海洋沉积物中铁、锰、锌、铬、铜、镍、钴、铅和镉的原子吸收测定

海洋环境及沉积地球化学的调查研究,常需同时了解多种元素在海洋底质中的含量及其分布规律.对于某些非金属及半金属元素,我们曾研究过应用碱性有机染料的萃取-光度测定法[1-3].原子吸收分光光度法则可以快速、准确地测定海洋沉积物中的许多种金属的含量[4-6],一般不需要大量的预处理.     

The behavior of Zn,Cd, Cu,Ni, Co,Fe, and Mn in anoxic baltic waters

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.     

Cd, Pb, Cu, Ni and Co distribution in the German Bight

Cd, Pb and Cu concentrations, dissolved and total, have been determined in the German Bight. In 1975, 1977, 1978, 1980 and 1983 water samples were collected at 215 sampling stations. In the 1983 mission samples were also analysed for Ni and Co. The samples were filtered and acidified immediately after collection. Analysis was performed by voltammetry.The analytical data indicate that a net portion of the Cd, the Weser being a distinct source for it, will cross the estuarine zone. Open sea Cd levels in the German Bight are about a factor 10 higher than North Atlantic values. Pb, being transported mainly with the suspended particulate phase (up to 99.5%), is better eliminated by sedimentation in the estuaries. Ni and Cu occur mainly in the dissolved phase. Pollution by Co is distinct in the Elbe, but the output is rapidly diluted to background contents below 10 ng kg⁻¹. An interpretation of the results from the different years yields a rather steady state situation in the German Bight.     

Distribution and stoichiometry of Al,Mn, Fe,Co, Ni,Cu, Zn,Cd, and Pb in seawater around the Juan de Fuca Ridge

A central theme of the ongoing GEOTRACES program is to improve the understanding of processes occurring at ocean interfaces with continents, sediments, and ocean crust. In this context, we studied the distributions of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb around the Juan de Fuca Ridge (JdFR) in total dissolvable (td), dissolved (d), and labile particulate (lp) fractions, which represent a fraction in unfiltered samples, filtered samples through an AcroPak capsule filter, and the difference between td and d, respectively. Al and Fe were dominated by lp-species, while Ni, Zn, and Cd were dominated by d-species with undetectable amounts of lp-species. Major findings in this study are as follows: (1) The continental margin (CM) provided large sources of Al, Mn, Fe, and Co from the surface to ~2000 m in depth. The supply from CM caused high surface concentrations of dMn and dCo, a subsurface (100–300 m depth) maximum of dCo, and intermediate (500–2000 m depth) maxima of lpAl and lpFe. The supply of dFe from CM was ~10 times that from the high-temperature hydrothermal activity at station BD21, which is located at ~3 km from the Middle Valley venting site and ~ 200 km from Vancouver Island. (2) DPb was maximum at the top layer of North Pacific Intermediate Water, probably owing to isopycnal transport of anthropogenic Pb via advection of subducted surface waters. Although dCo and dPb had different sources in the upper water, they showed a strong linearity below 300 m (r ² = 0.95, n = 38), indicating concurrent scavenging. (3) A high-temperature hydrothermal plume occurred at a depth of 2300 m at BD21, accounting for maxima of dAl, dMn, dFe, lpCu, and lpPb and a minimum of dCu. (4) Strong bottom maxima of lpAl, lpMn, lpFe, lpCo, and lpPb occurred above the abyssal plain at the western foot of the JdFR, indicating resuspension of sediments. However, bottom maxima of d-species were apparent only for dAl and dCu.     

Trends of trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) distributions at the oxic-anoxic interface and in sulfidic water of the Drammensfjord

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.     

Trace metals (Cd, Cr, Cu, Fe, Ni, Pb, and Zn) in feathers of Black-browed Albatross Thalassarche melanophrys attending the Patagonian Shelf

We investigated the concentrations of cadmium, chromium, copper, iron, nickel, lead and zinc among feather tissues in sexes of Black-browed Albatross Thalassarche melanophrys killed in longliners off Argentina in 2005. We found no different metal concentration with sex for cadmium, copper, iron, lead and zinc in feathers of adult birds, though there were significant body-size differences between sexes. However, the concentrations of trace metals differed significantly among the type of feather within individual bird. The mean concentrations of copper, iron, and zinc in breast feathers of T.?melanophrys were lower than those reported for the species from Georgias del Sur/South Georgia, the southern Indian Ocean and for other seabirds' worldwide. While cadmium fall within the known range of concentrations for bird feathers lead were not. Our results may be indicating that level of pollution in Patagonia may not be as negligible as previously thought at least for some trace metals.     

