Contribution of humic substances to the dissolved nitrogen pool in the Greenland Sea

The concentration and distribution of dissolved nitrogenous compounds was studied in the Greenland Sea in June 1991. Dissolved organic (DON) and inorganic nitrogen (DIN) were determined in seawater of different origin and depth. Dissolved organic matter was isolated on XAD-2 resin and fractionated into its non-humic hydrophilic (H1), and so-called humic components (hydrophobic acid, HbA, and hydrophobic neutral, HbN). From all fractions the DON content was subsequently determined. Total DON concentrations were about 5 μmol Ni⁻¹ in the surface and 3 μmol NI⁻¹ below depths of 150–200 m. DIN varied between 1.5 and 1.6 μmol NI⁻¹. There was a highly significant inverse correlation (r = −0.75) between DON and DIN suggesting a close coupling in the uptake and release of the different forms of nitrogen. The mean DON concentrations of the XAD-fractions were for HI = 2.3 μmol Ni⁻¹, for HbA = 0.8 μmol NI⁻ and for HbN = 1.0 μmol NI⁻¹. The average percentage contributions were, respectively, 56%, 19% and 25%. This means that about 56% of the total DON does not belong to the ‘humic fraction’. The HbN fraction was evenly distributed in the water column, without any obvious relationship with water masses, depth, or nutrient status. In contrast, the HbA fraction showed a significant correlation with total DON.     

Simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation: conditions for precise shipboard measurements

Appropriate conditions have been achieved for the accurate, rapid, and highly precise shipboard simultaneous determination of dissolved organic carbon and total dissolved nitrogen in seawater by high temperature catalytic oxidation. A nitrogen-specific Antek 705D chemiluminescence detector and a CO₂-specific LiCor Li6252 IRGA have been coupled in-series with a Shimadzu TOC-5000 organic carbon analyser. Precision of both simultaneous measurements is ≤1.5%, i.e. ±1 μmol C l⁻¹ and ±0.3 μmol N l⁻¹, respectively. Quality of analysis is not compromised by vibrations associated with ocean going research vessels.     

Inorganic and organic nitrogen cycling in the Southern California Bight

On the basis of mass balance calculations performed for nitrogen (N) uptake experiments in the Southern California Bight (SCB), it has been suggested that a significant portion of dissolved inorganic N (DIN) uptake results in the production of dissolved organic N (DON). To investigate this process, the fate of ammonium (NH₄⁺) and nitrate (NO₃⁻) uptake was quantified within the euphotic zone at three coastal stations in the SCB using ¹⁵N tracer techniques. Several trends in the fate of DIN and the production of DON were observed. First, production of particulate N (PN), from both NH₄⁺ and NO₃⁻, was quantitatively more important in near surface waters, while DON release dominated within the nitracline. Second, the percentage of gross N uptake released as DON was generally higher when NO₃⁻, rather than NH₄⁺, was the substrate. Third, the percentage of N released as DON was higher at night, relative to the day. Fourth, rates of DON release were significantly correlated to NH₄⁺ regeneration, suggesting that similar mechanisms are responsible for both processes—presumably grazing. The results of this study indicate that the DON pool is a sink for DIN uptake on the time scale of hours. One implication of this finding is that new production estimates based on ¹⁵NO₃⁻ uptake rates will likely underestimate particle flux out of the surface layer because the rate of NO₃⁻ uptake is underestimated due to loss of DO¹⁵N during the incubation. On time scales of months to years, however, the N that is taken up as NO₃⁻ and released as DON will likely contribute to export flux via incorporation of the dissolved phase during seasonal mixing into sinking particles or transport. The export of DON on these time scales argues for the use of gross uptake rates to calculate f-ratios.     

