Biogeochemical study of a coccolithophore bloom in the northern Bay of Biscay (NE Atlantic Ocean) in June 2004

The present paper synthesizes data obtained during a multidisciplinary cruise carried out in June 2004 at the continental margin of the northern Bay of Biscay. The data-set allows to describe the different stages of a coccolithophore bloom dominated by Emiliania huxleyi. The cruise was carried out after the main spring phytoplankton bloom that started in mid-April and peaked in mid-May. Consequently, low phosphate (PO₄ < 0.2 μM) and silicate (DSi < 2.0 μM) concentrations, low partial pressure of carbon dioxide (pCO₂) and high calcite saturation degree in surface waters combined with thermal stratification, probably favoured the blooming of coccolithophores. During the period of the year our cruise was carried out, internal tides induce enhanced vertical mixing at the continental shelf break leading to the injection of inorganic nutrients to surface waters that probably trigger the bloom. The bloom developed as the water-column stratified and as the water mass was advected over the continental shelf, following the general residual circulation in the area. The most developed phase of the bloom was sampled in a remote sensed high reflectance (HR) patch over the continental shelf that was characterized by low chlorophyll-a (Chl-a) concentration in surface waters (<1.0 μg L^?1), high particulate inorganic carbon (PIC) concentration (～8 μmol L^?1) and coccolithophore abundance up to 57 × 10⁶ cells L^?1. Transparent exopolymer particles (TEP) concentrations ranged between 15 and 75 μg C L^?1 and carbon content of TEP represented up to 26% of the particulate organic carbon (POC; maximum concentration of 15.5 μmol L^?1 in the upper 40 m). Integrated primary production (PP) ranged between 210 and 680 mg C m^?2 d^?1 and integrated calcification (CAL) ranged between 14 and 140 mg C m^?2 d^?1, within the range of PP and CAL values previously reported during coccolithophore blooms in open and shelf waters of the North Atlantic Ocean. Bacterial protein production (BPP) measurements in surface waters (0.3–0.7 μg C L^?1 h^?1) were much higher than those reported during early phases of coccolithophore blooms in natural conditions, but similar to those during peak and declining coocolithophorid blooms reported in mesocosms. Total alkalinity anomalies with respect to conservative mixing (ΔTA) down to ?49 μmol kg^?1 are consistent with the occurrence of biogenic precipitation of calcite, while pCO₂ remained 15–107 μatm lower than atmospheric equilibrium (372 μatm). The correlation between ΔTA and pCO₂ suggested that pCO₂ increased in part due to calcification, but this increase was insufficient to overcome the background under-saturation of CO₂. This is related to the biogeochemical history of the water masses due to net carbon fixation by the successive phytoplankton blooms in the area prior to the cruise, hence, the investigated area remained a sink for atmospheric CO₂ despite calcification.     

Abundance and size distribution of transparent exopolymer particles (TEP) in a coccolithophorid bloom in the northern Bay of Biscay

The distribution of transparent exopolymer particles (TEP) was investigated during a coccolithophorid bloom in the northern Bay of Biscay (North Atlantic Ocean) in early June 2006. MODIS chlorophyll-a (Chl-a) and reflectance images before and during the cruise were used to localize areas of important biological activity and high reflectance (HR). TEP profiles along the continental margin, determined using microscopic (TEP_micro) and colorimetric (TEP_color) methods, showed abundant (6.1×10⁶–4.4×10⁷ L^?1) and relatively small (0.5–20 μm) particles, leading to a low total volume fraction (0.05–2.2 ppm) of TEP_micro and similar vertical profiles of TEP_color. Estimates of carbon content in TEP (TEP-C) derived from the microscopic approach yielded surface concentration of 1.50 μmol C L^?1. The contribution of TEP-C to particulate organic carbon (POC) was estimated to be 12% (molar C ratio) during this survey. Our results suggest that TEP formation is a probable first step to rapid and efficient export of C during declining coccolithophorid blooms.     

