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1.
Anoxic sulfidic waters provide important media for studying the effect of reducing conditions on the cycling of trace metals. In 1987–1988, dissolved and particulate trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) concentrations were determined in the water column of the anoxic Drammensfjord basins, southeastern Norway. The iminodiacetic acid type chelating resin (Chelex 100) was used for the preconcentration of trace metals. The trace metal concentrations were determined using atomic absorption spectrophotometry (AAS), differential pulse polarography (DPP), and differential pulse-anodic stripping voltammetry (DP-ASV).It was observed that the trace metals Mn and Fe were actively involved in the processes of redox cycling (oxidationreduction and precipitation-dissolution) at the O2/H2S interface. The dissolved concentrations of Mn, Fe and Co showed maxima just below the O2/H2S interface. The seasonal enhancement in the maxima of both dissolved and particulate Mn and Fe at the redox cline is mainly governed by the downward movement of water which carries oxygen. An association of Co with the Mn cycle was observed, while the total dissolved Ni was decreased by only 10–35% in the anoxic waters. The dissolved concentrations of Cu, Zn, Pb and, to a lesser extent, Cd decreased in the anoxic zone.  相似文献   

2.
《Marine Chemistry》2001,73(3-4):215-231
In-situ benthic flux studies were conducted at three stations in Upper Galveston Bay twice during March 1996 to directly measure release rates of dissolved Mn, Fe, Ni and Zn from the sediments. Results showed reproducible increases with time in both replicate light and light–dark benthic chambers, resulting in average fluxes of −1200±780, −17±12, −1.6±0.6 and −2.4±0.79 μmol m−2 day−1 for Mn, Fe, Ni and Zn, respectively. Sediment cores collected during 1994–1996 showed that surficial pore water concentrations were elevated compared to overlying water column concentrations, suggesting diffusive release from the sediments. Diffusive flux estimates of Mn and Zn agreed in direction with chamber fluxes measured on the same date, but only accounted for 5–38% of the measured flux. Diffusive fluxes of Fe agreed with measured fluxes at the near Trinity River station but overestimated actual release in the mid and outer Trinity Bay regions, possibly due to inaccurate determination of the Fe pore water gradients or rapid oxidation processes in the overlying water at these stations.In general, measured fluxes of Mn and Ni were higher in the mid Trinity Bay region and suggested a mechanism for the elevated trace metal concentrations previously reported for this region of Galveston Bay. However, the fluxes of Fe were highest in close proximity to the Trinity River, supporting the elevated Fe concentrations measured in this region during this and other studies, and decreased towards middle and outer Trinity Bay. Trace metal turnover times were between 0.1 and 1.2 days for Mn, between 1.3 and 4.6 days for Fe, and between 27 and 100 days for Ni and 12–20 days Zn, and were considerably shorter than the average Trinity Bay water residence time (1.5 years) for this period. Comparing area averaged benthic inputs to Trinity River inputs shows the sediments to be a significant source of trace metals to Galveston Bay. However, while benthic inputs of trace metals were measured, water column concentrations remained low despite rapid turnover times for Mn and Fe, suggesting removal of these metals from the water column after release from the sediments.  相似文献   

3.
Particulate fluxes of trace elements (Al, Cd, Co, Cu, Fe, Mn, Ni, P, Ti, V and Zn) in the northeast Atlantic Ocean (three positions at latitudes from 33°N to 54°N along ∼20°W) were measured using time-series sediment traps between March 1992 and September 1994. Significant variabilities of fluxes with season and depth (1000 m to maximum of 4000 m) were observed only for ‘biogenic elements’, such as Cd, Ni, Zn or P. On the other hand, we found a distinct large-scale increase of fluxes into the deep-sea traps to the south for Al, Co, Fe, Mn and V. We attribute this latitudinal gradient to the increasing influence of the Saharan dust plume. The biogenic flux decreased towards the south. This trend was clearly visible for Cd and P only. The fluxes of other ‘nutrient-like’ elements, such as Ni or Zn, exhibited a general decrease between 53°N and 33°N. We compared our sedimentation flux data with published data from the western North Atlantic basins. For this purpose we corrected the deep-sea fluxes of Cu, Mn, Ni and Zn for their lithogenic fractions on the basis of Al, with average crustal material and granitic rocks as references. The comparison indicates that these ‘excess’ fluxes are a factor of at least 2 higher in the western basins for the selected elements. Estimated fluxes are in good agreement with reported atmospheric deposition in the two areas. The noted imbalance between the non-lithogenic atmospheric input of Mn and the determined ‘excess flux’ in the deep northeast Atlantic indicates an additional input in the form of a lateral flux of dissolved Mn(II) species and scavenging onto sinking particles. With respect to the mechanism of sedimentation, a unique behaviour is noticed for the refractory elements Co, Fe, Mn, Ti and V, which were found to correlate with the vertical transport of Al (clay). The ‘excess’ fluxes of Cu, Ni and Zn are linearly related to Corg, whereas the overall relation of Cd to P fluxes exhibits a molar Cd/P ratio of 2.0×10-4, which is close to the ratio in the dissolved fractions in the northeast Atlantic.  相似文献   