Nitrogen cycling in deep-sea sediments of the Porcupine Abyssal Plain, NE Atlantic

Rates of transformation, recycling and burial of nitrogen and their temporal and spatial variability were investigated in deep-sea sediments of the Porcupine Abyssal Plain (PAP), NE Atlantic during eight cruises from 1996 to 2000. Benthic fluxes of ammonium (NH₄) and nitrate (NO₃) were measured in situ using a benthic lander. Fluxes of dissolved organic nitrogen (DON) and denitrification rates were calculated from pore water profiles of DON and NO₃, respectively. Burial of nitrogen was calculated from down core profiles of nitrogen in the solid phase together with ¹⁴C-based sediment accumulation rates and dry bulk density. Average NH₄ and NO₃-effluxes were 7.4 ± 19 μmol m⁻² d⁻¹ (n = 7) and 52 ± 30 μmol m⁻² d⁻¹ (n = 14), respectively, during the period 1996–2000. During the same period, the DON-flux was 11 ± 5.6 μmol m⁻² d⁻¹ (n = 5) and the denitrification rate was 5.1 ± 3.0 μmol m⁻² d⁻¹ (n = 22). Temporal and spatial variations were only found in the benthic NO₃ fluxes. The average burial rate was 4.6 ± 0.9 μmol m⁻² d⁻¹. On average over the sampling period, the recycling efficiency of the PON input to the sediment was 94% and the burial efficiency hence 6%. The DON flux constituted 14% of the nitrogen recycled, and it was of similar magnitude as the sum of burial and denitrification. By assuming the PAP is representative of all deep-sea areas, rates of denitrification, burial and DON efflux were extrapolated to the total area of the deep-sea floor (>2000 m) and integrated values of denitrification and burial of 8 ± 5 and 7 ± 1 Tg N year⁻¹, respectively, were obtained. This value of total deep-sea sediment denitrification corresponds to 3–12% of the global ocean benthic denitrification. Burial in deep-sea sediments makes up at least 25% of the global ocean nitrogen burial. The integrated DON flux from the deep-sea floor is comparable in magnitude to a reported global riverine input of DON suggesting that deep-sea sediments constitute an important source of DON to the world ocean.     

Benthic fluxes of nitrogen in the tidal reaches of a turbid, high-nitrate sub-tropical river

Benthic fluxes of dissolved inorganic nitrogen (NO₃⁻ and NH₄⁺), dissolved organic nitrogen (DON), N₂ (denitrification), O₂ and TCO₂ were measured in the tidal reaches of the Bremer River, south east Queensland, Australia. Measurements were made at three sites during summer and winter. Fluxes of NO₃⁻ were generally directed into the sediments at rates of up to −225 μmol N m⁻² h⁻¹. NH₄⁺ was mostly taken up by the sediments at rates of up to −52 μmol N m⁻² h⁻¹, its ultimate fate probably being denitrification. DON fluxes were not significant during winter. During summer, fluxes of DON were observed both into (−105 μmol m⁻² h⁻¹) and out of (39 μmol m⁻² h⁻¹) the sediments. Average N₂ fluxes at all sampling sites were similar during summer (162 μmol N m⁻² h⁻¹) and winter (153 μmol N m⁻² h⁻¹). Denitrification was fed both by nitrification within the sediment and NO₃⁻ from the water column. Sediment respiration rates played an important role in the dynamics of nitrification and denitrification. NO₃⁻ fluxes were significantly related to TCO₂ fluxes (p<0.01), with a release of NO₃⁻ from the sediment only occurring at respiration rates below 1000 μmol C m⁻² h⁻¹. Rates of denitrification increased with respiration up to TCO₂ fluxes of 1000 μmol C m⁻² h⁻¹. At sediment respiration rates above 1000 μmol C m⁻² h⁻¹, denitrification rates increased less rapidly with respiration in winter and declined during summer. On a monthly basis denitrification removed about 9% of the total nitrogen and 16% of NO₃⁻ entering the Bremer River system from known point sources. This is a similar magnitude to that estimated in other tidal river systems and estuaries receiving similar nitrogen loads. During flood events the amount of NO₃⁻ denitrified dropped to about 6% of the total river NO₃⁻ load.     

