Nitrogen transformations as inferred from the activities of key enzymes in the Arabian Sea oxygen minimum zone

Vertical distributions of the potential activities of some key enzymes mediating nitrification and denitrification were investigated within the oxygen (O₂) minimum zone of the Arabian Sea at a number of locations between latitudes 17°N and 21°N and longitudes 63°E and 68°E so as to get an insight into the predominant biochemical mode(s) of production and consumption of nitrous oxide (N₂O). Results revealed that the dissimilatory nitrate (NO⁻₃) reduction activity was generally very low or absent within the σ_θ range 26.6–26.8, which corresponds to the Persian Gulf Watermass (PGW). Depth profiles of nitrate reductase (NaR), nitrite reductase (NiR) and ammonia monooxygenase (AMO) activities were compared with those of O₂, NO⁻₃, nitrite (NO⁻₂) and N₂O, and it is concluded that nitrifier denitrification rather than heterotrophic denitrification is active within the core of PGW. The presence of multiple peaks of AMO activity coinciding with distinct maxima in the O₂ profile and with a trend opposite to that of NaR activity indicates that the two processes, viz., classical and nitrifier denitrification, occur in discrete layers, probably determined by the variations in the ambient O₂ concentrations at various depths surrounding the PGW core. Further, it appears that at the depths where nitrifier denitrification is active in the absence of heterotrophic denitrification, N₂O builds up as its consumption may be inhibited by O₂. Possible reasons for the occurrence of appreciable nitrate deficit within the core of PGW, where dissimilatory NO⁻₃ reduction is lacking, are discussed.     

Vertical profiles of nitrous oxide and dissolved oxygen in marine sediments

The whole core squeezing method was used to simultaneously obtain profiles of nitrous oxide (N₂O), nitrogenous nutrients, and dissolved oxygen in sediments of Koaziro Bay, Japan (coastal water), the East China Sea (marginal sea), and the central Pacific Ocean (open ocean). In the spring of Koaziro Bay, subsurface peaks of interstitial N₂O (0.5–3.5 cm depth) were observed, at which concentrations were higher than in the overlying water. This was also true for nitrate (NO₃⁻) and nitrite (NO₂⁻) profiles, suggesting that the transport of oxic overlying water to the depth through faunal burrows induced in situ N₂O production depending on nitrification. In the summer of Koaziro Bay, sediment concentrations of N₂O, NO₃⁻ and NO₂⁻ were lower than in the overlying water. In most East China Sea sediments, both N₂O and NO₃⁻ decreased sharply in the top 0.5–2 cm oxic layer (oxygen: 15–130 μM), which may have indicated N₂O and NO₃⁻ consumption by denitrification at anoxic microsites. N₂O peaks at subsurface depth (0.5–6.5 cm) implied in situ production of N₂O and/or its supply from the overlying water through faunal burrows. However, the occurrence of the latter process was not confirmed by the profiles of other constituents. In the central Pacific Ocean, the accumulation of N₂O and NO₃⁻ in the sediments likely resulted from nitrification. Nitrous oxide fluxes from the sediments, calculated using its gradient at the sediment–water interface and the molecular diffusion coefficient, were −45 to 6.9 nmolN m⁻² h⁻¹ in Koaziro Bay in the spring, −29 to −21 nmolN m⁻² h⁻¹ in the summer, −46 to 37 nmolN m⁻² h⁻¹ in the East China Sea, 0.17 to 0.23 nmolN m⁻² h⁻¹ in the equatorial Pacific, and <±0.2 nmolN m⁻² h⁻¹ in the subtropical North Pacific, respectively.     

