Isotopic variation of fishes in freshwater and estuarine zones of a large subtropical coastal lagoon

We used stable C and N isotope ratios of tissues from 29 fish species from a large subtropical lagoon in southern Brazil to examine spatial variability in isotopic composition and vertical trophic structure across freshwater and estuarine habitats. Nitrogen isotope ratios indicated a smooth gradation in trophic positions among species, with most fishes occupying the secondary and tertiary consumer level. Fish assemblages showed a significant shift in their carbon isotopic signatures between freshwater and estuarine sites. Depleted carbon signatures (from −24.7‰ to −17.8‰) were found in freshwater, whereas more enriched signatures (from −19.1‰ to −12.3‰) were obtained within the estuarine zone downstream. Based on our survey of the C₃ and C₄ plants and isotopic values for phytoplankton and benthic microalgae reported for ecosystems elsewhere, we hypothesized that the observed δ¹³C differences in the fish assemblage between freshwater and estuarine sites is due to a shift from assimilating organic matter ultimately derived from C₃ freshwater marsh vegetation and phytoplankton at the freshwater site (δ¹³C ranging from −25‰ to −19‰), to C₄ salt-marsh (e.g. Spartina) and widgeon grass (Ruppia maritima), benthic microalgae and marine phytoplankton at the estuarine sites (from −18‰ to −12‰). Our results suggested that fish assemblages are generally supported by autochthonous primary production. Freshwater fishes that likely were displaced downstream into the estuary during periods of high freshwater discharge had depleted δ¹³C values that were characteristic of the upper lagoon. These results suggest that spatial foodweb subsidies can occur within the lagoon.     

Microscale gradients of planktonic microbial communities above the sediment surface in a mangrove estuary

The microscale (1 and 4 cm sampling resolution) distributions of chemical (O₂, NH₃, NO₃⁻, NO₂⁻, PO₄³⁻) and biological (Chl a, phytoplankton, bacterioplankton, viruses) parameters were measured in the 16 cm of water immediately overlaying the sediment-water interface (SWI) within a temperate mangrove estuary in South Australia during December 2003 and March 2004. Shear velocities (u_*) during the time of sampling were very low (<0.1 cm s⁻¹), and we consequently predict that resuspension of organisms and materials was negligible. In December 2003, profiles were often characterised by strong gradients in nutrients and organisms, with the highest concentrations often observed within 0.5 cm of the SWI. Microscale patterns in O₂, NH₃, NO₃⁻ and NO₂⁻ indicated that a variety of anaerobic and aerobic transformation processes probably occurred at the SWI and within profiles. Strong gradients in PO₄³⁻ were indicative of nutrient flux across the SWI as a consequence of degradation processes in the sediments. Pico- and nanophytoplankton concentrations were strongly correlated (p < 0.01) to PO₄³⁻, and exhibited 12- and 68-fold changes in abundance, respectively, with highest concentrations observed nearest to the SWI. Several bacterial subpopulations were discriminated using flow cytometry and significant shifts in the ‘cytometric structure’ of the bacterial community were observed within microscale profiles. Two populations of viruses were correlated to the phytoplankton and low DNA (LDNA) bacteria, and each exhibited elevated concentrations within 0.5 cm of the SWI. In March 2004, microscale distributions of O₂ and nutrients were more homogenous than in December 2003, and dissimilar microbial community structure and patterns were observed above the SWI. The patterns observed here support the prediction that benthic processes can strongly influence the ecology of planktonic communities in the overlaying water, and provide further evidence for the existence of microscale variability amongst communities of aquatic microorganisms.     

Short-term variability of fCO2 in seawater and air–sea CO2 fluxes in a coastal upwelling system (Ría de Vigo, NW Spain)

Coastal upwelling systems are regions with highly variable physical processes and very high rates of primary production and very little is known about the effect of these factors on the short-term variations of CO₂ fugacity in seawater (fCO₂^w). This paper presents the effect of short-term variability (<1 week) of upwelling–downwelling events on CO₂ fugacity in seawater (fCO₂^w), oxygen, temperature and salinity fields in the Ría de Vigo (a coastal upwelling ecosystem). The magnitude of fCO₂^w values is physically and biologically modulated and ranges from 285 μatm in July to 615 μatm in October. There is a sharp gradient in fCO₂^w between the inner and the outer zone of the Ría during almost all the sampling dates, with a landward increase in fCO₂^w.CO₂ fluxes calculated from local wind speed and air–sea fCO₂ differences indicate that the inner zone is a sink for atmospheric CO₂ in December only (−0.30 mmol m⁻² day⁻¹). The middle zone absorbs CO₂ in December and July (−0.05 and −0.27 mmol·m⁻² day⁻¹, respectively). The oceanic zone only emits CO₂ in October (0.36 mmol·m⁻² day⁻¹) and absorbs at the highest rate in December (−1.53 mmol·m⁻² day⁻¹).     

