Seasonal and depth variations in molecular and isotopic alkenone composition of sinking particles from the western North Pacific

Seasonal and depth variations in alkenone flux and molecular and isotopic composition of sinking particles were examined using a 21-month time-series sediment trap experiment at a mooring station WCT-2 (39°N, 147°E) in the mid-latitude NW Pacific to assess the influences of seasonality, production depth, and degradation in the water column on the alkenone unsaturation index U^K′₃₇. Analysis of the underlying sediments was also conducted to evaluate the effects of alkenone degradation at the water–sediment interface on U^K′₃₇. Alkenone sinking flux and U^K′₃₇-based temperature showed strong seasonal variability. Alkenone fluxes were higher from spring to fall than they were from fall to spring. During periods of high alkenone flux, the U^K′₃₇-based temperatures were lower than the contemporary sea-surface temperatures (SSTs), suggesting alkenone production in a well-developed thermocline (shallower than 30 m). During low alkenone flux periods, the U^K′₃₇-based temperatures were nearly constant and were higher than the contemporary SSTs. The nearly constant carbon isotopic ratios of C_37:2 and C_38:2 alkenones suggest that alkenones produced in early fall were suspended in the surface water until sinking. The alkenone sinking flux decreased exponentially with increasing depth. The decreasing trend was enhanced during the periods of high alkenone flux, suggesting that fresh and labile particles sank from spring to fall, while old and stable particles sank from fall to spring. The U^K′₃₇-based temperature usually increased with increasing depth. The preservation efficiency of alkenones was ∼2.7–5.2% at the water–sediment interface. Despite the significant degradation of the alkenones, there was little difference in U^K′₃₇ levels between sinking particles and the surface sediment.     

Use of lipids and their degradation products as biomarkers for carbon cycling in the northwestern Mediterranean Sea

Changes in phytoplankton composition and degradation of particulate organic matter (POM) in the northwestern Mediterranean Sea were studied using time-series sediment trap samples collected during the spring of 2003 at the DYFAMED station. Lipid biomarkers (pigments, fatty acids, sterols, acyclic isoprenoids, alkenones and n-alkanols) were used to identify the main contributors to the POM produced during two phytoplankton blooms, while the effects of photooxidation, autoxidation and biodegradation were differentiated using characteristic lipid degradation products. Traps collected material corresponding to pre-bloom, bloom and post-bloom periods. Pigment analyses in the integrated (0-200 m) water column samples indicated that diatoms dominated the initial stages of the bloom event, with smaller amounts of haptophytes and pelagophytes. During the second part of bloom event there was a switch to haptophyte dominance with significant contributions from diatoms and pelagophytes, and an increased contribution from cryptophytes. Fatty acid distributions in the trap samples reflected contributions from marine bacteria, phytoplankton and zooplankton. Photooxidation and autoxidation products of monounsaturated oleic, cis-vaccenic and palmitoleic acids were detected along with photooxidation products from the chlorophyll side-chain. The relatively good correlation between the variation of U₃₇^K′ index and specific phytol autoxidation product percentage allowed us to attribute the alterations of U₃₇^K′ observed during the pre-bloom period and in the deeper traps to the involvement of selective autoxidative degradation processes. A variety of sterol oxidation products formed by biohydrogenation, autoxidation and photooxidation were detected. Sterol degradation products appeared to be less suited than oxidation products of monounsaturated fatty acids for the precise monitoring of the degradation state of POM, but their stable functionalized cyclic structure constitutes a useful tool to estimate the part played by biotic and abiotic processes. In these waters, biotic degradation generally predominates, but abiotic degradation is not negligible and, as expected, the extent of biotic degradation increases with depth. To obtain a more complete picture of POM degradation, the use of a pool of lipid degradation products (i.e. from unsaturated fatty acids, the phytyl side-chain and sterols) should be employed.     