Total organic and inorganic carbon exchange through the Strait of Gibraltar in September 1997

The total organic carbon (TOC) and total inorganic carbon (C_T) exchange between the Atlantic Ocean and the Mediterranean Sea was studied in the Strait of Gibraltar in September 1997. Samples were taken at eight stations from western and eastern entrances of the Strait and at the middle of the Strait (Tarifa Narrows). TOC was analyzed by a high-temperature catalytic oxidation method, and C_T was calculated from alkalinity–pH_T pairs and appropriate thermodynamic relationships. The results are used in a two-layer model of water mass exchange through the Strait, which includes the Atlantic inflow, the Mediterranean outflow and the interface layer in between. Our observations show a decrease of TOC and an increase of C_T concentrations from the surface to the bottom: 71–132 μM C and 2068–2150 μmol kg⁻¹ in the Surface Atlantic Water, 74–95 μM C and 2119–2148 μmol kg⁻¹ in the North Atlantic Central Water, 63–116 μM C and 2123–2312 μmol kg⁻¹ in the interface layer, and 61–78 μM C and 2307–2325 μmol kg⁻¹ in the Mediterranean waters. However, within the Mediterranean outflow, we found that the concentrations of carbon were higher at the western side of the Strait (75–78 μM C, 2068–2318 μmol kg⁻¹) than at the eastern side (61–69 μM C, 2082–2324 μmol kg⁻¹). This difference is due to the mixing between the Atlantic inflow and the Mediterranean outflow on the west of the Strait, which results in a flux of organic carbon from the inflow to the outflow and an opposite flux of inorganic carbon. We estimate that the TOC input from the Atlantic Ocean to the Mediterranean Sea through the Strait of Gibraltar varies from (0.97±0.8)10⁴ to (1.81±0.90)10⁴ mol C s⁻¹ (0.3×10¹² to 0.56×10¹² mol C yr⁻¹), while outflow of inorganic carbon ranges from (12.5±0.4)10⁴ to (15.6±0.4)10⁴ mol C s⁻¹ (3.99–4.90×10¹² mol C yr⁻¹). The high variability of carbon exchange within the Strait is due to the variability of vertical mixing between inflow and outflow along the Strait. The prevalence of organic carbon inflow and inorganic carbon outflow shows the Mediterranean Sea to be a basin of active remineralization of organic material.     

Vertical flux of particulate Al,Fe, Pb,and Ba from the upper ocean estimated from 234Th/238U disequilibria

The vertical sinking flux of particulate Al, Fe, Pb, and Ba from the upper 250 m of the Labrador Sea has been estimated from measurements of ²³⁴Th/²³⁸U disequilibrium and the respective metal/²³⁴Th ratios in >53 μm size particles. ²³⁴Th-derived particulate metal fluxes include in situ scavenged metals, labile lithogenic metals, and metals derived from external input (e.g., atmospheric supply). In contrast to the POC/²³⁴Th ratio, particle size-fractionated (0.4–10 μm, 10–53 μm, and >53 μm) Al/²³⁴Th, Fe/²³⁴Th and Pb/²³⁴Th, and Ba/²³⁴Th ratios generally increase with depth and exhibit no systematic change with particle diameter. Sinking fluxes of particulate Al (2.47–22.3 μmol m⁻² d⁻¹), Fe (2.69–16.3 μmol m⁻² d⁻¹), Pb (2.85–70 nmol m⁻² d⁻¹), and Ba (0.13–2.1 μmol m⁻² d⁻¹) at 50 m (base of the euphotic zone) and 100 m (base of the mixed layer) are largely within the range of previous sediment trap results from other ocean basins. Estimates of the upper ocean residence time of Al (0.07–0.28 yr) and Pb (0.8–2.9 yr) are short compared to previously reported values. The settling rate of >53 μm particles calculated from the ²³⁴Th data ranges from 14 to 38 m d⁻¹.     

Vertical distribution of prokaryote production and abundance in the mesopelagic and bathypelagic layers of the Canada Basin,western Arctic: Implications for the mode and extent of organic carbon delivery

The vertical distributions of prokaryote heterotrophic production (³H-leucine incorporation rate) and abundance were investigated in the meso- and bathy-pelagic layers of the Canada Basin, western Arctic Ocean, during September 2009. Prokaryote production and abundance were high in the Pacific-origin water mass located in the upper mesopelagic layer (depth, 100–200 m). Below the halocline layer (depth, 300–3000 m), both the production and abundance decreased with depth, with log–log regression slopes of −1.33 and −0.77, respectively. Depth-integrated production and biomass in the meso- and bathy-pelagic layers was three- to five-fold lower than the corresponding values reported in the subpolar regions, whereas they were close to or lower than the corresponding values in oligotrophic subtropical regions. Prokaryote turnover times were estimated to be 1.1 and 6.1 years for meso- and bathy-pelagic layers, respectively, with the latter being among the longest turnover times reported for oceanic basins. We estimated prokaryote carbon demand in the water column (100–3000 m) to be on the order of 11 mg C m⁻² d⁻¹, which largely exceeds (by 38-fold) the sinking particulate organic carbon flux at depths of 120–200 m reported in the literature. This large carbon imbalance may be partly explained by organic carbon delivery by lateral intrusion of the Pacific-origin water mass into the upper mesopelagic layer.     

