (P) and manganese (Mn) in a 40-meter-deep subtropical reservoir (Shanmei Reservoir) in Fujian, southern China. In this seasonally stratified reservoir featured with high nutrient loading, the consistent trend in the ratio of dissolved inorganic nitrogen (DIN) to dissolved inorganic phosphorus (DIP) between the euphotic zone and the hypolimnion, coupled with its mirrored correlation with Chl-a concentration indicates that upward flux from the hypolimnion affects phytoplankton growth in the euphotic zone. The monthly variation of the depth-integrated multiple species of N and P indicates that during the stratification period in the hypoxic hypolimnion, approximately 80% of the DIP is removed, leading to a remarkable decoupling phenomenon between NH4+ and DIP. This process effectively increases the ratio of DIN to DIP in the hypolimnion, thereby significantly reducing the potential of algal blooms caused by the upward flux. A robust positive linear correlation between iron-manganese bound phosphorus (CBD-P) and particulate Mn was observed during stratification period implying that DIP was scavenged by sediment-released Mn throughout the water column. Vertical profiles during stratification showed that upward diffusion of Mn2+ facilitated the formation of Mn oxide zones near the oxycline. The most significant decrease in DIP inventory occurs when Mn oxide zones migrate either upwards from the bottom or downwards from the oxycline, indicating that the migration of Mn oxides on the vertical profile is a key factor in the decoupling of NH4+and DIP. Our findings underscore the importance of Mn cycling as an underappreciated DIP self-immobilization process in the water column of reservoirs characterized by high nutrient loading. Furthermore, we propose that denitrification and Mn cycling establish a consecutive feedback mechanism, preventing excessive nutrient accumulation in low oxygen bottom water. In the context of global changes, we anticipate a heightened prominence of this feedback mechanism.

Vertical Distribution and Seasonal Patterns of Candidatus Nitrotoga in a Sub-Alpine Lake.

The nitrite oxidizing bacterial genus Ca. Nitrotoga was only recently discovered to be widespread in freshwater systems; however, limited information is currently available on the environmental factors and seasonal effects that influence its distribution in lakes. In a one-year study in a dimictic lake, based on monthly sampling along a vertical profile, the droplet digital PCR quantification of Ca. Nitrotoga showed a strong spatio-temporal patchiness. A correlation ana-lysis with environmental parameters revealed that the abundance of Ca. Nitrotoga correlated with dissolved oxygen and ammonium, suggesting that the upper hypolimnion of the lake is the preferred habitat.

Different modeling approaches for inline biochemical monitoring over the VLP-making upstream stages using Raman spectroscopy.

This work aimed to set inline Raman spectroscopy models to monitor biochemically (viable cell density, cell viability, glucose, lactate, glutamine, glutamate, and ammonium) all upstream stages of a virus-like particle-making process. Linear (Partial least squares, PLS; Principal components regression, PCR) and nonlinear (Artificial neural networks, ANN; supported vector machine, SVM) modeling approaches were assessed. The nonlinear models, ANN and SVM, were the more suitable models with the lowest absolute errors. The mean absolute error of the best models within the assessed parameter ranges for viable cell density (0.01-8.83 × 106 cells/mL), cell viability (1.3-100.0 %), glucose (5.22-10.93 g/L), lactate (18.6-152.7 mg/L), glutamine (158-1761 mg/L), glutamate (807.6-2159.7 mg/L), and ammonium (62.8-117.8 mg/L) were 1.55 ± 1.37 × 106 cells/mL (ANN), 5.01 ± 4.93 % (ANN), 0.27 ± 0.22 g/L (SVM), 4.7 ± 2.6 mg/L (SVM), 51 ± 49 mg/L (ANN), 57 ± 39 mg/L (SVM) and 2.0 ± 1.8 mg/L (ANN), respectively. The errors achieved, and best-fitted models were like those for the same bioprocess using offline data and others, which utilized inline spectra for mammalian cell lines as a host.

Detecting Bound Ions in Ion Channels by Solid-State NMR Experiments on 15N-Labelled Ammonium Ions.