4.
In June 1981, dissolved Zn, Cd, Cu, Ni, Co, Fe, and Mn were determined from two detailed profiles in anoxic Baltic waters (with extra data for Fe and Mn from August 1979). Dramatic changes across the O2H2S interface occur in the abundances of Cu, Co, Fe, and Mn (by factors of ?100). The concentrations of Zn, Cd, and Ni at the redox front decrease by factors between 3 to 5.Equilibrium calculations are presented for varying concentrations of hydrogen sulfide and compared with the field data. The study strongly supports the assumption that the solubility of Zn, Cd, Cu, and Ni is greatly enhanced and controlled by the formation of bisulfide and(or) polysulfide complexes. Differences between predicted and measured concentrations of these elements are mainly evident at lower ΣH2S concentrations.Cobalt proved to be very mobile in anoxic regions, and the results indicate that the concentrations are limited by CoS precipitation. The iron (Fe2+) and manganese (Mn2+) distribution in sulfide-containing waters is controlled by total flux from sediment-water interfaces rather than by equilibrium concentrations of their solid phases (FeS and MnCO3). The concentrations of these metals are therefore expected to increase with prolonged stagnation periods in the basin.  相似文献   

5.
Vertical profiles of dissolved and particulate 210Po and 210Pb were measured across the redox transition zone at Station F1 in Framvaren Fjord, Norway. In this fjord, a sharp decrease in pH above the O2/H2S interface facilitates the aerobic dissolution of MnO2. In contrast, Fe(II) concentrations begin to increase only at the O2/H2S interface depth. Activity profiles reveal that dissolved 210Po and 210Pb are sequestered efficiently by particulates in surface waters. As polonium-210 and lead-210 activities descend down into the aerobic manganese reduction (AMR) zone, they are remobilized during the reductive dissolution of the carrier phase oxyhydroxides. Both 210Po and 210Pb are highly enriched at the O2/H2S interface where an active community of microbes, such as anoxygenic phototrophs (e.g., Chromatium, Chlorobium sp.), thrives. The coincident peaks in 210Po, 210Pb and microbial biomass suggest a strong biological influence on the behavior of these radionuclides. There is a strong covariance between the vertical distribution of Mn and Pb, indicating that their redox cycling is closely coupled and is likely microbially mediated.  相似文献   

6.
A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn2+ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl?1, indicating that the oxidation of Fe2+ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters.  相似文献   

7.
Fluxes of dissolved forms of iron and manganese across the sediment–water interface were studied in situ in the Gulf of Finland and the Vistula Lagoon (Baltic Sea), and in the Golubaya Bay (Black Sea) from 2001 to 2005. Fluxes were measured using chamber incubations, and sediment cores were collected and sliced to assess the porewater and solid phase metal distribution at different depths. Measured and calculated benthic fluxes of manganese and iron were directed out of sediment for all sites and were found to vary between 70–4450 and 5–1000 µmole m− 2 day− 1 for manganese and iron, respectively. The behavior of the studied metals at various redox conditions in the near-bottom water and in the sediment was the main focus in this study. Our results show the importance of bottom water redox conditions for iron fluxes. We measured no fluxes at oxic conditions, intermediate fluxes at anoxic conditions (up to 200 μmole m− 2 day− 1) and high fluxes at suboxic conditions (up to 1000 μmole m− 2 day− 1). Total dissolved iron fluxes were generally dominated by iron(II). Contribution of iron(III) to the total iron flux did not exceed 20%. Obtained fluxes of manganese at all studied regions showed a linear correlation (r2 = 0.97) to its concentration in the porewater of the top sediment layer (0–5 mm) and did not depend on dissolved oxygen concentrations of bottom water. Organically complexed iron and manganese were in most cases not involved in the benthic exchange processes.  相似文献   