Benzo[a]pyrene-dione-stimulated oxyradical production by microsomes of digestive gland of the common mussel, Mytilus edulis L

The potential of benzo[ a]pyrene (BaP) quinones (diones) to stimulate NAD(P)H-dependent hydroxyl radical (·OH) production (2-keto-4-methiolbutyric acid (KMBA) oxidation) by digestive gland microsomes of M. edulis was studied using iron/EDTA as a promotor of the Haber-Weiss reaction (O₂⁻ + H₂O₂ = ·OH + OH⁻ + O₂). Stimulation of basal rates of KMBA oxidation was observed for all three diones. Stimulation was similar for the 1,6- and 3,6-diones, but much less for the 6,12-dione, and greater for the NADH than the NADPH-dependent reaction, viz. % increases of 78 to 333 (NADH) compared to 0 to 78 (NADPH). Maximal KMBA oxidation was obtained at dione concentrations of 12.5 to 50 μm. Inhibition of KMBA oxidation by Superoxide dismutase and catalase indicated the involvement of respectively Superoxide anion radical (O₂⁻) and hydrogen peroxide (H₂O₂) in 1,6-dione stimulated NADPH-dependent · OH formation. The apparent K_m values of xenobiotic-stimulated KMBA oxidation were lower for BaP-diones than for the model redox cycling quinone menadione (2-methyl-1,4-naphthoquinone), viz. in μm, 0.6 to 14.6 (NADH) and 4.4 to 28.5 (NADPH) compared to 315 to 457 (NADH) and 72 to 103 (NADPH). The results are consistent with metabolism of BaP to diones and resultant enhanced generation of oxyradicals being a potential mechanism of pollutant-mediated toxicity in molluscs.     

Effects of irradiance on benthic and water column processes in a Gulf of Mexico estuary: Pensacola Bay, Florida, USA

We examined the effect of light on water column and benthic fluxes in the Pensacola Bay estuary, a river-dominated system in the northeastern Gulf of Mexico. Measurements were made during the summers of 2003 and 2004 on 16 dates distributed along depth and salinity gradients. Dissolved oxygen fluxes were measured on replicate sediment and water column samples exposed to a gradient of photosynthetically active radiation. Sediment inorganic nutrient (NH₄⁺, NO₃⁻, PO₄³⁻) fluxes were measured. The response of dissolved oxygen fluxes to variation in light was fit to a photosynthesis–irradiance model and the parameter estimates were used to calculate daily integrated production in the water column and the benthos. The results suggest that shoal environments supported substantial benthic productivity, averaging 13.6 ± 4.7 mmol O₂ m⁻² d⁻¹, whereas channel environments supported low benthic productivity, averaging 0.5 ± 0.3 mmol O₂ m⁻² d⁻¹ (±SE). Estimates of baywide microphytobenthic productivity ranged from 8.1 to 16.5 mmol O₂ m⁻² d⁻¹, comprising about 16–32% of total system productivity. Benthic and water column dark respiration averaged 15.2 ± 3.2 and 33.6 ± 3.7 mmol O₂ m⁻² d⁻¹, respectively Inorganic nutrient fluxes were generally low compared to relevant estuarine literature values, and responded minimally to light exposure. Across all stations, nutrient fluxes from sediments to the water column averaged 1.11 ± 0.98 mmol m⁻² d⁻¹ for NH₄⁺, 0.58 ± 1.08 mmol m⁻² d⁻¹ for NO₃⁻, 0.01 ± 0.09 mmol m⁻² d⁻¹ for PO₄³⁻. The results of this study illustrate how light reaching the sediments is an important modulator of benthic nutrient and oxygen dynamics in shallow estuarine systems.     

