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.     

Environmental controls on phytoplankton community composition in the Thames plume, U.K.

The aim of this study was to investigate controls on the phytoplankton community composition and biogeochemistry of the estuarine plume zone of the River Thames, U.K. using an instrumented moored buoy for in situ measurements and preserved sample collection, and laboratory-based measurements from samples collected at the same site. Instrumentation on the moored buoy enabled high frequency measurements of a suite of environmental variables including in situ chlorophyll, water-column integrated irradiance, macronutrients throughout an annual cycle for 2001 e.g. nitrate and silicate, and phytoplankton biomass and species composition. The Thames plume region acts as a conduit for fluvial nutrients into the wider southern North Sea with typical winter concentrations of 45 μM nitrate, 17 μM silicate and 2 μM phosphate measured. The spring bloom resulted from water-column integrated irradiance increasing above 60 W h m^− 2 d^− 1 and was initially dominated by a diatom bloom mainly composed of Nitzschia sp. and Odontella sinesis. The spring bloom then switched after  30 days to become dominated by the flagellate Phaeocystis reaching a maximum chlorophyll concentration of 37.8 μg L^− 1. During the spring bloom there were high numbers of the heterotrophic dinoflagellates Gyrodinium spirale and Katodinium glaucum that potentially grazed the phytoplankton bloom. This diatom–flagellate switch was predicted to be due to a combination of further increasing water-column integrated irradiance > 100 W h m^− 2 d^− 1 and/or silicate reaching potentially limiting concentrations (< 1 μM). Post spring bloom, diatom dominance of the lower continuous summer phytoplankton biomass occurred despite the low silicate concentrations (Av. 0.7 μM from June–August). Summer diatom dominance, generally due to Guinardia delicatula, was expected to be as a result of microzooplankton grazing, dominated by the heterotrophic dinoflagellate Noctiluca scintillans, controlling 0.7–5.0 μm ‘flagellate’ fraction of the phytoplankton community with grazing rates up to 178% of ‘flagellate’ growth rate. The Thames plume region was therefore shown to be an active region of nutrient and phytoplankton processing and transport to the southern North Sea. The use of a combination of moorings and ship-based sampling was essential in understanding the factors influencing nutrient transport, phytoplankton biomass and species composition in this shelf sea plume region.     

Organic biogeochemistry of the Darwin Mounds, a deep-water coral ecosystem, of the NE Atlantic

The Darwin Mounds are a series of small (5 m high, 75–100 m diameter) sandy features located in the northern Rockall Trough. They provide a habitat for communities of Lophelia pertusa and associated fauna. Suspended particulate organic matter (sPOM) reaching the deep-sea floor, which could potentially fuel this deep-water coral (DWC) ecosystem, was collected during summer 2000. This was relatively “fresh” (i.e. dominated by labile lipids such as polyunsaturated fatty acids) and was derived largely from phytoplankton remains and faecal pellets, with contributions from bacteria and microzooplankton. Labile sPOM components were enriched in the benthic boundary layer (10 m above bottom (mab)) relative to 150 mab. The action of certain benthic fauna that are exclusively associated with the DWC ecosystem (e.g. echiuran worms) leads to the subduction of fresh organic material into the sediments. The mound surface sediments are enriched in organic carbon, relative to off-mound sites. There is no evidence for hydrocarbon venting at this location.     

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.     

Relevance of peat draining rivers in central Sumatra for the riverine input of dissolved organic carbon into the ocean

Sources and discharges of dissolved organic carbon (DOC) from the central Sumatran river Siak were studied. DOC concentrations in the Siak ranged between 560 and 2594 μmol l⁻¹ and peak out after its confluence with the river Mandau. The Mandau drains part of the central Sumatran peatlands and can be characterized as a typical blackwater river due to its high DOC concentration, its dark brown-coloured, acidic water (pH 4.4–4.7) and its low concentration of total suspended matter (12–41 mg l⁻¹). The Mandau supplies about half of the DOC that enters the Siak Estuary where it mixes conservatively with ocean water. The DOC input from the Siak into the ocean was estimated to be 0.3 Tg C yr⁻¹. Extrapolated to entire Indonesia the data suggest a total Indonesian DOC export of 21 Tg yr⁻¹ representing 10% of the global riverine DOC input into the ocean.     