8.
《Marine Chemistry》2001,74(1):29-51
Major electron donors (H2S, NH4+, Mn2+, Fe2+) and acceptors (O2, NO3−, Mn(IV), Fe(III)), process rates (35SO42− reduction, dark 14CO2 fixation) and vertical fluxes were investigated to quantify the dominant biogeochemical processes at the chemocline of a shallow brackish fjord. Under steady-state conditions, the upward fluxes of reductants and downward fluxes of oxidants in the water column were balanced. However, changes in the hydrographical conditions caused a transient nonsteady-state at the chemocline and had a great impact on process rates and the distribution of chemical species. Maxima of S0 (17.8 μmol l−1), thiosulfate (5.2 μmol l−1) and sulfite (1.1 μmol l−1) occurred at the chemocline, but were hardly detectable in the sulfidic deep water. The distribution of S0 suggested that the high concentration of S0 was (a) more likely due to a low turnover than a high formation rate and (b) was only transient, caused by chemocline perturbations. Kinetic calculations of chemical sulfide oxidation based on actual conditions in the chemocline revealed that under steady-state conditions with a narrow chemocline and low reactant concentrations, biological sulfide oxidation may account for more than 88% of the total sulfide oxidation. Under nonsteady-state conditions, where oxic and sulfidic water masses were recently mixed, resulting in an expanded chemocline, the proportion of chemical sulfide oxidation increased. The sulfide oxidation rate determined by incubation experiments was 0.216 μmol l−1 min−1, one of the highest reported for stratified basins and about 15 times faster than the initial rate for chemical oxidation. The conclusion of primarily biological sulfide oxidation was consistent with the observation of high rates of dark 14CO2 fixation (10.4 mmol m−2 day−1) in the lower part of the chemocline. However, rates of dark 14CO2 fixation were too high to be explained only by lithoautotrophic processes. CO2 fixation by growing populations of heterotrophic microorganisms may have additionally contributed to the observed rates.  相似文献   

9.
We report a simplified synthesis, and some performance characteristics, for 8-hydroxyquinoline (8-HOQ) covalently bonded to a chemically resistant TosoHaas TSK vinyl polymer resin. The resin was used to concentrate trace metals from stored, acidified seawater samples collected from Jellyfish Lake, an anoxic marine lake in the Palau Islands. The Mn, Fe, and Zn profiles determined from the 8-HOQ resin extraction were similar to those determined using Chelex-100 resin. The Zn and Cd profiles did not exhibit removal by sulfide “stripping” in contrast to other anoxic marine basins. The profiles of Co and Ni also exhibited elevated concentrations in the anoxic hypolimnion. The solution speciation and saturation states for the metals were calculated using revised metal-bisulfide stability constants. The calculations suggest that the MS(HS)− species dominates the solution speciation for Mn, Co, Ni, Zn, Cd, and Pb. Cu(I) is modeled as the CuS− or Cu(HS)2− species, while Fe(II) behaves as the free Fe2+ cation. The Mn, Co, Ni, Cu and Cd concentrations appeared to be at least 10-fold undersaturated, while the Fe(II), Zn, and Pb concentrations were close to saturation with respect to their metal sulfides.  相似文献   

