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This study investigates the relationships among Ni, Cd and Pb's different chemical forms determined by different methodologies in coastal and transitional waters across a broad geographical scale. Concentrations were measured in spot samples and through passive sampling (DGT). High variability of metal concentrations was found among sampling sites and methodologies due to natural water fluctuations rather than to a given metal or method. Total dissolved metal concentrations in spot samples were lower than the EQS-WFD values. The labile fractions of Cd and Pb, measured in spot samples by Anodic Stripping Voltammetry and by DGT-ICPMS, were highly correlated. Similar labilities were found for Cd, while for Pb, the ASV labile fraction was ≈50% lower. These results reflect the pool of mobile and labile species available towards each technique kinetic window, and they seem not to be affected by discrete sampling flaws.

A phytoplankton bloom shown to be naturally iron (Fe) induced occurs north of the Crozet Islands (Southern Ocean) every year, providing an ideal opportunity to study dissolved trace metal distributions within an island system located in a high nutrient low chlorophyll (HNLC) region. We present water column profiles of dissolved nickel (Ni), zinc (Zn), cobalt (Co), cadmium (Cd), lead (Pb), aluminium (Al), and manganese (Mn) obtained as part of the NERC CROZEX program during austral summer (2004–2005). Two stations (M3 and M1) were sampled downstream (north) of Crozet in the bloom area and near the islands, along with a control station (M2) in the HNLC zone upstream (south) of the islands. The general range found was for Ni, 4.64–6.31 nM; Zn, 1.59–7.75 nM; Co, 24–49 pM; Cd, 135–673 pM; Pb, 6–22 pM; Al, 0.13–2.15 nM; and Mn, 0.07–0.64 nM. Vertical profiles indicate little island influence to the south with values in the range of other trace metal deprived regions of the Southern Ocean. Significant removal of Ni and Cd was observed in the bloom and Zn was moderately correlated with reactive silicate (Si) indicating diatom control over the internal cycling of this metal. Higher concentrations of Zn and Cd were observed near the islands. Pb, Al, and Mn distributions also suggest small but significant atmospheric dust supply particularly in the northern region.

Pore-fluid Fe isotopes may be a unique tracer of sediment respiration by dissimilatory Fe-reducing bacteria, but to date, pore-fluid Fe isotope measurements have been restricted to continental shelf settings. Here, we present δ56Fe values of pore fluids from two distinct sedimentary settings: (1) a riverine-dominated site on the northern California margin (Eel River shelf; 120 m water depth) and (2) biogenic opal-rich volcaniclastic deep-sea sediments from the Southern Ocean (north and south of the Crozet Plateau; 3000-4000 m water depth). The Fe isotope compositions of Crozet region pore fluids are significantly less fractionated (δ56Fe = +0.12‰ to -0.01‰) than the Eel River shelf (δ56Fe = -0.65‰ to -3.40‰) and previous studies of pore-fluid Fe isotopes, relative to average igneous rocks. Our data represent the first measurements of Fe isotope compositions in pore fluids from deep-sea sediments. A comparison of pore-fluid δ56Fe with the relative abundance of highly labile Fe in the reactive sedimentary Fe pool demonstrates that the composition of Fe isotopes in the pore fluids refl ects the different extent of sedimentary Fe redox recycling between these sites. © 2009 Geological Society of America.

The in situ annular flume, Voyager II, was deployed at three sites in the North Sea in order to investigate resuspension events, to determine the physical characteristics of the seabed, to determine the threshold of resuspension of the bed and to quantify erosion rates and erosion depths. These are the first controlled, in situ flume experiments to study resuspension in the North Sea, and were combined with long-term measurements of waves and currents. Resuspension experiments were undertaken at two muddy, and one sandy site: north of the Dogger Bank (DG: water depths ∼80 m, very fine, poorly sorted, very fine-skewed sediment experiencing seasonal thermal stratification of the water column along with oxygen depletion); the Oyster Grounds (OG: ∼40 m, similar bed properties, year round water column thermal stratification, Atlantic forcing); and in the Sean Gas Field (SGF: ∼20 m, moderately sorted, very coarse-skewed sand, and well mixed water column). The erosion thresholds of the bed were found to be 0.66–1.04 Pa (DG) and 0.91–1.27 Pa (OG), with corresponding erosion depths of 0.1–0.15 mm and 0.02–0.06 mm throughout the experiments. Evaluation of a year of current velocities from 2007 indicated that at OG, resuspension of the consolidated bed was limited to on average ∼8% of the time as a result of tidal forcing alone for short ( Resuspension of bed material and erosion rates were closely related to applied bed shear stresses, and eroded depths were significantly correlated with the physical properties of the bed. Therefore, while complex variations in biogeophysical factors affected the critical threshold of erosion, once exceeded, erosion rates were related to the nature of the sediment.

