Mercury methylation,demethylation and reduction rates in coastal and marine surface waters of the Mediterranean Sea

In situ experiments using isotopically labeled mercury species (¹⁹⁹Hg(II) and Me²⁰¹Hg) are used to investigate mercury transformation mechanisms, such as methylation, demethylation and reduction, in coastal and marine surface waters of the Mediterranean Sea. The aim of this work is to assess the relative contribution of photochemical versus biological processes to Hg transformation mechanisms. For this purpose, potential transformation rates measured under diurnal and dark incubation conditions are compared with major biogeochemical parameters (i.e. hydrological and biological data) in order to obtain the relative contribution of various biotic and abiotic mechanisms in both surface (high light) and bottom (low light) waters of the euphotic zone. The results demonstrate that coastal and marine euphotic zones are significant reactors for all Hg transformations investigated (i.e. methylation, demethylation, reduction). A major outcome demonstrates that Hg methylation is taking place in oxic surface seawater (0.3–6.3% day^− 1) and is mainly influenced by pelagic microorganism abundance and activities (phyto- and bacterioplankton). This evidences a new potential MeHg source in the marine water column, especially in oligotrophic deep-sea basins in which biogeochemistry is mostly governed by heterotrophic activity. For coastal and marine surface waters, although MeHg is mainly photochemically degraded (6.4–24.5% day^− 1), demethylation yields observed under dark condition may be attributed to microbial or chemical pathways (2.8–10.9% day^− 1). Photoreduction and photochemical reactions are the major mechanisms involved in DGM production for surface waters (3.2–16.9% day^− 1) but bacterial or phytoplanktonic reduction of Hg(II) cannot be excluded deeper in the euphotic zone (2.2–12.3% day^− 1). At the bottom of the euphotic zone, photochemical processes are thus avoided due to the attenuation of UV-visible sunlight radiation allowing biotic processes to be the most significant. These results suggest a new potential route for Hg species cycling in surface seawater and especially at the maximum biomass depth located at the bottom of the euphotic zone (i.e. maximum chlorophyll fluorescence). In this environment, DGM production and demethylation mechanisms are thus probably reduced whereas Hg methylation is enhanced by autotrophic and heterotrophic processes. Experimental results on mercury species uptake during these investigations further evidenced the strong affinity of MeHg for biogenic particles (i.e. microorganisms) that correspond to the first trophic level of the pelagic food web.     

Reprint of “Seasonal and daily variation of mercury evasion at coastal and off shore sites from the Mediterranean Sea”

Dissolved gaseous mercury (DGM) was measured continuously using two newly developed techniques and a manual technique. The continuous techniques were based on the equilibrium between the aqueous and gaseous phase (DGM = Hg_extr / H', Hg_extr is the measured mercury concentration in the gas phase, H' is the Henry's Law coefficient at the desired temperature). In order to calculate the annual mercury evasion from the Mediterranean Sea, diurnal and seasonal measurements of DGM, total gaseous mercury in air (TGM), water temperature and wind speed were performed. During August 2003, March–April 2004 and October–November 2004 measurements of these parameters were conducted on board the RV Urania. The continuous measurements of DGM showed a diurnal variation in concentration, at both coastal and off shore sites, with higher concentrations during daytime than nighttime. The concentration difference could be as large as 130 fM between day and night. The degree of saturation was calculated directly from the measurements, S = Hg_extr / TGM and was found to vary between the different seasons. The highest average degree of saturation (850%) and the largest variation in saturation (600–1150%) was observed during the summer. The spring showed the lowest variation (260–360%) and the lowest average degree of saturation (320%). The autumn also showed a large variation in saturation (500–1070%) but a lower average (740%) compared to the summer cruise. This might be explained by the temperature difference between the different seasons, since that parameter varied the most. The flux from the sea surface was calculated using the gas exchange model developed by Nightingale et al. [Nightingale, P.D., Malin, G., Law, C.S., Watson, A.J., Liss, P.S., Liddicoat, M.I., Boutin, J., Upstill-Goddard, R. C., 2000. In situ evaluation of air–sea gas exchange parameterization using novel conservative and volatile tracers. Global Biogeochemical Cycles, 14(1):373–387]. The evasion varied between the different seasons with the highest evasion during the autumn, 24.6 pmol m^− 2 h^− 1. The summer value was estimated to 22.3 pmol m^− 2 h^− 1 and the spring to 7.6 pmol m^− 2 h^− 1. Using this data the yearly evasion from the Mediterranean Sea surface was estimated to 77 tons.     

