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1.
Between 1980 and 1984 extensive studies were carried out in the Baltic Sea on trace metals (Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in water, suspended matter and sediments. The results enabled the influence of different factors on metal distribution patterns to be considered. The vertical profiles of dissolved and particulate metals in waters of the central deep basins reflect influences caused by oxygen deficiency and anoxic conditions in near-bottom water layers. Peculiarities at Station BY15 in the Gotland Deep included high dissolved Fe, Mn and Co concentrations and remarkable enrichment of Zn (0.64%), Cd (51 μg g−1) and Cu (0.15%) in particulate matter from the anoxic zone. Manganese-rich particles were accumulated above this layer.In fine-grained soft sediments below anoxic deep waters, maximum contents of Cd, Cu and Zn were observed, relative to other coring sites, between Bothnian Bay and Lübeck Bight. The Hg content in sediments probably reflects the joint flocculation with organic matter. Land-based sources seem to play the leading part for maximum lead contents.  相似文献   

2.
In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g−1), Cu (1330 μg g−1) and Cd (12 μg g−1) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (Kd) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.  相似文献   

3.
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   

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.
It is shown that the data of Kremling (1983) for iron concentrations in sulphidic basin water fit to a solubility curve assuming reasonable constants for FeS in equilibrium with Fe2+, Fe(HS)2 and FeHS2−. Explanations are offered for the fact that the iron and manganese concentrations are considerably lower in the Framvaren bottom water with high sulphide concentrations (6–8 mM) than in the Gotland Deep with lower sulphide concentrations (0.001–0.052 mM). For other trace metals (Co, Ni, Cu, Zn, Cd, Hg and Pb) equilibrium conditions do not seem to exist.  相似文献   

6.
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   

7.
Concentrations of Cd, Cu, Cr, Co, Ni, Zn, Fe, Mn, Pb, As, and Sb were determined in sediment trap and bottom sediment samples collected seasonally from a station on the eastern Turkish coast of the Black Sea. Cd, Pb and Mn concentrations were highest in the sediment trap samples except during the summer period, whereas Co, Ni, Zn and Fe levels were much lower than corresponding levels found in the surface sediments. Cu, Cr, As and Sb levels showed no definite trend with sediment type. In general, with the exception of Cr, relatively lower metal concentrations in the sediment trap material were determined in the summer period. The highest mass flux, 56.5 g m−2 day−1, was measured during autumn. The highest flux of heavy metals also occurred during autumn and was strongly dependent on particle mass flux. Based on these results, we suggest that the downward vertical transport of particulate heavy metals in this region is related to the high degree of land erosion and the resultant particulate flux dynamics, which occur here. It was noteworthy that the highest concentrations of Cd, Cu, Co, Zn, Fe and Sb in particles were measured during winter a finding which suggests that enhanced fossil fuel combustion, which occurs during this period in adjacent urban and industrial areas plays an important role in the metal composition of sinking particles in nearshore waters.  相似文献   

8.
Determinations of Cu, Co, Ni and Cd were carried out on 39 samples of surface seawaters from the Ligurian Sea, nearshore and offshore, between the Isola Capraia and Imperia. The concentrations of trace elements have been established employing the analytical method suggested by Le Meur and Courtot-Coupez (1973), by means of concentration of the sample by chelating resin, solvent extraction of the eluate and then by quantitative determination by AAS. The results obtained with this technique probably refer to ionic forms of the elements only. The Co concentration was lower than 0.15 μg 1−1 in 32 samples, with an average of 0.49 μg 1−1 for the others. For Cd, the greater number of samples had a content lower than 0.05 μg 1−1. For the others the mean concentration was 0.13 μg 1−1. The Ni had a mean concentration of 0.93 μg 1−1 and the average Cu content was 1.43 μg 1−1. Our data are in agreement with the values published by authors who have employed the same analytical technique. We observed that the offshore samples present a concentration lower than that in the nearshore samples.  相似文献   

