Numerical model simulations of continental shelf flows off northern California

The three-dimensional circulation on the continental shelf off northern California in the wind events and shelf transport (WEST) experiment region during summer 2001 is studied using the primitive equation regional ocean modeling system (ROMS). The simulations are performed with realistic topography and initial stratification in a limited-area domain with a high-resolution grid. Forcing consists of measured wind-stress and heat flux values obtained from a WEST surface buoy. The general response shows a southward coastal upwelling jet of up to and a weakening or reversal of currents inshore of the jet when upwelling winds relax. Model results are compared to WEST moored velocity and temperature measurements at five locations, to CODAR surface current observations between Pt. Reyes and Bodega Bay, and to hydrographic measurements along shipboard survey lines. The model performs reasonably well, with the highest depth-averaged velocity correlation (0.81) at the inshore mooring (40 m water depth) and lowest correlation (0.68) at the mid-depth mooring (90 m depth). The model shows generally stronger velocities than those observed, especially at the inshore moorings, and a lack in complete reversal of southward velocities observed when upwelling winds relax. The comparison of surface velocities with CODAR measurements shows good agreement of the mean and the dominant mode of variability. The hydrography compares closely at the southern and northern edges of the survey region (correlation coefficients between 0.90 and 0.97), with weaker correlations at the three interior survey lines (correlation coefficients between 0.44 and 0.76). Mean model fields over the summer upwelling period show slight coastal jet separation off Pt. Arena and significant separation off Pt. Reyes. The cape regions also experience relatively strong bottom velocities and nonlinearity in the surface flow. Across-shelf velocity sections examined along the shelf reveal a double jet structure that appears just north of Bodega Bay and shows the offshore jet strengthening to the south. We examine the dynamics during an upwelling and subsequent relaxation event in May 2001 in which the WEST measurements show evidence of a strong flow response. The alongshelf variability in the upwelling and relaxation response introduced by Pt. Reyes is evident. Analysis of term balances from the depth-averaged momentum equations helps to clarify the event dynamics in different regions over the shelf. A clear pattern in the nonlinear advection term is due to the spatial acceleration of the southward jet around the capes of Pt. Arena and Pt. Reyes during upwelling. Results from a three-dimensional Lagrangian analysis of water parcel displacement show significant southward displacement in the coastal jet region, including a strong signal from the double jet. Alongshelf variability in parcel displacements and upwelling source waters due to the presence of Pt. Arena and Pt. Reyes is also apparent from the Lagrangian fields. A cyclonic eddy-like recirculation feature offshore of Pt. Arena prior to the upwelling event causes large patches of onshore-displaced parcels. Additionally, across-shelf variability in the response of water parcels along the D line includes decreased vertical displacement and increased alongshelf displacement in the offshore direction.     

The carbon dioxide system and net community production within a cyclonic eddy in the lee of Hawaii

The dynamics of dissolved inorganic carbon (DIC) and processes controlling net community production (NCP) were investigated within a mature cyclonic eddy, Cyclone Opal, which formed in the lee of the main Hawaiian Islands in the subtropical North Pacific Gyre. Within the eddy core, physical and biogeochemical properties suggested that nutrient- and DIC-rich deep waters were uplifted by 80 m relative to surrounding waters, enhancing biological production. A salt budget indicates that the eddy core was a mixture of deep water (68%) and surface water (32%). NCP was estimated from mass balances of DIC, nitrate+nitrite, total organic carbon, and dissolved organic nitrogen, making rational inferences about the unobserved initial conditions at the time of eddy formation. Results consistently suggest that NCP in the center of the eddy was substantially enhanced relative to the surrounding waters, ranging from 14.1±10.6 (0–110 m: within the euphotic zone) to 14.2±9.2 (0–50 m: within the mixed layer) to 18.5±10.7 (0–75 m: within the deep chlorophyll-maximum layer) mmol C m⁻² d⁻¹ depending on the depth of integration. NCP in the ambient waters outside the eddy averaged about 2.37±4.24 mmol C m⁻² d⁻¹ in the mixed layer (0–95 m). Most of the enhanced NCP inside the eddy appears to have accumulated as dissolved organic carbon (DOC) rather than exported as particulate organic carbon (POC) to the mesopelagic. Our results also suggest that the upper euphotic zone (0–75 m) above the deep chlorophyll maximum is characterized by positive NCP, while NCP in the lower layer (>75 m) is close to zero or negative.     

