Zinc speciation in the Northeastern Atlantic Ocean

Measurements of zinc and zinc complexation by natural organic ligands in the northeastern part of the Atlantic Ocean were made using cathodic stripping voltammetry with ligand competition. Total zinc concentrations ranged from 0.3 nM in surface waters to 2 nM at 2000 m for open-ocean waters, whilst nearer the English coast, zinc concentrations reached 1.5 nM in the upper water column. In open-ocean waters zinc speciation was dominated by complexation to a natural organic ligand with conditional stability constant (log K_ZnL′) ranging between 10.0 and 10.5 and with ligand concentrations ranging between 0.4 and 2.5 nM. The ligand was found to be uniformly distributed throughout the water column even though zinc concentrations increased with depth. Organic ligand concentrations measured in this study are similar to those published for the North Pacific. However the log K_ZnL′ values for the North Atlantic are almost and order of magnitude lower than those reported by Bruland [Bruland, K.W., 1989. Complexation of zinc by natural organic-ligands in the central North Pacific. Limnol. Oceanogr., 34, 269–285.] using anodic stripping voltammetry for the North Pacific. Free zinc ion concentrations were low in open-ocean waters (6–20 pM) but are not low enough to limit growth of a typical oceanic species of phytoplankton.     

Organic complexation and its control of the dissolved concentrations of copper and zinc in the Scheldt estuary

Cathodic stripping voltammetry (CSV) is used to determine total (after UV-irradiation) and labile dissolved metal concentrations as well as complexing ligand concentrations in samples from the river Scheldt estuary. It was found that even at high added concentrations of catechol (1 m for copper and 0·4 m for iron) and of APDC (1 m for zinc) only part of the dissolved metal was labile (5–58% for copper, 34–69% for zinc, 10–38% for iron); this discrepancy could be explained by the low solubility of iron which is largely present as colloidal material, and by competition for dissolved copper and zinc by organic complexing ligands. Ligand concentrations varied between 28 and 206 n for copper and between 22 and 220 n for zinc; part of the copper complexing ligands could be sub-divided into strong complexing sites with concentrations between 23 and 121 n and weaker sites with concentrations between 44 and 131 n . Values for conditional stability constants varied between (logK′ values) 13·0 and 14·8 for strong and between 11·5 and 12·1 for weaker copper complexing ligands, whereas for zinc the values were between 8·6 and 10·6. The average products of ligand concentrations and conditional stability constants (a-coefficients) were 6 × 10² for zinc and 6 × 10⁶ for copper.The dissolved zinc concentration was found to co-vary with the zinc complexing ligand concentration throughout the estuary. It is argued that the zinc concentration is regulated, in this estuary at least, by interactions with dissolved organic complexing ligands. A similar relationship was apparent between the dissolved copper and the strong copper complexing ligand concentration. The total copper complexing ligand concentrations were much greater than the dissolved copper concentrations, suggesting that only strongly complexed copper is kept in solution.These results provide evidence for the first time that interactions of copper and zinc with dissolved organic complexing ligands determine the geochemical pathway of these metals.     

Cu complexation by organic ligands in the sub-arctic NW Pacific and Bering Sea

Cu speciation was characterized at three stations in the sub arctic NW Pacific and Bering Sea using cathodic stripping voltammetry with the competing ligands benzoylacetone and salicylaldoxime. A single ligand model was fit to the titration data, yielding concentrations throughout the water column of ∼3–4 nM, and conditional stability constants ranging from 10^12.7 to 10^14.1, this range being partly due to the choice of competing ligand. Free Cu²⁺ in surface waters was 2–4×10⁻¹⁴ M, in close agreement with values reported by previous workers in the NE Pacific using anodic stripping voltammetry (ASV). However, those results showed that complexation by strong organic ligands becomes unimportant below 200–300 m, while our data indicated Cu is strongly complexed to depths as great as 3000 m. Free Cu²⁺ concentrations in surface waters reported here and in previous work are close to the threshold value where Cu can limit the acquisition of Fe by phytoplankton.     

