Microchim Acta 153, 4549 (2006) DOI 10.

1007/s00604-005-0431-7

Original Paper Determination of Arsenic in Dolomites with a Simple Field Spectrometric Device
Katarzyna Stec1 , Andrzej Bobrowski2; , Kurt Kalcher3, Helmut Moderegger3, and Walter Goessler3
1 2 3

Institute of Refractory Materials, Toszecka 99, PL-44-100 Gliwice, Poland Department of Building Materials Technology, Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Al. Mickiewicza 30, PL-30-059 Krakow, Poland Institute of Chemistry, Analytical Chemistry, Karl-Franzens University, Universittsplatz 1, A-8010 Graz, Austria a

Received June 13, 2005; accepted September 13, 2005; published online November 7, 2005 # Springer-Verlag 2005

Abstract. A simple and an inexpensive procedure for the determination of total arsenic in dolomites is proposed. The method applies the spectrometric eld device Supralab SD which was initially designed for the determination of arsenic in drinking water. The method relies on the formation of the volatile AsH3 and its reaction with mercuric bromide, immobilized in a membrane, to yield a yellowish-brown reaction product, which is spectrophotometrically detected. The dolomite samples were rapidly dissolved in hot hydrochloric acid in an open vessel and then were analyzed with the portable instrument. The 3 s detection limit of the developed method was 0.1 mg L1 as in the solution containing dissolved dolomites. The time of As determination in the solution did not exceed 5 min. To validate the results obtained with the eld device, hydrogen generation inductively coupled plasma optical emission spectrometry (HG-ICP-OES) and inductively coupled plasma mass spectrometry (ICPMS) were used as reference methods using microwave-assisted mineralization. Excellent agreement between the methods was obtained.

Key words: Arsenic; dolomite samples; hydride generation; spectrophotometry; ICP-OES; ICP-MS; eld device; SupraLab.

Author for correspondence. E-mail: gcbobrow@cyf-kr.edu.pl

It has been found long ago that mineral salts, containing proper concentrations of Ca and Mg, consumed with the human diet are very important agents playing an essential role in the regulation of many biological processes and affecting human health. Dolomite used as an additive to food and to some medical formulations is the main source for these compounds. However, there exist restrictions concerning the admissible levels of the concentration of toxic elements present in dolomite applied in pharmaceutical, food and fertilizers industries. One of minor and trace components, which may be very toxic, is arsenic. The human organism can be seriously poisoned after consumption of 100 mg dose of inorganic arsenic [1]. On the other side arsenic in very low concentration is considered as a microelement which can stimulate the human body with respect to its basic metabolism. The Polish standard allows up to 0.0005% maximum concentration of this element in the mineral dolomite when added to food and pharmaceuticals [2]. For the above reasons the precise analytical control of the arsenic concentration in dolomites which are used in the mentioned industrial productions as well as in the production of

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K. Stec et al. where hydride generation is performed. The liberated arsine enters the cell and penetrates the impregnated lter reacting with the mercuric bromide and forming a yellowish-brown reaction product, which is monitored with an LED and a photodiode in transmittance mode. The apparatus was connected with a personal computer via an RS232 interface in case that monitoring of data is needed.

