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The interaction between thorium and marine organisms (cultured heterotrophic bacteria) was experimentally examined by using chemical equilibrium techniques. Thorium (Th) quantitatively reacts with a binding site on bacteria (Alteromonas, Vibrio, Pseudomonas and Flavobacterium) in 0.1 M HCl solution. According to mass balance analysis of adsorption experiment data, Th forms a 1:1 complex with a binding site similar in reactivity among bacteria used in this study, whose conditional stability constants are in the range from 10(6.63) to 10(7.07) M-1 under the experimental conditions of a 0.1 M HCl solution. The mole ratio of the strong ligand to organic carbon in bacteria ranged from 2.3 to 4.3 mmol/mol C. The strong ligand/carbon ratios in bacteria were more than one order of magnitude greater than in phytoplankton, zooplankton or other organic ligands in surface waters. The results suggest that the strong organic ligand reacting with Th is one of the functional groups commonly existing in oceanic microorganisms. The conditional stability constants of the Th complexes with the binding site in marine microorganisms are in the same order of magnitude as that with the strong ligand found in particulate and dissolved organic matter. These findings strongly suggest that the strong ligand in particulate and dissolved organic matter, reacting with trace metals under the conditions of seawater, originates from marine organisms. 相似文献
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The differences in quality of the conditional stability constants deduced from ligand titration and metal titration methods are theoretically examined. The ecological role of the metal-organic complexes in seawater was considered on the basis of the concept of the metal buffering capacity index which is calculated from the conditional stability constant and the organic ligand concentration. The results of theoretical examination of the effect of metal contamination on the uptake of metals by phytoplankton indicate that the ecological significance of metal-organic complexes is essentially in the metal-buffering action. This means that the activities of free metal ions are maintained at a native constant level against relatively small perturbations by the addition or uptake of metals in the marine environment. 相似文献
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Mobilization and transfer of atmospherically transported metals to major suspended particulate matter components in seawater have been studied in a multichamber leaching experiment. Data on the meteorological air mass history, enrichment factors and sequential extraction analysis indicate that the highly polluted marine aerosol samples collected on Helgoland are of anthropogenic origin. A significant fraction of the total cadmium (81%), zinc (58%), copper (41%), and lead (40%) was released in seawater within 1 h. When exposed to the aerosol and artificial suspended particulate matter components for another 100 h, a portion of the released metals ranging from 10 to 60% was readsorbed. Zinc and lead were scavenged by iron/manganese oxides or readsorbed by the aerosol particulates. Of the total scavenged copper portion 67% was bound to phytoplankton cell walls which evidences an ecological impact of the polluted marine aerosols even in the coastal environment. 相似文献
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To study biological effects on the particulate removal of chemical elements from seawater, sediment trap experiments were carried out successively ten times throughout the spring phytoplankton bloom in Funka Bay. Sediment traps were deployed every one to two weeks at 1, 40 and 80 m depths. The settling particles obtained were analyzed for trace metals, phosphate and silicate. The propagation of diatoms in spring results in larger particulate fluxes than that of dinoflagellates. The biogenic silicate concentration is higher in the earlier period, when diatoms are predominant, than in the subsequent period, when dinoflagellates are predominant. The concentrations of aluminum, iron, manganese and cobalt in the settling particles comprising largely biogenic particles are lower during phytoplankton bloom. The concentration of copper is not reduced by the addition of biogenic particles, and its vertical flux is approximately proportional to the total flux, indicating that its concentration in the biogenic particles is nearly equal to that in the non-biogenic particles. The results for nickel and lead show the same tendency as for copper. Cadmium is more concentrated in biogenic particles than in non-biogenic particles, and the concentration of cadmium in the settling particles decreases with depth, similarly to phosphate and organic matter. Thus, metals in seawater are segregated by biological affinities, and the degree of incorporation into biogenic particles is in the order Cd > Pb, Ni, Cu > Co > Mn, Fe, Al. Biogenic particles are the most important agent controlling the vertical distribution of metals in the ocean. They remove the metals from the surface water, transport them through the water column, and regenerate them in the deep. 相似文献