Recently, it has been proposed that anthropogenic CO2 emissions may affect marine ecosystems by causing ocean acidification. In particular, it is suggested that within acidified waters, calcifying organisms would be subject to malformation and enhanced dissolution. Here, we present evidence suggesting that this process occurs naturally where explosive volcanism deposits ash directly into ocean surface waters. Sediment cores from around the island of Montserrat, Lesser Antilles volcanic arc, contain distinct horizons of planktic fauna associated with recently deposited volcanic ash layers from the Soufrière Hills volcano. Within these layers are abundant thecosome pteropod shells that display evidence of partial dissolution and etching of their aragonitic shells, and appear to have suffered mass mortality during large eruptions from the volcano. Laboratory studies show that the acids bound to ash surfaces from the 2003 volcanic dome collapse event of the Soufrière Hills volcano could have caused the upper 5 m of the water column to become undersaturated with respect to aragonite. When combined with the large fluxes of acidic aerosols (principally as SO2) from the volcano during eruptions, it is proposed that volcanogenic ocean acidification by marine ash falls is a significant contributing factor to these observed mass mortality events.

article Natural iron fertilization processes are occurring around the Crozet Islands (46°26'S-52°18'E), thus relieving the water masses from the normally encountered High Nutrients Low Chlorophyll (HNLC) conditions of the Southern Ocean. During austral summers 2004/2005 and 2005/2006, iron and aluminium concentrations were investigated in large particles (N53 µm) collected from just below the mixed layer at stations under the influence of island inputs, and also in adjacent HNLC waters. These large particles are anticipated to sink out of the mixed layer, and to reflect the net effects of input and cycling of these elements in the overlying mixed layer. Labile and refractory fractions were determined by a two-stage leaching technique. Data showed that water masses downstream of the islands were enriched in total iron and aluminium (0.25-2.68 nmol L �1 and 0.34-3.28 nmol L �1 respectively), relative to the southern HNLC control sites (0.15-0.29 nmol L �1 for Fe and 0.12-0.29 nmol L �1 for Al), with only a small fraction (typically b1%) being acid leachable in both environments. Particulate iron predominantly derived from the island system represents a significant fraction of the total water column iron inventory and may complement dissolved Fe inputs that help support the high summer productivity around the Crozet islands.

The annual phytoplankton bloom occurring north of the Crozet Plateau provides a rare opportunity to examine the hypothesis that natural iron fertilization can alleviate high-nutrient low-chlorophyll (HNLC) conditions normally associated with the Southern Ocean. Therefore, during CROZet natural iron bloom and EXport experiment (CROZEX), a large multidisciplinary study performed between November 2004 and January 2005, measurements of total dissolved iron (DFe⩽0.2 μm) were made on seawater from around the islands and atmospheric iron deposition estimated from rain and aerosol samples. DFe concentrations were determined by flow injection analysis with N,N-dimethyl-p-phenylenediamine dihydrochloride (DPD) catalytic spectrophotometric detection. DFe concentrations varied between 0.086 and 2.48 nM, with low values in surface waters. Enrichment of dissolved iron (>1 nM) at close proximity to the islands suggests that the plateau and the associated sediments are a source of iron. Waters farther north also appear to be affected by this input of coastal and shelf origin, although dissolved iron concentrations decrease as a function of distance to the north of the plateau with a gradient of ∼0.07 nM km−1 at the time of sampling. Using lateral and vertical diffusion coefficients derived from Ra isotope profiles and also estimates of atmospheric inputs, it was then possible to estimate a DFe concentration of ∼0.55 nM to the north of the islands prior to the bloom event, which is sufficient to initiate the bloom, the lateral island source being the largest component. A similar situation is observed for other Sub-Antarctic Islands such as Kerguelen, South Georgia, that supply dissolved iron to their surrounding waters, thus enhancing chlorophyll concentrations.

