Food Chemistry 81 (2003) 463468 www.elsevier.

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Analytical, Nutritional and Clinical Methods

Chromium determination in foods by quadrupole inductively coupled plasmamass spectrometry with ultrasonic nebulization
Francesco Cubadda*, Silvana Giovannangeli, Francesca Iosi, Andrea Raggi, Paolo Stacchini
`, Laboratorio Alimenti, Viale Regina Elena 299, 00161 Rome, Italy Istituto Superiore di Sanita Received 20 August 2002; received in revised form 10 December 2002; accepted 10 December 2002

Abstract The analytical issues connected with chromium determination in foodstus by quadrupole inductively coupled plasmamass spectrometry (Q-ICP-MS) were addressed, including signal stability, spectral interferences and the use of mathematical correction equations. The analytical performance was compared to that of electrothermal atomisationatomic absorption spectrometry (ETAAAS), selected as reference method. Five food certied reference materials (CRMs), including two meat-based CRMs not previously characterized for their Cr content, were included in the study. The use of ultrasonic nebulization (UN) and the adoption of 53Cr as analytical mass allowed precise and accurate results to be obtained by Q-ICP-MS, with lower detection limits than ETA-AAS. # 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Chromium; Food analysis; Electrothermal atomisationatomic absorption spectrometry; Inductively coupled plasmamass spectrometry; Ultrasonic nebulization; Certied reference materials

1. Introduction Chromium is an essential element for humans having a role in maintaining normal glucose tolerance in the organism (Expert consultation WHO/FAO/IAEA, 1996). It potentiates the action of insulin and thus acts on carbohydrate, lipid and protein metabolism. Chromium dietary intake has been estimated in the range 2856 mg/day in many countries, but some surveys found remarkably higher levels (Anke, Muller, Trupschuch, Seifert, Jaritz, Holzinger, & Anke 2000; Lukaski, 2000; Tripathi, Raghunath, Vinod Kumar, & Krishnamoorthy, 1998; Ysart et al., 2000). These intakes are likely to meet nutritional requirements for healthy individuals, however chromium supplements have been introduced on the market. On the other hand, Cr is widely recognized as a potential food contaminant. Stainless steel may contain chromium at relatively high percentages. The metal or

* Corresponding author. Tel.: +39-06-49902740; fax: +39-0649387101. E-mail address: francesco.cubadda@iss.it (F. Cubadda).

its compounds are also used in electroplating and in surface treatment of food cans. Therefore Cr migration from cookware and cans has been postulated, even though only small quantities have been generally observed in foodstu as a result of leaching (Berg, Petersen, Pedersen, Petersen, & Madsen, 2000; Flint & Packirisamy, 1997; Jorhem & Slorach, 1987; Smart & Sherlock, 1985). Organic chromium compounds such as Cr picolinate have been reported to improve carcass characteristics and growth performance of breeding animals, especially in stressed individuals, and are proposed as supplements in swine production (Lindemann, 1999). However, the use of such compounds in zootechny is not authorized. Of the inorganic forms of chromium, Cr (VI) is considerably more toxic than Cr (III)which is the prevailing form in foodsand is classied as carcinogenic to humans (IARC, 1990). Hexavalent chromium is recognized as a hazardous water pollutant in environments degraded by industrial activities releasing chromate compounds. In the light of both the nutritional and the toxicological importance of Cr, the determination of its levels in foodstus is a matter of interest worldwide. In

0308-8146/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved. doi:10.1016/S0308-8146(03)00002-5