Eddy Diffusion Coefficients of Suspended Particulate Matter: Effects of Wind Energy Transfer and Stratification

Gross sedimentation rates (GSR) have been measured using sediment traps placed at nine different levels above the bed (0·3, 0·5, 0·8, 1·0, 2·0, 4·0, 6·0, 8·0 and 10·0 m). The sediment traps were deployed for 1·25 years and recovered 28 times during the study period. Low average GSR values of 5·5 g m^-2 day^-1 were obtained at 10·0 m, and high average GSR values of 114·8 g m^-2 day^-1 were obtained at 0·3 m. An expression for the eddy diffusion coefficient of suspended particulate matter (K_s), based on the measured GSR is given. The expression has been used for modelling of K_s at the different trap levels above the bed. High values (≈42 cm² s^-1) of K_s were obtained at the upper traps, whereas low values (≈2 cm² s^-1) were obtained near the bed. Comparison between level of turbulent energy in terms of shear stress at the boundaries of the water column, i.e. from the wind and the bed flow, showed that wind energy exceeded that of the bed flow by a factor 16. At 5·0 m K_s was positively correlated (r=0·66) to the eddy diffusion coefficient of momentum (K_m) derived from the wind energy transfer to the water, giving an average β of 0·5 for K_s =βK_m. The density difference between surface and bottom waters has been designated a parameter of stratification, and is discussed in relation to variations of K_s and K_m .     

Solubility of calcite in the ocean

The apparent solubility product K′_sp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of K′_sp at 25°C was 4.59·10⁻⁷ mole²/(kg seawater)² at 35‰S, 5.34·10⁻⁷ at 43‰S, and 3.24·10⁻⁷ at 27‰S. The apparent partial molal volume was found to be −34.4 cm³ at 25°C and −42.3 cm³ at 2°C from a linear fit of log(K′_sp ^P/K′_sp ¹). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.     

The influence of a mature cyclonic eddy on particle export in the lee of Hawaii

Mesoscale eddies may enhance primary production (PP) in the open ocean by bringing nutrient-rich deep waters into the euphotic zone, potentially leading to increased transport of particles to depth. This hypothesis remains controversial, however, due to a paucity of direct particle export measurements. In this study, we investigated particle dynamics using ²³⁴Th–²³⁸U disequilibria within a mesoscale cold-core eddy, Cyclone Opal, which formed in the lee of the Hawaiian Islands. ²³⁴Th samples were collected along two transects across Cyclone Opal as well as during a time-series within the eddy core during a decaying diatom bloom. Particulate carbon (PC), particulate nitrogen (PN) and biogenic silica (bSiO₂) fluxes at 150 m varied spatially and temporally within the eddy and strongly depended on the ²³⁴Th model formulation used (e.g., steady state versus non-steady state, inclusion of upwelling, etc.). Particle fluxes estimated from a steady state model assuming an upwelling rate of 2 m day⁻¹ yielded the best fit to sediment-trap data. These ²³⁴Th-derived particle fluxes ranged from 332±14 to 1719±53 μmol C m⁻² day⁻¹, 27±3 to 114±12 μmol N m⁻² day⁻¹, and 33±20 to 309±73 μmol Si m⁻² day⁻¹. Although PP rates within Cyclone Opal were elevated by a factor of 2–3, PC and PN fluxes were the same, within error, inside and outside of Cyclone Opal. The ratio of PC export to PP remained surprisingly low at <0.03 and similar to those measured in surrounding waters. In contrast, bSiO₂ fluxes within the eddy core were three times higher. Detailed analyses of ²³⁴Th depth profiles consistently showed excess ²³⁴Th at 100–175 m, associated with the remineralization and possible accumulation of suspended and dissolved organic matter from the surface. We suggest that strong microzooplankton grazing facilitated particulate organic matter recycling and resulted in the export of empty diatom frustules. Thus, while eddies may increase PP, they do not necessarily increase PC and PN export to deep waters. This may be a general characteristic of wind-driven cyclonic eddies of the North Pacific Subtropical Gyre and suggests that eddies may preferentially act as a silica pump, thereby playing an important role in promoting silicic-acid limitation in the region.     

