^1,5Petronela Anca Onache, ²Roxana Elena Ionete, ²Andreea Maria Iordache,
¹Alina Florea, ¹Dorin Ioan Sumedrea, ³Marina Iliescu, ⁴Doina Damian,
⁴Răzvan Filimon, ⁵Ovidiu TIŢA, ¹Andrei Tanase

¹National Research and Development Institute for Biotechnology in Horticulture Stefanesti - Arges, Romania, Street Bucuresti-Pitesti no 37, 117715

²National Research and Development Institute for Cryogenics and Isotopic Technologies – ICSI Rm. Valcea, Râmnicu Vâlcea, Romania, Street Uzinei no 4, 240050

³Research and Development Station for Viticulture and Vinification Blaj, Romania, Str Gh.Baritiu, No2, 515400, Alba County

⁴Research Station and Development for Viticulture and Vinification Iaşi, Romania, Str Mihail Sadoveanu no. 48, 700489

⁵Lucian Blaga” Sibiu University, Romania, Str. Ion Raţiu, No.5-7, 550012

Determination of heavy metals in soil and wine is very important for wine quality and consumer health, but at the same time it is a complementary tool for differentiating wines according to their geographical origin. In this work, soils and ten brands of wines originated from four major wine-growing areas of Romania (Iaşi, Babadag, Ştefăneşti and Blaj) were considered for performing a multielement (Cr, Ni, Cu, As, Pb, Hg, V, Sr, Mn, Zn, Fe) investigation in order to assess regional specificity. Heavy metals found in the investigated wines were below the limits imposed by European standards (O.I.V.) the elements concentrations following the trend: Zn>Fe>Mn>Sr>Ni>Cr>Cu>Pb>V>Hg>As. For the soils analyzed, the heavy metals content was found to be below the maximum permitted limit, except for Cu (135.45 mg/kg) from the Iaşi vineyard, which was at the permitted limit. The high values obtained for copper may be the result of different treatments with the Bordelaise solution for the vine. The elements CA, Mn and Hg observed from the research that they are predominantly of natural origin. Based on our results, a distinction has been made between wines according to their geographical origin, considering that the specific elements of discrimination Sr, Pb, and Ni for the Stefănesti vineyard (Muntenia region), Cr and Hg for the Babadag vineyard (Dobrogea region), Sr and V for the Iaşi vineyard (region of Moldova), respectively Fe and Zn for the Blaj vineyard (Transilvania region).

Wine, soil, heavy metals, ICP-MS, HR-CS-AAS, wine-growing area

1) Alkıs Mert I., Oz S., Atakol A., Yılmaz N., Ertan Anlı R., Atakol O., “Investigation of heavy metal concentrations in some Turkish wines”, Journal of Food Composition and Analysis 33, 2014, 105–110, http://dx.doi.org/10.1016/j.jfca.2013.11.006.

2) Almeida, C. M. R., & Vasconcelos, M. T. S. D., “Multielement composition of wines and their precursors including provenance soil and their potentialities as fingerprints of wine origin”, Journal of Agricultural Food Chemistry, 2003, 51(16), 4788– 4798. http://dx.doi.org/10.1016/j.foodchem.2008.05.043.

3) Arvanitoyannis, S., Katsota, M. N., Psarra, E. P., Soufleros, E. H. and Kallithraka, S., “Application of quality control methods for assessing wine authenticity: use of multivariate analysis (chemometrics),” Trends in Food Science and Technology, 1999, vol. 10, no. 10, pp. 321–336. . http://dx.doi.org/10.1016/S0924-2244(99)00053-9.

4) Bora, F.D., Bunea, C.I., Rusu, T. and Pop, N., “Vertical distribution and analysis of micro-, macroelements and heavy metals in the system soil-grapevine-wine in vineyard from North-West Romania”, Chemistry Central Journal, 2015, vol. 9:19, DOI 10.1186/s13065-015-0095-2.

5) Bora, F.D., Bunea, C., 2019. Bioacumularea metalelor în vița-de-vie. Editura Bioflux, Cluj-Napoca. eISBN 978-606-8887-55-5

6) Boschetti, W., Rampazzo, R. T., Dessuy M. B. et al., “Detection of the origin of Brazilian wines based on the determination of only four elements using high-resolution continuum source flame AAS”, Talanta, 2013, vol. 111, pp. 147–155.

7) Catarino Sofia, Capelo J.L., Curvelo-Garcia A.S. and De Sousa R.B., ”Evaluation of contaminant elements in Portuguese wines and original musts by high intensity focused ultrasound combined with inductively coupled plasma mass spectrometry”, Journal International, Science Vigne Vin, 2006, 40, no 2, pg. 91-101.

8) Cetó, X., Gutiérrez, J. M., Gutiérrez, M. et al., “Determination of total polyphenol index in wines employing a voltammetric electronic tongue”, Analytica Chimica Acta, 2012, vol. 732, pp. 172–179.

9) Coetzee, P. P., Steffens, F. E., Eiselen, R. J., Augustyn, O. P., Balcaen, L., & Vanhaecke, F. ”Multi-element analysis of South African wines by ICP-MS and their classification according to geographical origin”, Journal of Agricultural Food Chemistry, 2005, 52(13), 5060–5066 http://dx.doi.org/10.1021/jf048268n

10) Danezis G., Tsagkaris A., Brusic V., Georgiou C., “Food authentication: state of the art and prospects”, Curr. Opin. Food Science, 2016, vol.10, pp. 22–31.

