Spectrochimica Acta Part B 66 (2011) 9397

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Spectrochimica Acta Part B

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s a b

Analytical Note

A study of the direct determination of Cd, Cr, Cu, Pb and Zn in certied reference materials of soils by solid sampling electrothermal atomic absorption spectrometry
Peter Trk, Mria emberyov
Comenius University in Bratislava, Department of Analytical Chemistry, Faculty of Natural Sciences, 842 15 Bratislava, Slovak Republic

a r t i c l e

i n f o

a b s t r a c t
A simple and rapid method for the direct determination of Cd, Cr, Cu, Pb and Zn in soil was developed. The method was developed using three certied reference materials of soil: Eutric Cambisol, Orthic Luvisols and Rendzina, which differed in their matrix composition. Chemical modiers were essential to achieve reproducible and interference-free signals for the analytes studied. The best results were obtained with a Pd/ Mg(NO3)2 admixture for the determination of Cd, Pb and Zn and NH4F for Cu. The combination of W (as a permanent modier) and Mg(NO3)2 provided well-dened signal proles for Cr. The following spectral lines were used: Cd 228.8 nm, Cr 520.6 nm, Cu 218.2 nm, Pb 205.3 nm and Zn 307.6 nm. The limit of detection was 4.2 ng g 1 for Cd, 1.1 g g 1 for Cr, 0.5 g g 1 for Cu, 1.3 g g 1 for Pb and 8.6 g g 1 for Zn for the maximum sample mass used. Under optimized conditions, the analyte and matrix were separated effectively in situ, and aqueous standards could be used for calibration. 2010 Elsevier B.V. All rights reserved.

Article history: Received 27 February 2009 Accepted 10 December 2009 Available online 17 December 2010 Keywords: Solid sampling ETAAS Soil Methodology

1. Introduction The analysis of soil is a difcult and challenging task for the analytical chemist [1]. The total dissolution of soil requires the development of time-consuming procedures, which usually involve the use of hazardous reagents [2]. Depending on the procedure selected and the type of soil, satisfactory results are not always guaranteed due to the possible loss of an analyte [3], contamination or incomplete analyte recovery [46]. Solid sampling-electrothermal atomic absorption spectrometry (SS-ETAAS) is an extremely promising and powerful trace analysis strategy [7,8]. Nevertheless, it is still liable to matrix effects [9]. One of the most important preconditions for using SS-ETAAS is the use of aqueous standards for calibration, which requires in situ analyte/ matrix separation. The degree of difculty in achieving this mainly depends on the relative volatilities of the analyte and the matrix [10]. Most works published to date have dealt with situations in which the volatility of the analyte and the matrix differed substantially [11,12]. SS-ETAAS analyses of samples in which the analytes to be determined and the sample matrix were of similar volatility were studied by Belarra et al. [13]. In early works, the slurry sampling method was preferred to the solid sampling analysis of soils [1421]. Although slurry sampling ETAAS combines the advantages of conventional ETAAS and solid sampling (e.g., direct analysis without lengthy sample digestion), it

still requires the use of acids (e.g., hydrouoric acid) [1,22,23]. This makes the SS-ETAAS an attractive alternative to both conventional and slurry ETAAS. The intention of this work was to develop a reliable, rapid and simple method for the direct determination of Cd, Cr, Cu, Pb and Zn in soil by SS-ETAAS using three certied reference materials (CRMs) of soil for validation. Especially in the case of Cr determination in soils, the application of direct solid sampling is an attractive alternative to conventional atomic spectrometry methodology using sample decomposition because of the minimization of the risk of possible analyte loss during sample decomposition. Decomposition using HClO4, usually in combination with HNO3, has found considerable application in soil analysis. Depending on the type of the soil, Cr can be lost as volatile chromyl chloride, CrO2Cl2 [3,23]. The importance of this method is also the selection of analytical lines, which enable direct determination of the studied elements without necessary dilution of the sample. 2. Experimental 2.1. Instrumentation All measurements were performed using an AAS 5EA atomic absorption spectrometer (Analytik Jena AG, Jena, Germany). A laboratory-made device was used for solid sample introduction [24]. Hollow cathode lamps were supplied from G. L. E. (Berlin, Germany). Pyrolytically coated graphite tubes without the dosing hole and pyrolytically coated graphite platforms (Analytik Jena AG, Germany) were used in all experiments. An M500P ultra-microbalance

