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.     

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.     

Organic complexation of iron in the Southern Ocean

The chemical speciation of iron was determined in the Southern Ocean along a transect from 48 to 70°S at 20°E. Dissolved iron concentrations were low at 0.1–0.6 nM, with average concentrations of 0.25±0.13 nM. Organic iron complexing ligands were found to occur in excess of the dissolved iron concentration at 0.72±0.23 nM (equivalent to an excess of 0.5 nM), with a complex stability of log K_FeL′=22.1±0.5 (on the basis of Fe³⁺ and L′). Ligand concentrations were higher in the upper water column (top 200 m) suggesting in situ production by microorganisms, and less at the surface consistent with photochemical breakdown. Our data are consistent with the presence of stable organic iron-complexing ligands in deep global ocean waters at a background level of ∼0.7 nM. It has been suggested that this might help stabilise iron at levels of ∼0.7 nM in deep ocean waters. However, much lower iron concentrations in the waters of the Southern Ocean suggest that these ligands do not prevent the removal of iron (by scavenging or biological uptake) to well below the concentration of these ligands. Scavenging reactions are probably inhibited by such ligand competition, so it is likely that biological uptake is the chief cause for the further removal of iron to these low levels in waters that suffer from very low iron inputs.     

Influence of Asian monsoon and ENSO events on particle fluxes in the western subtropical Pacific

A time-series sediment trap was deployed from October 2007 to May 2011 in the western subtropical Pacific with the aim of understanding the seasonal and inter-annual variability on particle flux in response to El Niño-Southern Oscillation (ENSO) events. Total mass fluxes varied from 3.04 mg m⁻² day⁻¹ to 31.1 mg m⁻² day⁻¹, with high fluxes during February–April and low fluxes during other months. This seasonal variation was also characterized by a distinct change in the CaCO₃ flux between the two periods. The marked increase in particle flux during February–April may be attributed to enhanced biological productivity in surface waters caused by strong wind-driven mixing in response to the western North Pacific monsoon system. The 2009/10 strong El Niño was accompanied by a significant reduction in particle flux, whereas the La Niña had no recognizable effect on particle flux in the subtropical Pacific. In particular, in the mature phase of the 2009/10 strong El Niño, the fluxes of organic carbon and biogenic silica decreased by 70–80% compared with those during the normal period, implying that the El Niño acted to suppress biological productivity in surface waters. The suppression of biological productivity during the 2009/10 strong El Niño is attributed to the decrease in precipitation due to the shift in the western Pacific warm pool. This finding is opposite that of other studies of the western equatorial Pacific, where El Niño events were observed to result in an increase in biological productivity and particle flux. The difference in particle flux between the western equatorial and subtropical Pacific is attributed to the regional differences in oceanic and atmospheric circulation systems generated by the strong El Niño.     

Speciation of Fe in the Eastern North Atlantic Ocean

In the Eastern North Atlantic Ocean iron (Fe) speciation was investigated in three size fractions: the dissolvable from unfiltered samples, the dissolved fraction (<0.2 μm) and the fraction smaller than 1000 kDa (<1000 kDa). Fe concentrations were measured by flow injection analysis and the organic Fe complexation by voltammetry. In the research area the water column consisted of North Atlantic Central Water (NACW), below which Mediterranean Overflow Water (MOW) was found with the core between 800 and 1000 m depth. Below 2000 m depth the North Atlantic Deep Water (NADW) proper was recognised. Dissolved Fe and Fe in the <1000 kDa fraction showed a nutrient like profile, depleted at the surface, increasing until 500–1000 m depth below which the concentration remained constant. Fe in unfiltered samples clearly showed the MOW with high concentrations (4 nM) compared to the overlying NACW and the underlying NADW, with 0.9 nM and 2 nM Fe, respectively. By using excess ligand (Excess L) concentrations as parameter we show a potential to bind Fe. The surface mixed layer had the highest excess ligand concentrations in all size fractions due to phytoplankton uptake and possible ligand production. The ratio of Excess L over Fe proved to be a complementary tool in revealing the relative saturation state of the ligands with Fe. In the whole water column, the organic ligands in the larger colloidal fraction (between 0.2 μm and 1000 kDa) were saturated with Fe, whereas those in the smallest fraction (<1000 kDa) were not saturated with Fe, confirming that this fraction was the most reactive one and regulates dissolution and colloid aggregation and scavenging processes. This regulation was remarkably stable with depth since the alpha factor (product of Excess L and K′), expressing the reactivity of the ligands, did not vary and was 10¹³. Whereas, in the NACW and the MOW, the ligands in the particulate (>0.2 μm) fraction were unsaturated with Fe with respect to the dissolved fraction, thus these waters had a scavenging potential.     