Major contribution of autotrophy to microbial carbon cycling in the deep North Atlantic’s interior

Current estimates point to a mismatch of particulate organic carbon supply derived from the surface ocean and the microbial organic carbon demand in the meso- and bathypelagic realm. Based on recent findings that chemoautotrophic Crenarchaeota are abundant in the mesopelagic zone, we quantified dissolved inorganic carbon (DIC) fixation in the meso- and bathypelagic North Atlantic and compared it with heterotrophic microbial activity. Measuring ¹⁴C-bicarbonate fixation and ³H-leucine incorporation revealed that microbial DIC fixation is substantial in the mesopelagic water masses, ranging from 0.1 to 56.7 μmol C m⁻³ d⁻¹, and is within the same order of magnitude as heterotrophic microbial activity. Integrated over the dark ocean’s water column, DIC fixation ranged from 1–2.5 mmol C m⁻² d⁻¹, indicating that chemoautotrophy in the dark ocean represents a significant source of autochthonously produced ‘new organic carbon’ in the ocean’s interior amounting to about 15–53% of the phytoplankton export production. Hence, chemoautotrophic DIC fixation in the oxygenated meso- and bathypelagic water column of the North Atlantic might substantially contribute to the organic carbon demand of the deep-water microbial food web.     

Anchoring metabolic changes to phenotypic effects in the chlorophyte Scenedesmus vacuolatus under chemical exposure

In order to derive a causal understanding of toxic effects in organisms, ecotoxicology may benefit from linking molecular changes, evaluated by ‘omics’-techniques, to phenotypic observations. However, an approach to link these observation levels is still lacking.The aim of this study was to relate metabolic changes in the chlorophyte Scenedesmus vacuolatus to established parameters of toxicity. Therefore, synchronized cultures of the alga were exposed for 14 h to the phytotoxicant N-phenyl-2-naphthylamine (PNA) in the range of 0.00089 μmol L⁻¹ (environmental concentrations) up to 1.82 μmol L⁻¹. Cell growth and photosynthesis inhibition were evaluated but revealed no effect of PNA at experimental concentrations below 0.456 μmol L⁻¹. Changes in the biochemical composition of algae were measured by GC–MS in both polar and non-polar phases. PCA uncovered no separation in the multivariate pattern of mass spectral features at exposure concentrations below 0.00356 μmol L⁻¹ of PNA. However, a clear separation was detected at concentrations higher than 0.00713 μmol L⁻¹. A combined visualization of PCA results for metabolic changes and concentration–response relationships for growth and photosynthesis inhibition revealed (I) a two orders of magnitude higher sensitivity of metabolomics to detects changes after PNA exposure compared to the phenotypic parameters measured and (II) two types of metabolic responses: one group of features was reflecting pharmacological effects at low exposure concentrations and the second group corresponded to adverse effects along with conventional observations of toxicity.     

Dissolved and particulate organic carbon and nitrogen in the Northwestern Mediterranean

The distribution of dissolved organic carbon (DOC) and nitrogen (DON) and particulate organic carbon (POC) and nitrogen (PON) was studied on a transect perpendicular to the Catalan coast in the NW Mediterranean in June 1995. The transect covered a hydrographically diverse zone, including coastal waters and two frontal structures (the Catalan and the Balear fronts). The cruise was conducted during the stratified period, characterized by inorganic nutrient depletion in the photic zone and a well established deep chlorophyll a maximum. DOC concentrations were measured using a high-temperature catalytic oxidation method, and DON was determined directly, with an update of the Kjeldahl method, after removal of inorganic nitrogen.The ranges of DOC and DON concentrations were 44–95 μM-C and 2.8–6.2 μM-N. The particulate organic matter ranged between 0.9 and 14.9 μM-C and from 0.1 to 1.7 μM-N. The DOC : DON molar ratio averaged 15.5±0.4, and the mean POC : PON ratio was 8.6±0.6. The distribution of dissolved organic matter (DOM) was inverse to that of the salinity. The highest concentrations of DOM were found in coastal waters and in the stations affected by the Catalan front, located at the continental shelf break.It was estimated that recalcitrant DOM constituted 67% of the DOM pool in the upper 50 m. The data suggest that accumulation of DOC due to the decoupling of production and consumption may occur in the NW Mediterranean during stratification and that the organic matter exported from the photic layer is dominated by C-rich material.     