Distribution and Sources of Dissolved and Particulate Heavy Metals (Mn,Co, Ni,Cu, Zn,Cd, Pb) in Masan Bay,Korea

Ocean Science Journal - In this study, we investigated the spatial and temporal distribution and sources of dissolved and particulate heavy metals in Masan Bay, an area that for a long time has...     

The Role of Primary-Producer-Mediated Organic Complexation in Regional Variation in the Supply of Mn,Fe, Co,Cu, Ni and Zn to Oceanic,Non-Hydrothermal Ferromanganese Crusts and Nodules

Oceanic, non-hydrothermal ferromanganese crusts and nodules are variably enriched in Mn, Fe, Co, Cu, Ni and Zn. Comparison of the content of these elements in crusts and nodules with the level of primary productivity in the South Pacific Ocean suggests that primary-producer-mediated complexation of several of these elements by organic ligands in solution may contribute to explaining a pattern of distinctive associations observed between compositional variations for these elements in these deposits and variations in the level of primary productivity.     

Distribution of total Al,Cd, Co,Cu, Ni and Zn in the tongue of the ocean and the northwestern Atlantic Ocean

The elements Al, Cd, Co, Cu, Ni and Zn were concentrated from seawater using tetraethylenepentamine resin and analysed by atomic absorption spectrophotometry. The spatial distribution of these elements in the northwest Atlantic Ocean is discussed with respect to possible riverine inputs to the area from Puerto Rico.     

Vertical flux of particulate Al,Fe, Pb,and Ba from the upper ocean estimated from 234Th/238U disequilibria

The vertical sinking flux of particulate Al, Fe, Pb, and Ba from the upper 250 m of the Labrador Sea has been estimated from measurements of ²³⁴Th/²³⁸U disequilibrium and the respective metal/²³⁴Th ratios in >53 μm size particles. ²³⁴Th-derived particulate metal fluxes include in situ scavenged metals, labile lithogenic metals, and metals derived from external input (e.g., atmospheric supply). In contrast to the POC/²³⁴Th ratio, particle size-fractionated (0.4–10 μm, 10–53 μm, and >53 μm) Al/²³⁴Th, Fe/²³⁴Th and Pb/²³⁴Th, and Ba/²³⁴Th ratios generally increase with depth and exhibit no systematic change with particle diameter. Sinking fluxes of particulate Al (2.47–22.3 μmol m⁻² d⁻¹), Fe (2.69–16.3 μmol m⁻² d⁻¹), Pb (2.85–70 nmol m⁻² d⁻¹), and Ba (0.13–2.1 μmol m⁻² d⁻¹) at 50 m (base of the euphotic zone) and 100 m (base of the mixed layer) are largely within the range of previous sediment trap results from other ocean basins. Estimates of the upper ocean residence time of Al (0.07–0.28 yr) and Pb (0.8–2.9 yr) are short compared to previously reported values. The settling rate of >53 μm particles calculated from the ²³⁴Th data ranges from 14 to 38 m d⁻¹.     

长江口及邻近海域表层沉积物中Cu，Zn，Pb，Cr的分布特征

2005年10月-12月,对长江口北部和江苏南部海域进行了较为全面的沉积物化学调查,调查海域范围较广、布点密度较高,为全面深入地研究该海域的底质分布状况积累了重要的资料.分析研究了其中的表层沉积物中重金属Cu,Zn,Pb,Cr含量的分布特征;讨论了重金属与有机质的相关性,并以有机质含量作为环境因素的校正因子,判别了异常值;Cu,Zn,Pb的含量相互之间也呈明显正相关,除了由于三者有相似的地球化学性质之外,可能表明它们在本调查海域有相似的污染源.以平均富集因子对重金属的富集状况进行了评价,结果表明Cu为中度污染,Zn,Pb,Cr均为轻度污染,重金属的富集程度Cu>Zn>Cr>Pb.     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

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.     

