Spatial variability of nitrogen isotope ratios of particulate material from Northwest Atlantic continental shelf waters

Human encroachment on the coastal zone has led to concern about the impact of anthropogenic nitrogen (N) on estuarine and continental shelf waters. Western North Atlantic watershed budgets suggest that the export of human-derived N from estuaries to shelf waters off the east coast of the US may be significant; however, models based on water inputs and estimates of upwelling of deepwater nutrients to surface waters of the mid-Atlantic bight indicate that estuarine N may be a relatively minor component of the overall shelf N budget. Stable N isotope ratios could provide a means to assess the relative input of anthropogenic N to shelf waters, particularly since dissolved N from human sources has elevated δ¹⁵N values (range: 7–30‰). We collected particulate material from surface shelf waters off the US east coast from 2000 to 2005 at near-shore sample sites proximal to the mouth of six estuaries and corresponding sites farther offshore. Near-shore (mean 33.7 km from estuary mouth) δ¹⁵N values ranged from 5.5 to 7.7‰ Offshore values (mean 92.4 km from estuary mouth) were consistently lower than near-shore sites (average 4.7 ± 1.0‰ versus 6.8 ± 1.1‰), suggesting different N sources to near and offshore stations. Near-shore regions are often more productive, as mean monthly chlorophyll-a concentrations from the sea-viewing wide field-of-view sensor (SeaWiFS) were significantly higher at near-shore sites near the mouth of three of the six estuaries. A mass balance using a concentration-dependent mixing model with chlorophyll-a concentrations as a surrogate for dissolved inorganic nitrogen can account for all of the nitrogen at near-shore sites south of Cape Cod with estuarine nitrogen estimated to contribute 45–85% of the nitrogen to the near-shore surface particulate material. Our results support the hypothesis that estuarine nitrogen is influencing continental shelf ecosystems, and also provide preliminary evidence of the spatial extent of its influence on shelf waters in the mid-Atlantic bight.     

Nitrogen isotope patterns in the oxygen-deficient waters of the Eastern Tropical North Pacific Ocean

We analyzed the stable nitrogen isotope composition of an extensive set of samples of particulate matter (PM) and seawater nitrate collected during October/November 1997 along the Mexican coastline from 24° to 11.5°N. At the northern and southern end of our study area, the δ¹⁵N of PM ranged between 5 and 7‰ in the upper 200 m of the water column with higher values at intermediate depths. These data are very similar to those reported from other parts of the open ocean. In the oxygen minimum zone (OMZ), we found significantly higher δ¹⁵N values for suspended particles. Furthermore, the δ¹⁵N of nitrate (NO₃) was elevated within the OMZ and we found a strong relationship between the oxygen concentration, nitrate deficit and the ¹⁵N content of the nitrate. The core of the OMZ between 22°N, 105°W and 15°N, 110°W coincided with higher nitrate deficits and δ¹⁵N values relative to the stations near the boundaries. The δ¹⁵N of nitrate was highest, with values up to 18.7‰, where oxygen concentrations were below 1–2 μmol/l. This pattern is consistent with an overall nitrogen isotopic enrichment factor of 22.5‰ for denitrification in the core of the OMZ using the Rayleigh equation (closed-system approach). Results from a diffusion model (open-system approach), however, gave a fractionation factor of 30±7.5‰, implying that the Rayleigh formula only gives a lower estimate of the fractionation factor ε. The vertical flux of particles collected in short-term deployments (ca. 35 h) of a drifting sediment trap was not significantly correlated with the water column nitrate deficit. The isotopic signature of the nitrate within the gradient is very similar to the δ¹⁵N value of sedimenting particles, suggesting that there might be a strong link between the production and sedimentation of particles. Upward flux of nitrate across the thermocline can account for less than half of the particle flux leaving the mixed layer. Mixing and transport of nitrate across the lower boundary of the OMZ can lead to significant enrichment in the ¹⁵N content of deep waters, and our isotopic data imply that at least 14% of the nitrate in the waters below the OMZ originates from this source.     