Adsorption of dissolved phosphate onto loess particles in surface and deep Eastern Mediterranean water

The objective of this study was to examine whether dissolved inorganic phosphate (DIP) is removed from the Eastern Mediterranean Sea by adhering to atmospherically deposited loess particles sinking through the water column. In a series of radiolable experiments, loess from the Negev Desert, treated in various ways, was added to surface (SSW) and deep (DSW) seawater spiked with ³²PO₄⁻³. It was shown that when fresh loess reaches the Mediterranean SSW approximately 1.3 μmol P/g are released (11% of the total P concentration). Biological activity and inorganic particles removed similar amounts of the tracer (30–40%) from SSW. It was estimated that about 0.2 μmol P/g of ‘aged loess' (proxy of particles sinking into DSW), were removed from poisoned SSW and DSW, while there was minor adsorption when either nothing or quartz powder was added. The adsorbed DIP accounts for approximately 15% of the released P and is equivalent to about 2% of the remaining P (11.17 μmol P/g loess). Therefore, the process of DIP removal by atmospherically derived particles exists, but due to the higher release of P, the result is a net addition of dissolved atmospheric phosphorus in seawater. It is postulated that in actual SSW where dust concentrations are much lower, biological uptake out-competes inorganic adsorption, although it was demonstrated that the decrease in loess particle concentrations tends to increase their adsorption capacity. As the loess descends into the DSW it continues to remove DIP and thus transports phosphate from the water column to the sediments. A preliminary quantitative estimate suggests that the process of DIP removal by loess particles cannot explain the phosphate ‘deficit' in the Eastern Mediterranean DSW characterized by unusually high DIN/DIP ratios (27) reported by others.     

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.     

Uptake and metabolism of arsenate by anexic cultures of the microalgae Dunaliella tertiolecta and Phaeodactylum tricornutum

Axenic cultures of the microalgae species, Dunaliella tertiolecta and Phaeodactylum tricornutum were grown at arsenic (As) concentrations typically found in uncontaminated marine environments ( 2 µg L^− 1) under different phosphorus concentrations. D. tertiolecta accumulated higher arsenic concentrations (mean: 13.7 ± 0.7 µg g^− 1 dry mass) than P. tricornutum (mean: 1.9 ± 0.2 µg g−1 dry mass). Media phosphorus concentrations (0.6–3 mg/L) had little influence on microalgae growth rates or arsenic accumulation. Arsenic was present as lipid bound (29–38%; 4.2–9.5%), water-soluble (20–29%; 26–34%) and residue bound (41–45%; 57–69%) arsenic species in D. tertiolecta and P. tricornutum respectively. Hydrolysed lipids contained mostly glycerol arsenoribose (OH- ribose), dimethylarsinate (DMA) and inorganic arsenic (As(V)) moieties. Water-soluble species of microalgae were very different. D. tertiolecta contained inorganic arsenic (54–86%) with variable amounts of DMA (7.4–20%), arsenoriboses (5–25%) and traces of methylarsonate (MA) ( 1%). P. tricornutum contained mostly DMA (32–56%) and phosphate arsenoribose (PO₄-ribose, 23–49%) and small amounts of OH-ribose (3.8–6.5%) and As(V) (9–16%). Both microalgae contained an unknown cationic arsenic species. The residue fractions of both microalgae contained predominately inorganic arsenic (99–100%). These results show that at natural seawater arsenic concentrations, both algae take up substantial amounts of inorganic arsenic that is complexed with structural elements or sequestered in vacuoles as stable complexes. A significant portion is also incorporated into lipids. Arsenic is metabolised to simple methylated species and arsenoriboses.     

Alkaline phosphatase activity of water column fractions and seagrass in a tropical carbonate estuary, Florida Bay