The impact of resuspension on sediment mercury dynamics, and methylmercury production and fate: A mesocosm study

The objective of this study was to investigate the effects of resuspension on the fate and bioaccumulation of mercury (THg) and methylmercury (MeHg) in shallow estuarine environments, using mesocosms. Two 4-week experiments were conducted in July (Experiment 1) and October (Experiment 2) of 2001 with Baltimore Harbor sediments. Hard clams, Mercenaria mercenaria, were introduced into sediments for Experiment 2. Tidal resuspension (4 h on and 2 h off cycles) was simulated, with 3 replicate tanks for each treatment—resuspension (R) and non-resuspension (NR). Sediment cores were collected during the experiments for THg, MeHg, organic content and AVS analyses, and for the determination of methylation/demethylation using Hg stable isotopes (¹⁹⁹Hg(II) and CH₃¹⁹⁹Hg(II)). Zooplankton samples were collected once a week while clams were taken before and after Experiment 2 for THg and MeHg analyses. Our results suggest that the interplay between Hg methylation and MeHg degradation determines the overall MeHg pool in sediments. Sediment resuspension does not appear to directly impact the Hg transformations but can lead to changes in the association to Hg binding phases, influencing Hg methylation. The bioaccumulation results indicate that sediment resuspension can play an important role in transferring sediment MeHg into organisms.     

长江河口湿地互花米草入侵对沉积物中汞形态特征的影响研究

通过分析长江河口湿地典型植物根际沉积物柱样(0～40 cm)中总汞(THg)、甲基汞(MeHg)及其与粒度、总有机碳(TOC)、还原态硫等环境因子之间的关系,探讨了互花米草(Spartina alterniflora)入侵对沉积物中汞形态特征的影响及主控因子。结果表明:(1)不同植物(互花米草、芦苇(Phragmites communis)、海三棱藨草(Scirpus mariqueter)和水葱(Scirpus tabernaemontani))根际沉积物中THg均值为49.9～100.9 μg/kg,其与粒径小于16 μm颗粒物组分体积百分比及TOC含量之间存在显著正相关关系(r2=0.85,p<0.01;r2=0.58,p<0.01),这意味着沉积物中矿物?有机物复合体细颗粒物的空间分异决定着总汞的空间分异。互花米草入侵促进了细颗粒的沉积,进而间接促进了沉积物中总汞含量的增加。(2)不同植物根际沉积物中MeHg均值为0.3～1.4 μg/kg,MeHg/THg均值为0.4%～1.4%,互花米草、芦苇及海三棱藨草根际沉积物中MeHg含量及MeHg/THg值随深度增加不断减小,但无显著差异,表明了互花米草入侵对沉积物中汞甲基化过程的影响可能有限。Pearson相关分析表明,MeHg/THg与THg、TOC、酸挥发性硫之间不存在显著的正相关关系。硫的K边同步辐射结果进一步表明了硫形态(如有机硫和S2?)变化与MeHg变化关系不大。MeHg/THg值呈表层(0～8 cm)高,底层低的分布规律,表明了表层沉积物中汞的甲基化潜势较大,这可能与表层新鲜有机质(如藻类和植物凋落物)的不断供给及其降解过程密切相关,还需深入研究。     