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.     

Seasonality of particle-associated trace element fluxes in the deep northeast Atlantic Ocean

In the framework of the German contribution to the Joint Global Ocean Flux Study (JGOFS), deep-water fluxes of particle-associated trace elements were measured in the northeast Atlantic Ocean. The sinking particles were collected almost continuously from 1992 to 1996 at three time-series stations, L1 (33°N/22°W), L2 (47°N/20°W), and L3 (54°N/21°W), using sediment traps. The focus of the present study is the temporal variability of the particle-associated elemental fluxes of Al, Ca, Cd, Co, Cu, Fe, Mn, Ni, P, Pb, Ti, V, and Zn at a depth of 2000 m.A clear seasonality of the fluxes that persisted for several years was documented for the southernmost station (L1) at stable oligotrophic conditions in the area of the North Atlantic Subtropical Gyre East (NASTE). At L2 and L3, an episodic nature of the elemental fluxes was determined. Mesoscale eddies are known to frequently cause temporal and spatial variability in the flux of biogenic components in that area. These events modified the simple seasonal pattern controlled by the annual cycle at L2, in the North Atlantic Drift Region (NADR), and at L3, which was influenced by the Atlantic Arctic province (ARCT). All stations were characterized by an additional episodic lithogenic atmospheric supply reaching the deep sea.The integrated annual fluxes during the multi-year study revealed similar flux magnitudes for lithogenic elements (Al, Co, Fe, Ti, and V) at L2 and L3 and roughly twofold fluxes at L1. Biogenic elements (Cd, P, and Zn) showed the opposite trend, i.e., two to fourfold higher values at L2 and L3 than at L1. For Mn, Ni, and Cu, the spatial differences were smaller, perhaps because of the intermediate behavior, between lithogenic and biogenic, of these elements. Similarly, among the three study sites, there were no noticeable differences in the total annual flux of Pb.The respective lithogenic fractions of the deep-sea fluxes of Cd, Co, Cu, Mn, Ni, V, and Zn were subtracted based on the amount of Al, with the average composition of the continental crust as reference. This procedure allowed estimation of the labile trace element fraction (TE_exc) of the particles, i.e., TE taken up or scavenged during particle production and sedimentation. The ratios of TE_exc/P clearly demonstrated an enrichment of TE over labile P from biogenic surface material to the deep sea for Zn (factor 4–6), Mn (12–27), Ni (3–5), and Cu (9–25); an intermediate status for Co (0.5–2.2); and depletion for Cd vs. P (0.2–0.4). Surprisingly, the recycling behavior of excess Co was found to be similar to that of P. Hence, Co_exc behaved like a biogenic element; this is in contrast to total Co, which is dominated by the refractory lithogenic fraction.Moreover, it is argued that these excess elemental fluxes caused a loss of the dissolved elements in upper waters, since their transport reaches the deep-sea waters at 2000 m, a depth far below of deep-winter mixing and upwelling. The annual amount of excess TE exported from surface waters was estimated to be 1.3×10⁹ mol Zn y^?1, 4.4×10⁹ mol Mn y^?1, 4.9×10⁸ mol Ni y^?1, 2.2×10⁷ mol Cd y^?1, 7.4×10⁸ mol Cu y^?1, and 2.7×10⁷ mol Co y^?1 for the whole North Atlantic Ocean. Important primary sources that could replenish these losses are the aeolian and fluvial supply processes.     