Potential rates and environmental controls of denitrification and nitrous oxide production in a temperate urbanized estuary

Denitrification may play a major role in inorganic nitrogen removal from estuarine ecosystems, particularly in those subjected to increased nitrate and organic matter loads. The Douro estuary (NW Portugal) suffers from both problems: freshwater input of nitrate and organic load from untreated wastewater discharges. To assess how these factors might control sediment denitrification, a 12-month survey was designed. Denitrification potential and nitrous oxide (N₂O) production were measured at different locations using the slurry acetylene blockage technique. Denitrification rate ranged from 0.4 to 38 nmol N g⁻¹ h⁻¹, increasing towards the river mouth following an urban pollution gradient. N₂O production, a powerful greenhouse gas implicated on the destruction of the ozone layer, was significantly related with sediment organic matter and accounted for 0.5–47% of the N gases produced. Additional enrichment experiments were consistent with the results found in the environment, showing that sediments from the upper less urban stretch of the estuary, mostly sandy, respond positively to carbon and, inversely, in organic rich sediments from the lower estuary, the denitrification potential was limited by nitrate availability. The obtained results confirmed denitrification as an important process for the removal of nitrate in estuaries. The presence of wastewater discharges appears to stimulate nitrogen removal but also the production of N₂O, a powerful greenhouse gas, exacerbating the N₂O:N₂ ratio and thus should be controlled.     

A role for nitrite in the production of nitrous oxide in the lower euphotic zone of the oligotrophic North Pacific Ocean

Understanding the role of the oceans in the Earth's changing climate requires comprehension of the relevant metabolic pathways which produce climatically important trace gases. The global ocean represents one of the largest natural sources of nitrous oxide (N₂O) that is produced by selected archaea and/or bacteria during nitrogen (N) metabolism. In this study, the role of nitrite (NO₂⁻) in the production of N₂O in the upper water column of the oligotrophic North Pacific Subtropical Gyre was investigated, focusing primarily on the lower euphotic zone where NO₂⁻ concentrations at the primary NO₂⁻ maximum reached 195 nmol L⁻¹. Free-drifting sediment trap arrays were deployed to measure N cycle processes in sinking particulate material and the addition of selected N substrates to unpreserved sediment traps provided an experimental framework to test hypotheses regarding N₂O production pathways and controls. Sinking particles collected using NO₂⁻-amended, unpreserved sediment traps exhibited significant production of N₂O at depths between 100 and 200 m. Subsequent stable isotope tracer measurements conducted on sediment trap material amended with ¹⁵NO₂⁻ yielded elevated δ¹⁵N values of N₂O, supporting N₂O production via a NO₂⁻ metabolism pathway. Experiments on seawater collected from 150 m showed N₂O production via NO₂⁻ metabolism also occurs in the water-column and indicated that the concentration of NO₂⁻ relative to NH₄⁺ availability may be an important control. These findings provide evidence for the production of N₂O via nitrifer-denitrification in the lower euphotic zone of the open ocean, whereby NO₂⁻ is reduced to N₂O by ammonia-oxidizing microorganisms.     

Isotopic analyses of nitrate and nitrite from reference mixtures and application to Eastern Tropical North Pacific waters

Isotopic analyses of nitrate by the denitrifier method, and indeed by many other analytical methods, do not discriminate between nitrate and nitrite. For samples containing both chemical species, accurate isotopic analysis of nitrate requires either removal of nitrite or independent isotopic analysis of nitrite and subtraction of its contribution to the mixed isotopic signal. This study evaluates the application of a variety of available analytical approaches to the isotopic analysis of mixed nitrate and nitrite solutions, with the goal of producing accurate coupled isotopic analyses of both nitrate and nitrite. These methods are tested on mixtures of standard solutions of nitrate and nitrite, and then applied to the coupled δ¹⁵N and δ¹⁸O analyses of nitrate and nitrite in waters of the Eastern Tropical North Pacific (ETNP). Results from standard mixtures show that even for extreme values of nitrate and nitrite δ¹⁵N and δ¹⁸O, both nitrite removal by ascorbate and nitrite isotopic analysis and subtraction from the mixed isotopic signal yield nitrate δ¹⁵N and δ¹⁸O values that are close to the expected values. Application of these analyses to samples from the ETNP yielded δ¹⁵N_NO3 and δ¹⁸O_NO3 values as high as 21‰ vs. AIR and 19‰ vs. VSMOW, respectively. Conversely, very low δ¹⁵N values were observed in nitrite, with values ranging from − 7.2 to − 18.5‰ vs. AIR. Removal of nitrite from ETNP samples thus revealed differences of up to 5‰ between NO₃^- and NO₂^- + NO₃^- for both δ¹⁵N and δ¹⁸O. Moreover, the δ¹⁵N offset between co-occurring nitrate and nitrite is greater than expected from the action of denitrification alone and may provide a unique constraint on the processes involved in the cycling of nitrite in and around oxygen deficient zones. Finally, subtraction of the nitrite δ¹⁵N and δ¹⁸O from ETNP samples allows the extension of the Δ(15,18) tracer into suboxic regions containing nitrite. The magnitude and distribution of Δ(15,18) in these samples suggests an important role for nitrite reoxidation in nitrate isotope variations.     