Eutrophication and the rate of net nitrification in a coastal marine ecosystem

Rates of net nitrification were calculated for four large (13 m³) estuarine-based microcosms that had been subjected to inorganic nutrient enrichment. Calculated rates were based on two years of weekly nitrate and nitrite measurements and ranged from a maximum of 0·55 μmol NO₂₊₃⁻ produced l⁻¹ day⁻¹ in the control tank (no enrichment) to over 13 μmol NO₂₊₃⁻ produced l⁻¹ day⁻¹ in the most enriched tank (receiving 18·6 μmol NH₄ l⁻¹ day⁻¹). Almost all NO₂₊₃⁻ production was pelagic, little was benthic. Net NO₃⁻ production or net NO₂⁻ production dominated the net nitrification rates during different seasons. Good correlations were found between various oxidation rates and substrate concentrations. The calculated net nitrite production rates were 10 to 1000 times higher than previously reported rates for open ocean systems, demonstrating the potential importance of nitrification to estuarine systems.     

Multi-decadal synthesis of benthic–pelagic coupling in the western arctic: Role of cross-shelf advective processes

Using geographic information systems (GIS) software and geostatistical techniques, we utilized three decades of water-column chlorophyll a data to examine the relative importance of autochthonous versus allochthonous sources of reduced carbon to benthic communities that occur from the northern Bering to the eastern Beaufort Sea shelf. Spatial trend analyses revealed areas of high benthic biomass (>300 g m⁻²) and chlorophyll (>150 mg m⁻²) on both the southern and northern Chukchi shelf; both areas are known as depositional centers for reduced organic matter that originates on the Bering Sea shelf and is advected northward in Anadyr and Bering shelf water masses. We found a significant correlation between biomass and chlorophyll a in the Chukchi Sea, reflective of the strong benthic–pelagic coupling in a system that is utilized heavily by benthic-feeding marine mammals. In contrast, there was no significant correlation between biomass and chlorophyll in the Beaufort Sea, which by comparison, is considerably less productive (biomass and chlorophyll, <75 g m⁻² and <50 mg m⁻², respectively). One notable exception is an area of relatively high biomass (50–100 g m⁻²) and chlorophyll (80 mg m⁻²) near Barter Island in the eastern Beaufort Sea. Compared to other adjacent areas in the Beaufort Sea, the chlorophyll values in the vicinity of Barter Island were considerably higher and likely reflect a long-hypothesized upwelling in that area and close coupling between the benthos and autochthonous production. In the Bering Sea, a drop in benthic biomass in 1994 compared with previous measurements (1974–1993) may support earlier observations that document a decline in biomass that began between the 1980s and 1990s in the Chirikov Basin and south of St. Lawrence Island. The results of this study indicate that the benthos is an excellent long-term indicator of both local and physical advective processes. In addition, this work provides further evidence that secondary production on arctic shelves can be significantly augmented by reduced carbon advected from highly productive adjacent shelves.     

Major contribution from mesopelagic plankton to heterotrophic metabolism in the upper ocean

Measurements of plankton respiration and heterotrophic bacterial abundance and production were made at seven deep water stations within the upper 500 m of the Gulf of Mexico during the summer of 1995. Bacterial abundance [(1.1–4.6)×108 1⁻¹] and rates of bacterial production (2–19 nM C h⁻¹) and plankton respiration (50–245 nM O₂ h⁻¹) decreased with depth by four- to nine-fold, and were similar to those reported for oligotrophic waters. Bacterial turnover times increased with depth from approximately 1 to 5 days. Bacterial growth efficiencies decreased from 15% at the surface to 8% at 500 m. Depth-integrated plankton respiration exceeded known estimates of primary production for the region, suggesting that heterotrophic utilization of previously and concurrently produced organic matter (e.g. spring phytoplankton growth, and summer blooms of Trichodesmium sp.) was occurring during the summer. Estimates for the upper 500 m showed that roughly half of the bacterial biomass (56%), bacterial production (49%), and plankton respiration (60%) occurred below the euphotic zone. Routine oceanographic studies have focused exclusively on the metabolic activity occurring within the euphotic zone. Our measurements, however, indicate that mesopelagic plankton also contribute substantially to heterotrophic metabolism and nutrient cycling in the 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.     

