Microchemical Journal 63, 344 355 (1999) Article ID mchj.1999.1800, available online at http://www.idealibrary.

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Compensation of Ca and Na Interference Effects in Axially and Radially Viewed Inductively Coupled Plasmas
I. B. Brenner,* ,1 A. Le Marchand, C. Daraed, and L. Chauvet
*Environmental Analytical Laboratory, Ben Gurion University, Beersheva, Israel; and Jobin Yvon-Horiba, 16 18 rue du Canal, 91160 Longjumeau Cedex, France Received December 7, 1998; accepted July 1, 1999 The linear relationship between Ca and Na interferences and energy potentials for a wide range of atomic and ionic lines is used to compensate for variable intensity suppression in robust axially and radially viewed inductively coupled plasmas (ICPs). In the axial conguration, intensity attenuation varied from 0 to 40% in the presence of 0.5% Ca and Na. In the radially viewed ICP, interferences were smaller, varying from 5 to 15% for 0.5% Na and from 10 to 30% for 0.5% Ca. Signal attenuation was broadly a linear function of the energies of the spectral lines. These linear functions were estimated by using spectral lines covering the energy range from Sb I 206.833 (5.98 eV), Y II 371.209 and Sc II 361.384 (9.9 eV), Sc II 255.237 (11.42 eV), and Be II 313.042 (13.28 eV) nm. These functions were then used as variable internal standards to compensate for Ca, Na, and mixed CaNa matrix effects. Whereas analyte recoveries without compensation varied from about 40 to 90%, they varied mostly from 100 5% when these functions were used. In the presence of Ca and Na, the Mg II 280.270/Mg I 285.213 nm intensity ratio decreased from about 12 for an aqueous solution to 9 at 1.5 kW. Such values conrm that the radially and axially viewed ICPs were robust. 1999 Academic
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INTRODUCTION The axially viewed inductively coupled plasma with atomic emission (ICP-AES) has become accepted for the analysis of environmental samples owing to the 2- to 20-fold improvement in limits of detection (19). However, solute vaporization and easily ionized element (EIEs) interference effects in the cool plasma fringe can accompany this detection advantage. Sweeping the tail ame where these interferences predominate has diminished these effects. EIE and Ca interferences have also been subdued by increasing the robustness of the ICP, i.e., increasing rf power ( 1.2 kW), decreasing the aerosol ow rate ( 0.8 L/min), and employing a wide central torch injector ( 2 mm) (713). Despite plasma robustness, it has been observed that spectral line intensities decrease with increasing Na and in particular Ca concentration (8). It has also been shown that high-energy ion lines are more prone to interference than low-energy ion and atomic lines (6 9, 14 16). The impact of these matrix effects is important in the analysis of geological, environmental, and biological samples. In these applications, EIE and Ca contents vary considerably and unpredictably. Consequently, the composition of samples can differ markedly from the calibration standards, resulting in analytical bias. Therefore, matrix-match calibration procedures cannot be realistically applied. What is needed is a versatile procedure for compensating the variable effects of these concomitants.
1