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the past, considerable diculties have been experienced in obtaining reliable analytical data for this metal, whatever the technique used for detection (Reilly, 1991; Veillon & Patterson, 1999). These obstacles have been overcome due to the developments in the eld of analytical techniques for trace metal detection and analytical quality assurance; still Cr analysis at low levels is considered a challenge to the skill of the analyst. In the food control eld, this situation is reected by the paucity of reference materials with certied values for Cr, which in turn limits the possibility of adequately verify the accuracy of Cr analyses carried out by laboratories. In the last decade, inductively coupled plasmamass spectrometry has emerged as a powerful tool for the analysis of trace elements in all biological matrices including food, allowing rapid multielemental analyses to be performed with very low detection limits. This technique has the sensitivity required for Cr detection in foodstus, but suers from heavy spectral interferences aecting the major Cr isotopes utilized for the quantication of the element. Highly biased results were obtained in certication campaigns of food and environmental reference materials where ICP-MS was used without accounting for these interferences (Larsen, Pedersen, & McLaren, 1997; Quevauviller, van Raaphorst, & Muntau, 1996). A number of analytical approaches have been proposed to deal with this drawback, including higher resolution powers (sector-type ICP-MS instruments), alternative sample preparation methods (i.e. suited dissolution, separation procedures), use of mixed gases, and, in very recent times, the exploitation of new modied instruments equipped with collisional or dynamic reaction cells (Lam, McLaren, & Methven, 1995; Neubauer & Vo llkopf, 1999; Vanhaecke & Moens, 1999). In the present work, the results of a study carried out with the aim to elucidate the dierent analytical factors aecting chromium determination in foodstus by ICPMS are presented. The nal goal of our investigation was to nd out if there were robust and feasible analytical solutions which allowed routine chromium determination for food control purposes without complex changes in instrumentation and spectrometer operating conditions or lengthy procedures for sample treatment prior to analytical measurement, i.e. while taking advantage of the high sample throughput enabled from microwave (MW) closed vessel digestion followed by ICP-MS detection. Five food certied reference materials, spanning three orders of magnitude of Cr concentrations, were utilized in the study. Electrothermal atomisationatomic absorption spectrometry was selected as a bench mark in order to evaluate the overall performance of the analytical method developed.

2. Experimental 2.1. Samples and reagents The ve reference and certied reference materials were: the RM 8436 (Durum wheat our) and the SRM 1577b (Bovine liver)provided by the US National Institute of Standards and Technology (NIST)the BCR CRM 278R (Mussel tissue) and 184 (Bovine muscle)provided by the European Institute for Reference Materials and Measurements (IRMM)and DORM-2 (Dogsh muscle), obtained from the Canadian Institute for National Measurement StandardsNational Research Council (INMS-NRC). Calibration standards were prepared from a 1000 mg Cr l1 stock solution (BDH, Poole, England) by dilution with high purity deionized water (Milli-Q, Millipore, Molsheim, France). The standard for ETA-AAS and ICP-MS measurements were 0.5% v/v and 3% in ultrapure concentrated HNO3 (Carlo Erba Reagenti, Milan, Italy), respectively. The reagents used in sample digestion were ultrapure concentrated HNO3 and H2O2 (Merck, Darmstadt, Germany). In the study of spectral interferences, ultrapure Na2CO3 and NaCl (Merck, Darmstadt, Germany), were used as carbon and chlorine sources, respectively. 2.2. Sample preparation Sample treatment, including the digestion procedure by a Milestone MLS-1200 Mega MW oven (FKV, Bergamo, Italy), was described elsewhere (Cubadda, Raggi, Testoni, & Zanasi, 2002). Sample weight was 0.200.55 g depending on the material. Each CRM was digested in triplicate and made up to 2550 ml in polypropylene disposable tubes with high purity deionized water. 2.3. Instrumentation and analytical measurements For ETA-AAS analyses, a SIMAA 6000 spectrometer (Perkin-Elmer, Norwalk, CT, USA) with inverse longitudinal Zeeman-eect background correction and a transversely heated furnace was used. The instrument was equipped with a AS 72 autosampler (Perkin-Elmer, Norwalk, CT, USA). A furnace program with ashing and atomization temperatures of 1400 and 2400  C, respectively, was used. Calibration was performed with the method of standard addition. Other instrumental details and operating conditions are summarized in Table 1. For ICP-MS measurements, a quadrupole Sciex Elan 6000 ICP-MS (Perkin-Elmer, Norwalk, CT, USA), equipped with a ASX-500 autosampler model 510 and a ADX-500 autodilutor (both from CETAC Technologies, Omaha, NE, USA), was used. Two sample introduction systems were employed in this study: a