Silicon flux and distribution of biogenic silica in deep-sea sediments in the western North Pacific Ocean

We investigated biogenic silica, several biological components, and silicate in pore-water in the abyssal sediment to determine silicon flux of western North Pacific during several cruises. The surficial sediment biogenic silica content was high at high latitudes with the boundary running along the Kuroshio Extension, and maximum values (exceeding 20%) were found in the Oyashio region. In the subtropical region to the south, most stations showed less than 5% biogenic silica content. This distribution pattern reflected primary production and ocean currents in the surface layer very well. Pore-water samples were collected from 4 stations along the east coast of Japan. The highest asymptotic silicic acid concentration (670 μmol L^?1) in pore-water was observed at the junction of Kuroshio and Oyashio, followed by samples from the Oyashio region. It is at the southern station that the lowest value (450 μmol L^?1) was observed, and the primary production is low under the influence of Kuroshio there. The diffusive flux followed the same geographic trend as the asymptotic silicic acid concentrations did, ranging 77–389 mmol m^?2 yr ^?1. Multiple sampling of pore-water was conducted throughout the year at one station at high latitude. The average annual biogenic silica rain flux observed using sediment traps was 373 mmol m^?2 yr^?1; the diffusive flux and burial flux at the sediment–water interface were 305 and 9 mmol m^?2 yr^?1, respectively. We concluded that most of the settling silica particles dissolved and diffused at the sediment–water interface and approximately 3% only were preserved in this area. In addition, the obvious time lag observed between the peak rain flux and the maximum diffusive flux suggested that primary production in the surface layer has a great influence on the sedimentation environment of abyssal western North Pacific. These transitions of Si flux at the sediment–water interface were considerably greater in northwestern North Pacific than in southwestern North Pacific. In addition, a station in the Philippine Sea indicated high biogenic silica content because of Ethmodiscus ooze, which are scattered randomly on the sea floor in the subtropical region.     

Diel variations of the bathymetric distribution of zooplankton groups and biomass in Cap-Ferret Canyon,France

The bathymetric distribution, abundance and diel vertical migrations (DVM) of zooplankton were investigated along the axis of the Cap-Ferret Canyon (Bay of Biscay, French Atlantic coast) by a consecutive series of synchronous net hauls that sampled the whole water column (0–2000 m in depth) during a diel cycle. The distribution of appendicularians (maximum 189 individuals m⁻³), cladocerans (maximum 287 individuals m⁻³), copepods (copepods<4 mm, maximum 773 individuals m⁻³, copepods>4 mm, maximum 13 individuals m⁻³), ostracods (maximum 8 individuals m⁻³), siphonophores (maximum >2 individuals m⁻³) and peracarids (maximum >600 individuals 1000 m⁻³) were analysed and represented by isoline diagrams. The biomass of total zooplankton (maximum 18419 μg C m⁻³, 3780 μg N m⁻³) and large copepods (>4 mm maximum 2256 μg C m⁻³, 425 μg N m⁻³) also were determined. Vertical migration was absent or affected only the epipelagic zone for appendicularians, cladocerans, small copepods and siphonophores. Average amplitude of vertical migration was about 400–500 m for ostracods, some hyperiids and mysids, and large copepods, which were often present in the epipelagic, mesopelagic, and bathypelagic zones. Large copepods can constitute more than 80% of the biomass corresponding to total zooplankton. They may play an important role in the active vertical transfer of carbon and nitrogen.     