9.
During mesoscale Fe enrichment (SEEDS II) in the western North Pacific ocean, we investigated dissolved and particulate Co, Ni, Cu, Zn, Cd and Pb in seawater from both field observation and shipboard bottle incubation of a natural phytoplankton assemblage with Fe addition. Before the Fe enrichment, strong correlations between dissolved trace metals (Ni, Zn and Cd) and PO43−, and between particulate trace metals (Ni, Zn and Cd) and chlorophyll-a were obtained, suggesting that biogeochemical cycles mainly control the distributions of Ni, Zn and Cd in the study area. Average concentrations of dissolved Co, Ni, Cu, Zn, Cd and Pb in the surface mixed layer (0–20 m) were 70 pM, 4.9, 2.1, 1.6, 0.48 nM and 52 pM, respectively, and those for the particulate species were 1.7 pM, 0.052, 0.094, 0.46, 0.037 nM and 5.2 pM, respectively. After Fe enrichment, chlorophyll-a increased 3 fold (up to 3 μg L−1) during developing phases of the bloom (<12 days). Mesozooplankton biomass also increased. Particulate Co, Ni, Cu and Cd inside the patch hinted at an increase in the concentrations, but there were no analytically significant differences between concentrations inside and outside the patch. The bottle incubation with Fe addition (1 nM) showed an increase in chlorophyll-a (8.9 μg L−1) and raised the particulate fraction up to 3–45% for all the metals, accompanying changes in Si/P, Zn/P and Cd/P. These results suggest that Fe addition lead to changes in biogeochemical cycling of trace metals. The comparison between the mesoscale Fe enrichment and the bottle incubation experiment suggests that although Fe was a limiting factor for the growth of phytoplankton, the enhanced biomass of mesozooplankton also limited the growth of phytoplankton and the transformation of trace metal speciation during the mesoscale Fe enrichment. Sediment trap data and the elemental ratios taken up by phytoplankton suggest that export loss was another reason that no detectable change in the concentrations of particulate trace metals was observed during the mesoscale Fe enrichment.  相似文献   

10.
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   

11.
A column concentration-high resolution inductively coupled plasma mass spectrometry (ICP-MS) determination was applied to measure the total dissolved concentrations of Fe, Co, Ni, Cu and Zn in seawater collected from the subarctic North Pacific (~45°N) and the Bering Sea in July–September 1997. Total adsorbable Mn was determined on board by column electrolysis preconcentration and chemiluminescence detection. The vertical profiles for Fe, Ni and Zn were nutrient-like. The deep water concentration of Fe was ~0.5 nM in the northeast Pacific (18°-140°W) and increased to ~1 nM in the northwest Pacific (161°E) and ~2 nM in the Bering Sea (57°N, 180°E). The deep water concentrations for Ni and Zn in the Bering Sea were also 1.3–2 times higher than in the North Pacific. The profiles for Co and Cu were examined in the subarctic North Pacific, and results obtained were consistent with previous reports. There was a significant correlation between the concentrations of Co and Mn except for surface mixed layer. The profiles for total adsorbable Mn were similar to the reported profiles for total dissolvable Mn. The deep water concentration of Mn in the Bering Sea was also 4 times higher than in the North Pacific. Iron and zinc were depleted in surface water of the subarctic North Pacific. The relationship between these trace elements and nutrients suggests that these elements could be a limiting factor of phytoplankton productivity. In the Bering Sea, surface water contained ~0.3 nM of Fe. The Zn concentration, which was less than the detection limit in surface water, increased at shallower depths (~30 m) compared with the subarctic North Pacific. These results imply a higher flux of Fe and Zn to surface water in the Bering Sea. This in turn may cause the ecosystem in the Bering Sea characterized by a dominance of diatoms and high regenerated production.  相似文献   