F. Cubadda et al. / Food Chemistry 81 (2003) 463468 Table 1 Instrumental operating conditions for ETA-AAS and ICP-MS
ETA-AAS Instrument Wavelength Slit width Sample injection volume Absorbance measurement mode Graphite tubes Matrix modier ICP-MS Instrument Plasma RF generator Ar ow rate (L min1) Solution uptake rate Interface Sampler cone Skimmer cone Perkin-Elmer SIMAA 6000 357.9 nm 0.7 nm 10 ml Peak area Pyrolytic with Lvov platform Mg(NO3)2 Perkin-Elmer Sciex Elan 6000 Frequency: 40 MHz, power output 1000 W Plasma: 16, Auxiliary: 0.9; Nebulizer: 0.9 1 ml min1 Nickel, i.d.: 1.1 mm Nickel, i.d.: 0.9 mm Interface: 4 torr, Quadrupole: 2105 torra Dwell time 100 ms, sweeps/reading 20, readings/replicate 3, number of replicates 3 Peak hopping 103 Rh 52 Cr, 53Cr 13 C, 37Cl

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ignition was adopted throughout. Other details on the instrumentation and the operating conditions are summarized in Table 1. Both in ETA-AAS and ICP-MS measurements, digestion blanks were analysed together with samples belonging to the same analytical batch. Standards were run regularly after 68 sample measurements. Mean element concentrations together with standard deviations were calculated after blank subtraction. In ICPMS analyses, each measurement was done after 2 min of rinsing with a HNO3 solution (5% v/v) to overcome memory eects from preceding samples and an additional 1 min of sample pumping to allow stabilization of the instrument response. In each analytical run, the isotopes 13C and 37Cl were selected for monitoring C and Cl signal (masses 12 and 35 were avoided in order to prevent exceedingly intense signals).

3. Results and discussion The chromium concentrations of the ve CRMs measured by ETA-AAS are shown in Table 2. The certied or best estimated values are shown in the same table. For CRM 184 only a range of indicative values is available, while for SRM 1577b no information is given from the supplier about Cr levels. For the CRMs with a certied (best estimated) value, good agreement was observed with the ETS-AAS results. The found values were all inside the condence interval of the certied values and close enough to the means. As regards reproducibility, the coecients of variation were on average equal to 3.8% (7.0% maximum value in RM 8436). The results of the ICP-MS determinations with conventional nebulization and without correction for spectral interferences are shown in Table 3. Chromium has four stable isotopes, but only the two more abundant52Cr and 53Cr (natural abundance 83.8% and 9.5%, respectively)were selected for analyses. The

Scanning conditions

Scanning mode Internal standard Analytical masses Masses for interference correction

pneumatic nebulizer of the cross-ow type with a Scott type spray chamber and an ultrasonic nebulizer U-5000AT+ (CETAC Technologies, Omaha, NE, USA). Calibration was performed with both external standards and the method of standard addition. Diluted solutions were prepared with the same nitric acid concentration of calibration standards (3% v/v). Rhodium was selected as internal standard for correction of matrix eects and instrumental drift. Before operating the instrument, a warm up time of 3 h since plasma

Table 2 Results of chromium determination in food certied reference materials (mg g1 dry wt.)
Certied reference material Certied valuesa Mean RM 8436 (Durum wheat our) CRM184 (Bovine muscle) SRM 1577b (Bovine liver) CRM 278R (Mussel tissue) DORM-2 (Dogsh muscle)
a

Found values with ETA-AASd Mean 0.025 0.098 0.30 0.79 31.9 S.D. 0.002 0.004 0.01 0.02 0.5