Seasonal variability of δ15N in sinking particles in the Benguela upwelling region

Temporal changes in δ¹⁵N values of sinking particles collected with sediment traps in the Benguela upwelling regime off southwest Africa mirrored variations in the input of inorganic nitrogen to the surface water. Reductions in δ¹⁵N (to as low as 2.5‰) corresponded to low sea surface temperatures during austral spring and late austral autumn/early winter, indicating increased nitrate availability due to the presence of recently upwelled water. High particulate fluxes accompanied the low δ¹⁵N values and sea surface temperatures, reflecting increased productivity, fueled by the upwelled nutrients. High δ¹⁵N values (up to 13.1‰) coincided with high sea surface temperatures and low particle fluxes. In this area, the seaward extension of upwelling filaments, which usually occurs twice yearly, brings nutrient-rich water to the euphotic zone and leads to elevated productivity and relatively lower δ¹⁵N values of the particulate nitrogen. Satellite images of ocean chlorophyll show that productivity variations coincide with δ¹⁵N changes. The observed isotopic pattern does not appear to have been caused by variations in the species composition of the phytoplankton assemblage. Calculations based on δ¹⁵N of the sinking particulate nitrogen show that the surface nitrate pool was more depleted during late austral summer/early fall and mid-winter and that supply exceeded demand during the intense spring bloom and in late austral fall. The main uncertainty associated with these estimates is the effect of diagenesis on δ¹⁵N and possible variability in preservation of the isotope signal between periods of high and low particle flux.     

Nitrogen isotopic composition of sinking particles from the southern Bay of Bengal: Evidence for variable nitrogen sources

An 8-year record of N fluxes and δ¹⁵N of sinking particles from the deep southern Bay of Bengal, northern Indian Ocean, is presented. Fluxes and δ¹⁵N vary between ∼0.1 and 3 mg m⁻² day⁻¹ and ∼2‰ and 8‰, respectively. The seasonal variation is determined mainly by oceanographic processes coupled to the Indian monsoon system. The annual pattern of δ¹⁵N is characterized by minima during spring intermonsoon (∼March–May), when nutrient inputs to the euphotic zone should be low because of stratification, and lighter nitrate/particulate matter is expected to be advected from the central Bay. Highest δ¹⁵N are associated with peak fluxes during southwest monsoon (∼June–September), when the southern Bay comes under the influence of the SW monsoon current, which appears to advect particulate matter with distinctly higher δ¹⁵N. The impact of this process, however, varies interannually under the influence of factors such as ENSO and the Indian Dipole Mode. Weakened advection leads to relatively low N fluxes and reduced δ¹⁵N. The data highlight the necessity of multi-annual studies to comprehend the natural variability of a system.     

Biogeochemical studies on the transport of organic matter along the Otsuchi River watershed,Japan

The distributions and stable isotope ratios of biogenic nitrogen and carbon were investigated in detail along a small watershed in order to establish a biogeochemical framework for assessing the fate of organic matter. Forest ecosystems supply soluble and particulate materials to river systems which are depleted in ¹⁵N and ¹³C. The number of suspended particles and the concentrations of δ¹⁵N and δ¹³C in the river sediments increased along the watershed, indicating a change from river to marine ecosystems. Dramatic variation of δ¹⁵N and δ¹³C were observed in the intertidal sediments, where the progress of denitrification, discharge of domestic sewage, and the accumulation and the decomposition of macroalgae and seagrasses took place.The contribution of land-derived organic matter to estuarine sediments has been estimated from δ¹³C and from δ¹⁵N data. The contribution the landderived organo-silty-clay mineral was 70–100% in the inner bay sediments and 34–42% at the open bay. Possible factors that influence the variation of stable isotope ratios along the watershed are discussed. The relationship between the sizes of particles and isotope ratios clearly demonstrated that organo-silty-clay minerals with diameter smaller than 64 μm were the major source of land-derived refractory organics.     