10.
Dissolved and particulate trace metals (Cu, Cd, Pb, Zn, Ni, Fe and Mn) measured at six stations along the Scheldt estuary in October/November 1978 are compared with more recent data. Based on Ca content in the suspended matter, three distinct geochemical regions could be distinguished: the upper estuary (salinity 1–7) dominated by fluvial mud, mid-estuary (salinity 7–17) where the composition of the suspended matter remained relatively constant, and the lower estuary where marine mud prevailed. Re-suspension of sediments is the major factor controlling the composition of the particles in the upstream region. Anoxic conditions prevailed in the upper part of the estuary extending to a salinity of 15 in 1978, while at present the seaward boundary of the anoxic water body is located at less saline waters. Furthermore, the present-day metal load is much lower than in 1978. As a consequence of the changed situation, maxima in dissolved concentrations of redox-sensitive metals in the mid/lower estuary have moved as well, which affects the trace metal re-distribution pattern. In the anoxic zone, exchange processes between dissolved and particulate metal fractions were strongly redox regulated, with Fe and Mn as excellent examples. Iron was removed from the dissolved phase in the early stages of mixing resulting in an increase in the suspended particulate matter of the leachable ‘non-residual' Fe fraction from 2 to 3.5%. Due to its slower kinetics, removal of Mn from solution occurred in mid-estuary where oxygen concentrations increased. Cu, Cd and Zn on the contrary were mobilised from the suspended particles during estuarine mixing. External inputs of Pb, and to a lesser extent of Cu, in the lower estuary resulted in the increase of their particulate and the dissolved concentrations. Calculated Kd (distribution coefficient) values were used to assess the redistribution between the dissolved and particulate phase of the investigated metals. Due to the existence of the anoxic water body in the upper estuary, the importance of redox processes in determining the Kd values could be demonstrated. The sequence of Kd values in the upper estuary (Fe, Cd, Zn, Pb > Cu > Ni, Mn) is significantly different from that in the lower estuary (Fe > Mn > Pb, Ni, Zn, Cu, Cd). Thus, in such a dynamic estuary single metal-specific Kd values cannot be used to describe redistribution processes.  相似文献   

11.
The downward flux of Mn through the water column was directly measured using sediment traps. The Mn flux from the bottom sediment to the water column, and the removal rate of Mn in the bottom water were estimated from Mn gradients in the bottom water. The sediment traps were deployed more than ten times at the same station in Funka Bay, Japan. The trapped settling matter and filtered suspended matter samples were analyzed for Mn, Fe, Al and ignition loss. The observed downward flux of Mn through the water column in winter (1.3–2.8 μg/cm2 /day) was generally an order of magnitude larger than that in summer (0.13–0.45 μg/cm2 /day), and the Mn fluxes for both seasons were also greater than the accumulation rate of Mn in the bottom sediments (0.10 μg/cm 2/day). More Al was contained in the trapped settling matter than in the suspended matter, while Mn showed the opposite behavior. The Fe/Mn ratio of the residual fraction (obtained by subtracting the sediment component of the settling matter) was rather well correlated with the corresponding ratio in suspended matter. Settling particles are expected to scavenge suspended matter during their passage through the water column. The flux of Mn across the sediment—water interface was estimated from its vertical profiles in the water column to be 0.1–0.3 μg/cm2 day. The residence time of Mn in bottom water was about one to several months. These results suggest that Mn is actively recycled between the water column and the sediments of the coastal sea.  相似文献   

12.
Research is conducted on the following questions: 1) the seasonal and spacial changes of Fe2+ concentration in overlying water and interstitial water; 2) the profiles of Fe3+ and Fe2+and total Mn in solid phase of sediment; and 3) the estimation and comparison of Fe and Mn diffusion and deposition fluxes.The complex relation among the early diagenesis of iron, the grain size composition in solid phase of sediment and the factors of pH and Eh as well as dissolved oxygen are reflected by seasonal and space relation of Fe2+ change.The geochemical activity and role of iron and manganese during diagenetic processes is discussed and estimated by calculating and comparing deposition and diffusion fluxes of both the elements.  相似文献   