Elevated levels of productivity in the wake of Southern Ocean island systems are common despite the fact that they are encircled by high-nutrient low-chlorophyll (HNLC) waters. In the Crozet Plateau region, it has been hypothesized that iron from island runoff or sediments of the plateau could be fueling the austral summer phytoplankton bloom. Here, we use radium isotopes to quantify the rates of surface-ocean iron supply fueling the bloom in the Crozet Plateau region. A 1D eddy-diffusion-mixing model applied to a 228 Ra profile (t1/2 ¼ 5.75 years) at a station north of the islands suggests fast vertical mixing in the upper 300 m (Kz ¼ 11–100 cm 2 s � 1 ) with slower mixing between 300 and 1000 m (Kz ¼ 1.5 cm 2 s � 1 ). This estimate is discussed in the context of Kz derived from the CTD/LADCP data. In combination with the dissolved Fe profile at this location, we estimated a vertical flux of between 5.6 and 31 nmol Fe m � 2 d � 1 . The cross-plateau gradients in the short-lived radium isotopes, 224 Ra (t1/2 ¼ 3.66 d) and 223 Ra (t1/2 ¼ 11.4 d), yielded horizontal eddy diffusivities (Kh )o f 39 and 6.6 m 2 s � 1 , respectively. If we assume that the islands (surface runoff) alone were supplying dissolved Fe to the bloom region, then the flux estimates range from 2.3 to 14 nmol Fe m � 2 d � 1 . If the plateau sediments are considered a source of Fe, and conveyed to the bloom region through deep winter mixing combined with horizontal transport, then this flux may be as high as 64–390 nmol Fe m � 2 d � 1 . Combined, these Fe sources are sufficient to initiate and maintain the

Vertical profiles of trace metals were measured at 1-mm intervals by deploying DGT probes in sediment cores collected from the deep Atlantic Ocean (Feni Drift) before and after the spring phytoplankton bloom. DGT (diffusive gradients in thin-films) accumulates metals on a chelating resin after their diffusive transport through a layer of hydrogel. The mean concentration of metal in the porewaters at the surface of the device during its deployment was derived from the measured mass of metal. Well-defined laboratory systems were used to establish the reproducibility and accuracy of the DGT technique for measuring metals at 1-mm intervals. The Fe and Mn profiles showed the expected redox sequence with depth, with additional fine-scale (2–5 mm) features. The close correspondence between the Mn and Co profiles, on both coarse and fine scales, showed that their chemistry is closely coupled in sediments as well as water columns. Changes in the background concentrations of Cd, Cu, Ni and Zn with depth were well correlated with Mn and Co, but the four metals also displayed mm-scale maxima that were largely independent of Mn, Co or Fe. Two-dimensional measurements at a 100-μm resolution on a DGT probe, deployed in situ with an autonomous lander, showed that the maxima were most likely associated with near-spherical, highly localised sources. The results were consistent with release of Cd, Cu, Ni and Zn from organic and planktonic skeletal material. Where there was associated release of Mn and/or Fe, through their oxides acting as electron acceptors in the decomposition of the organic matter, trace metals could also be supplied by release from the oxides. The microniches responsible for high local concentrations of metals in the porewaters were hypothesised to be due to downward mixing of material by burrowing organisms, known to be prevalent in these sediments. Much of this material appeared to be present as faecal pellets of various origins, with sizes in the range of 50um to 1 cm.

DET (Diffusive equilibration in thin films) and DGT (diffusive gradients in thin films) have been deployed in situ using an autonomous benthic lander to measure concentrations and induced fluxes of Fe and Mn (DET/DGT) and trace metals (DGT) in pore waters at millimeter spatial resolutions. The newly developed deployment system is described, and based on these first results, its strengths and weaknesses are discussed. Deployments were made in the Western Black Sea in shelf sediments overlain by well‐oxygenated water at a water depth of 77 m. Maxima of the redox‐sensitive metals at 4 and 8 cm deep within the sediment indicated that two zones of reduction dominated the geochemistry. Sharp, but systematic, features were superimposed on this general picture and were well replicated in the profiles of Mn, Co, and Cd, but the sharp features in the Fe profile were offset from those of the others elements by several millimeters. Detection of this functional discrimination between Fe and Mn as regulators of trace metals would not have been possible using more conventional sampling procedures.

