Microchemical Journal 86 (2007) 102 111 www.elsevier.

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Simultaneous determination of hydride forming (As, Bi, Ge, Sb, Se, Sn) and Hg and non-hydride forming (Ca, Fe, Mg, Mn, Zn) elements in sonicate slurries of analytical samples by microwave induced plasma optical emission spectrometry with dual-mode sample introduction system
Henryk Matusiewicz , Mariusz lachciski
Politechnika Poznaska, Department of Analytical Chemistry, 60-965 Pozna, Poland Received 30 November 2006; accepted 13 December 2006 Available online 22 December 2006

Abstract A slurry sampling method for the simultaneous determination of hydride forming (As, Bi, Ge, Sb, Se, Sn) and Hg and non-hydride forming (Ca, Fe, Mg, Mn, Zn) elements, without total sample digestion has been developed using the commercial dual-mode sample introduction system (MSIS) coupled with microwave induced plasma optical emission spectrometry (MIP-OES) from biological and environmental reference materials and real samples. The main advantage of this system is its simultaneous determination of elements that form volatile vapor species and elements that do not, without any instrumental changes. Optimization of reaction, nebulization and instrumental conditions was performed to characterize the new system. Slurry concentration up to 4% m/v (particles b 100 m) prepared in 10% HNO3 containing 100 L of decanol, by application of ultrasonic agitation, was used with calibration by the standard addition technique. An ultrasonic probe was used to homogenize the slurry in the quartz cup just before its introduction into the reaction/nebulization system; the multimode sample introduction system (MSIS) combines the benefits of nebulization and vapor generation in a single device. Detection limits (LOD, 3blank, peak area) of 0.07, 0.29, 0.25, 0.10, 0.12, 0.14, 0.11, 0.28, 0.42, 0.02, 0.21 and 0.34 g g 1 were obtained for As, Bi, Ge, Sb, Se, Sn, Hg, Ca, Fe, Mg, Mn and Zn, respectively. The relative standard deviations were ca. 10%, adequate for slurry analysis. To test the accuracy, six certified reference materials were analyzed with the analyte concentrations mostly in the g g 1 level. Measured concentrations are in satisfactory agreement with certified values for the biological reference materials (LUTS-1, DOLT-2) and environmental reference materials (PACS-1, GWB 07302, NIST 2710, NBS 1633b), all adequate for slurry sampling. The method was successfully applied to the determination of the elements in real samples (coal fly ash, lake sediment, sewage). The method requires small amounts of reagents and reduces contamination and losses. 2007 Elsevier B.V. All rights reserved.
Keywords: Dual-mode sample introduction system; Analytical samples; Ultrasonic slurry sampling; Chemical vapor generation; Trace elements; Microwave induced plasma optical emission spectrometry

1. Introduction The chemical vapor generation (CVG) of hydrides and mercury is currently a very popular sample introduction technique used in analytical atomic spectrometry [16]. However, as a rule, CVG atomic spectrometric techniques require complete digestion of the samples prior to analysis. The digestion step is very critical, which increases both analysis time and the risk of sample contamination and/or losses of the analyte. A
Corresponding author. Tel.: +48 61 665 2312; fax: +48 61 665 2571. E-mail address: Henryk.Matusiewicz@put.poznan.pl (H. Matusiewicz). 0026-265X/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.microc.2006.12.002

simple alternative to circumvent the digestion of samples is the slurry sampling (nebulization), which combines the advantages of the solid and liquid sampling (presentation) [7]. The method of hydride generation (HG) directly from slurried samples has recently been reviewed by Matusiewicz [8], in which important aspects of the slurry sampling (SS) in relation to analytical atomic spectrometry was presented. The ability of the microwave induced plasma optical emission spectrometry (MIP-OES) technique to determine several elements simultaneously may be advantageously used in this context and seems to be an effective approach. Slurry nebulization has also proved to be useful for sample introduction into the MIP [9,10]. It