The distribution and speciation of mercury in the South and equatorial Atlantic

Mercury concentration and speciation were measured in surface and deep ocean waters of the South and equatorial Atlantic. In the surface waters, total Hg was 2.9±1.7 pM on average, with a significant fraction present as reactive Hg (1.7±1.2 pM). The reactive Hg fraction consisted of elemental Hg (Hg°) as the dominant species (1.2±0.8 pM). Measurements in surface waters also showed that Hg partitioned to the “colloidal” phase (0.33±0.28 pM) and was associated with particulate matter (0.1±0.05 pM). No dimethylmercury (DMHg;<0.01 pM) or monomethylmercury (MMHg; <0.05 pM) was detected in mixed layer samples. The highest DMHg concentrations were found in recently formed deep waters – Antarctic Intermediate Water and Antarctic Bottom Water and in the equatorial sub-thermocline region. Higher concentrations of DMHg coincided with higher values of apparent oxygen utilization, indicative of a link between microbial activity and methylated Hg production. The lowest-deep water DMHg concentrations were found in the core of the North Atlantic Deep Water. Incubation experiments on-board demonstrated that light enhanced the decomposition of DMHg, with MMHg as the major product. In deep waters, Hg° was still an important constituent and is likely formed as a decomposition product from MMHg. These results suggest that methylated Hg production occurs primarily in regions of high biological activity, and that ionic Hg is strongly complexed to organic matter (colloidal material) in open ocean surface waters.     

Water Column Distribution of Mercury Species in Permanently Stratified Aqueous Environments

Biogeochemical structures of three permanently stratified waterbodies were studied: a sea water basin (the Black Sea), an estuary (Hunnbunn fjord), and a freshwater lake (Nordbytjernet), with focus on the distributions of methylmercury (MeHg) and total mercury (THg). THg concentrations were similar in the sea water basin (0.2–1.8 ng/L) and the freshwater lake (0.8–1.2 ng/L), but significantly higher in the estuary (0.6–9.4 ng/L). An increase in the MeHg concentration and MeHg/THg ratio were found in the redox zone in all three basins, indicating bacterial production of MeHg in the aqueous phase. In the lake and estuary, the maximum MeHg concentration and MeHg/THg ratio were found in samples located closest to the bottom sediments, likely due to the formation of MeHg in surface sediments and subsequent diffusion to the overlying waters.     

The effect of resuspension on the fate of total mercury and methyl mercury in a shallow estuarine ecosystem: a mesocosm study

Sediments are the major repository of mercury in estuaries and could be a significant source of Hg to the overlying water column via release from the solid phase during resuspension. There is, however, little information on the effect of resuspension on Hg partitioning and release to the water column. The objective of this study was to determine the effect of resuspension on the cycling of THg and MeHg between the water column and the sediment. Tidal resuspension was simulated using the MEERC STORM facility. The facility can mimic both realistic bottom shear stress and water column turbulence simultaneously. There were three replicates of each resuspension (R) and no resuspension (NR) mesocosms. Two 4-week experiments were conducted in July and October of 2001: experiment 1 without clams and experiment 2 with clams. Both experiments showed that resuspension of muddy sediment introduced significantly higher particulate THg to the water column as TSS increased. The results suggest that THg was mostly bound to sediment particles with very little release during the resuspension events. In contrast, particulate MeHg was significantly lower in the R tanks where sediment particles with poor MeHg were dominant in the water column during the resuspension events. Dissolved THg and MeHg did not change in concert with changes in particulate load, suggesting that the dynamics between dissolved and particulate phases for both THg and MeHg cannot be explained by an equilibrium partitioning.     

Seasonal and daily variation of mercury evasion at coastal and off shore sites from the Mediterranean Sea