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Internal standardization has been used widely in ICP-AES to improve precision and accuracy. The use of a single internal standard to compensate for physical effects in the sample introduction system has been widely reported in the literature (8, 13, 1723). Brenner and co-workers (8, 20 22) used a Sc ion line for the multielement geoanalysis using a wide range of ICP spectrometers. The % RSDs were improved by up to one order of magnitude. Mermet and Ivaldi (17) used real-time internal standardization employing a segmented-array charge-coupled-device (SCCD) ICP spectrometer. Precision improvements up to a factor of 3 were obtained using a Sc ion line as the internal standard. Mermet concluded that a single spectral line fully compensates for intensity variations when the energy potentials of the analyte lines are similar to that of the internal standard. However, the efcacy for compensating matrix effects was not evaluated. Ivaldi and Tyson (18) used a similar instrumental setup with an axially viewed ICP. With Y II 371.030 nm as the internal standard, % RSDs for ion lines were improved by factors of 4 and amounted to 0.1 0.2%. However, RSDs for atom lines were not as good and varied from 0.2 to 0.7%. Compensation of plasma-related matrix effects was not investigated. Dubuisson et al. (13) and Romero et al. (19) demonstrated that a single internal standard could be used to compensate for Na-induced ionic spectral line intensity suppressions in a robust ICP. It was concluded that these variations, originating in the aerosol generation system, could be compensated by a single internal standard. However, none of these studies included the effect of Ca, which is an important element in environmental analysis and geoanalysis. Other investigators described the use of single internal standards to compensate for matrix effects. Brenner et al. (20 22) and Myers and Tracy (23) observed that EIE interference effects were markedly compensated when Sc II was used as the internal standard. Brenner et al. (8) used a single ionic line of Sc to improve the accuracy of determinations in the presence of Na and Ca using a robust axially viewed ICP. Variable interference effects were only partly compensated with this approach. Thus, several internal standards are required for improving accuracy. Ramsey and Thompson (14) performed high-accuracy analysis by ICP-AES using a parameter-related internal standard method (PRISM). This procedure compensated for systematic and random variations in the determination of major and minor elements in silicate rocks using Cd and Rb as the internal standards. However, the calibration standards were similar to the samples and the large concentration of Li (samples were fused with Li metaborate) probably acted as a buffer. Thompson and Ramsey (15, 16) evaluated matrix effects of Ca and other concomitants on ionic and atomic spectral lines differing in energy potentials (from 7.9 to 15.5 eV) in a radially viewed ICP. In the case of Ca, the linear correlation of line suppression and energy potential was very signicant. They concluded that the energy-dependent relationship was mainly due to a decrease in excitation efciency caused by energy withdrawal from the plasma. De Boer and Velterop (24) investigated matrix effects of Na and Ca in a radially viewed ICP using ultrasonic nebulization (USN). Sc II and Y II were used as internal standards. A large spread of data was obtained for the energyinterference correlation. Furthermore, Ca and Na concentrations were low 80 mg/L. Dubuisson et al. (13) evaluated the efciency of internal standardization for the compensation of Nainduced matrix effects in robust axially viewed and radially viewed ICPs. A single ionic spectral line of Ni (Ni II 231 nm) was employed. It was observed that in the axially viewed

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ICP, compensation was not as good as in the radially viewed conguration. Thus, it is crystal clear that there is need for a more versatile approach to internal standardization in geoanalysis, in particular for compensating effects of Ca in the plasma. Although interference effects can be correlated with energy potentials, the possibility of using empirical functions as a versatile method for compensating variable interference effects has not been fully evaluated. In the present study, Ca and Na interference effects in an axially and a radially viewed ICP were determined for a wide range of atomic and ionic spectral lines differing in energy potential. Subsequently, it was determined whether energyinterference functions could be determined and then applied to compensate Ca and Na interference effects. The Mg II 280.270/Mg I 285.213 nm intensity ratio (6 13, 1719, 25, 26) was used to quantify the robustness of the plasmas and to ensure that optimum excitation conditions prevailed. EXPERIMENTAL Instrumentation A JY (Jobin Yvon-Horiba, Longjumeau, France) Panorama multichannel, PMT-based, 0.6-m PaschenRunge polychromator was used for the axially viewed ICP measurements. A JY 124 CzernyTurner sequential spectrometer was employed for the radially viewed ICP experiments. Both instruments were equipped with holographic 3600 groove/mm gratings. Two rf power levels, 1.2 and 1.5 kW, were employed. In the axially viewed conguration, the outer fringe of the plasma was stripped away from the optical path by an end-on ow of argon (8 L/min). The outer sleeve of the torch was longer than that employed for radial observation (5 cm above the upper coil) and the top of the injector, 3 mm in diameter, was positioned about 0.2 mm below the intermediate tube. The viewing position was adjusted using the intensity of Mn II 257.610 nm. A conventional Meinhard pneumatic concentric nebulizer and a small cyclonic spray chamber was employed for minimum memory effects. In both systems, a patented TrassyMermet sheath gas tube (27) was installed between the spray chamber and the demountable torch. The additional sheath gas ow promoted the transfer of the Ca- and Na-laden aerosols into the axial column of the ICP. ICP operating conditions are listed in Table 1. Reagents Solutions containing up to 0.5% (v/v) Ca and Na were prepared from ultrapure single-element solutions (Spex Certiprep, Metuchen, NJ) which were spiked with 100 g/L of Spex multielement stock solutions. All solutions contained 1% (v/v) ultrapure nitric acid and 5 mg/L Mg for the determination of the Mg II 280.270/Mg I 285.213 nm intensity ratio. Solutions also contained 1 mg/L Sb, Be, Y, and Sc as the internal standards. Wavelength Selection The elements investigated, their spectral wavelengths, and energy potentials (excitation for atomic lines and sum of excitation and rst ionization potentials for ionic lines) are listed in Table 2. The range of energies varied from 3.82 eV for Cu I 324.754 nm to 16.81 eV for Mg II 279.079 nm. Spectral line interferences were insignicant and were not determined; however, background corrections were made on one or both sides of the