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should be noted here, that only very recently have Matusiewicz and lachciski [11] proposed a method for the determination of As, Sb, Se, Sn and Hg in analytical reference materials by HGMIP-OES using slurry sampling. On the other hand, Santos et al. [12] proposed a method for the determination of As, Hg, Sb, Se and Sn in sediments by on-line chemical vapor generation inductively coupled plasma optical emission spectrometry (ICP-OES) using slurry sampling. In addition, Ribeiro et al. [13] proposed a method for the determination of As, Hg, Sb, Se and Sn in environmental and geological reference materials, as acidified slurries, by flow injection coupled to a hydride generation system and determination by inductively coupled plasma mass spectrometry (ICP-MS). The minor disadvantage of these systems is the need for separate MIP-OES (or ICP-OES) analysis to determine the other elemental constituents of the sample. Normally, introduction of analytes/ samples by CVG and pneumatic nebulization (NEB) are performed separately by using different sample introduction systems. A survey of the literature [1425] indicates that a few papers describe analytical methods suitable for determination of hydride and non-hydride forming elements simultaneously from the solution, but, as far as we are aware, has not been applied for analysis of slurried samples, using the dual sample introduction systems. Wolnik et al. [14] described a tandem nebulization system in which a concentric Meinhard nebulizer is mounted in a Teflon spray chamber, joined to a cross-flow nebulizer and fitted to a spray chamber connected to the ICP torch. Hutton and Preston [15] described a simple modification to the nebulizer assembly that allows either sensitive hydride or conventional solution analysis to be performed with no downtime. Huang et al. [16,17] developed a nebulizer hydride generator systems in which large droplets of the acid sample aerosol from the pneumatic nebulizers were trapped by the impact wall of a hydride generators, and reacted with reductant. Fengzhou et al. [18] developed and integrated a nebulizer-hydride generator system in which the spray chamber for pneumatic nebulization was modified for hydride generation. Pohl and yrnicki [19] employed a Jobin Yvon hydride generation system (CMA) without a gasliquid phase separator for the determination of As, Bi, Se, Sn and non-hydride forming elements by the ICPOES technique. McLaughlin and Brindle [20] reported a multimode sample introduction system (MSIS) in which hydride formation takes place at the outlet of the two capillaries, located in a modified cyclonic spray chamber, that transport the sample and sodium borohydride solutions. The MSIS system provides convenient means of determining elements, either by nebulization or vapor generation, or simultaneously in the same device. Rojas et al. [21] used a modified V-groove with one additional channel to introduce the hydride solution. Asfaw and Wibetoe [22,23] applied a commercial MSIS for the determination of As, Bi, Sb, Se, introduced as the hydride, simultaneously with the other non-hydride forming elements (Ca, Cd, Co, Cu, Mg, Ni, K, P, Pb, S, Zn). Zoltan et al. [24] studied a modified crossflow-type nebulizer coupled with a conventional Scott doublepass spray chamber. In this case, they adapted two new channels into the nebulizer in order to introduce the hydride and acid solutions separately. Finally, Gmez et al. [25] explored a dual

nebulizer sample introduction system for simultaneous determination of volatile element hydrides and other elements. The system consists of two pneumatic nebulizers connected to the conventional spray chamber of the instrument via a simple adaptor. This configuration permits hydride generation but still allows other elements to be determined by pneumatic nebulization. To our knowledge, no paper(s) have been published for the simultaneous determination of hydride and non-hydride forming elements, using slurry sampling chemical vapor generation/pneumatic nebulization microwave induced plasma optical emission spectrometry with dual-mode sample introduction system. In this paper we will describe, for the first time, the development of a simultaneous multi-element SS-CVG/NEB-MIP-OES method (by using a continuous mode system) for the quantitative determination of As, Bi, Ge, Sb, Se, Sn, Hg and Ca, Fe, Mg, Mn, Zn in biological and environmental certified reference materials and real samples prepared as slurries, using a dualmode sample introduction system. It also describes the MIPOES instrumental operating parameters, as well as the simultaneous CVG and NEB experimental parameters and an evaluation of the main analytical figures of merit, and presents details of the analytical procedure including preparation of slurry samples for the determination of volatile hydrides and elemental mercury as well as other elements. Finally, accuracy was checked by the analysis of six certified reference materials (LUTS-1, DOLT-2, PACS-1, GWB 07302, NIST 2710, NBS 1633b). 2. Experimental 2.1. Instrumentation The measurements were performed with a simultaneous MIP-OES spectrometer equipped with a microwave plasma excitation source, which includes a TE101 integrated microwave resonator with a microwave power supply. The majority of the OES system and microwave plasma cavity assembly used for simultaneous multi-element analysis was essentially the same as described previously; [11] this will not be discussed again here.

Table 1 Instrumental parameters for He-MIP-OES Nominal microwave frequency/MHz Microwave cavity Microwave power/W Plasma torch Plasma viewing mode Plasma supporting gas flow rate/ml min 1 Integration time/s Determination Working wavelengths/nm 2450 TE101 rectangular 260 Quartz tube, 2.5 mm i.d. Axial 350 0.1 Simultaneous As 228.811; Bi 223.061 Ge 303.907; Sb 217.582 Se 196.026; Sn 242.949 Hg 253.652 Ca 393.336; Fe 238.204 Mg 285.213; Mn 257.611 Zn 213.857

