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Microchim Acta (2008) 161: 109–114

DOI 10.1007/s00604-007-0788-x
Printed in The Netherlands

Original Paper
Direct determination of iron in sand using solid sampling
graphite furnace atomic absorption spectrometry

Cı́ntia S. Silva1 , Cassiana S. Nomura2 , Joaquim A. Nóbrega3 , Pedro V. Oliveira1
Instituto de Quı́mica, Universidade de S~ao Paulo, S~ao Paulo, SP, Brazil
Centro de Ci^encias Naturais e Humanas, Universidade Federal do ABC, Santo Andre, SP, Brazil
Departamento de Quı́mica, Universidade Federal de S~ao Carlos, S~ao Carlos, SP, Brazil

Received 6 November, 2006; Accepted 27 February, 2007; Published online 6 June 2007
# Springer-Verlag 2007

Abstract. A fast and reliable method for the direct posed method and conventional flame atomic absorp-
determination of iron in sand by solid sampling tion spectrometry. The relative standard deviations
graphite furnace atomic absorption spectrometry was were lower than 25% (n ¼ 5). The tube and boat plat-
developed. A Zeeman-effect 3-field background cor- form lifetimes were around 1000 and 250 heating
rector was used to decrease the sensitivity of spectro- cycles, respectively.
meter measurements. This strategy allowed working
Keywords: Atomic absorption spectrometry; solid analysis;
with up to 200 mg of samples, thus improving the rep- sand; iron
resentativity. Using samples with small particle sizes
(1–50 mm) and adding 5 mg Pd as chemical modifier, The determination of iron in sand used as raw material
it was possible to obtain suitable calibration curves for glass manufacturing is a routine analysis in the
with aqueous reference solutions. The pyrolysis and glass industry. Iron traces can influence the optical
atomization temperatures for the optimized heating properties of glass, decreasing the ultraviolet radiation
program were 1400 and 2500  C, respectively. The transmittance. The absorption of ultraviolet radiation
characteristic mass, based on integrated absorbance, by species of this element can cause an undesirable
was 56 pg, and the detection limits, calculated consid- yellow or greenish-blue color in glass, caused by Fe(III)
ering the variability of 20 consecutive measurements of or Fe(II) ions, respectively [1]. Consequently, the cost
platform inserted without sample was 32 pg. The ac- of raw material is inversely proportional to the iron
curacy of the procedure was checked with the analy- concentration. Thus, iron must be determined in sand
sis of two reference materials (IPT 62 and 63). The for appropriate assessment of the value and to guar-
determined concentrations were in agreement with antee the desirable color characteristics of the pro-
the recommended values (95% confidence level). Five duced glass. Therefore, it is worth investigating a
sand samples were analyzed, and a good agreement procedure capable of direct solid sampling determina-
(95% confidence level) was observed using the pro- tion of iron in sand to speed up and facilitate proper
quality control.
Iron is usually determined in sand [2–4] and in glass
Correspondence: Pedro V. Oliveira, Instituto de Quı́mica, Uni-
versidade de S~ao Paulo, CP 26077, 05513-970 S~ao Paulo, SP, Brazil [1, 5–7] using different sample preparation and quan-
e-mail: tification approaches. In most of the methods, samples