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TABLE 1 ICP Operating Conditions for Axial and Radial Viewing Using Conventional Pneumatic Nebulization with the JY Panorama and JY 124 Spectrometer Systems JY 124, sequential Focal length (m) Generator (MHz) Rf power (kW) Torch Observation height Central injector Cooling gas (L/min) Sheath gas (mL/min) Cutoff gas Auxiliary Aerosol carrier (L/min) Nebulizer Spray chamber Solution delivery (mL/min) Peristaltic tubes Integration Number of integrations Preintegration (s) 0.64 40.86 1.2 and 1.5 Demountable Ryton 2 mm above IRZ Alumina, 3-mm i.d. 15 0.1 None None 0.7 Meinhard concentric Microcyclonic 1.5 Sample, 0.76 mm; drain, 1.14 mm 500 ms 5 40 JY Panorama, simultaneous polyscan 0.5 40.86 1.2 Demountable Ryton Alumina, 3-mm i.d. 16 0.1 End-on, Ar, 8 L/min 0.2 L/min 0.55 Meinhard concentric Microcyclonic 1.5 Sample, 0.76 mm; drain, 1.14 mm 10 s 5 40

analyte spectral lines. The Mg II 280.270/Mg I 285.213 nm intensity ratio was applied as a criterion for plasma robustness. Procedure for Determining Interference Factors Interference factors were expressed as the percent recovery of the spiked concomitant Ca and Na solutions after calibrating with a 1% HNO 3 solution containing the analytes of interest in a concentration of 100 g/L. The concomitant solutions matched with acid and containing 0.1 0.5% Ca and Na and 100 g/L of the analytes were analyzed as samples. Reagent blank corrections were made where necessary. The smaller the recovery, the larger was the interference. RESULTS Precision Short-term RSDs for all measurements were 1%. Uncompensated long-term precision (3 h) varied from 1 to 5%. With internal standardization, RSDs improved to 0.21%. Ca and Na Interference Effects As observed in previous studies (7, 8), analyte spectral lines listed in Table 2 (spectral lines are listed with increasing energy potential) responded differently to increasing concentrations of Na and Ca. In the axially viewed ICP, recoveries varied from 100% for Cu I 324.754 nm to about 60 70% for high-energy lines in the presence of 0.5% Ca and Na. Data in Table 2 show that matrix effects in the radially viewed ICP were smaller than