Corresponding author. Tel.: +421 2 60296309; fax: +421 2 60296706. E-mail address: zemberyova@fns.uniba.sk (M. emberyov). 0584-8547/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.sab.2010.12.005

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P. Trk, M. emberyov / Spectrochimica Acta Part B 66 (2011) 9397 Table 1 Characteristics of the resonance lines studied. Element Cd Cd Cr Cr Cr Cu Cu Cu Cu Pb Pb Pb Zn Zn
a b

(Sartorius, Goettingen, Germany) was used for weighing the samples onto the solid sampling platforms. Platforms covered with the tungsten permanent modier were treated with 40 50 L of 1 g L 1 of W stock solution using the heating program adopted from a paper by Vale et al. [25]. 2.2. Reagents and samples All solutions were prepared in deionized water from a Water PRO-PS system (Labconco, Kansas City, USA). Concentrated HNO3 was purchased from Merck (Darmstadt, Germany). Single-element calibration standards were prepared by diluting 1 g L 1 of single-element stock solutions (Darmstadt, Germany) in 0.14 mol L 1 HNO3. The Pd (10 g L 1) and W (1 g L 1) solutions were from Merck (Darmstadt, Germany). Mg(NO3)26 H2O, (suprapur quality, Merck, Darmstadt, Germany) was used for the preparation of mixed modier solutions. HF acid (40%) and ammonia solutions (25%) were of analytical grade (Lachema, Brno, Czech Republic). Triton X-100 (scintillation grade, Fluka, Buchs, Switzerland) of a nal concentration of 0.1% m/v was added to all the modier solutions. Argon (99.999%) was used as the purging gas with a ow-rate of 1.2 L min 1 in all stages, except for the auto zero and atomization stages in which the ow rate was reduced to 0.1 L min 1. CRMs of soils S-VM No. 12-1-07 Eutric Cambisol, S-MS No. 12-1-08 Orthic Luvisols and S-SP No. 12-1-09 Rendzina [26], with the total contents of the elements certied, were produced by the Institute of Radioecology and Applied Nuclear Techniques, Koice, Slovakia. 3. Results and discussion 3.1. Selection of analytical lines The primary analytical line of 228.8 nm was suitable for the determination of Cd because all the soils under study were noncontaminated soils. The lines of primary (357.9, 359.4, and 360.5 nm) and alternative resonance triplets of Cr (425.4, 427.5, and 429.0 nm) were not suitable for the direct determination of Cr in the soils tested due to their high sensitivities. As a consequence, an alternative analytical line of 520.6 nm was selected from the Cr nonresonance triplet (520.4, 520.6, and 520.8 nm). Cu has several resonance lines of various sensitivities suitable for ETAAS determination in a range from pg to g. For the measurements required in this study, the lines of the main resonance doublet (324.8 and 327.4 nm) were too sensitive, and the sensitivities at 224.4, 244.2 and 249.2 nm were too low for our purposes. Hence, the lines of choice were 216.5, 218.2 and 222.6 nm, respectively. However, with the soil CRMs examined, severe spectral interferences, which could not be eliminated with the deuterium background correction system, were observed at 216.5 nm. The alternative line of optimum sensitivity was at a wavelength of 218.2 nm. Another analytical line at 222.6 nm could be also used for determination; however, the sensitivity at this line was approximately 3-times lower than at the 218.2-nm line. For Pb, the main 217.0 nm and an alternative resonance line of 283.3 nm were too sensitive. As a consequence, a further alternative spectral line of 261.4 nm was investigated; however, it provided too narrow of a linear calibration range. The resonance line of 205.3 nm was found to be of suitable sensitivity and was used in the measurements. Despite being 4000-times less sensitive than the primary line (213.9 nm) for Zn, an alternative resonance line of 307.6 nm was sufcient in the determination of Zn. The characteristics of the analytical lines studied are summarized in Table 1.

