Oxygen and nutrient fluxes through the Straits of the Cretan Arc (March 1994–January 1995)

The Straits of the Cretan Arc are the gateways through which water exchanges between the Cretan Sea and the SE Ionian and NW Levantine Seas. Dissolved oxygen and nutrient fluxes have been quantified for the major straits — Antikithira, Kassos and Karpathos — by combining chemical bottle-sample data and current measurements obtained during the PELAGOS Project during 1994–1995. Two water masses, Cretan Deep Water (CDW) and Transitional Mediterranean Water (TMW) dominate the circulation through the straits and lead to a vertical redistribution of nutrients in the Eastern Mediterranean Sea.The transport of chemicals through the major straits of the Cretan Arc appears to be highly variable. In the Antikithira and Kassos Straits, a net export of oxygen and nutrients from the Cretan Sea towards the open waters of the Eastern Mediterranean was observed throughout the entire study period. In contrast, a net inflow of oxygen and nutrients of Levantine origin was taking place through the Karpathos Strait. It is concluded that the export of nutrients through the Antikithira and Kassos Straits are almost completely balanced by the net import through the Karpathos Strait.     

Temporal variability in oxygen and nutrient concentrations in the southern Aegean Sea and the Straits of the Cretan Arc

Nutrient and oxygen data collected in the southern Aegean Sea (Cretan Sea) and the straits of the Cretan Arc, during the four seasonal PELAGOS cruises in 1994–1995, are investigated and compared with data collected from 1987 to 1992 within the same area. During the cruises of the PELAGOS Project, nutrient enrichment of the intermediate layers of the Cretan Sea was observed, as a result of intrusion of ‘nutrient-rich, oxygen-poor’ Transition Mediterranean Water (TMW) compensating the Cretan Deep Water (CDW) outflow. TMW occupied the intermediate layers of the entire Cretan Sea. The concentrations of nutrients within this layer were often two times higher than those observed in the same area during previous studies undertaken before 1992 (increase 2.5 μmol/l of nitrate, 0.05 μmol/l of phosphate and 2.5μmol/l of silicate). The decrease of oxygen in this layer is about 0.8ml/l (35 μmol/l). Outflow of CDW occurs principally through the Antikithira and Kassos Straits (the two deeper straits of the Cretan Arc); it results in an increase of oxygen content but a decrease in the nutrient content of water in the deep and bottom layers outside the Cretan Sea. The major mesoscale features in the area have a major influence of the distributions and exchanges of nutrients and oxygen through the straits of the Cretan Arc. The surface and the intermediate layers were richer in nutrients and poorer in oxygen in spring (March 1994), than in autumn (September 1994).     

Water fluxes through the Cretan Arc Straits, Eastern Mediterranean Sea: March 1994 to June 1995

Five research cruises were undertaken incorporating ADCP sections along the Cretan Arc Straits and CTD surveys covering the entire area of the Straits and the Cretan Sea. In addition, six moorings (with 15 current meters) were deployed within the Straits, which monitored flows in the surface (50 m), intermediate (250 m), and deep (50 m from the bottom) layers. The ADCP, CM, and CTD datasets enable the derivation of water transports through the Cretan Arc Straits to be assessed. Flow structure through the Cretan Arc Straits is not the typical flow regime with a surface inflow and deep outflow, instead there is a persistent deep outflow of Cretan Deep Water (CDW) (σ_θ>29.2) with an annual mean of ˜0.6 Sv, through the Antikithira and Kassos Straits at depths below 400 m and 500 m, respectively. CDW outflowing transports are higher (˜0.8 Sv) in April–June, and lower (˜0.3 Sv) in October–December. Within the upper water layer (0–˜400 m), the transport and the water exchanges through the Straits are controlled by local circulation features, which weaken substantially below 200 m. The Asia Minor Current (AMC) influences the Rhodes and the Karpathos Straits, resulting in a net inflow of water. In contrast, the Mirtoan/West Cretan Cyclone influences the Antikithira and Kithira Straits, where there is a net outflow. In the Kassos Strait, there is a complex interaction between the East Cretan Cyclone, the Ierapetra Anticyclone and the westward extension of the Rhodes Gyre, which results in a variable flow regime. There is a net inflow in autumn and early winter, and a switch to a net outflow in early spring and summer. The total inflow and outflow, throughout all of the Straits, ranged from ˜2 to ˜3.5 Sv, with higher values in autumn and early winter and lower in summer. The AMC carries ˜2 Sv of inflow through the Rhodes and Karpathos Straits, and this accounts for 60–80% of the total inflow. About 10–15% of the total outflow is of CDW, and a further 45–70% occurs through the upper 400 m of the Kithira and Antikithira Straits. The Kassos Strait exhibits a net inflow of ˜0.7 Sv in autumn and early winter, with a net outflow of ˜0.5 Sv in early spring and summer.     

