Evaluation of the origin and fate of nitrate in the Abbotsford Aquifer using the isotopes of15N and18O in NO3−

Extensive NO₃⁻ contamination of groundwater in the Abbotsford aquifer to levels above drinking water limits is a major problem in the Fraser Lowlands of southwestern British Columbia, Canada. Nitrate concentrations in the aquifer ranged from 0 to 151 mg/l NO₃⁻, with a median concentration of 46 mg/l NO₃⁻. Of 117 wells sampled, 54% had NO₃⁻ concentrations exceeding the drinking water limit of 45 mg/1. Approximately 80% of the study area had groundwater NO₃⁻ concentrations exceeding 40 mg/1 NO₃⁻. Potential NO₃⁻ source materials were poultry manure N and synthetic NH₄ based fertilizers. Theδ¹⁵N of solid poultry manure samples ranged between + 7.9 and + 8.6‰ (AIR). Four brands of synthetic fertilizers commonly used hadδ¹⁵N values between −1.5 and −0.6‰. Ammonia volatilization caused theδ¹⁵N of groundwater NO₃⁻ produced from poultry manure N to range between +8 and +16‰. Theδ¹⁸O values of groundwater NO₃⁻, by contrast, mostly ranged between +2 and +5‰ (SMOW). This narrow range ofδ¹⁸O values fell within the expected range of NO₃⁻ produced by nitrification of reduced N forms such as poultry manure N and NH₄ fertilizers, and had a similar range ofδ¹⁸O values as NO₃⁻ in the upper part of the unsaturated zone below raspberry fields and beneath former manure piles. Theδ¹⁵N-NO₃⁻ andδ¹⁸O-NO₃⁻ data confirmed that NO₃⁻ in the aquifer was predominantly derived from poultry manure and to a lesser extent from synthetic fertilizers. Theδ¹⁸O-NO₃⁻ data further suggested the nitrification process occurred mainly in the summer months, with the soil NO₃⁻ produced subsequently flushed into the aquifer during fall recharge. Theδ¹⁵N-NO₃⁻andδ¹⁸O-NO₃⁻ data conclusively indicated that no significant bacterial denitrification is taking place in the Abbotsford aquifer.     

Evaluation of nitrate source in surface water of southwestern China based on stable isotopes

Stable isotope tracing and analysis play an important role in interpretation of hydrological and ecological processes at the watershed scale and can provide information regarding the flow path, water source, nutrient loss and biogeochemical cycles of a system. In this study, environmental isotopes (δ¹⁸O-H₂O, δD, δ¹⁵N-NO₃ ^?, δ¹⁸O-NO₃ ^?) and chemical compositions of surface water in Guizhou Province, China, were measured to evaluate the primary sources of nitrate and characterize the processes affecting nitrate as well as its correlation with vegetation cover in karstic areas. The δ¹⁵N and δ¹⁸O-NO₃ ^? levels ranged from +1.3 to +9.8 ‰ and +4.7 to +16.9 ‰, respectively, which indicated that nitrate in water from the investigated area primarily originated from nitrification of soil organic matter during the sampling period. There was also a wide range of isotopes in the water and high contents of nitrate in karstic areas with poor vegetation cover, indicating that water and nutrient loss were serious problems hindering plant growth in the study areas. For example, there was a positive relationship between isotopic composition and nitrate content in the natural forest and negative relationship in Libo County nearby, which suggested that the nitrate fate was affected by land use and human disturbance.     

Sediment-water oxygen and nutrient exchanges along the longitudinal axis of Chesapeake Bay: Seasonal patterns,controlling factors and ecological significance