12.
孔隙水是沉积物-海水界面链接沉积物颗粒和上覆水体的一个重要过渡相态,针对其研究可更好地了解痕量金属在固-液界面的早期成岩过程。近年来,针对孔隙水中痕量元素研究的方法较为匮乏,为此建立了一种分析测定海洋沉积物孔隙水中7种痕量金属元素(Mn、Cu、Zn、Ni、Cd、Co、Pb)的方法,该方法使用Nobias PA1树脂进行富集分离,再使用电感耦合等离子体质谱(ICP-MS)进行测试,可针对孔隙水中的痕量金属元素进行准确分析。通过实验结果发现该方法最优实验条件为: Nobias PA1树脂富集时的pH值为5.5~6.0,洗脱酸浓度为1.3 mol/L硝酸,体积为1 mL。同时,样品需进行紫外消解4 h以上以分解有机络合物,该消解步骤对Cu和Co这两种元素尤其重要。该方法通过加标回收获得Mn、Cu、Ni、Co和Pb的回收率在92%~100%, Zn和Cd的回收率分别为72%和82%; Mn、Cu、Zn、Ni的方法检出限范围为0.03~0.53 nmol/L, Cd、Co、Pb的方法检出限范围为2.66×10-3~8.60×10-3 nmol/L,满足孔隙水中痕量金属浓度的测试需求。同时,根据检出限计算的结果显示,孔隙水样品只需1 mL,即可应用该方法进行测试。应用该方法测试了一根采集于北黄海中部沉积物短柱的孔隙水样品,测试结果显示其垂相分布合理、较符合早期成岩过程规律。此研究为分析海洋沉积物孔隙水中痕量金属元素提供了一种准确而简便的方法。  相似文献   

13.
The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O2 within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values > 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer.The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals.  相似文献   

14.
“Dissolved” (< 0.4 μm filtered) and “total dissolvable” (unfiltered) trace element samples were collected using “clean” sampling techniques from four vertical profiles in the eastern Atlantic Ocean on the first IOC Trace Metals Baseline expedition. The analytical results obtained by 9 participating laboratories for Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, and Se on samples from station 4 in the northeast Atlantic have been evaluated with respect to accuracy and precision (intercomparability). The data variability among the reporting laboratories was expressed as 2 × SD for a given element and depth, and was comparable to the 95% confidence interval reported for the NASS seawater reference standards (representing analytical variability only). The discrepancies between reporting laboratories appear to be due to inaccuracies in standardization (analytical calibration), blank correction, and/or extraction efficiency corrections.Several of the sampling bottles used at this station were not adequately pre-cleaned (anomalous Pb results). The sample filtration process did not appear to have been a source of contamination for either dissolved or particulate trace elements. The trace metal profiles agree in general with previously reported profiles from the Atlantic Ocean. We conclude that the sampling and analytical methods we have employed for this effort, while still in need of improvement, are sufficient for obtaining accurate concentration data on most trace metals in the major water masses of the oceans, and to enable some evaluation of the biogeochemical cycling of the metals.  相似文献   

15.
The distributions of the trace metals iron (Fe), copper (Cu) and cadmium (Cd) along with hydrological parameters (salinity, temperature and reactive phosphate) across the New Zealand continental shelf near Otago Peninsula have been studied. This is a region in which the Subtropical Convergence (STC), a major oceanic front separating subtropical and subantarctic waters, is uniquely located close to land, permitting an examination of the influence of terrestrial sources of Fe and Cu on oceanic waters containing excess micronutrients. Acid-soluble (110 nmol kg−1) and dissolved (6.3 nmol kg−1) Fe concentrations were highest over the central shelf, and decreased rapidly across the mixing zone of the STC to about 5 nmol kg−1 for both forms. The distribution of acid-soluble and dissolved Cu were similar to their counterparts for Fe. Depth-concentration profiles for acid-soluble Fe and Cu suggest resuspension of shelf sediments is the main source. The ratio of oxine-labile to acid-soluble Fe varied from 0.03 to 0.26, with the highest values found in the near surface waters. Oxine-labile Fe and Cu also decreased in concentration in a seawards direction, and with depth, indicating the influence of near surface processes on the reactivity of these elements. Cd concentrations across the continental shelf were very low (<200 pmol kg−1) and exhibited no clear spatial trend and no correlation with phosphate. Comparison of the Cd/P ratio across the shelf indicated that the waters in this region were strongly depleted in Cd relative to P. Phosphate concentrations were lowest in neritic water and increased in the seawards direction because of mixing with nutrient-rich Subantarctic Surface Water.  相似文献   