Dry atmospheric deposition and diazotrophy as sources of new nitrogen to northwestern Mediterranean oligotrophic surface waters

Atmospheric dry deposition of nitrogen (N) and dinitrogen (N₂) fixation rates were assessed in 2004 at the time-series DYFAMED station (northwestern Mediterranean, 43°25′N, 7°52′E). The atmospheric input was monitored over the whole year. Dinitrogen fixation was measured during different seasonal trophic states (from mesotrophy to oligotrophy) sampled during nine cruises. The bioavailability of atmospherically deposited nutrients was estimated by apparent solubility after 96 h. The solubility of dry atmospheric N deposition was highly variable (from ∼18% to more than 96% of total N). New N supplied to surface waters by the dry atmospheric deposition was mainly nitrate (NO₃⁻) (∼57% of total N, compared to ∼6% released as ammonium (NH₄⁺)). The mean bioavailable dry flux of total N was estimated to be ∼112 μmol m⁻² d⁻¹ over the whole year. The NO₃⁻ contribution (70 μmol NO₃⁻ m⁻² d⁻¹) was much higher than the NH₄⁺ contribution (1.2 μmol NH₄⁺ m⁻² d⁻¹). The N:P ratios in the bioavailable fraction of atmospheric inputs (122.5–1340) were always much higher than the Redfield N:P ratio (16). Insoluble N in atmospheric dry deposition (referred to as “organic” and believed to be strongly related to anthropogenic emissions) was ∼40 μmol m⁻² d⁻¹. N₂ fixation rates ranged from 2 to 7.5 nmol L⁻¹ d⁻¹. The highest values were found in August, during the oligotrophic period (7.5 nmol L⁻¹ at 10 m depth), and in April, during the productive period (4 nmol L⁻¹ d⁻¹ at 10 m depth). Daily integrated values of N₂ fixation ranged from 22 to 100 μmol N m⁻² d⁻¹, with a maximum of 245 μmol N m⁻² d⁻¹ in August. No relationship was found between the availability of phosphorus or iron and the observed temporal variability of N₂ fixation rates. The atmospheric dry deposition and N₂ fixation represented 0.5–6% and 1–20% of the total biological nitrogen demand, respectively. Their contribution to new production was more significant: 1–28% and 2–55% for atmospheric dry deposition and N₂ fixation, respectively. The dry atmospheric input was particularly significant in conditions of water column stratification (16–28% of new production), while N₂ fixation reached its highest values in June (46% of new production) and in August (55%).     

The relationship between dissolved hydrogen and nitrogen fixation in ocean waters

Fixed nitrogen is a key nutrient involved in regulating global marine productivity and hence the global oceanic carbon cycle. Oceanic nitrogen (N₂) fixation is estimated to supply 8×10¹² moles N y^?1 to the ocean, approximately equal to current riverine and the atmospheric inputs of fixed N, and between 50 and 100% of current estimates of oceanic denitrification. However, the spatial and temporal variability of N₂ fixation remains uncertain, mostly because of the normal low resolution sampling for diazotroph distribution and fixation rates. It is well established that N₂ fixation, mediated by the enzyme nitrogenase, is a source of hydrogen (H₂), but the extent to which it leads to supersaturation of H₂ in oceanic waters is unresolved. Here, we present simultaneous measurements of upper ocean dissolved H₂ concentration (nmol L^?1), and rates of N₂ fixation (μmol N m^?3 d^?1), determined using ¹⁵N₂ tracer techniques (at 7 or 15 m), on a transect from Fiji to Hawaii. We find a significant correlation (r=0.98) between dissolved H₂ and rates of N₂ fixation, with the greatest supersaturation of H₂ and highest rates of N₂ fixation being observed in the subtropical gyres at the southern (～18°S) and northern (18°N) reaches of the transect. The lowest H₂ saturation and N₂ fixation were observed in the equatorial region between 8°S and 14°N. We propose that an empirical relationship between H₂ supersaturations and N₂ fixation measurements could be used to guide sampling for ¹⁵N fixation measurements or to aid the spatial interpolation of such measurements.     