Sediment-water oxygen and nutrient (NH₄ ⁺, NO₃ ^?+NO₂ ^?, DON, PO₄ ^3?, and DSi) fluxes were measured in three distinct regions of Chesapeake Bay at monthly intervals during 1 yr and for portions of several additional years. Examination of these data revealed strong spatial and temporal patterns. Most fluxes were greatest in the central bay (station MB), moderate in the high salinity lower bay (station SB) and reduced in the oligohaline upper bay (station NB). Sediment oxygen consumption (SOC) rates generally increased with increasing temperature until bottom water concentrations of dissolved oxygen (DO) fell below 2.5 mg l^?1, apparently limiting SOC rates. Fluxes of NH₄ ⁺ were elevated at temperatures >15°C and, when coupled with low bottom water DO concentrations (<5 mg l^?1), very large releases (>500 μmol N m^?2 h^?1) were observed. Nitrate + nitrite (NO₃ ^?+NO₂ ^?) exchanges were directed into sediments in areas where bottom water NO₃ ^?+NO₂ ^? concentrations were high (>18 μM N); sediment efflux of NO₃ ^?+NO₂ ^? occurred only in areas where bottom water NO₃ ^?+NO₂ ^? concentrations were relatively low (<11 μM N) and bottom waters well oxygenated. Phosphate fluxes were small except in areas of hypoxic and anoxic bottom waters; in those cases releases were high (50–150 μmol P m^?2 h^?1) but of short duration (2 mo). Dissolved silicate (DSi) fluxes were directed out of the sediments at all stations and appeared to be proportional to primary production in overlying waters. Dissolved organic nitrogen (DON) was released from the sediments at stations NB and SB and taken up by the sediments at station MB in summer months; DON fluxes were either small or noninterpretable during cooler months of the year. It appears that the amount and quality of organic matter reaching the sediments is of primary importance in determining the spatial variability and interannual differences in sediment nutrient fluxes along the axis of the bay. Surficial sediment chlorophyll-a, used as an indicator of labile sediment organic matter, was highly correlated with NH₄ ^?, PO₄ ^3?, and DSi fluxes but only after a temporal lag of about 1 mo was added between deposition events and sediment nutrient releases. Sediment O:N flux ratios indicated that substantial sediment nitrification-denitrification probably occurred at all sites during winter-spring but not summer-fall; N:P flux ratios were high in spring but much less than expected during summer, particularly at hypoxic and anoxic sites. Finally, a comparison of seasonal N and P demand by phytoplankton with sediment nutrient releases indicated that the sediments provide a substantial fraction of nutrients required by phytoplankton in summer, but not winter, especially in the mid bay region.     

Application of multiple-isotope and groundwater-age data to identify factors affecting the extent of denitrification in a shallow aquifer near a river in South Korea

The extent of denitrification in a small agricultural area near a river in Yangpyeong, South Korea, was determined using multiple isotopes, groundwater age, and physicochemical data for groundwater. The shallow groundwater at one monitoring site had high concentrations of NO₃-N (74–83 mg L^?1). The δ¹⁵N-NO₃ values for groundwater in the study area ranged between +9.1 and +24.6‰ in June 2014 and +12.2 to +21.6‰ in October 2014. High δ¹⁵N-NO₃ values (+10.7 to +12.5‰) in both sampling periods indicated that the high concentrations of nitrate in the groundwater originated from application of organic fertilizers and manure. In the northern part of the study area, some groundwater samples showed elevated δ¹⁵N-NO₃ and δ¹⁸O-NO₃ values, which suggest that nitrate was removed from the groundwater via denitrification, with N isotope enrichment factors ranging between ?4.8 and ?7.9‰ and O isotope enrichment factors varying between ?3.8 and ?4.9‰. Similar δD and δ¹⁸O values of the surface water and groundwater in the south appear to indicate that groundwater in that area was affected by surface-water infiltration. The mean residence times (MRTs) of groundwater showed younger ages in the south (10–20 years) than in the north (20–30 years). Hence, it was concluded that denitrification processes under anaerobic conditions with longer groundwater MRT in the northern part of the study area removed considerable amounts of nitrate. This study demonstrates that multi-isotope data combined with physicochemical data and age-dating information can be effectively applied to characterize nitrate contaminant sources and attenuation processes.     

Microbial nitrogen removal in a developing suburban estuary along the South Carolina coast

The conversion of undisturbed coastal regions to commercial and suburban developments may pose a threat to surface and groundwater quality by introducing nitrate-nitrogen (NO₃ ^?-N) from runoff of land-applied wastewater and fertilizers. Microbial denitrification is an important NO₃ ^?-N removal mechanism in coastal sediments. The objective of this study was to compare denitrification and nitrate conversion rates in coastal sediments from a golf course, suburban site, undeveloped marsh, and nonmarsh area near rapidly developing Hilton Head Island, South Carolina. Nitrous oxide was measured using gas chromatography and nitrate and ammonium concentrations were measured using a flow injection autoanalyzer in microcosms spiked, with 50 μg NO₃ ^?-N gdw^?1. The two marsh sites had the greatest ammonium production, which was correlated with fine sediment particle size and higher background sediment nitrate and surface water sulfate concentrations. The golf course swale had greatest denitrification rates, which were correlated with higher total carbon and organic nitrogen in sediments. Nitrate was consumed in golf course sediments to a greater extent than in the undeveloped marsh and upland freshwater sites, suggesting that the undeveloped sites and receiving estuaries may be more susceptible to nitrate contamination than the golf course swale and marsh under nonstorm conditions. Construction of swales and vegetated buffers using sediments with high organic carbon content as best management practices may aid in removing nitrate and other contaminants from runoff prior to its transport to the receiving marsh and estuary.     

