Chemical interferences, atomic

Minimizing Chemical Interferences The quantitative analysis of some elements is complicated by chemical interferences occurring during atomization. The two most common chemical interferences are the formation of nonvolatile compounds containing the analyte and ionization of the analyte. One example of a chemical interference due to the formation of nonvolatile compounds is observed when P04 or AP+ is added to solutions of Ca +. In one study, for example, adding 100 ppm AP+ to a solution of 5 ppm Ca + decreased the calcium ion s absorbance from 0.50 to 0.14, whereas adding 500 ppm POp to a similar solution of Ca + decreased the absorbance from 0.50 to 0.38. These interferences were attributed to the formation of refractory particles of Ca3(P04)2 and an Al-Ca-O oxide. 

Accuracy When spectral and chemical interferences are minimized, accuracies of 0.5-5% are routinely possible. With nonlinear calibration curves, higher accuracy is obtained by using a pair of standards whose absorbances closely bracket the sample s absorbance and assuming that the change in absorbance is linear over the limited concentration range. Determinate errors for electrothermal atomization are frequently greater than that obtained with flame atomization due to more serious matrix interferences. 

Atomic emission is used for the analysis of the same types of samples that may be analyzed by atomic absorption. The development of a quantitative atomic emission method requires several considerations, including choosing a source for atomization and excitation, selecting a wavelength and slit width, preparing the sample for analysis, minimizing spectral and chemical interferences, and selecting a method of standardization. 

Choice of Atomization and Excitation Source Except for the alkali metals, detection limits when using an ICP are significantly better than those obtained with flame emission (Table 10.14). Plasmas also are subject to fewer spectral and chemical interferences. For these reasons a plasma emission source is usually the better choice. 

When possible, quantitative analyses are best conducted using external standards. Emission intensity, however, is affected significantly by many parameters, including the temperature of the excitation source and the efficiency of atomization. An increase in temperature of 10 K, for example, results in a 4% change in the fraction of Na atoms present in the 3p excited state. The method of internal standards can be used when variations in source parameters are difficult to control. In this case an internal standard is selected that has an emission line close to that of the analyte to compensate for changes in the temperature of the excitation source. In addition, the internal standard should be subject to the same chemical interferences to compensate for changes in atomization efficiency. To accurately compensate for these errors, the analyte and internal standard emission lines must be monitored simultaneously. The method of standard additions also can be used. 

Accuracy When spectral and chemical interferences are insignificant, atomic emission is capable of producing quantitative results with accuracies of 1-5%. Accuracy in flame emission frequently is limited by chemical interferences. Because the higher temperature of a plasma source gives rise to more emission lines, accuracy when using plasma emission often is limited by stray radiation from overlapping emission lines. 

Sensitivity Sensitivity in flame atomic emission is strongly influenced by the temperature of the excitation source and the composition of the sample matrix. Normally, sensitivity is optimized by aspirating a standard solution and adjusting the flame s composition and the height from which emission is monitored until the emission intensity is maximized. Chemical interferences, when present, decrease the sensitivity of the analysis. With plasma emission, sensitivity is less influenced by the sample matrix. In some cases, for example, a plasma calibration curve prepared using standards in a matrix of distilled water can be used for samples with more complex matrices. 

The production of ground-state gaseous atoms which is the basis of flame spectroscopy may be inhibited by two main forms of chemical interference (a) by stable compound formation, or (b) by ionisation. 

Atomic absorption takes advantage of the fact that most of the atoms remain in the ground state, and are capable of absorbing radiation of the appropriate wavelength corresponding to Ah. Whereas a hot flame is preferred for flame photometry, a cooler flame is preferred for atomic absorption, except in cases where chemical interference may occur. 

Table 1 lists the temperatures of some commonly used flames for atomic absorption. A cool flame such as argon-hydrogen-entrained air or air-coal gas is usually not preferred because of increased danger of chemical interferences (see below). The most commonly used flame is the air-acetylene flame. 

There are a number of interferences that can occur in atomic absorption and other flame spectroscopic methods. Anything that decreases the number of neutral atoms in the flame will decrease the absorption signal. Chemical interference is the most commonly encountered example of depression of the absorption signal. Here, the element of interest reacts with an anion in solution or with a gas in the flame to produce a stable compound in the flame. For example, calcium, in the presence of phosphate, will form the stable pyrophosphate molecule. Refractory elements will combine with 0 or OH radicals in the flame to produce stable monoxides and hydroxides. Fortunately, most of these chemical interferences can be avoided by adding an appropriate reagent or by using a hotter flame. The phosphate interferences, for example, can be eliminated by adding 1 % strontium chloride or lanthanum chloride to the solution. The strontium or lanthanum preferentially combines with the phosphate to prevent its reaction with the calcium. Or, EDTA can be added to complex the calcium and prevent its combination with the phosphate. 