Spectral Line (nm) 228.8c 326.1 357.9 429.0 520.6b,c 216.5 218.2c 222.6 324.8 205.3c 261.4b 283.3 213.9 307.6c

Spectral Transition 5s5p(1P) 5 s2 5s5p(3P) 5 s2 3d44s4p(7P4) 3d54s 3d54p(7P2) 3d54s 3d54p(5P2) 3d54s(5S) 3d94s4p 3d104s 3d94s4p(2P1/2) 3d104s 3d94s4p(4D1/2) 3d104s 3d104p 3d104s 6p1/28 s1/2 6p2 1/2 6p1/26d 6p1/26p3/2 6p1/27 s1/2 6p21/2 4s4p(1P) 4 s2 4s4p(3P) 4 s2

Slopea (s ng 1) 3.23 0.00646 0.770 0.168 0.00941 0.0580 0.0892 0.0256 0.694 0.00797 0.00193 0.137 6.54 0.000885

Linear rangea (ng) 0.010.20 10.0200 0.12.0 0.210.0 10150 5.0020.0 2.5010.0 5.0040.0 0.101.00 5.0060.0 5.0030.0 0.202.00 0.0050.08 25.0350

Established with a gas ow-rate of 0.1 L min 1. Non-resonance lines with elevated ground state: 7593 cm 1 (Cr) and 7819 cm 1 (Pb). c Analytical spectral lines used in this work under the conditions shown in Table 2.

3.2. Selection of modiers and optimization of furnace program Ash-atomized curves, peak shapes and intensities of the background absorption signals were considered in the development of the temperature programs using both solid S-SP soil and the standard solutions. It is obvious that, with no modier applied, the background signal of the soils would be affected by their matrices. In the soil CRMs that were tested, the matrix consisted of Si (2031%), Al (5.89%), P (0.10.14%), Na (0.30.8%), Ca (0.56.3%), Mg (0.61.2%), K (1.83.1%) and Fe (2.73.7%). To avoid any loss of Cd, Pb and Zn, the use of a modier with an analyte-stabilization effect was essential [27,28]. Two modiers were tested: 10 g of Pd and a mixture of 10 g of Pd + 10 g of Mg(NO3)2 with the addition of Triton X-100 as a dispersing agent. The role of Triton X-100 was to improve the contact between the modier and the solid sample [25,29,30]. The amount of Mg(NO3)2, which served as the ashing aid, was not optimized. The pyrolysis and atomization curves were evaluated in the presence of both modiers. With the Pd modier, the atomic absorption proles of Cd, Pb and Zn from the solid soil CRM and from the liquid standards showed a signicant difference. The addition of Mg(NO3)2 to Pd reduced these differences, thus demonstrating that the matrix effect was completely eliminated; however, the sensitivity was decreased by 1020%, depending on the element. This fact is demonstrated in the example for Zn in the gure presented in the Supplementary data, Appendix A. This observation is in compliance with the ndings in the literature [31]. Temperatures of atomization from 1800 to 2200 C were found to be insufcient to volatilize the main matrix components (Al, Fe, Ca, Mg, Si, and P) to an extent that avoided the interferences. The Pd/Mg(NO3)2 admixture converted the analytes to a uniform form, and the presence of the ashing aid decreased the background signals such that it was possible to apply the optimum conditions of the furnace for the individual elements to all three types of soil, regardless of their composition. In the determination of Cu, which is less volatile than Cd, Pb and Zn, a modier of the analyte was not needed since there was no problem with loss of the analyte during pyrolysis. Instead, a modier of the matrix was found to be essential because a strong nonspecic absorption overlapping the signal of Cu was observed that was generated by silicon compounds released from the soil sample. A similar background signal appeared during the atomization of Cu from the aqueous standard in the presence of 300 g of silicon. As was previously reported [32], NH4F was used for the elimination of Al and Fe interferences by converting the refractory Al and Fe species

