Atomic emission spectrometry detection limits

The section on Spectroscopy has been retained but with some revisions and expansion. The section includes ultraviolet-visible spectroscopy, fluorescence, infrared and Raman spectroscopy, and X-ray spectrometry. Detection limits are listed for the elements when using flame emission, flame atomic absorption, electrothermal atomic absorption, argon induction coupled plasma, and flame atomic fluorescence. Nuclear magnetic resonance embraces tables for the nuclear properties of the elements, proton chemical shifts and coupling constants, and similar material for carbon-13, boron-11, nitrogen-15, fluorine-19, silicon-19, and phosphoms-31. 

Plasma sources were developed for emission spectrometric analysis in the late-1960s. Commercial inductively coupled and d.c. plasma spectrometers were introduced in the mid-1970s. By comparison with AAS, atomic plasma emission spectroscopy (APES) can achieve simultaneous multi-element measurement, while maintaining a wide dynamic measurement range and high sensitivities and selectivities over background elements. As a result of the wide variety of radiation sources, optical atomic emission spectrometry is very suitable for multi-element trace determinations. With several techniques, absolute detection limits are below the ng level. 

Conventional ICP-AES has similar detection limits to FA AS (although inferior to those of ICP-MS) and is much faster when many elements are determined in the same sample. The detection limits of modem, fast ICP-AES are equal to those of conventional, slow GFAAS. Table 8.31 compares the detection power of various atomic emission spectrometries. The greater... 

Boumans PWJM (1994) Detection limits and spectral interferences in atomic emission spectrometry. Anal Chem 66 459A... 

Brenner et al. [ 169] applied inductively coupled plasma atomic emission spectrometry to the determination of calcium (and sulfate) in brines. The principal advantage of the technique was that it avoided tedious matrix matching of calibration standards when sulfate was determined indirectly by flame techniques. It also avoided time-consuming sample handling when the samples were processed by the gravimetric method. The detection limit was 70 ig/l and a linear dynamic range of 1 g/1 was obtained for sulfate. 

The extension of inductively coupled plasma (ICP) atomic emission spectrometry to seawater analysis has been slow for two major reasons. The first is that the concentrations of almost all trace metals of interest are 1 xg/l or less, below detection limits attainable with conventional pneumatic nebulisation. The second is that the seawater matrix, with some 3.5% dissolved solids, is not compatible with most of the sample introduction systems used with ICP. Thus direct multielemental trace analysis of seawater by ICP-AES is impractical, at least with pneumatic nebulisation. In view of this, a number of alternative strategies can be considered ... 

Silicon has been determined directly in seawater by inductively coupled plasma atomic emission spectrometry with a detection limit of 0.3 xm silicon [42],... 

Arc/spark emission methods have been widely used for the determination of metals and some non-metals particularly as minor and trace constituents. In recent years, however, the technique has been extensively displaced by atomic absorption spectrometry, and plasma emission methods. Detection limits for many elements are of the order of 1-10 ppm (Table 8.3) and as... 

These methods were used to determine arsenic in certified sediments (Table 12.15). Conventional inductively coupled plasma atomic emission spectrometry is satisfactory for all types of samples, but its usefulness was limited to concentrations of arsenic greater than 5pg g-1 dry weight. Better detection limits were achieved using the flow-injection-hydride generation inductively coupled plasma technique in which a coefficient of variation of about 2% for concentrations of lOpg g 1 were achieved. 

In the test method, the coal or coke to be analyzed is ashed under controlled conditions, digested by a mixture of aqua regia and hydrofluoric acid, and finally dissolved in 1% nitric acid. The concentration of individual trace elements is determined by either inductively coupled plasma-atomic emission spectrometry (ICPAES) or inductively coupled plasma-mass spectrometry (ICPMS). Selected elements that occur at concentrations below the detection limits of ICPAES can be analyzed quantitatively by graphite furnace atomic absorption spectrometry (GFAA). 

Inductively coupled plasma atomic emission spectrometry has proved to be an excellent technique for the direct analysis of soil extracts because it is precise, accurate and not time-consuming, the level of matrix interference being very low. Of course, the graphite furnace technique yields better detection limits than the inductively coupled plasma procedure. 

IATA ICAP ICP ICP-AES ICP-MS ICV ID IDL IDW ISO International Air Transportation Association inductively coupled argon plasma inductively coupled plasma inductively coupled plasma-atomic emission spectrometry inductively coupled plasma-mass spectrometry initial calibration verification identification instrument detection limit investigation-derived waste International Standardization Organization... 

This method was developed as a second, independent method to complement the usual colorimetric procedure in the determination of a certified concentration of dissolved silica in a planned seawater reference material. Ion exclusion affords a separation of the dissolved silica not only from the major seawater cations but also from potentially interfering anions. The detection limit, conservatively estimated at 2.3ng g 1 as Si (0.08pM), is superior to that achievable by direct analysis by inductively coupled plasma atomic emission spectrometry. 

De la Calle Guntinas et al. [769] volatilised selenium from natural water samples by reaction with sodium tetraethylborate and measured the volatilised selenium by gas chromatography microwave-induced plasma atomic emission spectrometry. The detection limit for a 5mL sample was 8ppt. 

For clcmcnt-speciPc detection in GC, a number of dedicated spectrometric detection techniques can be used, for example, quartz furnace AAS or atomic Bu-orescence spectrometry (AFS) for Hg, or microwave-induced plasma atomic emission spectrometry (MIP-AES) for Pb or Sn. However, ICP-MS is virtually the only technique capable of coping, in the on-line mode, with the trace element concentrations in liquid chromatography (LC) and capillary electrophoresis (CE) efBuents. The femtogram level absolute LoDs may still turn out to be insufficient if an element present at the nanogram per milliliter level splits into a number of species, or when the actual amount of sample analyzed is limited to some nanoliters as in the case of CE or nanoBow HPLC. The isotope spcciPcity of ICP-MS offers a still underexploited potential for tracer studies and for improved accuracy via isotope dilution analysis. 

The low detection limits, relative lack of interference and broad linear domain of the measurements obtained with the ICP cleaiiy proved the superiority of this emission source over those previously used in analysis by atomic emission spectrometry. Since then, research on plasmas for use in analysis has continued to expand and the technique has continued to be developed. 

An ultrasonic nebulizer has been designed and used for inductively coupled plasma atomic emission spectrometry [60] and microwave induced plasma-atomic emission spectrometry [61]. The apparatus is inexpensive and can be operated conveniently. Using this nebulizer, the detection limits of many elements, such as phosphorus, aluminum, and silver, were much reduced compared with the limits obtained using an aerodynamic nebulizer [62-64], The ultrasonic nebulizer was found to be suitable for samples which have a high salt concentration. 

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