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TABLE 2 Determined, Predicted, and Compensated Trace Element Recoveries in 0.5% Na, Ca and Mixed Ca-Na Solutions. Axially Viewed and Radially Viewed ICPs. 1.2 kW. The Standard Error of the Predicted Value is in %. Det. - Determined Recoveries. Pred. - Predicted Recoveries from the Energy-Interference Functions. : Difference between Measured and Predicted Data (Residuals). Corr. Data Obtained by Implementing the Energy-Interference Functions SE: Standard Error of the Compensated Values
Axial, 0.5% Ca Pred 92.2 90.9 87.2 86.8 85.9 85.7 79.8 76.9 76.7 75.4 74.0 71.5 71.1 70.1 68.9 68.5 68.4 67.4 66.6 65.5 64.6 60.3 60.3 92.2 72.7 31.5 31.6 32.6 33.4 34.5 35.4 39.7 7.8 39.7 27.3 104.0 97.1 99.8 96.4 100.7 101.4 101.2 90.6 104.3 103.2 3.9 1.0 1.0 1.0 1.1 1.2 1.2 1.5 0.8 1.7 1.0 0.3 31.1 99.9 1.0 28.5 28.9 29.9 104.1 101.7 90.6 0.8 0.9 0.9 7.8 9.1 12.8 13.2 14.1 14.3 20.2 23.1 23.3 24.6 26.0 103.8 99.1 97.3 101.2 92.1 104.3 98.2 102.2 101.4 101.3 102.2 1.7 1.6 1.3 1.3 1.2 1.2 0.9 0.8 0.8 0.8 0.8 Corr SE Det Pred Corr SE Det Pred Corr SE Det Radial, 0.5% Na Radial, 0.5% Ca Radial, 0.25% Ca Pred 0.25% Na Corr SE

Axial, 0.5% Na

Element

Wavelength (nm)

Energy (eV)

Det

Pred

Corr

SE

Det

97.0 95.0 92.7 88.2 81.6 93.5 85.3 80.0 77.5 75.0 71.7

95.7 94.3 90.2 89.7 88.7 88.5 81.9 78.6 78.4 77.0 75.3

4.3 5.7 9.8 10.3 11.3 11.5 18.1 21.4 21.6 23.0 24.7

101.3 100.7 102.5 98.5 92.9 105.0 103.4 101.4 99.1 98.0 96.4

1.7 1.6 1.3 1.3 1.2 1.2 0.9 0.8 0.8 0.8 0.8

96.0 90.0 84.5 88.0 78.0 90.0 78.0 79.1 78.1 76.7 76.2

BRENNER ET AL.

75.0 71.0 63.0

72.5 72.1 71.0

27.5 27.9 29.0

102.5 98.9 92.0

0.8 0.8 0.9

75.6 72.8 60.7

Cu I Mg I Zn I Sb I Se I As I Sr II Y II Sc II Ti II V II Sc II Mg II Mn II Tl II Cr II Fe II Ca II Mo II Be II Co II Ni II Cd II Pb II Mg II Min Max Mean STD 77.1 70.4 73.2 68.9 69.2 75.4 71.0 68.9 88.0 88.0 73.7 73.6 72.9 72.4 71.7 71.1 68.3 68.3 89.3 89.3 26.3 26.4 27.1 27.6 28.3 28.9 31.7 10.7 31.7 10.7 103.4 96.8 100.3 96.5 97.5 104.3 102.7 95.6 104.3 98.7 2.6

324.754 285.213 213.856 206.833 196.026 193.695 407.771 371.029 361.384 337.279 311.071 255.237 280.27 247.61 190.8 267.716 259.94 317.933 202.032 313.042 228.616 231.604 226.502 220.353 279.079

3.82 4.34 5.8 5.98 6.32 6.4 8.74 9.9 9.99 10.5 11.07 11.42 12.07 12.21 12.6 12.95 13.09 13.15 13.23 13.28 13.7 14.02 14.46 14.79 16.51

67.6 75.0 73.0 66.4 67.5 63.3 69.0 66.0 63.0 63.0 97.0 76.4

69.7 69.5 69.3 69.1 67.9 67.0 65.8 64.9 60.0 60.0 95.7 76.4

30.3 30.5 30.7 30.9 32.1 33.0 34.2 35.1 40.0 4.3 40.0 23.6

68.8

88.0 87.4 84.0 88.0 86.5 84.8 81.0 81.7 81.8 80.2 80.0 76.9 72.0 74.8 70.4 71.5 74.6

89.3 88.4 86.0 85.7 85.1 85.0 81.1 79.2 79.1 78.2 77.3 76.7 75.6 75.4 74.8 74.2 73.9

10.7 11.6 14.0 14.3 14.9 15.0 18.9 20.8 20.9 21.8 22.7 23.3 24.4 24.6 25.2 25.8 26.1