Found values with UN-Q-ICP-MSe Mean 0.026 0.095 0.31 0.80 33.0 S.D. 0.002 0.005 0.01 0.02 0.5

c.i.b 0.009 0.06 5.5

0.023 [0.0760.153]c 0.78 34.7

Best estimated value for RM 8436. Uncertainty as half-width of the 95% condence interval of the mean. c Indicative range. d Detection limit: 0.17 mg l1 (estimated on the basis of the 3s criterion from the standard deviation (s) of 10 digestion blank determinations carried out during the same analytical run). e Isotope 53. Detection limit: 0.08 mg l1 (calculated as above).
b

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F. Cubadda et al. / Food Chemistry 81 (2003) 463468 Table 4 Apparent analyte concentrations in mg l1 originated at mass 52 and 53 by carbon and chlorine solutions. Experimental conditions: standard instrumental settings, pneumatic nebulization Isotope S.D. 0.006 0.02 0.03 0.09 0.5
52 53

Table 3 Biased results for chromium determination in food certied reference materials (mg g1 dry wt.)a Certied reference material Found values
52

Cr S.D. 0.02 0.05 0.05 0.08 0.4

53

Cr

Major interferences
40 40

C 100 mg l1 Mean S.D. 2.0 0.5

Cl 100 mg l1 Mean 0.2 2.3 S.D. 0.1 0.4

Mean RM 8436 (Durum wheat our) CRM184 (Bovine muscle) SRM 1577b (Bovine liver) CRM 278R (Mussel tissue) DORM-2 (Dogsh muscle)
a

Mean 0.076 0.17 0.33 1.44 34.4

0.35 0.58 0.70 1.54 34.6

Cr Cr

Ar12, 35Cl16OH Ar13C, 37Cl16O

16.5 2.0

Analysis performed with Q-ICP-MS, pneumatic nebulization, no correction for spectral interferences.

other two isotopes, 50Cr and 54Cr, were ruled out after a preliminary study, which showed the diculty in obtaining a stable signal and reliable analyte quantication in real samples. These isotopes suer from the isobaric interferences of 50Ti, 50V and 54Fe, respectively. Generally, these overlaps can be overcome by elemental correction equations based on relative natural abundances (e.g. 50Cr=50M[0.739726 (47Ti)+0.002506 (51V)). However, correction by elemental equations was ineective because of the low abundance of the two isotopes and the severity of isobaric and polyatomic interferences at m/z 50 and 54. While free of isobaric interferences from other elements, 52Cr and 53Cr are susceptible to potential interferences by a number of polyatomic species (52Cr: 36 Ar16O, 38Ar14N, 36Ar15NH, 40Ar12C, 35Cl17O, 35 16 Cl OH, 37Cl15N, 34S18O, 36S16O; 53Cr: 36Ar17O, 36 Ar16OH, 38Ar15N, 38Ar14NH, 40Ar13C, 37Cl16O, 35 17 Cl OH, 35Cl18O, 36S17O). The contribution of polyatomic ions generated by reagent solutions or the plasma (i.e. ArO, ArOH, ArN, ArNH) is appreciable only at low Cr concentrations and, in principle, can be corrected for by blank subtraction. On the other hand, the sulphur-containing species are unable to signicantly interfere with Cr determination at the S levels found in the food matrices analysed in this study. Dierent is the case of carbon argides arising from the residual carbon content of food after destruction of the organic matrix by MW digestion. The interference from ArC is severe (especially that of 40Ar12 on mass 52) and hampers accurate chromium determination in all the selected CRMs with the only exception on DORM-2, where the very high levels of the analyte make it almost negligible (Table 3). The apparent analyte concentrations originated by a carbon solution of 100 mg l1 in the experimental conditions adopted in this study and with the standard pneumatic nebulization as sample introduction system are shown in Table 4. If one consider that with MW digestion residual carbon contents of sample solutions can be of several tenths of mg l1, it

