Nitrate Flux Research Articles

A risk-based groundwater modeling framework in coastal aquifers: a case study on Long Island, New York, USA

A methodology is proposed to define indices for quantifying risks under the threat of reducing in groundwater levels, the existence of saltwater intrusion (SWI), and an increasing nitrate contamination load in submarine groundwater discharge (SGD). The proposed methodology considers coastal regions under geological heterogeneity and it is tested on a groundwater system in Nassau County of Long Island, New York (USA). The numerical model is constructed with the SEAWAT code. The parameter uncertainty of this model is evaluated by coupling the Latin hypercube sampling method (as a sampling algorithm) and Monte Carlo simulation to consider the uncertainty in both hydraulic conductivity and recharge rate. The indices are presented in spatial maps that classify areas of risk to potential threats. The results show that two of the water districts have a high risk under conditions of decreasing groundwater level. Salinity occurs in the southern and southwestern parts of the Nassau County aquifer and a considerable area of high risk of SWI is identified. Furthermore, the average SGD rate with the associated fluxes of nitrate is estimated as 81.4 million m3/year (average 0.8 tons of nitrate through SGD per year), which can adversely affect the quality of life in the local coastal ecosystems. The framework developed in this study could help the water district managers to identify high-risk areas for short-term and long-term planning and is applicable to other coastal settings.

New production across the shelf-edge in the northeastern North Sea during the stratified summer period

Abstract New production of organic matter from photosynthesis based on “new” nitrate transported into the illuminated surface layer fuels temperate ecosystems during periods of stratification when surface waters are nutrient limited. Published observations from the northeastern North Sea show a large spatial heterogeneity in vertical nitrate fluxes and suggest shelf edge mixing may be the major source for new production here during the stratified summer season. In the current study, we further investigate these empirical findings with a numerical model, where physical transports and mixing are evaluated against observations of temperature, salinity, nutrients and dissipation of turbulent kinetic energy. The relatively shallow central North Sea is separated from the deep Norwegian trench by a strong shelf edge current. This shelf edge frontal zone is characterized by a vertical separation of the surface and benthic boundary layers by an intermediate layer exhibiting low turbulence. A new nitrate assimilation model, driven by light and nitrate availability, is developed and applied for quantifying the potential for, and distribution of, new production in the area. New production in the frontal zone above the shelf edge is located in a narrow high productive (~100 mg C m−2 day−1) band. This is in qualitative accordance with observations. The model results also suggest, however, that new production of similar magnitude occurs above the deep Norwegian trench, where a shallow nutricline in combination with mesoscale eddy activity leads to increased transport of nitrate to the surface layer. Increased new production along the shelf edge could potentially impact ecosystem structure and may explain the relatively high species richness and fishing activity recorded in this part of the North Sea.

Short-Term Variability of Biological Production and CO2 System Around Dongsha Atoll of the Northern South China Sea: Impact of Topography-Flow Interaction

The short-term variabilities in temperature, salinity, nitrate, chlorophyll a (Chl a), and carbonate chemistry data (i.e., pH, partial pressure of CO2 (pCO2), total alkalinity, and dissolved inorganic carbon) were concurrently investigated in the shallow (~50 m) and deep (~300 m) water areas around Dongsha Atoll of the northern South China Sea (NSCS). The results show that surface temperature and pCO2 were lower but that upward nitrate flux and Chl a were higher in the upper euphotic zone at the shallow-water area than those at the deep-water area. We suggest that the observed contrasting biogeochemical properties between the two areas could be attributed to the impact of topography-flow interaction. As tidal currents (or any other horizontal currents) interacted with the shallow topography, they may induce vertical isotherm displacements (e.g., internal tides/internal waves) that may enhance turbulent mixing, and thus can transport more nutrient-replete subsurface water into the euphotic zone and stimulate phytoplankton production. The stimulated biological production and the cooling effect induced by topography-flow interaction may collectively drive surface pCO2 down in the shallow water area. Though the present short-term hydrological and CO2 data, which to our knowledge were concurrently investigated for the first time in the NSCS, reveal that the topography-flow interaction could be a favorable mechanism for atmospheric CO2 uptake around Dongsha Atoll, more long-term observations are still needed to confirm that the similar processes can repetitively take place in topography-flow interaction prevalent areas.