Sources of δ15N variability in sinking particulate nitrogen in the Cariaco Basin,Venezuela

Ten years of monthly observations of the δ¹⁵N of sinking particulate nitrogen (δ¹⁵N–PN (in ‰ versus atmospheric N₂)=[(¹⁵N/¹⁴N)_sample/(¹⁵N/¹⁴N)_standard)−1]1000) in the Cariaco Basin, Venezuela, confirm that the basin's bottom sediments store information about nitrogen dynamics related to seasonal and interannual variability in regional surface ocean processes. During the upwelling period of the southern Caribbean Sea (February–April), the δ¹⁵N–PN is similar to that of the thermocline nitrate (∼3.5‰). This nitrate is imported into the Cariaco Basin with Subtropical Underwater (SUW), which wells up near the coast. Thus, particles generated by phytoplankton photosynthesis during this productive period bear a sub-tropical North Atlantic isotopic imprint of N₂ fixation (low compared to the global average of nitrate δ¹⁵N≈5‰). During the non-upwelling period when surface waters are stratified (September–November), the δ¹⁵N–PN is also 3.5–4.0‰, and reflects a mixture of local N₂ fixation within the mixed layer, inputs of terrigenous organic matter and SUW nitrate consumption by phytoplankton below the mixed layer, which most likely exerts the strongest control on the δ¹⁵N–PN signal during this time. In the transition periods of May–July and December–January, the δ¹⁵N–PN increases to 4.5–6.5‰. This coincides with maxima of continental material fluxes (terrestrial PON δ¹⁵N is >6‰) into the Cariaco Basin. The δ¹⁵N signal in the sediments of the Cariaco Basin thus provides information about the relative strength of the local coastal upwelling, the relative input of continental material via river runoff, and local N₂ fixation. The findings contribute to interpretations of the basin's paleoclimatic nitrogen cycle variations based on observations of the sedimentary δ¹⁵N record at this location.     

Fluxes and sources of suspended organic matter in an estuarine turbidity maximum region during low discharge conditions

Water column concentrations of total suspended solids (TSS), particulate organic carbon (POC) and particulate nitrogen (PN) were measured at three different depths in four different locations bracketing the estuarine turbidity maximum (ETM) along the main channel of a temperate riverine estuary (Winyah Bay, South Carolina, USA). Measurements were carried out over full tidal cycle (over 24 h). Salinity, temperature, current magnitude and direction were also monitored at the same time throughout the water column. Tidally averaged net fluxes of salt, TSS, POC and PN were calculated by combining the current measurements with the concentration data. Under the extreme low river discharge conditions that characterized the study period, net landward fluxes of salt were measured in the lower part of the study area, suggesting that the landward transport through the main channel of the estuary was probably balanced by export out through the sides. In contrast, the net fluxes of salt in the upper reaches of the study area were near zero, indicating a closed salt balance in this part of the estuary. In contrast to salt, the net fluxes of TSS, POC and PN in the deeper parts of the water column were consistently landward at all four sites in Winyah Bay indicating the non-conservative behavior of particulate components and their active transport up the estuary in the region around the ETM.The carbon contents (%POC), carbon:nitrogen ratios (org[C:N]a) and stable carbon isotopic compositions (δ¹³C_POC) of the suspended particles varied significantly with depth, location and tidal stage. Tidally averaged compositions showed a significant increase up the estuary in the %POC and org[C:N]a values of suspended particles consistent with the preferential landward transport of carbon-rich particles with higher vascular plant debris content. The combination of tidal resuspension and flood-dominated flow appeared to be responsible for the hydrodynamic sorting of particles along the estuary that resulted in denser, organic-poor particles being transported landward less efficiently. The elemental and isotopic compositions indicated that vascular C₃ plants and estuarine algae were the major sources of the particulate organic matter of all the samples, without any significant contributions from salt marsh C₄ vegetation (Spartina alterniflora) and/or marine phytoplankton.     

Variability in the fractionation of stable isotopes during degradation of two intertidal red algae

Macroalgae contribute to intertidal food webs primarily as detritus, with unclear implications for food web studies using stable isotope analysis. We examined differences in the thallus parts of two South African rhodophytes (Gelidium pristoides and Hypnea spicifera) and changes in overall δ¹³C, δ¹⁵N signatures and C:N ratios during degradation in both the field and laboratory. We hypothesized that both degrading macroalgal tissue and macroalgal-derived suspended particulate material (SPM) would show negligible changes in δ¹³C, but enriched δ¹⁵N signatures and lower C:N ratios relative to healthy plants. Only C:N laboratory ratios conformed to predictions, with both species of macroalgae showing decomposition related changes in δ¹³C and significant depletions in δ¹⁵N in both the field and laboratory. In the laboratory, algal tissue and SPM from each species behaved similarly (though some effects were non-significant) but with differing strengths. Gelidium pristoides δ¹³C increased and C:N ratios decreased over time in tissue and SPM; δ¹⁵N became depleted only in SPM. Hypnea spicifera, δ¹³C, δ¹⁵N and C:N ratios all decreased during degradation in both SPM and algae.     