Alkenones and particulate fluxes in sediment traps from the central equatorial Pacific

We investigated a year-long (September 1992 to August 1993) time series of total mass, calcium carbonate, organic carbon, opal, and alkenone fluxes in sinking particles collected with sediment traps moored at 1770 and 4220 m in the central equatorial Pacific. The total mass fluxes varied from 14.7 to 68.7 mg/m²/day at 1770 m, with greater fluxes in October–November and February–April, and from 14.6 to 50.4 mg/m²/day with peak fluxes during October–November at 4220 m. High flux in the spring season shown at 1770 m was not indicated at 4220 m; instead, a slight increase was shown during a broad period from March to June. The calcium carbonate fluxes varied from 10.8 to 49.1 mg/m²/day with higher fluxes in October–November and March–April at 1770 m, and from 8.9 to 37.0 mg/m²/day with a higher flux in October–November at 4220 m. The organic carbon fluxes varied from 0.36 to 5.91 mg/m²/day, with higher fluxes in October–November and March–April at 1770 m, and from 0.72 to 2.58 mg/m²/day at 4220 m. The annual mean organic carbon flux was 1.84 and 1.28 mg/m²/day at 1770 and at 4220 m, respectively. These values were less than half of those reported for the EqPac sediment trap experiment. The opal fluxes varied from 0.55 to 4.4 mg/m²/day at 1770 m and from 1.23 to 2.95 mg/m²/day at 4220 m. Alkenone fluxes varied significantly from 0.05 to 0.84 μg/m²/day, with high values in November, February–March, and June at 1770 m. For the 4220 m trap, these values ranged from 0.05 to 0.25 μg/m²/day, with slightly higher fluxes in April–May and June–July, which followed periods of high alkenone fluxes observed in February–April and June–July, respectively, at 1770 m depth. These values were remarkably low compared with those reported by the previous studies at other sites. U₃₇^K′ values were constantly high >0.95 throughout the collection period. However, relatively low U₃₇^K′ values (0.92 and 0.93) were occasionally observed during February to March. Estimated alkenone temperatures from those U₃₇^K′ values were about 27–29°C and consistent with the observed temperature of the upper layer at ca.100 m depth. The seasonal change of the U₃₇^K′ values could be affected by not only water temperature but also the relative amount of ‘warm’ and ‘cold’ types of alkenone producer in the central equatorial Pacific.     

Biogenic fluxes in the Cariaco Basin: a combined study of sinking particulates and underlying sediments

The fluxes of total mass, organic carbon (OC), biogenic opal, calcite (CaCO₃) and long-chain C₃₇ alkenones (ΣAlk₃₇) were measured at three water depths (275, 455 and 930 m) in the Cariaco Basin (Venezuela) over three separate annual upwelling cycles (1996–1999) as part of the CARIACO sediment trap time-series. The strength and timing of both the primary and secondary upwelling events in the Cariaco Basin varied significantly during the study period, directly affecting the rates of primary productivity (PP) and the vertical transport of biogenic materials. OC fluxes showed a weak positive correlation (r²=0.3) with PP rates throughout the 3 years of the study. The fluxes of opal, CaCO₃ and ΣAlk₃₇ were strongly correlated (0.6<r²<0.8) with those of OC. The major exception was the lower than expected ΣAlk₃₇ fluxes measured during periods of strong upwelling. All sediment trap fluxes were significantly attenuated with depth, consistent with marked losses during vertical transport. Annually, strong upwelling conditions, such as those observed during 1996–1997, led to elevated opal fluxes (e.g., 35 g m⁻² yr⁻¹ at 275 m) and diminished ΣAlk₃₇ fluxes (e.g., 5 mg m⁻² yr⁻¹ at 275 m). The opposite trends were evident during the year of weakest upwelling (1998–1999), indicating that diatom and haptophyte productivity in the Cariaco Basin are inversely correlated depending on upwelling conditions.The analyses of the Cariaco Basin sediments collected via a gravity core showed that the rates of OC and opal burial (10–12 g m⁻² yr⁻¹) over the past 5500 years were generally similar to the average annual water column fluxes measured in the deeper traps (10–14 g m⁻² yr⁻¹) over the 1996–1999 study period. CaCO₃ burial fluxes (30–40 g m⁻² yr⁻¹), on the other hand, were considerably higher than the fluxes measured in the deep traps (∼10 g m⁻² yr⁻¹) but comparable to those obtained from the shallowest trap (i.e. 38 g m⁻² yr⁻¹ at 275 m). In contrast, the burial rates of ΣAlk₃₇ (0.4–1 mg m⁻² yr⁻¹) in Cariaco sediments were significantly lower than the water column fluxes measured at all depths (4–6 mg m⁻² yr⁻¹), indicating the large attenuation in the flux of these compounds at the sediment–water interface. The major trend throughout the core was the general decrease in all biogenic fluxes with depth, most likely due to post-depositional in situ degradation. The major exception was the relatively low opal fluxes (∼5 g m⁻² yr⁻¹) and elevated ΣAlk₃₇ fluxes (∼2 mg m⁻² yr⁻¹) measured in the sedimentary interval corresponding to 1600–2000 yr BP. Such compositions are consistent with a period of low diatom and high haptophyte productivity, which based on the trends observed from the sediment traps, is indicative of low upwelling conditions relative to the modern day.     

