Adnan Menderes University, 4th AACD Congress, 29 Sept-3 Oct.

2004, Kuadas-AYDIN, TURKEY Proceedings Book 285

Determination of Trace Element Contents in Cow Milk By ICP-MS

a

Songl Karaaslan AKSU, bAnl ETNOLU, a,beref GER

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Uludag Universty Science and Art Faculty Departmant of Chemistry,16059 Bursa-Turkey TUBTAK-Bursa Test and Analysis Laboratory , 16372 Bursa-Turkey

Abstract Trace element levels of cow milk were studied by ICP-MS. The importance and proper sample preparation method were shown. Interference effect cause by matrix was studied and the the accuracy of results were compared. Analytical of merits, such as LOD and LOQ lineer range were showned for different elements. 1. Introduction Milk is one of the important food for human nutrition thats why determination of trace element contents are increasing importance since last decades. Milk contains all the macronutrients namely protein, carbohyrates, fat , vitamins (A, D and B groups) and trace elements particularly calcium, phosphate, magnesium, zinc and selenium. It is well known that metals exist in several forms in nature, each one with specific biotoxicological activity. When metals are present as minor or trace components in substrates as food, they are probably associated with macromolecular compounds as proteins, lipids or carbohydrates (1). Altough, most common selected analyse method is Electrotermal Atomic Asorption Spectromety(ET-AAS), Induced Coupled Plasma Atomic Emission (ICP-AES)and Induced Coupled Plasma Mass Spectrometry (ICP-MS) is become an important tool besause of its multi element analysis capability(2,4). The limitation of its applications which were originated from matrix components are the important investigation subject of the new metod (high resolution ICP-MS ). The determination of some trace element has been successfuly applied for Cd and Zn in cow milk samples (1). In this study, the levels of As, Ba, Cr, Co, Cu, Cd, Mn, Ni, Pb and V in cow milk were studied. 2. Experimental 2.1 Apparatus and Conditions A Agilent 7500 ICP mass spectrometer was used. The operating conditions for ICP-MS shown in Table 1. Samples were digested by acid assisted microwave irridiation using Perkin Elmer Multiwave 3000. The heating program employed is shown in Table 2. Table 1 Operating conditions Spectrometer Nebulizer Outer gas flow rate (l/min) Carrier gas flow rate (l/min) RF power (W) Sampler/Skimmer Acquisition time Sampling depth Analytical masses

Agilent 7500 Babington type 15 1.18 1300 Nicel 9.98 sec 7 mm 75 As, 137Ba,53Cr, 59Co, 63Cu, 111Cd, 55Mn, 60Ni, 208Pb, 51V

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Adnan Menderes University, 4th AACD Congress, 29 Sept-3 Oct.2004, Kuadas-AYDIN, TURKEY Proceedings Book 285

Table 2 Heating program in MW Power Ramp 700 200 0 8:30 2:30

Hold 00:00 35:00 20:00

Fan 1 1 2

2.2 Reagents All reagent used are analtical grade purity. High-quality water, obtained using a Milli-Q system (Millipore 0.22 m), was used exclusively. 2.3 Sample Preparation Samples of milk were collected from Turkish marcet. Classical wet digestion: A sample of approximately 1g was weighed accurately in a 100 ml beaker, 10 ml of HNO3 and 3 ml H2O2 were added and mixture was heated . Most of the acids were evaporated then the residue was dissolved with 10 ml of 1 M HNO3. Microwave digestion: A microwave digestion system was used for the determination of trace elements . Approximately 0.5 g of milk was weighed into a 100 ml vessel, then 6 ml of % 65 HNO3 (Merck) and 1 ml % 30 H2O2 (Merck) were added. After MW digestion cycle, digestion solutions were added with deionized water so as to adjust the final volume to 10 ml. The calibration standardts were prepared from 1000 mg/l stock (Merck) solutions of As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb and V in % 2 HNO3 . 3 Results and Discussion For the quantification of As , the possible interference of the double ion 40 Ar 35 Cl on the signal at mass 75 was checked. Ba is close to %95 ionized in the Ar plasma and readily form 2+ ions which can interference with Ga and Zn isotopes. The main Cr isotopes can suffer interference from Ar, C, Cl, and S based species. Cd id almost %85 ionized in the Ar plasma. 60Ni is prefered for analysis as the majot isope, 58 Ni, suffers interference from both Fe and ArO. The presence of Ca can founds in the sample can also lead to interferences from CaO. A high level of K gives KO which interferences with Mn determination. Vanadium has two naturely occuring isotopes, only 51V should be used (50V is both low abundance and subject to interference from Cr and Ti isopes). V readily suffer interference from ClO and SOH species.

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Adnan Menderes University, 4th AACD Congress, 29 Sept-3 Oct.2004, Kuadas-AYDIN, TURKEY Proceedings Book 285

Table 3 Determination of As, Ba, Cr, Co, Cu, Cd, Mn, Ni, Pb and V in cow milk by ICP-MS Concentration (mg/kg) Method 1 Method 2 As ------Ba ---0.080.02 Cr 0.10.01 0.10.01 Co 0.010.0 0.010.0 Cu 0.03 0.01 0.060.02 Cd ---0.020.01 Mn 0.030.01 0.030.01 Ni 0.02 0.01 0.040.01 Pb 0.020.01 0.030.01 V 0.020.01 0.040.02 Method 1: Standard addition method in wet ashing sample Method 2: Standard addition method in microwave sample Table 4 Limit of Dedection values (mg/kg) of As, Ba, Cr, Co, Cu, Cd, Mn, Ni, Pb and V Method 1 Method 2 As 8.9 10-4 3.5 10-3 -3 Ba 3.9 10 1.4 10-3 -3 Cr 4.5 10 1.5 10-3 Co 2.1 10-3 1.8 10-3 -3 Cu 4.5 10 2.7 10-2 -4 Cd 4.9 10 3.6 10-3 -3 Mn 4.4 10 2.8 10-2 -3 Ni 8.8 10 1.4 10-2 -2 Pb 1.1 10 2.1 10-2 V 7.2 10-4 2.3 10-3 Method 1: Standard addition method in wet ashing sample Method 2: Standard addition method in microwave sample As a result of preleminery determination of elements in cow milk was found acceptable according to Codex Standart (5).

References 1) O. Abollino, M. Aceto, M.C. Bruzzoniti, E. Mentasti, C. Sarzanini. Anal. Chim. Acta 375 (1998) 299. 2) N. Campillo, P. Vnas, I. L. Garcia, M. H. Cordoba. Talanta 46 (1998) 615. 3) E. Ferrer, A. Algria, G. Courtois, R. Farre. Jour. of Chrom. A, 881 (2000)599. 4) M. R. Rubio, M.E. Sigrist, T. Encinas, E.E. Baroni, J. E. Coronel, J. C. Boggio, H. R. Beldomenico, Bulletin of Env. Cont. And Toxicology, 60 (1998) 164-167 5) Codex Alimentarius commision, CL 2004/15-MMP

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