Daily denitrification rates in floodplains under contrasting pedo-climatic and anthropogenic contexts: modelling at the watershed scale

Floodplains play a crucial role in water quality regulation via denitrification. This biogeochemical process reduces nitrate (NO3−), with aquifer saturation, organic carbon (OC) and N availability as the main drivers. To accurately describe the denitrification in the floodplain, it is necessary to better understand nitrate fluxes that reach these natural bioreactors and the transformation that occurs in these surface areas at the watershed scale. At this scale, several approaches tried to simulate denitrification contribution to nitrogen dynamics in study sites. However, these studies did not consider OC fluxes influences, hydrological dynamics and temperature variations at a daily time step. This paper focuses on a new model that allows insights on nitrate, OC, discharge and temperature influences on daily denitrification for each water body. We used a process-based deterministic model to estimate daily alluvial denitrification in different watersheds showing various pedo-climatic conditions. To better understand global alluvial denitrification variability, we applied the method to three contrasting catchments: The Amazon for tropical zones, the Garonne as representative of the temperate climate and the Yenisei for cold rivers. The Amazon with a high discharge, frequent flooding and warm temperature, leads to aquifers saturation, and stable OC concentrations. Those conditions favour a significant loss of N by denitrification. In the Garonne River, the low OC delivery limits the denitrification process. While Arctic rivers have high OC exports, the low nitrate concentrations and cold temperature in the Yenisei River hinder denitrification. We found daily alluvial denitrification rates of 73.0 ± 6.2, 4.5 ± 1.4 and 0.7 ± 0.2 kgN ha−1 y−1 during the 2000–2010 period for the Amazon, the Garonne and the Yenisei respectively. This study quantifies the floodplains influence in the water quality regulation service, their contribution to rivers geochemical processes facing global changes and their role on nitrate and OC fluxes to the oceans.

Phytoplankton growth and consumption by microzooplankton stimulated by turbulent nitrate flux suggest rapid trophic transfer in the oligotrophic Kuroshio

Abstract. The Kuroshio Current has been thought to be biologically unproductive because of its oligotrophic conditions and low plankton standing stocks. Even though vulnerable life stages of major foraging fishes risk being entrapped by frontal eddies and meanders and encountering low food availability, they have life cycle strategies that include growing and recruiting around the Kuroshio Current. Here we report that phytoplankton growth and consumption by microzooplankton are stimulated by turbulent nitrate flux amplified by the Kuroshio Current. Oceanographic observations demonstrate that the Kuroshio Current topographically enhances significant turbulent mixing and nitrate influx to the euphotic zone. Graduated nutrient enrichment experiments show that growth rates of phytoplankton and microheterotroph communities were stimulated within the range of the turbulent nitrate flux. Results of dilution experiments imply significant microzooplankton grazing on phytoplankton. We propose that these rapid and systematic trophodynamics enhance biological productivity in the Kuroshio.

Modeled Dynamics of Physical and Biological Processes in the Central California Current System From 1993 to 2016

AbstractA three‐dimensional physical‐biological model was used to study the dynamics of physical and biological processes in the central California Current System (CCS) from 1993 to 2016 and investigate its response to different climate modes. The variations of new production (NP) and nitrate fluxes in the central CCS showed robust seasonal and interannual variability. In the coastal upwelling region (0–150 km offshore), the variability of NP was associated with both coastal upwelling and alongshore nitrate advection. In the coastal transition zone (150–300 km offshore), it was related to nitrate fluxes that were determined primarily by the physics rather than nitrate concentration, with vertical mixing and offshore transport being dominant factors. In the offshore oceanic region (California Current; 300–1,000 km offshore), nitrate concentrations played a more important role in the variations of nitrate fluxes, and the NP variability was dominated by the nutrient supplies of vertical mixing and lateral transports. Although El Niño–Southern Oscillation can affect coastal upwelling, alongshore currents, and nitrate fluxes, the coastal NP responded to El Niño–Southern Oscillation mostly in the frequencies of <1 and >6 years. Pacific Decadal Oscillation and North Pacific Gyre Oscillation may affect the CCS ecosystem through large‐scale winds and stratification, modifying the circulation in the upper layer and leading to changes in nitrate concentration and NP.

