Instrumental speciation methods

In analytical work on speciation, methods of wet sample preparation are very important parts of the overall scheme of analysis. Constraints on preparation methods include low concentrations of analytes, often less than 0.1 mgg-1, stabilities of the analytes, and the need for suitable solutions for instrumental techniques of elemental determinations. Volume of sample and type of matrix must be considered. Procedures for the quantitative recoveries of organometallic compounds from sediments and organic matrices can be time-consuming. Their efficiencies and reliabilities must be thoroughly tested for each type of sample for analysis. 

Instruments and methods that can in near real time characterize more fully the speciated organic composition of secondary and combustion aerosols and that of the gas phase. In conjunction with laboratory studies, one may hope to use these techniques to elucidate the pathways and connect precursor volatile organic compounds to the nature of particulate matter. 

Almost all publications on substoichiometry which have appeared to date have dealt with the determination of the total amount of the element. Recently, some attention has been focused on the determination of the element of interest in different chemical states. This speciation of trace elements of interest is almost impossible by instrumental analytical methods alone. For example, suppose a sample contains the element of interest in different oxidation states, abbreviated as M(III) and M(V). If one state, e.g., M(III) can be determined, the total amount of M can be ascertained after appropriate reduction of M(V) to M(III) in the sample. Then the amount of M(V) can be estimated as the difference in the total amount of M and that of M(III) in sample. 

Instrumental Quantitative Analysis. Methods such as x-ray spectroscopy, oaes, and naa do not necessarily require pretreatment of samples to soluble forms. Only reUable and verified standards are needed. Other instmmental methods that can be used to determine a wide range of chromium concentrations are atomic absorption spectroscopy (aas), flame photometry, icap-aes, and direct current plasma—atomic emission spectroscopy (dcp-aes). These methods caimot distinguish the oxidation states of chromium, and speciation at trace levels usually requires a previous wet-chemical separation. However, the instmmental methods are preferred over (3)-diphenylcarbazide for trace chromium concentrations, because of the difficulty of oxidizing very small quantities of Cr(III). 

HPLC-QFAAS is also problematical. Most development of atomic plasma emission in HPLC detection has been with the ICP and to some extent the DCP, in contrast with the dominance of the microwave-induced plasmas as element-selective GC detectors. An integrated GC-MIP system has been introduced commercially. Significant polymer/additive analysis applications are not abundant for GC and SFC hyphenations. Wider adoption of plasma spectral chromatographic detection for trace analysis and elemental speciation will depend on the introduction of standardised commercial instrumentation to permit interlaboratory comparison of data and the development of standard methods of analysis which can be widely used. 

The species of components present will also be affected by oxidation-reduction, and pH. For example, iron is primarily in the Fe3+ (oxidized) or the Fe2+ (reduced) state depending on the oxidation-reduction potential of the soil. Speciation, which depends, in part, on the oxygen status of soil, is of environmental concern because some species are more soluble, such as Fe2+, and are thus more biologically available than others. The occurrence of a specific species is related to the chemistry occurring in a soil, which is related to its features. Thus, large features must be taken into consideration when studying soil chemistry and when developing analytical and instrumental methods. 

Instrumental Methods in Metal Ion Speciation, Imran AH and Hassan Y. Aboul-Enein... 

The Nickel Producers Environmental Research Association (NiPERA) is sponsoring research on the application of inductively coupled plasma-mass spectroscopy (ICP-MS) to isotopic analysis of nickel in biological samples, on the development of sampling instrumentation for assessing workers exposure to nickel in the nickel industry, and on methods for utilizing newly developed analytical methods, such as laser beam ionization mass spectrometry, for the identification and speciation of nickel compounds in powders and dusts with particular reference to nickel refining. 

I) Faradaic electrochemical methods. From a general analytical point of view, electrochemical techniques are very sensitive methods for identifying and determining the electroactive species present in the sample and, in addition, they also are able to carry out speciation studies, providing a complete description of the states of oxidation in which the ionic species are present in the object. Other applications and improvements obtained by their hyphenation with other instrumental techniques, such as atomic force microscopy (AFM), will be described in the following chapters. 

I. Ah, H.Y. Aboul-Enein, Instrumental methods in metal ions speciation Chromatography, capillary electrophoresis and electrochemistry, New York Taylor Francis (2006). 

Differential pulse voltammetric and polarographic methods described in this section represent a significant enhancement of the available instrumental analysis capabilities for the quantitative speciation of sulfide, thiosulfate, sulfite and of heteroaromatic sulfur moieties in coal conversion process streams and products. 

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