16.
The U-Tapao Canal is the main source of freshwater draining into the outer part of Songkhla Lake, which is the most important estuarine lagoon in Thailand. Songkhla Lake is located in southern Thailand between latitudes 7°08' and 7°50' N and longitudes 100°07' and 100°37' E. Acetic acid (HOAc)-soluble Cu, Fe, Mn, Pb, and Zn and the total concentration of these metals along with Al concentration, organic carbon, carbonate, sand, silt, and clay contents were determined in 4 sediment cores obtained at selected intervals from the mouth of the canal to 12 km upstream. Readily oxidizable organic matter in the cores varies from 1.52% to 7.30% and is generally found to decrease seaward. Total concentrations of Al (61.7–99.0 g kg−1; 2.29–3.67 mol kg−1), Cu (12.4–28.2 mg kg−1; 195–444 μmol kg−1), Fe (25.2–42.0 g kg−1; 451–752 mmol kg−1), Mn (0.22–0.49 g kg−1; 4.0–8.9 mmol kg−1), Pb (16.7–43.1 mg kg−1; 80.6–208 μmol kg−1), and Zn (48.6–122.7 mg kg−1; 0.74–1.88 mmol kg−1) vary to a certain extent vertically and seaward in the U-Tapao Canal core sediments. These concentrations are at or near natural levels and show no indication of anthropogenic contamination.Overall, the data show that total metal concentrations in the surface and near surface core sediments are enriched in varying degrees relative to Al in the order of Zn>Mn>Pb>Fe>Cu. Chemical partitioning shows that the enrichment in the surface and near surface sediments is related to the relatively high proportion of the total metal concentrations (Mn>Zn>Fe>Cu>Pb) that occur in the acetic acid-soluble (nondetrital) fraction, and they generally decrease with depth. Nondetrital Cu, Pb, and Zn likely derive from those metals held in ion exchange positions, certain carbonates, and from easily soluble amorphous compounds of Mn and perhaps those of Fe. Diagenetic processes involving Mn and to a lesser extent, Fe compounds, as well as the vertical changes in the oxidizing/reducing boundaries, appear to be the most important factors controlling the behavior of the metals in these cores. Organic matter and the aluminosilicate minerals, however, appear to be less important carriers of the metals studied.  相似文献   

17.
The bioaccessibility of metals (Al, Ca, Fe, Mn, Ag, Cd, Co, Cu, Ni, Pb, Sn, Zn) in oxic estuarine sediments has been evaluated using solutions of a commercially available protein (bovine serum albumin; BSA) that mimic the chemical conditions encountered in the gut environment of many deposit-feeding organisms. Over a 20 h incubation period with 5 g L− 1 BSA, metal mobilisation was generally biphasic in that a relatively short period of rapid release was succeeded by more gradual release or approach to equilibrium, although in some cases metal readsorption was evident during the time-courses. Availability to BSA, defined as metal released after 20 h relative to metal extracted by boiling aqua regia, was greatest for Cd, Ni, Ca and Zn and lowest for Fe and Mn, and correlated well with, but was an order of magnitude lower than, metal digested by acidified hydrogen peroxide. Time-courses conducted in the absence of the protein revealed that significant quantities of Ca and Mn were water-soluble, reflecting the partial dissolution of carbonates and hydrous Mn oxides, respectively. Additional experiments indicated a net increase in metal release with increasing BSA concentration and, with the exception of Ca and Mn, a substantial increase in metal mobilisation after sediment organic matter had been digested by peroxidation. These observations suggest that, apart from Ca and Mn, metal release proceeds via complexation with component amino acids of the protein, denudation of organic host phases, and exposure of inorganic, metal-bearing minerals. Accordingly, the bioaccessibility of a metal is predicted to be dependent on its (i) affinity for proteinaceous ligands, (ii) association with components of digestible sediment organic matter, and (iii) degree of binding at relatively weak sites on sediment phases that are exposed or modified by the action of proteins and other chemical constituents of the gut environment.  相似文献   