is clear how the real Cr levels of the original matrix can be completely obscured by the apparent concentration arising from 40Ar12. The interference of 40Ar13C on 53Crmeasured as apparent analyte concentrationsis about eight times lower. However, this isotope is 10 times more susceptible than 52Cr to the inuence of chlorine-containing polyatomic ions (Table 4), and the analyst should be aware of this when analysing, for instance, seafood. Also the use of chlorine-containing acids in the digestion procedure contributes to the chlorine content of digestates and thus should be avoided. The simplest way to attempt a solution to these interference problems is the use of correction equations, which subtract to the intensities of the analytes the signal resulting from interfering polyatomic ions (Ashley, 1992; Violante, Petrucci, Delle Femmine, & Caroli 1998). As an example, the correction equation for the determination of 53Cr was: 53Cr=53M(37ClCF), where the correction factor CF was equal to the ratio of the signal at mass 53 (37Cl16O) and 37 (Cl) produced by a pure Cl solution. CFs were calculated using both net (i.e. blank subtracted) and total intensities as determined by the analysis of carbon- and chlorine-containing solutions before each analytical run. Afterwards, a system of correction equations was entered into the instrument software. The results obtained (four analytical runs on dierent days) were enough accurate but were suciently precise only for DORM-2 and CRM 278R, the materials with the highest Cr levels. Coecients of variation of 10 19% were obtained for the other CRMs. In particular, in the case of RM 8436 (Cr certied value: 0.023 0.009 mg kg1), inter-run CVs as high as 36% were obtained (three non-consecutive measurements in each run), while the intra-run CV was equal to 19%. Several reasons account for this poor precision. When correction equations are used, the invariability of the ratio of the signal intensities included in the CF is assumed. However, this ratio is determined through a separate series of measurements before the analytical run and variations can occur especially if, subsequently, long analyses are performed. A way to minimize and control this phenomenon is to start the analysis soon after the determination of the CF and to check periodically the

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ecacy of the correction by analysing solutions containing the interfering element(s). If the signal ratio is constant and the correction works well, the apparent analyte concentration for the corrected masses should be zero. Another weakness of the use of correction equations is that the intensity of the interference is assumed to be the same in the digestates and in the aqueous solutions used for CF calculation, which in some cases may be not entirely true. For all these reasons mathematical equations generally give reliable results when only a minor part of the apparent concentration is due to interference, as happens for DORM-2 and CRM 278R and as previously demonstrated in the case of the Ca-containing polyatomic species interfering with Fe, Co, Ni (Cubadda et al., 2002). Another diculty of Cr determination when low analyte levels ( < 2 mg l1) are measured appears to be the signal instability exhibited by 52Cr and 53Cr, both on a short and on a long term time basis, despite internal standardization. A study conducted with four internal standards having dierent masses and ionization potential (Rh, Germanium, Indium, Yttrium), showed that the phenomenon is independent of the IS choice. Rh and In were found to be more ecient in minimizing short term variations, while Ge and Y were better for reducing long term drift, but on the whole the dierences among ISs were negligible and the signal instability was not overcome. This instability could be related to the variable eect of the polyatomic ions of O and N generated by reagent solutions and the plasma, which contribution at mass 52 and 53 could be not eciently compensated by internal standardization. This oblige the analyst to perform repeated measurement of external standards during the analytical run, followed by recalibration when deviations are observed from the target values. Hypothetically, an alternative solution could be the adoption of the method of standard addition, in which an internal calibration is performed for each sample within a short time period. However, when this method was tried in the present study it was found ineective in signicantly improving the results. All these diculties led to investigate whether a change in the sample introduction system could produce better results. Ultrasonic nebulization was selected in order to achieve a reduction in solvent-related spectral interferences, while increasing signal intensities and thus hopefully improving the detection limits. Solvent-related interferences are reduced with UN because of the solvent removal by the desolvation apparatus included in the device. Moreover, some studies found that desolvation was eective in removing Cl (as gaseous HCl) from sample aerosol and thus reduce the interference of chlorine-containing polyatomic ions (Minnich & Houk, 1998; Tittes Jakubowski, Stu lg, & Broekaert, 1994). wer, To With ultrasonic nebulization, the net signal intensities increased by a factor of 60 for 52Cr and 40 for 53Cr.

