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ismail alnatour                                                          natour@hotmail.com

 spectroscopy lab

 

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ICP-OES APPLICATIONS

The versatility of ICP-OES makes it a good analytical technique for a wide variety of applications.This versatility is due not only to the large number of elements that can be determined rapidly at trace levels but also to the wide variety of sample types that can be analyzed using the ICP-OES technique.

In this chapter,ICP-OES applications have been grouped into six generalized categories:Agricultural and Foods,Biological and Clinical,Geological,Environ-mental and Waters,Metals,and Organics.While an exhaustive review of each of these application areas is beyond the scope of this book,some examples of ICP-OES applications are discussed to give the reader an idea of the types of analyses where this technique has been used successfully.  Information regarding general application areas and specific applications can be obtained from a number of sources.Unfortunately,there is no one source that contains all the information needed to perform any and all ICP-OES analyses.For general discussions of applications,the books about ICP-OES by Boumans;Mon-taser and Golightly;and Thompson and Walsh are very good (see table 5-1).  For reviews of the latest ICP-OES applications,see the Fundamental and Applica-tions Reviews published in alternating years in the journal Analytical Chemistry.The Fundamental Reviews are categorized according to technique,e.g.,Emission Spectrometry.The Applications Reviews are categorized according to sample Related Drugs.The Journal of Analytical Atomic Spectrometry contains applications reviews in its “Atomic Spectrometry Updates”section.These reviews are a good starting place to search for references to specific analyses reported in the chemical literature.Also quite useful in locating literature references to specific applications are computer data base search services,such as CAS Online,available through various outlets.The journal Atomic Spectroscopy also publishes a biannual bibliog-raphy of atomic spectroscopy-related articles.

Detailed information about specific applications can be found in a number of sources.The ICP-OES books by Boumans and by Thompson and Walsh,while not exhaustive references,provide detailed information on some selected applications.  Many monographs,such as “Selected Methods of Trace Metal Analysis”by J.C.

Van Loon

General applications

“Inductively Coupled Plasma Emission Spectroscopy -Part 2”,P.W.J.

M.Boumans,ed.,Chemical Analysis,Vol.90,P.J.Elving,J.D.

Winefordner,eds.,John Wiley &Sons,New York,1987.

“Inductively Coupled Plasmas in Analytical Atomic Spectrometry”,A.  Montaser and D.W.Golightly,eds.,2nd Edition,VCH Publishers,Inc., New York,1992.

“A Handbook of Inductively Coupled Plasma Spectrometry”,M.

Thompson and J.N.Walsh,Blackie,Glasgow,1983.

Application Reviews

“Fundamental Reviews”,Analytical Chemistry 60,(1988).(published in even-numbered years)

“Applications Reviews”,Analytical Chemistry 59,(1987).(published in odd-numbered years)

“Atomic Spectrometry Updates”,Journal of Analytical Atomic Spectrometry,various issues.

Representative Journals

Analytical Chimica Acta

Analytical Chemistry

The Analyst

Applied Spectroscopy

Atomic Spectroscopy

Clinical Chemistry

Journal of Analytical Atomic Spectrometry

Journal of the Association of Official Analytical Chemists

Spectrochimica Acta,Part B

Talanta

chemistry and related topics contain the greatest amount of detailed information

about specific analyses.Table 5-1 contains a list of several such journals.While few organizations have the resources to subscribe to every journal containing papers on ICP-OES application,access to these journals is often available through univer-sity libraries and various cooperative loan programs.

Agricultural and Foods

The ICP-OES technique has been applied to the analysis of a large variety of agricultural and food materials.Types of samples include soils,fertilizers,plant materials,feedstuffs,foods,animal tissues,and body fluids.Analyses of these materials are required to determine levels of essential nutrients as well as levels of toxic elements in the materials.

Most agricultural and food materials are generally not in the form of dilute aqueous solutions nor are they readily soluble in distilled water.Therefore,analyses of these materials by ICP-OES often requires that rigorous sample preparation procedures be carried out prior to analysis.Fortunately for the analyst,the use of modern microwave sample digestion techniques is helping to simplify the sample prepara-tion steps for agricultural and food materials as well as many other sample types.  Some typical applications of ICP-OES in this area include determination of trace metals in beer and wine;analysis of infant formula for Ca,Cu,Fe,Mg,Mn,P,K,Na and Zn;determination of country origin of orange juice through trace element analysis;determination of 14 elements in peanuts;and analysis of soils for toxic metal contamination.

Biological and Clinical

As research reveals more information regarding the roles and behaviors of trace elements in biological systems,ICP-OES has become an important tool in the area of biological and clinical applications.Determinations by ICP-OES of essential,toxic and therapeutic trace elements are important in the medical research laboratories as well as in the clinical and forensic lab environments.

Of significant concern regarding trace element determinations in the biological and

clinical fields is the contamination of samples prior to their analysis.While it is always

important to consider sources of contamination when performing trace determina-tions

in any field,the biological and clinical area is particularly susceptible to errors

due to contamination originating in the sample collection and sample preparation

steps.The use of surgical equipment,such as scalpels,needles,scissors,and

forceps,often contaminates the sample with trace quantities of the very elements

being determined in the sample.For this reason,appropriate equipment should be

used to collect,process and store biological and clinical samples before analysis

by ICP-OES.