The Influence of Diapycnal Nutrient Fluxes on Phytoplankton Size Distribution in an Area of Intense Mesoscale and Submesoscale Activity off Concepción, Chile

AbstractMesoscale and submesoscale processes that contribute to localized increases in nutrients in the sunlit layer can stimulate phytoplankton growth and community changes, but the mechanisms involved remain sparsely documented with in situ data in the case of Eastern Boundary Upwelling Systems (EBUSs) and of most ocean regions. The role of diapycnal mixing in providing nutrients to the upper layer and in influencing phytoplankton size structure was analyzed in an area of intense mesoscale and submesoscale activity during the coastal upwelling season off Concepción (~36–37°S), the Humboldt Current EBUS. Diapycnal nutrient fluxes based on conductivity, temperature, and depth vertical eddy diffusivity (Kz) values (the Thorpe scale method) and on nutrient gradients were assessed in association with size‐fractionated chlorophyll‐a and microdiatom abundance derived from in situ sampling in an area including a mesoscale intrathermocline eddy (ITE) adjacent to a coastal upwelling front (CUF). The indirect estimates of Kz values spanned between 0.01 and 4 × 10−4 m2 s−1, and maxima in diapycnal nitrate flux per station ranged between 0.08 and 19.1 mmol m−2 day−1. Maxima in the upward fluxes were detected at the subsurface (15–40 m depth) in the CUF and ITE areas, coinciding with maxima in the micro‐ and nano‐chlorophyll‐a fractions and in microdiatom abundance. These results suggest that ITE and CUF features, as well as their interaction, can generate intense diapycnal mixing and, thereby, contribute to increasing nutrient availability below the mixed layer. In turn, these processes enhance the contribution of larger phytoplankton cells in the coastal transition zone of EBUSs.

Characterizing the impacts of land use on nitrate load and water yield in an agricultural watershed in Atlantic Canada

Excessive nitrate loading from agricultural non-point source is threatening the health of receiving water bodies at the global scale. Quantifying the drivers/sources of water and nitrate flux in watersheds and relating them to spatial and temporal land uses is essential for developing effective mitigation strategies. This study investigated the impact of land use on water yield and nitrate loading to surface water in a typical agricultural watershed in Prince Edward Island (PEI), Canada. We used historical streamflow and water quality records to calibrate the comprehensive hydrological model Soil and Water Assessment Tool (SWAT), which was setup with detailed annual land use records. The SWAT model performed well in predicting both daily streamflow and nitrate load. Land use demonstrated little impact on water yield but affected nitrate load significantly. Annual nitrate load ranged from 5.6 to 44.4 kg N ha−1 yr−1 for forest and soybean, respectively. Potato rotated land contributed 84.5% of annual nitrate load to the watershed. Source of water yield demonstrated high variability between the growing season and non-growing season. About 90% of water yield was contributed by groundwater during growing season, while runoff contributed over 60% of water yield during the non-growing season. Groundwater was the dominant source of nitrate loading for both seasons. The watershed estuary faced the highest threats from subbasins in the south western area due to the high nitrate load and proximity to the watershed outlet. Results by the machine learning algorithm random Forest analysis indicated that the climatic variables of temperature and precipitation were the top two factors affecting water yield, with a combined relative importance of 61%. Land use was the dominant factor affecting nitrate load, the relative importance of land use alone was ~50%. The results of this study provided critical insights for watershed management in Atlantic Canada.