Plankton copper requirements and uptake in the subarctic Northeast Pacific Ocean

We undertook the first measurements of metabolic Cu requirements (net Cu:C assimilation ratios) and steady-state Cu uptake rates (ρCu_ss) of natural plankton assemblages in the northeast subarctic Pacific using the short-lived radioisotope ⁶⁷Cu. Size-fractionated net Cu:C assimilation ratios varied ～3 fold (1.35–4.21 μmol Cu mol C^?1) among the stations along Line P, from high Fe coastal waters to the Fe-limited open ocean. The variability in Cu:C was comparable to biogenic Fe:C ratios in this region. As previously observed for Fe uptake, the bacterial size class accounted for half of the total particulate ρCu_ss. Interestingly, carbon biomass-normalized rates of Fe uptake from the siderophore desferrioxamine B (DFB) (ρFe_DFB; a physiological proxy for Fe-limitation) by the >20 μm size class were positively correlated with the intracellular net Cu:C assimilation ratios in this size class, suggesting that intracellular Cu requirements for large phytoplankton respond to increased Fe-limitation. At Fe-limited Ocean Station Papa (OSP), we performed short-term Cu uptake (ρCu_L) assays to determine the relative bioavailability of Cu bound to natural and synthetic ligands. Like the volumetric ρCu_ss measured along Line P, the bacterial size class was responsible for at least 50% of the total ρCu_L. Uptake rates of Cu from the various organic complexes suggest that Cu uptake was controlled by the oxidation state of the metal and by the metal:ligand concentration ratio, rather than the concentration of inorganic species of Cu in solution. Collectively, these data suggest that Cu likely plays an important role in the physiology of natural plankton communities beyond the toxicological effects studied previously.     

Microbial respiration in the Levantine Sea: evolution of the oxidative processes in relation to the main Mediterranean water masses

First data on microbial respiration in the Levantine Sea are reported with the aim of assessing the distribution of oxidative processes in association with the main Mediterranean water masses and the changing physical structure determined by the Eastern Mediterranean Transient. Respiratory rates, in terms of metabolic carbon dioxide production, were estimated from measured electron transport system activities in the polygonal area of the Levantine Sea (32.5–36.5 N Latitude, 26.0–30.25 E Longitude) and at Station Geo’95, in the Ionian Sea (35°34.88 N; 17°14.99 E). At the Levantine Sea, the mean carbon dioxide production rate decreased from the upper to the deeper layers and varied from 22.0±12.4 μg C h⁻¹ m⁻³ in the euphotic layer to 1.30±0.5 μg C h⁻¹ m⁻³ in the depth range between 1600 and 3000 m. Significant differences were found among upper, intermediate and bottom layers. The euphotic zone supported a daily carbon dioxide production of 96.6 mg C d⁻¹ m⁻² while the aphotic zone (between 200 and 3000 m) sustained a 177.1 mg C d⁻¹ m⁻² carbon dioxide production. In Station Geo’95, the carbon dioxide production rates amounted to 170.4 and 102.2 mg C d⁻¹ m⁻² in the euphotic and aphotic zones, respectively. The rates determined in the identified water masses showed a tight coupling of respiratory processes and Mediterranean circulation patterns. The increasing respiratory rates in the deep layers of the Levantine Sea are explained by the introduction of younger waters recently formed in the Aegean Sea.     

Dissolved organic carbon export and subsequent remineralization in the mesopelagic and bathypelagic realms of the North Atlantic basin

Dissolved organic carbon (DOC) data are presented from three meridional transects conducted in the North Atlantic as part of the US Climate Variability (CLIVAR) Repeat Hydrography program in 2003. The hydrographic sections covered a latitudinal range of 6°S to 63°N along longitudes 20°W (CLIVAR line A16), 52°W (A20) and 66°W (A22). Over 3700 individual measurements reveal unprecedented detail in the DOC distribution and systematic variations in the mesopelagic and bathypelagic zones of the North Atlantic basin. Latitudinal gradients in DOC concentrations combined with published estimates of ventilation rates for the main thermocline and North Atlantic Deep Water (NADW) indicate a net DOC export rate of 0.081 Pg C yr⁻¹ from the epipelagic zone into the mesopelagic and bathypelagic zones. Model II regression and multiple linear regression models applied to pairwise measures of DOC and chlorofluorocarbon (CFC-12) ventilation age, retrieved from major water masses within the main thermocline and NADW, indicate decay rates for exported DOC ranging from 0.13 to 0.94 μmol kg⁻¹ yr⁻¹, with higher DOC concentrations driving higher rates. The contribution of DOC oxidation to oxygen consumption ranged from 5 to 29% while mineralization of sinking biogenic particles drove the balance of the apparent oxygen utilization.     