Alkaline phosphatase activity in the western English Channel: Elevations induced by high summertime rainfall

Alkaline phosphatase activity (APA) was determined in bulk particulate material and in a single-cell (ELF) assay at station L4 in the western English Channel during the summer of 2007. Throughout this period, the UK experienced its heaviest summertime rainfall since records began in 1914; with the result that riverine run-off into coastal waters was also elevated relative to long-term averages. Between May and August 2007, three distinct periods of elevated river run-off were observed which resulted in salinity minima at L4 on days 141, 190 and 232. An extended period of high river run-off between days 170 and 210 was responsible for decreases in near-surface salinity at L4 from 35.2068 to a minimum on day 190 of 34.7422. This contributed to the development of haline stratification which supported the development of an intense bloom of the centric diatom Chaetoceros debelis, with maximum observed chlorophyll a concentration of 8.69 μg l⁻¹. Minima in salinity, and maxima in chlorophyll concentration on day 190 were coincident with a peak in river-derived dissolved inorganic nitrogen (DIN) of 1.9 μmol l⁻¹ which was >5 times greater than the summertime mean and 24 times the concentrations experienced at L4 on weeks immediately before and after. There was no accompanying increase in dissolved inorganic phosphorus (DIP), and the DIN:DIP ratio increased to 49. With the inherent phosphorus stress that this caused, rates of APA increased from <4 to 42.4 nmolP l⁻¹ h⁻¹. ELF analysis on day 197 identified two taxa actively expressing alkaline phosphatase: the dinoflagellate Prorocentrum micans and ciliate Tiarana sp.     

Distributions and seasonal variability of dissolved organic nitrogen in two estuaries in SW England

Nitrogen loadings to coastal waters have increased over the last century, resulting in deterioration in water quality. In this study we investigated the distributions and seasonality of dissolved organic nitrogen (DON), and its relationship to total dissolved nitrogen (TDN), for two anthropogenically influenced estuarine systems in southwest England. Concentrations of DON in both estuaries were generally < 80 μM. DON showed non-conservative distributions, resulting from external and internal inputs and in situ reactivity. DON contributed 38 ± 22% (range 4–79%, Yealm) and 36 ± 17% (range 4–84%, Plym) to the TDN pool, with lower values generally observed in the fresher samples relative to the more saline samples. DON was a larger fraction of the TDN pool during the summer and autumn relative to winter and spring, indicating the influence of bacterioplankton release on nitrogen cycling in the estuaries. Ammonification and nitrification were observed in the estuaries, processes which were reproduced in incubation experiments using bioreactors. The bioreactor experiments showed that 12% h^− 1 of the DON flux from the River Plym may be available to bacteria, indicating significant removal of DON during the residence time of the water in the estuary (a few days). The bioavailable nature of the DON means that this N fraction significantly adds to the eutrophication burden of the receiving coastal waters, and therefore cannot be ignored in environmental assessments.     

Nitrogen dynamics within a wind-driven eddy

Wind-driven cyclonic eddies are hypothesized to relieve nutrient stress and enhance primary production by the upward displacement of nutrient-rich deep waters into the euphotic zone. In this study, we measured nitrate (NO₃⁻), particulate carbon (PC), particulate nitrogen (PN), their stable isotope compositions (δ¹⁵N-NO₃⁻, δ¹³C-PC and δ¹⁵N-PN, respectively), and dissolved organic nitrogen (DON) within Cyclone Opal, a mature wind-driven eddy generated in the lee of the Hawaiian Islands. Sampling occurred in March 2005 as part of the multi-disciplinary E-Flux study, approximately 4–6 weeks after eddy formation. Integrated NO₃⁻ concentrations above 110 m were 4.8 times greater inside the eddy (85.8±6.4 mmol N m⁻²) compared to the surrounding water column (17.8±7.8 mmol N m⁻²). Using N-isotope derived estimates of NO₃⁻ assimilation, we estimated that 213±59 mmol m⁻² of NO₃⁻ was initially injected into the upper 110 m Cyclone Opal formation, implying that NO₃⁻ was assimilated at a rate of 3.75±0.5 mmol N m⁻² d⁻¹. This injected NO₃⁻ supported 68±19% and 66±9% of the phytoplankton N demand and export production, respectively. N isotope data suggest that 32±6% of the initial NO₃⁻ remained unassimilated. Self-shading, inefficiency in the transfer of N from dissolved to particulate export, or depletion of a specific nutrient other than N may have led to a lack of complete NO₃⁻ assimilation. Using a salt budget approach, we estimate that dissolved organic nitrogen (DON) concentrations increased from eddy formation (3.8±0.4 mmol N m⁻²) to the time of sampling (4.0±0.09 mmol N m⁻²), implying that DON accumulated at rate of 0.83±1.3 mmol N m⁻² d⁻¹, and accounted for 22±15% of the injected NO₃⁻. Interestingly, no significant increase in suspended PN and PC, or export production was observed inside Cyclone Opal relative to the surrounding water column. A simple N budget shows that if 22±15% of the injected NO₃⁻ was shunted into the DON pool, and 32±6% is unassimilated, then 46±16% of the injected NO₃⁻ remains undocumented. Alternative loss processes within the eddy include lateral exchange of injected NO₃⁻ along isopycnal surfaces, remineralization of PN at depth, as well as microzooplankton grazing. A 9-day time series within Cyclone Opal revealed a temporal depletion in δ¹⁵N-PN, implying a rapid change in the N source. A change in NO₃⁻ assimilation, or a shift from NO₃⁻ fueled growth to assimilation of a ¹⁵N-deplete N source, may be responsible for such observations.     