Apparent copper complexation capacity and conditional stability constants in north atlantic waters

Surface water samples were collected in the north Atlantic Ocean in July–August 1983. Their apparent complexation capacity for copper (CC_Cu) was determined on board, using differential pulse anodic stripping voltammetry under clean room conditions. Measurements were carried out by direct titrations as well as after equilibration of copper spikes. CC_Cu and conditional stability constants (K′) were calculated, by means of three different methods, which are compared.On the basis of salinity, temperature, silicate and phosphate concentrations the following surface waters could be distinguished: North Atlantic Drift (I), East Greenland Current (II), Labrador Current (III) and Gulf Stream waters (IV, V). CC_Cu and K′ were found to differ between these waters. The range of values for CC_Cu and their mean values given in parentheses, as calculated from van den Berg plots for waters I–IV are: I, 53–65 (59); II, 47–66 (55); III, 37–53 (45); IV, 20–42 (33) nM Cu. The range and mean values for log K′ are: I, 8.23–8.33 (8.28); II, 7.89–8.11 (7.98); III, 8.40–8.41 (8.41); IV, 7.90–8.21 (8.06).Information on complexation kinetics extracted from the titration curve revealed that k_f^′ is area-specific. The complexation rate constant in the northern part (Area I) is about two times larger than that in the southern area IV, (3.6 ± 0.3) and (2.2 ± 0.2) × 10⁴s⁻¹M⁻¹ Cu, respectively.Preliminary results for deep water samples suggest smaller but still existent CC_Cu and higher K′ than those found for surface waters.     

Physico-chemical Speciation of Lead in South San Francisco Bay

The speciation of lead at a site in the South San Francisco Bay was determined using a combination of physical size fractionation and electrochemical analyses. The ‘ total dissolvable ’ Pb was 8·1 nM from analysis of an acidified unfiltered sample. The ‘ dissolved ’ Pb was equal to 0·20 nM (41 ng l⁻¹), only 2·5% of the ‘ total dissolvable ’ Pb. The difference yielded the ‘ particulate ’ Pb equal to 7·9 nM (1·6 μg l⁻¹). Results from crossflow ultrafiltration indicated that almost all (0·19 nM) of the dissolved Pb was ‘ in solution ’ [<10K nominal molecular weight (MW)] and that colloidal Pb (10K MW to 0·2 μm)accounted for onlyc. 1% of the dissolved Pb at this station. This small concentration (0·01 nM) of colloidal Pb may be attributed to the low amount of organic carbon associated with colloid size fraction as determined by dissolved organic carbon analyses.The chemical speciation of lead was determined in the dissolved sample and ultrafiltered sub-sample. Differential pulse anodic stripping voltammetry (DPASV) on a thin mercury film (TMF) rotating glassy carbon disk electrode (RGCDE) was used to distinguish the kinetically labile inorganic species (Pb′) from the Pb-chelated by organic ligands (PbL_i). Lead titration results were similar for both samples revealing that Pb′, PbL_iand excess unbound ligands were present primarily in the ultrafiltrate, rather than in the colloidal phase. The titration data can be interpreted as dissolved Pb being influenced by two classes of Pb-binding ligands. In the dissolved sample, the concentration of the stronger class of ligands was [L₁]=0·89±0·35 nM, with a conditional stability constant ofK^cond_L1,Pb′=3±1×10¹⁰M⁻¹. The weaker class was [L₂]=12·8±1·9 nM, withK^cond_L1,Pb′=4±1×10⁸ M⁻¹. The presence of these ligands, in excess of the dissolved Pb, resulted in [Pb′]=7±2 pM and [Pb²⁺]=0·3 pM (62 pg l⁻¹). While less than 2·4% of the ambient Pb was ‘ in solution ’, it existed chiefly in the form of organic complexes with [PbL₁]=0·15 nM and [PbL₂]=0·03 nM. More significantly, there were large concentrations of unchelated Pb-binding ligands, (L_i′), available to buffer the free Pb²⁺concentration in the event of perturbations in dissolved Pb.     