Seasonal and spatial variability in N2O distribution in the Arabian Sea

Extensive measurements of nitrous oxide (N₂O) were made in the central and eastern Arabian Sea during the northeast monsoon (February–March), intermonsoon (April–May) and southwest monsoon (July–August) seasons. The latitudinal and longitudinal variations, along with seasonal changes with respect to winter convection and coastal upwelling, are clearly discernible. Vertical profiles collected down to 1000 m show that the Arabian Sea water column is supersaturated with N₂O at all depths. However, N₂O consumption at intermediate depths, coincident with the oxygen minimum and associated with sediment–water interfaces, and in the denitrifying zone, coincident with NO^-₂ secondary maxima, are also apparent. The N₂O concentration varies from ∼10 nM near the surface to about 80 nM in the secondary peak region (≈800 m). Interrelationships with chemical parameters suggest nitrification to be the main process for the production of N₂O in the oceanic water. Plots of apparent oxygen utilization vs production of N₂O indicate a consistent linear relationship for AOU between 0 and 200 μM.     

Nitrous oxide production and denitrification rates in estuarine intertidal saltmarsh and managed realignment zones

Increasing concerns over habitat loss and rising costs of sea defence maintenance due to rising sea levels, has seen increases in the practice of managed realignment and reflooding of former reclaimed areas of intertidal saltmarsh and mudflat around the world. These practices are taking place with little knowledge of their impact on soil biogeochemical processes. Rates of denitrification (using the acetylene inhibition technique) and nitrous oxide (N₂O) production were measured from a long-established saltmarsh (SM) and an adjacent, recently re-flooded managed realignment (MR) site comprising former arable land in the estuary of the River Torridge, Devon, UK. Incubations were carried out in closed chambers in which patterns of tidal flooding were simulated automatically. Measurements were made during periods of flood and non-flood over a total of four tidal inundations with estuarine water. During the latter two flooding episodes floodwater was amended with nitrate (NO₃⁻). Nitrous oxide production in the SM soil generally was lower than in the MR soil, with mean values and standard errors over the whole incubation of 0.27 ± 0.16 mg N₂O-N m⁻² h⁻¹ and 0.65 ± 0.15 mg N₂O-N m⁻² h⁻¹ respectively. Denitrification rates demonstrated a similar trend although generally were an order of magnitude higher than N₂O production, with mean rates and standard errors of 2.88 ± 1.12 mg N₂O-N m⁻² h⁻¹ in the SM soil and 3.39 ± 1.16 mg N₂O-N m⁻² h⁻¹ in the MR soil. The data suggest that both soils are net sinks for NO₃⁻ and net sources for N₂O. Both patterns of tidal inundation and floodwater chemistry affect the process rates in each soil differently. The impact of flooding with NO₃⁻ – amended water was greater on the SM soil than the MR soil, and it is likely that decomposing vegetation buried in the accreting sediments following reflooding at the MR site were supplying a source of N in the soil, and so process rates were less dependent upon external supplies. The act of managed realignment in intertidal zones could therefore result in an increase in mean production of N₂O in intertidal zones, at least in the short term.     

