痕量金属在海水中的存在形态和分析方法的研究进展

1研究意义痕量金属(trace metal),又称为痕量元素(trace element),是指在海水中浓度低于100μmol/kg的元素。痕量金属几乎参与了海洋生命的方方面面,从初级生产力中细胞质的形成到蛋白质的合成,几乎都离不开痕量金属。一些痕量金属,尤其是一些过渡金属,例如Mn、Fe、Ni、Co、Cu和Zn,对有机体的生长至关重要[1]。因此,海洋无机生物学家继对有机     

Chemical speciation of trace metals in seawater: Implication of particulate trace metals

Chemical speciation of particulate metals in seawater was examined theoretically. Mass balance considerations showed that the apparent conditional stability constant, defined for organically binding metals in suspended particles, coincides with the conditional stability constant determined for the corresponding metal-organic complexes dissolved in seawater. This hypothesis suggests that some metals, which are present as organic complexes (e.g. copper), are directly associated with particulate organic matter. Metals, whose free ion is buffered by organic and/or inorganic ligands, may be used as indicators of the presence of particulate organic matter in the marine environment.     

An intercalibration for trace metals in seawater

This paper describes the results of a recent international intercalibration experiment for trace metals in seawater. The results show that considerable improvements in analytical ability have been made for several metals at concentrations close to those found in offshore marine waters. Some systematic differences between the results of analyses of frozen and acidified samples are evident for most metals. The application of two different analytical techniques, atomic absorption spectrophotometry and anodic stripping voltammetry, appears to introduce relatively small differences in the results for copper and cadmium at near-natural concentrations.Two factors limiting our ability to conduct trace metal intercalibrations at the levels found in the deep ocean are the extent of tolerable contamination, especially for zinc and lead, and the degree to which the overall homogeneity of a group of intercalibration samples can be assured. Some reexamination of methods of sample preparation needs to be carried out before such low level calibrations can be effectively conducted.     

Comparison of sampling devices for trace metal determinations in seawater

The results of an intercomparison of three types of sampling device and three types of hydrowire, used for the collection of seawater samples for trace metal analysis, are presented. These devices were intercompared in an international experiment involving member states of the Intergovernmental Oceanographic Commission through the collection of mid-depth North Atlantic water samples at Panulirus Station near Bermuda. Of the commercially available sampling devices, modified GO-FLO samplers appear to yield the lowest concentration seawater samples with modified Niskin samplers having only slightly inferior capability. Both unmodified GO-FLO and Hydro-Bios samplers have similar, but generally poorer, abilities for the collection of uncontaminated samples. Of the three hydrowires intercompared, plastic-coated steel yields the lowest concentration samples for most metals. Kevlar and stainless-steel hydrowires appear to cause only slight contamination for some metals. Overall, the impression is obtained that differences between the levels of metals in the ocean reported by different laboratories is predominantly due to analytical, rather than sampling errors or artifacts.     

An in situ pump sampler for trace materials in seawater

A battery-powdered in situ pump sampler, capable of operation at full oceanic depths, has been designed, built and tested. The pump motor, sealed in a pressure-proof housing, is coupled magnetically to the pump head. Water is drawn through a filter then passed successively through an adsorption column and the pumphead and finally through a flowmeter. The unit as a whole is pivoted and vaned so that the intake is always pointed into the current. The selectivity of the sampler depends upon the choice of packing material used in the adsorption column or columns. Column materials specific for different classes of compounds have been tested in the laboratory and at sea. Preliminary results in the collection and measurement of Cu and Cd suggest that the pumping system is free from shipboard contamination.     

Multivariate geochemical investigation of trace metal pollution in Kuwait marine sediments

Three multivariate procedures (cluster analysis, discrimination and classification) were used to identify and characterize various types of marine sediments in Kuwait. Samples from 201 offshore locations were first clustered into five types of sediments with different metal concentrations (Ag, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V, Zn and Hg) and sedimentological characteristics (% TOC, carbonate, mean grain size and % size fraction < 63 μ). Discriminant functions were then developed in terms of trace metal concentrations to describe mathematically differences between the various sediment types. A classification procedure was also used to calculate the probability that each of 186 additional samples from coastal areas adjacent to suspected point sources of pollution may belong to each of the five sediment types. This analysis identified a sixth type of sediment dominating the area inside and near the entrance of Shuwaikh Port. Characterized by elevated levels of Ag, Cd, Cu, Hg, Pb and Zn, this type indicated the presence of a high level of metal pollution in the area.     