Aerobic ammonium oxidation in the oxycline and oxygen minimum zone of the eastern tropical South Pacific off northern Chile (∼20°S)

Aerobic NH₄⁺ oxidation rates were measured along the strong oxygen gradient associated with the oxygen minimum zone (OMZ) of the eastern tropical South Pacific off northern Chile (∼20°S) during 2000, 2003, and 2004. This process was examined by comparing NH₄⁺ rates of change during dark incubations, with and without the addition of allylthiourea, a classical inhibitor of the ammonia monooxygenase enzyme of ammonium-oxidizing bacteria. The contribution of aerobic NH₄⁺ oxidation in dark carbon fixation and NO₂⁻ rates of change were also explored. Thirteen samples were retrieved from the oxycline (252 to ⩽5 μM O₂; 15 to ∼65 m depth) and three from the oxygen minimum core (⩽5 μM O₂; 100–200 m depth). Aerobic NH₄⁺ oxidation rates were mainly detected in the upper part (15–30 m depth) of the oxycline, with rates ranging from 0.16 to 0.79 μM d⁻¹, but not towards the oxycline base (40–65 m depth). In the oxygen minimum core, aerobic NH₄⁺ oxidation was in the upper range and higher than in the upper part of the oxycline (0.70 and 1.0 μM d⁻¹). Carbon fixation rates through aerobic NH₄⁺ oxidation ranged from 0.18 to 0.43 μg C L⁻¹ d⁻¹ and contributed between 33% and 57% of the total dark carbon fixation, mainly towards the oxycline base and, in a single experiment, in the upper part of the oxycline. NO₂⁻ consumption was high (up to 10 μM d⁻¹) towards the oxycline base and OMZ core, but was significantly reduced in experiments amended with allylthiourea, indicating that aerobic NH₄⁺ oxidation could contribute between 8% and 76% of NO₂⁻ production, which in turn could be available for denitrifiers. Overall, these results support the important role of aerobic NH₄⁺ oxidizers in the nitrogen and carbon cycling in the OMZ and at its upper boundary.     

Biogeochemical responses to late-winter storms in the Sargasso Sea,II: Increased rates of biogenic silica production and export

Previous studies measuring biogenic silica production in the Sargasso Sea, all conducted when no phytoplankton bloom was in progress, have reported a mean rate of 0.4 mmol Si m^?2 d^?1 and maximum rate of 0.9 mmol Si m^?2 d^?1, the lowest rates yet recorded in any ocean habitat. During February/March of 2004 and 2005 we studied the effects of late-winter storms prior to seasonal stratification on the production rate, standing stock and vertical export of biogenic silica in the Sargasso Sea. In 2004, alternating storm and stratification events provided pulsed input of nutrients to the euphotic zone. In contrast, nearly constant storm conditions in 2005 caused the mixed layer to deepen to ～350 m toward the end of the cruise. Biogenic silica production rates in the upper 140 m were statistically indistinguishable between years, averaging ～1.0 mmol Si m^?2 d^?1. In early March 2004, a storm event entrained nutrients into the euphotic zone and, upon stabilization, vertically integrated biogenic silica in the upper 140 m nearly doubled in 2 days. Within 4 days, 75–100% of the accumulated biogenic silica was exported, sustaining a flux to 200 m of ～0.5 mmol Si m^?2 d^?1 (4× greater than export measured during February and March in the mid-1990s). In 2005, destabilization without stratification increased biogenic silica flux at 200 m up to two-fold above previously measured export in late winter, with little or no increase in water-column biogenic silica. Despite comprising <5% of total chlorophyll, diatoms accounted for an estimated 25–50% of the nitrate uptake in the upper 140 m and 35–97% of the particulate organic nitrogen export from the upper 200 m during both cruise periods. These previously unobserved brief episodes of diatom production and export in response to late-winter storms increase the estimated production and export of diatom-derived material in the Sargasso Sea in late winter by >150%, and increase estimated annual biogenic silica production in this region by ～8%.     