Typhoon-induced precipitation impact on nutrient and suspended matter dynamics of a tropical estuary affected by human activities in Hainan,China

Typhoons regularly hit the coasts along the northern South China Sea during summer monsoon. However, little is known on the effects of typhoon-related heavy precipitation on estuarine dynamics and coastal ecosystems. We analyzed physico-chemical characteristics, and concentrations and composition of dissolved and suspended matter in the Wenchang/Wenjiao Estuary (WWE) on the tropical island of Hainan, China, prior to and after typhoon Kammuri in August 2008. Before the typhoon, the estuary displayed vertical and horizontal gradients. High nutrient inputs from agriculture and widespread aquaculture were to a large extent converted into biomass inside the estuarine lagoon resulting in low export of nutrients to coastal waters and a mainly autochthonous origin of total suspended matter (TSM). Heavy typhoon-associated precipitation increased river runoff, which moved the location of the estuarine salinity gradient seaward. It resulted in an export of dissolved and particulate matter to coastal waters one day after the typhoon. Dissolved nutrients increased by up to an order of magnitude and TSM increased approximately twofold compared to pre-typhoon values. Lower δ¹³C_org and δ¹⁵N and elevated C/N ratios of TSM together with lower chlorophyll a (chl a) concentrations indicated an increased contribution of terrestrial material originating from typhoon-induced soil erosion. Local uptake of excess nutrients inside the lagoon was inhibited because of reduced water transparency and the lack of phytoplankton, which had been washed out by the initial freshwater pulse. Two weeks after the typhoon, TSM concentration and composition had almost returned to pre-typhoon conditions. However, physico-chemical properties and nutrients were still different from pre-typhoon conditions indicating that the estuarine system had not fully recovered. Unusually high chl a concentrations in the coastal zone indicated a phytoplankton bloom resulting from the typhoon-induced nutrient export. The typhoon-induced flushing of the WWE resulted in hyposalinity, reduced water transparency, siltation, as well as temporary eutrophication of coastal waters. These are physiological stressors, which are known to impair the performance of adjacent seagrass meadows and coral reefs. The predicted increase in typhoon frequency and intensity will lead to a frequently recurring exposure of coastal ecosystems to these threats, particularly in the South China Sea region where aquaculture is widespread and tropical cyclone frequency is at a maximum.     

Trophic relationships along a bathymetric gradient at the deep-sea observatory HAUSGARTEN

Deep-seafloor communities, especially those from the ice-covered Arctic, are subject to severe food limitation as the amount of particulate organic matter (POM) from the surface is attenuated with increasing depth. Here, we use naturally occurring stable isotope tracers (δ¹⁵N) to broaden our rudimentary knowledge of food web structure and the response of benthic organisms to decreasing food supplies along the bathymetric transect (～1300–5600 m water depth) of the deep-sea observatory HAUSGARTEN. Encompassing five trophic levels, the HAUSGARTEN food web is among the longest indicating continuous recycling of organic material typical of food-limited deep-sea ecosystems. The δ¹⁵N signatures ranged from 3.0‰ for Foraminifera to 21.4‰ (±0.4) for starfish (Poraniomorpha tumida). The majority of organisms occupied the second and third trophic level. Demersal fish fed at the third trophic level, consistent with results from stomach contents analysis. There were significant differences in the δ¹⁵N signatures of different functional groups with highest δ¹⁵N values in predators/scavengers (13.2±0.2‰) followed by suspension feeders (11.2±0.2‰) and deposit feeders (10.2±0.3‰). Depth (=increasing food limitation) affected functional groups in different ways. While the isotopic signatures of predators/scavengers did not change, those of suspension feeders increased with depth, and the reverse was found for deposit feeders. In contrast to the results of other studies, the δ¹⁵N signatures in POM samples obtained below 800 m did not vary significantly with depth indicating that changes in δ¹⁵N values are unlikely to be responsible for the depth-related δ¹⁵N signature changes observed for benthic consumers. However, the δ¹⁵N signatures of sediments decreased with increasing depth, which also explains the decrease found for deposit feeders. Suspension feeders may rely increasingly on particles trickling down the HAUSGARTEN slope and carrying higher δ¹⁵N signatures than the decreasing POM supplies, which elevates the δ¹⁵N value of their tissues. Our results imply that a depth-stratified approach should be taken to avoid a misinterpretation of data obtained at different depths.     