Adsorption of lead and cadmium ions on calcite in the Krka estuary

The adsorption of Pb²⁺ and of Cd²⁺ ions from calcareous Krka river water of various salinities (3, 14, 20 and 38 psu) on calcite (CaCO₃, Merck p.a.) was investigated. Simultaneous adsorption of Pb²⁺ and Cd²⁺ ions was studied as well. The results suggest that the two ions are adsorbed at different calcite surface sites; Pb²⁺ remained firmly bound to calcite at all salinities, whereas Cd²⁺ was firmly bound at low salinities and released at high salinities. Dissolved natural organic ligands at the freshwater-seawater interface (FSI; at 14 psu) promoted and below the FSI (at 20 psu) decreased the adsorption of Cd²⁺. The experiments were performed at metal concentrations of 8 × 10⁻⁸ mol l⁻¹ and at natural pH values around pH 8. Adsorbed amounts of trace metal ions were determined in filtered samples by differential pulse anodic stripping voltammetry (DPASV) with a three-electrode system, after 24 h of equilibration with calcite. Several adsorption models were tested, such as Freundlich's, Langmuir's and Schindler-Stumm's surface coordination model. Adsorption isotherms belong to S-1 class of empirical adsorption isotherms. None gave reasonable values of adsorption constants. The fractional partitioning of adsorbent to the solid phase when normalized to the quantity of adsorbent present (K_d) declined as solid concentration increased. It was found that the surface charge is not responsible for the observed effect. Instead, aggregate size increased, which effected a loss in surface area. This is a reasonable explanation for the observed S-shaped adsorption isotherms curves.     

Metabolic activity of pelagic copepods from 5,000 to 7,000 m depth of the western subarctic Pacific,as inferred from electron transfer system (ETS) activity

This study demonstrates reduced electron transfer system (ETS) activity of mixed copepods collected from 5,000 to 7,000 m depths [3.21 ± 1.25 μl O₂ (mg protein)⁻¹ h⁻¹ at 10°C] as compared with mixed copepods from 0 to 200 m depths [5.93 ± 1.66 μl O₂ (mg protein)⁻¹ h⁻¹ at 10°C] of the western subarctic Pacific. At the in situ temperature of 1.5°C, the 5,000–7,000 m ETS data, in terms of wet mass (WM)-specific respiration rates (R), is equivalent to [0.052 ± 0.021 μl O₂ (mg WM)⁻¹ h⁻¹] which is similar to or greater than those reported for selected copepods or mixed mesozooplankton from <5,000 m depth by previous workers.     

Increase of anthropogenic CO2 in the Pacific Ocean over the last two decades

The multiple-parameter linear regression method (Monitoring global ocean carbon inventories. Ocean Observing System Development Panel, Texas A&M University, College Station, TX, 1995, 54pp; Global Biogeochem. Cycles 13 (1999) 179) is used to compare inorganic carbon data from the GEOSECS CO₂ survey in the Pacific Ocean in 1973 to the WOCE/JGOFS global CO₂ survey in the 1990s. A model of total dissolved inorganic carbon (DIC) as a function of five variables (AOU, θ, S, Si, and PO₄) has been developed from the recent CO₂ survey data (namely CGC91 and CGC96) in the Pacific Ocean. After correcting for a systematic DIC offset of −30.3±7 μmol kg⁻¹ from the GEOSECS data, the residual DIC based on this model as computed from GEOSECS data has been used to estimate the anthropogenic CO₂ penetration in the Pacific Ocean. In the Northeast Pacific, we obtained an increase of CO₂ of 21.3±7.9 mol m⁻² over the period from GEOSECS in 1973 to CGC91 in 1991. This gives a mean anthropogenic CO₂ uptake rate of 1.3±0.5 mol m⁻² yr⁻¹ over this 17 year time period. In the South Pacific, north of 50°S between 180° and 120°W region, the integrated anthropogenic CO₂ inventory is estimated to be 19.7±5.7 mol m⁻² over the period from GEOSECS in 1974 to CGC96 in 1996. The equivalent mean CO₂ uptake rate is estimated to be 0.9±0.3 mol m⁻² yr⁻¹ over the 22 years. These results are compared with the isopycnal method (Nature 396 (1998) 560) to estimate the anthropogenic CO₂ signal in the Northeast Pacific (30°N, 152°W) at the crossover region between CGC91 and GEOSECS. The results of the isopycnal method are consistent with those derived from the MLR method. Both methods show an increase in anthropogenic CO₂ inventory in the ocean over two decades that is consistent with the increase expected if the ocean uptake has kept pace with the atmospheric CO₂ increase.     