Influence of water temperature and oxygenation on the aerobic metabolic scope of Atlantic cod (Gadus morhua)

Environmental influences (temperature and oxygenation) on cod metabolism and their impact on the ecology of this species were investigated. Limiting oxygen concentration curves (O₂ level ranging between 15 and 100% air saturation) were established at 2, 5 and 10°C. The standard metabolic rate (SMR), the maximum metabolic rate and the metabolic scope were then modelled as functions of temperature and/or oxygen saturation. The mean SMR at 2, 5 and 10°C were 19.8±4.9, 30.8±6.1 and 54.3±4.1 mg O₂ h⁻¹ kg⁻¹, respectively. Between 2 and 5°C, the active metabolic rate of cod almost doubled from 65 to 120 mg O₂ h⁻¹ kg⁻¹, to reach 177 mg O₂ h⁻¹ kg⁻¹ at 10°C. In terms of metabolic scope (MS), the temperature rise from 2 to 5°C resulted in a two-fold increase from 45 to 89 mg O₂ h⁻¹ kg⁻¹, with MS reaching 123 mg O₂ h⁻¹ kg⁻¹ at 10°C. Our proposed model describing the impact of temperature and oxygen level provides new insight into the energetic interactions which govern the relationship between Atlantic cod and its environment. We re-examined published experimental and field studies from the angle of the regulation of metabolic power. We suggest that, when faced with heterogeneous or unstable hydrological conditions, cod tend to behaviourally maximise their metabolic scope. Through this adaptive response, fish reduce energy budgeting conflicts and presumably increase the probability of routinely operating away from lethal boundaries.     

Changes in sediment processes across the western Irish Sea front

Sediment characteristics, sediment respiration (oxygen uptake and sulphate reduction) and sediment–water nutrient exchange, in conjunction with water column structure and phytoplankton biomass were measured at five stations across the western Irish Sea front in August 2000. The transition from thermally stratified (surface to bottom temperature difference of 2.3 °C) to isothermal water (14.3 °C) occurred over a distance of 13 km. The influence of the front on phytoplankton biomass was limited to a small region of elevated near surface chlorophyll (2.23 mg m⁻³; 50% > biomass in mixed waters). The front clearly marked the boundary between depositional sediments (silt/clays) with elevated sediment pigment levels (≈60 mg m⁻²) on the western side, to pigment impoverished (<5 mg m⁻²) sand, through to coarse sand and shell fragments on the eastern side. Maximal rates of sedimentary respiration on the western stratified side of the front e.g. oxygen uptake S2 (852 μmol O₂ m⁻² h⁻¹) and sulphate reduction at S1 (149 μmol SO₄²⁻ m⁻² h⁻¹), coupled to significant efflux of nitrate and silicate at the western stations indicate closer benthic–pelagic coupling in the western Irish Sea. Whether this simply reflects the input of phytodetritus from the overlying water column or entrapment and settlement of pelagic production from other regions of the Irish Sea cannot yet be resolved.     

Differences in trophodynamics of commercially important fish between artificial waterways and natural coastal wetlands

Extensive artificial waterways have replaced natural wetlands and created new estuarine habitats on the southern Queensland coast, Australia. Economically important fish species found in adjacent natural wetlands of mangrove, saltmarsh and seagrass also occur in the artificial waterways. Stable isotope analyses (δ¹³C, δ¹⁵N) were used to test whether the relative importance of basal sources of energy varied for foodwebs found in artificial (canals and tidal lakes) and natural waterways. None of the fish species differed in their isotope values between artificial waterways. In contrast, isotopic signatures of snub-nosed garfish (Arrhamphus sclerolepis; Hemiramphidae) varied greatly between natural and artificial waterways, having highly enriched δ¹³C values (−10.5‰) in natural wetlands, demonstrating reliance on seagrass (−11.4‰), and significantly less enriched values (−19.0‰) in artificial waterways, consistent with either local algal sources (−19.8 to −20.4‰) or a mixture of seagrass and other less enriched autotrophs from adjacent natural wetlands. Isotopic signatures of sand whiting (Sillago ciliata; Sillaginidae) were also significantly more enriched in natural (−18.2‰) than artificial (−21.0‰) habitats, but means were not far enough apart to distinguish between different sources of nutrition. δ¹³C values of yellowfin bream (Acanthopagrus australis; Sparidae) did not differ between artificial and natural habitats (about −20‰ in both). δ¹⁵N values of fish varied among habitats only for A. sclerolepis, which in artificial waterways had values enriched by 2‰ over those in natural waterways. This was consistent with a shift from seagrass (relatively depleted δ¹⁵N) as a source in natural habitat to algal sources (relatively enriched δ¹⁵N) in artificial habitats. This study provides some of the first evidence that at least some fish species rely on different autotrophs in artificial waterways than in adjacent natural wetlands.     