Calibration of sediment traps and particulate organic carbon export using 234Th in the Barents Sea

Profiles of particulate and dissolved ²³⁴Th (t_1/2=24.1 days) in seawater and particulate ²³⁴Th collected in drifting traps were analyzed in the Barents Sea at five stations during the ALV3 cruise (from June 28 to July 12, 1999) along a transect from 78°15′N–34°09′E to 73°49′N–31°43′E. ²³⁴Th/²³⁸U disequilibrium was observed at all locations. ²³⁴Th data measured in suspended and trapped particles were used to calibrate the catchment efficiency of the sediment traps. Model-derived ²³⁴Th fluxes were similar to ²³⁴Th fluxes measured in sediment traps based on a steady-state ²³⁴Th model. This suggests that the sediment traps were not subject to large trapping efficiency problems (collection efficiency ranges from 70% to 100% for four traps). The export flux of particulate organic carbon (POC) can be calculated from the model-derived export flux of ²³⁴Th and the POC/²³⁴Th ratio. POC/²³⁴Th ratios measured in suspended and trapped particles were very different (52.0±9.9 and 5.3±2.2 μmol dpm⁻¹, respectively). The agreement between calculated and measured POC fluxes when the POC/²³⁴Th ratio of trapped particles was used confirms that the POC/²³⁴Th ratio in trap particles is representative of sinking particles. Large discrepancies were observed between calculated and measured POC fluxes when the POC/²³⁴Th ratio of suspended particles was used. In the Barents Sea, vertical POC fluxes are higher than POC fluxes estimated in the central Arctic Ocean and the Beaufort Sea and lower than those calculated in the Northeast Water Polynya and the Chukchi Sea. We suggest that the latter fluxes may have been strongly overestimated, because they were based on high POC/²³⁴Th ratios measured on suspended particles. It seems that POC fluxes cannot be reliably derived from thorium budgets without measuring the POC/²³⁴Th ratio of sediment trap material or of large filtered particles.     

Seasonal variations in the nitrogen isotopic composition of settling particles at station K2 in the western subarctic North Pacific

Intensive observations using hydrographical cruises and moored sediment trap deployments during 2010 and 2012 at station K2 in the North Pacific Western Subarctic Gyre (WSG) revealed seasonal changes in δ ¹⁵N of both suspended and settling particles. Suspended particles (SUS) were collected from depths between the surface and 200 m; settling particles by drifting sediment traps (DST; 100–200 m) and moored sediment traps (MST; 200 and 500 m). All particles showed higher δ ¹⁵N values in winter and lower in summer, contrary to the expected by isotopic fractionation during phytoplankton nitrate consumption. We suggest that these observed isotopic patterns are due to ammonium consumption via light-controlled nitrification, which could induce variations in δ ¹⁵N(SUS) of 0.4–3.1 ‰ in the euphotic zone (EZ). The δ ¹⁵N(SUS) signature was reflected by δ ¹⁵N(DST) despite modifications during biogenic transformation from suspended particles in the EZ. δ ¹⁵N enrichment (average: 3.6 ‰) and the increase in C:N ratio (by 1.6) in settling particles suggests year-round contributions of metabolites from herbivorous zooplankton as well as TEPs produced by diatoms. Accordingly, seasonal δ ¹⁵N(DST) variations of 2.4–7.0 ‰ showed a significant correlation with primary productivity (PP) at K2. By applying the observed δ ¹⁵N(DST) vs. PP regression to δ ¹⁵N(MST) of 1.9–8.0 ‰, we constructed the first annual time-series of PP changes in the WSG. This new approach to estimate productivity can be a powerful tool for further understanding of the biological pump in the WSG, even though its validity needs to be examined carefully.     