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Table 2 Instrumental parameters used for chemical vapor generation and nebulization studies in sonicate slurries Sonication, continuous Ultrasound frequency/kHz Sonication amplitude/% W Sonication time/s Slurry concentration/% m v 1 Chemical vapor generation Spray chamber NaBH4/NaOH solution concentration/% m v 1 HNO3 solution concentration/% m m 1 Thiourea solution concentration/% m v 1 Decanol solution added volume/l NaBH4 solution flow rate/ml min 1 Sample flow rate/ml min 1 Argon flow rate/ml min 1 Nebulization Nebulizer Nebulizer argon flow rate/ml min 1 Sample flow rate/ml min 1 20 60/40 90 4 As, Bi, Ge, Sb, Se, Sn, Hg Multi-mode sample introduction system (MSIS) 1.5/0.1 10 10 100 3 3 600 Ca, Fe, Mg, Mn, Zn Burgener T2002 V-groove Babington 600 3

Analyzer (CMA) [26] (Jobin Yvon S.A.S., France) operated in combined conventional nebulization and hydride generation mode (dual-mode). Slurry sample was introduced using a manually controlled four channel peristaltic pump (Berghof, Model BSH960, Germany). Slurries (aerosols) were introduced into the MIP torch using a commercially available high solids nebulizers: a one-piece V-groove Babington type nebulizer (van de Plas Products, Leiden, The Netherlands) with a gas orifice of 0.1 mm and a slurry solution orifice of 0.8 mm and T2002 Burgener nebulizer (Burgener Research Inc., Mississauga, Canada), particularly well suited for high-solid samples and slurry samples, because the opening is rather large (425 m i.d.) compared with other nebulizers. The MSIS served as the reaction chamber/gasliquid separator. In dual-mode the acidified slurry sample passes through both the nebulizer sample line and the hydride generator sample line. The hydrides formed are introduced to the microwave plasma simultaneously with the sample aerosol by a stream of the nebulizer argon. The MSIS system has been described in detail in previous paper. [20]. The experimental conditions are given in Table 2. A schematic diagram of the entire SS-MSIS-MIP-OES system is shown in Fig. 1. 2.3. Sonication For sonication the slurries and sample homogenization, a Bandelin (Berlin, Germany) Model SONOPULS HD 70 (20 kHz, 70 W) ultrasonic homogenizer with a 2 mm high purity titanium probe (microtip) was used. This probe sonicator allows working with slurry volumes in the range 0.0525 ml. 25 ml quartz vessels were used and the probe was positioned about 5 mm from the bottom of the cell. In addition, for sample homogenization, a mechanical mixer (MA-10, ORMED, d, Poland) was used.

The operating conditions and the working wavelengths are listed in Table 1. These lines were pre-selected by the producer of the polychromator. 2.2. Chemical vapor generation and liquid nebulization dualmode system Chemical vapor generation and liquid nebulization was accomplished in the continuous mode using the commercial Multimode Sample Introduction System (MSIS) [20] (Marathon Scientific, Niagara Falls, Canada) and Concomitant Metals

Fig. 1. Component diagram of the elaborated SS-MSIS-MIP-OES system (not to scale).

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The samples for slurry preparation were weighed using an M2P microanalytical balance (Sartorius, Gttingen, Germany) with a resolution of 1 g (electronic weighing range up to 2 g). All real samples were ground in an ball mill Model TESTCHEM-S (Pszw, Poland) and passed through a b 80 m nylon sieve. The sieve was used as a cut-off size filter. Particle size distribution, based on a defined measurement of diameter, was investigated by observation under optical microscope (PZO, Warsaw, Poland). Linear measurements of particles are made by using a scale placed on top of particle image. 2.4. Gases and reagents

tone extraction of fatty matter has been carried out, this material is closer in nature and properties to the original matrix, thereby allowing more realistic scrutiny of analytical procedures for application to real samples. Analytical samples were selected that matched the matrix and element concentrations of samples from our current projects as closely as possible. The following real samples were used in this study: coal fly ash from Pozna Coal-fired Power Plant in Poland, lake sediment was obtained from lake in Pozna, Poland and sewage sludge from a municipal sewage purification plant (Pozna, Poland). 2.6. Recommended analytical procedures