Luminescence quenching of dissolved organic matter in seawater

To characterize more fully the nature of the fluorophores present in the dissolved organic matter found in seawater, steady state and time-resolved measurements of the luminescence quenching of a number of samples of marine dissolved organic matter with known quenchers, such as iodide, acrylamide and methyl viologen (MV) (1,1′-dimethyl-4,4′-bipyridinium), were compared. Quenching characteristics of these systems were analyzed using Stern-Volmer plots for both intensity and lifetime measurements. The bimolecular quenching constants, κ_q, for these quenchers were found to decrease in the order MV²⁺ (κ_q 10¹⁰M⁻¹s⁻¹) > I⁻ (κ_q 2 × 10⁹ M⁻¹ s⁻¹) >CH₂CHCONH₂ (κ_q 2 × 10⁸ M⁻¹ s⁻¹) for the samples measured. The results also show that different samples are quenched to differing extents by the quenchers studied, that ionic strength alters the quenching constants, and that both static and diffusional quenching mechanisms may operate.Such studies are appropriate to the quantification of the reactivity of the singlet states of the chromophores found within marine dissolved organic matter. Although excess energy of the singlet state may be readily transferred to another chemical species, the combination of competing physical deactivation paths and the low concentrations of efficient quenches in the oceans serves to lessen the direct chemical impact of this process.     

fCO2 variability at the CARIACO tropical coastal upwelling time series station

Monthly seawater pH and alkalinity measurements were collected between January 1996 and December 2000 at 10°30′N, 64°40′W as part of the CARIACO (CArbon Retention In A Colored Ocean) oceanographic time series. One key objective of CARIACO is to study temporal variability in Total CO₂ (TCO₂) concentrations and CO₂ fugacity (fCO₂) at this tropical coastal wind-driven upwelling site. Between 1996 and 2000, the difference between atmospheric and surface ocean CO₂ concentrations ranged from about − 64.3 to + 62.3 μatm. Physical and biochemical factors, specifically upwelling, temperature, primary production, and TCO₂ concentrations interacted to control temporal variations in fCO₂. Air–sea CO₂ fluxes were typically depressed (0 to + 10 mmol C m^{− 2} day^{− 1}) in the first few months of the year during upwelling. Fluxes were higher during June–November (+ 10 to 20 mmol C m^{− 2} day^{− 1}). Fluxes were generally independent of the slight changes in salinity normally seen at the station, but low positive flux values were seen in the second half of 1999 during a period of anomalously heavy rains and land-derived runoff. During the 5 years of monthly data examined, only two episodes of negative air–sea CO₂ flux were observed. These occurred during short but intense upwelling events in March 1997 (−10 mmol C m^{− 2} day^{− 1}) and March 1998 (− 50 mmol C m^{− 2} day^{− 1}). Therefore, the Cariaco Basin generally acted as a source of CO₂ to the atmosphere in spite of primary productivity in excess of between 300 and 600 g C m^{− 2} year^{− 1}.     

The recovery of microalgal production and biomass in a South African temporarily open/closed estuary, following mouth breaching

Mouth breaching is a recurrent event in temporarily open/closed estuaries (TOCEs). Such disturbances result in flushing and sediment scouring, reducing the microalgal biomass stock. The depletion of these microalgae may have negative repercussions in the form of depleted stocks of commercial fish, game fish, crustaceans and mollusks. The aim of this investigation was therefore: (1) to monitor the recovery of microalgal biomass and production following a breaching event; and (2) to determine the key environmental parameters influencing primary production during the open and recovery phases. Phytoplankton and benthic microalgal production was measured (¹⁴C-uptake method) successively during the closed, open and recovery phases of the Mdloti TOCE (South Africa). Upon breaching, 94–99% of microalgal biomass was washed out to sea through flushing and sediment scouring. A temporary recovery of phytoplankton and benthic microalgal biomass was observed during the open phase, but this was not sustained because of continual flushing and scouring of the sediment. During the re-closure (recovery phase), microalgal biomass immediately increased, reaching pre-breaching levels 35–40 days following the breaching event. In contrast to biomass, autochthonous pelagic primary production reached a maximum level (341 mg C m⁻² h⁻¹) during the open phase. Pelagic primary production normalized to biomass (P^B) significantly increased during the open phase. This is attributed to a favorable combination of optimum light conditions, high influx of macronutrients and high water temperatures (33 °C). Similarly, benthic primary production normalized to biomass (P^B) peaked during the open phase (35 mg C mg chl-a⁻¹ h⁻¹). Multivariate analysis showed that major variations in primary production were mainly controlled by temperature, dissolved inorganic nitrogen (DIN) to phosphorus (DIP) molar ratios (water-column and pore-water) and light extinction (K_d), all of which were regulated by the state of the mouth.     