Carbon and nitrogen stable isotope analysis of three types of oyster tissue in an impacted estuary

The stable isotope ratios of carbon (δ¹³C) and nitrogen (δ¹⁵N) of the muscle, ctenidia and viscera of the Sydney rock oyster, Saccostrea glomerata, showed the dilution and assimilation of tertiary treated sewage along an estuarine gradient. The enriched ¹⁵N values of oyster ctenidia and viscera from within 50 m of the sewage outfall indicated the use of ¹⁵N-enriched tertiary treated sewage effluent (16 ± 2.3‰) as a nutrient source. The effect of sewage nitrogen on oyster δ¹⁵N was localised, with oysters 5 km upstream and downstream of the outfall not significantly enriched. Viscera δ¹⁵N was most sensitive to sewage nutrients and δ¹³C significantly defined an ocean-to-estuarine gradient. High variance in isotope ratios of viscera compromised its use as an indicator of anthropogenic nutrients, and this also reduced the utility of whole-body stable isotope ratios. Ctenidia was the most useful indicator tissue of sewage discharge at the scale of this study, being consistently and significantly enriched in δ¹⁵N close to the sewage outfall and δ¹³C clearly defined an estuarine gradient with less internal variability than viscera. Muscle δ¹⁵N was least sensitive to sewage effluent and showed the least variability, making it more suited to investigations of anthropogenic nutrient enrichment over larger spatio-temporal scales.     

Origin and decomposition of sinking particulate organic matter in the deep water column inferred from the vertical distributions of its δN, δ and δ

Sinking particles were analyzed for their nitrogen isotopic ratio δ¹⁵N) of total particulate nitrogen (PN), stable carbon isotopic ratio (δ¹³C) and radioactive isotopic ratio (δ¹⁴C) of total particulate organic carbon (POC), at three different latitudinal (temperate, subpolar and equatorial) and geomorphological (trench, proximal abyssal plain and distal abyssal plain) sites in the western North Pacific Ocean using year-long time series sediment trap systems, to clarify the common vertical trends of the isotopic signals in deep water columns. Although the δ¹⁵N and δ¹³C values of sinking particulate organic matter (POM) were partly affected by the resuspension of sedimentary POM from the sea floor, especially in the trench, the changes in δ¹⁵N and δ¹³C values owing to the resuspension could be corrected by calculation of the isotopic mass balance from δ¹⁴C of sinking POC. After this correction, common downward decreasing trends in δ¹⁵N and δ¹³C values were obtained in the deep water columns, irrespective of the latitudes and depths. These coincidental isotopic signals between δ¹⁵N and δ¹³C values provide new constraints for the decomposition process of sinking POM, such as the preferential degradation of ¹⁵N- and ¹³C-rich compounds and the successive re-formation of the sinking particles by higher trophic level organisms in the deep water column.     

Origin and decomposition of sinking particulate organic matter in the deep water column inferred from the vertical distributions of its δN, δ and δ

Sinking particles were analyzed for their nitrogen isotopic ratio δ¹⁵N) of total particulate nitrogen (PN), stable carbon isotopic ratio (δ¹³C) and radioactive isotopic ratio (δ¹⁴C) of total particulate organic carbon (POC), at three different latitudinal (temperate, subpolar and equatorial) and geomorphological (trench, proximal abyssal plain and distal abyssal plain) sites in the western North Pacific Ocean using year-long time series sediment trap systems, to clarify the common vertical trends of the isotopic signals in deep water columns. Although the δ¹⁵N and δ¹³C values of sinking particulate organic matter (POM) were partly affected by the resuspension of sedimentary POM from the sea floor, especially in the trench, the changes in δ¹⁵N and δ¹³C values owing to the resuspension could be corrected by calculation of the isotopic mass balance from δ¹⁴C of sinking POC. After this correction, common downward decreasing trends in δ¹⁵N and δ¹³C values were obtained in the deep water columns, irrespective of the latitudes and depths. These coincidental isotopic signals between δ¹⁵N and δ¹³C values provide new constraints for the decomposition process of sinking POM, such as the preferential degradation of ¹⁵N- and ¹³C-rich compounds and the successive re-formation of the sinking particles by higher trophic level organisms in the deep water column.     