Few phosphorus-depleted coastal ecosystems have been examined for their ability to hydrolyze phosphomonoesters. We examined seasonal (August 2006–April 2007) alkaline phosphatase activity in Florida Bay, a phosphorus-limited shallow estuary, using fluorescent substrate at low concentrations (≤2.0 μM). In situ dissolved inorganic and organic phosphorus levels and phosphomonoester concentrations were also determined. Water column alkaline phosphatase activity was partitioned into two particulate size fractions (>1.2 and 0.2–1.2 μm) and freely dissolved enzymes (<0.2 μm). Water column alkaline phosphatase activity was also compared to leaf and epiphyte activity of the dominant tropical seagrass Thalassia testudinum. Our results indicate: (1) potential alkaline phosphatase activity in Florida Bay is high compared to other marine ecosystems, resulting in rapid phosphomonoester turnover times (2 h). (2) Water column alkaline phosphatase activity dominates, and is split equally between particulate and dissolved fractions. (3) Alkaline phosphatase activity was highest during cyanobacterial blooms, but not when normalized to chl a. These results suggest that dissolved, heterotrophic and autotrophic alkaline phosphatase activity is stimulated by phytoplankton blooms. (4) The dissolved alkaline phosphatase activity is relatively constant, while the particulate activity is seasonally and spatially dynamic, typically associated with phytoplankton blooms. (5) Phosphomonoester concentrations throughout the bay are low, even though potential hydrolysis rates are high. We propose that bioavailable dissolved organic P is hydrolyzed by dissolved and microbial alkaline phosphatase enzymes in Florida Bay. High alkaline phosphatase activity in the bay is also promoted by long hydraulic residence times. This background activity is primarily driven by carbon and phosphorus limitation of microorganisms, and regeneration of enzymes associated with cell lysis. Pulses of inorganic phosphorus and labile organic phosphorus and nitrogen may stimulate autotrophs, particularly cyanobacteria, which in turn promote biological activity that increase alkaline phosphatase activity of both autotrophs and heterotrophs in the bay.     

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.     

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).     

The biogeochemistry of major elements of the suspended particulate matter of the Cretan Sea

The biogeochemistry of the following elements Al, Fe, Si_bio, POC, PN_tot, Ca_bio, S_org, P and Mn has been studied within waters of the Cretan Sea in March and September 1994, as part of the PELAGOS project. Particulate aluminosilicate concentrations, exemplified by Al, are very low (<1 μgl⁻¹) especially in the upper waters. Higher concentrations occur below 200 m, especially at depths of 200 m and 500–700 m in the central and eastern areas, and are thought to result from sediment injections from the shelf edge and slope. The results for Si_bio, Ca_bio, P and S_org show much higher concentrations within the photic waters. Temporal and spatial high concentrations in these waters closely relate to the existence of cyclonic eddies on the east and west sides of the sea, while low concentrations are associated with an intervening anticyclonic eddy. However in September, discharge of Black Sea Water in the west sufficiently suppresses the thermocline to prevent upwelled water from reaching the surface and hence these substances are prevented from forming.Particulate Fe (expressed as Fe_excess) concentrations show much higher concentrations relative to Al in September, and are thought to result from additional atmospheric inputs. The low particulate Mn concentrations in the upper water compared with deeper waters are considered to be a product of photoinhibition of MnO_x precipitation from Mn(II).An attempt has been made to assess input/output budgets of Al, Ca, Fe and Mn through the Antikithira and Kassos Straits. Much of the outflows leave through the Kassos Strait and, except for Ca, net outflows through the Antikithira Straits are negligible.     

Accumulation of Cu and Zn in discarded antifouling paint particles by the marine gastropod, Littorina littorea

The short-term (5 day) accumulation of Cu and Zn in different tissues of the marine gastropod, Littorina littorea, has been studied in the presence of 10 mg l⁻¹ of antifouling paint particles and pre- or simultaneously contaminated algal food (Ulva lactuca). Accumulation of Cu was observed in the head–foot, digestive gland–gonad complex and gills to extents dependent on how and when food was contaminated and administered. However, retention of Zn was only observed in the gills and only when L. littorea and U. lactuca were simultaneously exposed to paint particles. Relative to the alga, faecal material was highly enriched in Zn, suggesting that the animal is able to rapidly eliminate this metal, most likely through the formation and egestion of insoluble phosphate granules. Thus, L. littorea is a useful biomonitor of marine contamination by antifouling applications in respect of Cu but not Zn.     

Further investigations on why POC concentrations differ in samples collected by Niskin bottle and in situ pump

Particulate organic carbon (POC) concentrations measured in bottles are often higher than those measured by in situ pumps when samples are taken concurrently. In previous work, we suggested that differential collection of zooplankton might explain this systematic discrepancy in POC between these small volume (bottle) and large volume (in situ pump) techniques. We have now further quantified the carbon contributed by zooplankton collected in the >70-μm particulate fractions from both bottles and pumps at sites in the Mediterranean Sea and Long Island Sound. Our results show that zooplankton abundance and lipid concentrations from zooplankton are one order of magnitude higher in the bottles than in the pumps, supporting the idea that part of the pump–bottle difference is due to collection of more zooplankton by the bottles. Particle washout off the 70-μm mesh used in the in situ pump may cause loss of some particles as well. However, zooplankton in the >70-μm fraction from the bottles contributed only about 1–2 μM POC, which cannot explain the up to 20 μM POC differences observed in this study. Thus, the mechanisms leading to such a large POC difference are still unclear and need to be further investigated. POC concentrations measured using microquartz filters were similar to those using glass fiber filters, suggesting that filter types cannot explain the higher POC observed in bottles, where glass fiber filters are normally used. Furthermore, we investigated several different pump inlet designs to determine how these might affect the ability of pumps to collect and retain large (>70 μm) particles, including zooplankton. The comparison among different pump inlets suggests that inlet design affects the efficiency and retention of large particles and that a sealed filter holder with a narrow right-angle tubular opening is the most efficient at catching/retaining zooplankton.     