Water masses and currents of deep circulation southwest of the Shatsky Rise in the western North Pacific

We conducted full-depth hydrographic observations in the southwestern region of the Northwest Pacific Basin in September 2004 and November 2005. Deep-circulation currents crossed the observation line between the East Mariana Ridge and the Shatsky Rise, carrying Lower Circumpolar Deep Water westward in the lower deep layer (θ<1.2 °C) and Upper Circumpolar Deep Water (UCDW) and North Pacific Deep Water (NPDW) eastward in the upper deep layer (1.3–2.2 °C). In the lower deep layer at depths greater than approximately 3500 m, the eastern branch current of the deep circulation was located south of the Shatsky Rise at 30°24′–30°59′N with volume transport of 3.9 Sv (1 Sv=10⁶ m³ s⁻¹) in 2004 and at 30°06′–31°15′N with 1.6 Sv in 2005. The western branch current of the deep circulation was located north of the Ogasawara Plateau at 26°27′–27°03′N with almost 2.1 Sv in 2004 and at 26°27′–26°45′N with 2.7 Sv in 2005. Integrating past and present results, volume transport southwest of the Shatsky Rise is concluded to be a little less than 4 Sv for the eastern branch current and a little more than 2 Sv for the western branch current. In the upper deep layer at depths of approximately 2000–3500 m, UCDW and NPDW, characterized by high and low dissolved oxygen, respectively, were carried eastward at the observation line by the return flow of the deep circulation composing meridional overturning circulation. UCDW was confined between the East Mariana Ridge and the Ogasawara Plateau (22°03′–25°33′N) in 2004, whereas it extended to 26°45′N north of the Ogasawara Plateau in 2005. NPDW existed over the foot and slope of the Shatsky Rise from 29°48′N in 2004 and 30°06′N in 2005 to at least 32°30′N at the top of the Shatsky Rise. Volume transport of UCDW was estimated to be 4.6 Sv in 2004, whereas that of NPDW was 1.4 Sv in 2004 and 2.6 Sv in 2005, although the values for NPDW may be slightly underestimated, because they do not include the component north of the top of the Shatsky Rise. Volume transport of UCDW and NPDW southwest of the Shatsky Rise is concluded to be approximately 5 and 3 Sv, respectively. The pathways of UCDW and NPDW are new findings and suggest a correction for the past view of the deep circulation in the Pacific Ocean.     

Particle export within cyclonic Hawaiian lee eddies derived from Pb–Po disequilibrium