Carbon and nitrogen stable isotopes in suspended matter and sediments from the Schelde Estuary

The C/N and stable C and N isotope ratios (δ¹³C, δ¹⁵N) of sedimentary and suspended particulate matter were determined in the Schelde Estuary. Suspended matter was divided into 2 to 5 size fractions by centrifugation. Four major pools of organic matter were recognized: riverine, estuarine, marine and terrestrial materials. Terrestrial organic matter (δ¹³C≈−26‰, δ¹⁵N≈3.5‰, C/N≈21) is important for the sedimentary pool, but suspended matter is dominated by the marine (δ¹³C≈−18‰, δ¹⁵N≈9‰, C/N≈8), riverine (δ¹³C≈−30‰, δ¹⁵N≈9‰, C/N≈7.5) and estuarine (δ¹³C≈−29‰, δ¹⁵N≈15‰, C/N≈8) end-members. In the upper estuary, the suspended matter size fractions vary systematically in their carbon and nitrogen biogeochemistry, with the small particles having low C/N ratios, depleted δ¹³C and enriched δ¹⁵N values relative to large particles. Moreover, sedimentary and suspended matter differ significantly in terms of C/N ratios (17 vs. 8.9), δ¹³C (−26.3 vs. −28.9‰) and δ¹⁵N (+6.9 vs. 12.0‰). In the lower estuary, suspended matter fractions are similar and sedimentary and suspended organic matter differ only in terms of δ¹³C (−23.5 vs. −20.1‰). Our data indicate that autochthonous organic matter contributes significantly to the total suspended matter and that the suspended organic matter composition cannot be explained in terms of conservative mixing of riverine and terrestrial sources on the one hand and marine sources on the other hand.     

Pelagic nitrogen dynamics in the Vietnamese upwelling area according to stable nitrogen and carbon isotope data

Upwelling and nitrogen (N) fixation provide new N for primary production off southern central Vietnam. Here we evaluate the roles of both N sources for zooplankton nutrition by comparing δ¹⁵N and δ¹³C values in nitrate, particulate organic matter (POM), and six net-plankton size fractions from monsoon and intermonsoon seasons. The δ¹³C values in POM and the net-plankton size fractions differed by 2–4‰ at any time. We assume that plankton from the POM filters was dominated by nano-and picoplankton as opposed to micro- and mesoplankton in the net-samples. The implications of this are discussed in terms of size differential pathways of C and N in the planktonic food web. We used δ¹⁵N to estimate the differences in N nutrition between the actual upwelling region and the oligotrophic area further offshore. The δ¹⁵N values of the net-plankton size fractions were depleted in δ¹⁵N by ca. 2‰ outside compared to inside the upwelling area during the monsoon season. We attribute these patterns to the additional utilization of N derived from N fixation. The concomitant findings of high N fixation rates reported earlier and low subthermocline nitrate (nitrate_sub) values of 2.9–3.6‰ support this conclusion. Net-plankton δ¹⁵N values increased with size, pointing to the dominance of higher trophic levels in the larger size fractions. According to a two source mixing model N fixation may have provided up to 13% of the N demand in higher trophic levels.     

Seasonal and decadal shifts in particulate organic matter processing and sedimentation in the Bering Strait Shelf region

We present data on the quality and quantity of particulate organic material deposited to the benthos in the Chukchi Sea. This analysis is undertaken by using ⁷Be, a short-lived radiotracer, which is associated with particle deposition, the stable carbon isotopic composition of organic material and its C/N ratio in the water column and within the sediments, and the inventories of chlorophyll a present in surface sediments. Using previously published data, we show that sedimentation processes in the regional Bering Strait ecosystem may have shifted in the past decade. Surface sediments collected in 2004 adjacent to the Russian coastline in the Chukchi Sea are less refractory in terms of carbon isotope ratios and C/N ratios than was observed for surface sediments at similar locations in 1995 and 1988. Based upon sediment ⁷Be and chlorophyll a inventories, short-term sedimentation on the shelf occurs immediately north of Bering Strait, and within and downstream of Barrow and Herald Canyons. Seasonal differences (i.e., ice-covered versus open-water conditions) in the quality of particulate organic carbon reaching the benthos appear to be small in the most productive waters, such as Barrow Canyon. However, in less productive waters, C/N ratios and δ¹³C values show seasonal variations. Once on the bottom, δ¹³C values in the organic fractions of the sediments are less negative than observed in settling material in the water column, which is commonly thought to result from biological processing within the sediments.     