high purity optical glass is very important. To determine low concentrations of arsenic in minerals mainly the spectrometric methods are used, such as electrothermal atomic absorption spectrometry (ET-AAS), inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). However, determination of arsenic traces in dolomites by means of ET-AAS or of ICP-OES may be troublesome on the account of matrix effects, caused by the presence of high concentration of Ca and Mg in the tested dolomite samples, or by the presence of chloride. The application of hydride generation (HG) pre-separation combined with spectrometric techniques has proved to be a powerful analytical tool for the determination of arsenic and other elements able to form volatile hydrides, which allows to avoid matrix effects, because Ca and Mg do not form volatile hydride compounds. The eld device, the SupraLab SD, has been recently designed to determine the concentration of arsenic and selenium in water samples [3, 4]. The principal design of this analytical method is based on the conversion of inorganic arsenic (arsenite and arsenate) to arsine by reduction using tetrahydroborate in hydrochloric acid and its ensuing release from the sample solution in a gas stream, which undergoes a chemical reaction within the detector cell (Gutzeit reaction) [5]. The yellowish-brown reaction product, formed from arsine and mercury bromide and probably consisting of mixtures of As(HgBr)nH3-n, is spectrophotometrically monitored. The main goal of the paper is to apply the above eld spectrophotometric device coupled with hydride generation [3, 4] to the rapid determination of the arsenic content in various high purity dolomite samples and to validate the results with ICP-MS and ICP-OES. Experimental
Methods and Instrumentation HG-Spectrophotometric Method with Supralab SD Device All spectrophotometric measurements were carried out using the Supralab SD (HELMOTEC. Kalsdorf, Austria [3] www.supra-lab. com). An Erlenmayer ask (100 cm3) is connected with the instrument and used for the generation of the hydride. The sodium tetrahydroborate reagent is added in form of tablets to the sample solution (tablet HyGen), which facilitates easy and simple operation in the eld. The core of the device is a lter, impregnated with mercuric bromide. The impregnated paper, the LED (light emitting diode) and the photodiode are arranged linearly in a measuring cell, which is mounted with its inlet directly onto the Erlenmayer ask,

HG-ICP-OES and ICP-MS HG-ICP-OES determinations were done with an ICP optical emission spectrometer (JOBIN YVON JY 36, www.jyemission.com) in combination with a hydride cassette [6], the corresponding mass spectrometric determination with an ICP-MS (Hewlett Packard 4500, www.chem.agilent.com), employing standard procedures. For the reference determinations with atomic spectrometry the dolomites were mineralized with a microwave digestion system (MLS-1200 MEGA, Milestone, www.spectro-lab.com.pl).

Reagents and Materials Nitric acid, hydrochloric acid, sodium hydroxide and standard arsenic solution (1 g dm3 ), all of analytical reagent grade, were purchased from Merck. Sodium tetrahydroborate tablets (HyGen) and the impregnated membranes (InMem, ReMem) were obtained from Helmotec. Deionised water was puried with a cartridge system from NANOpure BARNSTEAD.

Dolomite samples The dolomites were of Polish origin. In lithological respect they were homogeneous, white or yellow without any visible deposits or contaminations. The samples were washed and ground prior to analysis. The nely-ground dolomite samples with a grain size less than 63 mm were investigated. The composition of the dolomite samples comprising main and trace elements was given in [7]. Digestion of the Dolomite Samples. Three different procedures of the dolomite decomposition were elaborated. The digestion procedures were selected depending on the analytical techniques used for As determination. In the elaborated spectrophotometric method a simple procedure was used for the digestion of a small amount (0.01 g) of dolomite in hydrochloric acid, which made quick sample decomposition in eld conditions possible. The HCl present in the analysed solution provides the most suitable condition for the generation of arsine. In case of ICP AES and ICP MS procedures 0.5 g of sample was digested because the analyte was then used not only for the determination of As but also for the quantication of main and trace elements present in the dolomite [7]. For the multielements determination of the trace elements (including As) by means of the ICP MS technique the dolomite samples were digested in nitric acid, which, does not, as is the case with other mineral acids, interfere in the determination of other elements. In the ICP AES method the mixture of the acids (HCl and HNO3) was chosen so as to facilitate and reduce the time needed for the digestion process. The obtained solutions were strongly acidied no matter which digestion procedure was used. For determination with Supralab SD a simple open acid digestion procedure was applied. Aliquots of 0.01 g to 0.1 g, were weighed into 50 cm3 beakers and moistened with a few cm3 of deionised water. Hydrochloric acid (conc., 2 cm3) was added and the mixture was quickly heated for 2 minutes to dissolve the samples. Then, a further aliquot of 1 cm3 HCl was introduced. In case of the ve investigated dolomite samples containing less than 2.5% of SiO2,