Dissolved gaseous mercury (DGM) was measured continuously using two newly developed techniques and a manual technique. The continuous techniques were based on the equilibrium between the aqueous and gaseous phase (DGM = Hg_extr / H', Hg_extr is the measured mercury concentration in the gas phase, H' is the Henry's Law coefficient at the desired temperature). In order to calculate the annual mercury evasion from the Mediterranean Sea, diurnal and seasonal measurements of DGM, total gaseous mercury in air (TGM), water temperature and wind speed were performed. During August 2003, March–April 2004 and October–November 2004 measurements of these parameters were conducted on board the RV Urania. The continuous measurements of DGM showed a diurnal variation in concentration, at both coastal and off shore sites, with higher concentrations during daytime than nighttime. The concentration difference could be as large as 130 fM between day and night. The degree of saturation was calculated directly from the measurements, S = Hg_extr / TGM and was found to vary between the different seasons. The highest average degree of saturation (850%) and the largest variation in saturation (600–1150%) was observed during the summer. The spring showed the lowest variation (260–360%) and the lowest average degree of saturation (320%). The autumn also showed a large variation in saturation (500–1070%) but a lower average (740%) compared to the summer cruise. This might be explained by the temperature difference between the different seasons, since that parameter varied the most. The flux from the sea surface was calculated using the gas exchange model developed by Nightingale et al. [Nightingale, P.D., Malin, G., Law, C.S., Watson, A.J., Liss, P.S., Liddicoat, M.I., Boutin, J., Upstill-Goddard, R. C., 2000. In situ evaluation of air–sea gas exchange parameterization using novel conservative and volatile tracers. Global Biogeochemical Cycles, 14(1):373–387]. The evasion varied between the different seasons with the highest evasion during the autumn, 24.6 pmol m^− 2 h^− 1. The summer value was estimated to 22.3 pmol m^− 2 h^− 1 and the spring to 7.6 pmol m^− 2 h^− 1. Using this data the yearly evasion from the Mediterranean Sea surface was estimated to 77 tons.     

Trophic transfer of methylmercury and trace elements by tropical estuarine seston and plankton

Methylmercury (MeHg) and trace elements (TE), mercury, selenium, cadmium, lead and copper, were determined in a microbial loop composed by three size classes of autotrophic and heterotrophic microorganism samples, 1.2–70 μm (seston, SPM), 70–290 μm (microplankton) and ≥290 μm (mesoplankton) from five sampling stations within a polluted eutrophic estuary in the Brazilian Southeast coast and one external point under the influence of the bay. TE concentrations were within the range reported for marine microorganisms from uncontaminated locations. Microplankton was primarily composed of proto-zooplankton and diatoms (>90%) while approximately 50% of mesoplankton was composed mainly of copepods. MeHg and TE in samples did not differ among the five sampling stations within the bay. Cd, Pb and Cu in seston were higher in the stations sampled inside Guanabara Bay (0.67 μg Cd g⁻¹, 9.26 μg Pb g⁻¹, 8.03 μg Cu g⁻¹) than in the external one (0.17 μg Cd g⁻¹, 3.98 μg Pb g⁻¹ and 2.09 μg Cu g⁻¹). Hg, MeHg and Se did not differ among the five points within the more eutrophic waters of the estuary and the external sampling station. The trophic transfer of MeHg and Se was observed between trophic levels from prey (seston and microplankton) to predator (mesoplankton). The successive amplification of the ratios of MeHg to Hg with increasing trophic levels from seston (43%), to microplankton (59%) and mesoplankton (77%) indicate that biomagnification may be occurring along the microbial food web. Selenium, that is efficiently accumulated by organisms through trophic transference, was biomagnified along the microbial food web, while Hg, Cd, Pb, Cu did not present the same behavior. Concentrations differed between the three size classes, indicating that MeHg and TE accumulation were size-dependent. MeHg and TE concentrations were not related to the taxonomic groups' composition of the planktonic microorganisms. Results suggest the importance of the role of the trophic level and microorganism size in regulating element transfers. Eutrophication dilution may provide a process-oriented explanation for lower MeHg and TE accumulation by the three size classes of microorganisms collected at the five sampling stations within the bay.     

Molecular weight and chemical reactivity of dissolved trace metals (Cd,Cu, Ni) in surface waters from the Mississippi River to Gulf of Mexico