Compressed, ultrahigh-purity helium gas (N-50 purity, 99.999%) obtained from BOC GAZY (Pozna, Poland) was used as both the working gas supporting the plasma source and the carrier gas introducing vapors generated by the hydride generation and slurry aerosol to the plasma. Optimization of CVG and NEB and measurement of analytical figures of merit were both accomplished using stock solutions that contained 1 g ml 1 of the elements prepared by spiking the appropriate amounts of each 1000 g ml 1 atomic absorption standard solutions (Titrisol grade, Merck, Darmstadt, Germany) into a volumetric flask and diluting to volume. Working standard solutions were freshly prepared daily by diluting appropriate aliquots of the stock solution in high purity water. Sodium tetrahydroborate(III), used as reducing solution, was prepared daily, by dissolving NaBH4 pellets (Suprapure, Merck, Germany) in high purity water and stabilizing with 0.1% (m/v) NaOH (Suprapure, Merck, Darmstadt, Germany) solution to decrease its rate of decomposition, and was used without filtration. Thiourea was prepared by dissolving the powder (Fluka, Buchs, Switzerland) in water to yield a 7.5% solution. Ultra-high-purity commercial acids (HCl, HNO3) (Extra pure, Merck, Darmstadt, Germany) were used to prepare all reagents and samples. Decanol (pure, N 99%, Merck, Darmstadt, Germany) was used as the antifoaming agent. Water was initially deionized (Model DEMIWA 5 ROSA, Watek, Czech Republic) and then doubly distilled in a quartz apparatus (Hearaeus Bi18, Hanu, Germany). 2.5. Certified materials and samples Validation of the method described in this work was performed using six certified (standard) reference materials (CRMs, SRMs), which were chosen to represent solid sample matrices: LUTS-1 (Lobster Hepatopancreas), PACS-1 (Marine Sediment), DOLT-2 (Dogfish Liver) supplied by the National Research Council of Canada (NRCC), GBW 07302 (Stream Sediment) from NRC, China, SRM 1633b (Coal Fly Ash) and SRM 2710 (Montana Soil) supplied by NIST (USA). It should be stressed that LUTS-1 is a slurried biological material obtained through mechanical homogenization of lobster hepatopancreas tissue. Since no pretreatment, such as ace-

2.6.1. General The whole analytical procedure consists of various steps concerning: (i) formation of the slurry and sonication procedure; (ii) generation of the hydrides AsH3, BiH3, GeH4, SbH3, H2Se, SnH4 and Hg0 vapor, and elements Ca, Fe, Mg, Mn and Zn liquid nebulization and (iii) measurement by MIP-OES. 2.6.2. Formation of the slurry and sonication procedure The NRCC LUTS-1 lobster hepatopancreas reference material was provided as 10.3 g of homogeneous slurry. The material was diluted with water to a total volume of 100 ml, containing HNO3 and thiourea, and the mixture was stored for 30 min. An aliquot of slurry sample was then withdrawn from the flask and placed into a reaction vessel. Before being measured, 100 l of decanol (antifoaming agent) was added to the final volume of the slurry. Although no data are available characterizing the actual particle size of the LUTS-1 material, it must be less than 50 m and certainly less than 100 m [27]. In addition, it was demonstrated that different particle sizes do not significantly affect the results, and the samples can be used in their original particle size (b 120 m) [12]. The slurry preparation was based on a previous work [11]. The certified solid samples (fine powders) were analyzed in their original particle size (b 100 m). The real samples were ground in a ball mill to a final particle size of around b 80 m. An aliquot of 300 mg of each reference solid samples and real samples was accurately weighed and placed in a flask, where 9 ml of 10% HNO3 and 1 ml of 10% of thiourea were added, to make up a 3% m/v slurry, and the mixture was stored for 30 min. Slurries were pretreated by sonication at 60% of the ultrasonic probe power setting (ca. 40 W) for 5 min. The slurry sample was then withdrawn for the flask and placed into a reaction vessel. Before being measured, 100 l of decanol was added to the final volume of the slurry. To avoid settling and agglomeration, slurried samples were mechanically and vigorously stirred during the sampling and introduction into a MSIS, therefore, no rehomogenization was needed before each measurement. Blanks were processed through an identical procedure. 2.6.3. Simultaneous hydride generation and conventional nebulization procedure The procedures for hydride generation of slurry samples and liquid nebulization of samples were accomplished in MSIS [20].

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When manually operated in combined conventional nebulization and vapor generation mode (dual-mode), the hydrides and elemental mercury were generated continuously and were introduced into the MIP source; the liquid and slurry samples were introduced via the Babington nebulizer to the MIP. A Berghof peristaltic pump was used to feed the nebulizer with the sample, and with the acidic slurry sample and sodium borohydride solutions. The waste slurry solution was rapidly removed from the chamber to drains by peristaltic pump. The MSIS was rinsed by aspiration acidic water for approximately 30 s after injection of each slurry replicate (the washout time is about 30 s). 2.6.4. SS-MSIS-MIP-OES analysis The plasma was ignited momentarily inserting an isolated high purity tantalum wire into the quartz discharge tube and was allowed to warm up for a period of about 15 min prior to analysis. After completion of the generation and nebulization, the released gaseous products (hydrides, Hg0 and hydrogen) and slurry sample aerosol were transported into the MIP source for excitation by the He carrier gas. The measurement conditions were optimized based in signal-to-background ratio (S/B). Net analyte emissions were calculated by taking the simultaneous difference of measured emission intensities for sample and background (blank). Instrumental settings and operational parameters with the use of the experimental MIP-OES, hydride generation and nebulization systems are shown in Tables 1 and 2. Analytical blanks were also carried through the entire procedure outlined above, to correct for possible contaminants in the reagents used for slurry sample preparation. Quantification of As, Bi, Ge, Sb, Se, Sn, Hg, Ca, Fe, Mg, Mn, Zn was made by the standard addition technique. All detection limits were calculated for raw, unsmoothed data based on a 3 criterion of the background (blank) counts. The limit of detection (LOD), corresponding to a measurement level 3 above the mean blank intensity, was obtained by using procedural blank solutions. 3. Results and discussion 3.1. Concomitant Metals Analyzer (CMA) versus Multimode Sample Introduction System (MSIS) for vapor generation The hydride vapor generation accessories (two dual-mode commercial systems described in the Experimental Section) that
Fig. 3. The effect of ultrasonication time on the emission intensities of elements by SS-MSIS-MIP-OES system.