Determination of As in Dolomites with a Simple Field SD after digestion no precipitate was observed in the solutions. Only for the Niwnice sample, containing ca. 18% SiO2, the digestion process was not complete. After cooling, solutions were diluted with deionised water to 50 cm3 in a volumetric ask. Solutions were determined directly with the Supralab SD analyser. For HG-ICP-OES purpose the samples were decomposed in the microwave multi-digestion system. Subsamples of 0.5 g plus 5 cm3 HCl and 1 cm3 HNO3 were added to the digestion vessels, which were placed in the carousel of MW oven and heated accordingly. After digestion, solutions were transferred to the 100 cm3 volumetric ask and diluted with deionised water. The total digestion time was 3 hrs. The line at 193,759 nm was used for the measurement. For ICP-MS determination of As, the dolomite samples were also digested in the microwave multi-digestion system in nitrogen atmosphere. 0.5 g of subsamples and 5 cm3 HNO3 were placed in vessels of MW system and decomposed. Total digestion time was equal to 3 hrs. Before ICP MS determination the solution were 1000 times diluted with deionised water. Mass 75 was monitored with the instrument. Analytical Procedure for the As Determination with Supralab SD. The impregnated lter paper (InMem) is inserted into the detector cell between LED and photodiode. In order to absorb hydrogen sulphide and selenide from the sample solution a second membrane impregnated with lead acetate (ReMem) is placed in front of the reactive membrane in the gas stream. A dened amount of the solution of dissolved dolomite (50 cm3) is transferred to the reaction vessel (Erlenmayer ask equipped with a Teon-coated stirring bar). A tablet of sodium borohydride (HyGen) is added to the sample solution. Then the connector of the cell was set immediately onto the ask. At the same time recording of the response curve was started. The sample output curve was registered on a personal computer with the corresponding software. The reaction (generation of arsenic hydride) was in all cases nished after three minutes. In order to check sorption of the arsine, lead impregnated lters (commercially available ReMem) and cottons were tested for their effect on the hydride. It was found that practically no notable amount of the generated arsine is retained in both cases. Optical inspection of the lters (InMem) by eye after reaction did not show any inhomogeneities of the colour due to non-uniform impregnation. In order to avoid analytical errors and artefacts it is necessary that the measuring cell should be mounted immediately on the ask after adding the sodium borohydride tablet. Delay may cause loss of arsine gas and may produce erroneous results. Also, the dissolution of the samples must be performed carefully in order to avoid losses by spraying. The evaluation of the concentration of arsenic in the sample solution was done by the internal calibration curve of the instrument supplied by the producer.

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employed. The light source was the integrated photo diode with an emission maximum of 450 nm. As reaction matrix the commercially available membranes impregnated with mercuric bromide were used (Gutzeit reaction with arsine); after the use usually a yellowish-reddish colour could be observed. The instrument displays the concentration of arsenic in the water sample already, but nevertheless a calibration curve was established with standard solutions of arsenic acidied in the same way as the dolomite samples (Fig. 1). The signal was evaluated as the difference of the initial intensity of light and the lowest value of the measured intensity (given as bits) after the reaction, obtained in all cases in less than three minutes. The calibration curve corresponded in fact

Fig. 1. Calibration curve as obtained with the portable device SupraLab; difference (i0 i) of the signal (i) and the signal obtained before reaction (i0, 1000 bits), given in bits

Results and Discussion Optimization of Spectrophotometric Method Employing Supralab DF Instrumentation For the spectrophotometric method for the determination of arsenic in dolomite the sample solution should not contain signicantly more than 10 mg dm3 As in order to be in the optimum working range of the instrument. For the determination of As in dolomite samples the standard conguration of the instrument was

Fig. 2. Dependence of the signal on the concentration of arsenic with the signal calculated as absorption

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Table 1. Arsenic concentration (mean s) in dolomite samples determined by means of the three spectrometric methods1 Sample number 1 2 3 4 5 6
1 2

K. Stec et al.

Source2 Oldrzychowice Niwice Waliszw o Re dziny I Pogorzyce I Pogorzyce II

Supralab FD [mg=kg] 0.59 0.02 30.26 0.25 10.3 0.6 0.51 0.03 8.09 0.08 5.72 0.52

ICP-AES [mg=kg] 0.59 0.02 30.12 0.27 10.0 0.5 0.51 0.02 8.09 0.08 5.7 0.5

ICP-MS [mg=kg] 0.58 0.02 29.90 0.37 10.0 0.2 0.55 0.03 8.50 0.43 6.80 0.14

The mean of 9 determinations (3 measurements of each of the 3 parallelly digested dolomite sample). Source indicates the sampling place in Poland.