It is generally assumed that estuarine mixing is continuous for metals from terrestrial sources, gradually decreasing towards the open ocean endmember. Here we show that, chemical reactivity, determined by ion exchange method, and molecular weight distributions, obtained using cross-flow ultrafiltration, of dissolved Cd, Cu, and Ni in the surface waters of the Gulf of Mexico varied systematically across the estuarine mixing zone of the Mississippi River. Most size or chemical affinity fractions of dissolved metals (<0.4 μm) were linearly related to salinity (10.8–36.6), suggesting that the distribution of these elements was mainly controlled by continuous mixing processes. Dissolved concentrations across the salinity gradient ranged for Cd: 87–187 pM; Cu: 1.4–18.3 nM; and Ni: 2.6–18.8 nM, with highest values near the Mississippi river mouth, and lowest concentrations in a warm core ring in the Gulf of Mexico. Dissolved Cd was mostly present as a truly dissolved (<10 kDa, 97 ± 1%) and cationic fraction (Chelex-100 extractable, 94 ± 4%). A novel observation across the estuarine mixing zone was that colloidal metal concentrations were identical to either inert (for Cu, Ni) or AMPG-labile anionic (Cu, Cd) fractions. The difference in behavior between Cu and the other two metals might indicate differences in the biopolymeric nature of the metal–organic chelates. In particular, the anionic-organic Cd fractions accounted for just 3 ± 1%, on average. However, for Cu, it was 24 ± 4%, and for Ni, it was 9 ± 6%. The fractions of the total dissolved metal fractions that were “inert” averaged 31 ± 10% for Cu and 29 ± 12% for Ni. Small but noticeable amounts (6 ± 3%) of dissolved inert Cd fractions were also present. Apparent non-local transport processes, likely associated with cross-shelf sediment resuspension processes, could have been responsible for the relatively high concentrations of ‘inert’ and ‘anionic’ metal fractions in high salinity coastal waters, and accounting for the persistence of metals bound to humic substances in the Gulf of Mexico.     

Effects of oxic and anoxic filtration on determined methyl mercury concentrations in sediment pore waters

Accurate determination of methyl mercury (MeHg) concentrations in sediment pore waters is crucial for an improved understanding of mercury (Hg) biogeochemistry, and for improved risk assessment of Hg contaminated sites. In the present study, effects of oxic (air) and anoxic (N₂) filtration (after centrifugation) on determined pore water MeHg concentrations were investigated in severely Hg contaminated pulp fibre sediments from two estuaries of the Bothnian Sea, Sweden. MeHg was determined in the filtrate using species-specific isotope dilution gas chromatography inductively coupled plasma mass spectrometry (SSID–GC–ICPMS), after ethylation with sodium tetraethylborate. Determined concentrations of MeHg were greater after anoxic filtration than after oxic filtration for all samples investigated, with MeHg(N₂)/MeHg(air) ratios ranging between 3.4 and 343. Adsorption to newly formed Fe(III)/Mn(III/IV)-oxy/hydroxide surfaces is proposed as the main mechanism responsible for MeHg removal during oxic filtration. This is supported by decreases in dissolved Fe and Mn concentrations during oxic filtration, and by decreases in dissolved sulphur concentrations during oxic filtration in the samples with largest effect on MeHg concentrations. The latter is explained by adsorption of SO₄²⁻ to newly formed Fe(III)/Mn(III/IV)-oxy/hydroxide surfaces. The effect of oxidation during filtration on pore water MeHg concentrations was largest in samples in which FeS(s) was not present, but with calculated pe-values below − 3. Thus, our results indicate that the largest errors with respect to pore water MeHg concentrations when filtering in air can be expected in samples with an intermediate redox potential, possibly buffered by a mixture of oxidation sensitive Fe(II/III) minerals.     

Environmental impact factors and mercury speciation in the sediment along Fujian and eastern Guangdong coasts

Concentrations of total mercury (THg) and methyl mercury (MeHg) were determined for 32 surface sediments collected along the coastal line of Fujian Province and eastern Guangdong Province. The spatial distributions of THg and MeHg and their environmental impact factors were investigated. The average concentrations of THg and MeHg in the sediments were 31.5 ng/g and 0.096 ng/g, respectively. Both sediment THg and MeHg concentrations showed relatively high value in the Minjiang Estuary and the coastal areas of Quanzhou and Putian. The concentrations overall decreased as the distance to the shoreline increased. The correlations among environmental impact factors and THg, MeHg were analyzed. The sediment THg concentration was highly correlated to the concentrations of organic matter, copper, total nitrogen (TN) and total phosphorus (TP), and significantly correlated to pH value of the bottom seawater and concentration of sediment sulfide. The sediment MeHg concentration was highly correlated to the concentrations of organic matter and copper, and significant correlated to the concentrations of sulfide, TN, TP and pH value of the bottom seawater.     

