Deciphering and quantifying nitrate sources and processes in the central Yellow Sea using dual isotopes of nitrate.

Anthropogenic activities pose significant challenges to the accumulation of coastal nitrogen (N). Accurate identification of nitrate (NO3-) sources is thus essential for mitigating excessive N in many marginal seas. We investigated the dual isotopes of NO3- in the central Yellow Sea to elucidate the sources and cycling processes of NO3-. The results revealed significant spatial variability in NO3- concentrations among the Yellow Sea Surface Water (YSSW), Changjiang Diluted Water (CDW), Yellow Sea Cold Water Mass (YSCWM), and Taiwan Warm Current Water (TWCW). Stratification played a crucial role in restricting vertical nutrient transport, leading to distinct nutrient sources and concentrations in different water masses. The dual NO3- isotopic signature indicated that atmospheric deposition was the primary source of surface NO3-, contributing approximately 30 % to the NO3- in the YSSW. In the NO3--rich CDW, the heavier δ15N-NO3- and δ18O-NO3- suggested incomplete NO3- assimilation. Organic matter mineralization and water stratification played crucial roles in the accumulation of nutrients within the YSCWM and TWCW. Notably, regenerated NO3- accounted for approximately half of the NO3- stored in the YSCWM. A synthesis of NO3- dual isotope data across the coastal China seas revealed significant spatial and seasonal variations in the N source. The study emphasized the dynamics of coastal NO3- supply, which are shaped by the complex interconnections among marine, terrestrial, and atmospheric processes. Our approach is a feasible method for exploring the origins of N amidst the escalating pressures of anthropogenic nutrient pollution in coastal waters.

Changes in fronts regulate nitrate cycling in Zhanjiang Bay: A comparative study during the normal wet season, rainstorm, and typhoon periods.

Typhoons and rainstorms (>250 mm/day) are extreme weather events changing hydrological characteristics and thus nitrogen (N) cycle in coastal waters. However, responses of N cycle to rainstorms and typhoons and their underlying mechanisms need to be elucidated. In this study, we conducted an analysis of a comparative dataset encompassing concentrations of nitrate (NO3-), ammonium (NH4+), dissolved oxygen (DO), chlorophyll a (Chl a), hydrological parameters, dual isotopic composition of NO3- (δ15N-NO3- and δ18O-NO3-) in Zhanjiang Bay during three distinct periods: the normal wet season, rainstorm, and typhoon periods. After the rainstorm, the salinity front in Zhanjiang Bay was more weakened and steadier than that during the normal wet season, mainly because onshore wind and a large amount of freshwater was inputted into the ocean surface. This weakened and steady salinity front strengthened water stratification and provided a favorable condition for phytoplankton blooms. Correspondingly, evident NO3- deficits coincided with elevated δ15N-NO3- and δ18O-NO3- values indicated that sufficient NO3- sustained phytoplankton blooms, leading to NO3- assimilation during the rainstorm period. By contrast, due to the onshore wind induced by the typhoon, the salinity front in Zhanjiang Bay was more intensified and unsteady after the typhoon than the normal wet season. The salinity front after the typhoon was unsteady enough to enhance vertical mixing in the water column. Relatively high DO concentrations suggested that enhanced vertical mixing after the typhoon support freshly organic matter decomposition and nitrification via oxygen injection from the air into the water column. In addition, NO3- deficits coincided with elevated δ15N-NO3- values and δ18O-NO3- values demonstrated the coexistence of NO3- assimilation during the typhoon period. This study suggests that the changing processes involved in NO3- cycling after typhoons and rainstorms are associated with the stability and intensity of the salinity front altered by these weather events.

Seasonal variation of nitrogen biogeochemical processes constrained by nitrate dual isotopes in cascade reservoirs, Southwestern China.

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 (δ15N-NO3- and δ18O-NO3-) were conducted in a karst watershed (Wujiang River) in southwest China. The results showed that NO3--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 NO3--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 NO3--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.

Assessing Seasonal Nitrate Contamination by Nitrate Dual Isotopes in a Monsoon-Controlled Bay with Intensive Human Activities in South China.

Nitrate (NO3-) dual isotope analysis was performed in Zhanjiang Bay, which is a closed bay with intensive human activities in South China, to investigate seasonal changes in the main NO3- sources and their biogeochemical processes in the monsoon-controlled climate. The relatively low N/P ratios in Zhanjiang Bay suggests that nitrogen (N) is a limiting nutrient, which indicates that the increase of N is favorable for phytoplankton proliferation. However, a sufficient amount of ammonium was found in our study area owing to intensive human activities, which can support biological processes. Thus, less NO3- biological processes were found, indicating that NO3- isotopic characteristics may reveal details of the mixing from various sources. The Bayesian mixing model showed that NO3- in the upper bay originated from manure (43%), soil N (30%), N fertilizer (17%), and N precipitation (10%) during winter, which reflects the local human activities; while NO3- sources during summer were mainly N fertilizer (36%), soil N (32%), and manure (31%), indicating the source as the runoff from the upper river basin. Our results suggest that nitrate dual-isotope was very useful for tracing the main NO3- sources in the condition of the sufficient ammonium, and runoff exerted an important impact on the shift in NO3- sources between both the local source and the source from the upper river basin during the two seasons in this monsoon-controlled bay.

Anoxic nitrogen cycling in a hydrocarbon and ammonium contaminated aquifer.

Nitrogen fate and transport through contaminated groundwater systems, where N is both ubiquitous and commonly limits pollutant attenuation, must be re-evaluated given evidence for new potential microbial N pathways. We addressed this by measuring the isotopic composition of dissolved inorganic N (DIN = NH4+, NO2-, and NO3-) and N functional gene abundances (amoA, nirK, nirS, hszA) from 20 to 38 wells across an NH4+, hydrocarbon, and SO42- contaminated aquifer. In-situ N attenuation was confirmed on three sampling dates (0, +6, +12 months) by the decreased [DIN] (4300 - 40 µM) and increased δ15N-DIN (5‰-33‰) over the flow path. However, the assumption of negligible N attenuation within the plume was complicated by the presence of alternative electron acceptors (SO42-, Fe3+), both oxidizing and reducing functional genes, and N oxides within this anoxic zone. Active plume N cycling was corroborated using an NO2- dual isotope based model, which found the fastest (∼10 day) NO2- turnover within the N and electron donor rich central plume. Findings suggest that N cycling is not always O2 limited within chemically complex contaminated aquifers, though this cycling may recycle the N species rather than attenuate N.