Dissolved organic carbon, nitrogen and phosphorus in the N-E Atlantic and the N-W Mediterranean with particular reference to non-refractory fractions and degradation

Dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) measured in deep profiles in the N-E Atlantic and in the N-W Mediterranean in the period 1984–2002 are described. After accurate validation, they show close agreement with those previously published.Classic profiles were obtained, with concentrations decreasing in deep waters. In the Mediterranean and in the Atlantic comparable concentrations were found in the 1500–2000 m waters, 44–46 μmol l⁻¹ DOC, 2.6–2.8 μmol l⁻¹ DON and 0.02–0.03 μmol l⁻¹ DOP. In the surface layers, DOC concentrations were higher, but DON and DOP concentrations lower, in the Mediterranean than in the Atlantic, leading to higher element ratios in the Mediterranean. In autumn, values were, respectively, DOC:DON 17 vs. 14, DOC:DOP 950 vs. 500 and DON:DOP 55 vs. 35. The data suggest an increase in DOC and DON in the North Atlantic Central Water over 15 years, which may be linked to the North Atlantic climatic oscillations.Refractory DOM found in the 1500–2000 m layer exhibited C:N:P ratios of 1570:100:1. The labile+semi-labile (=non-refractory) DOM (nrDOM) pool was computed as DOM in excess of the refractory pool. Its contribution to total DOM above the thermocline in the open sea amounted to 25–35% of DOC, 30–35% of DON, and 60–80% of DOP. Element ratios of the nrDOM varied among stations and were lower than those of refractory DOM, except for C:N in the Mediterranean: nrDOC:nrDON 10–19, nrDOC:nrDOP 160–530 and nrDON:nrDOP 15–38. The specific stoichiometry of DOM in the Mediterranean led us to postulate that overconsumption of carbon is probably a main process in that oligotrophic sea.By coupling non-refractory DOM stoichiometry and relationships between the main DOM elements in the water column, the relative mineralization of C, N and P from DOM was studied. Below the thermocline, the preferential removal of phosphorus with regard to carbon from the semi-labile DOM can be confirmed, but not the preferential removal of nitrogen. In the ocean surface layers, processes depend on the oceanic area and can differ from deep waters, so preferential carbon removal seems more frequent. Bacterial growth efficiency data indicate that bacteria are directly responsible for mineralization of a high proportion of DON and DOP in the deep water.     

Determination of dissolved nucleic acids in seawater by the fluorescence dye, ethidium bromide

A new method for the determination of dissolved double-stranded deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) in seawater was developed, evaluated and used to study the fates of these nucleic acids in marine ecosystems. These nucleic acids, which were pre-concentrated on a hydroxyapatite column, were determined fluorometrically by the use of ethidium bromide dye, which binds specifically to the double-stranded polynucleotide. No dissolved organic matter coexisting in the pre-concentrated sample solution interfered in the analysis of DNA and RNA. Column recoveries of DNA and RNA in a sample volume of up to 11 were 93% and 97%, respectively, and 90% of both at 51. The detection limits of DNA and RNA concentrated from a 51 sample by this fluorometric method were 0.6 and 1.1 μg l⁻¹, respectively. The concentration of dissolved nucleic acids in the waters from Tokyo Bay and Sagami Bay showed great variation in space and time. DNA ranged from 1 to 32 μg l⁻¹, and RNA from below the detection limit to 34 μg l⁻¹. The total amount of phosphorus in nucleic acids was an important fraction (12.9 ± 8.2%) of the dissolved organic phosphorus (DOP) and showed a good correlation with DOP.     

