Abstract
The scope of this study was the development, optimization and validation of an analytical method for the determination of selected heavy metals and trace elements (As, Hg, Se, Cd, Cu, Pb, Mn, Fe, Ni, Zn, Cr) in milk powder, using microwave-assisted digestion. A statistical experimental design approach using central composite design (CCD) was carried out, to investigate the effects of three independent pretreatment variables (final digestion temperature (°C), HNO3 concentration (in % w/v), microwave hold time) on the heavy metal recovery of spiked undigested milk powder sample and to calculate the variable factor values which produce the optimum recovery. CCD results revealed that the optimum digestion conditions, with respect to maximum recovery were as follows: temperature 190 °C, HNO3 56.8% w/v, and digestion time of 8.47 min. The method was fully validated. Recoveries for all metals ranged between 92 and 108% while intra-day repeatability was below 6.59% (rsd). A certified reference material (ERM BD 150) that included 8 out of the total 11 heavy metals of the present study (Hg, Se, Cd, Cu, Pb, Mn, Ni, and Zn) was used to test the accuracy of the method where acceptable recovery values ranging between 96 and 107% were obtained. High heavy metal recoveries, short digestion time, and low acid consumption were the advantages of the pretreatment method. The analytical process was successfully applied for the determination of heavy metals in different milk samples from the Greek market. Heavy metal concentrations for Ni, Cr, Pb, Cd, Se, Mn, and Cu measured in this study reached 307, 102, 8.01, 5.96, 60.2, 519, and 438 μg/kg wet weight (ww), respectively. Zn and Fe were found at concentrations ranging 3.21–8.39 and 0.170–10.1 mg/kg ww, respectively. Risk assessment based on the WHO tolerable daily intake levels and the calculated target hazard quotients revealed that the consumption of the selected milk samples is considered safe.
Similar content being viewed by others
References
Ahmad, M., Roy, S. P. K., Sarwar, N., Morshed, S., Alam, M.K., Matin, A., & Kobra, K. T. (2016) Contamination of raw fresh milk, market pasteurized milk and powdered milk by toxic heavy metals in Bangladesh, Scientific Research Journal (SCIRJ), 4(2):19–24
Ahmed M, Khaleeq A, Huma R, Qadir MA, Shafiq MI, Israr A, Ali A, Shahzad S (2016) Optimization and validation procedure for elemental composition of fresh and pasteurized milk in Pakistan employing microwave digestion followed by ICP-OES: a contribution to risk assessment. Food Anal Methods 9:2933–2942
Alloway BJ (2009) Soil factors associated with zinc deficiency in crops and humans. Environ Geochem Health 31:537–548
Alonso Castillo ML, Vereda Alonso E, Siles Cordero MT, Cano Pavón JM, García de Torres A (2011) Fractionation of heavy metals in sediment by using microwave assisted sequential extraction procedure and determination by inductively coupled plasma mass spectrometry. Microchem J 98:234–239
ATSDR (2004) Toxicological profile for copper. In: Registry AfTSaD (Hrsg)
ATSDR (2005) Toxicological profile for zinc. In: Registry AfTSaD (Hrsg)
Baker JC (1987) Lead poisoning in cattle. Vet Clin North Am Food Anim Pract 3:137–147
Bakircioglu D, Kurtulus YB, Ucar G (2011) Determination of some traces metal levels in cheese samples packaged in plastic and tin containers by ICP-OES after dry, wet and microwave digestion. Food Chem Toxicol 49:202–207
Becker W, Jorhem L, Sundström B, Grawé KP (2011) Contents of mineral elements in Swedish market basket diets. J Food Compos Anal 24:279–287
Beckett ST (2009) Industrial chocolate manufacture and use, fourth edition, 1–688 pp
Bermejo-Barrera P, Moreda-Piñeiro A, Muñiz-Naveiro O, Gómez-Fernández AMJ, Bermejo-Barrera A (2000) Optimization of a microwave-pseudo-digestion procedure by experimental designs for the determination of trace elements in seafood products by atomic absorption spectrometry. Spectrochim Acta B At Spectrosc 55:1351–1371
