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MICROCHEMICAL JOURNAL $2, 96-100 (1995) Determination of Cadmium and Lead in Blood Reference Samples by Simultaneous Graphite Furnace Atomic Absorption Spectrometry" Anupama Deval anp Josep SNEDDON? Department of Chemistry, MeNeese State University, Lake Charles, Louisiana 70609 Received February 2, 1994; accepted October 10, 1994 Cadmium and lead concentrations at low ypfiter levels were determined in blood reference samples using simultaneous graphite furnace atomic absorption spectrometry with acceptable accu- racy, Use of ammonium dihydrogen phosphate allowed an elevated ashing temperature of 60°C 10 be used, which allowed the blood matrix to be removed without loss of cadmium and lead. The ability eously offers a reduced analysis time. © 1995 Asem. Ps. ns INTRODUCTION Cadmium and lead are two elements which can cause toxicity in humans and which are present in human body fluids at low g/liter concentrations (1). There is a continual need and desire to determine accurately these low concentrations in blood. One of the tect niques which has been proposed for this analysis is graphite furnace atomic absorption spectrometry (AAS), with its capability of low detection limits and generally acceptable accuracy. However, it is a relatively slow technique with typical analysis times of around 2 min per sample and has generally been regarded as a single element technique. Recent work from this laboratory has shown the potential of multielement AAS using a flame atomizer (2-4) and more recently using the graphite furnace as the atomizer (5). Multi- element AAS has been reviewed by Sneddon et al. (6). This work is a continued study of multielement graphite fumace AAS for the simul- taneous determination of cadmium and lead in blood reference samples. to determine two elements simulta EXPERIMENTAL, Instrumentation ‘A Thermo Jarrell Ash 8000 automated simultaneous AA/AE spectrophotometer, equipped with a Model 188 controlled temperature furnace (CTF) and a FASTAC aerosol sample deposition system, was used in this work (Thermo Jarrell Ash Corp., Franklin, MA). Simultaneous detection of the two elements was achieved using only one photo- multiplier and a galvanometer-driven grating in the monochromator. This mechanism allows the instrument to scan the full spectrum (180-900 nm) in 20 ms. Pyrocoated delayed atomization cuvettes (DAC), Smith-Hiefije background correction, Visimax II " Presented, in put atthe 49th Southwest Regional American Chemical Soc October 25-27, 1993. To whom correspond Meeting in Austin, Texas, we should be addressed (0026-268X/95 $12.00 Copyrign © 1988 by Acabami Pres. lc [All ips of pedo uy fr ere CADMIUM AND LEAD DETERMINATIONS, 97 hollow cathode lamps, and an R106 UH photomultiplier were used in this work. Peak area absorbance measurements were used throughout this work Instrumental Parameters ‘The compromise instrumental parameters developed and used in this work are shown in Tables I and 2. Reagents and Procedure The chemical modifiers used in this work, ammonium dihydrogen phosphate, NH,H,PO4, (9.999% pure), and magnesium nitrate, Mg(NO,), - 6 HO (99.99% pure), were obtained from Johnson Matthey, Materials Technology (England). A concentration of 0.1% chemical modifier was used in all solutions (blood reference and standard solu- tions) in this work. Cadmium and lead stock solutions were 1000 j.g/ml and were diluted with double deionized water daily or when required. All glassware was detergent washed, acid rinsed, and finally rinsed with double-deionized water. When optimizing the ashing stage. the concentrations of cadmium and lead were chosen to give a peak area absorbance of between 0.1 and 0.2, typically 20 g/ml of lead and 4 g/ml of cadmium, The precision ranged from 2 to 5%, Aqueous solutions of cadmium and lead were used to construct calibration curves and in standard additions. Dilution of the blood was desirable in order to dilute potential interferences but also to allow the use of the FASTAC sample intro- duction system, When the levels of cadmium and lead to be determined approached the detection limit, dilution was reduced or eliminated. In this case, the blood reference samples and standard solutions were introduced manually by pipette, typically 20-1 volumes. This was necessary to prevent the FASTAC sample introduction system from becoming blocked. Standard additions and Smith-Hiefije background correction were used throughout the analysis. In all cases, cadmium and lead were simultaneously