However, no remarkable improvement was obtained for 52 Cr as regard the signal intensity of the analyte versus background, measured as the ratio of the intensities of a 1 mg l1 Cr solution and the calibration blank. Dierently, this ratio was at least doubled in the case of 53Cr, thus overcoming a major limitation of this isotope i.e. the limited counting statistics which aects the precision of measurements in the conventional operating mode. Furthermore, 53Cr showed a signicant improvement in signal stability. As far as C and Cl related interferences are concerned, a noticeable eect was obtained. Chlorine interference was greatly reduced for the two Cr isotopes. Unexpectedly, also carbon interference was signicantly reduced for both isotopes and brought to negligible levels in the case of 53Cr. The results obtained for the ve CRMs with 53Cr and the application of the standard addition method are shown in Table 2. These results agreed well with those obtained by ETA-AAS (no statistical signicant dierence was detected by paired t-tests with P=0.05) and with the available certied values. Contrary to the case of conventional nebulization, very good statistics were obtained for linear regression of standard additions (on average r2=0.9996 and 0.9948 for 53Cr and 52Cr respectively, number of additions=3). The reproducibility was also good, with variation coecients on average equal to 4.2 and inside the range 1.76.8 (maximum value in RM 8436). An attempt was made to correct for the residual C interference on 52Cr and obtain results comparable with those of 53Cr. Unfortunately, 13C signal was found to be very unstable in UN conditions and this precluded achieving better results for the major Cr isotope. Interestingly, the opposite was found when a correction equation was used to compensate for Cl interference on 53 Cr. The inclusion of the correction produced a 510 time enhancement of the signal ratio analyte/background and led to a further improvement of the detection limit. In the case of the CRM 278R (mussel tissue), which contains high levels of chlorine, the corrected result was appreciably more accurate of that obtained without the inclusion of any mathematical equation (0.78 0.03 vs. 0.80 0.04 mg Cr g1). A nal remark shall be done on how the CF included in these equations were determined. In fact, during the entire study, the CFs were calculated starting from both net and total intensities. When the dierent CFs were compared, the best results were obtained with the former. The same result was found in the correction of 40 Ar12C interference with conventional nebulization, which agree with the ndings of other authors (Krush brega, Amarisiriwardena, & Barnes, evska, Waheed, No 1998). In this latter case, a heavy underestimation of real Cr concentrations was observed when total intensities were used for CF calculation.

