Atomic emission spectrometry with inductively coupled plasma excitation

FAAS atomic absorption spectrometry with flame atomization, ICP-OES atomic emission spectrometry with inductively coupled plasma excitation, GF-AAS atomic absorption spectrometry with graphite furnace atomization, ICP-MS mass spectrometry with inductively coupled plasma ionization... 

Atomic Emission Spectrometry with Inductively Coupled Plasma Excitation (ICP-AES)... 

As shown in the discussion above, there are a multiplicity of desirable and undesirable features of OID s that impact their general application as detectors in analytical atomic emission spectrometry. It is therefore appropriate to compare, in a critical and objective sense, the experimental figures of merit of these devices vis-a-vis the classical polychromator photomultiplier approach. These comparisons should be performed virtually on a continuing basis because of advances in performances, not only of the array detectors themselves but also in the associated spectroscopic excitation sources. An evaluation of the overall performance figures of merit of OID s when they are employed in conjunction with induction-coupled plasma excitation is of particular current interest because of the popularity that this source is attaining for the simultaneous determination of the elements at all concentration levels. In this paper we present such an evaluation for self-scanned, photodiode array detectors... 

Whatever the analytical method and the determinand may be, the greatest care should be devoted to the proper selection and use of internal standards, careful preparation of blanks and adequate calibration to avoid serious mistakes. Today the Antarctic investigator has access to a multitude of analytical techniques, the scope, detection power and robustness of which were simply unthinkable only two decades ago. For chemical elements they encompass Atomic Absorption Spectrometry (AAS) [with Flame (F) and Electrothermal Atomization (ETA) and Hydride or Cold Vapor (HG or CV) generation]. Atomic Emission Spectrometry (AES) [with Inductively Coupled Plasma (ICP), Spark (S), Flame (F) and Glow Discharge/Hollow Cathode (HC/GD) emission sources], Atomic Fluorescence Spectrometry (AFS) [with HC/GD, Electrodeless Discharge (ED) and Laser Excitation (LE) sources and with the possibility of resorting to the important Isotope... 

There is also a standard test method for determination of major and minor elements in coal ash by inductively coupled plasma (ICP)-atomic emission spectrometry (ASTM D-6349). In the test method, the sample to be analyzed is ashed under standard conditions and ignited to constant weight. The ash is fused with a fluxing agent followed by dissolution of the melt in dilute acid solution. Alternatively, the ash is digested in a mixture of hydrofluoric, nitric, and hydrochloric acids. The solution is analyzed by (ICP)-atomic emission spectrometry for the elements. The basis of the method is the measurement of atomic emissions. Aqueous solutions of the samples are nebulized, and a portion of the aerosol that is produced is transported to the plasma torch, where excitation and emission occurs. Characteristic line emission spectra are produced by a radio-frequency inductively coupled plasma. A grating monochromator system is used to separate the emission lines, and the intensities of the lines are monitored by photomultiplier tube or photodiode array detection. The photocurrents from the detector... 

An inductively-coupled plasma (ICP) is an effective spectroscopic excitation source, which in combination with atomic emission spectrometry (AES) is important in inorganic elemental analysis. ICP was also considered as an ion source for MS. An ICP-MS system is a special type of atmospheric-pressure ion source, where the liquid is nebulized into an atmospheric-pressure spray chamber. The larger droplets are separated from the smaller droplets and drained to waste. The aerosol of small droplets is transported by means of argon to the torch, where the ICP is generated and sustained. The analytes are atomized, and ionization of the elements takes place. Ions are sampled through an orifice into an atmospheric-pressure-vacuum interface, similar to an atmospheric-pressure ionization system for LC-MS. LC-ICP-MS is extensively reviewed, e.g., [12]. 

In the last 20 years atomic spectroscopy has made great strides, particularly with the introduction of new improved optic designs and detection methods. These improvements have led to superior resolution of the wavelengths of the excited atoms and detection techniques measuring lower levels of metals with ease. After a slow and problematic start, inductively coupled plasma optical emission spectrometry (ICP-OES) has become an established technique in most laboratories analysing a wide range of sample matrices reporting accurate and precise results. 

This chapter deals with optical atomic, emission spectrometry (AES). Generally, the atomizers listed in Table 8-1 not only convert the component of samples to atoms or elementary ions but, in the process, excite a fraction of these species to higher electronic stales.. 4, the excited species rapidly relax back to lower states, ultraviolet and visible line spectra arise that are useful for qualitative ant quantitative elemental analysis. Plasma sources have become, the most important and most widely used sources for AES. These devices, including the popular inductively coupled plasma source, are discussedfirst in this chapter. Then, emission spectroscopy based on electric arc and electric spark atomization and excitation is described. Historically, arc and spark sources were quite important in emission spectrometry, and they still have important applications for the determination of some metallic elements. Finally several miscellaneous atomic emission source.s, including jlanies, glow discharges, and lasers are presented. 

Inductively coupled plasma atomic emission spectrometry (ICP-AES) involves a plasma, usually argon, at temperatures between 6000 and 8000 K as excitation source. The analyte enters the plasma as an aerosol. The droplets are dried, desol-vated, and the matrix is decomposed in the plasma. In the high-temperature region of the plasma, molecular, atomic, and ionic species in various energy states are formed. The emission lines can then be exploited for analytical purposes. Typical detection limits achievable for arsenic with this technique are 30 J,g As/L (23). Due to the rather high detection limit, ICP-AES is not frequently used for the determination of arsenic in biological samples. The use of special nebulizers, such as ultrasonic nebulization, increases the sample transport efficiency from 1-2% (conventional pneumatic nebulizer) to 10-20% and, therefore, improves the detection limits for most elements 10-fold. In addition to the fact that the ultrasonic nebulizer is rather expensive, it was reported to be matrix sensitive (24). Inductively coupled plasma atomic emission spectrometry is known to suffer from interferences due to the rather complex emission spectrum consisting of atomic as... 

Figure 1 Eiectron sheii configurations in terms of energy ieveis. Arrows depict permissibie transitions by absorption and excitation (ascending) or radiation and photon emission (descending), a and b represent excitation, c is ionization, d is ionization pius excitation, e is ion emission, and f, g, and h are atom emissions. (Reproduced with permission from Boss CB and Freeden KJ (1989) Concepts, instrumentation and Techniques. Inductively Coupled Plasma Atomic Emission Spectrometry, Perkin Eimer Corp.)...

Minute amounts of sample material ablated with the focused radiation of a pulsed laser are transported into an independent excitation source, e.g., inductively coupled plasma (ICP) for further atomization, excitation, or ionization. The detection of target atoms after laser ablation (LA) is performed by hyphenated techniques using optical emission or mass spectrometry LA-ICP-OES laser ablation-lCP-optical emission spectroscopy LA-ICP-MS laser ablation-l CP-mass spectrometry... 

Preferred methods in trace determination of the elements include atomic absorption spectrometry (AAS), optical emission spectrometry (OES) with any of a wide variety of excitation sources [e.g., sparks, arcs, high-frequency or microwave plasmas (inductively coupled plasma, ICP microwave induced plasma, MIP capacitively coupled micro-wave plasma, CMP), glow discharges (GD). hollow cathodes, or laser vaporization (laser ablation)], as well as mass spectrometry (again in combination with the various excitation sources listed), together with several types of X-ray fluorescence (XRF) analysis [51]. 

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