The Importance of Microbial Iron Sulfide Oxidation for Nitrate Depletion in Anoxic Danish Sediments

Nitrate (NO₃ ^?) reduction processes are important for depleting the NO₃ ^? load from agricultural source areas before the discharge water reaches surface waters or groundwater aquifers. In this study, we experimentally demonstrate the co-occurrence of microbial iron sulfide oxidation by NO₃ ^? (MISON) and other NO₃ ^?-depleting processes in a range of contrasting sediment types: sandy groundwater aquifer, non-managed minerotrophic freshwater peat and two brackish muddy sediments. Approximately 1/3 of the net NO₃ ^? reduction was caused by MISON in three of the four environments despite the presence of organic carbon in the sediment. An apparent salinity limitation to MISON was observed in the most brackish environment. Addition of high surface area synthetically precipitated iron sulfide (FeS _x ) to the aquifer sediment with the lowest natural FeS _x reactivity increased both the relative fraction of NO₃ ^? reduction linked to MISON from approximately 30–100 % and the absolute rates by a factor of 17, showing that the potential for MISON-related NO₃ ^? reduction is environmentally significant and rate limited by the availability of reactive FeS _x .     

Sources of groundwater nitrate revealed using residence time and isotope methods

Nitrate concentrations approaching and greater than the maximum contaminant level are impairing the viability of many groundwater basins as drinking water sources. Nitrate isotope data are effective in determining contaminant sources, especially when combined with other isotopic tracers such as stable isotopes of water and ³H–He ages to give insight into the routes and timing of NO₃ inputs to the flow system. This combination of techniques is demonstrated in Livermore, CA, where it is determined that low NO₃ reclaimed wastewater predominates in the NW, while two flowpaths with distinct NO₃ sources originate in the SE. Along the eastern flowpath, δ¹⁵N values greater than 10‰ indicate that animal waste is the primary source. Diminishing concentrations over time suggest that contamination results from historical land use practices. The other flowpath begins in an area where rapid recharge, primarily of low-NO₃ imported water (identified by stable isotopes of water and a ³H–He residence time of <1 year), mobilizes a significant local NO₃ source, bringing groundwater concentrations up to 53 mg NO₃ L⁻¹. In this area, artificial recharge of imported water via local arroyos increases the flux of NO₃ to the regional aquifer. The low δ¹⁵N value (3.1‰) in this location implicates synthetic fertilizer. In addition to these anthropogenic sources, natural NO₃ background levels between 15 and 20 mg NO₃ L⁻¹ are found in deep wells with residence times greater than 50 a.     

Effect of rising atmospheric CO2 on sediment and water 15N interactions in experimental riparian wetland

The experiment was conducted to ascertain net production and consumption rates of ¹⁵NH₄ ⁺ and ¹⁵NO₃ ^? for water and sediment in a wetland. This was done using ¹⁵N isotope pool dilution methodology under ambient and elevated atmospheric CO₂ concentrations in experimental riparian wetlands to obtain the gross N transformation rates. The ¹⁵N budget for sediment was also estimated. The results suggested that the differences in high proportion of ¹⁵N concentration in the overlying water body under elevated CO₂ could be attributed to the low production and high consumption rates of ¹⁵NH₄ ⁺ in sediment. The elevated CO₂ effect on production and consumption of NH₄ ⁺ decreased by 144 % (P = 0.014) and increased by 153 % (P = 0.009), respectively. Thereby, ¹⁵NH₄ ⁺ production rates are negatively related with ¹⁵NO₃ ^? consumption rates and this accounted for the decreases in net ¹⁵NO₃ ^? consumption under CO₂ enrichment in the wetland sediment by 11 % (P = 0.528). Therefore, ¹⁵NO₃ ^? production and consumption rates may strongly depend on NH₄ ⁺ production. Inorganic ¹⁵N and total ¹⁵N exported from sediment to overlying water body by the effect of CO₂ were 41 % (P = 0.071) and 18 % (P = 0.000), respectively. Therefore, low net ¹⁵NH₄ ⁺ production and high ¹⁵NH₄ ⁺ consumption rates under elevated CO₂ may partly explain the significant reduction of N from the sediment.     