we were using for these investigations allow us to select from two basic dual-modes of operation. Preliminary experiments were performed by MIP-OES using aqueous standard solutions of volatile vapors (hydrides and elemental Hg). It was determined that the generation efficiency of the volatile element species did depend on the type of reactors used. An evidence of the more efficient transfer of analytes into the vapor phase using MSIS is revealed in Fig. 2. MSIS appeared to offer some advantages, such as improved signal intensities from 10% for Hg to 24% for Bi over the CMA and more efficient mixing of the slurry sample and reductant. It was concluded that the MSIS gave superior performance over the CMA, reflecting the higher vapor generation/transport efficiency of this device. Overall, the MSIS was chosen for all the subsequent experiments. 3.2. Slurry preparation procedure For the purpose of slurry homogenization and extracting the elements into the aqueous phase and making it available for the vapor generation reaction and nebulization, a simple sample pretreatment step was included such as addition of nitric acid and sonication. In order to avoid foaming, decanol (100 l) was added to the mixture [11]. No particles larger than 100 m were detected during the microscopic examination of the reference material slurries. It was confirmed that the grinding of real samples prior to the slurry preparation increases the element signals. For practical reasons a particle size of b 80 m, selected previously [11], was adopted for MSIS system. In general, a particle size of b 100 m was selected for the slurry preparation. The influence of ultrasonication time in the range of 17 min of agitation on the analytical signals using a titanium probe is shown in Fig. 3. An analysis of this figure indicates that the emission intensity signals remain constant starting from 5 min of sonication. Thus the shortest possible time (5 min) was chosen to decrease time for the whole analytical procedure. Fig. 4 depicts the influence of the ultrasonic power on the repeatability and emission intensity of the analytical signals, which was also investigated. Almost the same repeatability (RSD 10%) was observed for ultrasonication power in the range of 545 W. In general, for all analytical lines of studied vapor forming elements, S/B ratios usually tend to level off after the ultrasonic power approaching 40 W (Fig. 4). As a result of this consideration on the above influences, a compromised power of

Fig. 2. Comparison of vapor generation efficiency using MSIS and CMA.

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Fig. 4. The effect of ultrasonication power on the emission intensities of elements by SS-MSIS-MIP-OES system.

deration on the above influences, an optimized power of 260 W was selected as an acceptable value and a practical working range. The effect of plasma (support) helium gas flow rate was also optimized in our experiments. An increase in the plasma gas flow rate, up to 400 ml min 1, leads to a more effective transportation of the vapors to the plasma. For As, Sb and Sn, the maximum signal intensities was observed at plasma flow rate of 350 ml min 1 than for the other four analytes, as shown in Fig. 6. As a compromise, a stable plasma gas flow rate of 350 ml min 1 was adopted. It was also observed that the carrier gas stream flow rate has a more significant influence on the emission intensities than the plasma support gas flow rate (see below). 3.4. Selection of vapor generation conditions

40 W was selected as an acceptable value and a practical working range. With the 70 W ultrasonic processor used in combination with the 2 mm microtip, amplitude values higher than 70% should be avoided so as to prevent the slurry spilling out of the vessel. 3.3. Establishment of MIP-OES operating conditions The optimization of wavelength was not carried out because the wavelengths used for the determination were pre-selected by the producer of the polychromator. The MIP is normally operated at low power levels in the range 50150 W. In this work, the stable He plasma could be maintained at a level of greater than 100 W forward power. Below 100 W power input, no stable discharge was produced. Between 100 and 300 W, neither the intensities of spectral lines nor the S/B ratios showed such a dependence on the power that this would point to a pronounced optimum. In addition, the stability of the background and lines signals did not significantly vary with power in the stated range. As expected, an increase of intensity was observed with increasing power. However, the signal stability deteriorates above 260 W. In general, for all analytical lines of studied vapor forming elements, S/B ratios usually tent to level off after the microwave power approaching 260 W (Fig. 5). The intensities of spectral lines also level, but more slowly. As a result of this consi-