Many biological and clinical samples are either too small or contain elemental concentrations too low for ICP-OES analysis using conventional pneumatic sample introduction.In these cases,it is often necessary to turn to alternate sample introduction techniques such as ultrasonic nebulization,electrothermal vaporiza-tion, or hydride generation,or preconcentration techniques such as ion exchange or solvent extraction.

Examples of ICP-OES analyses of biological and clinical samples include determi-nations of Cr,Ni and Cu in urine;Al in blood;Cu in brain tissue;Se in liver;Cr in feces;Ni in breast milk;B,P and S in bone;and trace elements in oyster and tuna tissues.

Geological

Geological applications of ICP-OES involve determinations of major,minor and trace compositions of various rocks,soils,sediments,and related materials.The major use of ICP-OES in this field is for prospecting purposes.The technique is also used for applications such as determining origins of rock formations and for marine geochemistry.

Preparation of geological samples for analysis by ICP-OES often involves the use of lithium metaborate fusion reactions,especially for materials containing high levels of silica.Acid dissolutions are also commonly used for many geological materials.  Of major concern for geological applications of ICP-OES is the elimination of residues that may be present following acid digestion or dissolution of a fusion bead.  Careful selection of the nebulizer used with the ICP instrument can help to reduce problems caused by high salt and residue concentrations.  Typical applications of ICP-OES for analysis of geological samples include deter-mination of U in ore grade material;analysis of river sediments for several metals; analysis of carbonate drill cores for major,minor and trace elements;determination of rare earth elements in rock formations;and analysis of plankton for several elements.

Environmental and Waters

The area of environmental analysis is quite a broad topic,covering many different

types of ICP-OES applications.Many of these applications,such as analyses of

soils,sediments,and animal and plant tissues,overlap areas covered previously in

this chapter and will not be addressed in this section.This still leaves a number of

5-4 Concepts,Instrumentation,and Techniques.important environmental ICP-OES applications,not the least of which are the

analyses of various types of water.Other important environmental ICP-OES appli-cations include analyses of sewage sludge,domestic and industrial refuge,coal and coal fly ash,and dust and other airborne particulates.

The analysis of water can be the simplest of all ICP-OES applications,depending on the type of water being analyzed and the required measurement levels and protocols.Fresh waters generally require only that the sample be stabilized with a mineral acid before analysis by ICP-OES.Some waters may require filtering to remove particulates.For analyses requiring very low detection levels,it may be necessary to perform some kind of preconcentration step prior to analysis.Ultra-sonic nebulizers are also useful for improving sensitivity for such analyses.Analyses of sewage sludge,various refuses,and coal and coal fly ash require more rigorous sample preparation while collection of airborne particulates requires use of air filtering techniques.

Examples of environmental ICP-OES applications include various water quality analyses as required by the U.S.Environmental Protection Agency;determination of Fe,Cd,Cu,Mo,Ni,V,and Zn in seawater;determination of phosphorus in municipal wastewater;determination of heavy metals in inner-city dust samples; and trace metal analysis of coal fly ash.

Metals

ICP-OES is used widely for the determination of major,minor and trace elemental constituents in metals and related materials.The technique is used for analysis of raw materials,production control,and quality control for final products as well as in the developmental lab environment.Sample preparation is generally through acid digestions,except for oxide materials which often require use of fusion techniques.  Analysis of metals is also the most likely use of solid sampling techniques such as spark or laser ablation with ICP-OES instruments.

A particular difficulty associated with metals analysis by ICP-OES is the potential for a large number of spectral interferences since many metals exhibit very complex emission spectra.Use of a high-resolution spectrometer and spectral interference correction techniques are often required for metals analyses by ICP-OES.  Some representative applications of ICP-OES for the analysis of metals and related materials include determination of toxic,trace and major constituents in coal and slags;analysis of low alloy steels for As,B,Bi,Ce,La,P,Sn and Ta;high-precision determination of Si in steels;determination of contaminants in high-purity Al;and analysis of superconducting materials for trace contaminants.

Concepts,Instrumentation,and Techniques 5-5.Organics

Analysis of organic solutions by ICP-OES is important not only for analyzing organic-based materials such as petroleum products but also for a wide variety of other applications.For many of the analyses from the other application categories discussed in this chapter,it is necessary to perform sample preparation in which the final form of the analyte is contained in an organic solvent.For example,solvent extraction for the purpose of preconcentrating analyte species is a widely used sample preparation technique for ICP-OES.Also considered under the category of organic analyses would be introduction of organic effluents and vapors from high performance liquid chromatography (HPLC)and gas chromatography (GC)sepa-rations.  While analysis of organics by ICP-OES is generally straightforward,there are often some special requirements.For example,introduction of organic matrices into the ICP discharge usually requires that the ICP be operated at a higher RF power than is normally required for aqueous samples.Sometimes it is also necessary to use special nebulizers or torch injector tubes.When a peristaltic pump is used to transport the sample to the nebulizer,special consideration must be made regarding the chemical resistance of the pump tubing used with respect to the organic solvent.  The analysis of used lubricating oils for trace metal content is one of the more popular applications for organics analysis by ICP-OES.Some other applications include analysis of solvent-extracted geological materials for trace elemental com-position; determination of lead in gasoline;determination of Cu,Fe,Ni,P,Si and V in cooking oils;analysis of organophosphates for trace contaminants;and determi-nation of major and trace elements in antifreeze.