Spatial and Temporal Variability of Sediment Organic Matter Recycling in Two Temperate Eutrophicated Estuaries

This paper deals with the spatial and seasonal recycling of organic matter in sediments of two temperate small estuaries (Elorn and Aulne, France). The spatio-temporal distribution of oxygen, nutrient and metal concentrations as well as the organic carbon and nitrogen contents in surficial sediments were determined and diffusive oxygen fluxes were calculated. In order to assess the source of organic carbon (OC) in the two estuaries, the isotopic composition of carbon (δ ¹³C) was also measured. The temporal variation of organic matter recycling was studied during four seasons in order to understand the driving forces of sediment mineralization and storage in these temperate estuaries. Low spatial variability of vertical profiles of oxygen, nutrient, and metal concentrations and diffusive oxygen fluxes were monitored at the station scale (within meters of the exact location) and cross-section scale. We observed diffusive oxygen fluxes around 15 mmol m^?2 day^?1 in the Elorn estuary and 10 mmol m^?2 day^?1 in the Aulne estuary. The outer (marine) stations of the two estuaries displayed similar diffusive O₂ fluxes. Suboxic and anoxic mineralization was large in the sediments from the two estuaries as shown by the rapid removal of very high bottom water concentrations of NO _x ^? (>200 μM) and the large NH₄ ⁺ increase at depth at all stations. OC contents and C/N ratios were high in upstream sediments (11–15 % d.w. and 4–6, respectively) and decreased downstream to values around 2 % d.w. and C/N ≤ 10. δ ¹³C values show that the organic matter has different origins in the two watersheds as exemplified by lower δ ¹³C values in the Aulne watershed. A high increase of δ ¹³C and C/N values was visible in the two estuaries from upstream to downstream indicating a progressive mixing of terrestrial with marine organic matter. The Elorn estuary is influenced by human activities in its watershed (urban area, animal farming) which suggest the input of labile organic matter, whereas the Aulne estuary displays larger river primary production which can be either mineralized in the water column or transferred to the lower estuary, thus leaving a lower mineralization in Aulne than Elorn estuary. This study highlights that (1) meter scale heterogeneity of benthic biogeochemical properties can be low in small and linear macrotidal estuaries, (2) two estuaries that are geographically close can show different pattern of organic matter origin and recycling related to human activities on watersheds, (3) small estuaries can have an important role in recycling and retention of organic matter.     

Combined use of 15N and 18O of nitrate and 11B to evaluate nitrate contamination in groundwater

Isotopic composition of NO₃ (δ¹⁵N_NO3 and δ¹⁸O_NO3) and B (δ¹¹B) were used to evaluate NO₃ contamination and identify geochemical processes occurring in a hydrologically complex Basin and Range valley in northern Nevada with multiple potential sources of NO₃. Combined use of these isotopes may be a useful tool in identifying NO₃ sources because NO₃ and B co-migrate in many environmental settings, their isotopes are fractionated by different environmental processes, and because wastewater and fertilizers may have distinct isotopic signatures for N and B. The principal cause of elevated NO₃ concentrations in residential parts of the study area is wastewater and not natural NO₃ or fertilizers. This is indicated by some samples with elevated NO₃ concentrations plotting along δ¹⁵N_NO3 and NO₃ mixing lines between natural NO₃ from the study area and theoretical septic-system effluent. This conclusion is supported by the presence of caffeine in one sample and the absence of samples with elevated NO₃ concentrations that fall along mixing lines between natural NO₃ and theoretical percolate below fertilized lawns. Nitrogen isotopes alone could not be used to determine NO₃ sources in several wells because denitrification blurred the original isotopic signatures. The range of δ¹¹B values in native ground water in the study area (−8.2‰ to +21.2‰) is large. The samples with the low δ¹¹B values have a geochemical signature characteristic of hydrothermal systems. Physical and chemical data suggest B is not being strongly fractionated by adsorption onto clays. δ¹¹B values from local STP effluent (−2.7‰) and wash water from a domestic washing machine (−5.7‰) were used to plot mixing lines between wastewater and native ground water. In general, wells with elevated NO₃ concentrations fell along mixing lines between wastewater and background water on plots of δ¹¹B against 1/B and Cl/B. Combined use of δ¹⁵N and δ¹¹B in the study area was generally successful in identifying contaminant sources and processes that are occurring, however, it is likely to be more successful in simpler settings with a well-characterized δ¹¹B value for background wells.     