Molecular and isotopic constraints on the sources of suspended particulate organic carbon on the northwestern Atlantic margin

The abundance, carbon isotopic composition (Δ¹⁴C and δ¹³C), and lipid biomarker (alkenones and saturated fatty acids) distributions of suspended particulate organic matter were investigated at three stations centered on the 2000, 3000, and 3500 m isobaths over the New England slope in order to assess particulate carbon sources and dynamics in this highly productive and energetic region. Transmissometry profiles reveal that particle abundances exhibit considerable fine structure, with several distinct layers of elevated suspended particulate matter concentration at intermediate water depths in addition to the presence of a thick bottom nepheloid layer at each station. Excluding surface water samples, the Δ¹⁴C values of particulate organic carbon (POC) indicated the presence of a pre-aged component in the suspended POC pool (Δ¹⁴C<+38‰). The Δ¹⁴C values at the 3000 m station exhibited greater variability and generally were lower than those at the other two stations where the values decreased in a more systematic matter with increasing sampling depth. These lower Δ¹⁴C values were consistent with higher relative abundances of terrigenous long-chain fatty acids at this station than at the other two stations. Two scenarios were considered regarding the potential provenances of laterally transported POC: cross-shelf transport of shelf sediment (Δ¹⁴C=?140‰) and along-slope transport of the slope sediment proximal to the sampling locations (Δ¹⁴C=?260‰). Depending on the scenario, isotopic mass balance calculations indicate allochthonous POC contributions ranging between 15% and 54% in the meso- and bathy-pelagic zone, with the highest proportions at the 3000 m station. Alkenone-derived temperatures recorded on suspended particles from surface waters closely matched in-situ temperatures at each station. However, alkenone-derived temperatures recorded on particles from the subsurface layer down to 250 m were lower than those of overlying surface waters, especially at the 3000 m station, implying supply of phytoplankton organic matter originally produced in cooler surface waters. AVHRR images and temperature profiles indicate that the stations were under the influence of a warm-core ring during the sampling period. The low alkenone-derived temperatures in the subsurface layer coupled with the lower Δ¹⁴C values for the corresponding POC suggests supply of OC on resuspended sediments underlying cooler surface waters distal to the study area, possibly further north or west. Taken together, variations in Δ¹⁴C values, terrigenous fatty acid abundances, and alkenone-derived temperatures among the stations suggest that input of laterally advected OC is a prominent feature of POC dynamics on the NW Atlantic margin, and is spatially heterogeneous on a scale smaller than the distance between the stations (<150 km).     

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.     

Seasonal record for alkenones in sedimentary particles from the Gulf of Maine

C_37–39 alkenones and C₃₆ alkenoates, biomarkers of haptophyte origin, were measured in a 10-month sediment trap times series from the Wilkinson Basin in the Gulf of Maine (GOM). Highest biomarker flux to the seabed was observed in summertime, the period when surface waters are stratified and a persistent, subsurface chlorophyll maximum (SCM) exists within the upper thermocline and at the base of the euphotic zone throughout the GOM. Comparison of biomarker content and composition of sediment trap particles and underlying surface sediments indicates significant loss (>50%) of signal due to the impact of early diagenesis. Despite such loss, however, C₃₇ alkenone unsaturation patterns (U₃₇^K′) are not altered. Estimates of algal growth temperature made from analysis of U₃₇^K′ in these sedimentary materials correspond with water temperature measured at the SCM, identifying this biological oceanographic feature as a key site of alkenone export production to the GOM sediment record. Given the common occurrence of SCM in surface waters of the world ocean, particularly the expansive oligotrophic regions of the subtropical to temperate ocean, export of alkenones produced within such features is a potentially widespread biological oceanographic phenomenon which shapes the sediment record for these biomarkers.     