Flameless atomic absorption spectrometric techniques offer a high sensitivity (5xl0 ug Se) but are not simple nor free from interference, due to the high volatility of selenium. This technique is suitable specially for direct analysis of samples and its additional advantage lies in possibilities of chemical treatment of samples in the graphite cell in order to diminish chemical interferences. 

One notable chemical interference occurs when atomization is hindered due to an unusually strong ionic bond between the ions in the ionic formula unit. A well-known example occurs in the analysis of a sample for calcium. The presence of sulfate or phosphate in the sample matrix along with the calcium suppresses the reading for calcium because of limited atomization due to the strong ionic bond between calcium and the sulfate and phosphate ions. This results in a low reading for the calcium in the sample in which this interference exists. The usual solution to this problem is to add a substance to the sample that would chemically free the element being analyzed, calcium in our example, from the interference. 

Examples (/ ) Chemical Interferences due to Anion (P04 ) Phosphate ions have been found to interfere with determination of Mg and Ca by AAS. The absorption due to Mg and Ca are appreciably weaker in the presence of P043 ions than in their absence. This is evidently on account of the formation of fairly stable phosphates of Mg and Ca which do not readily split-up into the respective atoms in the mantle of a flame. 

Chemical Interference due to Cations In certain specific cases cations also interfere in atomic absorption measurements, for instance Boron interferes with Mg and Ca whereas aluminium interferes with alkaline earth elements. 

Flame atomic absorption spectrometry can be used to determine trace levels of analyte in a wide range of sample types, with the proviso that the sample is first brought into solution. The methods described in Section 1.6 are all applicable to FAAS. Chemical interferences and ionization suppression cause the greatest problems, and steps must be taken to reduce these (e.g. the analysis of sea-water, refractory geological samples or metals). The analysis of oils and organic solvents is relatively easy since these samples actually provide fuel for the flame however, build-up of carbon in the burner slot must be avoided. Most biological samples can be analysed with ease provided that an appropriate digestion method is used which avoids analyte losses. 

There has been interest in the low radiative background, low quenching argon-hydrogen diffusion flame. The temperature of this flame is too low to prevent severe chemical interferences and therefore the argon-separated air-acetylene flame has been most widely used. The hot nitrous oxide-acetylene flame (argon separated) has been used where atomization requirements make it essential. In all cases, circular flames, sometimes with mirrors around them, offer the preferred geometry. 

Chemical interference is caused by any component of the sample that decreases the extent of atomization of analyte. For example, SO and PO hinder the atomization of Ca2+, perhaps by forming nonvolatile salts. Releasing agents are chemicals that are added to a sample to decrease chemical interference. EDTA and 8-hydroxyquinoline protect Ca2+ from the interfering effects of SO and PO. La3+ also can be used as a releasing agent, apparently because it preferentially reacts with PO and frees the Ca2+. A fuel-rich flame reduces certain oxidized analyte species that would otherwise hinder atomization. Higher flame temperatures eliminate many kinds of chemical interference. 

Chemical interferences arise from the formation of thermally stable compounds such as oxides in the flame. The use of electrothermal atomization, a hotter nitrous oxide-acetylene flame or the addition of a releasing agent such as lanthanum can help reduce the interference. 

Metals can be conveniently determined by emission spectroscopy using inductively coupled plasma (ICP). A great advantage of ICP emission spectroscopy as applied to environmental analysis is that several metals can be determined simultaneously by this method. Thus, multielement analysis of unknown samples can be performed rapidly by this technique. Another advantage is that, unlike atomic absorption spectroscopy, the chemical interference in this method is very low. Chemical interferences are generally attributed to the formation of molecular compounds (from the atoms) as well as to ionization and thermochemical effects. The principle of the ICP method is described below. 

Chemical interferences take place in FLAA analysis when atoms are bound into... 

Although the problem of oxide formation is greatly reduced in GFAA analysis because atomization occurs in an inert atmosphere, the technique is nevertheless susceptible to chemical interferences. The chemical composition of the sample matrix can have a major effect on the analysis, and the magnitude of this effect must be determined and taken into consideration in the analysis of each new, unknown or a particularly complex matrix. 

In atomic absorption spectroscopy (AAS) both ionization and chemical interferences may occur. These interferences are caused by other ions in the sample and result in a reduction of the number of neutral atoms in the flame. Ionization interference is avoided by adding a relatively high amount of an easily ionized element to the samples and calibration solutions. For the determination of sodium and potassium, cesium is added. To eliminate chemical interferences from, for example, aluminum and phosphate, lanthanum can be added to the samples and calibration solutions. 

In the framework of the currently developing concept of chemical interference, of primary interest are co-factors transferring chemical groups, hydrogen atoms or electrons. 

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