Cretan deep water outflow into the Eastern Mediterranean

A simple hydraulic model is used to estimate the deep water fluxes of Cretan Deep Water (CDW), through the Cretan Arc Straits and into the Eastern Mediterranean Basins. The input to the model consists of the height of the deep water reservoir above sill depth and its density difference from the overlying water masses. Data from four hydrographic cruises, which took place in 1995, 1991 and 1987, are used to estimate the depth of the reservoir above the sill and the density difference. The results show a significant CDW outflow of 0.75×10⁶ m³ s⁻¹ in early 1995. The outflow of CDW through Kassos Strait, in the east, is 0.53×10⁶ m³ s⁻¹, while 0.22×10⁶ m³ s⁻¹ outflows through the Antikithira Strait in the west. The model results agree with fluxes estimated from current meter observations.The CDW outflow has been neither steady nor uniform during the period 1987–95. In the Kassos Strait, the outflow commenced in 1987 and increased rapidly until 1991; since then, it appears to have stabilised. In the Antikithira Strait, in contrast, the outflow has increased steadily since 1987. Such modifications in the CDW outflow are associated with changes in its hydrographic characteristics. The salinity of CDW increased constantly, by approximately 0.1, between 1987 and 1995 while its temperature warmed, between 1987 and 1991, and then cooled.     

Oceanographic controls on the carbon isotopic compositions of sinking particles from the Cariaco Basin

This study examined the relationship between carbon isotopic composition of sinking organic matter (OM) and the biological, physical and chemical properties of the surface ocean in the Cariaco Basin. The ¹³C/¹²C ratio of OM (δ¹³C_org) in sinking particles was determined on sediment trap samples from four depths collected from 1996 to 1999 as part of the CArbon Retention In A Colored Ocean time series. Water column properties, including temperature, productivity, chlorophyll and concentration of dissolved CO₂, were concurrently measured on monthly cruises. The δ¹³C_org varied from a high of –17.7‰ to a low of –22.6‰ during the study period. The variation of the δ¹³C_org throughout seasonal cycles was directly proportional to the strength of upwelling and was negatively correlated with temperature (r²=0.64). During the 1996–1997 upwelling event, the strongest during the study period, the δ¹³C_org increased by 4.4‰ whereas during the 1998–1999 upwelling event, the weakest during the study period, the δ¹³C_org only increased by 3.3‰. Contrary to most previous studies, we observed a negative relationship (r²=0.53) between [CO_2 aq] and the estimated isotopic fractionation factor (ε_p). However, there was no correlation between ε_p and the calculated growth rates indicating that there was non-diffusive uptake of carbon into phytoplankton cells. It thus appears that [CO_2 aq] does not control the δ¹³C_org in the water column of the study site. The best explanation for the isotopic enrichment observed is a carbon concentrating mechanism (CCM) in phytoplankton. The existence of a CCM in phytoplankton has major implications for the interpretation of the δ¹³C_org in the Cariaco Basin.     