Kinetic study reveals weak Fe-binding ligand,which affects the solubility of Fe in the Scheldt estuary

The chemistry of dissolved Fe(III) was studied in the Scheldt estuary (The Netherlands). Two discrete size fractions of the dissolved bulk (< 0.2 μm and < 1 kDa) were considered at three salinities (S = 26, 10 and 0.3).Within the upper estuary, where fresh river water meets seawater, the dissolved Fe concentration decreases steeply with increasing salinity, for the fraction < 0.2 μm from 536 nM at S = 0.3 to 104 nM at S = 10 and for the fraction < 1 kDa from 102 nM to 36 nM Fe. Further downstream, in the middle and lower estuary, this decrease in the Fe concentration continues, but is far less pronounced. For all samples, the traditionally recognised dissolved strong organic Fe-binding ligand concentrations are lower than the dissolved Fe concentrations.Characteristics of dissolved Fe-binding ligands were determined by observing kinetic interactions with adsorptive cathodic stripping voltammetry. From these kinetic experiments we concluded that apart from the well-known strong Fe-binding organic ligands (L, logK′ = 19–22) also weak Fe-binding ligands (P) existed with an α value (binding potential = K′ · [P]) varying between 10^11.1 and 10^11.9. The presence of this relatively weak ligand explained the high concentrations of labile Fe present in both size fractions in the estuary. This weak ligand can retard or prevent a direct precipitation after an extra input of Fe.The dissociation rate constants of the weak ligand varied between 0.5 × 10^− 4 and 4.3 × 10^− 4 s^− 1. The rate constants of the strong organic ligand varied between k_d = 1.5 × 10^− 3–17 × 10^− 2 s^− 1 and k_f = 2.2 × 10⁸–2.7 × 10⁹ M^− 1 s^− 1. The dissociation rate constant of freshly amorphous Fe-hydroxide was found to be between 4.3 × 10^− 4 and 3.7 × 10^− 3 s^− 1, more labile or equal to the values found by Rose and Waite [Rose, A.L., Waite, T.D., 2003a. Kinetics of hydrolysis and precipitation of ferric iron in seawater. Environ. Sci. Technol., 37, 3897–3903.] for freshly precipitated Fe in seawater.Kinetic rate constants of Fe with the ligand TAC (2-(2-Thiazolylazo)-p-cresol) were also determined. The formation rate constant of Fe(TAC)₂ varied between 0.1 × 10⁸ and 3.6 × 10⁸ M^− 1 s^− 1, the dissociation rate constant between 0.2 × 10^− 5 and 17 × 10^− 5 s^− 1 for both S = 26 and S = 10. The conditional stability constant of Fe(TAC)₂ (β_Fe(TAC)2′) varied between 22 and 23.4 for S = 10 and S = 26 more or less equal to that known from the literature (logβ_Fe(TAC)2′ = 22.4; [Croot, P.L., Johansson, M., 2000. Determination of iron speciation by cathodic stripping voltammetry in seawater using the competing ligand 2-(2-Thiazolylazo)-p-cresol (TAC). Electroanalysis, 12, 565–576.]). However, at S = 0.3 the logβ_Fe(TAC)2′ was 25.3, three orders of magnitude higher. Apparently the application of TAC to samples of low salinity can only be done when the correct β_Fe(TAC)2′ is known.     