Impact of submarine hydrothermal vents on the metal composition of krill and its excretion products

We have measured the metal composition and estimated the excretion rate of trace elements (Ag, Cd, Co, Cu, Ni, Pb, V and Zn) by Antarctic krill (Euphausia superba) in three locations (two located within a submarine hydrothermal vent field and one away from it) along the Antarctic Peninsula region of the Southern Ocean. Results indicated that krill excreted large amounts of Ag, Cu, Pb and Zn, (range: 1.9–41.2 pmol Ag g DW^? 1 h^? 1, 15.3–26.8 nmol Cu g DW^? 1 h^? 1, 308.7–1118.3 pmol Pb g DW^? 1 h^? 1 and 24.4–76.5 nmol Zn g DW^? 1 h^? 1), compared with the non-significant or undetectable release rates of Cd, Co, Ni and V. The metal composition of the excreted material from krill collected in the area of hydrothermal activity was similar to the metal composition reported for suspended particles emitted from those vents. Our results suggest that krill recycling of Ag, Cu, Pb and Zn could potentially influence trace metal concentrations in the water column of the Bransfield region of the Southern Ocean, and that the original source of metals to these waters may be hydrothermal vents.     

Photochemical production of hydrogen peroxide in Antarctic Waters

Photochemical production rates of hydrogen peroxide (H₂O₂) were determined in Antarctic waters during two research cruises. The first cruise was from mid-October to mid-November, 1993, in the confluence of the Weddell and Scotia Seas, and the second cruise was in December, 1994, along the coast of the Antarctic Peninsula. During these cruises, midday sea-surface production rates ranged from 2.1 to 9.6 nM h⁻¹, with an average rate of 4.5 nM h⁻¹. Production rates were consistently smaller than rates determined at lower latitudes (>9 nM h⁻¹), primarily due to the colder temperatures and lower ultraviolet irradiances in polar waters. In situ production rates were determined with a free-floating drifter that was deployed for 12–14 h. Production rates, averaged over the deployment time, were highest at or near the surface (ca. 2.4–3.5 nM h⁻¹) and decreased rapidly with depth to 0.1–0.7 nM h⁻¹ at 10–20 m. The decrease in production rates with depth generally paralleled the decrease in ultraviolet irradiance in the water column. Production rates of hydrogen peroxide in Antarctic seawater were largely controlled by the ultraviolet irradiance in the water column, although there was some evidence for production in the blue region of the solar spectrum. A laboratory study was conducted to determine the wavelength dependence of the apparent quantum yield for the photochemical formation of hydrogen peroxide in Antarctic waters. Apparent quantum yields determined at 0°C decreased from 0.74×10⁻³ mol einstein⁻¹ at 290 nm to 1.0×10⁻⁵ mol einstein⁻¹ 410 nm. At 20°C, apparent quantum yields for the photochemical production of hydrogen peroxide were within a factor of two of apparent quantum yields determined in temperate waters at 20–25°C. Sunlight-normalized H₂O₂ production rates were determined as a function of wavelength using noontime irradiance data from Palmer Station, Antarctica. A decrease in stratospheric ozone from 336 to 151 Dobson units resulted in a predicted 19–42% increase in the photoproduction of H₂O₂ at the sea surface in Antarctic waters. The magnitude of this increase depends on the concentration and absorbance characteristics of dissolved organic matter in the photic zone, as well as on other factors such as cloudiness and decreasing solar zenith angle that tend to lower photochemical rates offsetting increases due to stratospheric ozone depletion.     

Enhancement of particulate organic carbon export flux induced by atmospheric forcing in the subtropical oligotrophic northwest Pacific Ocean

The effects of extreme atmospheric forcing on the export flux of particulate organic carbon (POC) in the warm oligotrophic nitrogen-limited northwest Pacific Ocean were examined in 2007 during the spring Asian dust storm period. Several strong northeast monsoon events (maximum sustained wind speeds approaching 16.7 m s^? 1, and gusts up to 19.0 m s^? 1) accompanied by dust storms occurred during a 1-month period. The cold stormy events decreased surface water temperature and induced strong wind-driven vertical mixing of the water column, resulting in nutrient entrainment into the mixed layer from subsurface waters. As a result, the export flux of POC ranged from 49 to 98 (average value = 71 ± 16) mg m^? 2 day^? 1, approximately 2–3 times greater than average values in other seasons. As dry and wet deposition of nitrogen attributable to Asian dust storm events does not account for the associated increases in POC stocks in this N-limited oligotrophic oceanic region, the enhancement of POC flux must have been caused by nutrient entrainment from subsurface waters because of the high winds accompanying the dust storm events.     