Kinetic affinity index informs the divisions of nitrate flux in aerobic denitrification

Aerobic denitrification is attracting increasing attention since its advantage of complete nitrogen removal in a single aerobic reactor with simplified configurations. This study investigated the nitrate kinetic affinity (half-saturation index, Km) by an isolated aerobic denitrifier named P. balearica strain RAD-17. It turned out that strain RAD-17 had a high Km of 162.5 mg-N/L and maximum nitrate reduction rate of 21.7 mg-N/(L•h), enabling it to treat high-strength nitrogen wastewater with high efficiency. Further analysis illustrated that Km was the critical value for the change of growth yield rate along initial nitrate concentrations. Nitrogen balance results elucidated an opposite nitrogen flux to cell synthesis and nitrogen loss during aerobic denitrification. Moreover, the expression of functional genes provided proofs for these phenotypic results at transcriptional level. Consequently, Km could be an indicator for nitrate flux division directing to respiration and assimilation in aerobic denitrifiers, shedding light on its regulation for wastewater treatment.

Response of Nitrogen Loss Flux in Purple Soil Sloping Field to Reduced Fertilizer and Combining Straw

The purple soil sloping field is considered as the main source of sediment and non-point source pollution in the Three Gorges Reservoir area. To prevent and control the non-point source pollution, it is indispensable to explore the characteristics of nitrogen loss in the overland flow and interflow of purple soil sloping field in Three Gorges Reservoir area. The purple soil sloping runoff plots, located in the Shibaozhai Experimental Station of Chengdu Institute of Chinese Academy of Sciences in Zhongxian County, Chongqing, were studied. The experiment included no fertilization treatment (CK), traditional fertilization treatment (T1), amended fertilization treatment (T2), and reduced fertilizer with straw treatment (T3). According to the data of volume of the interflow and runoff and the leach concentration and flux of nitrogen forms under rapeseed-maize rotation system, the response of nitrogen leaching flux to reduce fertilizer with straw application can be definite in purple soil sloping plots. The results show that the ratio of interflow to total runoff is 60.14%-88.56%, and the flux of nitrogen leaching in the interflow accounts for 72.88%-92.35% of total nitrogen loss flux. Ammonium was mainly leached by the overland flow. In addition, nitrate was mainly leached by the interflow and was the main form of nitrogen leaching. The fluxes of ammonium and nitrate under different treatments followed the order T1 > T2 > T3 > CK. The total nitrogen flux of T3 was 20.07 kg·(hm2·a)-1, which was 43.59% and 39.55% lower than that of T1 and T2, respectively. The reduced fertilizer with straw application significantly decreased the leaching flux of ammonium, nitrate, and total nitrogen, and weakened the effect on runoff nitrogen leaching in the purple soil sloping plots.

Dependence of Wet Depositions of Sulfates and Nitrates in Primorskii Krai on Cyclone Trajectories

An analysis is made of the cyclone trajectories for 2003–2013 in order to gain insight into the influence of their genesis on the generation of the flow of wet depositions of acid-forming substances over the territory of Primorsky krai and a part of the water area of the Sea of Japan. All the cyclones crossing the region of interest during the period under investigation have been considered. Seven types of cyclones have been identified according to the location of their genesis and trajectories. Annual and seasonal variability of their number of occurrence as well as variability in pressure at the cyclone center has been shown for each of them. Using precipitation data from EANET monitoring station Primorskaya, concentrations and deposition fluxes of sulfates and nitrates have been calculated for each cyclone type. It is shown that more than half of all sulfates and nitrates deposited at the stations with precipitation caused by the cyclones originating outside the territory of the Russian Federation. A significant correlation of variability in mean annual deposition fluxes of sulfates and nitrates in precipitation of these cyclones is indicative of the common sources of input of acid-forming substances into precipitation of the five cyclone types.