Volume transport and distribution of deep circulation at 165°W in the North Pacific

We conducted full-depth hydrographic observations between 8°50′ and 44°30′N at 165°W in 2003 and analyzed the data together with those from the World Ocean Circulation Experiment and the World Ocean Database, clarifying the water characteristics and deep circulation in the Central and Northeast Pacific Basins. The deep-water characteristics at depths greater than approximately 2000 dbar at 165°W differ among three regions demarcated by the Hawaiian Ridge at around 24°N and the Mendocino Fracture Zone at 37°N: the southern region (10–24°N), central region (24–37°N), and northern region (north of 37°N). Deep water at temperatures below 1.15 °C and depths greater than 4000 dbar is highly stratified in the southern region, weakly stratified in the central region, and largely uniform in the northern region. Among the three regions, near-bottom water immediately east of Clarion Passage in the southern region is coldest (θ<0.90 °C), most saline (S>34.70), highest in dissolved oxygen (O₂>4.2 ml l^?1), and lowest in silica (Si<135 μmol kg^?1). These characteristics of the deep water reflect transport of Lower Circumpolar Deep Water (LCDW) due to a branch current south of the Wake–Necker Ridge that is separated from the eastern branch current of the deep circulation immediately north of 10°N in the Central Pacific Basin. The branch current south of the Wake–Necker Ridge carries LCDW of θ<1.05 °C with a volume transport of 3.7 Sv (1 Sv=10⁶ m³ s^?1) into the Northeast Pacific Basin through Horizon and Clarion Passages, mainly through the latter (～3.1 Sv). A small amount of the LCDW flows northward at the western boundary of the Northeast Pacific Basin, joins the branch of deep circulation from the Main Gap of the Emperor Seamounts Chain, and forms an eastward current along the Mendocino Fracture Zone with volume transport of nearly 1 Sv. If this volume transport is typical, a major portion of the LCDW (～3 Sv) carried by the branch current south of the Wake–Necker and Hawaiian Ridges may spread in the southern part of the Northeast Pacific Basin. In the northern region at 165°W, silica maxima are found near the bottom and at 2200 dbar; the minimum between the double maxima occurs at a depth of approximately 4000 dbar (θ～1.15 °C). The geostrophic current north of 39°N in the upper deep layer between 1.15 and 2.2 °C, with reference to the 1.15 °C isotherm, has a westward volume transport of 1.6 Sv at 39–44°30′N, carrying silica-rich North Pacific Deep Water from the northeastern region of the Northeast Pacific Basin to the Northwest Pacific Basin.     

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%).     

Particulate organic carbon export fluxes and size-fractionated POC/234Th ratios in the Ligurian,Tyrrhenian and Aegean Seas

Measurements of ²³⁴Th/²³⁸U disequilibria and particle size-fractionated (1, 10, 20, 53, 70, 100 μm) organic C and ²³⁴Th were made to constrain estimates of the export flux of particulate organic C (POC) from the surface waters of the Ligurian, Tyrrhenian and Aegean Seas in March–June 2004. POC exported from the surface waters (75–100 m depth) averaged 9.2 mmol m⁻² d⁻¹ in the Ligurian and Tyrrhenian Seas (2.3±0.5–14.9±3.0 mmol m⁻² d⁻¹) and 0.9 mmol m⁻² d⁻¹ in the Aegean Sea. These results are comparable to previous measurements of ²³⁴Th-derived and sediment-trap POC fluxes from the upper 200 m in the Mediterranean Sea. Depth variations in the POC/²³⁴Th ratio suggest two possible controls. First, decreasing POC/²³⁴Th ratios with depth were attributed to preferential remineralization of organic C. Second, the occurrence of maxima or minima in the POC/²³⁴Th ratio near the DCM suggests influence by phytoplankton dynamics. To assess the accuracy of these data, the empirical ²³⁴Th-method was evaluated by quantifying the extent to which the ²³⁴Th-based estimate of POC flux, P_POC, deviates from the true flux, F_POC, defined as the p-ratio (p-ratio=P_POC/F_POC=S_Th/S_POC, where S=particle sinking rate). Estimates of the p-ratio made using Stokes’ Law and the particle size distributions of organic C and ²³⁴Th yield values ranging from 0.93–1.45. The proximity of the p-ratio to unity implies that differences in the sinking rates of POC- and ²³⁴Th-carrying particles did not bias ²³⁴Th-normalized POC fluxes by more than a factor of two.     