Biological control of trace metal residence time and speciation: A review and synthesis

The recent literature on control of trace metal concentrations and speciation was reviewed. The dominant mechanism in control of concentration for most metals appears to be adsorption on biologically produced particulate matter. Some proportion of the metals removed from the surface waters by this mechanism are put back into solution in deeper water by bacterial decomposition of the particles; as a result, many trace metals display distributions in the water column resembling those of the inorganic nutrients. The residence time, as classically defined, cannot be calculated with sufficient accuracy to provide useful information. Since the main method for removal of trace metals from surface waters appears to be physical and biological, rather than strictly chemical, speciation studies in homogeneous systems, particularly those systems which are completely inorganic, appear unlikely to furnish useful information on actual species distributions in the oceans.     

Improved dithiocarbamate/oxine solvent extraction method for the preconcentration of trace metals from seawater using metal exchange back-extraction

A rapid single extraction procedure using dithiocarbamate complexing agent, a di-isobutyl ketone (DIBK) organic phase and Hg exchange back-extraction is described for the simultaneous quantitative preconcentration of Cd, Co, Cu, Fe, Ni, Pb and Zn in seawater. An 8-hydroxyquinoline (oxine) extraction technique is also presented for the subsequent determination of Mn using the same reagents and operating system. The proposed method gave quantitative spike recoveries for all metals and was in excellent agreement with the certified results for CASS-3 marine reference seawater. Blanks and detection limits are in the low ppt range. The method gives a preconcentration factor of 72 for an 80-ml sample, facilitating the analysis of pristine seawater samples.     

Intercomparison of different methods for the determination of trace metals in seawater

During a cruise on the North Sea and the North East Atlantic, about 90 samples were obtained from various depths. Concentrations of cadmium, copper, lead, nickel and zinc were determined by atomic absorption spectroscopy after separation/concentration using two different extraction methods. One, using APDC and MIBK, was applied directly on board while the other, using a mixture of dithiocarbamates and freon, was applied after storage under acid conditions. About half of the samples were also analysed for cadmium, copper and lead using ASV. The results of these determinations are intercompared. Consistent results were obtained for cadmium with the two extraction methods and for lead with the freon extraction method and ASV. In the other cases discrepancies were found.     

Solubility of hydrous ferric oxide and iron speciation in seawater

Iron solubility equilibria were investigated in seawater at 36.22‰ salinity and 25°C using several filtration and dialysis techniques. In simple filtration experiments with 0.05 μm filters and Millipore ultra-filters, ferric chlorides fluorides, sulfates, and FeOH²⁺ species were found to be insignificant relative to Fe(OH)₂⁺ at p[H⁺] = ?log [H⁺] greater than 6.0. Hydrous ferric oxide freshly precipitated from seawater yielded a solubility product of ${}^1\text{K}{}_{\mathrm{<mtext>so</mtext>}}\text{=}\text{[Fe}{}^{\mathrm{3+}}\text{][H}{}^{\mathrm{+}}\text{]}{}^{\mathrm{?3}}\text{= 4.7 · 10}{}^5$. Solubility studies based on the rates of dialysis of various seawater solutions and on the filtration of acidified seawater solutions indicated the existence of the Fe(OH)₃⁰ species. The formation constant for this species can be calculated as ${}^1\text{β}{}_3\text{=}\text{[Fe(OH)}{}_3{}^0\text{] [H}{}^{\mathrm{+}}\text{]}{}^3\text{/[Fe}{}^{\mathrm{3+}}\text{] = 2.4 · 10}{}^{\mathrm{?14}}$. The Fe(OH)₄^? species is present at concentrations which are negligible compared to Fe(OH)₂⁺ and Fe(OH)₃⁰ in the normal pH range of seawater. However, there is at least one other significant ferric complex in seawater above p[H⁺] = 8.0 (possibly with bicarbonate, carbonate, or borate ions) in addition to the Fe(OH)₂⁺ and Fe(OH)₃⁰ species.     