DOC dynamics in the meso and bathypelagic layers of the Mediterranean Sea

Seven years (2001–2008) of dissolved organic carbon (DOC) vertical profiles were examined in order to assess the main processes determining DOC concentration and distribution in the meso- and bathypelagic layers of the Mediterranean Sea. As expected, DOC showed high and highly variable concentrations in the surface layer of 57–68 μM (average values between 0 and 100 m), with a decrease to 44–53 μM between 200 and 500 m. Deep DOC distribution was strongly affected by deep-water formation, with a significant increase to values of 76 μM in recently ventilated deep waters, and low concentrations, comparable to those observed in the open oceanic waters (34–45 μM), where the oldest, deep waters occurred. In winter 2004/2005 a deep-water formation event was observed and the consequent DOC export at depth was estimated to range between 0.76–3.02 Tg C month^–1. In the intermediate layer, the main path of the Levantine Intermediate Water (LIW) was followed in order to estimate the DOC consumption rate in its core. Multiple regression between DOC, apparent oxygen utilization (AOU), and salinity indicated that 38% of the oxygen consumption was related to DOC mineralization when the effect of mixing was removed. In deep waters of the southern Adriatic Sea a DOC decrease of 6 μM, together with an AOU increase of 9 μM, was observed between the end of January 2008 and the end of June 2008 (5 months). These data indicate a rate of microbial utilization of DOC of about 1.2 μM C month⁻¹, with 92% of the oxygen consumption due to DOC mineralization. These values are surprisingly high for the deep sea and represent a peculiarity of the Mediterranean Sea.     

Copper complexation by fulvic acid affects copper toxicity to the larvae of the polychaete Hydroides elegans

Copper toxicity is influenced by a variety of environmental factors including dissolved organic matter (DOM). We examined the complexation of copper by fulvic acid (FA), one of the major components of DOM, by measuring the decline in labile copper by anodic stripping voltammetrically (ASV). The data were described using a one-site ligand binding model, with a ligand concentration of 0.19 μmol site mg⁻¹ C, and a log K′ of 6.2. The model was used to predict labile copper concentration in a bioassay designed to quantify the extent to which Cu–FA complexation affected copper toxicity to the larvae of marine polychaete Hydroides elegans. The toxicity data, when expressed as labile copper concentration causing abnormal development, were independent of FA concentration and could be modeled as a logistic function, with a 48-h EC₅₀ of 58.9 μg l⁻¹. However, when the data were expressed as a function of total copper concentration, the toxicity was dependent on FA concentration, with a 48-h EC₅₀ ranging from 55.6 μg l⁻¹ in the no-FA control to 137.4 μg l⁻¹ in the 20 mg l⁻¹ FA treatment. Thus, FA was protective against copper toxicity to the larvae, and such an effect was caused by the reduction in labile copper due to Cu–FA complexation. Our results demonstrate the potential of ASV as a useful tool for predicting metal toxicity to the larvae in coastal environment where DOM plays an important role in complexing metal ions.     

Biogeochemical responses to late-winter storms in the Sargasso Sea,I—Pulses of primary and new production

We have hypothesized that the weekly/biweekly passage of winter storms in the subtropical open ocean destabilizes the water column leading to pulsed NO₃^? inputs, resulting in new production that is not accounted for in most annual estimates. This paper presents data on nitrogen and carbon cycling in the Sargasso Sea at approximately daily resolution, during the period prior to seasonal stratification in 2004 and 2005; these data permit us to assess the importance of winter storms for introducing NO₃^? and the contribution of these inputs to annual new and export production. The two sampling years were in stark contrast to each other with 2004 characterized by periods of relative calm between winter storms, and 2005 characterized by nearly continuous storm activity. As a result, temporal variability in mixed layer depth (MLD) and euphotic zone [NO₃^?] were very different between years. MLDs in 2004 increased to >150 m in response to the passage of storms and then rapidly shoaled to <100 m leading to the pulsed injection of NO₃^? (～100 nmol l^?1) into the lower half of the euphotic zone, while in 2005 MLDs were consistently >300 m and euphotic zone [NO₃^?]>100 nmol l^?1. Despite the very different [NO₃^?], rates of daily NO₃^? uptake were similar from year to year because of significant nocturnal uptake in 2004. Similar rates of new production did not translate into similar rates of particulate nitrogen and carbon export however, as observed export from the upper 200 m was 2–5-fold greater in 2004 than in 2005. Furthermore, the decrease of particulate nitrogen and carbon flux with depth between 200 and 400 m in 2004 was substantially lower than in 2005; this is consistent with the observed biological response in which diatoms and coccolithophores exhibited rapid growth following pulsed NO₃^? inputs in 2004. A combination of data from the Bermuda Testbed Mooring, which provides a longer temporal record than the cruise, and the observations presented in this study show that in the winter of 2004, there were 8–10 storm events that likely resulted in pulsed NO₃^? inputs. Summed over all the events, new production prior to seasonal stratification was estimated to be ～0.12–0.18 mol N m^?2 or ～14–21% of current annual estimates.