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Particulate trace metals (PTM), organic carbon (POC), and organic nitrogen (PON) were measured in a series of surface bucket samples collected between the New England coast of the United States and Bermuda. PTM concentrations were lower or equivalent to the lowest PTM concentrations reported in the literature. Examination of the relative variations in PTM with respect to particulate aluminum and carbon led to the conclusion that organic matter was the probable regulator of PTM abundance in open-ocean surface waters and was important in this respect for continental shelf and slope waters as well.Enrichment factors of trace metals relative to their crustal abundances were found to be similar in the atmosphere sampled in Bermuda and in Sargasso Sea surface water particulate matter. A simplistic vertical flux model was constructed which showed atmospheric input of trace metals to the Sargasso Sea to be of the same approximate magnitude as the rate of removal of PTM from the mixed layer by sinking in association with POC. Essentially all of the particulate Al, Fe, and Mn in the Sargasso Sea mixed layer was attributed to aeolian sources. The fate of other atmospherically derived trace metals in the Sargasso Sea mixed layer was suggested to be a function of their solubility in seawater. 相似文献
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To clarify the nature of organic metal complexes dissolved in seawater, a ligand exchange reaction between ligands of natural origin and an aminopolycarboxylic acid (EDTA) was used to determine the conditional stability constants of organic metal complexes. The results indicate that more than two organic molecules complexed with copper and zinc exist in surface seawater. It is found that the conditional stability constants of these naturally-occurring organic metal complexes are 1–3 orders of magnitude higher than those of EDTA-Cu and EDTA-Zn complexes. These estimates of the conditional stability constants for the dominant species of organic copper and zinc complexes are 1011.8 and 109.3, respectively, at pH 8.1. The results indicate that these naturally-occurring organic metal complexes are stable species and not easily dissociated or displaced with others in the marine environment. 相似文献
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To evaluate the applicability of a diffusive gradient in thin film (DGT) probe for monitoring dissolved metals in coastal seawater, DGT-labile metal concentrations were compared with total dissolved metal concentrations using spiked and natural seawater samples in the laboratory and transplanted mussels (Mytilus galloprovincialis). This was achieved through the simultaneous deployment of DGT probes and transplanted mussels in Ulsan Bay during winter and summer. DGT-labile metal concentrations were 45% (Cu) ~ 90% (Zn) of total dissolved concentrations, and the order of non-labile concentrations was Cu > Pb > Co ~ Ni > Cd ~ Zn in both metal-contaminated and non-contaminated seawater samples, which was similar to the order of stability of metal complexes in the Irving–Williams series. The overall variability of the DGT probe results within and between tanks was less than 10% (relative standard deviation: RSD) for all the metals tested during a 48-h deployment. The accumulation of metals, as determined by DGT probes, represented the spatial gradients better than the transplanted mussels did for all of the metals tested, and the extent of metal accumulation in mussels differed depending on the metal. The comparison of results for the DGT probe and the transplanted mussels in two seasons (winter and summer) suggested that metal accumulation in mussels was controlled by the physiological factors of mussels and partly by their diet (particulate metal loadings). The DGT probe could be used as a monitoring tool for dissolved metals in coastal seawater because its results explained only labile species. When using the DGT probe, slightly more than half of the total dissolved concentration in seawater samples for all the metals investigated displayed timeintegrated properties and distinct spatial gradients from pristine to metal-contaminated seawater. 相似文献
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采集胶州湾表层和底层海水样品，分析了Cu、Cr、Cd、Pb、Ni、Co等痕量金属在海水中的空间分布特征及其在不同分子量溶解有机质中的分配特征，并探讨了痕量金属?溶解有机质分配机理及浮游生物活动与盐度等环境因素对该分配过程的影响。结果表明，胶州湾海水中痕量金属呈近岸浓度较高的分布特征，在湾东北部出现高值区，Cd和Pb还分别在湾口与湾中部出现高值区。胶州湾海水中痕量金属平均有70.1%分配于低分子量(<1 kDa)组分中，其中Cu和Cd低分子量组分所占平均比例分别达79.0%与77.6%，Cr、Ni和Co稍低，分别为71.5%、67.3%及66.9%，Pb则仅为58.2%。海水中的溶解有机碳也以低分子量组分为主，所占比例平均达73.1%，且光谱特征显示低分子量溶解有机质中类腐殖质含量更高，含有丰富的羧基和羟基，金属配合能力较高，导致痕量金属多分配于低分子量溶解有机质中。高分子量溶解有机质(>1 kDa)所占比例与叶绿素a浓度呈显著正相关，表明浮游植物初级生产通过释放高分子量溶解有机质影响海水痕量金属?溶解有机质的分配过程。胶州湾湾顶盐度较低海域痕量金属高分子量组分略高，可能是生物活动及陆源输入(产生更多高分子量溶解有机质)与盐度(低盐有利于高分子量有机质的稳定性)共同作用的结果。 相似文献
10.