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.     

Seasonal variability of dissolved oxygen,percent oxygen saturation,and apparent oxygen utilization in the Atlantic and Pacific Oceans

Using objectively analyzed seasonal fields of dissolved oxygen content, percent oxygen saturation, and apparent oxygen utilization (AOU), we describe the large-scale seasonal variability of oxygen for the Atlantic and Pacific Oceans in the upper 400 m. The winter minus summer basin zonal averages of AOU reveal a two-layer feature in both the Atlantic and the Pacific, for both hemispheres. Biological activity and seasonal stratification in the summer give the upper 50–75 m of the water column in each basin a lower AOU in summer than winter. Greater mixing of upper ocean waters in winter gives the 75–400 m layer lower AOU values in that season. The basin integral seasonal volumes of oxygen for both the North Atlantic and the North Pacific mirror what is occurring in the atmosphere, indicating that there is a seasonal flux of oxygen across the air–sea interface. Winter total O₂ volume in the ocean is above the annual mean; the summer volume is below. Larger seasonal differences in the total O₂ content are observed in the North Atlantic Ocean than the North Pacific Ocean. A seasonal net outgassing (SNO) of 8.3×10¹⁴ moles O₂ is calculated from basin means, which is 25% higher than previous results.     

Oxygen distribution and aerobic respiration in the north and south eastern tropical Pacific oxygen minimum zones

Highly sensitive STOX O₂ sensors were used for determination of in situ O₂ distribution in the eastern tropical north and south Pacific oxygen minimum zones (ETN/SP OMZs), as well as for laboratory determination of O₂ uptake rates of water masses at various depths within these OMZs. Oxygen was generally below the detection limit (few nmol L⁻¹) in the core of both OMZs, suggesting the presence of vast volumes of functionally anoxic waters in the eastern Pacific Ocean. Oxygen was often not detectable in the deep secondary chlorophyll maximum found at some locations, but other secondary maxima contained up to ~0.4 µmol L⁻¹. Directly measured respiration rates were high in surface and subsurface oxic layers of the coastal waters, reaching values up to 85 nmol L⁻¹ O₂ h⁻¹. Substantially lower values were found at the depths of the upper oxycline, where values varied from 2 to 33 nmol L⁻¹ O₂ h⁻¹. Where secondary chlorophyll maxima were found the rates were higher than in the oxic water just above. Incubation times longer than 20 h, in the all-glass containers, resulted in highly increased respiration rates. Addition of amino acids to the water from the upper oxycline did not lead to a significant initial rise in respiration rate within the first 20 h, indicating that the measurement of respiration rates in oligotrophic Ocean water may not be severely affected by low levels of organic contamination during sampling. Our measurements indicate that aerobic metabolism proceeds efficiently at extremely low oxygen concentrations with apparent half-saturation concentrations (K_m values) ranging from about 10 to about 200 nmol L⁻¹.     

The seasonal succession of zooplankton in the Southern Ocean south of Australia,part I: The seasonal ice zone