Complexation of calcium and copper with carbohydrates: Implications for seawater speciation

The extent of complexation of calcium(II) and copper(II) with 33 carbohydrates found in seawater has been determined potentiometrically using calcium and copper ion-selective electrodes. The measurements were performed in an essentially neutral aqueous medium at 25°C in 0.70 M KNO₃.Neutral sugars form very weak 1:1 complexes with Ca(II) and Cu(II) ions. Sugars with carboxylate groups from much stronger complexes. K′_Cu(II) >K′_Ca(II)) for a given sugar. The extent of complexation is dependent on the conformation of the sugar ligand.     

The influence of organic matter and atmospheric deposition on the particulate trace metal concentration of northwest Atlantic surface seawater

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.     

阳离子交换树脂吸附石墨炉原子吸收法测定海水中痕量铜、铅、镉

用阳离子交换树脂吸附石墨炉原子吸收法测定海水中痕量Cu,Pb,Cd。实验选定了最佳的测定条件。结果表明,在弱碱性条件下,Cu,Pb,Cd能同时被阳离子交换树脂定量吸附。方法的相对标准偏差<3﹪,样品加标回收率93﹪～102﹪,检出限分别为Cu 0.06μg/L,Pb 0.06μg/L,Cd 0.005μg/L。本法操作简便、快速、无干扰、无污染,已用于海水中铜、铅、镉的分析,取得了令人满意的结果。     

An investigation of methods commonly used for the selective removal and characterization of trace metals in sediments

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.     

一种移动式海水痕量元素洁净采集实验室的设计

痕量元素及其同位素采集、预处理和分析在海洋研究中具有重要的作用，由于含量极低，在采样、样品预处理及分析过程中容易受到外界污染源沾污。通过在一个20尺标准超高集装箱内制作一套移动式海水痕量元素洁净采集实验室，完成对实验室空间设计、空气质量控制，样品快速转移，实现水样上船后快速进入到洁净环境中，减少样品暴露在大气中时间，在洁净环境中高效完成样品取样、过滤和预处理等操作。所有操作满足GEOTRACES组织有关痕量元素采集的规范要求，从源头上保证分析测试结果的可靠性。     

NOBIAS PA1螯合树脂富集——ICP-MS定量测定近海水体中的稀土元素

稀土元素是海洋中一类极为重要的地球化学过程的示踪剂,但因其浓度多在pmol/kg数量级,分析测试一直是难点,为了使稀土元素在海洋研究中得到更广泛的应用,必须对海洋中低浓度的稀土元素进行准确测量。本研究建立了NOBIAS PA1螯合树脂富集—ICP-MS法,可以对近海的小体积水样中的稀土元素进行高准确度、高精密度分析。研究表明,调节样品溶液pH为4.59~4.69、清洗溶液为6 mL 0.05 mol/L NH_4AC、洗脱溶液为2 mL 1 mol/L HNO_3时,实验测试条件为最优。本方法对稀土元素的回收率在94%~106%,检出限范围为0.001~0.424 pmol/kg,分析精密度优于5%(n=5)。本研究所建立的方法,可用于河水、海水与河口盐度梯度区稀土元素的分析。     

Measurement of the redox speciation of iron in seawater by catalytic cathodic stripping voltammetry

Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (Fe_R) in the absence and presence of 2 μM Dp, Fe_R being defined as that which was complexed by 20 μM NN at pH 6.9 in the presence of 1.8 mM H₂O₂ and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for Fe_R. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for Fe_R, iron(III) and iron(II), respectively, using a 60 s deposition time.The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of Fe_R ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column.     

An international intercalibration for mercury in seawater

An intercalibration between 32 laboratories in 16 countries was conducted using acidified and ultraviolet-irradiated seawater. One sample was natural seawater but two were spiked with mercuric chloride, 15.4 and 143 ngl^?1, respectively. The results show, for the majority of the laboratories, good accuracy and precision in the recovery of spikes but they also demonstrate that the most serious errors in low-level determinations are systematic.     

An improved method for the determination of ammonia in seawater

The Liddicoat, Tibbitts and Butler method for the determination of ammonia in seawater has been noticeably improved by replacing the UV lamp with a 300 VA tungsten lamp. The characteristics so achieved, a low blank value (0.012 ± 0.002a.u.), a good molar absorptivity (23.90 × 10⁻³) and a reasonably short reaction time (1 h), are such that this modified procedure is more convenient for routine work in chemical oceanography.