Spring–summer cycling of DOC, DON and inorganic N in a highly seasonal system encompassing the Northeast Water Polynya, 1993

Dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and inorganic nutrient concentrations were determined in samples from an area encompassing the Northeast Water Polynya from June to August 1993. In June, still ice-covered polynya area surface waters (PySW) had significantly higher (p<0.05) DOC concentrations (110 μM, n=68) than surface water outside the polynya area (96 μM, n=6). Melting ice and ice algae are suggested as DOC sources. DOC concentrations found in this study are consistent with other studies showing higher DOC concentrations in the Arctic than in other ocean areas. As the productive season progressed, DOC concentrations in Polynya surface water (PySW) decreased (p<0.05) from 110 to 105 μM, while DON concentrations increased (p<0.05) from 5.6 to 6.1 μM, causing a significant decrease (p<0.05) in the C : N ratios of DOM from spring (C : N ratio 20) to summer (C : N ratio 17). We found a significant (p<0.05) decrease in the DOM C : N ratio in all water masses within the polynya area as the productive season progressed. DON was the largest fraction of total dissolved nitrogen (TDN) in PySW and surface waters outside the polynya area. TDN was calculated as the sum of DON, nitrate, nitrite and ammonium concentrations. DON increased (p<0.05) from 62% to 73% of TDN in PySW from spring to summer, a result of increasing DON concentrations and decreasing inorganic nitrogen concentrations over the productive season. The seasonal accumulation of DON and the corresponding decrease in nitrate concentrations in waters with primary production indicate that it is important to take the DON pool into account when estimating export production from nitrate concentration decreases in surface waters. PySW TDN concentrations decreased (p<0.05) from 9.1 (n=61) to 8.6 μM (n=60) from spring (May 25 through June 19) to summer (July 1 through July 27). The seasonal decrease in surface water TDN concentrations corresponded to increases in TDN concentrations in deeper water masses within the Polynya. Most of the TDN increase in deep water was in the form of DON. A possible explanation is that PON was dissolved (partially remineralized) in the water column at mid depths, causing increases in the DON concentration. Transfer of N from PySW (with a short residence time in the polynya area) to Polynya Intermediate Water and deep waters of the Norske and Westwind Trough with multi-year residence times keeps N from leaving the polynya area. In spring, nutrients from degradation of OM in PyIW could support primary production. The role of PyIW as an OM trap could be important in supporting primary production in the polynya area.     

Laboratory study of nitrogen and phosphorus remineralization during the decomposition of coastal plankton and seston

The decomposition of cultured marine phytoplankton (Skeletonema costatum) and natural estuarine seston from Narragansett Bay, RI, was studied at two temperatures (8°C and 18°C) in bottles containing sterile bay-water (30‰) and in bay-water with micro-organisms small enough to pass through a glass fibre filter (nominally < 1μ). About 50% of the particulate organic nitrogen (PON) and particulate phosphorus (PP) was immediately released to the water in dissolved organic forms from both types of organic matter. Comparison of changes in the dissolved organic nitrogen (DON) fraction in the sterile and non-sterile systems indicated that nearly all of the DON initially released was subsequently remineralized. Ammonification proceeded only in non-sterile bay-water. 20–25% of the PP was converted to dissolved inorganic-P (DIP) fraction after only 7 h in both sterile and non-sterile bay-water. Following autolytic releases of DON, DOP and DIP the initial rates of N and P remineralization were temperature dependent: Q₁₀ values for PON and PP decay during first phase of microbially mediated decomposition ranged from 1·3 to 6·4. Rates of remineralization then slowed so that about equal amounts of nutrients were remineralized (45–50% of the N and 57–60% of the P in the phytoplankton and 60–63% of the N and 36–60% of the P in the natural seston) after 30 days storage at either temperature. During 30 days of decomposition in non-sterile seawater the N/P ratios in the dissolved inorganic fractions converged on the ratios of total-N/total-P initially present in the bottles. Kinetic analysis of the decay of total organic-N (TON) and total organic-P (TOP) in the non-sterile systems and analysis of similar sets found in the literature showed that the initial stages of the decomposition of N and P from planktonic POM in vitro could be modelled as the sequential decay, at first-order rates, of two particulate fractions. The first, more labile, fraction comprised about 60% of the particulate N and P. First-order rate constants (−k, base e) for decomposition during the 1st and 2nd phases were 0·02 to 0·2 day⁻¹ and 0·003 to 0·02 day⁻¹, respectively. The decay rates are far too slow to account for the ‘rapid in situ recycling’ of nutrients needed to support phytoplankton production when other means of nutrient resupply (by advection, fixation, rainfall, etc.) are very low.     