Between November 2001 and March 2002 an Australian/Japanese collaborative study completed six passes of a transect line in the Seasonal-Ice Zone (south of 62°S) along 140°E. Zooplankton samples were collected with a NORPAC net on 22–28 November, and a Continuous Plankton Recorder on 10–15 January, 11–12 February, 19–22 February, 25–26 February, and 10–11 March. Zooplankton densities were lowest on 22–28 November (ave=61 individuals (ind) m⁻³), when almost the entire transect was covered by sea ice. By 10–15 January sea surface temperature had increased by ∼2 °C across the transect line, and the study area was ice-free. Total zooplankton abundance had increased to maximum levels for the season (ave=1301 ind m⁻³; max=1979 ind m⁻³), dominated by a “Peak Community” comprising Oithona similis, Ctenocalanus citer, Clausocalanus laticeps, foraminiferans, Limacina spp., appendicularians, Rhincalanus gigas and large calanoid copepodites (C1–3). Total densities declined on each subsequent transect, returning to an average of 169 ind m⁻³ on 10–11 March. The seasonal density decline was due to the decline in densities of “Peak Community” taxa, but coincided with the rise of Euphausia superba larvae into the surface waters, increased densities of Salpa thompsoni, and an increased contribution of C4 to adult stages to the populations of Calanoides acutus, Calanus propinquus and Calanus simillimus. The seasonal community succession appeared to be influenced by the low sea ice extent and southward projection of the ACC in this region. The relatively warm ACC waters, together with low krill biomass, favoured high densities of small grazers during the January/February bloom conditions. The persistence of relatively warm surface waters in March and the seasonal decrease in chlorophyll a biomass provided favorable conditions for salps, which were able to penetrate south of the Southern Boundary.     

Evaluation of the budget for silicic acid in Cascadia Basin deep water

Between 2 and 3 km depth, North Pacific deep waters contain a plume of water with high silicic acid concentrations. The plume extends outward from Cascadia Basin (the Washington Margin), where waters can contain in excess of 200 μM off the coast of Oregon and Washington. To identify the source of the high Si concentrations in Cascadia Basin, we measured silicic acid and germanium concentrations in deep waters, and their fluxes from sediments using incubated cores. The mean flux of silicic acid into bottom waters is 0.81±0.05 mmol/m²-day, and the Ge/Si ratio of this flux is 0.7±0.1 μmol/mol. A box model, incorporating these results with hydrographic data, indicates that (1) no more than 5% of the silicic acid added to Basin deep waters can have a hydrothermal source (either hot or warm seeps), and (2) the total input of silicic acid to Basin deep waters is 0.06±0.02 Tmol/y. This input is nearly all from remineralized biogenic debris and should contribute about 0.5% of the 14 Tmol/y that are estimated to be necessary to maintain the North Pacific plume.     

Bacterioplankton and phytoplankton biomass and production during summer stratification in the northwestern Mediterranean Sea

We examined bacterioplankton biomass and heterotrophic production (BHP) during summer stratification in the northwestern Mediterranean in four successive stratification seasons (June–July of 1993–1996). Values of phytoplankton biomass and primary production were determined simultaneously so that the data sets for autotrophic and heterotrophic microbial plankton could be compared. Three standard stations were set along a transect from Barcelona to the channel between Mallorca and Menorca, representing coastally influenced shelf waters, frontal waters over the slope front, and open sea waters. Conversion factors from ³H-leucine incorporation to BHP were empirically determined and varied between 0.29 and 3.25 kg C mol^-1. Bacterial biomass values were among the lowest found in any marine environment. BHP values (between 0.02 and 2.5 μg C L^-1 d^-1) were larger than those of low nutrient low chlorophyll areas such as the Sargasso Sea and lower than those from high nutrient low chlorophyll areas such as the equatorial Pacific. Growth rates of bacterioplankton were highest at the slope front (0.20 d^-1) and lowest at the open sea station (0.04 d^-1). Phytoplankton growth rates were similar at the three stations (∼0.50 d^-1). Integrated values of bacterioplankton biomass, BHP and bacterial growth rates did not show significant differences among years, but differences between the three stations were clearly significant. Phytoplankton biomass, primary production, and phytoplankton growth rates did not show significant differences either with year or with station. As a consequence the bacterioplankton to phytoplankton biomass (BB/BPHY) and production (BHP/PP) ratios varied from the coastal to the open sea stations. The BB/BPHY ratio was 0.98 at the coast and ∼0.70 at the other two stations. These ratios are similar to those found in other oligotrophic marine environments. The BHP/PP ratio was 0.83 at the coast, 0.36 at the slope and 0.09 at the open sea station. The last value is also similar to values found in other oligotrophic marine environments. Vertical distribution of these ratios was also examined.The comparison of microbial parameters at the three stations indicates a different kind of relationship between bacterioplankton and phytoplankton in oligotrophic open sea waters and in coastal, nutrient-richer waters. According to such parameters and to the values of the BB/BPHY and BHP/PP ratios, open waters in the northwestern Mediterranean (despite their relatively short distance from the shore) were intermediate between the extremely oligotrophic waters of the eastern Mediterranean or the Sargasso Sea and the more productive waters of the equatorial Pacific.     