Determination of picomolar iron in seawater by double Mg(OH)2 precipitation isotope dilution high-resolution ICPMS

A low-blank pre-concentration procedure is described for the analysis of picomolar iron (Fe) in seawater by isotope dilution high-resolution inductively coupled plasma mass-spectrometry (HR-ICPMS). The procedure uses a two-step Mg(OH)₂ co-precipitation procedure to extract Fe from a 50 ml seawater sample into a 100 μl 4% nitric acid (HNO₃) solution followed by HR-ICPMS measurement. The high pre-concentration ratio ( 500:1) achieved by the procedure minimizes the Fe blank due to ICPMS instrumental Fe background and results in a detection limit of  2 pM and a precision of  4% at the 50 pM Fe level. The measurement of a low-Fe seawater sample spiked with gravimetric Fe standard shows that the method can clearly distinguish 0.01 nM Fe from 0.02 nM Fe in seawater with high accuracy. The method is demonstrated by the analysis of dissolved Fe in the equatorial Pacific Ocean.     

Isolation of colloidal monomethyl mercury in natural waters using cross-flow ultrafiltration techniques

A series of experiments was conducted to evaluate the appropriateness of cross-flow ultrafiltration (CFUF) techniques for the determination of the phase speciation of monomethyl mercury (MeHg) in natural waters. Spiral-wound cartridge (Amicon S1Y1) and Miniplate (Amicon) were evaluated for their nominal molecular weight cut-offs of 1 and 10 kDa, respectively. The ultrafiltration behavior of standard macromolecules showed that the permeation of high molecular weight (HMW) organic macromolecules was not significant when a concentration factor (CF)>15 was used. The retention of low molecular weight (LMW) molecules was significant, especially at a low CF<5, suggesting that the use of a high CF (15) will minimize the retention of LMW molecules. Sorptive losses of MeHg in the solution phase to the 1 kDa membrane were negligible, but MeHg bound to HMW macromolecules was still retained (20%), even with a preconditioned membrane. The mass balance recovery of MeHg during ultrafiltration averaged 101±15% (n=7) and 105±14% (n=5) for the 1 and 10 kDa membranes, respectively. Sample storage over 24 h caused significant coagulation (47%) of the <10 kDa MeHg into the 10 kDa–0.45 μm colloidal or the particulate MeHg pool. The 1 kDa–0.45 μm colloidal MeHg in Galveston Bay and the Trinity River water samples accounted for 40–48% of the filter-passing MeHg, although the most abundant fraction (52–60%) of MeHg was the truly dissolved fraction (<1 kDa). The partition coefficient between the colloidal (1 kDa–0.45 μm) and truly dissolved MeHg (average log K_C=5.2) was higher than the partition coefficient based on particle/filter-passing (average log K_D=4.6) or particle/truly dissolved MeHg (average log K_P=4.8), suggesting that MeHg has stronger affinity for natural colloids than macroparticulate materials (>0.45 μm).     

Benthic foraminifera living in Gulf of Mexico bathyal and abyssal sediments: Community analysis and comparison to metazoan meiofaunal biomass and density