Particle export from the upper waters of the oligotrophic ocean may play a crucial role in the global carbon cycle. Mesoscale eddies have been hypothesized to inject new nutrients into oligotrophic surface waters, thereby increasing new production and particle export in otherwise nutrient deficient regimes. The E-Flux Program was a large multidisciplinary project designed to investigate the physical, biological and biogeochemical characteristics of cold-core cyclonic eddies that form in the lee of the Hawaiian Islands. There, we investigated particle dynamics using ²¹⁰Pb–²¹⁰Po disequilibrium. Seawater samples for ²¹⁰Pb and ²¹⁰Po were collected both within (IN) and outside (OUT) of two cyclones, Noah and Opal, at different stages of their evolution as well as from the eddy generation region. Particulate carbon (PC), particulate nitrogen (PN) and biogenic silica (bSiO₂) export fluxes were determined using water-column PC, PN, and bSiO₂ inventories and the residence times of ²¹⁰Po. PC and PN fluxes at 150 m ranged from 1.58±0.10 to 1.71±0.16 mmol C m⁻² d⁻¹ and 0.22±0.02 to 0.30±0.02 mmol N m⁻² d⁻¹ within Cyclones Opal and Noah. PC and PN fluxes at OUT stations sampled during both cruises were of similar magnitudes, 1.69±0.16 to 1.67±0.16 mmol C m⁻² d⁻¹ and 0.30±0.03 to 0.26±0.03 mmol N m⁻² d⁻¹. The bSiO₂ fluxes within Cyclone Opal were 0.157±0.010 mmol Si m⁻² d⁻¹ versus 0.025±0.002 mmol Si m⁻² d⁻¹ at OUT stations. These results of minimal PC and PN export, but significant eddy-induced bSiO₂ fluxes, agree very well with other studies that used a variety of direct and indirect methods. Thus, our results suggest that using elemental inventories and residence times of ²¹⁰Po is another independent and robust method for determining particle export and should be investigated more fully.     

Analysis of marine DOC using a dry combustion method

As part of a continuing effort to verify and improve measurements of marine dissolved organic carbon (DOC), we combusted dried sea salts + adhered organic matter to assay DOC concentrations in representative samples from the Atlantic and Pacific oceans. Combustions were performed overnight at 580 °C in sealed tubes, and oxidation of organic materials occurred via a novel mechanism, thermal sulfate reduction: 2H₂SO₄ + CH₂O → 2SO₂ + 3H₂O + CO₂Measured DOC concentrations ranged from 43 to 114 μM C, with highest values observed in inshore surface samples from Woods Hole Harbor, and lowest values observed in twelve deep offshore Atlantic and Pacific waters. Stable carbon isotope values determined for all samples were near − 22%., consistent with a predominantly marine phytoplankton origin for DOC. A seasonal study in Woods Hole Harbor showed no significant temporal trend in nearshore DOC concentrations. Problems associated with sample storage and contamination during drying steps prevented highly precise (± 1 μM) DOC concentration determinations; however, an improved drying and measurement system is outlined (Appendix A) for possible future dry-combustion studies of DOC concentrations.     

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

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

Benthic microalgal biomass in sediments of Onslow Bay, North Carolina

Sediment samples were collected at stations along cross-shelf transects in Onslow Bay, North Carolina, during two cruises in 1984 and 1985. Station depths ranged from 11 to 285 m. Sediment chlorophyll a concentrations ranged from 0·06 to 1·87 μg g⁻¹ sediment (mean, 0·55), or 2·6–62·0 mg m². Areal sediment chlorophyll a exceeded water column chlorophyll a a at 16 of 17 stations, especially at inshore and mid-shelf stations. Sediment ATP concentrations ranged from 0 to 0·67 μg g⁻¹ sediment (mean, 0·28). Values for both biomass indicators were lowest in the depth range including the shelf break (50–99 m). Organic carbon contents of the sediments were uniformly low across the shelf, averaging 0·159% by weight. Photography of the sediments revealed extensive patches of microalgae on the sediment surface.Our data suggest that viable benthic microalgae occur across the North Carolina continental shelf. The distribution of benthic macroflora on the North Carolina shelf indicates that sufficient light and nutrients are available to support primary production out to the shelf break. Frequent storm-induced perturbations do not favour settling of phytoplankton, an alternative explanation for the presence of microalgal pigments in the sediments. Therefore, we propose that a distinct, productive benthic microflora exists across the North Carolina continental shelf.     