The rate of generation of volatile vapors greatly depends on the concentration of NaBH4 and acidity. However, substantial optimization of the generation parameters for the analyte vapors was not undertaken, as this information was already available from our own observations [11]. The concentration of 1.5% NaBH4, stabilized with 0.1% (m/v) of NaOH was adopted. This appears intuitively correct, since these factors are an integral part of the hydride generation reaction. To optimize the sample and reductant flow rate for multielement determinations, first the optimum flow for each individual element was estimated in the range of 16 ml min 1 (Fig. 7). It was observed that when the flow rate was low (13 ml min 1), the emission intensities increased with the flow rate; when the flow rate went up to 3 ml min 1, the emission intensities reached maximum; however with the further increase of the flow rate (above 3 ml min 1), the emission intensities decreased for all elements. Therefore, in this study a 3 ml min 1 sample and reductant flow rate was chosen. The helium carrier gas flow through the MSIS system (continuous mode generation system) is one of the basic parameters influencing the transport the hydride vapors and elemental mercury into the microwave plasma torch, so the determination sensitivity. In our work, the intensities of vapor forming elements significantly depended on the gas flow rate. The vapors were stripped from the vapor generator and were transported at helium flow rates in the range 2001200 ml min 1. It is evident

Fig. 5. Influence of microwave forward power on the emission intensity of the elements in the vapor generation technique.

Fig. 6. Influence of plasma (support) helium flow rate on the emission intensity of the elements in the vapor generation technique.

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Fig. 7. Influence of sample and reductant uptake rate on the emission intensity of the elements in the vapor generation technique.

Fig. 9. The influence of acid type on the emission intensities of As, Se and Hg in the Dogfish Liver (DOLT-2) slurry.

that the use of low carrier gas flow can successfully reduce high analyte losses caused by sorption on the inner surfaces of the apparatus (cyclonic chamber and transport tubing). On the other hand, higher carrier gas flow rates (N 600 ml min 1) can result in a decrease in emission intensity for all elements. The interaction between NaBH4 and the helium flow is in accordance with the fact that the two factors together determine the amount of gas sent through the system. Thus, a carrier He flow rate of 600 ml min 1 was selected, which was adequate to transport all the generated vapors completely and independent of the elements oxidation state. The dependence of the analytical signals for the hydride forming elements and elemental mercury on the carrier gas flow rate is depicted in Fig. 8. The effect of hydrochloric acid and nitric acid on net emission intensities of three pilot elements (As, Se, Hg) was also investigated and is shown in Fig. 9. As is shown for all three analytes studied, the signal intensity was affected by the nature of the acid, nitric acid. Thus, a 10% of HNO3 was chosen for the slurry preparation and for the generation of hydride vapors and elemental Hg. On the other hand, a pre-reduction step is needed to overcome possible errors in total analyte hydride determination. Thiourea is an efficient reductant/masking agent for hydride generation in the presence of a high concentration of transition metals such as Cu [24]. Thiourea has been efficiently used for the reduction of hydride forming elements, i.e., reduction of As(V), Sb(V), Se(VI) and Sn(IV) to the lower oxidation states As(III), Sb(III), Se(IV) and Sn(II). A concentration of 1%

(m/v) of thiourea and a contact time of 30 min were selected as convenient for the pre-reduction of all element species. In this case, the introduction of a reductant or masking agent like thiourea is recommended in order to avoid any loss of sensitivity during hydride generation. 3.5. Selection of nebulization conditions Our interest in the quantitative determination of element concentrations in slurries, solutions which contain large quantities of particles, has led us to do a comparison study of a commercially available nebulizers. Single mode sample introduction with a nebulizer with a relative large opening is needed for introduction of the slurries to hinder clogging. The V-groove Babington-type and T2002 Burgener nebulizers are well known and will not be detailed here, therefore were chosen for introduction of slurry samples into the MIP source. MSIS spray chamber was used with both nebulizers. All measurements to compare the effectivity of both nebulizers were performed with the same generator and with the He/ He plasma. For each individual nebulization system the S/B ratios showed small mutual differences within each of the specific wavelength. Consequently, simultaneous multi-element analysis employing any of the nebulization system examined requires no compromise with respect to the flow rate of the nebulizing gas. None of the nebulization systems examined exclusively produced the highest S/B ratios for all 5 spectral lines considered. For two nebulization systems tested we have determined the limits of detection for Ca, Fe, Mg, Mn and Zn. Concerning these pneumatic nebulizers we have observed that performance are very similar, also the RSD observed are close. For routine analysis the combination of MSIS with Babington nebulizer represents probably the best choice because performances are satisfactory and blocking is less likely than with the more brittle Burgener T2002 nebulizer and other high solid nebulizers. 3.6. Analytical figures of merit

Fig. 8. Influence of carrier helium flow rate on the emission intensity of the elements in the vapor generation technique.