Oyster (<Emphasis Type="Italic">Crassostrea virginica</Emphasis>) Aquaculture Shifts Sediment Nitrogen Processes toward Mineralization over Denitrification

Filter-feeding bivalves, like oysters, couple pelagic primary production with benthic microbial processes by consuming plankton from the water column and depositing unassimilated material on sediment. Conceptual models suggest that at low to moderate oyster densities, this deposition can stimulate benthic denitrification by providing denitrifying bacteria with organic carbon and nitrogen (N). While enhanced denitrification has been found at oyster reefs, data from oyster aquaculture are limited and equivocal. This study measured seasonal rates of denitrification, as well as dissimilatory nitrate reduction to ammonium (DNRA), and dissolved inorganic N fluxes at a rack and bag eastern oyster (Crassostrea virginica) aquaculture farm. Consistent with models, denitrification was enhanced within the farm, with an average annual increase of 350% compared to a reference site. However, absolute denitrification rates were low relative to other coastal systems, reaching a maximum of 19.2 μmol m^?2 h^?1. Denitrification appeared to be nitrate (NO₃ ^?) limited, likely due to inhibited nitrification caused by sediment anoxia. Denitrification may also have been limited by competition for NO₃ ^? with DNRA, which accounted for an average of 76% of NO₃ ^? reduction. Consequently, direct release of ammonium (NH₄ ⁺) from mineralization to the water column was the most significant benthic N pathway, with seasonal rates exceeding 900 μmol m^?2 h^?1 within the farm. The enhanced N processes were spatially limited however, with significantly higher rates directly under oysters, compared to in between oyster racks. For commercial aquaculture farms like this, with moderate oyster densities (100–200 oysters m^?2), denitrification may be enhanced, but nonetheless limited by biodeposition-induced sediment anoxia. The resulting shift in the sediment N balance toward processes that regenerate reactive N to the water column rather than remove N is an important consideration for water quality.     

Anaerobic ammonium oxidation by nitrite (anammox): Implications for N2 production in coastal marine sediments

The respiratory reduction of nitrate (denitrification) is acknowledged as the most important process that converts biologically available nitrogen to gaseous dinitrogen (N₂) in marine ecosystems. Recent findings, however, indicate that anaerobic ammonium oxidation by nitrite (anammox) may be an important pathway for N₂ formation and N removal in coastal marine sediments and in anoxic water columns of the oceans. In the present study, we explored this novel mechanism during N mineralization by ¹⁵N amendments (single and coupled additions of ¹⁵NH₄⁺, ¹⁴NO₃⁻ and ¹⁵NO₃⁻) to surface sediments with a wide range of characteristics and overall reactivity. Patterns of ^29/30N₂ production in the pore water during closed sediment incubations demonstrated anammox at all 7 of the investigated sites. Stoichiometric calculations revealed that 4% to 79% of total N₂ production was due to this novel route. The relative importance of anammox for N₂ release was inversely correlated with remineralized solute production, benthic O₂ consumption, and surface sediment Chl a. The observed correlations indicate competition between reductants for pore water nitrite during early diagenesis and that additional factors (e.g. availability of Mn-oxides), superimposed on overall patterns of diagenetic activity, are important for determining absolute and relative rates of anammox in coastal marine sediments.     

Influencing factors and significance of organic and inorganic nitrogen isotopic compositions in lacustrine sedimentary rocks

Comprehensive nitrogen biogeochemical cycle has been reconstructed for representative lacustrine organic-rich sedimentary rock in China, namely the Triassic Yanchang Formation (YF, 199–230 Ma) in Ordos and the Cretaceous Qingshankou Formation (QF, 86–92 Ma) in Songliao basins, by evaluating the organic and inorganic nitrogen isotopic compositions rather than only organic or bulk nitrogen isotopic compositions. The results indicate that the nitrogen isotope values of bulk rock (δ¹⁵N_bulk) in the non-metamorphic stage are significantly different from that of kerogen, which challenge the conceptual framework of sedimentary nitrogen isotope interpretation. The δ¹⁵N_bulk from the YF and QF were lower than their respective the nitrogen isotope values of kerogen (δ¹⁵N_ker), with offsets up to ～5.1‰, which have the inverse relationship for the metamorphosed rock. Thermal evolution did not significantly modify the δ¹⁵N of bulk rock and kerogen. The δ¹⁵N of sediments from the YF (δ¹⁵N_bulk, 1.6‰–5.6‰) were lower than that of rock from the QF (δ¹⁵N_bulk, 10.2‰–15.3‰). The nitrogen isotope values of silicate incorporated nitrogen (δ¹⁵N_sil) were slightly lower than those of the δ¹⁵N_ker in the YF and obviously lower for the QF. The fact that different nitrogen cycles occur in the YF and QF due to the different depositional redox conditions leads to different isotopic results. The YF water environment dominated by oxic conditions is not conducive to the occurrence of denitrification and anammox, and no abundant N₂ loss leads to the relatively light δ¹⁵N_bulk. In the stratified water for the QF, redox transition zone promotes denitrification and anammox, resulting in the heavy δ¹⁵N_bulk of rock and promotes the DNRA, resulting in heavy δ¹⁵N_ker and low δ¹⁵N_sil.     

