Spectral interference correction

The best way to avoid spectral interferences is to separate interfering elements before the measurement (see Chapter 5), to separate the interfering species by high resolution (HR) capabilities (Chapter 2) or to remove the interference by collision/reaction ceU technology (Chapter 8). 

Inductively Coupled Plasma Mass Spectrometry Handbook 

Quite often these possibilities are not available or not applicable, either due to a lack of appropriate technology or financial or personnel constraints. The following section covers how isobaric and molecular interferences can be corrected for under these circumstances. 

In ICP-MS measurements, interferences caused by an isobaric overlap of another element p are corrected by the following equation  

In this equation the index al represents the interfered isotope of the element a while the index p 1 represents the interfering isotope of element p. /fpi/pa represents the measured isotope amount ratio P l/p2, where P2 is a non-interfered isotope of element p. Since the interference is present, this ratio cannot be accurately measured in the sample and therefore has to be replaced with a value derived from an alternative source. Most ICP-MS instruments simply replace the ratio I3i/I32 by the reported lUPAC ratio value. ° They do not consider mass discrimination effects, despite the fact that equation (4.1) only deals with measured intensities, which are intrinsically affected by mass discrimination. For measurements requiring higher accuracy, especially isotope ratio measurements, this fact has to be taken into account and the interference correction has to be modified accordingly. 

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Although their resolving capability is far more powerful than quadrupole-based instruments, there is a sacrifice in sensitivity if extremely high resolution is used, which can often translate into a degradation in detection capability for some elements, compared to other spectral interference correction approaches. A full review of magnetic sector technology for ICP-MS is given in Chapter 8. 

The empiricid method of spectral interference correction uses interference correction factors. These factors are determined by analyzing the ngle-element, high-purity solutions under conditions matching as closely as possible those used for test specimen analysis. Unless plasma conditions can be accurately reproduced from day to day, or for longer periods, interference correction factors found to affect the results significantly must be redetermined each time specimens are analyzed. 

An important question to consider when using a flame as an atomization source, is how to correct for the absorption of radiation by the flame. The products of combustion consist of molecular species that may exhibit broad-band absorption, as well as particulate material that may scatter radiation from the source. If this spectral interference is not corrected, then the intensity of the transmitted radiation decreases. The result is an apparent increase in the sam-... 

Minimizing Spectral Interferences The most important spectral interference is a continuous source of background emission from the flame or plasma and emission bands from molecular species. This background emission is particularly severe for flames in which the temperature is insufficient to break down refractory compounds, such as oxides and hydroxides. Background corrections for flame emission are made by scanning over the emission line and drawing a baseline (Figure 10.51). Because the temperature of a plasma is... 

To produce an analytical method, the operator must select the power level of the plasma, the wavelength for each element (preferably free from spectral interferences), and the vewing height at which the plasma is to be seen for each element. Further, it may be necessary to apply background correction intervals are set using the graphics capability. 

Analyte dilution sacrifices sensitivity. Matrix matching can only be applied for simple matrices, but is clearly not applicable for complex matrices of varying composition. Accurate correction for matrix effect is possible only if the IS is chosen with a mass number as close as possible to that of the analyte elements). Standard addition of a known amount of the element(s) of interest is a safe method for samples of unknown composition and thus unknown matrix effect. Chemical separations avoid spectral interference and allow preconcentration of the analyte elements. Sampling and sample preparation have recently been reviewed [4]. 

Practically all classical methods of atomic spectroscopy are strongly influenced by interferences and matrix effects. Actually, very few analytical techniques are completely free of interferences. However, with atomic spectroscopy techniques, most of the common interferences have been studied and documented. Interferences are classified conveniently into four categories chemical, physical, background (scattering, absorption) and spectral. There are virtually no spectral interferences in FAAS some form of background correction is required. Matrix effects are more serious. Also GFAAS shows virtually no spectral interferences, but... 

Spectral interferences may arise from the close proximity of other emission lines or bands to the analyte line or by overlap with it. They can often be eliminated or minimized by increasing the resolution of the instrumentation, e.g. changing from a filter photometer to a grating spectrophotometer. Alternatively, another analyte line can be selected for measurements. Correction for background emission is also important and is made by monitoring the emission from a blank solution at the wavelength of the analyte line or by averaging measurements made close to the line and on either side of it. 

Interferences in atomic absorption measurements can arise from spectral, chemical and physical sources. Spectral interference resulting from the overlap of absorption lines is rare because of the simplicity of the absorption spectrum and the sharpness of the lines. However, broad band absorption by molecular species can lead to significant background interference. Correction for this may be made by matrix matching of samples and standards, or by use of a standard addition method (p. 30 et seq.). 

Instrumental correction for background absorption using a double beam instrument or a continuum source has already been discussed (p. 325). An alternative is to assess the background absorption on a non-resonance line two or three band-passes away from the analytical line and to correct the sample absorption accordingly. This method assumes the molecular absorption to be constant over several band passes. The elimination of spectral interference from the emission of radiation by the heated sample and matrix has been discussed on page 324 et seq. 

Kola H, Peramaki P, Valimaki I. Correction of spectral interferences of calcium in sulfur determination by inductively coupled plasma optical emission spectroscopy using multiple hnear regression. J. Anal. At. Spectrom. 2002 17 104-108. 

H. Martens and E. Stark, Extended multiplicative signal correction and spectral interference subtraction new preprocessing methods for near infrared spectroscopy, J. Pharm. Biomed. Anal, 9, 625-35 (1991). 