Basin-scale distribution of NH<Subscript>4</Subscript><Superscript>+</Superscript> and NO<Subscript>2</Subscript><Superscript>−</Superscript> in the Pacific Ocean

We used more than 25,000 nutrient samples to elucidate for the first time basin-scale distributions and seasonal changes of surface ammonium (NH₄ ⁺) and nitrite (NO₂ ^?) concentrations in the Pacific Ocean. The highest NH₄ ⁺, NO₂ ^?, and nitrate (NO₃ ^?) concentrations were observed north of 40°N, in the coastal upwelling region off the coast of Mexico, and in the Tasman Sea. NH₄ ⁺ concentrations were elevated during May–October in the western subarctic North Pacific, May–December in the eastern subarctic North Pacific, and June–September in the subtropical South Pacific. NO₂ ^? concentrations were highest in winter in both hemispheres. The seasonal cycle of NH₄ ⁺ was synchronous with NO₂ ^?, NO₃ ^?, and satellite chlorophyll a concentrations in the western subtropical South Pacific, whereas it was synchronous with chlorophyll-a but out of phase with NO₂ ^? and NO₃ ^? in the subarctic regions.     

Distributions, sources and atmospheric fluxes of nitrous oxide in Jiaozhou Bay

The distributions, sources and atmospheric fluxes of nitrous oxide (N₂O) in the seawater of Jiaozhou Bay were investigated during four surveys in 2003 to evaluate this area as a source of N₂O to the atmosphere. N₂O concentrations in both the surface and bottom waters of Jiaozhou Bay showed obvious variability with both seasons and tidal cycles. Atmospheric fluxes of N₂O in Jiaozhou Bay showed seasonal and spatial variations, with the highest values occurring in summer and the lowest in winter. The annual emission of N₂O from the bay was estimated to be 1.09 × 10⁶–2.23 × 10⁶ mol yr⁻¹. N₂O in the water column of Jiaozhou Bay was found to come from several external sources including riverine water, sewage water and groundwater input, among which the riverine input was dominant while the groundwater input was rather limited. The spatial variation in distribution and atmospheric fluxes of N₂O in Jiaozhou Bay was influenced by the input of polluted river waters and sewage effluent along the eastern coast, which highlights the effects of human impacts on N₂O emission rates.     

Nitrous oxide and methane in the Atlantic Ocean between 50°N and 52°S: Latitudinal distribution and sea-to-air flux

We discuss nitrous oxide (N₂O) and methane (CH₄) distributions in 49 vertical profiles covering the upper ∼300 m of the water column along two ∼13,500 km transects between ∼50°N and ∼52°S during the Atlantic Meridional Transect (AMT) programme (AMT cruises 12 and 13). Vertical N₂O profiles were amenable to analysis on the basis of common features coincident with Longhurst provinces. In contrast, CH₄ showed no such pattern. The most striking feature of the latitudinal depth distributions was a well-defined “plume” of exceptionally high N₂O concentrations coincident with very low levels of CH₄, located between ∼23.5°N and ∼23.5°S; this feature reflects the upwelling of deep waters containing N₂O derived from nitrification, as identified by an analysis of N₂O, apparent oxygen utilization (AOU) and NO₃⁻, and presumably depleted in CH₄ by bacterial oxidation. Sea-to-air emissions fluxes for a region equivalent to ∼42% of the Atlantic Ocean surface area were in the range 0.40–0.68 Tg N₂O yr⁻¹ and 0.81–1.43 Tg CH₄ yr⁻¹. Based on contemporary estimates of the global ocean source strengths of atmospheric N₂O and CH₄, the Atlantic Ocean could account for ∼6–15% and 4–13%, respectively, of these source totals. Given that the Atlantic Ocean accounts for around 20% of the global ocean surface, on unit area basis it appears that the Atlantic may be a slightly weaker source of atmospheric N₂O than other ocean regions but it could make a somewhat larger contribution to marine-derived atmospheric CH₄ than previously thought.     