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.     

Bifurcation analysis of 3D ocean flows using a parallel fully-implicit ocean model

To understand the physics and dynamics of the ocean circulation, techniques of numerical bifurcation theory such as continuation methods have proved to be useful. Up to now these techniques have been applied to models with relatively few degrees of freedom such as multi-layer quasi-geostrophic and shallow-water models and relatively low-resolution (e.g., 4° horizontal resolution) primitive equation models. In this paper, we present a new approach in which continuation methods are combined with parallel numerical linear system solvers. With this implementation, we show that it is possible to compute steady states versus parameters (and perform fully implicit time integration) of primitive equation ocean models with up to a few million degrees of freedom.     

Oxidation of copper(I) in seawater at nanomolar levels

The oxidation and reduction of nanomolar levels of copper in air-saturated seawater and NaCl solutions has been measured as a function of pH (7.17–8.49), temperature (5–35 °C) and ionic strength (0.1–0.7 M). The oxidation rates were fitted to an equation valid at different pH and ionic strength conditions in sodium chloride and seawater solutions:

The reduction of Cu(II) was studied in both media for different initial concentrations of copper(II). When the initial Cu(II) concentration was 200 nM, the copper(I) productions were 20% and 9% for NaCl and seawater, respectively. The effect of speciation of copper(I) reduced from Cu(II) on the rates was studied. The Cu(I) speciation is dominated by the CuCl₂⁻ species. On the other hand, the neutral chloride CuCl species dominates the Cu(I) oxidation in the range of 0.1 M to 0.7 M chloride concentrations.     

Effect of seasonal changes in bottom water oxygenation on sediment N oxides and N2O cycling in the coastal upwelling regime off central Chile (36.5°S)

An intensive and seasonal coastal upwelling process, which attains maximal expression during late austral spring and summer, drives well-known changes in organic matter production and, therefore, in O₂ content in the water column. These variables have a concomitant effect on N sediment processes over the continental shelf off central Chile (36.5°S), which, in turn, can affect the , , and N₂O content in the bottom water. Hydrographic characteristics, benthic and fluxes, and denitrification rates were measured from 1998 to 2001 (with at least seasonal frequency). In order to elucidate how benthic N₂O recycling responds to different O₂ and nutrient levels and how it affects the bottom water N₂O content, net N₂O cycling was measured in December 2001 in sediment slurry incubations under different manipulated dissolved O₂ levels (anoxic: 0 μM; hypoxic: 22.3 μM; oxic: 44.6 μM) and without (natural) and with the addition of and (enriched experiments). Dissolved O₂ and contents (and also ) showed clear seasonal patterns according to the oceanographic regime, i.e., from hypoxic waters rich in nutrients during the upwelling season to oxic waters with less nutrient contents during the non-upwelling season. The bottom water, on the other hand, was influenced by benthic organic mineralization, which consumes O₂ as well as other electron acceptor N-species such as . Benthic fluxes (2.62-5.08 mmol m⁻² d⁻¹) were always directed into the sediments, whereas denitrification rates varied from 0.6 to 2.9 mmol m⁻² d⁻¹. N₂O was also consumed at rates of 5.53 and 4.56 μmol m⁻² d⁻¹ under anoxia and hypoxia, but N₂O consumption rates were reduced to almost half under oxic conditions in both natural and a -enriched experiments. With the -enriched experiments, however, N₂O consumption was very high (up to 24.25 μmol m⁻² d⁻¹) under anoxic and hypoxic conditions, suggesting that high levels induce more N₂O reduction to N₂ by denitrification. N₂O production rates were only measured when oxic conditions were observed in the -enriched experiment, suggesting some role of nitrification. Thus, N cycling in the sediments seems to affect the observed , NO²⁻, and N₂O content in the bottom water and, therefore, in the entire water column due to vertical advection associated with coastal upwelling.     

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.     

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.     