The distribution of zinc,nickel, manganese,cadmium, copper,and iron in some surface waters from the world ocean

Determinations of Zn, Ni, Mn, Cd, Cu, and Fe have been carried out on 51 near-shore and 38 open-ocean surface seawaters from various regions of the World Ocean.The concentrations of the trace metals have been established in the open-ocean waters, and have been used as “baselines” to evaluate trace-metal enhancement in near-shore regions. The factors by which the trace metals are enriched in near-shore regions vary from one element to another and, according to the highest concentration factors found, decrease in the order Zn = Mn > Cd = Cu = Ni.These elements exhibit differences in their distributions between near-shore and open-ocean waters, and they have been divided into two types on this basis: Type I, in which the largest number of samples in both shelf and open-ocean waters lie in the same concentration range. Zinc, cadmium, and copper are Type I elements. Type 2, in which the largest number of samples of near-shore waters lie in a higher concentration range than the largest number of samples of open-ocean waters. Nickel and manganese are Type 2 elements.The concentrations of Mn, Cd and Zn are similar in open-ocean surface waters from the South Atlantic and Indian Ocean, but Cu and Ni have higher concentrations in the former ocean.There is considerable variation in the concentrations of the trace metals in near-shore surface waters from various regions of the World Ocean. These variations are discussed in detail.     

Regional variations in Mn,Ni, Cu,and Co of ferromanganese nodules from a basin in the Southeast Pacific

Deep-sea nodules from the Southeast Pacific (northern sector of the Nazca Plate) have been studied regarding their metal content, shapes, and sedimentary environment. The area investigated lies in the southern boundary region of the equatorial zone of high biological productivity. The nodules accumulate by two different growth processes: (1) early diagenetic growth by supply from pore water and (2) hydrogenetic growth by supply from near-bottom sea-water. These growth processes lead to different genetic types of nodules. Considering the $\text{Mn}\text{Fe}$ ratio, the examined basin can clearly be divided in three ferromanganese facies. The $\text{Mn}\text{Fe}$ quotient increases generally from south to north, whereas Ni and Cu concentrations show a distinct maximum in the mid facies at a $\text{Mn}\text{Fe}$ ratio of about 5. Computing the correlation of $\text{Mn}\text{Fe}$ quotient versus (Ni+Cu), hyperbolic regressions show the best coefficients of correlation and separate the quantity of nodules in two groups. The ascending and the descending hyperbola represent two geochemical ranges which are controlled by different accumulation mechanisms.     

Metal-organic complexes in seawater — An investigation of naturally occurring complexes of Cu,Zn, Fe,Mg, Ni,Cr, Mn and Cd using high-performance liquid chromatography with atomic fluorescence detection

Metal-organic complexes were isolated from coastal seawater by adsorption onto octadecyl-bonded silica (SEP-PAK cartridges) and injected into a high-performance liquid chromatograph. Trace metals were identified in the eluate by a four-channel non-dispersive atomic fluorescence detector. Organic complexes of copper, zinc, iron, magnesium, nickel and manganese were found to be present but no complexes of chromium or cadmium were detected. The complexes covered a wide range of polarities with no specific complexes being predominant. Interference from the stainless-steel chromatograph was negligible. The technique provides a minimum estimate of the amount of metal organics and it is suggested that a significant fraction of the metal organics present are too polar to be completely retained by the SEP-PAK cartridges. Typical values of the amounts of trace metal isolated by this technique corresponded to concentrations in the original seawater of >65 ngl^?1 (Cu), >27 ngl^?1 (Fe) and >41 ngl^?1 (Zn).     

Spatial distribution of gut juice extractable Cu,Pb and Zn in sediments from the Pearl River Estuary,Southern China

In this study, we compared the spatial distribution of total metals (Cu, Pb, and Zn) and bioaccessible metals, which were quantified by incubating sediments with the digestive fluid of sipunculans Sipunculus nudus, in natural sediments of the Pearl River Estuary (PRE). The spatial distribution of bioaccessible metal was not the same as that of total metals in PRE sediments, which were mainly controlled by fine-grained size, total organic carbon (TOC) and Fe. Geochemical factors were important in interpreting this different spatial variation. The similar spatial variations of bioaccessible Cu and total Cu were related to TOC in PRE sediments. Differently from the total Zn, a higher bioaccessible Zn was detected near the West Channel of PRE because of a lower TOC. However, the distribution of bioaccessible Pb was not significantly related to any sediment geochemistry. This study provides a more accurate view of metal pollution in the PRE natural sediments.     