Pan-Arctic Ocean Primary Production Constrained by Turbulent Nitrate Fluxes

Arctic Ocean primary productivity is limited by light and inorganic nutrients. With sea ice cover declining in recent decades, nitrate limitation has been speculated to become more prominent. Although much has been learned about nitrate supply from general patterns of ocean circulation and water column stability, a quantitative analysis requires dedicated turbulence measurements that have only started to accumulate in the last dozen years. Here we present new observations of the turbulent vertical nitrate flux in the Laptev Sea, Baffin Bay, and Young Sound (North-East Greenland), supplementing a compilation of 13 published estimates throughout the Arctic Ocean. Combining all flux estimates with a Pan-Arctic database of in situ measurements of nitrate concentration and density, we found the annual nitrate inventory to be largely determined by the strength of stratification and by bathymetry. Nitrate fluxes explained the observed regional patterns and magnitudes of both new primary production and particle export on annual scales. We argue that with few regional exceptions, vertical turbulent nitrate fluxes can be a reliable proxy of Arctic primary production accessible through autonomous and large-scale measurements. They may also provide a framework to assess nutrient limitation scenarios based on clear energetic and mass budget constraints resulting from turbulent mixing and freshwater flows.

Beyond the trends: The need to understand multiannual dynamics in aquatic ecosystems

Beyond the trends: The need to understand multiannual dynamics in aquatic ecosystems

Efficacy of in situ well-based denitrification bio-barrier (WDB) remediating high nitrate flux in groundwater near a stock-raising complex

This study assessed the feasibility of an in situ well-based denitrification bio-barrier (WDB) for managing groundwater contaminated with high-strength nitrate. To evaluate the efficacy of WDB using fumarate as a carbon source and/or electron donor, three sequential single-well push-pull tests (SWPPTs) were conducted at six test sites. The values of the isotope enrichment factor (ɛ) ranging from −6.5‰ to −22.6‰ and the detection and degradation of nitrite and nitrous oxide confirmed complete in situ denitrification of nitrate to nitrogen gas. The ratio of the first-order rate coefficient of fumarate to nitrate (k1,fum/k1,NO3) was obtained to estimate the amount and frequency of fumarate injection for the effective design of WDB. At three sites, the ratios ranged from 0.67 to 0.80, while the other two sites showed higher ratios of 2.97 and 2.20 than the theoretical values and significant amounts of sulfate reduction, theoretically equivalent to 6.5% of total fumarate consumption. Considering the theoretical mole ratio of fumarate to nitrate of 0.98, the amount and frequency of fumarate injection is site specific. During the operating WDB, the average annual nitrate mass degraded (95% CI) was 2.2 ± 1.0 kg N/yr/well. The amount of N reduced by one well of WDB is equivalent to treating 110 m3 of groundwater at 30 mg N/L to the level of 10 mg N/L for one year. WDB would be an effective remediation option for managing high nitrate flux in groundwater.

Seasonal variability of nitrate flux in the Northern part of Karangbolong Karst Aquifer, Central Java

Kalisirah Springs and Jumbleng Spring are located in the northern part of Karangbolong Karst Area, Kebumen Regency. Tracer tests for underground rivers and field surveys indicate that the catchment areas of these two karst springs have the dominant land use of dry land farm and plantation. The condition of the catchment area will affect the chemical content of water resources in karst aquifers. Dry land farm and plantation use fertilizer in the process of planting, but in practice, there is nitrogen lost due to the washing process by rainwater. Karst landforms also have cavities and fissures that allow applied fertilizer to enter the karstic aquifer directly. This study aims to determine the nitrogen flux fluctuations in the form of nitrate (N) in Kalisirah Springs and Jumbleng Springs along with their relationship with discharge and rainfall. The data used in this study were primary data, which included data of the water level, rainfall, water chemistry samples, and the agricultural planting calendar. The N content was analyzed using hydrograph to determine the response of N flux to the discharge. Recording the amount of N used in agricultural activities in the catchment area was conducted by calculating the area of agricultural land use using Topographic Map of Indonesia, and the triangulation method was used to determine fertilizer characteristics in the catchment area. Kalisirah catchment area lost 56.09 % N, while the Jumbleng catchment area lost 57.53 % N. The extent of this loss is influenced by land use conditions which will have implications for the number and frequency of fertilization.