Bezerra MA, Santelli RE, Oliveira EP, Villar LS, Escaleira LA (2008) Response surface methodology (RSM) as a tool for optimization in analytical chemistry. Talanta 76:965–977
Box GEP, Wilson KB (1951) On the experimental attainment of optimum conditions. J R Stat Soc Ser B Methodol 13:1–45
Bratakos MS, Lazos ES, Bratakos SM (2002) Chromium content of selected Greek foods. Sci Total Environ 290:47–58
Brzóska MM, Moniuszko-Jakoniuk J (2001) Interactions between cadmium and zinc in the organism. Food Chem Toxicol 39:967–980
Caggiano R, Sabia S, D'Emilio M, Macchiato M, Anastasio A, Ragosta M, Paino S (2005) Metal levels in fodder, milk, dairy products, and tissues sampled in ovine farms of southern Italy. Environ Res 99:48–57
Capar SG, Cunningham WC (2000) Element and radionuclide concentrations in food: FDA Total Diet Study 1991-1996. J AOAC Int 83:157–177
Cominos X, Athanaselis S, Dona A, Koutselinis A (2001) Analysis of total mercury in human tissues prepared by microwave decomposition using a hydride generator system coupled to an atomic absorption spectrometer. Forensic Sci Int 118:43–47
Commission EC (2006) Commission Regulation (EC) No 1881/2006 of 19 December 2006 setting maximum levels for certain contaminants in foodstuffs (text with EEA relevance)
Coni E, Bocca A, Ianni D, Caroli S (1995) Preliminary evaluation of the factors influencing the trace element content of milk and dairy products. Food Chem 52:123–130
D'Ilio S, Petrucci F, D'Amato M, Di Gregorio M, Senofonte O, Violante N (2008) Method validation for determination of arsenic, cadmium, chromium and lead in milk by means of dynamic reaction cell inductively coupled plasma mass spectrometry. Anal Chim Acta 624:59–67
Diagomanolin V, Farhang M, Ghazi-Khansari M, Jafarzadeh N (2004) Heavy metals (Ni, Cr, Cu) in the Karoon waterway river, Iran. Toxicol Lett 151:63–68
EPA USA (2008), Region 8, United States, Environmental Protection Agency. Baseline human health risk assessment for the standard mine site Gunnison County. Syracuse Research Corporation, Colorado
FAO/WHO (1993) Evaluation of certain food additives and contaminants (41st report of the joint FAO/WHO expert committee on food additives). WHO Technical Report Series No 837
FAO/WHO (2012): Joint FAO/WHO food standards program: Codex committee on contaminants in foods (Editorial amendments to the general standard for contaminants and toxins in food and feed), sixth session, Maastricht, Netherlands, 26–30 march, 2012; CX/CF 2/6/11
Gustavo González A, Ángeles Herrador M (2007) A practical guide to analytical method validation, including measurement uncertainty and accuracy profiles. Trends Anal Chem 26:227–238
Ip CCM, Li X-D, Zhang G, Wai OWH, Li Y-S (2007) Trace metal distribution in sediments of the Pearl River estuary and the surrounding coastal area, South China. Environ Pollut 147:311–323
Jeng SL, Lee SJ, Lin SY (1994) Determination of cadmium and lead in raw milk by graphite furnace atomic absorption spectrophotometer. J Dairy Sci 77:945–949
Jitmanee K, Oshima M, Motomizu S (2005) Speciation of arsenic(III) and arsenic(V) by inductively coupled plasma-atomic emission spectrometry coupled with preconcentration system. Talanta 66:529–533
Kazi TG, Jalbani N, Baig JA, Kandhro GA, Afridi HI, Arain MB, Jamali MK, Shah AQ (2009) Assessment of toxic metals in raw and processed milk samples using electrothermal atomic absorption spectrophotometer. Food Chem Toxicol 47:2163–2169
Khan K, Khan H, Lu Y, Ihsanullah I, Nawab J, Khan S, Shah NS, Shamshad I, Maryam A (2014b) Evaluation of toxicological risk of foodstuffs contaminated with heavy metals in swat, Pakistan. Ecotoxicol Environ Saf 108:224–232