A new, multi-purpose autonomous benthic lander is described, and preliminary experimental data are presented relating to deployments in the Atlantic Frontier (eastern north Atlantic) during the recent UK Thematic Programme ‘BENBO’. The autonomous lander was deployed at two contrasting sites — Site A (mouth of Rockall Trough; 3570 m) and Site B (Hatton-Rockall Bank; 1100 m) — before and following the spring-time surface ocean phytoplankton bloom (May & July, 1998, respectively). Diffusive oxygen uptake and nutrient flux data were obtained using two interchangeable modules — a profiling oxygen micro-electrode unit and a benthic chamber unit. Diffusive O 2 uptake across the sediment–water interface and the O 2 penetration depths within the sediment were determined from the oxygen micro-profiles. The shallower site, which had previously received phyto-detrital input, had a comparatively large diffusive oxygen uptake within the sediment (1.2 mmol m −2 d −1 ) and a maximum penetration depth of only 21 mm. The deeper site had greater oxygen penetration depths (∼80 mm) but a lower diffusive oxygen uptake of 0.6 mmol m −2 d −1 , indicative possibly of little or no phyto-detrital input. Visual observations of retrieved sediment cores support this conclusion, however Site A has also displays generally lower organic content and lower macrobenthic biomass which may contribute to this observation. Nutrient pore water profile data indicated fluxes of nitrate of 0.161 mmol m −2 d −1 and phosphate 0.0008 mmol m −2 d −1 into the overlying water. However, the benthic chamber studies showed virtually no change in nutrient concentrations, due probably to the relatively short deployment time used.

Data are provided on the long-term average trace metal composition of aerosols collected at two urban (Liverpool and Preston) and one rural (Lancaster) site on the UK mainland coastal rim of the NE Irish Sea. There are variations in the trace metal composition of aerosols at the urban and rural sites, with evidence of local urban `hot spot’ sources of Ni, Zn and Cr. Data from the three sites are combined to give an average trace metal composition of the aerosol at the NE Irish Sea UK coastal sites. This aerosol has higher average concentrations and EFcrust values for some trace metals, e.g. Ni and Cr, than those at other Western European coastal sites but, relative to crustal material, there is general `uniformity of composition’ in the extent to which Ni, Cr, Cu, Zn and Pb are enriched in all the coastal aerosols. To estimate the composition of the aerosol transported to the NE Irish Sea across the UK mainland coast, the coastal strip is partitioned into urban and rural regions and an average trace metal composition for the `whole rim’ aerosol is given. This is used to make an `upper limit’ estimate of the trace metal composition of the aerosol transported to open-sea regions of the NE Irish Sea, which shows a generally similar enrichment of trace metals, relative to crustal material, as that of the North Sea aerosol.

The concentrations of dissolved and particulate Cu, Fe, Mn and Pb have been determined in four cores obtained from the north-eastern Irish Sea. The diffusional fluxes of Cu, Pb and Mn from the sediments have been estimated from the concentration gradients between the porewaters and the overlying seawater. The concentrations of Cu, Pb and Mn in marine aerosols and rainwater have been obtained from a long-term collection campaign and used to determine their atmosphere-coastal ocean fluxes. The results show that of the total inputs (from rivers, direct wastes, dumping, atmospheric deposition and sediment-water exchange), the atmospheric component constitutes about 6% of the total Cu input, whereas sediment-water fluxes contribute about 34%. For Pb the atmospheric input is 3% and the flux from the sediments is 29%. The amounts of Cu and Pb diffusing from the coastal sediments are similar to the sum of the quantities entering via the rivers and direct waste inputs from industrial and domestic sources. These estimates of metal fluxes have important consequences for the long-term environmental health of the Irish Sea.