13.
In the framework of the German contribution to the Joint Global Ocean Flux Study (JGOFS), deep-water fluxes of particle-associated trace elements were measured in the northeast Atlantic Ocean. The sinking particles were collected almost continuously from 1992 to 1996 at three time-series stations, L1 (33°N/22°W), L2 (47°N/20°W), and L3 (54°N/21°W), using sediment traps. The focus of the present study is the temporal variability of the particle-associated elemental fluxes of Al, Ca, Cd, Co, Cu, Fe, Mn, Ni, P, Pb, Ti, V, and Zn at a depth of 2000 m.A clear seasonality of the fluxes that persisted for several years was documented for the southernmost station (L1) at stable oligotrophic conditions in the area of the North Atlantic Subtropical Gyre East (NASTE). At L2 and L3, an episodic nature of the elemental fluxes was determined. Mesoscale eddies are known to frequently cause temporal and spatial variability in the flux of biogenic components in that area. These events modified the simple seasonal pattern controlled by the annual cycle at L2, in the North Atlantic Drift Region (NADR), and at L3, which was influenced by the Atlantic Arctic province (ARCT). All stations were characterized by an additional episodic lithogenic atmospheric supply reaching the deep sea.The integrated annual fluxes during the multi-year study revealed similar flux magnitudes for lithogenic elements (Al, Co, Fe, Ti, and V) at L2 and L3 and roughly twofold fluxes at L1. Biogenic elements (Cd, P, and Zn) showed the opposite trend, i.e., two to fourfold higher values at L2 and L3 than at L1. For Mn, Ni, and Cu, the spatial differences were smaller, perhaps because of the intermediate behavior, between lithogenic and biogenic, of these elements. Similarly, among the three study sites, there were no noticeable differences in the total annual flux of Pb.The respective lithogenic fractions of the deep-sea fluxes of Cd, Co, Cu, Mn, Ni, V, and Zn were subtracted based on the amount of Al, with the average composition of the continental crust as reference. This procedure allowed estimation of the labile trace element fraction (TEexc) of the particles, i.e., TE taken up or scavenged during particle production and sedimentation. The ratios of TEexc/P clearly demonstrated an enrichment of TE over labile P from biogenic surface material to the deep sea for Zn (factor 4–6), Mn (12–27), Ni (3–5), and Cu (9–25); an intermediate status for Co (0.5–2.2); and depletion for Cd vs. P (0.2–0.4). Surprisingly, the recycling behavior of excess Co was found to be similar to that of P. Hence, Coexc behaved like a biogenic element; this is in contrast to total Co, which is dominated by the refractory lithogenic fraction.Moreover, it is argued that these excess elemental fluxes caused a loss of the dissolved elements in upper waters, since their transport reaches the deep-sea waters at 2000 m, a depth far below of deep-winter mixing and upwelling. The annual amount of excess TE exported from surface waters was estimated to be 1.3×109 mol Zn y?1, 4.4×109 mol Mn y?1, 4.9×108 mol Ni y?1, 2.2×107 mol Cd y?1, 7.4×108 mol Cu y?1, and 2.7×107 mol Co y?1 for the whole North Atlantic Ocean. Important primary sources that could replenish these losses are the aeolian and fluvial supply processes.  相似文献   

14.
Spring profiles of microbial production derived from the dark incorporation of tritiated leucine and tritiated thymidine in the northwest Mediterranean show an exponential decline with depth. Assuming this to represent a steady-state balance between microbial respiration and the downward flux of carbon, the downward flux is estimated as (1−/)p/b, where p is the microbial production, their gross growth efficiency and b the coefficient of exponential decline with depth. Summer profiles, ranging over about 3° of latitude and 4° of longitude, were well fitted by a two-component exponential decline, suggesting two distinct microbial substrates. Values of b for the more rapidly declining component varied between 0.01 and 0.06 m−1 according to location. In the case of the slower component, b was estimated as 0.002 m−1, and did not vary significantly over the region. Estimated fluxes of carbon at the surface are 123–335 mg m−2 d−1 for the fast and 95 mg m−2 d−1 for the slow component. Below about 200 m, carbon flux is dominated by the slow component. Flux estimates are compatible with flux estimates from sediment traps in the same region. The observed changes between the spring and summer profiles, combined with the horizontal homogeneity of the summer profiles below 200 m, are consistent with a downward transport of about 5–10 m d–1, implying a significant dispersive component to the observed fluxes.  相似文献   