Effects of stratification and mesoscale eddies on Kuroshio path variation south of Japan

Bimodality of the Kuroshio current path south of Japan is investigated, focusing on the effects of stratification and mesoscale eddies. For this purpose, wind-driven numerical experiments are executed in barotropic and two-layered ocean models. Stratification has two effects on the path selection of the Kuroshio south of Japan. First, it makes an alongshore path stable at intermediate wind stress strength τ₀ by arresting an eddy southeast of Kyushu. This enables an alongshore path to appear in the entire experimental range of τ₀. Second, the upper limit of τ₀ which allows a meandering path decreases from ( in the Sverdrup transport at the Tokara Strait) to () as Δρ/ρ₀ increases from 2.0×10^-3 to 4.0×10^-3. While an anticyclonic eddy imposed upstream (southeast of Kyushu) can cause the transition from an alongshore to a meandering path, it occurs most easily when (). The transition from a meandering to an alongshore path requires an eddy imposed downstream (east of the meandering segment) which suppresses redevelopment of the meandering segment and breaks the balance between the advective and beta effects. Applicability of the results to previously observed path variations is discussed.     

The transient oasis: Nutrient-phytoplankton dynamics and particle export in Hawaiian lee cyclones

Macronutrients, photosynthetic pigments, and particle export were assessed in two eddies during the E-Flux I and III cruises to investigate linkages between biogeochemical properties and export flux in Hawaiian lee cyclonic eddies. Cyclone Noah (E-Flux I), speculated to be in the ‘decay’ stage, exhibited modest increases in macronutrients and photosynthetic pigments at the eddy center compared to ambient waters. Cyclone Opal (E-Flux III) also exhibited modest increases in macronutrient concentrations, but a 2-fold enhancement in total chlorophyll a (TChl a) concentration within the eddy center. As indicated by fucoxanthin concentrations, the phytoplankton community in the deep chlorophyll maximum (DCM) of Opal was comprised mainly of diatoms. During an 8-day time series in the center of Opal, TChl a concentration and fucoxanthin in the DCM decreased by 50%, which was potentially triggered by silicic acid limitation. Despite the presence of a substantial diatom bloom, Opal did not deliver the expected export of particulate carbon and nitrogen, but rather a large biogenic silica export (4-fold increase relative to export in surrounding waters). Results suggest that controls on the life cycle of a Hawaiian lee cyclone are likely a combination of physical (eddy dynamics), chemical (nutrient limitation), and biological (growth and grazing imbalance) processes. Comparisons between Noah and Opal and previously studied cyclones in the region point to a relationship between the spin-up duration of a cyclone and the resulting biological response. Nonetheless, Hawaiian lee cyclones, which strongly influence the biogeochemistry of areas 100's of km in scale in the subtropical North Pacific Ocean, still remain an enigma.     

Depth-stratified phytoplankton dynamics in Cyclone Opal, a subtropical mesoscale eddy

As part of E-Flux III cruise studies in March 2005, we investigated phytoplankton community dynamics in a cyclonic cold-core eddy (Cyclone Opal) in the lee of the Hawaiian Islands. Experimental incubations were conducted under in situ temperature and light conditions on a drift array using a two-treatment dilution technique. Taxon-specific estimates of growth, grazing and production rates were obtained from analyses of incubation results based on phytoplankton pigments, flow cytometry and microscopy. Cyclone Opal was sampled at a biologically and physically mature state, with an 80–100 m doming of isopycnal surfaces in its central region and a deep biomass maximum of large diatoms. Depth-profile experimentation defined three main zones. The upper (mixed) zone (0–40 m), showed little compositional or biomass response to eddy nutrient enrichment, but growth, grazing and production rates were significantly enhanced in this layer relative to the ambient community outside of the eddy. Prochlorococcus spp. dominated the upper mixed layer, accounting for 50–60% of its estimated primary production both inside and outside of Opal. In contrast, the deep zone of 70–90 m showed little evidence of growth rate enhancement and was principally defined by a 100-fold increase of large (>20-μm) diatoms and a shift from Prochlorococcus to diatom dominance (80%) of production. The intermediate layer of 50–60 m marked the transition between the upper and lower extremes but also contained an elevated biomass of physiologically unhealthy diatoms with significantly depressed growth rates and proportionately greater grazing losses relative to diatoms above or below. Microzooplankton grazers consumed 58%, 65% and 55%, respectively, of the production of diatoms, Prochlorococcus and the total phytoplankton community in Cyclone Opal. The substantial grazing impact on diatoms suggests that efficient recycling was the major primary fate of diatom organic production, consistent with the low export fluxes and selective export of biogenic silica, as empty diatom frustules, in Cyclone Opal.     