Lina Fernandes G.N. Nayak D. Ilangovan D.V. Borole 《Estuarine, Coastal and Shelf Science》2011,91(3):388-399
Two core sediment samples; one from inner part (ManI) and the other closer to the mouth (ManII); were collected from the intertidal regions of Manori, a tidally influenced creek near Mumbai, India. Both the cores were subjected to various geochemical analyses to determine parameters such as pH, sediment components, total organic carbon, total nitrogen, total phosphorus and selected metals viz., Fe, Mn, Cu, Pb, Co, Ni, Zn, Cr, Al, Ca and V. Analysis of 210Pb activity was employed to assess the sediment deposition trend of the area. The data was further processed using factor and cluster analyses. The results indicate that the sediments from site ManI, had finer sediment composition, higher porosity, organic matter and metal contents but exhibited an erratic decline in 210Pb activity downcore. Also ManI showed higher C:N ratio and enrichment factor values as compared to site ManII. The inner area (ManI) probably received a greater input of organic matter from the erosion of terrestrial matter as well as domestic and industrial discharge. Sediments from site ManII had typical marine organic matter composition (lower C:N ratio). The concentration of metals at this site was also low indicating the contents were getting diluted by freshwater and seawater mixing. 相似文献
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本文根据1987年5月宁波—舟山深水港海域水体中有机物分布,初步讨论了有机物在水体中的行为。海水中溶解态的有机物与有机物总量存在如下关系:[DOM]/[TOM]=0.611[TOM]~(-0.899)。并且在通常状况下,调查海区水体中的有机物随悬浮颗粒物的增加而增高,其关系式为:[TOM]=0.65e~(0.0011〔SS〕)。认为该海区的悬浮物是制约有机物行为的主要因素之一。 相似文献
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The anthropogenic contribution of trace metals to settling particulate matter (SPM) and surficial sediments was determined on the high-energy continental shelf adjacent to Sydney, Australia. Settling particulate matter and surficial sediment was collected in the vicinity of a major sewage outfall and at five control sites on the middle shelf (80-100 m water depth). Sediment traps were deployed on 10 occasions for up to 2 weeks during the summer and winter of 1995 and SPM was analyzed for Ag, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn. Cobalt, Fe, Mn and Ni act conservatively in SPM and in sediments regionally and are used as normalizing elements to determine anthropogenic enrichment. Surficial sediments and SPM are enriched in Ag, Cr, Cu, Pb and Zn near a major ocean outfall and at four of the five control sites, although sewage particles contribute < 5% of trace metals in the total sample. Silver is the most sensitive trace metal tracer for establishing the presence of sewage particulate matter. Sewage particulate matter flux near the outfall was estimated using a two end-member mixing model and is below 0.5 g m(-2) day(-1) during all deployment periods. The mean sewage particulate matter flux at sampling locations 30 km and 60 km north of the outfall are <0.13 g m(-2) day(-1) and <0.01 g m(-2) day(-1), respectively, indicating an efficient dispersal of anthropogenic material on this high energy continental shelf. 相似文献
13.
Rob F. Nolting Wim Helder Hein J. W. de Baar Loes J. A. Gerringa 《Journal of Sea Research》1999,42(4):2393
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
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Reed Van Valin 《Marine Chemistry》1982,11(6):535-564
The characterization of solid phase-associated transition metals is important in understanding solid—seawater interactions. This has proven to be a difficult problem because of the complex nature of most sediments and suspended particulate matter. Many chemical techniques have been proposed to describe sedimentary metal phases. Most rely on characterizing equivalent chemical reactivities from the various metal phases rather than the characterization of the actual physical phases with which the metals are associated. In this study, several of the most widely used trace metal extraction techniques are compared for many of the most commonly measured transition metals using a variety of naturally occurring major marine sediment types. All solid concentrations are normalized to total metal values as obtained by neutron activation and X-ray fluorescence analyses.One weak, four intermediate strength, and two strong metal extraction methods were studied individually. The weak method had the lowest degree of extraction efficiency, but dissolved all solid carbonate phases. Its probable inability to retain released metals quantitatively in solution is a major problem. Three of the four intermediate methods are similar. The other and simplest of the four methods (0.5 N HCl), released much lower amounts of most metals studied when compared to these other three. It cannot be classified as a weak method, however, as it does attack some moderately resistant solid phases. Only one of the other three intermediate methods (a reducing acetic acid solution), was relatively free from analytical difficulties and it is preferred for this reason. The two strong extraction methods are quite similar, with neither yielding total metal concentrations.A five-step sequential extraction scheme was also evaluated. The results were generally quite good, both with regard to metal phase fractionation and overall total extraction of available metals. Based on the results of this study, a sequential extraction scheme is a useful method for characterizing solid phase-associated transition metals. 相似文献
15.