Transient Eastern Mediterranean deep waters in response to the massive dense-water output of the Aegean Sea in the 1990s

We present a detailed account of the changing hydrography and the large-scale circulation of the deep waters of the Eastern Mediterranean (EMed) that resulted from the unique, high-volume influx of dense waters from the Aegean Sea during the 1990s, and of the changes within the Aegean that initiated the event, the so-called ‘Eastern Mediterranean Transient’ (EMT). The analysis uses repeated hydrographic and transient tracer surveys of the EMed in 1987, 1991, 1995, 1999, and 2001/2002, hydrographic time series in the southern Aegean and southern Adriatic Seas, and further scattered data. Aegean outflow averaged nearly 3 × 10⁶ m³ s⁻¹ between mid-1992 and late 1994, and was largest during 1993, when south and west of Crete Aegean-influenced deep waters extended upwards to 400 m depth. EMT-related Aegean outflow prior to 1992, confined to the region around Crete and to 1800 m depth-wise, amounted to about 3% of the total outflow. Outflow after 1994 up to 2001/2002, derived from the increasing inventory of the tracer CFC-12, contributed 20% to the total, of 2.8 × 10¹⁴ m³. Densities in the southern Aegean Sea deep waters rose by 0.2 kg/m³ between 1987 and 1993, and decreased more slowly thereafter. The Aegean waters delivered via the principal exit pathway in Kasos Strait, east of Crete, propagated westward along the Cretan slope, such that in 1995 the highest densities were observed in the Hellenic Trench west of Crete. Aegean-influenced waters also crossed the East Mediterranean Ridge south of Crete and from there expanded eastward into the southeastern Levantine Sea. Transfer into the Ionian mostly followed the Hellenic Trench, largely up to the trench’s northern end at about 37°N. From there the waters spread further west while mixing with the resident waters. Additional transfer occurred through the Herodotus Trough in the south. Levantine waters after 1994 consistently showed temperature–salinity (T–S) inversions in roughly 1000–1700 m depth, with amplitudes decreasing in time. The T–S distributions in the Ionian Sea were more diverse, one cause being added Aegean outflow of relatively lower density through the Antikithira Strait west of Crete. Spreading of the Aegean-influenced waters was quite swift, such that by early 1995 the entire EMed was affected. and strong mixing is indicated by near-linear T–S relationships observed in various places. Referenced to 2000 and 3000 dbar, the highest Aegean-generated densities observed during the event equaled those generated by Adriatic Sea outflow in the northern Ionian Sea prior to the EMT. A precarious balance between the two dense-water source areas is thus indicated. A feedback is proposed which helped triggering the change from a dominating Adriatic source to the Aegean source, but at the same time supported the previous long-year dominance of the Adriatic. The EMed deep waters will remain transient for decades to come.     

Parameterization of iron and manganese cycling in the Black Sea suboxic and anoxic environment

New and published data on the distribution and speciation of manganese and iron in seawater are analyzed to identify and parameterize major biogeochemical processes of their cycling within the suboxic (15.6σ_t16.2) and anoxic layers (σ_t16.2) of the Black Sea. A steady-state transport-reaction model is applied to reveal layering and parameterize kinetics of redox and dissolution/precipitation processes. Previously published data on speciation of these elements in seawater are used to specify the nature of the transformations. Two particulate species of iron (Fe(III) hydroxide and Fe(II) sulfide) are necessary to adequately parameterize the vertical profile of suspended iron, while three particulate species (hydrous Mn(IV) oxide, Mn(II) sulfide, and Mn(II) carbonate) are necessary to describe the profile of suspended manganese. In addition to such processes as mixing and advection, precipitation, sinking, and dissolution of manganese carbonate are found to be essential in maintaining the observed vertical distribution of dissolved Mn(II). These results are used to interpret the observed difference in the form of vertical distribution for dissolved Mn(II) and Fe(II). Redox transformations of iron and manganese are coupled via oxidation of dissolved iron by sinking suspended manganese at σ_t16.2±0.2 kg m⁻³. The particulate manganese, necessary for this reaction, is supplied through oxidation of dissolved Mn(II). The best agreement with observations is achieved when nitrate, rather than oxygen, is set to oxidize dissolved Mn(II) in the lower part of the suboxic layer (15.90σ_t16.2). The results support the idea that, after sulfides of these metals are formed, they sink with particulate organic matter. The sinking rates of the particles and specific rates of individual redox and dissolved-particulate transformations have been estimated by fitting the vertical profile of the net rate.     