Dissolved and particulate aluminum in the Columbia River and coastal waters of Oregon and Washington: Behavior in near-field and far-field plumes

The distribution of dissolved (soluble and total) and particulate (leachable and total) aluminum was examined in the Columbia River and estuary, in near-field and far-field river plumes, and in adjacent coastal waters of Washington and Oregon during the River Influence on Shelf Ecosystems (RISE) cruise of May/June 2006. Dissolved and particulate aluminum (Al) concentrations were significantly greater in the river than in the coastal waters that mixed to form the plume. Dissolved Al concentrations in the Columbia River (∼80 nM) were low relative to other major rivers. Leachable and total particulate Al concentrations within the river reached concentrations greater than 1000 nM and 18,000 nM, respectively. Dissolved Al within the Columbia River estuary showed a significant removal (∼60%) at salinities between 0 and 10 with salt-induced flocculation of colloidal Al complexes and enhanced particle scavenging being probable explanations for aluminum removal. Dissolved and particulate Al concentrations were significantly greater in near-field plumes relative to surrounding coastal waters. As the plume advected from near-field to far-field away from the river mouth, dilution of the plume with lower dissolved Al surface waters as well as particle scavenging along the flow path appeared to be controlling dissolved Al distributions. Particle settling as well as dilution with lower particle-load waters led to observed decreases in particulate Al as the plume moved from near-field to far-field. However, the percent-leachable particulate aluminum in both near-field and far-field plumes was remarkably constant at ∼7%. Dissolved and particulate Al in a far-field plume over 100 km southwest of the Columbia River mouth were over an order-of-magnitude greater than surrounding waters, illustrating the importance of the Columbia River plume as a mechanism for transporting Al offshore. Aluminum could be used to trace the input of biologically-required elements such as iron into waters off the shelf.     

Processes influencing dissolved iron distributions below the surface at the Atlantic Ocean–Celtic Sea shelf edge

Shelf break systems are highly dynamic environments. However little is known about the influence that benthic interactions and water mass mixing may have on vertical distributions of iron in these systems. Dissolved Fe (< 0.4 μm) concentrations were measured in samples from nine vertical profiles across the upper slope (150–2950 m water depth) at the Atlantic Ocean–Celtic Sea shelf break. Dissolved iron concentrations varied between less than 0.2 and 5.4 nM, and the resulting detailed section showed evidence of a range of processes influencing the Fe distributions. The near sea floor data were interpreted in terms of release and removal processes. The concentrations of dissolved Fe present in near seabed waters were consistent with release of Fe from in situ remineralisation of particulate organic matter at two upper slope stations, and possibly release from pore water upon resuspension on shelf. Lateral transport of dissolved iron was evident from elevated Fe concentrations in an intermediate nepheloid layer and its advection along isopycnals. Surface waters at the shelf break also showed evidence of vertical mixing of deeper iron-rich waters. These waters contained macronutrients that sustained primary productivity in these otherwise nutrient-depleted surface waters. The data also suggest some degree of stabilisation of relatively high concentrations of iron, presumably through ligand association or as colloids. This study supports the view that lateral export of dissolved iron to the interior of the ocean from shelf and coastal zones and may have important implications for the global budget of oceanic iron.     

The Irish Sea: Is it eutrophic?

The question of whether the Irish Sea is eutrophic is addressed by reviewing the evidence for anthropogenic nutrient enrichment, elevated phytoplankton production and biomass and undesirable disturbance in the context of the EU and OSPAR definitions of eutrophication. Winter concentrations of dissolved available inorganic phosphate (DAIP), nitrogen (DAIN as nitrate and nitrite) and silicate (Si) in coastal waters and concentrations of DAIP and Si in offshore waters of the Irish Sea are elevated relative to winter Celtic Sea shelf break concentrations (0.5 μM DAIP, 7.7 μM DAIN and 2.7 μM Si). Significant, negative nutrient salinity relationships and analysis of the Isle of Man nutrient time-series indicate that the elevated Irish Sea levels of DAIP and DAIN are the result of anthropogenic enrichment with highest concentrations (≈2.0 μM DAIP, 30 μM DAIN and 17 μM Si) measured in near shore eastern Irish Sea waters.     