18.
During the August 1993 Intergovernmental Oceanographic Commission's Contaminant Baseline Survey cruise to the high latitude North Atlantic, determinations of total dissolved sulfide (TDS=free sulfide, H2S(g)+HS−+S2−, plus dissolved metal–sulfide complexes), free sulfide, and carbonyl sulfide (OCS) were made along a horizontal transect and at six vertical profile stations. Unlike data from lower latitudes, the distributions of OCS and TDS were remarkably uniform, with surface water OCS averaging 108 pmol/l and TDS averaging 58 pmol/l; free sulfide was below the detection limits of 5 pmol/l at all stations. The vertical profiles of both OCS and TDS show surface maxima and rapid decreases into the major thermocline. For OCS this is indicative of production via photolysis of dissolved organic sulfur compounds, while TDS may be produced from the hydrolysis of OCS. The concentrations of OCS are similar to those found in coastal waters, and suggests that these sub-polar regions may be large OCS sources to the troposphere during summer. However, it is unclear whether higher concentrations of OCS precursors, a long photo period during summer, or slow rates of removal by hydrolysis due to low temperatures are responsible for the elevated OCS levels. TDS concentrations are primarily controlled by the rate of OCS hydrolysis, production by phytoplankton, and oxidative loss by oxygen and iodate. Both of the losses are affected by trace metal complexation, and to examine this, freshly collected seawater was amended by hydrogen sulfide gas and trace metal additions, and the concentration of free sulfide monitored as a function of metal concentration. This allowed the determinations of conditional stability constants for metal sulfides, with the log Kcond of Cd(HS)+ being 8.0±0.5, 7.0±0.6 for Ni(HS)+, and 7.4±0.7 for Zn(HS)+; attempts at measuring the Kcond of Cu(HS)+ were thwarted by the apparent reduction of Cu(II) to Cu(I) by sulfide. Using these constants in an equilibrium speciation model indicates that on average about 75% of the measured TDS was free, with the remaining fraction complexed with Ni, Cd, and Zn (in order of decreasing percentages). While closer to the field observations than would be found with stability constants reported by other workers, these values are still at variance with the actual speciation (i.e., <30% free). This suggests that the stability constants for Cd, Ni, and Zn are somewhat higher than found, thus reducing the concentration of free sulfide. Nevertheless, these speciation data are important for balancing the TDS budget since the loss by iodate oxidation of free sulfide exceeds all production estimates.  相似文献   

19.
The present study was undertaken for assessing the level of heavy metals such as iron, manganese, zinc, copper, nickel, cadmium, lead, and cobalt in recent sediment samples of Safaga Bay, Egypt. Concentration of heavy metals in sediments shows significant variability and ranges from 863.37 to 1144.93 ppm for Fe, 64.29–586.8 ppm for Mn, 2.7–12.68 ppm for Zn, 3.01–7.2 ppm for Pb, 1.53–3.29 ppm for Ni, 0.55–1.57 ppm for Co, 0.16–1.37 ppm for Cu, and 0.22–0.4 ppm for Cd.

Sediment pollution assessments were carried out using an enrichment factor and geoaccumulation index. The calculation of enrichment factor showed that Cd is enriched by 4.1 due to phosphate sources in Safaga Bay. The Geoaccumulation index results revealed that there are positive and negative correlations between Fe, Zn, Mn, Pb, Ni, Cu, Co, and Cd indicating that these metals have complicated geochemical behaviors.  相似文献   

20.
In different samples of Mytilus galloprovincialis Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb and Zn were determined by AAS. The mussels were taken from 11 sites in the Port of La Spezia. Typical concentration ranges (μ/g dry weight) were as follows: Cd, 2.0–6.8; Co, 0.8–3.2; Cr, 5.8–19.5; Cu, 6.9–33.7; Hg, 0.15–0.38; Mn, 11.8–37.8; Ni, 1.3–10.9; Pb, 13.9–44.6 and Zn, 203–379.Other samples were collected at 4 sites on the Promontory of Portofino and the following values were obtained: Cd, 0.8–1.1; Co, 2.6–2.9; Cu, 3.3–4.2; Hg, 0.09–0.15; Mn, 6.3–9.1; Ni, 1.2–2.4; Zn, 120–140.  相似文献   

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