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.     

Time-series observation of POC fluxes estimated from 234Th in the northwestern North Pacific

Time-series measurements of ²³⁴Th activities and particulate organic carbon (POC) concentrations were made at time-series stations (K1, K2, K3, and KNOT) in the northwestern North Pacific from October 2002 to August 2004. Seasonal changes in POC export fluxes from the surface layer (∼100 m) were estimated using ²³⁴Th as a tracer. POC fluxes varied seasonally from approximately 0 to 180 mg C m⁻² d⁻¹ and were higher in spring–summer than in autumn–winter. The export ratio (e-ratio) ranged from 6% to 55% and was also higher in spring–summer. Annual POC fluxes were estimated to be 31 g C m⁻² y⁻¹ in the subarctic region (station K2) and 23 g C m⁻² y⁻¹ in the region between the subarctic and subtropical gyres (station K3). POC fluxes and e-ratios in the northwestern North Pacific were much higher than those in most other oceans. The annual POC flux corresponded to 69% of annual new production estimated from the seasonal difference of the nutrient in the Western Subarctic Gyre (45 g C m⁻² y⁻¹). These results indicate that much of the organic carbon assimilated in the surface layer of the northwestern North Pacific is transferred to the deep ocean in particulate form. Our conclusions support previous reports that diatoms play an important role in the biological pump.     

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.     

The influence of the south-west monsoon upon the nutrient biogeochemistry of the Arabian Sea

Variations in the nutrient concentrations were studied during two cruises to the Arabian Sea. The situation towards the end of the southwest monsoon season (September/October 1994) was compared with the inter-monsoonal season during November and December 1994. Underway surface transects showed the influence of an upwelling system during the first cruise with deep, colder, nutrient-rich water being advected into the surface mixed layer. During the southwesterly monsoon there was an area of coastal Ekman upwelling, bringing colder water (24.2°C) into the surface waters of the coastal margin. Further offshore at about 350 km there was an area of Ekman upwelling, as a result of wind-stress curl, north of the Findlater Jet axis; this area also had cooler surface water (24.6°C). Further offshore (>1000 km) the average surface temperatures increased to >27°C. These waters were oligotrophic with no evidence of the upwelling effects observed further inshore. In the upwelling regions nutrient concentrations in the close inshore coastal zone were elevated (NO₃=18 μmol l^-1, PO₄=1.48 μmol l^-1); higher concentrations also were measured at the region of offshore upwelling off the shelf, with a maximum nitrate concentration of 12.5 μmol l^-1 and a maximum phosphate concentration of 1.2 μmol l^-1. Nitrate and phosphate concentrations decreased with increasing distance offshore to the oligotrophic waters beyond 1400 km, where typical nitrate concentrations were 35.0 nmol l^-1 (0.035 μmol l^-1) in the surface mixed layer. A CTD section from the coastal shelf, to 1650 km offshore to the oligotrophic waters, clearly showed that during the monsoon season, upwelling is one of the major influences upon the nutrient concentrations in the surface waters of the Arabian Sea off the coast of Oman. Productivity of the water column was enhanced to a distance of over 800 km offshore. During the intermonsoon period a stable surface mixed layer was established, with a well-defined thermocline and nitracline. Surface temperature was between 26.8 and 27.4°C for the entire transect from the coast to 1650 km offshore. Nitrate concentrations were typically between 2.0 and 0.4 μmol l^-1 for the transect, to about 1200 km where the waters became oligotrophic, and nitrate concentrations were then typically 8–12 nmol l^-1. Ammonia concentrations for the oligotrophic waters were typically 130 nmol l^-1, and are reported for the first time in the Indian Ocean. The nitrogen/phosphorus (N/P) ratios suggest that phytoplankton production was potentially nitrogen-limited in all the surface waters of the Arabian Sea, with the greatest nitrogen limitation during the intermonsoon period.