A dual-isotope approach to the nitrogen hydrochemistry of an urban aquifer

The potential for exploitation of urban aquifers is partly dependent on understanding the distribution and fate of urban N sources, such as sewage and fertilisers, that can limit the use of groundwater for public supplies. To investigate the application of the dual-isotope approach to understanding the N hydrochemistry of urban groundwater, this paper presents δ¹⁵N–NO₃⁻ and δ¹⁸O–NO₃⁻ data collected from two multi-level piezometers in the Sherwood sandstone aquifer beneath Nottingham in the English Midlands, UK. At one multi-level piezometer (Old Basford), depth sample measurements of δ¹⁵N–NO₃⁻ in the range +9.2 to +11.4 ‰ and δ¹⁸O–NO₃⁻ in the range +8.2 to +10.9‰, together with NO₃⁻ nitrate concentrations from 31.7 to 66.7 mg/l, are evidence for nitrification of sewage-derived inputs. In contrast, at the other multi-level piezometer (the Meadows), isotopically enriched samples (δ¹⁵N–NO₃⁻ in the range +24.3 to +42.2 ‰ and δ¹⁸O–NO₃⁻ in the range +20.5 to +29.4‰) are evidence for denitrification, although the compositional range of δ¹⁵N–NO₃⁻ does not identify the N source without corroborating data. For the Meadows location, a cross-plot of δ¹⁵N–NO₃⁻ versus δ¹⁸O–NO₃⁻ gave an enrichment of the ¹⁵N isotope relative to the ¹⁸O isotope by a factor of 1.9, within the range of 1.3–2.1 reported for denitrification in other studies. This study has shown that the dual-isotope approach provides improved understanding of N sources and fate in the urban environment but further work is required to identify nitrification pathways to provide more confidence in the application and interpretation of δ¹⁸O–NO₃⁻ measurements.     

Nitrogen flow and the interaction of Boston harbor with Massachusetts Bay

This paper summarizes evidence that most of the considerable nitrogen loading (～8, 470 mmol total N m^?2 yr^?1) to Boston Harbor (Massachusetts, USA) is expelled to shallow shelf waters of Massachusetts Bay, where it strongly influences ecological dynamics. Examination of nitrogen concentrations in the harbor, compared with loading, indicated that removal processes are active in the harbor. Comparison to other estuarine systems showed that the harbor’s nitrogen concentrations are consistent with its loading, if they are corrected for tidal flushing effects on the water residence time. Furthermore, extensive measurements of sediment denitrification confirmed that rates of N₂ gas loss are high in an absolute sense (～600–800 mmol N m^?2 yr^?1) but nonetheless remove only a small portion (<10%) of the annual land-derived nitrogen loading. Burial in sediments apparently removes only about 2% of the N input, implying export to offshore environments as the major removal process (～88–90% of N input). Western Massachusetts Bay receiving waters were examined for a signature of export from the harbor. Data consistently show a gradient of decreasing nitrogen concentrations from the harbor to about 10–20 km into the bay. In many cases, plots of nitrogen concentrations versus salinity show nearly conservative mixing character, which implies virtual export. Seasonally, the data suggest most of the export from the harbor in winter is as dissolved inorganic forms (NH₄ ⁺, NO₃ ^?, NO₂ ^?). In summer, export is dominated by the outflow of organic nitrogen forms. Chlorophyll export is evident as well, suggesting that the nutritional coupling of the harbor and bay in summer involves organic fertilization of the bay’s surface water. Finally, high-resolution studies over different stages of the tidal cycle help refine understanding of the advection of chlorophyll and stimulation of in situ chlorophyll growth at the seaward edge of the tidal excursion into the bay.     