Physical dynamics and biological implications of Cyclone Noah in the lee of Hawaii during E-Flux I

Quasi-synoptic observations of the horizontal and vertical structure of a cold-core cyclonic mesoscale eddy feature (Cyclone Noah) were conducted in the lee of Hawai’i from November 4–22, 2004 as part of the E-Flux interdisciplinary collaborative research program. Cyclone Noah appears to have spun up to the southwest of the ‘Alenuihaha Channel (between Maui and Hawai’i) as a result of strong and persistent northeasterly trade winds through the channel. Shipboard hydrographic surveys 2.5 months later suggest that Noah weakened and was in a hypothesized spin-down phase of its life cycle. Although the initial surface expression of Noah was limited in scale to 40 km in diameter and, as evidenced by surface temperatures, 2–3 °C cooler than the surrounding waters, depth profiles revealed a fully developed semi-elliptical shallow feature (200 m), 144 km long and 90 km wide (based on sigma-t=23 kg m⁻³) with tangential speeds of 40–80 cm s⁻¹, and substantial isopycnal doming. Potential vorticity distribution of Noah suggests that radial horizontal flow of the core water was inhibited from the surface to depths of 75 m, with high vorticity confined above the sigma-t=23.5 kg m⁻³ isopycnal surface. Upward displacements of isopycnal surfaces in the eddy's center (50 m) were congruent with enhanced pigment concentrations (0.50 mg m⁻³). Comparisons of the results obtained for E-Flux I (Noah) and E-Flux III (Opal) suggest that translation characteristics of cyclonic Hawaiian lee eddies may be important in establishing the biogeochemical and biological responses of the oligotrophic ocean to cyclonic eddies.     

Diatoms in the desert: Plankton community response to a mesoscale eddy in the subtropical North Pacific

As part of the E-Flux project, we documented spatial variability and temporal changes in plankton community structure in a cold-core cyclonic eddy in the lee of the Hawaiian Islands. Cyclone Opal spanned 200 km in diameter, with sharply uplifted isopycnals (80–100 m relative to surrounding waters) and a strongly expressed deep chlorophyll a maximum (DCM) in its central core region of 40 km diameter. Microscopic and flow cytometric analyses of samples from across the eddy revealed dramatic transitions in phytoplankton community structure, reflecting Opal's well-developed physical structure. Upper mixed-layer populations in the eddy resembled those outside the eddy and were dominated by picophytoplankton. In contrast, the DCM was composed of large chain-forming diatoms dominated by Chaetoceros and Rhizosolenia spp. Diatoms attained unprecedented levels of biomass (nearly 90 μg C l⁻¹) in the center of the eddy, accounting for 85% of photosynthetic biomass. Protozoan grazers displayed two- to three-fold higher biomass levels in the eddy center as well. We also found a distinct and persistent layer of senescent diatom cells overlying healthy populations, often separated by less than 10 m, indicating that we were sampling a bloom in a state of decline. Time-series sampling over 8 days showed a successional shift in community structure within the central diatom bloom, from the unexpected large chain-forming species to smaller forms more typical of the subtropical North Pacific. The diatom bloom of Cyclone Opal was a unique, and possibly extreme, example of biological response to physical forcing in the North Pacific subtropical gyre, and its detailed study may therefore help to improve our predictive understanding of environmental controls on plankton community structure.     