Benthic foraminiferal biomass, density, and species composition were determined at 10 sites in the Gulf of Mexico. During June 2001 and 2002, sediment samples were collected with a GoMex box corer. A 7.5-cm diameter subcore was taken from a box core collected at each site and sliced into 1-cm or 2-cm sections to a depth of 2 or 3 cm; the >63-μm fraction was examined shipboard for benthic foraminifera. Individual foraminifers were extracted for adenosine triphosphate (ATP) using a luciferin–luciferase assay, which indicated the total ATP content per specimen; that data was converted to organic carbon. Foraminiferal biomass and density varied substantially (2–53 mg C m⁻²; 3600–44,500 individuals m⁻², respectively) and inconsistently with water depth: although two 1000-m deep sites were geographically separated by only 75 km, the foraminiferal biomass at one site was relatively low (9 mg C m⁻²) while the other site had the highest foraminiferal biomass (53 mg C m⁻²). Although most samples from Sigsbee Plain (>3000 m) had low biomass, one Sigsbee site had >20 mg foraminiferal C m⁻². The foraminiferal community from all sites (i.e. bathyal and abyssal locales) was dominated by agglutinated, rather than calcareous or tectinous, species. Foraminiferal density never exceeded that of metazoan meiofauna at any site. Foraminiferal biomass, however, exceeded metazoan meiofaunal biomass at 5 of the 10 sites, indicating that foraminifera constitute a major component of the Gulf's deep-water meiofaunal biomass.     

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.     

Benthic remineralization at the land–ocean interface: A case study of the Rhône River (NW Mediterranean Sea)

Biogeochemical processes in sediments under the influence of the Rhône River plume were studied using both in situ microelectrodes and ex situ sediment core incubations. Organic carbon (OC) and total nitrogen (TN) content as well as stable carbon isotopic composition of OC (δ¹³C_OC) were analysed in 19 surface sediments to determine the distribution and sources of organic matter in the Rhône delta system. Large spatial variations were observed in both the total O₂ uptake (5.2 to 29.3 mmol m⁻² d⁻¹) and NH₄⁺ release (−0.1 to −3.5 mmol m⁻² d⁻¹) rates at the sediment–water interface. The highest fluxes were measured near the Rhône River mouth where sedimentary OC and TN contents reached 1.81% and 0.23% respectively. Values of δ¹³C_OC ranged from −26.83‰ to −23.88‰ with a significant seawards enrichment tracing the dispersal of terrestrial organic matter on the continental shelf. The amount of terrestrial-derived OC reaches 85% in sediments close to the Rhône mouth decreasing down to 25% in continental shelf sediments. On the prodelta, high terrestrial OC accumulation rates support high oxygen uptake rates and thus indicating that a significant fraction of terrestrial OC is remineralized. A particulate organic carbon (POC) mass balance indicates that only 3% of the deposited POC is remineralized in prodelta sediments while 96% is recycled on the continental shelf. It was calculated that a large proportion of the Rhône POC input is either buried (52%) or remineralized (8%), mostly on the prodelta area. The remaining fraction (40%) is either mineralized in the water or exported outside the Rhône delta system in dissolved or particulate forms.     

Co-variance of dissolved Fe-binding ligands with phytoplankton characteristics in the Canary Basin

Dissolved Fe and ligand concentrations and the Fe-binding strength of the organic ligands were measured in samples from the upper water column (150 m) of the oligotrophic waters of the Canary Basin (eastern North Atlantic Ocean). Concentrations of major nutrients, phytoplankton abundance and photosynthetic characteristics were also measured in the same samples.The concentrations of dissolved Fe and dissolved organic ligands were low with mean values of 0.31 ± 0.18 nM Fe and 1.79 ± 0.73 nEq of M Fe(n = 47), respectively. The conditional binding constant varied between 10^19.8–10^22.7 (n = 47). The largest variation with depth in the ligand concentrations (between 4.78 and 1.1 nEq of M Fe) was observed in the upper layer, above the Deep Chlorophyll Maximum (DCM located between 80 and 100 m), with high surface values in stations at 18 and 34.At the DCM where Fe was depleted, the ligand concentrations were still relatively high showing the same trend with depth as the amount of phytoplankton cells. Here 62% of the vertical variation in ligand concentrations can be explained by parameters describing phytoplankton cell abundance or biomass and orthosilicic acid concentration, which could reflect diatom growth. Ligand concentrations below the maximum of the DCM (n = 4) showed good linear positive relationships with the total phytoplankton biomass as well as with 2 out of 4 distinguished groups of phytoplankton (Synechococcus and pico-eukaryote I).In the maximum of the DCM and below this maximum the phytoplankton origin of the dissolved organic ligands of Fe is very probable. Data suggest a release of ligands by cell lysis and not by an active production. However, the origin in the surface layer is more difficult to explain. Although the amount of phytoplankton cells in the surface layer is reduced, it is still  25% of the cell concentration observed in the DCM. High concentrations of organic ligands could then be a remnant of past blooms or present production under nutrient depleted conditions. Input of Sahara dust can be another source of ligands.