deter- mined. RESULTS AND DISCUSSION Chemical Modification Results showed that cadmium was lost in the ashing stage at around 250°C (see Fig. ta) before the blood matrix could be removed at around 450-S00°C. In order to prevent this from happening, it was desirable to make the cadmium less volatile. This was achieved by using a magnesium nitrate chemical modifier, which allowed an ashing temperature of around 500°C or by using ammonium dihydrogen phosphate, which allowed an ashing temperature of 650°C (see Fig. 1a) to be used before loss of cadmium, The lead was lost TABLE | Instrumental: Spectrometer Parameters Cadmium Lead ‘Wavelength (nm) 2288 2170 Lamp curcent (mA) 50 30 Background current (mA) 30 20 Bandwidth (nm) 10 10 Background correction Smith-Hiefte 98 DEVAL AND SNEDDON TABLE 2 Instrumental: Time/Temperature Program for the CTF Atomizer ‘Temperature Ramp time Hold time ‘Step number Step cc ) 1 Injection/dry 110 2 2 Ashing 1 10 10 3 Ashing 2 « 0 4 Atomization 1700 1 4 5 Clean 2000 0 4 The temperature was varied in the ashing stage at around 500°C (see Fig. 1b) without a chemical modifier. The use of magnesium nitrate allowed an ashing temperature of 700°C and ammonium dihydrogen phosphate an ashing temperature of 700°C (see Fig. 1b) before loss of lead occurred. Based on these results, ammonium hydrogen phosphate was used as the chemical modifier throughout this work. Analytical Performance Characteristics The analytical performance characteristics for the determination of cadmium and lead by simultaneous graphite furnace atomic absorption spectrometry are shown in Table 3. The detection limit was calculated directly as KS,y/m, where K is the confidence factor (in this case, 3), Sj, is the standard deviation of the blank measurement, and m is the calibration curve slope. The detection limits for cadmium and lead to simultaneous graph- ite furnace AAS were 0.24 and 1.06 jxgiliter, respectively. The precision was determined at a concentration five times the detection limit and was calculated for 10 consecutive 02 a 8 s 5 go < 3 é 0.0 — . ° 200 400 600 800 1000 Temperature, °C Fic. 1a Ashing profile of cadmium: (E) no modifier; (}) magnesium nitrate; and (¢) ammonium dihydro- ‘gen phosphate. CADMIUM AND LEAD DETERMINATIONS 99 o2 B 8 : 2 3 2 < os 2 < 3 Ey ood er eee ee Temperature, °C Fic. Ib, Ashing profile of lead: (E) no modifier: (J) magnesium nitrate; and (#) ammonium dihydrogen phosphate. measurements of cadmium and lead using blood referen: to be acceptable (<5%) (see Table 3). ample number 190 and found Accuracy Accuracy for the determination of cadmium and lead by simultaneous graphite furnace AAS was assessed by comparison to standard blood reference samples. Blood laboratory reference samples were obtained from the Center for Disease Control (CDC) in Atlanta, GA. Sample preparation was limited to dilution provided the levels to be determined were above the detection limit. This dilution was determined from preliminary experiments involving standard solutions and a pooled blood sample. These samples are certified for blood lead concentrations and information on the cadmium concentration is not certified but given for reference purposes. The results obtained by this method compared to the standard or given values are shown in Table 4, For both elements the results obtained were not always exactly identical to the reference or given values but were close enough so that the differences were not statistically significant TABLES Analytical Performance Characteristics for the Determi Cadmium and Lead by Simultaneous Graphite Furnace Atomic Absorption Spectrometry tion of Detection limit Linearity Precision (ugflter) (ughler) (%) Cadmium 024 Detection limit—17 221 Lead 106 Detection limit 100 DEVAL AND SNEDDON TABLE 4 s between This Method and St indard Reference or Given Values Comparison of Conce Cadmium Lead Cenified (ugflter) ¥0 140204 190 51201 290 Be +04 590 9.0 204 690. 48201 37404 790 i904 16.0 = 0.4 atomic absorption spectrometry. Due to the al elements, there is considerable time saving. ACKNOWLEDGMENTS ‘The authors acknowledge Gerald R, Dulude and John J. 1. Delves, HT. ical, 1984, 3, 279-288. 2. Farah, K, S.; Sneddon, J. Anal. Lett, 1993, 26(4), 709-719. 3. Thiem, T. Li Lee, ¥, I: Sneddon, J. Microchem. J., 1993, 48, 65-71 4, Farah, K. S.: Sneddon, J. Talanta, 1993, 40(6). 879-882 5. Sneddon, J: Farah, K. S. Specirose, Lert, 1994, 27(2 6, Sneddon, J; Farah, B. D.; Parah, K.S. Micrachem. J. 318-325,

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