15.
Iron coordination and redox reactions in synthetic and coastal seawater were investigated at nanomolar concentrations using 59Fe radiometry and ion-pair solvent extraction of iron chelated by sulfoxine (8-hydroxyquinoline-5-sulfonate) and BPDS (bathophenanthroline disulfonate). Using sulfoxine, we determined the rate at which the monomeric Fe(III) hydroxide species present in seawater of pH 8 are complexed by the microbial siderophore deferriferrioxamine B and the synthetic chelator EDTA (ethylenediaminetetraacetic acid). Forward rate constants of 2 × 106M−1s−1 and 20 M−1s−1, respectively, were obtained. The kinetics of these reactions have not been measured previously at pH values near that of seawater. Conditional equilibrium constants measured for the Fe(III)-EDTA system are consistent with published stability constants for EDTA complexes and for Fe(III) hydrolytic equilibria minus the neutral Fe(OH)3o species, suggesting it is not quantitatively significant near pH 8. Commercial humic acid was found to have sufficient affinity for iron to compete with Fe(III) hydrolysis in seawater, and limited evidence was obtained for an interaction with dissolved organic matter in coastal seawater.In our investigations of redox reactions using BPDS to trap Fe(II) produced in the medium, we observed enhanced photoreduction of Fe(III) by humic acid as well as reduction induced by solutes released from phytoplankton in seawater of pH 8. Although the method is sensitive enough to work at near-oceanic levels of iron, the difficulty in distinguishing Fe(II) generated by Fe(III)-BPDS interactions from Fe(II) produced by other means limits its utility. This analytical ambiguity may be generalizable to other methods which measure ferrous iron in seawater using Fe(II)-specific ligands.  相似文献   

16.
We propose a geochemical parameter, “metal flux” in evaluating hydrogenetic Co-rich ferromanganese crust deposits in the Pacific seamount area, that is based on physical, chemical, and geological characterization of the integrated growth piles of crusts. We calculated the metal flux for fifteen sites from different depths ranging between 900-6000m from different seamounts. The secular and areal variations of metal flux indicate a strong geological controls, and also can be a reliable tool for estimating an economic potential of the crusts. The Co flux decreases with increasing water depth, followed by almost constant flux of Ni and Mn. The Al and Fe fluxes vary with regions, indicating higher values in the western regions near the island arc probably related to a supply from the Asian continents. The results imply that Co, a redox sensitive metal element, is controlled by redox conditions of seawater, while Fe and Al are by terrigenous input. The metal flux reflects global and regional conditions and controls the compositional diversity of metals, thus consequently, the parameter can be a reliable powerful tool to estimate or single out more potential areas.  相似文献   

17.
Stoichiometry among bioactive trace metals in the Chukchi and Beaufort Seas   总被引：1，自引：1，他引：0  
The distribution of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in seawater was investigated in the Chukchi and Beaufort Seas of the western Arctic Ocean in September 2000. The unfiltered and filtered seawater samples were used for determination of total dissolvable metal (TDM) and dissolved metal (DM), respectively. The concentration of labile particulate metal (LPM) was estimated with the difference between that of TDM and DM. The concentrations of TDAl, TDMn, TDFe, TDCo and TDPb varied substantially in the study area. The high concentrations occurred at stations near the Bering Strait, in the Mackenzie delta, and above reductive sediments on the shelf and slope. These elements were mostly dominated by labile particulate species, such as Fe?CMn oxides and species adsorbed on terrestrial clay. DCo was correlated with DMn over the study area (r?=?0.78, n?=?135), and the slope of the regression line was 27 times higher at a pelagic station than at a shelf station. TDNi, TDCu, TDZn and TDCd showed relatively small variations and were generally dominated by dissolved species. There was a moderate correlation between DCd and phosphate for all samples (r?=?0.79), whereas there were no significant correlation between the other DMs and nutrients. TDNi and TDCu showed a remarkable linearity for most stations except those near the Bering Strait (R 2?=?0.95, n?=?126). These results suggest that biogeochemical cycling including uptake by phytoplankton and remineralization from settling particles has only minor control over the distribution of trace metals in this area. Using the present data, the annual input of bioactive trace metals form the Bering Strait and the Mackenzie River was estimated. Also, the trace metal compositions of major water masses were evaluated. The dissolved elemental ratio was P:Al:Mn:Fe:Co:Ni:Cu:Zn:Cd?=?1:1.2?×?10?2:4.4?×?10?4:1.4?×?10?3:3.7?×?10?5:3.7?×?10?3:1.4?×?10?3:4.5?×?10?3:2.2?×?10?4 for Canada Basin deep water (CBDW). This ratio was significantly different from that for Pacific deep water and Bering Sea water, suggesting substantial modification of the trace metal compositions of seawater in the study area.  相似文献   

