Seawater trace metals

Approaches to the Preparation of Seawater Trace Metal Reference Materials... 

The committee recommends the development of two reference materials for seawater trace metal analysis ... 

A significant proportion of the needs for reference materials for seawater trace metal studies would be addressed by the preparation of these materials. Although the total iron concentration of these reference materials should be provided, these materials clearly will be useful for studies of other important metals such as zinc, manganese, copper, molybdenum, cobalt, vanadium, lead, aluminum, cadmium, and the rare earth elements. With careful planning, such water samples should be useful for analysis of dissolved organic substances as well. The collection sites should be chosen carefully to provide both a high and a low concentration reference material for as many metals as possible. 

NASS-5 Natural Seawater Trace Metals NRC-INMS, Canada... 

Anodic-stripping voltaimnetry (ASV) is used for the analysis of cations in solution, particularly to detemiine trace heavy metals. It involves pre-concentrating the metals at the electrode surface by reducmg the dissolved metal species in the sample to the zero oxidation state, where they tend to fomi amalgams with Hg. Subsequently, the potential is swept anodically resulting in the dissolution of tire metal species back into solution at their respective fomial potential values. The detemiination step often utilizes a square-wave scan (SWASV), since it increases the rapidity of tlie analysis, avoiding interference from oxygen in solution, and improves the sensitivity. This teclmique has been shown to enable the simultaneous detemiination of four to six trace metals at concentrations down to fractional parts per billion and has found widespread use in seawater analysis. 

Quigley, M. N. Vernon, E. Determination of Trace Metal Ion Concentrations in Seawater, /. Chem. Educ. 1996, 73, 671-675. 

Trace metals can serve as essential nutrients and as toxic substances (Sunda et al, 1991 Frausto da Silva and Williams, 1991). For example, cobalt is a component of vitamin B-12. This vitamin is essential for nitrogen fixing algae. In contrast, copper is toxic to marine phytoplankton at free ion concentrations similar to those found in seawater (Sunda and... 

National Research Coundl Canada (1992) Certified Reference Material NASS-4 Open Ocean Seawater Reference Material for Trace Metals. National Research Council of Canada. Ottawa. National Research Council Canada (1995) Certified Reference Material CARP-i Groimd Whole Carp Reference Material for Organochlorine Compounds. National Research Council of Canada, Ottawa. 

It was generally agreed that any determinations of trace metals carried out on seawater prior to about 1975 are questionable, principally due to the adverse effects of contamination during sampling, which were then little understood and lead to artificially high results. It is only in the past few years that methods of adequate sensitivity have become available for true ultra-trace metal determinations in water. 

Shipboard analysis for the sampling of trace metals in seawater has been discussed by Schuessler and Kremling [2] and Dunn et al. [3]. Teasdale et al. have reviewed methods for collection of sediment pore-waters using in situ dialysis samples [4]. Bufflap and Allen [5] compared centrifugation, squeezing, vacuum filtration, and dialysis methods for sediment pore-water sampling. 

Several round-robin intercalibrations for trace metals in seawater [26-30] have demonstrated a marked improvement in both analytical precision and numerical agreement of results among different laboratories. However, it has often been claimed that spurious results for the determination of metals in seawater can arise unless certain sampling devices and practical methods of sampler deployment are applied to the collection of seawater samples. It is therefore desirable that the biases arising through the use of different, commonly used sampling techniques be assessed to decide upon the most appropriate technique ) for both oceanic baseline and nearshore pollution studies. 

Scarponi et al. [93] concluded that filtration of seawater through uncleaned membrane filters shows positive contamination by cadmium, lead, and copper. In the first filtrate fractions, the trace metal concentration maybe increased by a factor of two or three. During filtration, the soluble impurities are leached from the filter, which is progressively cleaned, and the metal concentration in the filtrate, after passage of 0.8 -11 of seawater, reaches a stable minimum value. Thus it is recommended that at least one litre of seawater at natural pH be passed through uncleaned filters before aliquots for analysis are taken... 

Olaffson J (1981) Trace Metals in Seawater. In Wong CS et al. (eds) Proceedings of a NATO Advanced Research Institute on Trace Metals in Seawater, 30/3-3/4/81, Sicily, Italy. Plenum Press, New York, NY, USA... 

