Speciation operational

Ho M.D., Evans G.J. Operational speciation of cadmium, copper, lead and zinc in the NIST standard reference materials 2710 and 2711 (Montana soil) by the BCR sequential extraction procedure and flame atomic absorption spectrometry. Anal Commun 1997 34 353-364. 

In operationally defined speciation the physical or chemical fractionation procedure applied to the sample defines the fraction isolated for measurement. For example, selective sequential extraction procedures are used to isolate metals associated with the water/acid soluble , exchangeable , reducible , oxidisable and residual fractions in a sediment. The reducible, oxidisable and residual fractions, for example, are often equated with the metals associated, bound or adsorbed in the iron/manganese oxyhydroxide, organic matter/sulfide and silicate phases, respectively. While this is often a convenient concept it must be emphasised that these associations are nominal and can be misleading. It is, therefore, sounder to regard the isolated fractions as defined by the operational procedure. Physical procedures such as the division of a solid sample into particle-size fractions or the isolation of a soil solution by filtration, centrifugation or dialysis are also examples of operational speciation. Indeed even the distinction between soluble and insoluble species in aquatic systems can be considered as operational speciation as it is based on the somewhat arbitrary definition of soluble as the ability to pass a 0.45/Am filter. 

As in various areas of analytical chemistry, there is a growing trend in operational speciation studies to apply chemometric techniques in order to both (1) improve experimental design and (2) gain as much useful information as possible from experimental results. 

An operational definition is considerably more practical. Operationally determined species are defined by the methods used to separate them from other forms of the same element that may be present. The physical or chemical procedure that isolates the particular set of metal species is used to define the set. Metals extracted from soil with an acetate buffer is an operational definition of a certain class. Lead present in airborne particles of less than 10 pm is another. In water analyses, simply filtering the sample before acidification can speciate the analytes into dissolved and insoluble fractions. These procedures are sometimes referred to as fractionation, which is probably a more properly descriptive term than speciation, as speciation might imply that a particular chemical species or compound is being determined. When such operational speciation is done, careful documentation of the protocol is required, since small changes in procedure can lead to substantial changes in the results. Standardized methods are recommended, as results cannot be compared from one laboratory to another unless a standard protocol is followed [124], Improvements in methodology must be documented and compared with the currently used standard methods to produce useful, readily interpretable information. 

More widely applied to determine the potential, plant and human bioavailability are the methods of PTMs speciation which involve selective chemical extraction techniques. Estimation of the plant- or human-available element content of soil using single chemical extractants is an example of functionally defined speciation, in which the function is plant or human availability. In operationally defined speciation, single extractants are classified according to their ability to release elements from specific soil phases. Selective sequential extraction procedures are examples of operational speciation (Ure and Davidson, 2002). 

Considering the doubts and criticisms directed at operational speciation procedures because of the potential perturbation of the equilibrium of the system... 

Howe, S. E., Davidson, C. M., and McCartney, M. (1999). Operational speciation of uranium in inter-tidal sediments from the vicinity of a phosphoric acid plant by means of the BCR sequential extraction procedure and ICP-MS./.At. Specirom. 14(2), 163. 

Table 7.33 reports the main characteristics of GC-ICP-MS. Since both GC and ICP-MS can operate independently and can be coupled within a few minutes by means of a transfer line, hyphenation of these instruments is even more attractive than GC-MIP-AES. GC-ICP-MS is gaining popularity, probably due to the fact that speciation information is now often required when analysing samples. Advantages of GC-ICP-MS over HPLC-ICP-MS are its superior resolution, resulting in sharper peak shapes and thus lower detection limits. GC-ICP-MS produces a dry plasma when the separated species reach the ICP they are not accompanied by solvent or liquid eluents. This reduces spectral interferences. Variations on the GC-ICP-MS... 

Walker, S.W. Jamieson, H.E., Lanzirotti, A., Andrade, C.F. 2005. Determining arsenic speciation in iron oxides derived from a gold-roasting operation Application of... 

Delhi soils by studying its speciation in the soil profile and to assess if there was any spatial variability. Soils representing the Aravali Ridge and the alluvial floodplains of river Yamuna were collected as a single, undisturbed core up to a depth of lm and the profile differentiated into four layers- 0-17 cm, 17-37 cm, 37-57 cm, and 57-86 cm. Pseudo total Aluminum and Iron in the soils were speciated into the operationally defined species (weakly exchangeable, organic matter complexes, amorphous oxides and hydroxides, and crystalline or free oxides) by widely recommended selective extraction procedures. Both A1 and Fe in these soils are bound predominantly as Fe oxides and silicates and have only very low percentages in the easily mobilizable pools. 