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F. Cubadda et al. / Food Chemistry 81 (2003) 463468 Flint, G. N., & Packirisamy, S. (1997). Purity of food cooked in stainless steel utensils. Food Additives and Contaminants, 14, 115 126. IARC. (1990). Monographs on the evaluation of the carcinogenic risk of chemicals to humans: chromium, nickel and welding. Lyon: WHO, International Agency for Research on Cancer. Jorhem, L., & Slorach, S. (1987). Lead, chromium, tin, iron and cadmium in foods in welded cans. Food Additives and Contaminants, 4, 309316. brega, J., Amarisiriwardena, D., & Krushevska, A., Waheed, S., No Barnes, R. M. (1998). Reducing polyatomic interferences in the ICP-MS determination of chromium and vanadium in biouids and tissues. Applied Spectroscopy, 52, 205211. Lam, J. W. H., McLaren, J. W., & Methven, B. A. J. (1995). Determination of chromium in biological tissues by inductively coupled plasma mass spectrometry. Journal of Analytical Atomic Spectrometry, 10, 551554. Larsen, E. H., Pedersen, G. A., & McLaren, J. W. (1997). Characterization of National Food Agency shrimp and plaice reference materials for trace elements and arsenic species by atomic and mass spectrometric techniques. Journal of Analytical Atomic Spectrometry, 12, 963968. Lindemann, M. D. (1999). Chromium and swine nutrition. Journal of Trace Elements in Experimental Medicine, 12, 149161. Lukaski, H. C. (2000). Magnesium, zinc, and chromium nutriture and physical activity. American Journal of Clinical Nutrition, 72(suppl.), 585 S-593S. Minnich, M. G., & Houk, R. S. (1998). Comparison of cryogenic and membrane desolvation for attenuation of oxide, hydride and hydroxide ions and ion containing chlorine in inductively coupled plasma mass spectrometry. Journal of Analytical Atomic Spectrometry, 13, 167174. Neubauer, K., & Vo llkopf, U. (1999). The benets of a dynamic reaction cell to remove carbon and chloride-based spectral interferences in ICP-MS. Atomic Spectroscopy, 20, 6468. Quevauviller, P., van Raaphorst, J. G., & Muntau, H. (1996). Certication of chromium in a range of environmental certied reference materials. TRAC-Trends in Analytical Chemistry, 15, 259266. Reilly, C. (1991). Metal contamination of food. London: Elsevier. Smart, G. A., & Sherlock, J. C. (1985). Chromium in foods and the diet. Food Additives and Contaminants, 2, 139147. Tittes, W., Jakubowski, N., Stu lg, G., & Broekaert, J. A. C. wer, D., To (1994). Reduction of some selected spectral interferences in inductively coupled plasma mass spectrometry. Journal of Analytical Atomic Spectrometry, 9, 10151020. Tripathi, R. M., Raghunath, R., Vinod Kumar, A., & Krishnamoorthy, T. M. (1998). Intake of chromium by the adult population of Mumbay city. Environmental Monitoring and Assessment, 53, 379389. Vanhaecke, F., & Moens, L. (1999). Recent trends in trace element determination and speciation using inductively coupled plasma mass spectrometry. Fresenius Journal of Analytical Chemistry, 364, 440451. Veillon, C., & Patterson, K. Y. (1999). Analytical issues in nutritional chromium research. Journal of Trace Elements in Experimental Medicine, 12, 99109. Violante, N., Petrucci, F., Delle Femmine, P., & Caroli, S. (1998). Study of possible polyatomic interference in the determination of Cr in some environmental matrices by inductively coupled plasma mass spectrometry. Microchemical Journal, 59, 269277. Ysart, G., Miller, P., Croasdale, M., Crews, H., Robb, P., Baxter, M., de LArgy, C., & Harrison, N. (2000). 1997 UK total diet study dietary exposures to aluminium, arsenic, cadmium, chromium, copper, lead, mercury, nickel, selenium, tin and zinc. Food Additives and Contaminants, 17, 775786.

4. Conclusion Chromium analysis of foodstus not rich in Cl and with a simple organic matrix can be carried out after MW digestion with Q-ICP-MS resorting to both 52Cr and 53Cr, if the analyte level in the digestates is > 100 mg l1, and to 53Cr if the analyte is in the range 10100 mg l1. At lower Cr concentrations a correction equation must be used in order to compensate for the ArC interference. In this latter case, the best results are obtained with 52Cr and the correction is eective above 23 mg l1, whereas it leads to imprecise results for lower analyte levels. Accurate and precise Cr determination down to 0.1 mg l1 and below can be performed resorting to ultrasonic nebulization and selecting the 53Cr isotope as analytical mass, with an additional correction for ClO if signicant amounts of Cl are present in the sample. Following these ndings, the chromium levels of ve food CRMs, including two meat-based CRMs not previously characterized for their Cr content, could be ascertained by Q-ICP-MS. The selected CRMs covered a wide range of analyte concentrations and were representative of dierent staple food (meat, seafood, cereal grains). The results obtained by UN-Q-ICP-MS were in good agreement with those obtained by ETA-AAS and with the available certied (or best estimated) values for the selected CRMs.

Acknowledgements This work, which was carried out as a part of the project Alimenti di origine animale: valutazione dei residui di sostanze chimiche impiegate in zootecnia, was supported by a grant from the Ministero della Salute (Ministry of Health) of Italy. References
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