The effects of semi-lunar spring and neap tidal change on nitrification, denitrification and N2O vertical distribution in the intertidal sediments of the Yangtze estuary, China

To explore the influences of semi-lunar spring and neap tidal changes on nitrogen cycling in intertidal sediments, a comparative study among waterlogged, desiccated and reflooded systems was carried out in August 2005 and February 2006 by analyzing nitrification, denitrification and N₂O depth profiles in the intertidal flats of the Yangtze estuary. Laboratory experiments showed that alternating emersion and inundation resulted in the significant changes in nitrification and denitrification rates in the intertidal sediment systems. Due to the desiccation-related effects, lowest nitrification and denitrification rates were observed in the desiccated sediment cores. Highest nitrification and denitrification rates were however detected in the waterlogged and reflooded systems, respectively. It is hypothesized that the highest nitrification rates in the waterlogged sediments were mainly attributed to higher nitrifier numbers and NH₄⁺ being more available, whereas the availability of NO₃⁻ might dominate denitrification in the reflooded sediments. In addition, the highest N₂O concentrations were detected in the reflooded sediment cores, and the lowest found in the dried sediment cores. It was also shown that N₂O in the intertidal sediments was mainly from nitrification under the desiccated condition. In contrast, N₂O in the intertidal sediments was produced mainly via denitrification under the waterlogged and reflooded conditions. It is therefore concluded that the semi-lunar tidal cycle has a significant influence on nitrification, denitrification and N₂O production in the intertidal sediment systems.     

The effect of a tidal cycle on the dynamics of nutrients in a tidal estuary in the Seto Inland Sea, Japan

A 24 hour time series survey was carried out during a spring tide (tidal range ca.2 m) of May 1995 on a tidal estuary in the Seto Inland Sea, Japan, in the context of an integrated program planned to quantify the dynamics of biophilic elements (carbon, nitrogen and phosphorus) and the roles played by the macrobenthos on the processes. Three stations were set along a transect line of about 1.4 km, which linked the river to the rear to the innermost part of the subtidal zone. Every hour, at each station, measurements were made of surface water temperature, salinity and dissolved oxygen concentration, and surface water was collected for the determination of nutrients [NH₄ ⁺−N, (NO₃ ⁻+NO₂ ⁻)−N, PO₄ ³⁻−P and Si (OH)₄−Si]. During the ebb flow, riverine input of silicate and nitrate+nitrite significantly increased the concentrations of both the intertidal and the subtidal stations. Conversely, during the high tide, river nutrient concentrations were lowered by the mixing of fresh water with sea water. As a result, best (inverse) correlations were found at the river station for salinity against silicate (y=-2.9 Sal.+110.7,r ²=0.879) and nitrate+nitrite (y=-1.3 Sal.+48.4,r ²=0.796). In contrast, ammonium nitrogen concentrations were higher at intermediate salinities. Indeed, no significant correlation was found between salinity and ammonium. The effect of the macrobenthos, which is abundant on the intertidal flat, is discussed as a biological component that influences the processes of nutrient regeneration within the estuary. The effect of the tidal amplitude is an important one in determining the extent of the variations in nutrient concentrations at all three stations, which were stronger between the lower low tide and the higher high tide.     

N2, N2O and O2Profiles in a Tagus Estuary Salt Marsh

Vertical gas profiles of N₂, N₂O and O₂were obtained in intact sediment cores from a Tagus estuary salt marsh using membrane inlet mass spectrometry. This technique allows direct measurements of dissolved gas concentrations with minimal disturbance. O₂concentrations decreased sharply with depth, becoming undetectable below 14mm. Denitrification products (N₂and N₂O) occurred in the surface layer of the sediment where O₂was present. Diffusion of N₂and N₂O from the anaerobic zone, denitrification in anaerobic microsites and aerobic denitrification are possible explanations for this observation. N₂was the sole product of denitrification in control sediment cores probably because of the great demand for electron acceptors in this sediment. The addition of NO₃ ⁻ and CH₃CO₂ ⁻ increased the concentrations of N₂and N₂O in the sediment. Significantly higher concentrations in treated cores occurred between 1·5 and 2·0cm for N₂and between 0·5 and 1·5cm for N₂O. The peak in N₂concentration occurred in the anaerobic zone of the sediment, close to the aerobic–anaerobic interface while the peak in N₂O concentration occurred above this interface where concentrations of O₂were approximately 10μM. This is indicative that, in this sediment, production of N₂O is less sensitive to the presence of O₂than reduction of N₂O to N₂.     