98.7 99.0 98.0 102.3 101.4 99.8 99.9 102.5 102.7 102.0 102.7 100.2 96.4 99.4 95.6 97.3 100.7

1.2 1.1 0.9 0.9 0.8 0.8 0.6 0.5 0.5 0.5 0.5 0.5 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.7 0.7 0.8 0.8 1.0 0.5 1.2 1.2 0.2

92.0 90.2 85.0 88.2 89.0 85.8 83.5 83.2 84.5 82.0 81.8 80.4 75.3 75.0 74.6 73.1 75.5 79.5 75.0 76.3 73.0 74.8 77.0 73.0 73.0 92.0 92.0

91.1 90.3 88.0 87.7 87.2 87.1 83.4 81.6 81.5 80.7 79.8 79.2 78.2 78.0 77.4 76.8 76.6 76.4 76.3 75.7 75.2 74.5 74.0 71.3 71.3 91.1 91.1

8.9 9.7 12.0 12.3 12.8 12.9 16.6 18.4 18.5 19.3 20.2 20.8 21.8 22.0 22.6 23.2 23.4 23.6 23.7 24.3 24.8 25.5 26.0 28.7 8.9 28.7 8.9

100.9 99.9 97.0 100.5 101.8 98.7 100.1 101.6 103.0 101.3 102.0 101.2 97.1 97.0 97.2 96.3 98.9 103.1 98.7 100.6 97.8 100.3 103.0 101.7 96.3 103.1 100.9 2.2

1.0 0.9 0.8 0.7 0.7 0.7 0.5 0.5 0.5 0.4 0.4 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.6 0.6 0.6 0.7 0.9 0.4 1.0 1.0 0.2

97.9 105.5 103.7 97.3 99.6 96.3 103.2 101.1 103.0 92.0 105.5 100.0 3.8

0.9 0.9 0.9 0.9 1.0 1.0 1.1 1.2 1.5 0.8 1.7 1.0 0.3

72.5 65.5 67.2 63.0 66.2 66.0 61.5 60.7 96.0 75.9

95.0 91.7 89.0 92.6 94.5 96.2 87.1 86.4 88.4 87.5 86.3 86.8 83.0 81.8 80.1 82.8 82.8 86.0 86.1 82.0 86.6 80.7 83.5 86.4 81.0 80.1 96.2 80.1

94.3 93.7 92.1 91.9 91.5 91.4 88.9 87.6 87.5 86.9 86.3 85.9 85.2 85.0 84.6 84.2 84.1 84.0 83.9 83.9 83.4 83.0 82.6 82.2 80.3 80.3 94.3 80.3

5.7 6.3 7.9 8.1 8.5 8.6 11.1 12.4 12.5 13.1 13.7 14.1 14.8 15.0 15.4 15.8 15.9 16.0 16.1 16.1 16.6 17.0 17.4 17.8 19.7 5.7 19.7 19.7

100.7 98.0 96.9 100.7 103.0 104.8 98.2 98.8 100.9 100.6 100.0 100.9 97.8 96.8 95.5 98.6 98.7 102.0 102.2 98.1 103.2 97.7 100.9 104.2 100.7 95.5 104.8 99.8 2.5

1.1 1.0 0.9 0.8 0.8 0.8 0.6 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.7 0.7 0.7 0.9 0.5 1.1 0.5 0.2

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FIG. 1. Comparison of Na, Ca (0.5% (v/v)), and mixed NaCa interference effects in axially viewed and radially viewed ICPs; (a) Axially viewed ICP; (b) radially viewed ICP. 1.2 kW.