Piracicaba. Merck): 5 mg Pd and 5 mg Pd þ 3 mg Mg. Additionally. solid sample dilution is no pling platform. which hard in routine analysis: the time spent for total diges. are submitted to grinding.and 3-field mode Zeeman-effect graphite furnace atomic absorption spectrometry is background corrector. solutions were prepared containing Pd(NO3)2 and Mg(NO3)2 The technique has been successfully proposed as a (Suprapur. depending on the analytical technique used for A ZEEnit+ 60 atomic absorption spectrometer (AnalytikjenaAG. it yields good analytical results while (AnalytikjenaAG). tion is too long (around 4 h) [8]. Five sand samples were quartered. this technique order to comminute sand samples. Samples trices [9–12].110 C. the favorable characteristics of this technique [12]. still unexploited. acid decomposition using hy. A pyrolytic graphite tube atomizer and boat-type platform were inherently more suitable for direct analysis of solids. NJ. All program is one of the most important attributes of measurements were based on integrated absorbance values con- SS-GF-AAS. trivial operation. The instrumental parameters were set as recom- mended by the manufacturer. Spectral interferences by successive dilutions of a 1000 mg L1 Fe(III) stock solution are more pronounced when a solid sample is directly (Merck. Considering this argument. Brazil) were used. 10]. and the possibility of contamina- Experimental tion in each one of the successive steps.0 mA. safety aspects related to HF manipulation. such as high sensitivity and spectral bandpass ¼ 0. Despite the advantages achieved using SS-GF-AAS. drofluoric. (Millipore. Germany). Bedford. Instrumentation backs. requiring no digested solutions. being capable of A ball mill grinder 8000 M Spex CertiPrep (Spex. performing heterogeneity assessment measurements. Malvern. The heating 3-field mode Zeeman-effect background corrector was 0. Analytical reagent grade HNO3 (Synth.998% (v=v) (Air Liquid Brasil. HCl and H2SO4 (Merck. Darmstadt. USA) equipped with vials and balls of tungsten carbide was used in Despite its favourable characteristics. HF (Mallinckrodt. chemical modifiers are less effective for solution of appropriate concentration and 10 mL of chemical modifier (5 mg Pd). was used for the determination of iron in acid- being relatively inexpensive. USA) with a precision spectrometry (SS-GF-AAS) combines a lot of advan. Silva et al. A flame atomic absorption spectrometer. since it is possible to eliminate matrix trolled by Windows NT+ software. robust. homogeneous samples. USA). of 0. SP. For in. Jena. size or increasing the mass used for the determina. Sand samples were weighed on a microbalance Solid sampling graphite furnace atomic absorption Auto Balance AD-4 (Perkin-Elmer. and sulfuric acids. either decreasing the particle Diadema. the final acidity of the digest could cause some draw. automated sampler dispersion unit. measurements. the particle size distribution was measured using a Mastersizer S polydisperse par- presents a number of challenges to be overcome: ticle analyzer (Malvern Instruments. the aim metric [5–7] methods. could be used for quality control in the glass industry. in Calibration was performed using 10 mL of Fe(III) aqueous general. Iron reference solutions were prepared tion can improve the precision. used throughout. the relative standard deviation of the results (about 10%) All solutions were prepared with high purity de-ionized water (18 M cm) obtained from a Milli-Q water purification system is worse than for slurry or liquid sampling. zer. After grinding. dried in a stove at 105  C for 1 h.8 T. dangerous or corrosive reagents. Norwalk. Germany) equipped with a transversely heated graphite atomi- Compared to other spectrochemical techniques. lution in acid medium for posterior determination by the possibility of using them in sand quality control is adsorptive stripping voltammetric [1] or spectrophoto. applied current ¼ 4. SP. AAS is more difficult than for GF-AAS [9. Metuchen. tageous characteristics. Brazil). powerful analytical method for trace and ultra-trace element determinations in several kinds of solid ma. model AA5-FL. dry ashing for organic in different matrices is still reduced. S~ao Paulo. The following chemical modifier atomised [9. The spectrometer was operated with a hollow cathode lamp for iron (wavelength ¼ 248. GF-AAS instrumentation to element determination and ground in a ball mill for 30 min. Mexico). fusion and disso. . of this study is to establish an adequate set of experi- Acid digestion procedures for sand analysis may mental conditions to allow the direct determination of have some characteristics that make their application iron in sand using modern instrumentation.2 nm). in spite of all material elimination. components during the drying and pyrolysis steps. nitric. Argon 99. S. However. The magnetic field strength used for relative ease of sample introduction.3 nm. Additionally. transferred with a micropipette onto the sam- direct solid sampling. application of modern SS. Brazil) was used as protective and purge gas. an inverse and transversal 2.001 mg. 10]. for which a decrease in the instru- mental sensitivity or prior dilution of solids with an Reagents appropriate solid buffer are some alternatives. UK) with an MS-17 calibration in solid sampling analysis by SS-GF. and a manual solid sampling accessory was used. Brazil) distilled in a quartz sub-boiling still (Marconi.