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(mainly oxide) to volatile AlF3 and FeF3 during the pyrolysis step. In this work, NH4F was used as a matrix modier for removing the majority of silicon compounds during pyrolysis by converting nonvolatile silicon species (mainly oxide) to volatile SiF4. The optimum quantity of NH4F modier of 100 g was derived from plotting the integrated background absorbance of Cu in S-SP soil versus the modier quantity, added to the solid sample as an aqueous solution. In the gure in the Supplementary data, Appendix B, the efciency of NH4F for removing silicon from the soil matrix can be seen. With 2000 g of W as a permanent modi er used in the determination of Cr, tailing of the signals was almost completely suppressed, while the memory effect retained. The addition of 10 g of Mg(NO3)2 to W led to a substantial improvement. Its optimum quantity was determined by interpolation from plotting the integrated absorbance of Cr in S-SP soil versus the weight of the modier. In addition, tungsten in the W/Mg(NO3)2 admixture prevented Cr carbide formation, and Mg(NO3)2 facilitated the atomization efciency of Cr as a result of the reaction between refractory chromium carbide and MgO as a product of the thermal decomposition of Mg (NO3)2. Atomic absorption signals of Cr from liquid standards and from S-SP soil certied reference material in the absence or presence of the modiers tested are shown in Fig. 1. Although the memory effect was not entirely eliminated, considerably better results were obtained. Without the addition of the analyte modier, the atomic absorption proles of more refractory elements (Cu and Cr) showed more similarities between the solid soil samples and aqueous standards. Although Cr and Cu differed in their thermal stability within the individual soils examined (by approximately 100 C in S-SP) and the background signal for Cu in S-SP was almost twice that of the signals for the other two CRMs, a temperature of 2300 C for Cu and 2600 C for Cr was found suitable for all the soils studied. A general procedure was proposed with the maximum temperatures of pyrolysis at which the analytes were stable in all soils. The optimum working conditions for the determination of Cd, Cr, Cu, Pb and Zn are given in Table 2. The same temperature program for the particular element was applied to all the CRMs used. The same sample sequence was applied to all elements: after every ve measurements of the sample, a blank was measured, followed by a liquid standard to check for the sensitivity. In the case of Cr, this approach had an additional benecial effect, resulting in the regeneration of the tungsten carbide layer in the platform. As it was shown previously

Table 2 Optimized operating conditions for analysis of soil CRMs with SS-ETAAS. Conditions Element Cd Instrumental parameters Resonance line 228.8 (nm) Slit (nm) 0.2 Lamp current 5.0 (mA) D2 Background correction Heating programmea,b Pyrolysisc Temperature 400/700d, (C) 600e Ramp 50/50 (C s 1) Hold (s) 20/20 Atomizationf Temperature 1800 (C) 2500 Ramp (C s 1) Hold (s) 4 Modier 20 g Pd + 10 g Mg(NO3)2 Linear range 0.050.2 (ng) Sample weight 0.200.60h (mg) Cr 520.6 0.2 20.0 no Cu 218.2 0.2 10.0 D2 Pb 205.3 0.5 15.0 D2 Zn 307.6 0.5 4.5 D2