Dissolved manganese and silicic acid in the Columbia River plume: A major source to the California current and coastal waters off Washington and Oregon

The spatial distributions of dissolved manganese and nutrients were examined in the Columbia River plume off Oregon and Washington during the summer of 2004 and 2005 as part of the River Influence on Shelf Ecosystems (RISE) program. Factors influencing the hydrochemical characteristics of the freshly formed and aged Columbia River plume were investigated. Hydrographic data and nutrient concentrations were used to delineate three distinct water sources for the Columbia River Plume: California Current surface water, coastal upwelled water, and Columbia River water. The warm, intermediate salinity, nutrient poor California Current water contains low levels of dissolved manganese (< 5 nM) and silicic acid (< 5 μM), and is depleted in nitrate. The cold, high salinity, nutrient rich, freshly upwelled water is highly variable (2–20 nM) in dissolved manganese and can be as high as  45 μM in silicic acid and  30 μM nitrate. The variable Columbia River has summer temperatures ranging from  13 to 24 °C, high silicic acid concentrations (ranging from  120 to 200 μM), and lower nitrate concentrations (ranging from  2 to 20 μM). During the summer, the concentrations of silicic acid and dissolved manganese can exceed 100 μM and 200 nM, respectively, in near-field Columbia River plumes. These values are markedly greater than those of surface coastal waters (even during upwelling conditions). As the plume advects and mixes, the concentrations of these two constituents remain relatively high within plume waters. The concentrations of dissolved manganese in the near-field plume vary with tidal amplitude, exhibiting much higher concentrations for a given salinity during spring tides than during neap tides. For example, the Columbia River plume at a salinity of 20 has a concentration of dissolved manganese of  240 nM during spring tides, as compared to only  60 nM during low amplitude tides. Silicic acid concentrations in the near-field plume remain relatively constant throughout the tidal month. Calculations indicate there is roughly an equivalent yearly delivery of dissolved manganese and silicic acid to the coastal waters off Oregon and Washington by upwelled waters and by the Columbia River plume.     

Distribution of yttrium and rare earths in Florida Bay sediments

The distribution of yttrium and rare earth elements (YREEs) in surface sediments was measured on samples collected from 40 stations in Florida Bay (June 2000 and February 2001). Florida Bay is the largest shallow carbonate estuary in South Florida with nearly pristine conditions. It receives fresh waters from some rivers and several canals from the Everglades which contribute rare earth elements and metals to the Bay. This paper is the first extensive study of YREEs in Florida Bay. Concentrations of YREEs (Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) were determined by ICP-MS. The YREEs show a similar distribution pattern for the two months studied. The maximum concentrations were found in the western and north-central zones (near the Everglades) and the minimum concentrations were found in the south-central zone near the Florida Keys. The pattern of YREEs in Florida Bay sediments correlated strongly with those in the North American Shale Composite, indicating a dominant crustal source for these elements. However, the REE concentrations in Florida Bay sediments are depleted with respect to NASC. All REEs exhibited a strong correlation with Fe and Al from continental input and river runoff from the Everglades. The heavy REEs and Y showed a strong correlation with Al (R² > 0.84). The light and medium REEs showed a strong correlation with Fe (R² > 0.9). Correlations of all the YREEs with Mn were slightly lower (R²  0.7–0.75). The concentration of all the YREEs, Al and Fe are dependent on the bottom types and zones in the Bay, except Mn which decreases as it moves from the land to the sea.     

Dissolved organic carbon, nitrogen and phosphorus in the N-E Atlantic and the N-W Mediterranean with particular reference to non-refractory fractions and degradation

Dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) measured in deep profiles in the N-E Atlantic and in the N-W Mediterranean in the period 1984–2002 are described. After accurate validation, they show close agreement with those previously published.Classic profiles were obtained, with concentrations decreasing in deep waters. In the Mediterranean and in the Atlantic comparable concentrations were found in the 1500–2000 m waters, 44–46 μmol l⁻¹ DOC, 2.6–2.8 μmol l⁻¹ DON and 0.02–0.03 μmol l⁻¹ DOP. In the surface layers, DOC concentrations were higher, but DON and DOP concentrations lower, in the Mediterranean than in the Atlantic, leading to higher element ratios in the Mediterranean. In autumn, values were, respectively, DOC:DON 17 vs. 14, DOC:DOP 950 vs. 500 and DON:DOP 55 vs. 35. The data suggest an increase in DOC and DON in the North Atlantic Central Water over 15 years, which may be linked to the North Atlantic climatic oscillations.Refractory DOM found in the 1500–2000 m layer exhibited C:N:P ratios of 1570:100:1. The labile+semi-labile (=non-refractory) DOM (nrDOM) pool was computed as DOM in excess of the refractory pool. Its contribution to total DOM above the thermocline in the open sea amounted to 25–35% of DOC, 30–35% of DON, and 60–80% of DOP. Element ratios of the nrDOM varied among stations and were lower than those of refractory DOM, except for C:N in the Mediterranean: nrDOC:nrDON 10–19, nrDOC:nrDOP 160–530 and nrDON:nrDOP 15–38. The specific stoichiometry of DOM in the Mediterranean led us to postulate that overconsumption of carbon is probably a main process in that oligotrophic sea.By coupling non-refractory DOM stoichiometry and relationships between the main DOM elements in the water column, the relative mineralization of C, N and P from DOM was studied. Below the thermocline, the preferential removal of phosphorus with regard to carbon from the semi-labile DOM can be confirmed, but not the preferential removal of nitrogen. In the ocean surface layers, processes depend on the oceanic area and can differ from deep waters, so preferential carbon removal seems more frequent. Bacterial growth efficiency data indicate that bacteria are directly responsible for mineralization of a high proportion of DON and DOP in the deep water.     

Transport of copper from the Bering Sea to the northwestern North Pacific

Dissolved copper concentrations in surface waters of the Bering Sea ranged from 106 to 882 ngl^–1. Higher concentrations were found in continental shelf waters. In the northwestern North Pacific dissolved copper ranged from 54 to 140 ngl^–1. Particulate copper concentrations varied regionally and seasonally from 6 to 79 ngl^–1. Regionally averaged particulate copper concentrations decreased from 175 to 33g g^–1 against an increase in suspended materials because of the dilution effects of biological fractions. Apparent sporadic increases in copper concentrations were found in the mixing area of the Kuroshio and the Oyashio waters. The feature is attributed to the lateral distribution of different water types rather than to the upwelling of deeper waters by eddies. In the same area west of 160E, waters with high concentrations of dissolved copper (96±9 ngl^–1) were found. Their origin appears to be the continental shelf of the Bering Sea. In spite of intensive biological activity, a considerable fraction of copper added to shelf waters was transported to the area off Japan via the circulation in the Bering Sea and the Oyashio current.     

Uncertainties in the preparation of Ra Mn fiber standards

Delayed coincidence counters (RaDeCC), used for measuring ²²³Ra and ²²⁴Ra preconcentrated from water onto MnO₂-impregnated acrylic fiber (“Mn-fiber”), require a standard Mn-fiber column that has a precisely known activity of ²²⁴Ra for calibration. This may be done by adding an aged ²²⁸Th standard solution to adsorb both ²²⁸Th and its daughter ²²⁴Ra quantitatively onto a Mn fiber. We used both seawater and deionized water (DIW) for testing the adsorption efficiency of Th and Ra onto Mn fibers. Our experimental results show that more than 50% of thorium (²³²Th and ²²⁸Th) breaks through the Mn-fiber column when DIW is used as a medium. However, near quantitative recoveries are obtained if filtered (0.45 μm) seawater is used to prepare the standard. In the case of pure DIW, the pH (initial pH  5.3) rises to > 10 after passing through the column while seawater (initial pH  7.8) changes to  7.2. Thus, the lack of thorium adsorption in DIW may be attributed to this huge increase of pH and the consequent formation of Th(OH)₄ and polyhydroxyl colloids. Based on these observations, we recommend that one should use either artificial seawater or natural seawater (which has negligible ²²⁴Ra and ²²⁸Th) as a loading solution after 0.45 μm filtration. In addition, the thorium adsorption efficiency should be confirmed either by thorium analysis of the effluent solution or long-term monitoring of the supported ²²⁴Ra on the Mn fiber using the RaDeCC. Similar cautions are likely necessary for making ²²³Ra standards by adsorption of ²²⁷Ac onto Mn fibers.     

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.     