Mesozooplankton biomass and grazing responses to Cyclone Opal, a subtropical mesoscale eddy

As part of E-Flux III cruise studies in March 2005, plankton net collections were made to assess the effects of a cyclonic cold-core eddy (Cyclone Opal) on the biomass and grazing of mesozooplankton. Mesozooplankton biomass in the central region of Cyclone Opal, an area of uplifted nutricline and a subsurface diatom bloom, averaged 0.80±0.24 and 1.51±0.59 g DW m⁻², for day and night tows, respectively. These biomass estimates were about 80% higher than control (OUT) stations, with increases more or less proportionately distributed among size classes from 0.2 to >5 mm. Though elevated relative to surrounding waters south of the Hawaiian Islands (Hawai’i lee), total biomass and size distribution in Cyclone Opal were almost exactly the same as contemporary measurements made at Stn. ALOHA, 100 km north of the islands, by the HOT (Hawaii Ocean Time-series) Program. Mesozooplankton biomass and community composition at the OUT stations were also similar to ALOHA values from 1994 to 1996, preceding a recent decadal increase. These comparisons may therefore provide insight into production characteristics or biomass gradients associated with decadal changes at Stn. ALOHA. Gut fluorescence estimates were higher in Opal than in ambient waters, translating to grazing impacts of 0.11±0.02 d⁻¹ (IN) versus 0.03±0.01 d⁻¹ (OUT). Over the depth-integrated euphotic zone, mesozooplankton accounted for 30% of the combined grazing losses of phytoplankton to micro- and meso-herbivores in Opal, as compared to 13% at control stations. Estimates of active export flux by migrating zooplankton averaged 0.81 mmol C m⁻² d⁻¹ in Cyclone Opal and 0.37 mmol C m⁻² d⁻¹ at OUT stations, 53% and 24%, respectively, of the carbon export measured by passive sediment traps. Migrants also exported 0.18 mmol N m⁻² d⁻¹ (117% of trap N flux) in Cyclone Opal compared to 0.08 mmol N m⁻² d⁻¹ (51% of trap flux) at control stations. Overall, the food-web importance of mesozooplankton increased in Cyclone Opal both in absolute and relative terms. Diel migrants provided evidence for enhanced export flux in the eddy that was missed by sediment trap and ²³⁴Th techniques, and migrant-mediated flux was the major export term in the observed bloom-perturbation response and N mass balance of the eddy.     

Cobalt, manganese, and iron near the Hawaiian Islands: A potential concentrating mechanism for cobalt within a cyclonic eddy and implications for the hybrid-type trace metals

The vertical distributions of cobalt, iron, and manganese in the water column were studied during the E-Flux Program (E-Flux II and III), which focused on the biogeochemistry of cold-core cyclonic eddies that form in the lee of the Hawaiian Islands. During E-Flux II (January 2005) and E-Flux III (March 2005), 17 stations were sampled for cobalt (n=147), all of which demonstrated nutrient-like depletion in surface waters. During E-Flux III, two depth profiles collected from within a mesoscale cold-core eddy, Cyclone Opal, revealed small distinct maxima in cobalt at 100 m depth and a larger inventory of cobalt within the eddy. We hypothesize that this was due to a cobalt concentrating effect within the eddy, where upwelled cobalt was subsequently associated with sinking particulate organic carbon (POC) via biological activity and was released at a depth coincident with nearly complete POC remineralization [Benitez-Nelson, C., Bidigare, R.R., Dickey, T.D., Landry, M.R., Leonard, C.L., Brown, S.L., Nencioli, F., Rii, Y.M., Maiti, K., Becker, J.W., Bibby, T.S., Black, W., Cai, W.J., Carlson, C.A., Chen, F., Kuwahara, V.S., Mahaffey, C., McAndrew, P.M., Quay, P.D., Rappe, M.S., Selph, K.E., Simmons, M.P., Yang, E.J., 2007. Mesoscale eddies drive increased silica export in the subtropical Pacific Ocean. Science 316, 1017–1020]. There is also evidence for the formation of a correlation between cobalt and soluble reactive phosphorus during E-Flux III relative to the E-Flux II cruise that we suggest is due to increased productivity, implying a minimum threshold of primary production below which cobalt–phosphate coupling does not occur. Dissolved iron was measured in E-Flux II and found in somewhat elevated concentrations (0.5 nM) in surface waters relative to the iron depleted waters of the surrounding Pacific [Fitzwater, S.E., Coale, K.H., Gordon, M.R., Johnson, K.S., Ondrusek, M.E., 1996. Iron deficiency and phytoplankton growth in the equatorial Pacific. Deep-Sea Research II 43 (4–6), 995–1015], possibly due to island effects associated with the iron-rich volcanic soil from the Hawaiian Islands and/or anthropogenic inputs. Distinct depth maxima in total dissolved cobalt were observed at 400–600 m depth, suggestive of the release of metals from the shelf area of comparable depth that surrounds these islands.     