18.
The Arcachon lagoon is a 156 km2 temperate mesotidal lagoon dominated by tidal flats (66% of the surface area). The methane (CH4) sources, sinks and fluxes were estimated from water and pore water concentrations, from chamber flux measurements at the sediment–air (low tide), sediment–water and water–air (high tide) interfaces, and from potential oxidation and production rate measurements in sediments. CH4 concentrations in waters were maximal (500–1000 nmol l−1) in river waters and in tidal creeks at low tide, and minimal in the lagoon at high tide (<50 nmol l−1). The major CH4 sources are continental waters and the tidal pumping of sediment pore waters at low tide. Methanogenesis occurred in the tidal flat sediments, in which pore water concentrations were relatively high (2.5–8.0 μmol l−1). Nevertheless, the sediment was a minor CH4 source for the water column and the atmosphere because of a high degree of anaerobic and aerobic CH4 oxidation in sediments. Atmospheric CH4 fluxes at high and low tide were low compared to freshwater wetlands. Temperate tidal lagoons appear to be very minor contributor of CH4 to global atmosphere and to open ocean.  相似文献   

19.
Concentrations of Se in the pore-water and in the solid phase, and the concentrations of other diagenetic constituents (Fe, Mn, phosphate, ammonium and I) in pore-water, were determined in a sediment core from a 350-m deep station in the lower St. Lawrence Estuary. The concentration of dissolved Se in pore-water was 2.1 nmol kg−1 at the surface of the core, increasing to a maximum of 7.6 nmol kg−1 at a depth of 12 cm, and thereafter decreasing gradually with depth. This profile is similar to the profiles of Fe and phosphate, whose concentration maxima occur around 10 cm. The concentration of total sedimentary Se remained almost constant with depth (≈ 0.75 mg kg−1); however, a significant enrichment of oxalate-leachable Se was observed in the top 2 cm. The sedimentary cycling of Se appears to be closely related to that of Fe: adsorption of Se onto Fe oxyhydroxide at or near the sediment-water interface, release of the adsorbed Se by the reduction of Fe oxyhydroxide, and removal by formation of ferroselite (FeSe2) at depth. The pore-water flux of Se was estimated by two different methods, firstly from the pore-water gradient, and secondly by applying a box model to the oxalate-leachable solid-phase Se data. The methods agree well both giving values for the flux of 0.11 nmol cm−2 year−1. This agreement suggests that the loss of labile Se in the sediment is balanced by the upward flux of dissolved Se.  相似文献   

20.
The biogeochemistry of trivalent iron, manganese, and cobalt in the oceans is dominated by soluble complexes formed with high-affinity organic ligands that are believed to be microbial siderophores or similar biogenic chelating agents. Desferrioxamine B (DFOB), a trihydroxamate siderophore found in both terrestrial and marine environments, has served as a useful model for a large class of microbial siderophores in studies of 1:1 complexes formed with trivalent iron and manganese. However, no data exist concerning DFOB complexes with Co(III), which we hypothesize should be as strong as those with Fe(III) and Mn(III) if the current picture of the ocean biogeochemistry of the three trivalent metals is accurate. We investigated the complexation reaction between DFOB and Co(III) in aqueous solution at seawater pH using base and redox titrations, and then characterized the resulting 1:1 complex Co(III)HDFOB+ using X-ray absorption, resonance Raman spectroscopy, and quantum mechanical structural optimizations. We found that the complex stability constant for Co(III)HDFOB+ (log K [Co(III)HDFOB+] = 37.5 ± 0.4) is in fact five and seven orders of magnitude larger than that for Fe(III)HDFOB+ (log K[Fe(III)HDFOB+] = 32.02) and Mn(III)HDFOB+ (log K[Mn(III)HDFOB+] = 29.9), respectively. Spectroscopic data and the supporting theoretical structural optimizations elucidated the molecular basis for this exceptional stability. Although not definitive, our results nevertheless are consistent with the evolution of siderophores as a response by bacteria to oxygenation, not only because of sharply decreasing concentrations of Fe(III), but also of Co(III).  相似文献   

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