Trace elements and elemental species

Determination of Trace Elements and Elemental Species Using Isotope Dilution Inductively Coupled Plasma Mass Spectrometry... 

The list of elements and their species listed above is not exhaustive. It is limited to the relatively simple compounds that have been determined by an important number of laboratories specializing in speciation analysis. Considering the economic importance of the results, time has come to invest in adequate CRMs. There is a steadily increasing interest in trace element species in food and in the gastrointestinal tract where the chemical form is the determinant factor for their bioavailability (Crews 1998). In clinical chemistry the relevance of trace elements will only be fully elucidated when the species and transformation of species in the living system have been measured (ComeUs 1996 Cornelis et al. 1998). Ultimately there will be a need for adequate RMs certified for the trace element species bound to large molecules, such as proteins. 

Fingerova H, Koplik R (1999) Study of minerals and trace element species in soybean flour. Fresenius J Anal Chem 363 545-549. 

The principal advantage of the ion microprobe (as opposed to the Auger microprobe) is the ability to obtain depth profiles for trace elemental species present in the analytical volume. The characterization of coal fly ash clearly illustrates this point (11-14). Auger detection limits are comparable to BSCA, and thus only elements with bulk concentrations greater than 1% by weight in fly ash (Si, Al, Fe, Ca, S, Na, K) can be... 

Environmental Monitoring of Selected Elements, Group Elements and Trace Element Species... 

Few trace element species can be analysed in natural samples directly. Ion selective electrodes (ISE) allow measurements of metal ion activity (Cu2+, Cd2+) however, their use in the marine environment is limited due to low sensitivity and interference by Cl-. 

Development of chemical speciation schemes which can be directly related to measures of bioavailability - This would allow the determination of which active trace element species merit the most intensive research from the standpoint of environmental perturbation. Some studies have attempted to correlate metal fractions determined by a particular technique (operationally defined speciation) with those that are bioavailable (functionally defined speciation) (Larsen and Svensmark, 1991 Buckley, 1994 Deaver and Rodgers, 1996). However, any correlation is only empirical and more research is required to achieve an understanding of the mechanisms involved in bioavailability and to develop rational predictive models. 

Gercken, B. and Barnes, R.M. (1991) Determination of lead and other trace element species in blood by size exclusion chromatography and inductively coupled plasma/mass spectrometry. Anal. Chem., 63, 283-287. 

Specialists in speciation analytics are interested in various chemical species and the physical forms that certain elements assume. Here are some examples of the physicochemical forms of trace element species in water bodies ... 

Sorbed trace element species may range from simple cations to complex polynuclear hydroxides formed by hydrolysis and condensation in solution or... 

The concentration of free metal species in soil solution is controlled by several factors, the most significant of which are thermody-namic/kinetic parameters. Mathematical approaches to modeling soil solution -solid-phase equilibria - are broadly described in numerous publications (Lindsay 1979, Sposito etal. 1984, Waite 1991, Wolt 1994, Sparks 1995, Suarez 1999), and several models for calculating activity coefficients for trace metals are overviewed and discussed. Waite (1991) concluded that mathematical modeling clearly has a place in extending the information that can be obtained on trace element species distributed by other methods and will be of practical use in systems for which determination of concentrations of all species of interest is impossible because of sensitivity constrains or other analytical difficulties . 

The preliminary study reported here is part of an investigation of the abundances and nature of trace-element species in crude oils. Neutron activation... 

In aquatic sediments or soils, there are also a range of trace elements species ranging from ions exchanged to particles, to those bound to organic matter or in various inorganic forms (e.g., oxides, carbonates, sulfides) or as more inert crystalline mineral phases. As in waters, speciation studies in soils and sediments are generally undertaken to better understand the bioavailability of toxic substances and to investigate transport pathways to and from other parts of the ecosystem. Sediment and soil pore waters (soil solutions) are of particular interest because they are in equilibrium with the solid phase and are the medium for contaminant uptake by plants and many other biota. The techniques used for speciation analysis in these aqueous samples differ little from those for waters. 