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.     

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.     

Effect of changes in water salinity on ammonium, calcium, dissolved inorganic carbon and influence on water/sediment dynamics

The effect of a sudden increase in salinity from 10 to 37 in porewater concentration and the benthic fluxes of ammonium, calcium and dissolved inorganic carbon were studied in sediments of a small coastal lagoon, the Albufera d'Es Grau (Minorca Island, Spain). The temporal effects of the changes in salinity were examined over 17 days using a single diffusion-reaction model and a mass-balance approach. After the salinity change, NH₄⁺-flux to the water and Ca-flux toward sediments increased (NH₄⁺-flux: 5000–3000 μmol m⁻² d⁻¹ in seawater and 600/250 μmol m⁻² d⁻¹ in brackish water; Ca-flux: −40/−76 meq m⁻² d⁻¹ at S=37 and −13/−10 meq m⁻² d⁻¹ at S=10); however, later NH₄⁺-flux decreased in seawater, reaching values lower than in brackish water. In contrast, Ca-flux presented similar values in both conditions. The fluxes of dissolved inorganic carbon, which were constant at S=10 (55/45 mmol m⁻² d⁻¹), increased during the experiment at S=37 (from 30 mmol m⁻² d⁻¹ immediately after salinity increase to 60 mmol m⁻² d⁻¹ after 17 days).In brackish conditions, NH₄⁺ and Ca²⁺ fluxes were consistent with a single diffusion-reaction model that assumes a zero-order reaction for NH₄⁺ production and a first-order reaction for Ca²⁺ production. In seawater, this model explained the Ca-flux observed, but did not account for the high initial flux of NH₄⁺.The mass balance for 17 days indicated a higher retention of NH₄⁺ in porewater in the littoral station in seawater conditions (9.5 mmol m⁻² at S=37 and 1.6 mmol m⁻² at S=10) and a significant reduction in the water consumption at both sites (5 mmol m⁻² at S=37; 35/23 mmol m⁻² at S=10). In contrast, accumulation of dissolved inorganic carbon in porewater was lower in seawater incubations (−10/−1 meq m⁻² at S=37; 50/90 meq m⁻² at S=10) and was linked to a higher efflux of CO₂ to the atmosphere, because of calcium carbonate precipitation in water (675/500 meq m⁻²). These results indicate that increased salinity in shallow coastal waters could play a major role in the global carbon cycle.     

Measurement of dissolved oxygen using optodes in a FerryBox system

Optode sensors can provide detailed information on concentrations of dissolved oxygen, which in turn may be used to quantify variations in net primary productivity. Throughout 2005 and 2006 the performance of commercially available oxygen optodes was examined, one in each year. The optode was part of an autonomous measurement system (FerryBox) on a ferry operating between Portsmouth (UK) and Bilbao (Spain). On crossings during which water samples were collected manually, the optode outputs were compared to measurements of dissolved oxygen made by Winkler titrations. The optodes maintained good stability with no evidence of instrumental drift during the course of a year. Over the observed concentration range (230–330 mM m⁻³) the optode data were approximately 2% low in both years. By fitting the optode data to the Winkler data the median difference between the optode and Winkler measurements is reduced to less than 1 mM m⁻³ (0.3%) in both years. The most appropriate calibration factor for 2005 was corrected O₂ = Optode O₂ × 1.018 and for 2006 the corresponding equation is corrected O₂ = Optode O₂ × 0.884 + 36.8. The standard deviation (95%) of the difference between the individual Winkler measurements was 5 mM m⁻³ and 3 mM m⁻³ in 2005 and 2006 respectively.Calculation of the oxygen saturation anomaly is required for calculation of the air sea exchange of oxygen and net biological production. This calculation requires the use of both salinity and temperature data. Salinity is measured to better than 0.1 so the corresponding error in anomaly is less than 0.2 mM m⁻³. Distortion of the temperature data is present due to warming of the water pumped to the optode. In winter this warming at the optode may be as great as 0.4 °C. The difference in the pumped water temperature can be corrected for by reference to other measurements of sea surface temperature reducing the error to less than 1 mM m⁻³.