500/1500 50/100 20/20 2600 3000 8 10 g Mg(NO3)2 + 2000 g Wg 50150 0.201.00h

500/ 1000 50/100 20/20 2300 3000 4 100 g NH4F 2.510 0.20 0.30h

400/900d, 800e 50/50 20/20 2200 2500 3 20 g Pd + 10 g Mg(NO3)2 1560 0.303.00h

400/850d, 800e 50/50 20/20 2000 2500 3 20 g Pd + 10 g Mg(NO3)2 50300 0.304.50h

a Drying of samples was carried out in two steps at 110; 150 C with ramp 20 C s 1 and 20 s; 40 s duration with maximum argon ow (1.2 L min 1). b After atomization, the graphite atomizer was cleaned by heating up to 2500 C (Cd, Cu, Pb and Zn) or 2600 C (Cr) for 3 s and with maximum argon ow (1.2 L min 1). c Maximum argon ow-rate (1.2 L min 1). d With 20 g Pd + 10 g Mg(NO3)2 modier. e With 25 g Pd modier. f Mini ow conditions (0.1 L min 1). g Permanent modier. h Maximum sample mass applicable (to provide signal within the linear range of calibration curve).

[33], the utilization of a W permanent modier alone in Solid Sampling ETAAS analysis of environmental samples can lead to pronounced matrix accumulation on the platform. The blank run (when only Mg(NO3)2 solution is atomized) could help to remove the matrix residues from the platform, ensuring a reproducible atomization surface. The linear calibration plots established from the

Table 3 Analytical characteristics of method developed. Element Cd Cd Cr Cu Pb Pb Zn Zn Fig. 1. Atomic absorption signals of Cr from liquid standards and from S-SP soil certied reference material in absence or presence of modiers tested (1 50 ng Cr(III) in 10 L aqueous solution without modier, Aint = 0.407 s; 2 50 ng Cr(III) in presence of 2000 g W, Aint = 0.463 s; 3 50 ng Cr(III) in presence of 2000 g W + 10 g Mg (NO3)2, Aint = 0.548 s; 4 50.6 ng Cr in 0.579 mg soil certied reference material S-SP in presence of 2000 g W + 10 g Mg(NO3)2, Aint = 0.552 s). Modier Pd Pd + Mg(NO3)2 Wc + Mg(NO3)2 NH4F Pd Pd+ Pd Pd+ Mg(NO3)2 moa (ng) 0.0014 0.0016 0.50 0.091 0.54 0.57 5.0 5.6 LOD (g g 1) 0.00376 0.00424 1.14 0.510 1.24 1.37 5.18 8.65 LOQ (g g 1) 0.0125 0.0141 3.80 1.67 4.13 4.55 17.3 28.9 Platform lifetimeb N 200 100 N 100d 50 N 200 100 N 200 140

a Characteristic mass calculated from calibration curve established from measurements of liquid standards in presence of selected modier. b Platform lifetime expressed in number of rings with no adverse effect on the analytical characteristics. c Permanent modier. d Lifetime of graphite tube reduced due to deterioration of its outer wall.

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Table 4 Results of determinations (given as mean value standard deviation) of Cd, Cr, Cu, Pb and Zn in soil certied reference materials (CRM) using linear calibration curve (number of replicates 10). Soil element S-MS Determined (g g 1) 0.211 0.041a 92.3 10.0 19.3 2.8 19.5 2.4 a 61.5 5.6 a Certied (g g 1) 0.198 0.029 87.4 3.2 21.2 1.7 18.9 2.2 63.7 4.2 e. p. 6.6 5.6 9.0 3.2 3.5 S-VM Determined (g g 1) 0.229 0.055 77.9 9.8 28.7 3.3 18.7 2.7 a 87.1 6.1a
a

S-SP Certied (g g 1) 0.214 0.038 79.8 5.8 30.0 2.1 19.8 2.1 88.8 3.3 e. p. 7.0 2.4 4.3 5.5 1.9 Determined (g g 1) 0.261 0.054 85.3 8.2 30.1 2.7 39.9 4.0 a 116 6a
a

Certied (g g1) 0.258 0.032 87.4 10.4 30.9 1.9 41.3 4.4 119 7

e. p. 1.2 2.4 2.6 3.4 2.5

Cd Cr Cu Pb Zn

e.p. error percentage, calculated: (|certied value determined value|)/certied value) 100. a Determined using linear calibration curve established with aqueous standard solutions and 2.0 g L 1 palladium + 1.0 g L 1 magnesium nitrate + 0.1% Triton X-100 in solution as modier.