A suspended-particle rosette multi-sampler for discrete biogeochemical sampling in low-particle-density waters

To enable detailed investigations of early stage hydrothermal plume formation and abiotic and biotic plume processes we developed a new oceanographic tool. The Suspended Particulate Rosette sampling system has been designed to collect geochemical and microbial samples from the rising portion of deep-sea hydrothermal plumes. It can be deployed on a remotely operated vehicle for sampling rising plumes, on a wire-deployed water rosette for spatially discrete sampling of non-buoyant hydrothermal plumes, or on a fixed mooring in a hydrothermal vent field for time series sampling. It has performed successfully during both its first mooring deployment at the East Pacific Rise and its first remotely-operated vehicle deployments along the Mid-Atlantic Ridge. It is currently capable of rapidly filtering 24 discrete large-water-volume samples (30–100 L per sample) for suspended particles during a single deployment (e.g. >90 L per sample at 4–7 L per minute through 1 μm pore diameter polycarbonate filters). The Suspended Particulate Rosette sampler has been designed with a long-term goal of seafloor observatory deployments, where it can be used to collect samples in response to tectonic or other events. It is compatible with in situ optical sensors, such as laser Raman or visible reflectance spectroscopy systems, enabling in situ particle analysis immediately after sample collection and before the particles alter or degrade.     

The Manila clam population in Arcachon Bay (SW France): Can it be kept sustainable?

The venerid clam Ruditapes philippinarum is the most prominent suspension-feeding bivalve inhabiting muddy intertidal seagrass beds in Arcachon Bay (SW France). It is exploited by fishermen, and Arcachon Bay ranks number one in France in terms of production and total biomass of this species. Previous studies revealed a decrease in the standing stock of R. philippinarum since 2003 and unbalanced length–frequency distributions with a lack of juveniles and of adults > 40 mm. Consequently, the population dynamics of this bivalve were studied at four intertidal sites and one oceanic site in Arcachon Bay. As clam size structure did not allow classical dynamics computations, field monitoring was coupled with field experiments (tagging–recapture) over two years. Monitoring of condition index and gonadal maturation stages highlighted a high variability in spawning number and intensity between sites. Recruitment events in the exploited area varied spatially but with uniformly low values. Von Bertalanffy Growth Function (VBGF) parameters (K, L_∞) were determined using Appeldoorn and ELEFAN methods. In the exploited sites in the inner lagoon, K was relatively high (mean = 0.72 yr^? 1) but L_∞ was low (mean = 41.1 mm) resulting in a moderate growth performance index (Φ′ = 2.99). Growth parameters were not correlated with immersion time and L_∞ was different between sites. Comparison of mortality coefficients (Z) between cage experiments and field monitoring suggested that fishing accounts for 65–75% of total adult mortality. Low recruitment, a low growth rate and a normal mortality rate led to low somatic production (4.1 and 8.7 g Shell-Free Dry Weight (SFDW) m^? 2 yr^? 1) and an annual P/B ratio from 0.44 to 0.92 yr^? 1. Under current conditions, the possibility of a sustainable population in Arcachon Bay will strongly depend on recruitment success and fishing management.     

Air–sea CO2 fluxes in the north-eastern shelf of the Gulf of Cádiz (southwest Iberian Peninsula)

An intra-annual investigation of the fugacity of CO₂ (fCO₂) has been conducted in surface waters of the north-eastern shelf of the Gulf of Cádiz (SW Iberian Peninsula) in four cruises made in 2006 and 2007. Intra-annual variability of fCO₂ was assessed and is discussed in terms of mixing, temperature and biology. In the study area of the shelf, thermodynamic control over fCO₂ predominates from early May to late November, and this is opposite and similar in magnitude to the net biological effect. However, biological control over fCO₂ predominates during winter. The results suggest that surface waters in the coastal area are under-saturated with respect to atmospheric CO₂ during most of the year; therefore they represent a sink for atmospheric CO₂ between November and May (? 1.0 mmol m^? 2 day^? 1), but a weak source in June (1.3 mmol m^? 2 day^? 1). In contrast, the coastal ecosystems studied (the lower estuary of Guadalquivir Estuary and Bay of Cádiz) acted as a weak sink for atmospheric CO₂ during February (? 1.3 mmol m^? 2 day^? 1) and as a source between May and November (2.6 mmol m^? 2 day^? 1). The resulting mean annual CO₂ flux in the north-eastern shelf of the Gulf of Cádiz was ? 0.07 mol m^? 2 year^? 1 (? 0.2 mmol m^? 2 day^? 1), indicating that the area acts as a net sink on an annual basis.     