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.     

Inputs of iron,manganese and aluminium to surface waters of the Northeast Atlantic Ocean and the European continental shelf

Dissolved Fe, Mn and Al concentrations (dFe, dMn and dAl hereafter) in surface waters and the water column of the Northeast Atlantic and the European continental shelf are reported. Following an episode of enhanced Saharan dust inputs over the Northeast Atlantic Ocean prior and during the cruise in March 1998, surface concentrations were enhanced up to 4 nmol L^− 1 dFe, 3 nmol L^− 1 dMn and 40 nmol L^− 1 dAl and returned to 0.6 nmol L^− 1 dFe, 0.5 nmol L^− 1 dMn and 10 nmol L^− 1 dAl towards the end of the cruise three weeks later. A simple steady state model (MADCOW, [Measures, C.I., Brown, E.T., 1996. Estimating dust input to the Atlantic Ocean using surface water aluminium concentrations. In: Guerzoni. S. and Chester. R. (Eds.), The impact of desert dust across the Mediterranean, Kluwer Academic Publishers, The Netherlands, pp. 301–311.]) was used which relies on surface ocean dAl as a proxy for atmospheric deposition of mineral dust. We estimated dust input at 1.8 g m^− 2 yr^− 1 (range 1.0–2.9 g m^− 2 yr^− 1) and fluxes of dFe, dMn and dAl were inferred. Mixed layer steady state residence times for dissolved metals were estimated at 1.3 yr for dFe (range 0.3–2.9 yr) and 1.9 yr for dMn (range 1.0–3.8 yr). The dFe residence time may have been overestimated and it is shown that 0.2–0.4 yr is probably more realistic. Using vertical dFe versus Apparent Oxygen Utilization (AOU) relationships as well as a biogeochemical two end member mixing model, regenerative Fe:C ratios were estimated respectively to be 20 ± 6 and 22 ± 5 μmol Fe:mol C. Combining the atmospheric flux of dFe to the upper water column with the latter Fe:C ratio, a ‘new iron’ supported primary productivity of only 15% (range 7%–56%) was deduced. This would imply that 85% (range 44–93%) of primary productivity could be supported by regenerated dFe. The open ocean surface data suggest that the continental shelf is probably not a major source of dissolved metals to the surface of the adjacent open ocean. Continental shelf concentrations of dMn, dFe, and to a lesser extent dAl, were well correlated with salinity and express mixing of a fresher continental end member with Atlantic Ocean water flowing onto the shelf. This means probably that diffusive benthic fluxes did not play a major role at the time of the cruise.     

Methylmercury production in sediments of Chesapeake Bay and the mid-Atlantic continental margin