Helium Isotopes in Pacific Waters from Adjacent Region of Honshu, Japan

We have measured helium isotopic ratios of thirty-seven Pacific water samples from various depths collected in adjacent regions of Honshu, Japan. The ³He/⁴He ratios vary significantly from 0.989 R _atm to 1.208 R _atm where R _atm is the atmospheric ratio of 1.39 × 10⁻⁶. The mid-depth (750–1500 m) profile of ³He/⁴He ratios at ST-1 located Northwestern Pacific Ocean east of Japan (Off Joban; 37°00′ N, 142°40′ E) is significantly different from that at ST-2 of the Northern Philippine Sea south of Japan (Nankai Trough; 33°07′ N, 139°59′ E), suggesting that these waters were separated by a topographic barrier, the Izu-Ogasawara Ridge. Taking ³He/⁴He data of the Geosecs expeditions in the western North Pacific, an extensive plume of 15% excess ³He relative to the air may be traced at ST-1 over 12,000 kilometers to the northwest of the East Pacific Rise where the mantle helium may originate. The 20% excess found at ST-2 may be attributable to the additional source of the subduction-type mantle helium in the Okinawa Trough. A 15% excess of ³He has also been discovered at a depth of about 1000∼1500 m at ST-3 adjacent to Miyakejima Island (33°57′ N, 139°22′ E) and ST-4 of Sagami Bay (35°00′ N, 139°22′ E). It is confirmed that mid-depth all over the western North Pacific water is affected by the mantle helium with a high ³He/⁴He ratio. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Thorium isotopes as tracers of particles dynamics and deep water circulation in the Indian sector of the Southern Ocean (ANTARES IV)

Dissolved and particulate samples were collected to study the distribution of thorium isotopes (²³⁴Th, ²³²Th and ²³⁰Th) in the water column of the Indian sector of the Southern Ocean (from 42°S to 47°S and from 60°E to 66°E, north of the Polar Front) during Austral summer 1999. Vertical profiles of excess ²³⁰Th (²³⁰Th_xs) increases linearly with depth in surface water (0–100 m) and a model was applied to estimate a residence time relative to the thorium scavenging (τ_scav). Low τ_scav in the Polar Front Zone (PFZ) are found, compared to those estimated in the Subtropical Front Zone (STZ). Changes in particle composition between the PFZ and STZ could influence the ²³⁰Th_xs scavenging efficiency and explain this difference. An innovative coupling between ²³⁴Th and ²³⁰Th_xs was then used to simultaneously constrain the settling velocities of small (0.6–60 μm) and large (above 60 μm) particles. Although the different hydrological and biogeochemical regimes visited during the ANTARES IV cruise did not explain the spatial variation of sinking velocity estimates, our results indicate that less particles may reach the seafloor north (60 ± 2 m d^− 1, station 8) than south of the Agulhas Return Current (119 ± 23 and 130 ± 5 m d^− 1 at stations 3 and 7, respectively). This information is essential for understanding particle transport and by extension, carbon export. In the deep water column, the ²³⁰Th_xs concentrations did not increase linearly with depth, probably due to lateral transport of North Atlantic Deep Water (NADW) from the Atlantic to the Indian sector, which renews the deep waters and decreases the ²³⁰Th_xs concentrations. A specific ²³⁰Th_xs transport model is applied in the deep water column and allows us to assess a “travel time” of NADW ranging from 2 to 15 years.     

Evaluation of abyssal meiobenthos in the eastern central Pacific (Clarion-Clipperton fracture zone)

Meiobenthos were sampled from 17 stations in the abyssal deep-sea system of the central Pacific centered around 14°N, 130°W at depths 4960–5154m, during the Nixo 47 R/V Jean Charcot cruise. Meiofaunal density range from 45–89 ind. 10cm². Predominant taxa are nematodes (84–100%) and copepods (0–10%). Rotifera, Polychaeta, and Acarina also occur. Nematodes are uniformly distributed spatially with 45 species or so; Monhysteridae is the dominant taxon, and Syringolaimus sp. (Ironidae) co-occurs faithfully. Low biomass (0.4–70.6μg 10cm²) are attributed to supposed dwarfism of metazoan meiofauna and very high proportion (60–80%) of juveniles and pre-adult forms. The majority of protozoans and metazoans are detritus- or deposit-feeders; in addition symbiotic associations, coprophagy and gardening activities are frequent. In such an oligotrophic environment, low food supply may limit meiofaunal abundance, biomass and maturation, and to a lesser extent species richness.