Nutrient Concentrations are High in the Turbid Waters of the Colorado River Delta

We studied the seasonal change of the spatial distribution of nitrite (NO^-₂), nitrate (NO^-₃), reactive phosphate (PO^3-₄), and silicate (SiO₂) in the Colorado River Delta. We also generated 24-h time series at one location to study their short-period variability. The delta is a negative estuary. During summer, salinity may be as high as 40. Amplitude of spring tides is as large as 9 m, and this causes great water turbidity by sediment resuspension. Nutrient concentrations were high throughout the whole year, with lower values towards the oceanic region. Maximum nutrient values in the river delta were 15, 53, 11·5 and 92 μM, for NO^-₂, NO^-₃, PO^3-₄, and SiO₂, respectively. Most values were under 2, 40, 5, and 60 μM, for NO^-₂, NO^-₃, PO^3-₄, and SiO₂, respectively. Our nutrient data show no clear seasonal pattern. Possibly, high NO^-₃ values in the delta are due to groundwater input, mostly at the internal extreme, and high NO^-₂, PO^3-₄, and SiO₂ values are due to resuspension of sediments and mixing of porewaters with the water column, caused mainly during spring tides. In the case of NO^-₂, oxidation of NH⁺₄ in the water column would be part of the mechanism. This would explain the high negative correlation between NO^-₃ and sea-level, and the relatively low correlation between the other nutrients and sea-level, for the time series generated at a single location.     

Impact of trace metals on denitrification in estuarine sediments of the Douro River estuary,Portugal

Denitrification influences the nitrogen budget in estuaries by removing fixed nitrogen from the inorganic pool; rates are dependent on both geological and geographic conditions as well as increasing anthropogenic impacts. In this study the effects of copper (Cu), chromium (Cr), zinc (Zn), cadmium (Cd) and lead (Pb), on the denitrification pathway were evaluated in subtidal and intertidal sediments of the Douro River estuary. Dinitrogen, N₂O and NO₂⁻ production rates were measured in triplicate slurries of field samples under different treatments of metal concentrations. Results demonstrated that similar metal amendments led to different site responses for denitrification, suggesting that variations in sediment properties (metal concentrations, grain size, organic matter content, etc.) and/or differences in denitrifying community tolerance modulate the level of metal toxicity. Denitrifying communities in subtidal muddy sediments were not affected by increasing concentrations of metals. In contrast, intertidal sandy sites revealed high sensitivity to almost all trace metals tested; almost complete inhibition by Cr (95%) and Cu (85%) was observed for 98 and 79 μg per gram of wet sediment respectively, and by Zn (92%) at the highest concentration added (490 μg per gram of wet sediment). Moreover, the addition of trace metals stimulated N₂O and NO₂⁻ accumulation in intertidal sandy (Zn, Cu, Cr and Cd) and muddy sediments (Cu and Zn), demonstrating a pronounced inhibitory effect on specific steps within the denitrification enzymatic system. In summary, the results obtained suggest that, according to the type of estuarine sediment, trace metals cannot only reduce total N removal from an estuary via denitrification but also can enhance the release of N₂O, a powerful greenhouse gas.     