Solid-state NMR allows for the study of membrane proteins under physiological conditions. Here we describe a method for detection of bound ions in the selectivity filter of ion channels using solid-state NMR. This method employs standard 1H-detected solid-state NMR setup and experiment types, which is enabled by using 15N-labelled ammonium ions to mimic potassium ions.

Sources and processes affecting the abundances of atmospheric NHx using δ15N over northwestern Indo-Gangetic plain.

Ammonia (NH3) is the major constituent among all the reactive nitrogen species present in the atmosphere, and the most essential species for secondary inorganic aerosol formation. Recent satellite-based observations have identified the Indo-Gangetic Plain (IGP) as a major hotspot of global NH3 emission; however, the major sources and atmospheric processes affecting its abundance are poorly understood. The present study aims to understand the wintertime sources of NH3 over a semi-urban site (Patiala, 30.3°N, 76.4°E, 249 m amsl) located in the IGP using species specific δ15N in PM2.5. A distinct diurnal variation in the stable isotopic signature of total nitrogen (δ15N-TN) and ammonium (δ15N-NH4+) were observed; although, average day and night time concentrations of TN and NH4+ were similar. Mixing model results using δ15N-NH3 reveal the dominance of non-agricultural emissions (NH3 slip: 47 ± 24%) over agricultural emissions (24 ± 11%), combustion sources (19 ± 14 %), and biomass burning (10 ± 8%) for atmospheric NH3. Diurnal variability in source contributions to NH3 was insignificant. Further, significantly negative correlations of δ15N-NH4+ with ambient relative humidity (RH) and daytime NO3--N concentration were observed, and attributed to the possibility of NH4NO3 volatilization during day-time owing to lower RH and higher temperature, resulting in isotopic enrichment of the remaining NH4+ in aerosol phase. This study, a first of its type from India, highlights the importance of non-agricultural NH3 emissions over the agriculture dominated IGP region, and the role of local meteorology on the isotopic fractionation of δ15N in aerosol NH4+.

Enhancing selective ammonium transport in membrane electrochemical systems.

Recovering ammonia nitrogen from wastewater is a sustainable strategy that simultaneously addresses both nitrogen removal and fertilizer production. Membrane electrochemical system (MES), which utilizes electrochemical redox reactions to transport ammonium ions through cation exchange membranes, has been considered as an effective technology for ammonia recovery from wastewater. In this study, we develop a mathematical model to systematically investigate the impact of co-existing ions on the transport of ammonium (NH4+) ions in MES. Our analysis elucidates the importance of pH values on both the NH4+ transport and inert ion (Na+) transport. We further comprehensively assess the system performance by varying the concentration of Na+ in the system. We find that while the inert cation in the initial anode compartment competes with NH4+ transport, NH4+ dominates the cation transport in most cases. The transport number of Na+ surpasses NH4+ only if the fraction of Na+ to total cation is extremely high (>88.5%). Importantly, introducing Na+ ions into the cathode compartment significantly enhances the ammonia transport due to the Donnan dialysis. The analysis of selective ion transport provides valuable insights into optimizing both selectivity and efficiency in ammonia recovery from wastewater.

Assessment of two non-invasive techniques for measuring turbulent benthic fluxes in a shallow lake.

Benthic fluxes refer to the exchange rates of nutrients and other compounds between the water column and the sediment bed in aquatic ecosystems. Their quantification contributes to our understanding of aquatic ecosystem functioning. Near-bed hydrodynamics plays an important role at the sediment-water interface, especially in shallow lakes, but it is poorly considered by traditional measuring techniques of flux quantification, such as sediment incubations. Thus, alternative sampling techniques are needed to characterize key benthic fluxes under in-situ hydrodynamic conditions. This study aimed to evaluate the performance of two promising methods: relaxed eddy accumulation (REA) and mass transfer coefficient (MTC). We applied them in a hyper-eutrophic shallow lake to measure the fluxes of ammonium, phosphate, iron, and manganese ions. For the first time, REA revealed hourly nutrient flux variations, indicating a strong lake biogeochemical dynamics at short time-scales. Daily average fluxes are of similar orders of magnitude for REA and MTC for ammonium (24 and 42 mmol m2 d-1), manganese (1.0 and 0.8), and iron (0.8 and 0.7) ions. They are one order of magnitude higher than fluxes estimated from sediment incubations, due to the difficulty in reproducing in-situ oxygen and hydrodynamic conditions in the laboratory. Although the accuracy of both techniques needs to be improved, the results revealed their potential: REA follows the short-term biogeochemical dynamics of sediments, while MTC could be widely used for lake monitoring because of its simpler implementation.