Population dynamics and secondary production of the cockle Cerastoderma edule: A comparison between Merja Zerga (Moroccan Atlantic Coast) and Arcachon Bay (French Atlantic Coast)

Cockle (Cerastoderma edule) population dynamics were studied at the southern limit of the distribution of this marine bivalve in Merja Zerga, Morocco. Parameters such as growth, mortality, and production were compared with those of a population at Arcachon Bay (France) a site in the center of the cockle's range. At each sampling period between two and three cohorts were simultaneously observed at each site and the average total abundance was usually higher at Merja Zerga. Recruitment occurred at both sites in spring when temperature rose above 19 °C, independently of the month. In Merja Zerga, winter recruitment was also observed at one occasion, following high sediment disturbance. The first year (2005–06) at Merja Zerga, the mortality rate was close to nil for juveniles and was Z = 1.5 yr^? 1 for adults, providing a high production (64 g dry weight m^? 2 yr^? 1). At Arcachon during the same period, the juvenile mortality rate was Z = 10.9 yr^? 1, the adult mortality rate was 3.4 yr^? 1 and production was 26 gDW m^?2 yr^? 1. The second year (2006–07), mortality after recruitment was much higher (Z = 8.6 yr^? 1, for juveniles) and similar to what was observed at Arcachon (Z = 8.4 yr^? 1). Mortality rate of adults was higher at Merja Zerga (Z = 3.0 yr^? 1) than at Arcachon (Z = 1.5 yr^? 1). Production was lower at Arcachon than at Merja Zerga although growth performances were higher at Arcachon. The higher growth performance at Arcachon (Φ′ = 3.3) was mainly due to high asymptotic length (L_∞ = 38 mm) and was related to low intraspecific competition compared to Merja Zerga where cockle abundance was higher (Φ′ = 3.1, L_∞ = 31 mm). P/B was low in both sites and slightly higher at Arcachon (1.1–1.5 against 1.0–1.1 yr^? 1). At Arcachon, recruitment was correlated with temperature, a peak occurring when temperature rose above 19 °C (June–July). At Merja Zerga, recruitment was already 2–3 months earlier but was not significantly correlated to temperature.This study showed that population dynamics of cockles at the southern limit of this distribution fell in the range of what was observed elsewhere in the North-Eastern Atlantic coast. Most factors that were involved in population regulation (intraspecific competition, predation and sediment dynamics) were not strictly dependent on latitude. The direct role of temperature (latitude dependent factor) was not obvious. Variation in temperature could explain the recruitment delay between Arcachon and Merja Zerga and the low maximum shell length at Merja Zerga.     

Rapid lateral particle transport in the Argentine Basin: Molecular 14C and 230Thxs evidence

Recent studies have revealed that lateral transport and focusing of particles strongly influences the depositional patterns of organic matter in marine sediments. Transport can occur in the water column prior to initial deposition or following sediment re-suspension. In both cases, fine-grained particles and organic-rich aggregates are more susceptible to lateral transport than coarse-grained particles (e.g., foraminiferal tests) because of the slower sinking velocities of the former. This may lead to spatial and, in the case of redistribution of re-suspended sediments, temporal decoupling of organic matter from coarser sediment constituents. Prior studies from the Argentine Basin have yielded evidence that suspended particles are displaced significant distances (100–1000 km) northward and downslope by strong surface and/or bottom currents. These transport processes result in anomalously cold alkenone-derived sea-surface temperature (SST) estimates (up to 6 °C colder than measured SST) and in the presence of frustules of Antarctic diatom species in surface sediments from this area. Here we examine advective transport processes through combined measurements of compound-specific radiocarbon ages of marine phytoplankton-derived biomarkers (alkenones) from core tops and excess ²³⁰Th (²³⁰Th_xs)-derived focusing factors for late Holocene sediments from the Argentine Basin. On the continental slope, we observe ²³⁰Th_xs-based focusing factors of 1.4–3.2 at sites where alkenone-based SST estimates were 4–6 °C colder than measured values. In contrast, alkenone radiocarbon data suggest coeval deposition of marine biomarkers and planktic foraminifera, as alkenones in core tops were younger than, or similar in age to, foraminifera. We therefore infer that the transport processes leading to the lateral displacement of these sediment components are rapid, and hence probably occur in the upper water column (<1500 m).     