The method of standard additions is a useful procedure for checking the accuracy of a determination and overcoming interferences when the composition of the sample is unknown. It should be noted that the method cannot be used to correct for spectral interferences and background changes. At least three aliquots of the sample are taken. One is left untreated to the others known additions of the analyte are made. The additions should preferably be about 0.5x, x and 2x, where x is the concentration of the unknown. It should also be noted that the volume of the addition should be negligible in comparison with the sample solution. This is to prevent dilution effects... 

Spectral interferences from the overlap of molecular bands and lines (e g. the calcium hydroxide absorption band on barium at 553.55 nm) cannot be so easily dismissed. Lead seems to be particularly prone to such non-specific absorption problems at the 217.0 nm line (e g. sodium chloride appears to give strong molecular absorption at this wavelength). This type of problem is encountered in practical situations, but can sometimes be removed by the technique of background correction (see Section 2.2.5.2). 

Spectral interferences. These interferences result from the inability of an instrument to separate a spectral line emitted by a specific analyte from light emitted by other neutral atoms or ions. These interferences are particularly serious in ICP-OES where atomic spectra are complex because of the high temperatures of the ICP. Complex spectra are most troublesome when produced by the major constituents of a sample. This is because spectral lines from other analytes tend to be overlapped by lines from the major elements. Examples of elements that produce complex line spectra are Fe, Ti, Mn, U, the lanthanides and noble metals. To some extent, spectral complexity can be overcome by the use of high-resolution spectrometers. However, in some cases the only choice is to select alternative spectral lines from the analyte or use correction procedures. 

An alternative to quantitative analysis by ICP-MS is semiquantitative analysis, which is generally considered as a rapid multielement survey tool with accuracies in the range 30-50%. Semiquantitative analysis is based on the use of a predefined response table for all the elements and a computer program that can interpret the mass spectrum and correct spectral Interferences. This approach has been successfully applied to different types of samples. The software developed to perform semiquantitative analysis has evolved in parallel with the instrumentation and, today, accuracy values better than 10% have been reported by several authors, even competing with typical ones obtained by quantitative analysis. The development of a semiquantitative procedure for multielemental analysis with ICP-MS requires the evaluation of the molar response curve in the ICP-MS system (variation of sensitivity as a function of the mass of the measured isotope) [17]. Additionally, in the development of a reliable semiquantitative method, some mathematical approaches should be employed in order to estimate the ionisation conditions in the plasma, its use to correct for ionisation degrees and the correction of mass-dependent matrix interferences. 

ETAAS was also combined with PLS by Baxter et al. [76] to determine As in marine sediments. They demonstrated that the classical standard additions method does not correct for spectral interferences (their main problem) because of mutual interactions between the two analytes of interest (As and Al). PLS-2 block was applied to quantify simultaneously both elements (PLS-2 block is the notation for the PLS regression when several analytes are predicted simultaneously it is not widely applied, except when the analytes are... 

Z. Zhang and X. Ma, Methods for correction of spectral interferences in inductively coupled plasma atomic emission spectrometry, Ciirr. Top. Anal. Chem., 3, 2002, 105-123. 

Spectral interferences, such as line overlaps, are prevalent and must be corrected for accurate quantitative analysis. With a scanning instrument it may be possible to move to an interference free line. With a direct reader, sophisticated computer programs apply mathematical corrections based on factors previously determined on multi-element standards. 

Martens, H. and Stark, E., Extended Multiplicative Signal Correction and Spectral Interference Subtraction New Preprocessing Methods for Near Infrared Spectroscopy /. Pharm. Biomed. 

Several types of interference effects may contribute to inaccuracies in the determination of major and minor elements. The interferences can be classified as spectral, physical, and chemical. Spectral interferences involve an overlap of a spectral line from another element, unresolved overlap of molecular band spectra, background contribution from continuous or recombination phenomena, and background contribution from stray light from the line emission of high-concentration elements. The second effect may require selection of an alternative wavelength. The third and fourth effects can usually be compensated by a background correction adjacent to the analyte line. 

Spectral interferences from ion-atom recombination, spectral line overlaps, molecular band emission, or stray light can occur that may alter the net signal intensity. These can be avoided by selecting alternate analytical wavelengths and making background corrections. 

To reduce the detrimental effects of spectral interferences on element quantitation, laboratories select the spectral lines that are least affected by the background, and use the background compensation and interelement correction routines as part of the analytical procedure. The instrument software uses equations to compensate for overlapping spectral lines the effectiveness of these equations in eliminating spectral interferences must be confirmed at the time of sample analysis. That is why laboratories analyze a daily interelement correction standard (a mixture of all elements at a concentration of 100mg/l) to verify that the overlapping lines do not cause the detection of elements at concentrations above the MDLs. 

An alternative to MSA in ICP-MS analysis is the internal standard technique. One or more elements not present in the samples and verified not to cause an interelement spectral interference are added to the digested samples, standards, and blanks. Yttrium, scandium, and other rarely occurring elements or isotopes are used for this purpose. Their response serves as an internal standard for correcting the target analyte response in the calibration standards and for target analyte quantitation in the samples. This technique is very useful in overcoming matrix interferences, especially in high solids matrices. 

With this technique, problems may arise with interference, such as background absorption—the nonspecific attenuation of radiation at the analyte wavelength caused by matrix components. To compensate for background absorption, correction techniques such as a continuous light source (D2-lamp) or the Zeeman or Smith-Hieftje method should be used. Enhanced matrix removal due to matrix modification may reduce background absorption. Nonspectral interference occurs when components of the sample matrix alter the vaporization behavior of the particles that contain the analyte. To compensate for this kind of interference, the method of standard addition can be used. Enhanced matrix removal by matrix modification or the use of a L vov platform can also reduce nonspectral interferences. Hollow cathode lamps are used for As, Cu, Cr, Ni, Pb, and Zn single-element lamps are preferred, but multielement lamps may be used if no spectral interference occurs. 

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