very well to the displayed values of arsenic concentrations as evaluated by the instruments internal calibration curve, not deviating more than two percent (mean of three determinations) over the whole range. The signal shown in Fig. 1 corresponds to the intensity decrease of light due to the formation a coloured reaction product (Gutzeit reaction). The initial intensity is set automatically to 1000 (bits); this transformation of the shown signals into absorption units is possible by forming the corresponding logarithmic ratio (Fig. 2). Such calibration graphs relating absorbance to As concentration show linearity up to around 10 mg dm3 As in the solution. The detection limit (3 s) was found 0.07 mg dm3 arsenic in the investigated solution, corresponding well with 0.1 ppb indicated by the producer. The limit of quantication (10 s) was determined as 0.23 mg dm3 . The reproducibility of the determination with the same dolomite sample solution was typically 1% RSD, the repeatability with the same sample, but dissolved individually ranged from 1 to 10% RSD (3 determinations). The analysis time was around six minutes including dissolution and measurement. The total time for the whole procedure, including weighing, was less than ten minutes. Severe interferences may arise from antimony if it is present in the sample in a tenfold excess or more (mass-to-mass ratio). Sulphide, selenite, tellurite do not interfere even in a hundred fold excess because they are absorbed from the gas stream by lead acetateimpregnated membrane. The comparison of the results of the As determination in various dolomite samples obtained by the three methods is presented in Table 1. The results for samples 1 to 4 agree very well with all three methods. Sample 5 deviates 5 percents from the ICP-MS result which represents still an acceptable result. Higher deviations were observed with the sample 6 between plasma spectroscopic and photometric determinations (19%), but in this case obviously the mere dissolution of the

dolomite in hydrochloric acid seems to be inferior to the micro-wave assisted digestion over three hours. Arsenic seems to be included in some silicate residue, and is therefore not accessible for the determination. Nevertheless, for a quick eld method with a portable instrument, also this result is still acceptable. Conclusions A rapid and simple method for the determination of arsenic in dolomite samples was developed, using a portable spectrometric device. The results usually agree very well with atomic optical and mass spectrometric methods using microwave assisted digestion, supposed that arsenic is not retained in silicate residues. All the investigated methods possess the sufcient sensitivity and similar precision, however, the cost of the applied instrumentation is considerable different. The method of the As determination in dolomite samples based on coupling the hydride generation technique with spectrophotometric detection in the eld device ensures to obtain a low LOD (0.1 mg dm3 As in the solution, [3]), wide linearity range, lack of interferences from the Ca and Mg matrix elements, good precision and accuracy. The analytical procedure enables to perform eld analysis after the simple and quick digestion of the dolomites samples in hydrochloric acid what can also be easy executed in eld conditions. When comparing the ability of the three investigated methods of the As determination in dolomites it can concluded that the spectrophotometric method with Supralab eld device could be a method of choice due to its sufcient sensitivity, simplicity, high speed of the analysis and low cost of apparatus. It may be concluded that new method using the device Supralab SD has some unique advantages in comparison with other methods and is well suitable for trace determinations of arsenic in dolomites used for pharmaceutical purpose.

Determination of As in Dolomites with a Simple Field SD Acknowledgement. Financial support from the AGH-University of Science and Technology (Project no. 11.11.160.698) and from the CEEPUS project Pl-110 is kindly acknowledged.

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[3] SupraLab SD Instruction Manual, HELMOTEC 2002; http:==www.supra-lab.com [4] Omanovic E, Moderreger H, Kalcher K (2002) Anal Lett 35: 943 [5] Buckett J, Dufeld W D, Milton R F (1955) Analyst 80: 141 [6] Stec K, Bobrowski A (1999) Ceramics building materials (in Polish) 3: 81 [7] Stec K (2003) PhD Thesis, AGH-University of Science and Technology, Krakw o

References
[1] Bowen H J M (1966) Trace elements in biochemistry. Academic Press, London-New York [2] Polish standard ZN-86=MO-126, IMO Gliwice