Determination of trace metals in seawater represents one of the most challenging tasks in chemical analysis because the parts per billion (ppb) or sub-ppb levels of analyte are very susceptible to matrix interference from alkali or alkaline-earth metals and their associated counterions. For instance, the alkali metals tend to affect the atomisation and the ionisation equilibrium process in atomic spectroscopy, and the associated counterions such as the chloride ions might be preferentially adsorbed onto the electrode surface to give some undesirable electrochemical side reactions in voltammetric analysis. Thus, most current methods for seawater analysis employ some kind of analyte preconcentration along with matrix rejection techniques. These preconcentration techniques include coprecipitation, solvent extraction, column adsorption, electrodeposition, and Donnan dialysis. 

In the determination of cadmium in seawater, for both operational reasons and ease of interpretation of the results it is necessary to separate particulate material from the sample immediately after collection. The dissolved trace metal remaining will usually exist in a variety of states of complexation and possibly also of oxidation. These may respond differently in the method, except where direct analysis is possible with a technique using high-energy excitation, such that there is no discrimination between different states of the metal. The only technique of this type with sufficiently low detection limits is carbon furnace atomic absorption spectrometry, which is subject to interference effects from the large and varying content of dissolved salts. 

Electrothermal atomic absorption spectrophotometry with Zeeman background correction was used by Zhang et al. [141] for the determination of cadmium in seawater. Citric acid was used as an organic matrix modifier and was found to be more effective than EDTA or ascorbic acid. The organic matrix modifier reduced the interferences from salts and other trace metals and gave a linear calibration curve for cadmium at concentrations < 1.6 pg/1. The method has a limit of detection of 0.019 pg/1 of cadmium and recoveries of 95-105% at the 0.2 pg of cadmium level. 

Stolzberg [143] has reviewed the potential inaccuracies of anodic stripping voltammetry and differential pulse polarography in determining trace metal speciation, and thereby bio-availability and transport properties of trace metals in natural waters. In particular it is stressed that nonuniform distribution of metal-ligand species within the polarographic cell represents another limitation inherent in electrochemical measurement of speciation. Examples relate to the differential pulse polarographic behaviour of cadmium complexes of NTA and EDTA in seawater. 

Ruzic [278 ] considered the theoretical aspects of the direct titration of copper in seawaters and the information this technique provides regarding copper speciation. The method is based on a graph of the ratio between the free and bound metal concentration versus the free metal concentration. The application of this method, which is based on a 1 1 complex formation model, is discussed with respect to trace metal speciation in natural waters. Procedures for interpretation of experimental results are proposed for those cases in which two types of complexes with different conditional stability constants are formed, or om which the metal is adsorbed on colloidal particles. The advantages of the method in comparison with earlier methods are presented theoretically and illustrated with some experiments on copper (II) in seawater. The limitations of the method are also discussed. 

In order to overcome the problem of the high nonspecific absorption, alternative procedures have been tested, which involve prior separation of the trace metals from the salt matrix. Examples of extraction of trace metals from seawater as chelates with subsequent determination by electrothermal atomic absorption spectrometric procedures have been described [381,382], but these and similar methods are seldom effective and satisfactory when the matrix is very complex and the analyte concentration very low. 

Statham [448] has optimised a procedure based on chelation with ammonium dithiocarbamate and diethylammonium diethyldithiocarbamate for the preconcentration and separation of dissolved manganese from seawater prior to determination by graphite furnace atomic absorption spectrometry. Freon TF was chosen as solvent because it appears to be much less toxic than other commonly used chlorinated solvents, it is virtually odourless, has a very low solubility in seawater, gives a rapid and complete phase separation, and is readily purified. The concentrations of analyte in the back-extracts are determined by graphite furnace atomic absorption spectrometry. This procedure concentrates the trace metals in the seawater by a factor of 67.3. 

When a 350 ml seawater sample was spiked with 54Mn and taken through the chelation, extraction, and back-extraction procedures, the observed recovery of the radio-tracer was 100.6%. Estimates of detection limits for manganese based on sets of both shipboard and shore laboratory separations are of the order of 0.1 nmol/1. The accuracy of the technique is demonstrated by data from the ICES fifth-round intercalibration exercise for trace metals in seawater [449 ]. 