Reynolds number dependence of mixing in a lock-exchange system from direct numerical and large eddy simulations

Turbulent mixing of water masses of different temperatures and salinities is an important process for both coastal and large-scale ocean circulation. It is, however, difficult to capture computationally. One of the reasons is that mixing in the ocean occurs at a wide range of complexity, with the Reynolds number reaching , or even higher.In this study, we continue to investigate whether large eddy simulation (LES) can be a reliable computational tool for stratified mixing in turbulent oceanic flows. LES is attractive because it can be times faster than a direct numerical simulation (DNS) of stratified mixing in turbulent flows. Before using the LES methodology to compute mixing in realistic oceanic flows, however, a careful assessment of the LES sensitivity with respect to Re needs to be performed first. The main objectives of this study are: (i) to investigate the performance of different LES models at high Re, such as those encountered in oceanic flows; and (ii) to study how mixing varies as a function of Re. To this end, as a benchmark we use the lock-exchange problem, which is described by unambigous and simple initial and boundary conditions. The background potential energy, which accurately quantifies irreversible mixing in an enclosed system, is used as the main criterion in a posteriori testing of LES.This study has two main achievements. The first is that we investigate the accuracy of six combinations of two different classes of LES models, namely eddy-viscosity and approximate deconvolution types, for 3×10³Re3×10⁴, for which DNS data is computed. We find that all LES models almost always provide significantly more accurate results than cases without LES models. Nevertheless, no single LES model that is persistently superior to others over this Re range could be identified. Then, an ensemble of the four best performing LES models is selected in order to estimate mixing taking place in this system at Re=10⁵ and 10⁶, for which DNS is presently not feasible. Thus the second achievement of this study is to quantify mixing taking place in this system over an Re range that changes by three orders of magnitude. We find that the background potential energy increases by about 67% when Re is increased from Re=10³ to Re=10⁶, within the computation period, with the most significant increase taking place from Re=3×10³ to Re=10⁵.     

Nutrient gradients from the eutrophic Changjiang (Yangtze River) Estuary to the oligotrophic Kuroshio waters and re-evaluation of budgets for the East China Sea Shelf

Eutrophication has become an overwhelming phenomenon in the coastal environment off the Changjiang (Yangtze River) Estuary, illustrated by an increase in nutrient concentration, frequent red-tide events and hypoxia in near-bottom waters, while the open East China Sea Shelf and Kuroshio waters remain oligotrophic. Observations made in the Changjiang Estuary and the East China Sea in 1999–2003 cover a broad range of hydrographic and chemical properties. The concentration gradients of nutrients across the shelf indicate that high levels from land-sources are constrained to the coastal and inner-shelf region by the complex circulation regime. In surface waters, nutrient species gradually decrease from eutrophic coastal to oligotrophic open shelf waters, depending on the hydrographic stages of the Changjiang, although biological uptake and regeneration in the upper water column can produce patchy character of nutrient distribution. Taiwan Current Warm Water and Kuroshio Surface Water are devoid of nutrients. Remineralization of nutrient species takes place in the near-bottom waters in the inner-shelf following extensive bacterial demand for organic matter. Hence the burial efficiency is low with regard to the biogenic species, either allochthonous or autochthonous, or both. The Kuroshio Sub-surface Waters are rich in nutrients, and their incursion into the East China Sea can be tracked by salinity and temperature, reaching within water depth of 50–100 m at mid-shelf. Relative to shelf waters, the Kuroshio intrusion is characterized by high and DIP/DOP ratios. In the water column, the ratio of DIP/DOP to is higher than the Redfield P/N value, suggesting rapid regeneration of phosphorus relative to nitrogen in the East China Sea. The results of a box-model suggest that the East China Sea Shelf do likely not export substantial amounts of dissolved biogenic elements to the open Northwest Pacific Ocean.     

Chromium(VI) reduction by sulphur(IV) in aqueous solutions

The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔH_app of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression

−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]²