Asynchronous characteristics of Feammox and iron reduction from paddy soils in Southern China.

Recently, the newly discovered anaerobic ammonium oxidation coupled with iron reduction (i.e., Feammox) has been proven to be a widespread nitrogen (N) loss pathway in ecosystems and has an essential contribution to gaseous N loss in paddy soil. However, the mechanism of iron-nitrogen coupling transformation and the role of iron-reducing bacteria (IRB) in Feammox were poorly understood. This study investigated the Feammox and iron reduction changes and microbial community evolution in a long-term anaerobic incubation by 15N isotope labeling combined with molecular biological techniques. The average rates of Feammox and iron reduction during the whole incubation were 0.25 ± 0.04 µg N g-1 d-1 and 40.58 ± 3.28 µg Fe g-1 d-1, respectively. High iron oxide content increased the Feammox rate, but decreased the proportion of Feammox-N2 in three Feammox pathways. RBG-13-54-9, Brevundimonas, and Pelomonas played a vital role in the evolution of microbial communities. The characteristics of asynchronous changes between Feammox and iron reduction were found through long-term incubation. IRB might not be the key species directly driving Feammox, and it is necessary to reevaluate the role of IRB in Feammox process.

Ammonium depletion associated with the COVID-19 pandemic in the Mexican Caribbean.

The Mexican Caribbean contributes significantly to Mexico's gross national product. The number of tourists declined from 16.7 million in 2019 to 8.8 million in 2020 due to the COVID-19 pandemic, with a rapid recovery of 13.5 million in 2021. Wastewater discharge is the primary contamination source associated with the tourism sector's demand for goods and services. Water quality could improve due to fewer tourists arriving during the COVID-19 sanitary emergency. This study aimed to quantify ammonium concentrations at eleven locations to evaluate water quality during the sanitary restriction due to the pandemic in the Mexican Caribbean. The ammonium concentrations were 85 % (Nov-2019), 89 % (Feb-2020), and 86 % (Feb-2021) higher than in Nov-2020, where six of the eleven sampled stations were below the detection limit (0.15 µM). Lower ammonium concentrations coincide with the sanitary restriction period and a decrease in affluent tourists.

Removal of PAHs, TSS, oils and fats from ammonium-rich coke wastewater by granular filtration.

Coke wastewater is a complex industrial wastewater due to its high content of toxic compounds such as cyanides, thiocyanates, phenols, tar, oils, and fats. After a series of treatments, wastewater with a high ammonium content is obtained (around 4,150 mg·L-1). A stripping process is used to reduce it. Certain pollutants in the influent, such as tar, polycyclic aromatic hydrocarbons (PAHs), oils, fats and total suspended solids (TSS), interfere with stripping and therefore must be previously removed. In this study, the performance of a pilot-scale airlift sand filter was evaluated under real conditions for the reduction of the concentration of tar, PAHs, oils, fats and TSS, before stripping. Prior to the sand filter, a cationic flocculant was added to the influent (2 ppm). High (10 mm.min-1), medium (7.5 mm.min-1) and low sand speeds (1.9-2.6 mm.min-1) were assessed. The latter conditions gave the best results: a decrease of 98.2% in TSS, 99.7% in oils, fats and grease and 97.6% in PAHs. The final effluent (≤ 1.6 mg PAHs·L-1, ≤ 5 mg TSS·L-1 and ≤ 0.05 mg·L-1 of fats, oils and grease) was suitable for the stripping process.

Nitrogen isotopic characteristics of aerosol ammonium in a Chinese megacity indicate the reduction from vehicle emissions during the lockdown period.