Bender and coworkers [450,451] determined total and soluble manganese in seawater. The samples were collected into 500 ml polyethylene bottles. All samples were brought to pH 2 with nitric acid free of trace metals, and stored in individual zip-lock plastic bags to minimise contamination. 

Figure 5.18 is an absorbance versus time plot obtained by Hoenig and Wollast [681] for the determination of trace metals in seawater. It shows the absorbance profiles of the desired elements as a function of the atomisation temperature. The scale starts with cadmium, for which the absorption signal appears around 400 °C, followed by lead (756 °C), copper (1000 °C), manganese (1200 °C), nickel (1300 °C), and chromium (140 °C). 

The extension of inductively coupled plasma (ICP) atomic emission spectrometry to seawater analysis has been slow for two major reasons. The first is that the concentrations of almost all trace metals of interest are 1 xg/l or less, below detection limits attainable with conventional pneumatic nebulisation. The second is that the seawater matrix, with some 3.5% dissolved solids, is not compatible with most of the sample introduction systems used with ICP. Thus direct multielemental trace analysis of seawater by ICP-AES is impractical, at least with pneumatic nebulisation. In view of this, a number of alternative strategies can be considered ... 

Bloxham et al. [842] have reviewed the application of ICP-MS to the determination of trace metals in seawater. 

A poly(acrylaminophosphamic-dithiocarbamate) chelating fibre hasbeen used to preconcentratrate several trace metals in seawater by a factor of 200 [957]. The elements included beryllium, bimuth, cobalt, gallium, silver, lead, cadmium, copper, manganese, and indium. ICP-MS was used for detection. 

Table 5.8. Optimum analysis wavelengths and detection limits for six trace metals in seawater...

Brugmann [784] discussed different approaches to trace metal speciation (bioassays, computer modelling, analytical methods). The electrochemical techniques include conventional polarography, ASV, and potentiometry. ASV diagnosis of seawater was useful for investigating the properties of metal complexes in seawater. Differences in the lead and copper values yielded for Baltic seawater by methods based on differential pulse ASV or AAS are discussed with respect to speciation. 

Bond et al. [791 ] studied strategies for trace metal determination in seawater by ASV using a computerised multi-time domain measurement method. A microcomputer-based system allowed the reliability of the determination of trace amounts of metals to be estimated. Peak height, width, and potential were measured as a function of time and concentration to construct the database. Measurements were made with a potentiostat polarographic analyser connected to the microcomputer and a hanging drop mercury electrode. The presence of surfactants, which presented a matrix problem, was detected via time domain dependent results and nonlinearity of the calibration. A decision to pretreat the samples could then be made. In the presence of surfactants, neither a direct calibration mode nor a linear standard addition method yielded precise data. Alternative ways to eliminate the interferences based either on theoretical considerations or destruction of the matrix needed to be considered. 

Sipos et al. [789] have described a procedure for the simultaneous determination of copper and mercury in seawater down to the ng/1 range using differential pulse ASV at a gold electrode. Pretreatment is necessary, and comprises UV irradiation to release the trace metal bound to dissolved organic matter. 

Mart et al. [793] and Valenta et al. [794] have described two differential pulse ASV methods for the determination of cadmium, lead, and copper in arctic seawater. After a previous plating of the trace metals into a mercury film on a rotating electrode with a highly polished glassy carbon as substrate, they were stripped in the differential pulse mode. The plating was done in situ. 

Holzbecker and Ryan [825] determined these elements in seawater by neutron activation analysis after coprecipitation with lead phosphate. Lead phosphate gives no intense activities on irradiation, so it is a suitable matrix for trace metal determinations by neutron activation analysis. Precipitation of lead phosphate also brings down quantitatively the insoluble phosphates of silver (I), cadmium (II), chromium (III), copper (II), manganese (II), thorium (IV), uranium (VI), and zirconium (IV). Detection limits for each of these are given, and thorium and uranium determinations are described in detail. Gamma activity from 204Pb makes a useful internal standard to correct for geometry differences between samples, which for the lowest detection limits are counted close to the detector. 

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