Variability of internal tide energy, mixing and nitrate fluxes in response to changes in stratification on the northeast New Zealand continental shelf

ABSTRACT A 4-month time series of water column temperature structure on the shelf of North Island New Zealand is used to calculate the energy in the internal tide as stratification evolved between spring and summer. Average total energy in the internal tidal wave was 200 J m−2, with peaks reaching 600 J m−2. Wave energy was weakly correlated with stratification (r = 0.2) and with the spring-neap cycle of tidal currents (r = 0.17). Overall there was little predictability in internal tide behaviour in response to the physical environment. Reduction in wave energy was associated with a downwelling-favourable wind event which reduced stratification by mixing and by removing deeper water off the shelf. Vertical eddy diffusivity driven by internal wave dissipation ranged between 5.6 × 10−5 and 3.2 × 10−4 m2 s−1. Combined with nitrate data this diffusivity resulted in diapycnal nitrate fluxes towards the sea surface of 1.6–2.2 mmol m−2 day−1. Strong stratification in summer reduced the eddy diffusivity but had little effect on nitrate flux as a strengthened vertical nitrate gradient compensated for the reduced diffusivity. This compensation will be important when predicting how stronger stratification in a warmer climate might alter diapycnal nutrient supplies to the upper ocean.

A ten year record of nitrate retention and solute trends in a Wisconsin sand plains stream: temporal variation at multiple scales

Nitrate retention is an important ecosystem service provided by streams which reduces nitrogen loads to downstream ecosystems. However, most inferences about nitrate retention and uptake in streams are based on measurements at sub-annual scales. Our objective was to evaluate variation in nitration retention and solute concentrations at weekly to decadal time scales. We measured nitrate and chloride concentration, nitrate flux and nitrate retention in Emmons Creek, a groundwater-dominated, nitrate-rich stream in central Wisconsin during a 10-year period. We used a two-station mass balance approach to measure nitrate retention while accounting for groundwater inputs. Surface water nitrate concentration, nitrate yield and nitrate retention exhibited strong seasonal variation. Seasonal Kendall tests revealed positive trends for surface water discharge, nitrate and chloride concentrations and groundwater chloride concentration, but not nitrate retention. Generalized additive mixed models (GAMM), accounting for serial autocorrelations, also indicated positive trends in surface water nitrate and chloride concentrations but no trend for nitrate retention. Nitrate retention averaged 370 mg NO3-N m−2 d−1 (± 316 SD) and was highest during the spring (512 mg NO3-N m−2 d−1 ± 319), followed by summer (460 ± 322), fall (340 ± 281) and winter (165 ± 212). Nitrate retention rates in Emmons Creek were relatively high compared to most published estimates. However, our results suggest that Emmons Cr. may have saturated its capacity to retain nitrate during a period when nitrate yield from its watershed increased, which is an important finding given the increases in N availability in many regions of earth.

Partitioning between atmospheric deposition and canopy microbial nitrification into throughfall nitrate fluxes in a Mediterranean forest