The influence of subsurface hydrology on nutrient supply and smooth cordgrass (Spartina alterniflora) production in a developing barrier island marsh

The supply of nutrients from surface and subsurface water flow into the root zone was measured in a developing barrier island marsh in Virginia. We hypothesize that high production of tall-formSpartina alterniflora in the lower intertidal zone is due to a greater nitrogen input supplied by a larger subsurface flux. Individual nitrogen inputs to the tall-form and short-formS. alterniflora root zones were calculated from water flow rates into the root zone and the nutrient concentration corresponding to the source of the flow. Total dissolved inorganic nitrogen (DIN) input (as ammonium and nitrate) was then calculated using a summation of the hourly nutrient inputs to the root zone over the entire tidal cycle based on hydrologic and nutrient data collected throughout the growing season (April–August) of 1993 and 1994. Additionally, horizontal water flow into the lower intertidal marsh was reduced experimentally to determine its effects on nutrient input and plant growth. Total ammonium (NH₄ ⁺) input to the tall-formS. alterniflora root zone (168 μmoles 6 h^?1) was significantly greater relative to the short-form (45 μmoles 6 h^?1) during flood tide. Total NH₄ ⁺ input was not significantly different between growth forms during ebb tide, and total nitrate (NO₃ ^?) and total DIN input were not significantly different between growth forms during either tidal stage. During tidal flooding, vertical flow from below the root zone accounted for 71% and horizontal flow from the adjacent mudflat accounted for 19% of the total NH₄ ⁺ input to the tall-formS. alterniflora root zone. Infiltration of flooding water accounted for 15% more of the total NO₃ ^? input relative to the total NH₄ ⁺ input at both zones on flood tide. During ebb tide, vertical flow from below the root zone still accounted for the majority of NH₄ ⁺ and NO₃ ^? input to both growth forms. After vertical flow, horizontal subsurface flow from upgradient accounted for the next largest percentages of NH₄ ⁺ and NO₃ ^? input to both growth forms during ebb tide. After 2 yr of interrupted subsurface horizontal flow to the tall-formS. alterniflora root zone, height and nitrogen content of leaf tissue of treatment plants were only slightly, but significantly, lower than control plants. The results suggest that a dynamic supply of DIN (as influenced by subsurface water flows) is a more accurate depiction of nutrient supply to macrophytes in this developing marsh, relative to standing stock nutrient concentrations. The dynamic subsurface supply of DIN may play a role in spatial patterns of abovegroundS. alterniflora production, but determination of additional nitrogen inputs and the role of belowground production on nitrogen demand need to also be considered.     

Sediment-water oxygen and nutrient fluxes in a river-dominated estuary

Sediment oxygen uptake and net sediment-water fluxes of dissolved inorganic and organic nitrogen and phosphorus were measured at two sites in Fourleague Bay, Louisiana, from August 1981, through May 1982. This estuary is an extension of Atchafalaya Bay which receives high discharge and nutrient loading from the Atchafalaya River. Sediment O₂ uptake averaged 49 mg m^?2 h^?1. On the average, ammonium (NH₄ ⁺) was released from the sediments (mean flux =+129 μmol m^?2 h^?1), and NO₃ ^? was taken up (mean flux =?19 μmol m^?2h^?1). However, very different NO₃ ^? fluxes were observed at the two sites, with sediment uptake at the upper, river-influenced, high NO₃ ^? site (mean flux =?112 μmol m^?2 h^?1) and release at the lower, marine-influenced low NO₃ ^? site (mean flux =+79 μmol m^?2 h^?1). PO₄ ^3? fluxes were low and often negative (mean flux =?8 μmol m^?2 h^?1), while dissolved organic phosphorus fluxes were high and positive (mean flux =+124 μmol m^?2 h^?1). Dissolved organic nitrogen fluxes varied greatly, ranging from a mean of +305 μmol m^?2 h^?1 at the lower bay, to ?710 μmol m^?2 h^?1 at the upper bay. Total dissolved nitrogen and phosphorus fluxes indicated the sediments were a nitrogen (mean flux =+543 μmol m^?2 h^?1) and phosphorus source (mean flux =+30 μmol m^?2 h^?1) at the lower bay, and a nitrogen sink (mean flux =?553 μmol m^?2 h^?1) and phosphorus source (mean flux =+17 μmol m^?2 h^?1) in the upper bay. Mean annual O∶N ration of the positive inorganic sediment fluxes were 27∶1 at the upper bay and 18∶1 at the lower bay. Based on these data we hypothesize that nitrification and denitrification are important sediment processes in the upper bay. We further hypothesize that Atchafalaya River discharge affects sediment-water fluxes through seasonally high nutrient loading which leads to net nutrient uptake by sediments in the upper bay and release in the lower bay, where there is less river influnces.     