Abundance, size distribution, and stable carbon and nitrogen isotopic compositions of marine organic matter isolated by tangential-flow ultrafiltration

Tangential-flow ultrafiltration was used to isolate particulate and high-molecular-weight dissolved material from seawater collected at various depths and geographic regions of the Pacific and Atlantic Oceans. Ultrafiltration proved to be a relatively fast and efficient method for the isolation of hundreds of milligrams of material. Optical and electron microscopy of the isolated materials revealed that relatively fragile materials were recovered intact. Depth-weighted results of the size distribution of organic matter in seawater indicated that ˜ 75% of marine organic carbon was low-molecular-weight (LMW) dissolved organic carbon (< 1 nm), ˜ 24% was high-molecular-weight (HMW) dissolved organic carbon (1–100 nm), and ˜ 1% was particulate organic carbon (> 100 nm). The distribution of carbon in surface water was shifted to greater relative abundances of larger size fractions, suggesting a diagenetic sequence from macromolecular material to small refractory molecules. The average C:N ratios of particulate organic matter (POM) and HMW dissolved organic matter (DOM) were 7.7 and 16.7, respectively. Differences in C:N ratios between POM and HMW DOM were large and invariant with depth and geographic region, indicating that the aggregation of HMW DOM to form POM must be of minor significance to overall carbon dynamics. The stable carbon isotope composition (δ¹³C) of POM averaged −22.7%. in surface water and −25.2%. in subsurface water. Several possible explanations for the observed isotopic shift with depth were explored, but we were unable to discern the cause. The δ¹³C of HMW DOM samples was relatively constant and averaged −21.7%., indicating a predominantly marine origin for this material. The δ¹⁵N values of POM were highly variable (5.8–15.4%.), and the availability of nitrate in surface waters appeared to be the major factor influencing δ¹⁵N values in the equatorial Pacific. In the upwelling region nitrate concentrations were relatively high and δ¹⁵N values of POM were low, whereas to the north and south of the upwelling nitrate concentrations were low and δ¹⁵N values were high. The δ¹⁵N values of HMW DOM reflected the same trends observed in the POM fraction and provided the first such evidence for biological cycling of dissolved organic nitrogen (DON). Using the observed δ¹⁵N values and an estimate of meridional advection velocity, we estimated a turnover time of 0.3 to 0.5% day⁻¹ for HMW DON. These results suggest a major role for DON in the upper ocean nitrogen cycle.     

Dissolved organic matter in the subterranean estuary of a volcanic island,Jeju: Importance of dissolved organic nitrogen fluxes to the ocean

We observed the origin, behavior, and flux of dissolved organic carbon (DOC), dissolved organic nitrogen (DON), colored dissolved organic matter (CDOM), and dissolved inorganic nitrogen (DIN) in the subterranean estuary of a volcanic island, Jeju, Korea. The sampling of surface seawater and coastal groundwater was conducted in Hwasun Bay, Jeju, in three sampling campaigns (October 2010, January 2011, and June 2011). We observed conservative mixing of these components in this subterranean environment for a salinity range from 0 to 32. The fresh groundwater was characterized by relatively high DON, DIN, and CDOM, while the marine groundwater showed relatively high DOC. The DON and DIN fluxes through submarine groundwater discharge (SGD) in the groundwater of Hwasun Bay were estimated to be 1.3 × 10⁵ and 2.9 × 10⁵ mol d^− 1, respectively. In the seawater of Hwasun Bay, the groundwater-origin DON was almost conservative while about 91% of the groundwater-origin DIN was removed perhaps due to biological production. The DON flux from the entire Jeju was estimated to be 7.9 × 10⁸ mol yr^− 1, which is comparable to some of the world's large rivers. Thus, our study highlights that DON flux through SGD is potentially important for delivery of organic nitrogen to further offshore while DIN is readily utilized by marine plankton in near-shore waters under N-limited conditions.     