The analytical performance characteristics were evaluated for each element. The limit of detection (LOD) calculated using

H. Matusiewicz, M. lachciski / Microchemical Journal 86 (2007) 102111 Table 3 Analytical figures of merit

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Element Blank RSD Detection limit (g g 1) (%) Present worka Literature (g g 1) Ref. [11] Ref. [12] Ref. [14] Ref. [16] Ref. [18] Ref. [19] Ref. [20] Ref [22] Ref. [23] Ref. [24] Ref [25] g g 1 g g 1 ng ml 1 ng ml 1 ng ml 1 ng ml 1 ng ml 1 g g 1 g g 1 ng ml 1 ng ml 1 As Bi Ge Sb Se Sn Hg Ca Fe Mg Mn Zn
a b

0.13 0.36 0.32 0.17 0.19 0.20 0.18 0.52 0.46 0.19 0.29 0.20

10 10 11 9 12 10 10 13 11 9 10 11

0.07 0.29 0.25 0.10 0.12 0.14 0.11 0.28 0.42 0.02 0.21 0.34

0.06 b 0.08 0.15 0.12 0.10

0.5 0.2 0.1 6 0.1

3 0.9 20 0.7 0.5 6 6 1 b1 7

7.5 0.6 8.3 3.3 6.8 1.0 9.0

0.4 0.9 0.55 0.65 0.3 4 1

4.4 4.6 4.4 1.5 2.2 0.50 0.32 2.3

9.45 10.27 9.94 18.58 4.26 0.08 0.14 0.08

0.0016

0.0062 0.0097 0.006 0.680

0.52 1.3 4.7

3 19 10 0.1 3 3 1

For sample weights of 400 mg in a final slurry concentration of 4%. Not determined. Ref [11] MIP-OES; Ref [14,16,1820,22,24,25] ICP-OES; Ref [23] ICP-MS.

the IUPAC recommendation (based on a 3blank criterion), determined by 10 repetitive measurements of the blank involving the entire process, and obtained by use of the compromise operating conditions are summarized in Table 3 and are based on the raw, unsmoothed data. Since no detection limits, for all elements, obtained by identical technique are available, the results are compared only with those obtained by both the introduction of solutions by conventional nebulization and the generation of vapors (hydrides and elemental mercury) ICPOES techniques [11,12,14,16,1820,2225], and in addition with this same technique [11]. Table 3 shows the detection limits obtained with the current system and those for different hydride generating systems designs and where simultaneous determination of hydride forming and non-hydride forming elements has been reported. From Table 3 it can be seen that the

detection limits for hydride forming elements of the developed procedure are better, as reported previously by others [11,12,14,16,1820,2225]. For the conventional elements, a significant improvement for all studied elements was obtained [14,16,1820,2325]. The precision of replicate determinations was calculated from the RSD (%) of the mean of five replicate measurements of element standard using a mass 50-fold above the LOD. Precision was in the range of approximately 10% (evaluated as peak area) and is probably largely determined by the instability of the microwave plasma source. These values can be considered satisfactory, especially owing to the large number of parameters governing the performance of the coupled technique. In other words, this reflects the cumulative imprecision of all of the sample slurry handling, vapor generation,

Table 4 Determination of hydride and non-hydride forming elements (concentrations in g g 1 SD of three parallel analyses) in reference materials using SS-MSIS-MIP-OES method Element NRCC LUTS-1 Found value As Bi Ge Sb Se Sn Hg Ca Fe Mg Mn Zn
a b

NRCC PACS-1 Certified value 2.83 0.13 3.0b 3.0b 3.0b 0.641 0.054 3.0b 0.0167 0.0022 203 33 11.6 0.9 89.5 4.1 1.2 0.13 12.4 0.8 Found value 205 17 2.79 0.26 1.84 0.19 169 18 1.01 0.13 39.1 3.87 4.40 0.32 19345 2314 46312 3920 14641 1028 477 38 795 86 Certified value 211 11 3.0b 2.0b 171 14 1.09 0.11 41.1 3.1 4.57 0.16 20870 1044 48680 974 14530 581 470 14 824 25

NRCC DOLT-2 Found value 16.0 1.8 2.86 0.19 1.90 0.15 2.91 0.24 5.69 0.47 2.78 0.22 2.12 0.17 c Certified value 16.6 1.1 3.0b 2.0b 3.0b 6.06 0.49 3.0b 1.99 0.10

2.71 0.34 2.79 0.31 2.86 0.25 2.83 0.27 0.654 0.068 2.88 0.24 b DLa 192 26 12.8 1.7 83.1 9.4 1.4 0.18 11.7 1.3

Below detection limit. Added amount. c Not determined.