those in the axially viewed ICP. Signal suppression varied from about 5 to 20% for 0.5% Na and from 10 to 30% for 0.5% Ca. Spectral responses for mixed solutions containing 0.25% Ca and 0.25 and 0.1% Na did not deviate signicantly from the general interference trend of the single-element Ca and Na solutions. Figures 1a, 1b, 2a, and 2b, arranged in order of increasing energy potential, compare Na and Ca interference effects in the axially and radially viewed ICPs. In the axially viewed ICP, as observed previously (8, 9), Ca interferences were larger than those of Na. The Na interference trend in the radially viewed ICP differed signicantly from that observed in the axially viewed ICP. Whereas Na interferences were signicantly energy dependent in the axially viewed ICP, they were more uniform in the radially viewed ICP for the spectral lines investigated, especially in the mid-energy region, i.e., between about 10 and 12 eV. In addition, Ca effects were less pronounced in the radially viewed plasma. Although the amount of interference produced by solutions containing equal concentrations of Ca and Na (0.25 0.25%) was smaller than that observed for Ca only, the pattern of interference was not signicantly different from that produced by 0.5% Ca. The relatively uniform interference effect of Na on spectral lines having energy potentials 11 eV was also observed by Romero et al. (25) and Dubuisson et al. (28). These workers concluded that aerosol formation and generation are mainly responsible for the observed Na interference effects in robust ICPs. Signal reduction was related to a decrease in solvent transport rate owing to the smaller droplet size of the tertiary aerosol.

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FIG. 2. As in Fig. 1. Comparison of interference effects in axially viewed and radially viewed ICPs: (a) Na; (b) Ca.

Effect of rf Power Figures 3a and 3b illustrate the effect of rf power on the interferences of 0.5% Na and Ca. An increase of power from 1.2 to 1.5 kW did not signicantly improve the percent recovery in the presence of Na. In contrast, there was a large reduction in Ca interference effects at 1.5 kW. Indeed, Figure 4 illustrates Na-to-Ca interference ratios as a function of energy potential of the spectral line at two power levels. At 1.2 kW, the matrix effect due to Ca was pronounced for spectral lines 11 eV. This effect was subdued for these lines at 1.5 kW. Relation between Interference Effects and Energy Potentials of the Spectral Lines Figures 5a e illustrate the relation between the percent recoveries of the analytes in Ca, Na, and CaNa mixed solutions for axially viewed and radially viewed ICPs at 1.2 kW. It is evident that there is a good linear correlation between Ca- and Na-induced interference effects and energy potentials of the spectral lines selected. It can be seen that the percent recoveries of Sb I 206.833, Sc II 255.237 and 361.384, Y II 371.029, and Be II 313.042 nm plot close to the line of best t for all the data. These spectral lines, covering the response range, were used to estimate interference energy potential functions. These diagrams also indicate that the minimum recoveries of high-energy lines were about 60% in the axially viewed ICP, whereas they were about 70 80% in the radially viewed ICP.

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FIG. 3. Effect of rf power on Na and Ca (0.5%) interferences in a radially viewed ICP: (a) Na; (b) Ca.

Compensation Using Energy PotentialInterference Functions Statistical data (Table 3) indicate that the linear functions relating interference effects to spectral line energies in the axially viewed ICP were more signicant than those for the radially viewed ICP ( 0.9448 to 0.9327 vs 0.8490 and 0.9207 for Na and Ca, respectively).

FIG. 4. Ratio of Na-to-Ca interference effects in a radially viewed ICP. Na and Ca, 0.5%.

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FIG. 5. Linear relationship between percent recovery and energy potentials in axially viewed and radially viewed ICPs for 0.5% Na and Ca and mixed NaCa (0.25 0.25% Ca and Na) solutions: (a) axially viewed ICP, Na; (b) axially viewed ICP, Ca; (c) radially viewed ICP, Na; (d) radially viewed ICP, Ca; (e) radially viewed ICP, NaCa. 1.2 kW.