The role of agricultural versus vehicle emissions in urban atmospheric ammonia (NH3) remains unclear. The lockdown due to the outbreak of COVID-19 provided an opportunity to assess the role of source emissions on urban NH3. Concentrations and δ15N of aerosol ammonium (NH4+) were measured before (autumn in 2017) and during the lockdown (summer, autumn, and winter in 2020), and source contributions were quantified using SIAR. Despite the insignificant decrease in NH4+ concentrations, significantly lower δ15N-NH4+ was found in 2020 (0.6 ± 1.0‰ in PM2.5 and 1.4 ± 2.1‰ in PM10) than in 2017 (15.2 ± 6.7‰ in PM2.5), which indicates the NH3 from vehicle emissions has decreased by∼50% during the lockdown while other source emissions are less affected. Moreover, a reversed seasonal pattern of δ15N-NH4+ during the lockdown in Changsha has been revealed compared to previous urban studies, which can be explained by the dominant effect of non-fossil fuel emissions due to the reductions of vehicle emissions during the lockdown period. Our results highlight the effects of lockdown on aerosol δ15N-NH4+ and the importance of vehicle emissions to urban atmospheric NH3, providing conclusive evidence that reducing vehicle NH3 emissions could be an effective strategy to reduce PM2.5 in Chinese megacities.

Large Seasonal Variation in Nitrogen Isotopic Abundances of Ammonia Volatilized from a Cropland Ecosystem and Implications for Regional NH3 Source Partitioning.

Ammonia (NH3) volatilization from agricultural lands is a main source of atmospheric reduced nitrogen species (NHx). Accurately quantifying its contribution to regional atmospheric NHx deposition is critical for controlling regional air nitrogen pollution. The stable nitrogen isotope composition (expressed by δ15N) is a promising indicator to trace atmospheric NHx sources, presupposing a reliable nitrogen isotopic signature of NH3 emission sources. To obtain more specific seasonal δ15N values of soil NH3 volatilization for reliable regional seasonal NH3 source partitioning, we utilized an active dynamic sampling technique to measure the δ15N-NH3 values volatilized from maize cropping land in northeast China. These values varied from -38.0 to -0.2‰, with a significantly lower rate-weighted value observed in the early period (May-June, -30.5 ± 6.7‰) as compared with the late period (July-October, -8.5 ± 4.3‰). Seasonal δ15N-NH3 variations were related to the main NH3 production pathway, degree of soil ammonium consumption, and soil environment. Bayesian isotope mixing model analysis revealed that without considering the seasonal δ15N variation in soil-volatilized NH3 could result in an overestimate by up to absolute 38% for agricultural volatile NH3 to regional atmospheric bulk ammonium deposition during July-October, further demonstrating that it is essential to distinguish seasonal δ15N profile of agricultural volatile NH3 in regional source apportionment.

Atmospheric organic nitrogen deposition around the Danjiangkou Reservoir: Fluxes, characteristics and evidence of agricultural source.

Dissolved organic nitrogen (DON) deposition was the substantial component of dissolved total nitrogen (DTN) deposition in the world's nitrogen deposition hot spots areas. However, the information on the importance for DON deposition and its sources was still scarce, which limited the comprehensive assessment of the ecological threat from nitrogen deposition. Six sampling sites around the Danjiangkou Reservoir were set up to collect the dry and wet deposition samples from October 2017 to September 2021. The results showed that dry and wet DTN deposition averaged 34.72 kg ha-1 yr-1 and 22.27 kg ha-1 yr-1, respectively. Dry NH4+-N, NO3--N and DON deposition averaged 14.28 kg ha-1 yr-1, 5.91 kg ha-1 yr-1 and 14.53 kg ha-1 yr-1, respectively. Wet NH4+-N, NO3--N and DON deposition averaged 11.14 kg ha-1 yr-1, 3.89 kg ha-1 yr-1and 7.24 kg ha-1 yr-1, respectively. The contributions of DON to DTN were 41.85% (in dry deposition) and 32.50% (in wet deposition), respectively. Dry DON deposition varied between 26.44 kg ha-1 yr-1 and 9.11 kg ha-1 yr-1, and significantly differed among six sampling sites (P < 0.05). The different intensity of agricultural activities disturbance at the sampling sites was the important reason for the spatial variations of DON deposition. DON deposition was significantly correlated with ammonium nitrogen (NH4+-N) deposition (P < 0.05). According to the results of positive matrix factorization (PMF) model, agriculture source contributed significantly to the DON deposition, the contributions at six sampling sites ranged from 45.8% to 73.7% in dry deposition, and from 56.8% to 81.6% in wet deposition. In summary, our findings found that agricultural activities were the important factors influencing the spatial patterns of DON deposition around Danjiangkou Reservoir and provided new evidence for the anthropogenic source of DON deposition in China.