Stable C and N isotopic composition of sinking particles and zooplankton over the southeastern Bering Sea shelf

Stable carbon and nitrogen isotopic composition of zooplankton, suspended particulate organic matter (SPOM), and sinking particles collected using sediment traps were measured for samples obtained from the southeastern Bering Sea middle and outer shelf during 1997–1999. The quantity of material collected by the middle shelf sediment trap was greater in both spring and late summer and fall than in early and mid-summer. The δ¹⁵N of SPOM, sinking material and zooplankton showed greater inter-annual variability at the middle shelf site (M2) than at the outer shelf site (M3). Zooplankton and sinking organic matter collected by M2 sediment traps became more depleted in ¹⁵N from 1997 through 1999, associated with a change from unusually warm to unusually cold conditions. Suspended and sinking organic matter and zooplankton collected from M3 decreased only slightly in δ¹⁵N from 1998 to 1999. SPOM, zooplankton, and sediment trap samples collected at M2 were usually enriched in δ¹⁵N and δ¹³C over those from M3. However, in 1999 sediment trap samples from the middle shelf were enriched in ¹³C over M3 material, but the δ¹⁵N of samples from the two sites was similar. The geographic pattern could be explained greater productivity over the middle shelf, associated with either isotopically heavy nitrogen being regenerated from sediments, or with utilization of a greater fraction of the available inorganic nitrogen pool during most years.     

Stable isotope constraints on the nitrogen cycle of the Mediterranean Sea water column

We used the nitrogen isotope ratio of algae, suspended particles and nitrate in the water column to track spatial variations in the marine nitrogen cycle in the Mediterranean Sea. Surface PON (5–74 m) was more depleted in ¹⁵N in the eastern basin (−0.3±0.5‰) than in the western basin (+2.4±1.4‰), suggesting that nitrogen supplied by biological N₂ fixation may be an important source of new nitrogen in the eastern basin, where preformed nitrate from the Atlantic Ocean could have been depleted during its transit eastward. The δ¹⁵N of nitrate in the deep Mediterranean (∼3‰ in the western-most Mediterranean and decreasing toward the east) is significantly lower than nitrate at similar depths from the North Atlantic (4.8–5‰), also suggesting an important role for N₂ fixation. The eastward decrease in the δ¹⁵N of surface PON is greater than the eastward decrease in the δ¹⁵N of the subsurface nitrate, implying that the amount of N₂ fixation in the eastern Mediterranean is great enough to cause a major divergence in the δ¹⁵N of phytoplankton biomass from the δ¹⁵N of the nitrate upwelled from below. Variations in productivity associated with frontal processes, including shoaling of the nitracline, did not lead to detectable variations in the δ¹⁵N of PON. This indicates that no differential fertilization or productivity gradient occurred in the Almerian/Oran area. Our results are consistent with a lack of gradient in chlorophyll-a (chl-a) and nitrate concentration in the Alboran Sea. ¹⁵N enrichment in particles below 500 m depth was detected in the Alboran Sea with respect to surface PON, reaching an average value of +7.4±0.7‰. The δ¹⁵N in sinking particles caught at 100 m depth (4.9–5.6‰) was intermediate between suspended surface and suspended deep particles. We found a consistent difference in the isotopic composition of nitrogen in PON compared with that of chlorophyll (Δδ¹⁵N[PON-chlorin]=+6.4±1.4‰) in the surface, similar to the offset reported earlier in cultures for cellular N and chl-a. This indicates that δ¹⁵N of phytoplankton biomass was retained in surface PON, and that alteration of the isotopic signal of PON at depth was due to heterotrophic activity.