Atmospherically-promoted photosynthetic activity in a well-mixed ecosystem: Significance of wet deposition events of nitrogen compounds

Wet atmospheric deposition of dissolved N, P and Si species is studied in well-mixed coastal ecosystem to evaluate its potential to stimulate photosynthetic activities in nutrient-depleted conditions. Our results show that, during spring, seawater is greatly depleted in major nutrients: Dissolved Inorganic Nitrogen (DIN), Dissolved Inorganic Phosphorus (DIP) and Silicic acid (Si), in parallel with an increase of phytoplanktonic biomass. In spring (March–May) and summer (June–September), wet atmospheric deposition is the predominant source (>60%, relative to riverine contribution) for nitrates and ammonium inputs to this N-limited coastal ecosystem. During winter (October–February), riverine inputs of DIN predominate (>80%) and are annually the most important source of DIP (>90%). This situation allows us to calculate the possibility for a significant contribution to primary production in May 2003, from atmospheric deposition (total input for DIN ≈300 kg km⁻² month⁻¹). Based on usual Redfield ratios and assuming that all of the atmospheric-derived N (AD-N) in rainwater is bioavailable for phytoplankton growth, we can estimate new production due to AD-N of 950 mg C m⁻² month⁻¹, during this period of depletion in the water column. During the same episode (May 2003), photosynthetic activity rate, considered as gross primary production, was estimated to approximately 30 300 mg C m⁻² month⁻¹. Calculation indicates that new photosynthetic activity due to wet atmospheric inputs of nitrogen could be up to 3%.     

Nutrient flux in the Rhode River: Tidal transport of microorganisms in brackish marshes

Concentrations of bacteria, chlorophyll a, and several dissolved organic compounds were determined during 11 tidal cycles throughout the year in a high and a low elevation marsh of a brackish tidal estuary. Mean bacterial concentrations were slightly higher in flooding (7·1 × 10⁶ cells ml⁻¹) than in ebbing waters (6·5 × 10⁶ cells ml⁻¹), and there were no differences between marshes. Mean chlorophyll a concentrations were 36·7 μg l⁻¹ in the low marsh and 20·4 μg l⁻¹ in the high marsh. Flux calculations, based on tidal records and measured concentrations, suggested a small net import of bacterial and algal biomass into both marshes. Over the course of individual tidal cycles, concentrations of all parameters were variable and not related to tidal stage. Heterotrophic activity measured by the uptake of ³H-thymidine, was found predominantly in the smallest particle size fractions (< 1·0 μm). Thymidine uptake was correlated with temperature (r = 0·48, P < 0·01), and bacterial productivity was estimated to be 7 to 42 μg Cl⁻¹ day⁻¹.     

Ammonium input to the sea via large sewage outfalls-Part 2: Effects of ammonium on growth and photosynthesis of southern California phytoplankton cultures

Cultures of six marine phytoplankton were grown at ammonium concentrations ranging up to 200 μg-atom NH₄---N litre⁻¹. Only the growth of dinoflagellates, Gymnodinium splendens and Gonyaulax polyedra was inhibited at the two highest concentrations used. In 3-h photosynthetic ¹⁴CO₂ uptake experiments, only Gymnodinium was inhibited at concentrations of NH₄---N greater than 100 μg-atom litre⁻¹. We conclude that the increased ammonium concentrations found near Southern California sewage outfalls would not be inhibiting to phytoplankton in the vicinity of such outfalls.     

Nutrient dynamics and seasonal succession of phytoplankton assemblages in a Southern European Estuary: Ria de Aveiro, Portugal

The spatial and temporal dynamics of dissolved inorganic nitrogen, dissolved phosphate, dissolved silica and chlorophyll a were measured seasonally at eight stations in the Ria de Aveiro. Between December 2000 and September 2001, the seasonal succession of phytoplankton assemblages, inferred after the spatial and seasonal variation of silica and of chlorophyll a concentrations, showed that diatoms (μmol Si L⁻¹) dominated from late autumn until early spring, while chlorophytes (μg Chl a L⁻¹) bloomed during late spring and summer. The Si:N:P ratios and Si concentrations indicated no seasonal depletion in dissolved silica, as in other temperate systems, possibly because of abnormal precipitation and flood events prolonging the supply of dissolved Si to the system. The Si:N:P ratios suggested P limitation at the system level. Despite the relative proportions of available nutrients, the mean phosphorus concentration (5.3 μmol L⁻¹) was above the reported half-saturation constants for P uptake by phytoplankton. Thus, in Ria de Aveiro, the seasonal succession of phytoplankton assemblages may also be dependent on the grazing capacity of the pelagic community through top-down regulation.     