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Table 5 Determination of hydride and non-hydride forming elements (concentrations in g g 1 SD of three parallel analyses) in reference materials using SS-MSIS-MIP-OES method Element NRC GBW 07302 Found value As Bi Ge Sb Se Sn Hg
a b

NIST SRM 2710 Certified value 6.2 1.8 1.64 0.34 1.70 0.82 0.46 0.34 0.21b 29.00 8.19 0.04 0.02 Found value 99 12 2.83 0.28 2.74 0.36 18.63 1.23 1.41 0.41 2.73 0.34 6.04 0.73 Certified value 105 8 3.0c 3.0c 19.4 1.8 1.52 0.14 3.0c 6.25 0.19

NBS SRM 1633 b Found value 59 7 2.79 0.29 1.91 0.21 6.68 0.71 8.97 1.2 2.94 0.26 0.17 0.04 Certified value 61 6 3.0c 2.0c 6.9 0.6 9.4 0.5 3.0c 0.14 0.02

5.8 0.4 1.57 0.18 1.62 0.15 0.42 0.04 0.15 0.02 27.6 2.64 b DLa

Below detection limit. Non-certified value. c Added amount.

nebulization, transfer of vapors and aerosols, excitation and detection steps, and possibly a function of particle size. 3.7. Validation of the method by analysis of reference materials To ensure the accuracy and precision of the developed analytical method on the determination of hydride and non-hydride forming elements, six reference materials, were chosen because they were the closest in nature to real biological and environmental samples. The results obtained for the analysis of reference materials by ultrasonic slurry HG-MSIS-MIP-OES method using both the external calibration technique and the technique of standard additions, are summarized in Tables 4 and 5. The results obtained by the external calibration technique do not agree with certified values for any reference material, indicating that calibration against aqueous solution could not produce accurate results, therefore calibration was achieved using the technique of analyte additions. All experimental concentrations agreed fairly well with the certified interval element values. Although no interference study was undertaken, it is obvious that there are no systematic errors due to the presence of the matrices. The precision of replicate determinations was typically around 10% RSD.
Table 6 Determination of hydride and non-hydride forming elements (concentrations in g g 1 SD of three parallel analyses) in real samples using SS-MSIS-MIP-OES method Element As Bi Ge Sb Se Sn Hg Ca Fe Mg Mn Zn
a

3.8. Element determinations in selected real samples The proposed method was applied to the determination of total hydride forming and non-hydride forming elements in some real slurry and solid samples using the experimental conditions previously optimized. The results for the samples analyzed using the evaluated method are given in Table 6. In all cases, the calibration was achieved using the technique of standard additions. The precision of replicate determinations is typically better than 10% RSD. 4. Conclusion The MSIS nebulizer system applied in this work has potential benefits in MIP-OES for the simultaneous determination of some hydride forming elements (As, Bi, Ge, Sb, Se, Sn) and volatile vapors (Hg) and conventional elements (Ca, Fe, Mg, Mn, Zn) in the certified reference materials and real samples using slurry sampling (SS-MSIS-MIP-OES). This approach retains the multi-element capability of OES detection with simultaneous determination under compromised experimental conditions of various hydride forming elements and mercury and non-hydride forming elements (conventional elements), from aqueous slurries, with MIP-OES detection. This technique can easily be applied to the determination of total elements and is suitable for use as an alternative to wet sample decomposition and/or dissolution procedures, which are usually the slowest steps of the method. Thus, the sample pretreatment is minimal and is reduced to a slurry preparation procedure (although sample preparation is not entirely eliminated) at room temperature and normal pressure. A particle size of below 100 m has been found adequate for direct vapor generation and nebulization. Memory effects were not observed in this system, avoiding the need for long washing times between samples. It can be said that with compromise operating conditions the obtained detection limits, below g g 1, were adequate for the analyzed samples and good recoveries were obtained for the elements determined. In addition, this technique significantly reduces the hazardous laboratory wastes and low reagent consumption, the fume-hood emission, the analysis time and sample contamination.

Coal fly ash 20.1 2.3 2.82 0.25 b DLa 10.16 0.98 4.09 0.34 15.1 1.6 2.09 0.27 27521 3050 30358 3241 15729 1712 325 37 722 76

Lake sediment 3.12 0.29 1.24 0.16 b DLa 3.07 0.31 1.84 0.23 10.16 1.08 b DLa 15320 1734 13543 1402 9725 1032 842 106 279 34

Sewage 13.4 1.2 2.28 0.23 b DLa 2.61 0.24 2.30 0.27 13.8 1.6 2.46 0.29 12948 1435 9824 1013 6750 715 563 65 412 49

Below detection limit.

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Potentially, the proposed analytical method offers interesting perspectives for the direct determination of other hydride forming and non-hydride forming elements based on the use of a slurry of the sample and is attractive alternative for laboratories not equipped with ICP-OES or ICP-MS. This MSIS nebulizer system is easily interfaced to MIP-OES apparatus (commercially available MIP-OES/MS instruments: MIP-MS P-7000, Hitachi, Japan; MIP-OES FY510 and FY1010, Little Swan Instruments Co., Ltd., China). Extension of this approach to the determination of other hydride forming and non-hydride forming elements based on the use of a slurry sampling and application to analysis of other reference materials and real samples will also be evaluated. Acknowledgement We are grateful to acknowledge the financial support by the State Committee for Scientific Research (KBN), Poland, Grant No. 3 T09A 140 27. References
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