Abstract Microbial activity plays a central role in nitrogen (N) cycling, with effects on forest productivity. Although N biotransformations, such as nitrification, are known to occur in the soil, here we investigate whether nitrifiers are present in tree canopies and actively process atmospheric N. This study was conducted in a Mediterranean holm oak (Quercus ilex L.) forest in Spain during the transition from hot dry summer to cool wet winter. We quantified —N and —N fluxes for rainfall (RF) and throughfall (TF) and used δ15N, δ18O and Δ17O to elucidate sources of . Finally, we characterized microbial communities and abundance of nitrifiers on foliage, RF and TF water through metabarcoding and quantitative polymerase chain reaction respectively. NO3—N fluxes at the site were larger in TF than RF, suggesting a contribution from dry deposition, as also supported by δ15N and δ18O. However, Δ17O indicated that about 20% of in TF derived from canopies nitrification in August, after a severe drought, with a lower proportion in September (≈8%). This seasonal partitioning between biologically and atmospherically derived coincided with a decreasing trend of the abundance of archaeal nitrifiers. Tree canopies and TF had more diverse microbial communities than RF. Yet, RF showed higher variability in microbial composition, likely associated with the origin of air masses. Synthesis. Atmospheric N deposition is significantly altered after passing through tree canopies. While nitrification has been proposed as one of the mechanisms responsible for these changes, very few studies directly investigate its occurrence. Here, we showed that nitrification by epiphytic leaf microbes contributed to increasing NO3 in TF and that nitrifiers' activity was reduced going from the dry and hot summer to the cool winter. Overall, these results highlight the power of coupling microbial community analysis, functional gene amplification and stable isotope approaches to examine ecosystem‐scale processes.

Contrasting behavior of nitrate and phosphate flux from high flow events on small agricultural and urban watersheds

Soluble nutrient flux is increasingly implicated in the degradation of receiving water quality. With high-frequency sensors, river discharge along with nitrate and orthophosphate concentrations were collected over 2 years. We examined how storms (16 events) affected the dissolved nutrient flux in two watersheds with contrasting landcover—urban and agricultural. The adjacent watersheds, both < 7 km2, had very similar soil, slope, relief, and physiography. Wastewater is conveyed outside of the watersheds minimizing this nutrient source. Cumulative nitrate and orthophosphate fluxes in the agricultural watershed were substantially higher than the urban watershed. In both watersheds, a disproportionate amount of discharge, higher orthophosphate concentrations and flux occurred during the highest flow events—approximately 50–70% of flux occurring in the highest 5% of daily discharge. The nitrate flux was dampened compared to discharge during storm events. Baseflow accounted for 66% of the nitrate flux and had higher or comparable concentrations than storm events. The pattern of flux and concentration within storm events also differed for the two solutes. Nitrate exhibited positive hysteresis (higher concentrations on the rising limb of the hydrograph) and magnification of flux during the first flush of storm runoff. In contrast, orthophosphate concentrations were lower on the rising limb and flux during the first flush of storm runoff was dampened. In addition to targeting source reductions, orthophosphate flux may require runoff reducing strategies (i.e., enhanced infiltration) from large runoff events. First flush stormwater management practices combined with enhancement/protection of groundwater nitrate sinks (e.g., riparian wetlands) may help reduce nitrate fluxes.

Microbial metabolite fluxes in a model marine anoxic ecosystem.

Permanently anoxic regions in the ocean are widespread and exhibit unique microbial metabolic activity exerting substantial influence on global elemental cycles and climate. Reconstructing microbial metabolic activity rates in these regions has been challenging, due to the technical difficulty of direct rate measurements. In Cariaco Basin, which is the largest permanently anoxic marine basin and an important model system for geobiology, long-term monitoring has yielded time series for the concentrations of biologically important compounds; however, the underlying metabolite fluxes remain poorly quantified. Here, we present a computational approach for reconstructing vertical fluxes and in situ net production/consumption rates from chemical concentration data, based on a 1-dimensional time-dependent diffusive transport model that includes adaptive penalization of overfitting. We use this approach to estimate spatiotemporally resolved fluxes of oxygen, nitrate, hydrogen sulfide, ammonium, methane, and phosphate within the sub-euphotic Cariaco Basin water column (depths 150-900m, years 2001-2014) and to identify hotspots of microbial chemolithotrophic activity. Predictions of the fitted models are in excellent agreement with the data and substantially expand our knowledge of the geobiology in Cariaco Basin. In particular, we find that the diffusivity, and consequently fluxes of major reductants such as hydrogen sulfide, and methane, is about two orders of magnitude greater than previously estimated, thus resolving a long-standing apparent conundrum between electron donor fluxes and measured dark carbon assimilation rates.