Nutrient (N,P and Si) and carbon partitioning in the stratified NW Mediterranean

The distribution of nutrients and carbon in the different pools present in the three functional layers (the upper, biogenic layer, the thermocline layer, and the deeper, biolythic layer) of the stratified NW Mediterranean Sea was examined. The stoichiometry between dissolved inorganic nutrients, which had low concentrations in the surface waters, indicated a deficiency in nitrogen, relative to phosphorus, and an excess nitrogen relative to phosphorus within the thermocline, as well as a general silicate deficiency relative to both N and P, even extending to the biolythic layer. The dissolved organic matter was highly depleted in N and, particularly, in P relative to C, with average DOC/DON ratios >60 and DOC/DOP ratios >1500 in all three layers. The particulate pool was also depleted in N and P relative to C, particularly in the biolythic layer. The concentration of biogenic silica was low relative to C, N and P, indicating that diatoms were unlikely to contribute a significant fraction of the seston biomass. Most (>80%) of the organic carbon was present as dissolved organic carbon. Total organic N and P comprised 50–80% of the N and P pool in the biogenic layer, and decreased with depth to represent 10–25% of these nutrient pools in the biolythic layer. The high total N:P ratios in all three depth layers (N/P ratio >20) indicated an overall phosphorus deficiency in the system. The high P depletion of the dissolved organic matter must derive from a very rapid recycling of the P-rich molecules within DOM, and the increasing C/N ratio of DOM with depth indicates that N is also recycled faster than C in the DOM. Because of the uniform depth distribution of the total dissolved nitrogen concentration, the increase in the percent inorganic N and the decline in the percent dissolved organic N with depth indicates that there must be biological transformations between these pools, with a dominance of DON production in surface waters and remineralisation in the underlying layers, from which dissolved inorganic nitrogen is supplied back to the biogenic layer. Downward fluxes of DON and DOC were estimated at 200–250 μmol N m⁻² d⁻¹ and 1.4–2.1 mmol C m⁻² d⁻¹, respectively, while there should be little or no export of P as dissolved organic matter. The downward DON flux exceeded the diffusive DIN supply of about 145 μmol N m⁻² d⁻¹ to the biogenic layer, suggesting that allochthonous N inputs must be important in the region.     

Dissolved organic nitrogen dynamics in the North Sea: A time series analysis (1995–2005)

Dissolved organic nitrogen (DON) dynamics in the North Sea was explored by means of long-term time series of nitrogen parameters from the Dutch national monitoring program. Generally, the data quality was good with little missing data points. Different imputation methods were used to verify the robustness of the patterns against these missing data. No long-term trends in DON concentrations were found over the sampling period (1995–2005). Inter-annual variability in the different time series showed both common and station-specific behavior. The stations could be divided into two regions, based on absolute concentrations and the dominant times scales of variability. Average DON concentrations were 11 μmol l⁻¹ in the coastal region and 5 μmol l⁻¹ in the open sea. Organic fractions of total dissolved nitrogen (TDN) averaged 38 and 71% in the coastal zone and open sea, respectively, but increased over time due to decreasing dissolved inorganic nitrogen (DIN) concentrations. In both regions intra-annual variability dominated over inter-annual variability, but DON variation in the open sea was markedly shifted towards shorter time scales relative to coastal stations. In the coastal zone a consistent seasonal DON cycle existed with high values in spring–summer and low values in autumn–winter. In the open sea seasonality was weak. A marked shift in the seasonality was found at the Dogger Bank, with DON accumulation towards summer and low values in winter prior to 1999, and accumulation in spring and decline throughout summer after 1999. This study clearly shows that DON is a dynamic actor in the North Sea and should be monitored systematically to enable us to understand fully the functioning of this ecosystem.