Nitrate photolysis in seawater by sunlight

The photolysis of nitrate in seawater by sunlight has been re-examined using abiotic seawater and naturally occurring concentrations. Photochemical formation of nitrite from nitrate was observed. First-order nitrate photolysis rate coefficients calculated from nitrite appearance (corrected for concomitant nitrite photolysis) ranged from 0 to 2.3 yr^?1, median 0.7 yr^?1. The coefficients did not correlate well with water chemistry, but decreased with increasing light dose. A first-order rate coefficient of 0.4 yr^?1 was calculated for the primary photochemical process $\text{NO}{}_3{}^{\mathrm{?}}\text{+}\text{h}\text{υ =}\text{NO}{}_2{}^{\mathrm{?}}\text{+ O(}{}^3\text{P)}$ under sea surface equatorial insolation and cloudiness conditions. However, no significant nitrate concentration decreases could be detected, suggesting an upper limit for the net first-order nitrate loss rate coefficient of 0.3 yr^?1. The data thus imply some conversion in the reverse sense: NO₂^? + hυ →→ NO₃^?.If our median rate estimate applies to surface oceanic conditions, nitrate photolysis proceeds at roughly 0.02–0.5% of the rate of N incorporation during primary production. It is thus not a significant NO₃-N sink. Since such reactive species as oxygen atoms, nitrogen dioxide, and hydroxyl radicals are produced, the reaction may have significant consequences in seawater. However, nitrite photolysis is almost certainly a more significant process.The results show internal inconsistencies and our rates are markedly different from those calculated using data from other studies. Nitrate photolysis rates are theoretically concentration- and light dose-dependent. Whether these dependencies explain the apparent discrepancies is unclear, as methodological effects may also be involved. The system requires further study.     

Seasonal cycle of N2O vertical distribution and air-sea fluxes over the continental shelf waters off central Chile (∼36°S)

The continental shelf off central Chile is subject to strong seasonal coastal upwelling and has been recognized as an important outgassing area for, amongst others, N₂O, an important greenhouse gas. Several physical and biogeochemical variables, including N₂O, were measured in the water column from August 2002 to January 2007 at a time series station in order to characterize its temporal variability and elucidate the physical and biogeochemical mechanisms affecting N₂O levels. This 4-year time series of N₂O levels reveals seasonal variability associated basically with hydrographic and oceanographic regimes (i.e., upwelling and non-upwelling). However, a noteworthy temporal evolution of both the vertical distribution and N₂O levels was observed repeatedly throughout the entire study period, allowing us to distinguish three stages: winter/early spring (Stage I), mid-spring/mid-summer (Stage II), and late summer/early autumn (Stage III).Stage I presents low N₂O, the lowest surface saturation ever registered (from 64% saturation) in a period of high O₂, and a homogeneous column driven by strong wind; this distribution is explained by physical and thermodynamic mechanisms. Stage II, with increasing N₂O concentrations, agrees with the appearance of upwelling-favourable wind stress and a strong influence of oxygen-poor, nutrient-rich equatorial subsurface waters (ESSW). The N₂O build-up creates a “hotspot” (up to 2426% N₂O saturation) and enhanced concentrations of (up to 3.97 μM) and (up to 4.6 μM) at the oxycline (4-28 μM) (∼20-40 m depth). Although the dominant N₂O sources could not be determined, denitrification (mainly below the oxycline) appears to be the dominant process in N₂O accumulation. Stage III, with diminishing N₂O concentrations from mid-summer to early autumn, was accompanied by low N/P ratios. During this stage, strong bottom N₂O consumption (from 40% saturation) was suggested to be mainly driven by benthic denitrification.Consistent with the evolution of N₂O in the water column over time, the estimated air-sea N₂O fluxes were low or negative in winter (−9.8 to 20 μmol m⁻² d⁻¹, Stage I) and higher in spring and summer (up to 195 μmol m⁻² d⁻¹, Stage II), after which they declined (Stage III). In spite of the occurrence of ESSW and upwelling events throughout stages II and III, N₂O behaviour should be a response of the biogeochemical evolution associated with biological productivity and concomitant O₂ levels in the water and even in the sediments. The results presented herein confirm that the study area is an important source of N₂O to the atmosphere, with a mean annual N₂O flux of 30.2 μmol m⁻² d⁻¹; however, interannual variability could not yet be properly characterized.     