Manganese oxide-loaded activated carbon for ammonium removal from wastewater: the roles of adsorption and oxidation.

The urgent need to address the severe issue of nitrogen pollution has prompted the search for a functional and easy recycling material. In this study, manganese oxides (MnOx) were loaded on activated carbon (AC), resulting in a composite known as AC-MnOx, for efficient ammonium removal from aqueous solutions. The results indicated a remarkable 15.6-fold increase in ammonium removal efficiency and a fivefold enhancement in removal capacity for AC-MnOx (3.20 mg/g) compared to AC. Under specific conditions (initial NH4+-N concentration of 15 mg/L, adsorbent dose of 2.5 g, pH of 6.5, and temperature of 35 ℃), the highest achieved ammonium removal efficiency reached 94.6%. Furthermore, the study distinguishes the contributions of catalytic oxidation and adsorption in the removal process. The adsorption process was effectively modeled using pseudo-second-order kinetics and Langmuir isotherm models. Interestingly, the amount of oxidation conversion (Ntur) exhibited a linear relationship with the dosage when the initial ammonium concentration was sufficiently high, while the relationship between initial ammonium concentration and the ratio of Ntur to adsorption capacity (Nsur) followed a negative exponential trend. The removal mechanisms involved electrostatic interaction between ammonium and the negatively charged dehydrogenated hydroxyl groups (- OHsur) or cation tunnel in crystal structures of MnOx, ion exchange adsorption, and the oxidation impact of MnOx. This research provides valuable insights into the application of immobilized MnOx media for ammonium removal. Moreover, filling AC-MnOx into constructed wetlands (CW) proved to be an effective method for reducing ammonium pollution, demonstrating its potential in the field of engineering wastewater treatment.

Revisiting the dynamics of gaseous ammonia and ammonium aerosols during the COVID-19 lockdown in urban Beijing using machine learning models.

The concentration of atmospheric ammonia (NH3) in urban Beijing substantially decreased during the COVID-19 lockdown (24 January to 3 March 2020), likely due to the reduced human activities. However, quantifying the impact of anthropogenic interventions on NH3 dynamics is challenging, as both meteorology and chemistry mask the real changes in observed NH3 concentrations. Here, we applied machine learning techniques based on random forest models to decouple the impacts of meteorology and emission changes on the gaseous NH3 and ammonium aerosol (NH4+) concentrations in Beijing during the lockdown. Our results showed that the meteorological conditions were unfavorable during the lockdown and tended to cause an increase of 8.4 % in the NH3 concentration. In addition, significant reductions in NOx and SO2 emissions could also elevate NH3 concentrations by favoring NH3 gas-phase partitioning. However, the observed NH3 concentration significantly decreased by 35.9 % during the lockdown, indicating a significant reduction in emissions or enhanced chemical sinks. Rapid gas-to-particle conversion was indeed found during the lockdown. Thus, the observed reduced NH3 concentrations could be partially explained by the enhanced transformation into NH4+. Therefore, the sum of NH3 and NH4+ (collectively, NHx) is a more reliable tracer than NH3 or NH4+ alone to estimate the changes in NH3 emissions. Compared to that under the scenario without lockdowns, the NHx concentration decreased by 26.4 %. We considered that this decrease represents the real decrease in NH3 emissions in Beijing due to the lockdown measures, which was less of a decrease than that based on NH3 only (35.9 %). This study highlights the importance of considering chemical sinks in the atmosphere when applying machine learning techniques to link the concentrations of reactive species with their emissions.

The performance and mechanism of tetracycline and ammonium removal by Pseudomonas sp. DX-21.