Ammonium excretion by benthic invertebrates and sediment-water nitrogen flux in the Gulf of Mexico near the Mississippi River outflow

Benthic macroinvertebrate biomass and ammonium excretion rates were measured at four stations in the Gulf of Mexico near the Mississippi River mouth. Calculated areal excretion rates were then compared to sediment-water nitrogen fluxes measured in benthic bottom lander chambers at similar stations to estimate the potential importance of macroinvertebrate excretion to sediment nitrogen mineralization. Excretion rates for individual crustaceans (amphipods and decapods) was 2–21 nmoles NH₄ ⁺ (mg dry weight)^?1 h^?1. The mean excretion rates for the polychaetes, Paraprionaspio pinnata [6–12 nmoles NH₄ ⁺ (mg dry weight)^?1h^?1] and Magelona sp. [27–53 nmoles NH₄ ⁺ (mg dry weight)^?1h^?1], were comparable or higher than previous measurements for similar size benthic or pelagic invertebrates incubated at the same temperature (22±1°C). Although the relatively high rates of excretion by these selective feeders may have been partially caused by experimental handling effects (e.g., removal from sediment substrates), they probably reflected the availability of nitrogen-rich food supplies in the Mississippi River plume. When the measured weight-specific rates were extrapolated to total areal biomass, areal macroinvertebrate excretion estimates ranged from 7 μmole NH₄ ⁺ m^?2h^?1 at a 40-m deep station near the river mouth to 18 μmole NH₄ ⁺ m^?2h^?1 at a shallower (28-m deep) station further from the river mouth. The net flux of ammonium and nitrate from the sediments to the water measured in bottom lander chambers in the same region were 15–53 μmole NH₄ ⁺ m^?2h^?1 and ?25–21 μmole NO₃ ^? m^?2h^?1. These results suggest that excretion of NH₄ ⁺ by macroinvertebrates could be a potentially important component of benthic nitrogen regeneration in the Mississippi River plume-Gulf shelf region.     

Nitrogen Retention in Coastal Marine Sediments—a Field Study of the Relative Importance of Biological and Physical Removal in a Danish Estuary

The aim of this study was to elucidate the relative importance of physical versus biological loss processes for the removal of microphytobenthic (MPB) bound nitrogen in a coastal environment at different times of the year via a dual isotope labeling technique. We used ⁵¹Cr, binding to inorganic sediment particles but not participating in any biological processes, and ¹⁵N–NO₃ ^?, taken up by the MPB and turned over as part of the MPB nitrogen pool. Retention, down-mixing, and export of ¹⁵N were due to both biological and physical processes, so that by comparing retention of the two isotopes, we were able to discern the relative importance of physical and biological processes. The isotope marking was supplemented with measurements of sediment chlorophyll biomass and oxygen fluxes, allowing us to evaluate MPB biomass as well as primary production vs. respiration in the sediment. In spring/early summer, the system was characterized by tight N cycling and high N retention: any remineralized N was immediately taken up and retained in the MPB biomass. In late summer and autumn, the system was still physically stable, but high biological mediated N losses were observed. In early winter, the system was physically dominated due to low MPB biomasses and activity combined with a significant storm event. Our data support the hypothesis that the relative balance between physical and biological processes in determining retention and removal of MPB-bound nitrogen changes seasonally.     

Natural abundance of 15N in particulate organic matter in the North Pacific Ocean

The abundance of ¹⁵N in particulate organic matter in the euphotic layer of the North Pacific Ocean was investigated. δ¹⁵N values ranged from ?1.7 to +9.7% relative to atmospheric nitrogen. ¹⁵N contents in plankton samples collected in the central and northwestern North Pacific were inversely correlated with concentrations of NO^?₃. The ¹⁵N contents of Trichodesmium sp. (?1.7 to +0.5%) and associated Zooplankton (ca. + 2%) were low, suggesting the significance of nitrogen supply via molecular nitrogen fixation which is assumed to involve little isotope fractionation. The variation of ¹⁵N in particulate organic nitrogen in the euphotic layer of the ocean can be explained by biochemical isotope fractionation in the assimilation of nitrate and fixation of molecular nitrogen.