A recently defined and new objective has been trace element speciation, which provides information about the physical/chemical state of the trace elements. Species separated by chemical methods are subsequently determined by instrumental or radiochemical activation analysis. 

Gercken B, Barnes RM (1991) Determination of lead and other trace element species... 

Other limitations on phytoplankton growth are chemical in nature. Nitrogen, in the form of nitrate, nitrite and ammonium ions, forms a basic building material of a plankton s cells. In some species silicon, as silicate, takes on this role. Phosphorus, in the form of phosphate, is in both cell walls and DNA. Iron, in the form of Fe(III) hydroxyl species, is an important trace element. Extensive areas of the mixed layer of the upper ocean have low nitrate and phosphate levels during... 

Today dynamic SIMS is a standard technique for measurement of trace elements in semiconductors, high performance materials, coatings, and minerals. The main advantages of the method are excellent sensitivity (detection limit below 1 pmol mol ) for all elements, the isotopic sensitivity, the inherent possibility of measuring depth profiles, and the capability of fast direct imaging and 3D species distribution. 

In general, three basic kinds of sorption mechanisms for trace elements in geologic aqueous systems can be distinguished (56). Due to non-specific forces of attraction between sorbent and the solute, a physical adsorption may occur. This sorption mechanism results in the binding of species from the solution in several consecutive layers on exposed solid surfaces. This would be a rapid non-selec-tive and reversible process, fairly independent of nuclide concentration and only little dependent on ion exchange capacity of the solid. 

Sediment Analysis. Sediment is the most chemically and biologically active component of the aquatic environment. Benthic invertebrate and microbial life concentrate in the sediment, a natural sink for precipitated metal forms, and an excellent sorbent for many metal species. TTie extent to which potentially toxic trace element forms bind to sediment is determined by the sediment s binding intensity and capacity and various solution parameters, as well as the concentration and nature of the metal forms of interest. Under some conditions sediment analyses can readily indicate sources of discharged trace elements. 

Before examining selenium in some detail, as an illustration of the phenomena under consideration, let us note here that although oxidative UPD of sulfur can be achieved from sulfide solutions, the oxidative UPDs of Se and Te are complicated by the fact that, unlike sulfides, the Se and Te species are not very stable in aqueous solutions they tend to react with even traces of O2, to form the corresponding element. 

A current area of interest is the use of AB cements as devices for the controlled release of biologically active species (Allen et al, 1984). AB cements can be formulated to be degradable and to release bioactive elements when placed in appropriate environments. These elements can be incorporated into the cement matrix as either the cation or the anion cement former. Special copper/cobalt phosphates/selenates have been prepared which, when placed as boluses in the rumens of cattle and sheep, have the ability to decompose and release the essential trace elements copper, cobalt and selenium in a sustained fashion over many months (Chapter 6). Although practical examples are confined to phosphate cements, others are known which are based on a variety of anions polyacrylate (Chapter 5), oxychlorides and oxysulphates (Chapter 7) and a variety of organic chelating anions (Chapter 9). The number of cements available for this purpose is very great. 

Further afield, in 1978 the Japanese National Institute for Environmental Studies (NIES) started the production of a series of biological and environmental matrix CRMs, certified for a number of trace elements (Okamoto and Fuwa 1985). Recently also the certification of metal species in some materials was reported (Okamoto and Yoshinaga 1999). 

Today it has become clear that the effect of trace elements in living systems, in food, and in the environment depends on the chemical form in which the element enters the system and the final form in which it is present. The form, or species, clearly governs its biochemical and geochemical behaviour. lUPAC (the International Union for Pure and Applied Chemistry) has recently set guidelines for terms related to chemical speciation of trace elements (Templeton et al. 2000). Speciation, or the analytical activity of measuring the chemical species, is a relatively new scientific field. The procedures usually consist of two consecutive steps (i) the separation of the species, and (2) their measurement An evident handicap in speciation analysis is that the concentration of the individual species is far lower than the total elemental concentration so that an enrichment step is indispensable in many cases. Such a proliferation of steps in analytical procedure not only increases the danger of losses due to incomplete recovery, chemical instability of the species and adsorption to laboratory ware, but may also enhance the risk of contamination from reagents and equipment. 

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