K.A. Hunter 《Marine Chemistry》1980,9(1):49-70
Concentrations of particulate Fe, Mn, Ni, Cu, Zn, Cd and Pb have been measured in surface microlayer and subsurface seawater samples collected in the North Sea adjacent to the East Anglian coast, in an area subject to a considerable fluvial input of clay minerals. The results are interpreted by estimating the magnitudes of different processes affecting particulate matter in the microlayer: atmospheric deposition, Brownian diffusion, gravitational settling, bubble flotation and mixing. Both Fe and Mn are strongly depleted in the microlayer, evidently as a result of gravitational settling of Fe- and Mn-bearing mineral particles out of the microlayer. These particles are mixed into the surface region from the water column beneath. Microlayer enrichment of Cu, Zn and Pb was also observed and probably results from flotation of particles attached to rising bubbles. In one set of samples, however, the marked enrichment of these elements, as well as Ni, may result instead from deposition of particles from the atmosphere directly onto the water surface. 相似文献
16.
Olivier Radakovitch Vincent Roussiez Patrick Ollivier Wolfgang Ludwig Christian Grenz Jean-Luc Probst 《Estuarine, Coastal and Shelf Science》2008
Fluxes of the heavy metals chromium (Cr), cobalt (Co), nickel (Ni), copper (Cu), lead (Pb), cadmium (Cd) and zinc (Zn) delivered by rivers to the Gulf of Lion (NW Mediterranean Sea) were estimated over a three year study of the River Rhone and its smaller tributaries. Most of the particulate metal fluxes (80–90%) delivered by these rivers occurred within a very short period of time (less than 12%), a typical trend for the Mediterranean environment, where highly contrasting hydrological regimes were observed over the year. Temporal and spatial variations in the fluxes of these particulate metals were driven by the fluxes in both water discharge and suspended particulate matter load. On the shelf, these particulate metal fluxes, largely arising from the Rhone watershed, were two to ten times more important than those resulting from atmospheric deposition. Co, Cr and Ni in the rivers and on the shelf surface sediments were mainly natural and associated with the finest particles. Cd and Phosphorus appeared to be associated with the silt fraction and to be enriched in the prodelta areas. Pb, Zn and Cu were more closely associated with the organic matter content and also showed enrichment in the organic rich prodeltaic sediments. Anthropogenic influences diminished offshore, except for Pb and Zn which could be supplied from the atmosphere by man-made aerosols. Although most of the metals tended to be enriched in the prodelta areas, these did not constitute a permanent sink due to resuspension processes affecting these shallow depths. A resuspension experiment conducted on sediment cores from the Rhone prodelta demonstrated that metal deposited on the surface layer, especially those associated with the organic matter, may be resuspended; this should be taken into account for a complete understanding of the biogeochemical cycle of these metals. 相似文献
17.
The relative contributions of adsorption to particulate surfaces, complexation with surface-active organic ligands and uptake by micro-organisms were evaluated with respect to their importance in the surface microlayer enrichment (‘partitioning’) of Cd, Pb and Cu. The contributions of each process were inferred from field data in which partitioning of the dissolved and particulate forms of Cd, Pb and Cu, total and dissolved organic carbon, particles and total bacteria were observed. In the South San Francisco Bay estuary, particle enrichment appears to control trace metal partitioning. Trace metal association with the particulate phase and the levels of partitioning observed were in the order Pb > Cu > Cd and reflect the calculated equilibrium chemical speciation of these metals in computer-simulated seawater matrices. 相似文献
18.