Seasonal Study of Methane and Nitrous Oxide in the Coastal Waters of the Southern Baltic Sea

Atmospheric and dissolved methane (CH₄) and nitrous oxide (N₂O) were measured in the unique coastal ecosystem of theBoddenwaters, including the western Oder estuary, (southern Baltic Sea) during five campaigns between 1994 and 1997. The CH₄saturations, ranging from 105–15 500%, showed great spatial and temporal variability with maximum values in September and minimum values in December. The N₂O saturations were in the range of 91–312% with a maximum in March. Enhanced concentrations of both gases were observed only in the western Oder estuary near the mouth of the Peene River. Thus, we conclude that the distributions of CH₄and N₂O in the investigatedBoddenwaters are, directly or indirectly, linked to the Peene River runoff and not to the Oder River. Our estimate of the annual CH₄emissions from theBoddenwaters to the atmosphere indicates a significant contribution (c. 17%) to the overall CH₄emissions from the Baltic Sea. In contrast, theBoddenwaters represent only a small source for atmospheric N₂O.CH₄production rates estimated from sediment slurry experiments revealed a significant spatial variability and indicated that methanogenic activity was related to acetate consumption in the surface sediment layer. Sedimentary CH₄production might depend on different amounts of accumulation of organic material.     

Nitrogen and phosphorus transport between Fourleague Bay, LA, and the Gulf of Mexico: the role of winter cold fronts and Atchafalaya River discharge

Nutrient fluxes were measured between Fourleague Bay, a shallow Louisiana estuary, and the Gulf of Mexico every 3 h between February 1 and April 30, 1994 to determine how high velocity winds associated with cold fronts and peak Atchafalaya River discharge influenced transport. Net water fluxes were ebb-dominated throughout the study because of wind forcing and high volumes of water entering the northern Bay from the Atchafalaya River. Flushing time of the Bay averaged <8 days; however, more rapid flushing occurred in response to northerly winds with approximately 56% of the volume of the Bay exported to the Gulf in 1 day during the strongest flushing event. Higher nitrate+nitrite (NO₂+NO₃), total nitrogen (TN), and total phosphorus (TP) concentrations were indicative of Atchafalaya River input and fluxes were greater when influenced by high velocity northerly winds associated with frontal passage. Net exports of NO₂+NO₃, TN, and TP were 43.5, 98.5, and 13.6 g s⁻¹, respectively, for the 89-day study. An average of 10.6 g s⁻¹ of ammonium (NH₄) was exported to the Gulf over the study; however, concentrations were lower when associated with riverine influence and wind-driven exports suggesting the importance of biological processes. Phosphate (PO₄) fluxes were nearly balanced over the study with fairly stable concentrations indicating a well-buffered system. The results indicate that the high energy subsidy provided by natural pulsing events such as atmospheric cold fronts and seasonal river discharge are efficient mechanisms of nutrient delivery to adjacent wetlands and nearshore coastal ecosystems and are important in maintaining coastal sustainability.     

The nitrogen isotopic composition of dissolved nitrate in the Yangtze River (Changjiang) estuary,China

The nitrogen isotopic composition of dissolved nitrate (δ¹⁵N-NO₃⁻) in surface water of the Yangtze River estuary was determined in four seasons of 2006. δ¹⁵N-NO₃⁻ ranged from 0.4‰ to 6.5‰ and varied with seasons and geographic regions, reflecting the dynamics of nitrogen cycling in the estuarine ecosystem. δ¹⁵N-NO₃⁻ was markedly lower in February than in other seasons and exhibited conservative mixing, which was probably attributed to the NO₃⁻ being sourced from the atmospheric deposition and agricultural fertilizer. In the upper estuary, the influence of riverine inputs was important during all surveys. In the turbidity maximum zone, nitrification was found with nitrate depleted in ¹⁵N in May, whereas denitrification resulting in heavy δ¹⁵N-NO₃⁻ played an important role in August. More enriched δ¹⁵N-NO₃⁻ values coinciding with losses of nitrate concentrations based on the conservative mixing model were found in the adjacent marine area in May, and may reflect obvious phytoplankton assimilation of dissolved nitrate. In this manner, δ¹⁵N-NO₃⁻ may be a sensitive indicator of nitrogen sources and biogeochemical processing existing in this estuary in conjunction with the variations of dissolved nitrate and other environmental factors.