Dissolved iron in the Australian sector of the Southern Ocean (CLIVAR SR3 section): Meridional and seasonal trends

We report measurements of dissolved iron (dFe, <0.4 μm) in seawater collected from the upper 300 m of the water column along the CLIVAR SR3 section south of Tasmania in March 1998 (between 42°S and 54°S) and November–December 2001 (between 47°S and 66°S). Results from both cruises indicate a general north-to-south decrease in mixed-layer dFe concentrations, from values as high as 0.76 nM in the Subtropical Front to uniformly low concentrations (<0.1 nM) between the Polar Front and the Antarctic continental shelf. Samples collected from the seasonal sea-ice zone in November–December 2001 provide no evidence of significant dFe inputs from the melting pack ice, which may explain the absence of pronounced ice-edge algal blooms in this sector of the Southern Ocean, as implied by satellite ocean-color images. Our data also allow us to infer changes in the dFe concentration of surface waters during the growing season. South of the Polar Front, a comparison of near-surface with subsurface (150 m depth) dFe concentrations in November–December 2001 suggests a net seasonal biological uptake of at least 0.14–0.18 nM dFe, of which 0.05–0.12 nM is depleted early in the growing season (before mid December). A comparison of our spring 2001 and fall 1998 data indicates a barely discernible seasonal depletion of dFe (0.03 nM) within the Polar Frontal Zone. Further north, most of our iron profiles do not exhibit near-surface depletions, and mixed-layer dFe concentrations are sometimes higher in samples from fall 1998 compared to spring 2001; here, the near-surface dFe distributions appear to be dominated by time-varying inputs of aerosol iron or advection of iron-rich subtropical waters from the north.     

Particulate organic carbon fluxes to the ocean interior and factors controlling the biological pump: A synthesis of global sediment trap programs since 1983

Particulate organic carbon (POC) is vertically transported to the oceanic interior by aggregates and their ballasts, mainly CaCO₃ and biogenic opal, with a smaller role for lithogenic aerosols through the mesopelagic zone. Diel migrating zooplankton communities effect vertical transport and remineralization of POC in the upper layers of the ocean. Below 1.5 km, the presence of zooplankton is reduced and thus the aggregates travel mainly by gravitational transport. We normalized the fluxes of POC, CaCO₃, and biogenic opal from data published on samples collected at 134 globally distributed, bottom-tethered, time-series sediment trap (TS-trap) stations to annual mole fluxes at the mesopelagic/bathypelagic boundary (m/b) at 2 km and defined them as F_m/bC_org, F_m/bC_inorg, and F_m/bSi_bio. Using this global data set, we investigated (1) the geographic contrasts of POC export at m/b and (2) the supply rate of ∑CO₂ to the world mesopelagic water column. F_m/bC_org varies from 25 (Pacific Warm Pool) to 605 (divergent Arabian Sea) mmolC m⁻² yr⁻¹; F_m/bC_inorg varies from >8 (high latitude Polar Oceans) or 15 (Pacific Warm Pool) to 459 (divergent Arabian Sea) mmolC m⁻² yr⁻¹; and F_m/bSi_bio, the most spatially/temporally variable flux, ranges from 6 (North Atlantic Drift) to 1118 (Pacific Subarctic Gyre) mmolSi m⁻² yr⁻¹. The oceanic region exhibiting the highest POC flux over a significantly large region is the area of the North Pacific Boreal Gyres where the average F_m/bC_org = 213, F_m/bC_inorg = 126, and F_m/bSi_bio = 578 mmol m⁻² yr⁻¹. F_m/bC_org and F_m/bC_inorg are particularly high in large upwelling margins, including the divergent Arabian Sea and off Cape Verde. One of the data sets showing the lowest flux over a significant region/basin is F_m/bC_org = 39, F_m/bC_inorg = 69, and F_m/bSi_bio = 22 mmol m⁻² yr⁻¹ in the North Pacific subtropical/tropical gyres; Pan-Atlantic average fluxes are similar except F_m/bSi_bio fluxes are even lower. Where C_org/C_inorg and Si_bio/C_inorg are <1 defines the “Carbonate Ocean”, and where these ratios are ?1 defines the “Silica Ocean”. The Carbonate Ocean occupies about 80% of the present world pelagic ocean between the two major oceanographic fronts, the North Pacific Polar Front and the Antarctic Polar Front, and the Silica Ocean is found on the polar sides of these fronts. The total global annual fluxes of F_m/bC_org, F_m/bC_inorg, and F_m/bSi_bio at m/b calculated by parameterizations of the export flux data from 134 stations are surprisingly similar; 36.2, 33.8, and 34.6 teramol yr⁻¹ (120, 112, and 114 mmol m⁻² yr⁻¹), respectively, resulting in a near uniform binary ratio between the above three elements of about one. The global ternary % ratios estimated from 152 TS-trap samples of the three elements are 35:32:33. From our global F_m/bC_org and a published model estimate of the global export production, we estimate the regeneration rate of CO₂ through the mesopelagic zone by the biological pump is 441 teramolC yr⁻¹. Based on our global F_m/bC_inorg and recently estimated global primary production of PIC, 36-86 teramolC yr⁻¹ of PIC is assumed to be dissolved within the upper 2 km of the water column.     