Size distribution of colloidal trace metals and organic carbon during a coastal bloom in the Baltic Sea 总被引：1，自引：0，他引：1
Johan Ingri Susanna Nordling Jenny Larsson Jenny Rnnegrd Nina Nilsson Ilia Rodushkin Ralf Dahlqvist Per Andersson
rjan Gustafsson 《Marine Chemistry》2004,91(1-4):117-130
The physico-chemical speciation of organic carbon and selected metals was measured during a coastal bloom in Ekhagen Bay, Baltic Sea, using ultrafiltration.One important objective with the study was to see if any depletion of trace metals could be measured in the directly bioavailable fraction (<1000 Da, the soluble low molecular weight fraction, LMW) during a plankton bloom. Filters with five different cut-offs were used (1 kD (1000 Da), 5 kD, 10 kD, 100 kD and 0.22 μm) in order to delineate the size distribution of colloidal organic carbon (COC) and trace metals.During the bloom in May, LMW Al, Co, Cu, Mn and Ni concentrations decreased although the colloidal and particulate concentrations were relatively high. Data show that desorption of colloidal and particulate bound trace metals to the LMW fraction was slower than the process depleting the LMW fraction.Estimates of the maximum active uptake of Cu, Ni and Mn by the phytoplankton, and the loss of non-bioactive Al from the LMW fraction, indicate that processes other than active uptake by phytoplankton must contribute to the observed depletion of trace metals in the LMW fraction. Hence, in order to estimate the bioavailable pool of trace metals for plankton during bloom conditions, these other processes must be understood and quantified.Transparent Exopolymeric Particles (TEP, reflecting sugar-rich phytoplankton exudates) increased around eight times during the plankton bloom. We hypothesize that the formation of TEP is a process that might be important for the transfer of trace metals from the LMW to the particulate fraction during the phytoplankton bloom, but the significance of TEP for this depletion in Baltic Sea surface water remains to be shown. 相似文献
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D.J. Mackey 《Marine Chemistry》1982,11(2):169-181
Amberlite XAD-1 resin was examined to test its suitability for extracting organic complexes of copper, zinc and iron from seawater. At low flow rates and at loading capacities far below theoretical values, the adsorption of these metals is not reproducible and the results are reminiscent of the behaviour observed when the adsorption capacity is being exceeded or flow rates are too high. It is suggested that the resin also adsorbs small but significant amounts of inorganic ions from seawater and that this effect makes the resin unsuitable for quantitative measurements of trace metal speciation. 相似文献
20.
《Marine Chemistry》2002,78(1):29-45
The distribution of several trace metals has been studied in the surface waters of Galveston Bay, Texas, in order to assess the impact of complexation with organic and reduced sulfur species on the partitioning of trace metals between particulate and aqueous species. The distribution of trace metals in the filter-passing fraction (<0.45 μm) showed two apparent trends: (1) the carrier phase metals (i.e., Fe and Mn) were largely removed in the Anahuac Channel region, which was dominated by direct Trinity River inputs; (2) the other metals (Cd, Cu, Ni, Pb, and Zn) showed non-conservative mixing behaviour, with mid-salinity maxima, within the estuarine regions of Galveston Bay. The average percentage of metal in the filter-passing fraction, as compared to the total metal load, decreased in that region from 95% to 9% in the order Ni>Cu>Cd>Zn>Pb>Mn>Fe, while an increasing trend was found in the same sequence for the acid-leachable fractions. The average values of Kd1, the particle-water partition coefficient, expressed as the ratio of weak acid-leachable particulate fractions to the filter-passing fractions, increased in the order Ni<Cu<Cd<Zn<Mn<Pb<Fe. This sequence is consistent with the relative importance of particulate transport of these trace metals from estuaries to coastal oceans. The observed decrease of Kd1 of Cu with increasing concentrations of suspended particulate matter (SPM), also called the “particle concentration effect” (PCE), can be eliminated when the free ionic, rather than the total concentration of Cu in the filter-passing fraction is used for calculating this ratio. A particle concentration effect would be expected if the binding of these trace metals by particles is mediated by solution (i.e., filter-passing) phase ligands. Complexation of Cd, Cu, Ni, Pb, and Zn with reduced sulfur species could be one of the causes for the observed linear correlations between metals and reduced sulfur species in both the filter-passing and filter-retained fractions. Significant correlations between Cu in the weak acid-leachable fraction and chlorophyll a (Chl a) concentrations suggest biological mediation of Cu uptake into the particulate fraction. 相似文献