Khan N, Jeong IS, Hwang IM, Kim JS, Choi SH, Nho EY, Choi JY, Park KS, Kim KS (2014a) Analysis of minor and trace elements in milk and yogurts by inductively coupled plasma-mass spectrometry (ICP-MS). Food Chem 147:220–224
Korn MGA, Morte ESB, dos Santos DCMB, Castro JT, Barbosa JTP, Teixeira AP, Fernandes AP, Welz B, dos Santos WPC, dos Santos EBGND, Korn M (2008) Sample preparation for the determination of metals in food samples using spectroanalytical methods—a review. Appl Spectrosc Rev 43:67–92
Leivuori M (1998) Heavy metal contamination in surface sediments in the Gulf of Finland and comparison with the Gulf of Bothnia. Chemosphere 36:43–59
Licata P, Trombetta D, Cristani M, Giofrè F, Martino D, Calò M, Naccari F (2004) Levels of “toxic” and “essential” metals in samples of bovine milk from various dairy farms in Calabria, Italy. Environ Int 30:1–6
Llorent-Martínez EJ, De Córdova MLF, Ruiz-Medina A, Ortega-Barrales P (2012) Analysis of 20 trace and minor elements in soy and dairy yogurts by ICP-MS. Microchem J 102:23–27
Lloyd KE, Fellner V, McLeod SJ, Fry RS, Krafka K, Lamptey A, Spears JW (2010) Effects of supplementing dairy cows with chromium propionate on milk and tissue chromium concentrations. J Dairy Sci 93:4774–4780
Low KH, Zain SM, Abas MR (2012) Evaluation of microwave-assisted digestion condition for the determination of metals in fish samples by inductively coupled plasma mass spectrometry using experimental designs. Int J Environ Anal Chem 92:1161–1175
Mansour SA (2014) Heavy metals of special concern to human health and environment, Practical Food Safety: Contemporary Issues and Future Directions, pp. 213–233
Maruta T, Suzuki M, Takeuchi T (1970) Interferences of acids in atomic absorption spectrophotometry. Anal Chim Acta 51:393–398
McNamara JP, Valdez F (2005) Adipose tissue metabolism and production responses to calcium propionate and chromium propionate. J Dairy Sci 88:2498–2507
Mendil D (2006) Mineral and trace metal levels in some cheese collected from Turkey. Food Chem 96:532–537
Meshref AMS, Moselhy WA, Hassan NE-HY (2014) Heavy metals and trace elements levels in milk and milk products. J Meas Charact 8:381–388
Ngah CWZCW, Yahya MA (2012) Optimisation of digestion method for determination of arsenic in shrimp paste sample using atomic absorption spectrometry. Food Chem 134:2406–2410
Ozdemir S, Dundar MS, Sengorur B, Senol AS (2009) Lead and zinc content of cows’ milk affected by varying traffic density. Int J Environ Pollut 36:411–417
Patra RC, Swarup D, Kumar P, Nandi D, Naresh R, Ali SL (2008) Milk trace elements in lactating cows environmentally exposed to higher level of lead and cadmium around different industrial units. Sci Total Environ 404:36–43
Pérez-Carrera A, Alvarez-Gonçalvez CV, Fernández-Cirelli A (2016) Transference factors as a tool for the estimation of arsenic milk concentration. Environ Sci Pollut Res 23:16329–16335
Pérez A, Lorenzo ML, Cabrera C, López MC (2002) Influence of enrichment with vitamins and minerals on the bioavailability of iron in cows' milk. J Dairy Res 69:473–481
Pettersson J, Olin Å (1991) The rate of reduction of selenium(VI) to selenium(IV) in hydrochloric acid. Talanta 38:413–417
Pilarczyk R, Wójcik J, Czerniak P, Sablik P, Pilarczyk B, Tomza-Marciniak A (2013) Concentrations of toxic heavy metals and trace elements in raw milk of Simmental and Holstein-Friesian cows from organic farm. Environ Monit Assess 185:8383–8392
Qin LQ, Wang XP, Li W, Tong X, Tong WJ (2009) The minerals and heavy metals in cow’s milk from China and Japan. J Health Sci 55:300–305
Rahimi E (2013) Lead and cadmium concentrations in goat, cow, sheep, and buffalo milks from different regions of Iran. Food Chem 136:389–391
Ramirez JH, Costa CA, Madeira LM (2005) Experimental design to optimize the degradation of the synthetic dye Orange II using Fenton's reagent. Catalysis Today 107–108, 68–76