measurements of aqueous standards and generalized standard addition procedure were utilized for quantication [33,34]. 3.3. Figures of merit and analytical characteristics of the developed method The results obtained from the calibration based on liquid standards and on the solid S-SP of varying masses as the calibrants showed that the linear range (LR) was narrower with the solid calibrant. This phenomenon was also reported by Vale et al. [25]. Such a deviation from linearity can be explained by the fact that atomization of the analyte from a sample of higher mass is affected by the evaporation of the sample matrix. Therefore, the maximum sample mass applied to the method developed was the maximum mass that provided a signal within the linear part of the calibration plot. Since the deviation in the slopes of linear calibration plots for the liquid and solid calibrants were within 5%, the more convenient liquid standards were used for calibration. The limit of detection (LOD) and limit of quantication (LOQ) were estimated from ve subsequent blank measurements including handling, weighing the platform and adding the modiers and surfactant. The LOD and LOQ (expressed as three- and ten-times, respectively), the standard deviation of the blank measurements calculated for the maximum sample mass used for the determination and other analytical characteristics are summarized in Table 3. 3.4. Analytical results The analytical results obtained with the three CRMs of soil using liquid calibration curves for evaluation are summarized in Table 4. The extension of the results is presented in Appendix C. Quantication based on the linear calibration curves with the liquid standards and by the standard addition technique did not show a statistically signicant difference (t-test, p N 0.05); all the results were within the condence limits of the certied values. The use of linear calibration makes the procedure suitable for the routine application to samples of similar composition as the soils examined in this study. The decrease in RSD with the increasing analyte concentration conrms the observations published previously [25,29,31]. Another important issue related to the SS-ETAAS, in particular, is adequate homogeneity of a sample. In agreement with Vale et al. [9], our opinion is that a 10% RSD of an accurate result is much more acceptable than a 1% RSD of a result that is affected by systematic errors due to analyte loss or contamination during sample preparation. In this work, we have used the soil CRMs that were prepared after the requirement for the preparation of CRMs in which the homogeneity was controlled. The determination in this work was repeated minimally 1015 times. The real soil samples also should be prepared in compliance with the ISO Standard 11464:2006, or any other relevant document [26,35].

4. Conclusion A method developed for the determination of Cd, Cr, Cu, Pb and Zn in soils by the SS-ETAAS was optimized using three certied reference materials of soils differing in the contents of the elements studied and matrix composition. Experiments were performed to optimize working conditions, which were comprised of the following: 1. the use of alternative (less sensitive) spectral lines to avoid disadvantages arising from the conventional approaches to the deliberate reduction of the sensitivity (e.g., sample dilution with carbon powder or increased gas ow-rate during atomization), 2. selection of the most suitable chemical modier(s) to achieve successful in situ analyte/matrix separation, 3. optimization of sample mass to study potential interferences, other adverse effects and methods for their elimination. Under optimized furnace conditions and with suitable matrix and/or analyte modiers, it was possible to minimize the matrix effect in the determination of all ve elements. In addition, liquid calibration solutions can be used to establish the calibration plot. The method was optimized such that it was possible to apply the same working conditions to the determination of a particular element in all three CRMs, regardless of their composition. The determination of Cr in soils by solid sampling, in particular, is an attractive alternative to the somewhat problematic conventional atomic spectrometry methodology using wet decomposition. Because these CRMs are not representative of all soil types, we recommend that this method be applied to the SS-ETAAS analysis of soils of similar composition and soil type as the soils examined in this study. Acknowledgements Financial support from the Scientic Grant Agency of the Ministry of Education of the Slovak Republic VEGA/1/0430/08 and Centre of Excellence AP VVCE-0070-07 is gratefully acknowledged. Appendix A. Supplementary data Supplementary data to this article can be found online at doi:10.1016/j.sab.2010.12.005. References
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