Iron in the soil samples was also speciated to yield the following operationally defined species of Fe ... 

The concentrations of the four A1 species occurring in each layer of the soil profile are expressed as a percentage of the A1 content of the specific soil layer. While Alpstot increased with depth of the profile, the contribution of the operationally defined A1 species towards speciation however decreased with depth (Figure 3a-d). The maximum differentiation of Alpstotas A1, A1, A1, and A1 was 8.51% which was observed in the surface layer while the mean contribution was 5.43 1.60%. On the contrary, in 37-57 cm depth which had the most abundant Alpstot, the mean share of the A1 species (2.72 0.75%) was the lowest contribution to A1 in all the layers of the soil profile. This implied that pseudo total A1 in these depths are predominantly bound as silicates and hence are not available for speciation under the experimental conditions. 

On the basis of the preceding discussion, it should be obvious that ultratrace elemental analysis can be performed without any major problems by atomic spectroscopy. A major disadvantage with elemental analysis is that it does not provide information on element speciation. Speciation has major significance since it can define whether the element can become bioavailable. For example, complexed iron will be metabolized more readily than unbound iron and the measure of total iron in the sample will not discriminate between the available and nonavailable forms. There are many other similar examples and analytical procedures that must be developed which will enable elemental speciation to be performed. Liquid chromatographic procedures (either ion-exchange, ion-pair, liquid-solid, or liquid-liquid chromatography) are the best methods to speciate samples since they can separate solutes on the basis of a number of parameters. Chromatographic separation can be used as part of the sample preparation step and the column effluent can be monitored with atomic spectroscopy. This mode of operation combines the excellent separation characteristics with the element selectivity of atomic spectroscopy. AAS with a flame as the atom reservoir or AES with an inductively coupled plasma have been used successfully to speciate various ultratrace elements. 

In the earlier volume of this book, the chapter dedicated to transition metal peroxides, written by Mimoun , gave a detailed description of the features of the identified peroxo species and a survey of their reactivity toward hydrocarbons. Here we begin from the point where Mimoun ended, thus we shall analyze the achievements made in the field in the last 20 years. In the first part of our chapter we shall review the newest species identified and characterized as an example we shall discuss in detail an important breakthrough, made more than ten years ago by Herrmann and coworkers who identified mono- and di-peroxo derivatives of methyl-trioxorhenium. With this catalyst, as we shall see in detail later on in the chapter, several remarkable oxidative processes have been developed. Attention will be paid to peroxy and hydroperoxide derivatives, very nnconunon species in 1982. Interesting aspects of the speciation of peroxo and peroxy complexes in solntion, made with the aid of spectroscopic and spectrometric techniqnes, will be also considered. The mechanistic aspects of the metal catalyzed oxidations with peroxides will be only shortly reviewed, with particular attention to some achievements obtained mainly with theoretical calculations. Indeed, for quite a long time there was an active debate in the literature regarding the possible mechanisms operating in particular with nucleophilic substrates. This central theme has been already very well described and discussed, so interested readers are referred to published reviews and book chapters . 

The combustion process activates mineral ash with the result that leachates extract relatively high proportions of elements whose concentrations in potable water are limited. We are as yet some way from understanding the speciations of these elements in combustion waste as well as the geochemical evolution of waste in its disposal environment. Preliminary studies show that the design, construction, and operation of disposal sites have a major influence on releases. The underlying geochemical processes are at present only known in outline and provide a fascinating field for interdisciplinary studies. 

Argon plasmas are used in optical emission spectrometry to atomise and ionise elements leading to the emission of characteristic spectral lines. Hence, a plasma torch (7-8 000 K) can be used for ionisation in mass spectrometry. Ions produced in the plasma are introduced into the mass analyser through a small orifice (called a skimmer) placed in the axial direction. Because the mass spectrometer is operated under a vacuum, the ions are sucked into the mass analyser through the skimmer. An aqueous solution of the sample can be aspirated into the plasma or, alternatively, the plasma can be placed at the exit of a gas chromatograph (e.g. speciation of organo-metallic compounds by GC/ICP-MS). Since all chemical bonds are broken in the plasma, the only accessible information is that concerning the concentration of monoatomic ions (Fig. 16.19). 

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