Rodríguez Rodríguez EM, Delgado Uretra E, Díaz Romero C (1999) Concentrations of cadmium and lead in different types of milk. Zeitschrift fur Lebensmittel -Untersuchung und -Forschung 208:162–168
Sánchez Rojas F, Bosch Ojeda C, Cano Pavón JM (2010) Experimental design in the optimization of a microwave acid digestion procedure for the determination of metals in biomorphic ceramic samples by inductively coupled plasma mass spectrometry and atomic absorption spectrometry. Microchem J 94:7–13
Shahbazi Y, Ahmadi F, Fakhari F (2014) Determination of Pb, Cd, Zn, Cu, and Se concentrations in milk and dairy products by cathodic/anodic stripping voltammetry. Journal of Food and Drug Analysis
Simsek O, Gültekin R, Oksüz O, Kurultay S (2000) The effect of environmental pollution on the heavy metal content of raw milk. Die Nahrung 44:360–363
Soylak M, Tuzen M, Souza AS, Korn MGA, Ferreira SLC (2007) Optimization of microwave assisted digestion procedure for the determination of zinc, copper and nickel in tea samples employing flame atomic absorption spectrometry. J Hazard Mater 149:264–268
Spears JW (2000) Micronutrients and immune function in cattle. Proc Nutr Soc 59:587–594
Stanovič R, Árvay J, Hauptvogl M, Tomáš J, Kováčik A, Záhorcová Z, Slávik M (2016) Determination of heavy metals concentration in raw sheep milk from mercury polluted area. Potravinarstvo 10:95–99
Sutter EMM, Leroy MJF (1978) Nature of the interference of nitric acid in the determination of nickel and vanadium by atomic absorption spectrometry with electrothermal atomization. Anal Chim Acta 96:243–249
Suturović Z, Kravić S, Milanović S, Crossed D, Signurović A, Brezo T (2014) Determination of heavy metals in milk and fermented milk products by potentiometric stripping analysis with constant inverse current in the analytical step. Food Chem 155:120–125
Tokuda Y, Kashima M, Kayo M, Nakazato N, Stein GH (2006) Cocoa supplementation for copper deficiency associated with tube feeding nutrition. Intern Med 45:1079–1085
Vahčić N, Hruškar M, Marković K, Banović M, Colić IB (2010) Essential minerals in milk and their daily intake through milk consumption. Mljekarstvo 60:77–85
Van Dael P, Vlaemynck G, Van Renterghem R, Deelstra H (1991) Selenium content of cow’s milk and its distribution in protein fractions. Z Lebensm Unters Forsch 192:422–426
Vidovic M, Sadibasic A, Cupic S, Lausevic M (2005) Cd and Zn in atmospheric deposit, soil, wheat, and milk. Environ Res 97:26–31
Yanardag R, Orak H (1999) Selenium content of milk and milk products of Turkey. II. Biol Trace Elem Res 68:79–95
Yanus RL, Sela H, Borojovich EJC, Zakon Y, Saphier M, Nikolski A, Gutflais E, Lorber A, Karpas Z (2014) Trace elements in cocoa solids and chocolate: an ICPMS study. Talanta 119:1–4
Yokel RA (2009) Manganese flux across the blood-brain barrier. NeuroMolecular Med 11:297–310
Yokoi K, Konomi A, Otagi M (2009) Iron bioavailability of cocoa powder as determined by the Hb regeneration efficiency method. Br J Nutr 102:215–220
Zhang Y, Adeloju SB (2008) Flow injection-hydride generation atomic absorption spectrometric determination of selenium, arsenic and bismuth. Talanta 76:724–730
Zhuang P, McBride MB, Xia H, Li N, Li Z (2009) Health risk from heavy metals via consumption of food crops in the vicinity of Dabaoshan mine, South China. Sci Total Environ 407:1551–1561
Author information
Authors and Affiliations
Corresponding author
Additional information
Responsible editor: Philippe Garrigues
Electronic supplementary material
ESM 1
(DOCX 572 kb)
Rights and permissions
About this article
Cite this article
Evgenakis, E., Christophoridis, C. & Fytianos, K. Method optimization for heavy metal determination in milk powder: application to milk samples from Greece. Environ Sci Pollut Res 25, 26766–26779 (2018). https://doi.org/10.1007/s11356-017-9863-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11356-017-9863-y