Despite a large macronutrient reservoir, the Southern Ocean has low levels of chlorophyll, primarily due to low iron availability. Exceptions to this situation are island systems where natural terrestrial iron inputs allow the development of large blooms. Particulate organic carbon (POC) and particulate (labile and refractory) iron analyses were performed on large (>53 μm) particles collected at the base of the mixed layer within such a system (the Crozet Islands) and in adjacent high-nutrient, low-chlorophyll (HNLC) waters. Biogenic iron was obtained by removal of estimated lithogenic Fe from the total Fe present. We combine these data with 234Th measurements to determine downward particulate Fe fluxes. Fluxes of Fe ranged from 4 to 301 nmol m−2 d−1 (labile), not detectable to 50 μmol m−2 d−1 (biogenic), and from 3 to 145 μmol m−2 d−1 (total) and, on average, were approximately four times larger below the highly productive, naturally iron-fertilized region than below the adjacent HNLC area. Downward labile iron fluxes are close to the sum of dissolved terrestrial, atmospheric, and upwelled iron calculated from the Planquette et al. (2007), model. Refractory iron fluxes are ∼2 orders of magnitude larger, and these can only have come from particles advected from the plateau itself. The “biogenic Fe,” is a substantial fraction (0–76, mean 23%) of the total particulate Fe to the north of the islands. The origin of this Fe pool must be dominantly biological conversion from the lithogenic fraction, as other supply terms including aeolian, deep mixing, and lateral advection of dissolved Fe are inadequate to account for the magnitude of this Fe. Inclusion of the offshore biologically available fraction of the lithogenic iron flux is therefore required to calculate fully the yield of carbon exported per unit iron injected.

The addition of iron to high- nutrient, low- chlorophyll regions induces phytoplankton blooms that take up carbon(1-3). Carbon export from the surface layer and, in particular, the ability of the ocean and sediments to sequester carbon for many years remains, however, poorly quantified(3). Here we report data from the CROZEX experiment(4) in the Southern Ocean, which was conducted to test the hypothesis that the observed north - south gradient in phytoplankton concentrations in the vicinity of the Crozet Islands is induced by natural iron fertilization that results in enhanced organic carbon flux to the deep ocean. We report annual particulate carbon fluxes out of the surface layer, at three kilometres below the ocean surface and to the ocean floor. We find that carbon fluxes from a highly productive, naturally iron-fertilized region of the sub- Antarctic Southern Ocean are two to three times larger than the carbon fluxes from an adjacent high-nutrient, low- chlorophyll area not fertilized by iron. Our findings support the hypothesis that increased iron supply to the glacial sub- Antarctic may have directly enhanced carbon export to the deep ocean(5). The CROZEX sequestration efficiency(6) ( the amount of carbon sequestered below the depth of winter mixing for a given iron supply) of 8,600 mol mol(-1) was 18 times greater than that of a phytoplankton bloom induced artificially by adding iron(7), but 77 times smaller than that of another bloom(8) initiated, like CROZEX, by a natural supply of iron. Large losses of purposefully added iron can explain the lower efficiency of the induced bloom(6). The discrepancy between the blooms naturally supplied with iron may result in part from an underestimate of horizontal iron supply.

The vertical color transition from brown to gray-green in marine sediments is linked to the Fe redox boundary and is commonly used as a proxy for biogeochemical state. We combine time-lapse sediment profile imaging with diffusive gradient thin (DGT) gels to obtain simultaneous in situ measurements of sediment color profiles, pore-water Fe and Mn profiles, and qualitative estimates of faunal activity at the Oyster Ground and North Dogger (North Sea). Analysis of Fe and Mn profiles using generalized additive modeling reveals that high variability between profiles within the sites makes it difficult to determine any intersite differences in trace metal behavior. At the Oyster Ground, the depth of sediment color transition (4.78 +/- 0.76 cm) was not significantly different from the Fe redox boundary (7.67 +/- 4.04 cm). At the North Dogger, there was a significant discrepancy between the depth of the sediment color transition (2.86 +/- 0.78 cm) and the Fe redox boundary (10.17 +/- 1.04 cm), which most likely results from high sulfate reduction rates at the North Dogger, leading to complexation of reduced iron to a form not available to the DGT technique. The differences in the coupling of sediment color and the Fe redox boundary between stations is likely to be related to variations in recent infaunal bioturbation activity, rather than variations in sediment source or fundamental differences in bulk sediment chemistry. Our results highlight the importance of the infaunal community in mediating Fe and Mn cycles, which are key pathways in the degradation of organic matter, and suggest that descriptions of bulk chemistry alone may be insufficient to understand the dynamics of biogeochemical cycling.