Atmospheric input of dissolved inorganic phosphorus and silicon to the coastal northwestern Mediterranean Sea: Fluxes,variability and possible impact on phytoplankton dynamics

One hundred twelve rainwater samples collected from 1986 to 2003 at the signal station of Cap Ferrat (France, NW Mediterranean coast) were analysed for phosphate and silicate contents. This sampling site is affected by a European urban-dominated background material, with episodic Saharan dust inputs. The input of dissolved inorganic phosphorus (DIP) and dissolved inorganic silicon (DISi) was calculated. The most significant loadings of DIP and DISi were selected in order to assess their potential impact on phytoplankton dynamics, particularly in oligotrophic conditions, when surface waters are nutrient-depleted. The theoretical new production triggered by DIP and DISi inputs (NP_atmo) was estimated through Redfield calculations. The maximum theoretical DIP-triggered NP_atmo was up to 670 mg C m⁻² in October, at the end of the oligotrophic period (135 mg C m⁻³ in the 5 m-thick surface layer). During the same period, the daily integrated primary production measured at the DYFAMED site (NW Mediterranean Sea) was on average 219 mg C m⁻² d⁻¹ within the 0–100 m depth water column, while the mean daily primary production in the 5 m-thick surface layer was 1.6 mg C m⁻³ d⁻¹. However, high NP_atmo due to high DIP inputs might be episodically limited by lower DISi inputs, which may consequently lead to episodic preferential growth of non-siliceous phytoplanktonic species.     

Contrasting life-histories,secondary production,and trophic structure of Peracarid assemblages of the bathyal suprabenthos from the Bay of Biscay (NE Atlantic) and the Catalan Sea (NW Mediterranean)

The life-histories and the secondary production of four dominant peracarid crustaceans (the mysids Boreomysis arctica and Parapseudomma calloplura, the amphipod Rhachotropis caeca, and the isopod Ilyarachna longicornis) in bathyal depths of the Bay of Biscay (NE Atlantic; between 383 and 420 m) and the Catalan Sea (Northwestern Mediterranean; between 389 and 1355 m) were established. Both the Atlantic and the Mediterranean populations of the major part of the target-species had two generations/year with mean cohort-production intervals (CPI) ranging from 5.5 mo for Ilyarachna longicornis to 6.3 mo for Parapseudomma calloplura. The Hynes method showed secondary production to vary in the Bay of Biscay between 0.113 mg DW m⁻² yr⁻¹ for I. longirostris and 3.069 mg DW m⁻² yr⁻¹ for P. calloplura, with P/B ratios between 4.57 (I. longirostris) and 7.93 (Boreomysis arctica). In the Catalan Sea, production varied between 0.286 mg DW m⁻² yr⁻¹ for I. longirostris and 1.096 mg DW m⁻² yr⁻¹ for P. calloplura, with P/B between 5.72 (I. longirostris) and 6.66 (P. calloplura). Application of two different empiric models to the whole peracarid assemblage gave similar levels of secondary production in both study areas (between 29.26 and 32.14 mgDWm⁻² yr⁻¹ in the Bay of Biscay; between 26.23 and 26.54 mg DW m⁻² yr⁻¹ in the Catalan Sea). From the analysis of gut contents of 22 species the dominant species in each study area were assigned to two basic trophic levels, detritus feeders and predators. Also, cumulative curves of dominance showed high diversity (low dominance) for peracarid assemblages distributed at mid-bathyal depths (524–693 m) both in the Bay of Biscay off Arcachon and in the Catalan Sea off Barcelona. We also discuss and compare, both within and between areas, how environmental features may explain the observed diversity patterns, the trophic structure, and the production results obtained for the suprabenthos assemblages.     

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.     

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.