Methylmercury (MeHg) concentration and production rates were studied in bottom sediments along the mainstem of Chesapeake Bay and on the adjoining continental shelf and slope. Our objectives were to 1) observe spatial and temporal changes in total mercury (HgT) and MeHg concentrations in the mid-Atlantic coastal region, 2) investigate biogeochemical factors that affect MeHg production, and 3) examine the potential of these sediments as sources of MeHg to coastal and open waters. Estuarine, shelf and slope sediments contained on average 0.5 to 1.5% Hg as MeHg (% MeHg), which increased significantly with salinity across our study site, with weak seasonal trends. Methylation rate constants (k_meth), estimated using enriched stable mercury isotope spikes to intact cores, showed a similar, but weaker, salinity trend, but strong seasonality, and was highly correlated with % MeHg. Together, these patterns suggest that some fraction of MeHg is preserved thru seasons, as found by others [Orihel, D.M., Paterson, M.J., Blanchfield, P.J., Bodaly, R.A., Gilmour, C.C., Hintelmann, H., 2008. Temporal changes in the distribution, methylation, and bioaccumulation of newly deposited mercury in an aquatic ecosystem. Environmental Pollution 154, 77] Similar to other ecosystems, methylation was most favored in sediment depth horizons where sulfate was available, but sulfide concentrations were low (between 0.1 and 10 μM). MeHg production was maximal at the sediment surface in the organic sediments of the upper and mid Bay where oxygen penetration was small, but was found at increasingly deeper depths, and across a wider vertical range, as salinity increased, where oxygen penetration was deeper. Vertical trends in MeHg production mirrored the deeper, vertically expanded redox boundary layers in these offshore sediments. The organic content of the sediments had a strong impact on the sediment:water partitioning of Hg, and therefore, on methylation rates. However, the HgT distribution coefficient (K_D) normalized to organic matter varied by more than an order of magnitude across the study area, suggesting an important role of organic matter quality in Hg sequestration. We hypothesize that the lower sulfur content organic matter of shelf and slope sediments has a lower binding capacity for Hg resulting in higher MeHg production, relative to sediments in the estuary. Substantially higher MeHg concentrations in pore water relative to the water column indicate all sites are sources of MeHg to the water column throughout the seasons studied. Calculated diffusional fluxes for MeHg averaged  1 pmol m^− 2 day^− 1. It is likely that the total MeHg flux in sediments of the lower Bay and continental margin are significantly higher than their estimated diffusive fluxes due to enhanced MeHg mobilization by biological and/or physical processes. Our flux estimates across the full salinity gradient of Chesapeake Bay and its adjacent slope and shelf strongly suggest that the flux from coastal sediments is of the same order as other sources and contributes substantially to the coastal MeHg budget.     

Silver in the subarctic northeast Pacific Ocean: Explaining the basin scale distribution of silver

Five vertical profiles of silver (Ag) in the subarctic northeast Pacific are presented. Dissolved (< 0.2 μm) Ag concentrations within the surface mixed layer range from 6–25 pM, with the highest observed values at the most coastal site. Elevated Ag concentrations at this station are most likely attributable to the estuarine circulation in the Juan de Fuca Strait. One open-ocean station (P20) exhibited a strong surface Ag maximum. The station was located at the edge of a Haida eddy which raises the possibility that such eddies transport Ag seaward from the coastal zone. Ag concentrations in the deep waters ranged from 60–80 pM. These measurements are consistent with other recent Ag data collected in the Pacific. Ag profiles throughout the Pacific Ocean yield a strong positive correlation between Ag concentration and dissolved silicic acid concentration. However, Ag is depleted relative to silicic acid at intermediate depths where dissolved O₂ concentrations are low, implying a possible removal of Ag from oxygen-depleted waters by scavenging and/or precipitation.     

Antarctic Intermediate Water influence on Mediterranean Sea Water outflow

This study of the mixing of Mediterranean Sea Water (MW) with the surrounding waters was made possible by the Semane 2002 cruise (Sortie des Eaux Meditérranéennes dans l'Atlantique Nord-Est) that took place in the Gulf of Cadiz in July 2002. Potential temperature, salinity, oxygen, nutrients and CFC data are used to describe the water masses present in the Gulf. In the southern part of the basin, a water mass characterised by low oxygen, high nutrient and low CFC concentrations occurs along the African continental slope. This water has been identified as the modified Antarctic Intermediate Water (AAIW). It has been previously observed south of this section, at the latitude of the Canary Islands, as a northward flow between the African shelf and the islands. The modified AAIW found in the Gulf of Cadiz is situated at a density of 27.5 kg m⁻³. Above, at 27.3 kg m⁻³, the lower limb of the North Atlantic Central Water is observed as a salinity minimum. The modified AAIW enters the Gulf of Cadiz along the south-western part of the continental shelf. It flows cyclonically and exits north-westward. In the northern part of the gulf, due to the presence of the Mediterranean Undercurrent (MU), the AAIW flows off the coast. An optimum multiparameter analysis was conducted to evaluate the influence of the AAIW on the MW northwest of the basin. We show that the AAIW is present in the lower core of the MU at a proportion of 12.9±8.2% and is absent in the upper core.