The determined, predicted (without compensation), and corrected recoveries of these analytes are given in Table 2. Predicted values were determined by linear extrapolation to the line of best t. Slope factors were then applied to determine the corrected recoveries. Recoveries of up to 60% were improved to about 90 95%. Of interest is the fact that in the case of the radially viewed ICP, spectral line intensities, including those of the internal standards, were measured sequentially. It can be concluded that this approach resulted in a considerable improvement of accuracy when Sb I 206.833, Y II 371.029, Sc 361.384 and 255.237, and Be II 313.042 nm were used as the internal standards. Plasma Robustness The Mg II 280.270/Mg I 285.213 nm intensity ratios for the axially viewed and radially viewed ICPs are presented in Fig. 6. In an aqueous solution at 1.5 kW, the ratio amounted to 12. The ratio decreased with increasing concentration of Ca and Na and was about 9.5 for 5000 mg/L Ca. The ratio decreased when the rf power was reduced to 1.2 kW. In the axially viewed ICP, the ratio was about 10.5 for an aqueous solution and about 8 for 0.5% Ca. In the presence of 0.5% Na, the ratio was 10.5. These values are comparable with those determined by Dubuisson et al. (13). The small effect of Na in robust ICPs was noted previously by Mermet and co-workers, who concluded that interferences due to Na

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FIG. 5Continued

were derived mainly from the aerosol generation and transport systems and not in the plasma (25, 28). It can be concluded that the experiments described in this study were conducted with a robust ICP. DISCUSSION AND CONCLUSIONS Accurate compensation of EIE and Ca interferences is a crucial factor in geoenvironmental and biological analysis using axially viewed ICPs. Although improving plasma robustness minimizes matrix effects, intensity suppression persists for spectral lines of low- and high-energy potentials. In the case of Na, recent studies indicate that line intensity attenuation for intermediate-energy spectral lines can be attributed mainly to

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BRENNER ET AL. TABLE 3 Statistical Data of Linear EnergyInterference Factor Functions R (X,Y) SE of R 0.072 0.081 0.12 0.081 0.076 0.087 t 18.55 16.13 8.72 13.25 68.1 15.25 F 174.5 133.8 54.2 111.4 152.6 155.2 N 23 22 23 22 22 22

Na AX Ca AX Na RAD Ca RAD Ca 2500 Ca 2500

Na 500 RAD Na 2500 RAD

0.9448 0.9327 0.8490 0.9207 0.9349 0.9412

interferences in the aerosol generation and transport systems. However, suppression of high-energy spectral line intensities by Ca has been widely attributed to energy withdrawal required to atomize the high-salt aerosols. This is accompanied by a decrease in the excitation temperature and robustness of the plasmas, indicated by the decrease in the Mg II 280.270/Mg I 285.213 nm intensity ratio. It appears that these interference effects in axially viewed ICPs are larger than those of the radially viewed ICPs as borne out here and by other data (6 8, 13). This could be due to several factors: a. In certain axially viewed ICP congurations, the observation zone includes regions in the coil and in the plasma fringe where interferences prevail. b. The cutoff gas may be inefcient in deecting the interference zone or the impact of cold gas could result in interference effects. The main conclusion of this study is the application of energyinterference functions for compensating EIE and Ca matrix variations on ionic and atomic spectral lines, in particular for those having low- and high-energy potential. The proximity of Sb I 206.833, Sc II 255.237 and 361.384, Y II 371.029, and Be II 313.042 nm to the linear regression lines of best t for all the data indicates that these functions can be calculated by using these elements only. The utilization of such interference energy equations overcomes the

FIG. 6. Mg II 280/Mg I 285 nm intensity ratios in axially viewed and radially viewed ICPs. Values obtained at 1.5 kW are also indicated.

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setback of variable response of ionic and atomic lines in the presence of EIEs and Ca. With this approach, the accuracy was markedly improved even when the internal standards were measured in the sequential mode. It is worth noting that as long as the interference energy functions are linear, the proposed procedure will compensate for the affect of a particular matrix on a second concomitant. In cases where internal standard elements need to be determined, alternate spectral lines of appropriate energy can be selected. We have also stated that the procedure is for geoanalysis and environmental analysis. It should be mentioned that the method may not be suitable for all axially viewed ICP congurations and applications. ACKNOWLEDGMENTS
I.B.B is grateful to Y. Lang, Director of the Emission Spectroscopy Division of Jobin Yvon-Horiba (retired), for providing the opportunity to evaluate interference effects in JY axially viewed and radially viewed ICP systems. Facilities for performing this work were generously provided by O. Rogerieux and C.-V. Phan.

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