Copper speciation in estuarine waters by forward and reverse titrations

The chemical speciation of copper in the estuarine waters of the Vigo Ria was determined by titrations with salicylaldoxime (reverse copper titrations) and with copper (forward titrations). The forward titrations quantified the concentrations of ligands present in excess whereas the reverse titrations demonstrated the presence of low concentrations of very strong binding ligands, approximately matching the copper concentration. The data obtained by the reverse titrations indicated that copper was about 10× stronger bound than data based on the usual forward titrations.The copper concentration in these ria waters was low at 5 nM with a minor mid-estuarine maximum of 8 nM. These copper levels are amongst the lowest reported for estuarine waters and therefore represent uncontaminated waters. The concentration of inorganic copper was very low across the ria at  10–100 fM, except at Bouzas harbour (salinity 35.5) where it was raised to  1 pM due to copper contamination, in waters affected by the port facilities, to total levels of 15 to 20 nM copper, exceeding the concentration of the very strong ligand detected by the reverse titrations.     

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.     

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.     

Trace metal concentrations in the Ross Sea and their relationship with nutrients and phytoplankton growth

Dissolved and particulate trace metal concentrations (dissolved Fe, Zn, Cd, Co, Cu and Ni; particulate Fe, Mn and Al) were measured along two transects in the Ross Sea during austral summer of 1990. Total Fe concentrations in southern Ross Sea and inshore waters were elevated >3.5 times that of northern waters. Dissolved Zn, Cd and Co concentrations were lower by factors of 4.5, 3.5 and 1.6 in southern surface waters relative to northern waters. Dissolved Cu and Ni concentrations were similar in both areas. Elevated Fe concentrations coincided with areas of increased productivity, phytoplankton biomass and nutrient drawdown, indicating that Fe is an important factor controlling the location of phytoplankton blooms in the Ross Sea. Particulate concentrations of Fe, Mn and Al indicate two possible sources of iron to the Ross Sea, resuspension of continental shelf sediments and iron incorporated in annual sea ice and released with meltwaters.     

Copper complexing ligands and organic matter characterization in the northern Adriatic Sea

The study on dissolved organic ligands capable to complex copper ions (L_T), surface-active substances (SAS) and dissolved organic carbon (DOC) in the Northern Adriatic Sea station (ST 101) under the influence of Po River was conducted in period from 2006–2008. The acidity of surface-active organic material (Ac_r) was followed as well. The results are compared to temperature and salinity distributions. On that way, the contribution of the different pools of ligands capable to complex Cu ions could be determined as well as the influence of aging and transformation of the organic matter. The L_T values in the investigated period were in the range of 40–300 nmol l⁻¹. The range of DOC values for surface and bottom samples were 0.84–1.87 mg l⁻¹ and 0.80–1.30 mg l⁻¹, respectively. Total SAS concentrations in the bottom layer were 0.045–0.098 mg l⁻¹ in equiv. of Triton-X-100 while those in the surface layer were 0.050–0.143 mg l⁻¹ in equiv. of Triton-X-100. The majority of organic ligands responsible for Cu binding in surface water originate from new phytoplankton production promoted by river borne nutrients. Older, transformed organic matter, possessing higher relative acidity, is the main contributor to the pool of organic ligands that bind copper in the bottom samples. It was estimated that 9% of DOC in surface samples and 12% of DOC in the bottom samples are present as ligands capable to complex copper ions.