Food analysis speciation

ORGANIC TRACE ANALYSIS, SPECIATION Environmental protection, food inspection... 

A. M. Cairo, M. C. Mejuto, Review application of chromatographic and electrophoretic methodology to the speciation of organomercury compounds in food analysis,... 

Similar demands for speciation of trace elements exist for food analysis. Substantial differences in the biological availability are known for several essential elements and depend on the form in which they are present in the diet. The chemical bases for these differences are known for cobalt, iron, and chromium but not for zinc, copper, and selenium. The importance of speciation in food analysis is best demonstrated by the example of iron. That element, when part of heme compounds, is well absorbed, and there is little influence on the absorption by other factors in the diet. Nonheme iron, on the other hand, is not readily absorbed and, in addition, is subject to many influences from dietary ingredients those influences are poorly understood and probably not completely known (14). 

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. 

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. 

Principles and Characteristics The fastest growing area in elemental analysis is in the use of hyphenated techniques for speciation measurement. Elemental spe-ciation analysis, defined as the qualitative identification and quantitative determination of the individual chemical forms that comprise the total concentration of an element in a sample, has become an important field of research in analytical chemistry. Speciation or the process yielding evidence of the molecular form of an analyte, has relevance in the fields of food, the environment, and occupational health analysis, and involves analytical chemists as well as legislators. The environmental and toxicological effects of a metal often depend on its forms. The determination of the total metal content... 

Applications Speciation analysis is particularly important in plant and animal biochemistry and nutrition (food/food supplements), clinical biochemistry, industrial chemistry and environmental chemistry. In the... 

The discipline of analytical chemistry is wide and catholic. It is often difficult for a food chemist to understand the purist concerns of a process control chemist in a pharmaceutical company. The former deals with a complex and variable matrix with many standard analytical methods prescribed by Codex Alimentarius, for which comparability is achieved by strict adherence to the method, and the concept of a true result is of passing interest. Pharmaceuticals, in contrast, have a well-defined matrix, the excipients, and a well-defined analyte (the active) at a concentration that is, in theory, already known. A 100-mg tablet of aspirin, for example, is likely to contain close to 100 mg aspirin, and the analytical methods can be set up on that premise. Some analytical methods are more stable than others, and thus the need to check calibrations is less pressing. Recovery is an issue for many analyses of environmental samples, as is speciation. Any analysis that must... 

By far the most common type of plasma used for speciation analysis is the inductively coupled plasma (ICP) with mass spectrometry (MS) or atomic emission spectrometry (AES) detection. The performance of the ICP-MS system has been well documented since its development in the early 1980s by the Gray and Houk research groups [14,15], and it is now used for a wide variety of applications such as environmental, clinical, geological, food, and industrial analysis. 

Speciation analysis, on the other hand, plays a pivotal role in a more realistic assessment of the impact on human health of the intake of potentially toxic elements through the diet (see also Chapters 16-22 in this book). Recent studies on chemical speciation of As in rice showed that the percentage of the inorganic As (III) and As (V) species, i.e., the most toxic ones, range from 11 to 91 percent, a much higher percentage than in other foods [45, 46],... 

The nutritional, chemical, biological, and toxicological properties of a chemical element are known to be critically dependent on the form in which it occurs in food. The recognition of this fact has spurred the development of species-selective (speciation) analytical methods for food additives and contaminants. According to the IUPAC s dehnition, speciation analysis deals with the analytical activities of identification and/or measurement of the quantities of one or more individual chemical species in a given sample [1], The analytical approach is usually based on the combination of a chromatographic separation technique with an element-specif>c detection technique. The former ensures that the analyte compound leaves the column unaccompanied by other species of the analyte element, whereas the latter enables a sensitive and specil>c detection of the target element. Coupled (also called hyphenated) techniques have become a fundamental tool for speciation analysis and have been discussed in many published reviews [2D6]. 

The choice of hyphenated techniques available for speciation analysis in foods is schematically shown in Figure 16.1. In the most frequent cases a separation technique, for example, GC, HPLC, electrochromatography or GE, is combined with ICP-MS. 

Figure 16.1. Coupled techniques used in speciation analysis of foods.

Figure 16.3. Arsenic species of interest in food speciation analysis.

Human milk can be considered the optimal food for infants. It contains all the macronutrients and micronutrients necessary for the correct development of the newborn and at the adequate levels. When infants are not breast-fed, or breastfeeding is discontinued very early, formula milks are used instead. Therefore, it is important to evaluate the capacity of formulas to deliver satisfactory quantities of minerals and trace elements that can be bioavailable to the children in order to cover their biological needs. This fact explains the need to perform trace elements speciation analysis in formula milk. Thus, the speciation results obtained in formulas and published so far are critically evaluated here and compared with those obtained in human milk. 

In recent years several applications of the HC1 proteolysis have been published in the field of Se speciation, for example, as regards Se-enriched lactic acid bacteria [66], mullet and cockles [8], and algae [67], where the technique provided extraction efficiencies of greater than 90 percent and preserved the integrity of the selenoamino acids. The general usefulness of this method of Se speciation is, however, questionable. Sometimes the authors do not state clearly whether phenol - an essential compound for the prevention of oxidation of SeCys - was used or not. In practice, neither phenol nor the short-duration MW-assisted irradiation can prevent the alteration of selenoamino acids [68-71], At the moment, no final conclusion on the applicability of HC1 proteolysis can be drawn, as CRMs certified for SeCys are still unavailable. On the other hand, an Se extraction efficiency of 80-90 percent can be achieved with this method only if either proteins are at least partly separated from the other components of the matrix, for example, separate analysis of fish muscles is carried out [8], or a considerable portion of Se is originally contained in inorganic forms in the sample, as observed by B Hymer and Caruso [1] in the case of Se-enriched food supplements. 

In one word, a possibly low in vitro extraction efficiency does not necessarily go together with low Se bioavailability. The powdered basic samples of Se speciation (Se-enriched yeast, Allium ssp., wheat flour, etc.) - albeit they are food materials or food supplements - are far less complex than real foodstuffs. At the same time, they facilitate sample preparation and the assessment of Se supply from prepared food materials through the analysis of some raw food materials. 

In most cases, as detailed in Table 19.1, the reported extraction efficiency and chromatographic recovery values for Se speciation analysis carried out on the usual samples Allium ssp., Se-enriched yeast, and food supplements) have been... 

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