To remove ammonium and tetracycline (TC) from wastewater, a new strain, DX-21, was isolated and exhibited simultaneous removal ability. The performance of DX-21 in TC removal, its removal mechanism, and the potential toxicities of the degradation products were investigated with genomics, mass spectrometry, density functional theory calculations, quantitative structure-activity relationship analyses, and Escherichia coli exposure experiments. DX-21 exhibited removal of ammonium (9.64 mg·L-1·h-1) via assimilation, and TC removal (0.85 mg·L-1·h-1) primarily occurred through cell surface bio-adsorption and biodegradation. Among the 12 identified degradation products, the majority exhibited lower toxicities than TC. Moreover, potential degradation pathways were proposed, including hydroxylation and deamination. Furthermore, DX-21 possessed TC resistance genes, various oxygenases and peroxidases that could potentially contribute to TC degradation. DX-21 colonized activated sludge and significantly enhanced the biodegradation of TC. Therefore, DX-21 showed potential for treating wastewater containing both ammonium and TC.

Effective abatement of ammonium and nitrate release from sediments by biochar coverage.

Inorganic forms of N from sediments and runoff water, among others, remain some of the key sources of pollution of water bodies. However, the release of NH4+-N from sediment to water can be effectively reduced by biochar coverage due to high adsorption capacity, unlike NO3-N, where biochar has a low affinity. The feasibility of biochar coverage to abate NO3--N release needs to be evaluated. This study collected four sediments from Lake Taihu (China). Three types of biochar pyrolyzed from ordinary wastes, coconut shell (coBC), algal and excess sludge, were prepared to cover them and were incubated for 90 days. Results showed that the terminal total nitrogen (TN) and NO3--N concentrations decreased from 5.35 to 2.31-3.04 mg/L, 3.05 to 0.34-1.11 mg/L, respectively. CoBC coverage showed the best performance for reducing NO3--N release flux from 26.99 ± 0.19 to 9.30 ± 0.02 mg/m2·d (63.6 %). Potential denitrifiers, such as Flavobacterium and Exiguobacterium, were enriched in the biochar-coverage layer, and the absolute abundance of N-related functional genes (narG, nirS, nosZ and anammox) was increased by 1.76-4.21 times (p < 0.05). Jar tests by 15N isotope labeling further indicated that biochar addition increased the denitrification and anammox rates by 53.5-83.4 %. Experiments combining exogenous organic­carbon addition and 15N labeling demonstrated that biochar's key role was regulating organic matter's bioavailability. Analysis with partial least square path modeling (PLS-PM) implied biochar with higher adsorption enhanced the denitrification and anammox processes in sediments via modifying the niche with suitable DOC, TN, and pH. This study suggested that biochar coverage could effectively abate NO3--N release from sediments by affecting the denitrification and anammox processes.

From Soil to River: Revealing the Mechanisms Underlying the High Riverine Nitrate Levels in a Forest Dominated Catchment.

Elevated riverine nitrate (NO3-) levels have led to increased eutrophication and other ecological implications. While high riverine NO3- levels were generally ascribed to anthropogenic activities, high NO3- levels in some pristine or minimally disturbed rivers were reported. The drivers of these unexpectedly high NO3- levels remain unclear. This study combined natural abundance isotopes, 15N-labeling techniques, and molecular techniques to reveal the processes driving the high NO3- levels in a sparsely populated forest river. The natural abundance isotopes revealed that the NO3- was mainly from soil sources and that NO3- removal processes were insignificant. The 15N-labeling experiments also quantitatively showed that the biological NO3- removal processes, i.e., denitrification, dissimilatory NO3- reduction to ammonium (DNRA), and anaerobic ammonia oxidation (anammox), in the soils and sediments were weak relative to nitrification in summer. While nitrification was minor in winter, the NO3- removal was insignificant relative to the large NO3- stock in the catchment. Stepwise multiple regression analyses and structural equation models revealed that in summer, nitrification in the soils was regulated by the amoA-AOB gene abundances and NH4+-N contents. Low temperature constrained nitrification in winter. Denitrification was largely controlled by moisture content in both seasons, and anammox and DNRA could be explained by the competition with nitrification and denitrification on their substrate (nitrite-NO2-). We also revealed the strong hydrological control on the transport of soil NO3- to the river. This study effectively revealed the mechanisms underlying the high NO3- levels in a nearly pristine river, which has implications for the understanding of riverine NO3- levels worldwide.