Behaviors of dissolved and particulate Co,Ni, Cu,Zn, Cd and Pb during a mesoscale Fe-enrichment experiment (SEEDS II) in the western North Pacific

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.     

Phosphorus and metals bound to organic matter in coastal sediments - An investigation of complexes of P,Cu, Zn,Fe, Mn,Ni, Co and Ti by inductively coupled plasma-atomic emission spectrometry with sephadex gel chromatography

Phosphorus and metals bound to organic matter were separated from coastal sediments of Harima Sound in Seto Inland Sea, Japan by extraction with NaOH and fractionated by Sephadex G-25 chromatography. Phosphorus and metals were determined in the eluates by a multi-channel, inductively coupled plasma-atomic emission spectrometer. Phosphorus and Cu, Zn, Fe, Mn, Ni, Cr, Co and Ti bound to organic matter with high molecular weights (OMHMW) (MW ? 5000) were found to be present in the sediments, but no Mo or V were found. The technique provides minimum estimates of the amounts of P and metals bound to organic matter. These organic complexes show surface enrichment in a sediment core (0–20 cm) and their contents decrease with depth. Also, the amounts of eighteen elements, namely: P, Fe, Mn, Zn, Cu, Si, Al, Ti, Pb, Co, Ni, Cr, Mo, V, Na, K, Ca and Mg, in H₂O, ammonium acetate at pH 7 and 5, hydrogen peroxide, hydroxylamine hydrochloride and hydrogen fluoric acid soluble fractions have been determined with a selective chemical leaching technique for the ²¹⁰Pb-dated sediment core sample. Considerable amounts of P (6–19%) and Cu (5–21%) were associated with organic matter, in contrast to other metals such as Fe, Mn, Zn, Ni, Cr, Co and Ti which were associated with sulfide and silicate.     

Spatial and temporal distribution of Fe, Ni, Cu and Pb along 140°E in the Southern Ocean during austral summer 2001/02

The distribution of dissolved (D) and acid-dissolvable (AD) Fe, Ni, Cu and Pb in the upper water column (0–300 m depth) was determined in the Australian sector of the Southern Ocean (140°E meridian) during three cruises conducted between November 2001 and March 2002. For Ni and Cu, there was no significant difference in concentration between dissolved and acid-dissolvable species. DNi and DCu showed significant (P = 0.01) positive correlations with silicate, phosphate and nitrate, reflecting their strong nutrient-type behaviour. For Fe and Pb, the acid-dissolvable concentration mostly exceeded the dissolved concentration, reflecting the importance of labile particulate species for these elements. DPb decreased between January and February in the Polar Frontal Zone and in Antarctic continental shelf water. ADPb maxima occurred in the Antarctic Zone, resulting in a maximum AD/D ratio of 7. The mean DFe concentration in the surface mixed layer was 0.3 nM in the sub-Antarctic zone, 0.4 nM in the Polar Frontal Zone, 0.5 nM in the Antarctic Zone and increased southward beyond the Antarctic Divergence and towards the continent. DFe did not show a clear temporal change in its horizontal distribution, which was in contrast to the other nutrients and trace metals. ADFe substantially increased in Antarctic continental shelf water where the AD/D ratio reached 11. The following conclusions can be drawn from these data. (1) Ni and Cu exist exclusively as dissolved species and their distributions are mainly controlled by their biogeochemical cycling, similar to those of the major nutrients. (2) Pb is dominated by particulate species. The distribution of DPb is temporally and spatially variable due to a sporadic source and strong scavenging. (3) DFe is rather a minor fraction of total Fe in Antarctic continental shelf water where shelf sediments and Antarctic sea-ice appear to be strong sources for Fe. There is substantial temporal variation in the supply of Fe to the upper water column. DFe in the mixed layer of the open Southern Ocean is maintained at low concentrations throughout summer due to uptake by phytoplankton and scavenging.