11) Dugo, G., La Pera, L., Pellicanó, T. M., Di Bella, G. and D'Imperio, M., “Determination of some inorganic anions and heavy metals in D.O.C. Golden and Amber Marsala wines: statistical study of the influence of ageing period, colour and sugar content”, Food Chemistry, 2015, vol. 91, no. 2, pp. 355–363.

12) De Villiers, A., Vanhoenacker, G., Majek, P. and Sandra, P., “Determination of anthocyanins in wine by direct injection liquid chromatography–diode array detection–mass spectrometry and classification of wines using discriminant analysis”, Journal of Chromatography A, 2004, vol. 1054, no. 1-2, pp. 195–204.

13) Everstine K., Spink J., Kennedy S., “Economically motivated adulteration (EMA) of food: common characteristics of EMA incidents”, Journal of Food Protection, 2013, vol. 76, pp. 723–735.

14) Fabani, M. P., Ravera, M. J. A. and Wunderlin, D. A. “Markers of typical red wine varieties from the Valley of Tulum (San Juan-Argentina) based on VOCs profile and chemometrics,” Food Chemistry, 2013, vol. 141, no. 2, pp. 1055–1062.

15) Fiket, Z, Mikac, N, Kniewald, G. “Arsenic and other trace elements in wines of eastern Croatia”, Journal of Food Chemistry, 2011, vol.126, pp. 941–947.

16) Franquet-Griell, H., Checa, A., Núñez, O., Saurina, J., Hernández-Cassou, S. and Puignou, L., “Determination of polyphenols in spanish wines by capillary zone electrophoresis. Application to wine characterization by using chemometrics”, Journal of Agricultural and Food Chemistry, 2012, vol. 60, no. 34, pp. 8340–8349.

17) Gallagher, L. T., Heo, J. S., Lopez, M. A. et al., “Pattern-based discrimination of organic acids and red wine varietals by arrays of synthetic receptors”, Supramolecular Chemistry, 2012, vol. 24(2), pp. 143–148

18) Geana,I., Iordache, A., Ionete, R., Marinescu, A., Ranca, A., Culea M., “Geographical origin identification of Romanian wines by ICP-MS elemental analysis”, Journal of Agricultural Food Chemistry, 2013, vol. 138, pp. 1125-1134, Available: https://www.journals.elsevier.com/food-chemistry

19) Gogoașă, I., Maruțoiu, C., Gergen, I., Rada, M., Tigae, C., “The use of vegetables as indicators in determining the environment pollution”, Rev Chim., 2005, Vol. 56, pp.1275-1276.

20) Goamez Maria del Mar Casteneira, Brandt R., Jakubowski N., Andersson J.T., “Changes of the metal composition in German white wines through the winemaking process. A study of 63 elements by inductively coupled plasma−mass spectrometry”, Journal Agricultural and Food Chemistry, 2004, 52, 2953−2961

21) Grindlay G., Moraa J., Gras L., de Loos-Vollebregt Margaretha T.C., “Ultratrace determination of Pb, Se and As in wine samples by electrothermal vaporization inductively coupled plasma mass spectrometry”, Analytica Chimica Acta, doi:10.1016/j.aca.2009.05.020

22) Grindlay G., Moraa J., Gras L., de Loos-Vollebregt Margaretha T.C., “Atomic spectrometry methods for wine analysis: A critical evaluation and discussion of recent applications”, Analitica Chimica Acta, 2011, pg 15, doi:10.1016/j.aca.2011.02.050

23) Héberger, K., Csomós, E. and Simon-Sarkadi, L., “Principal component and linear discriminant analyses of free amino acids and biogenic amines in Hungarian wines”, Journal of Agricultural and Food Chemistry, 2003, vol. 51, no. 27, pp. 8055–8060.

24) Huang, X. Y., Jiang, Z. T., Tan, J., Li, R., “Geographical Origin Traceability of Red Wines Based on Chemometric Classification via Organic Acid Profiles”, Journal of Food Quality, vol. 2017, Article ID 2038073, 7 pages, https://doi.org/10.1155/2017/2038073.

25) Huzum, R, Iancu, O.G., Buzgar, N., “Geochemical distribution of selected trace elements in vineyard soils from the Huşi area, Romania”, Carpath J Earth Environ Science, 2012, vol.7 (3), pp.61–70.

26) Jakubowski N., Brandt R., Stuewer D., Eschnauer H.R., Görtges S., “Analysis of wines by ICP-MS: Is the pattern of the rare earth elements a reliable fingerprint for the provenance?”, Fresenius Journal Analitical Chemistry, 1999, 364, pg.424–428

27) Kiss, J. and Sass-Kiss, A., “Protection of originality of Tokaji Aszú: amines and organic acids in botrytized wines by high-performance liquid chromatography”, Journal of Agricultural and Food Chemistry, 2005, vol. 53, no. 26, pp. 10042–10050.

28) Košir, I. J., Lapornik, B., Andrenšek, S., Wondra, A. G., Vrhovšek, U. and Kidrič, J., “Identification of anthocyanins in wines by liquid chromatography, liquid chromatography-mass spectrometry and nuclear magnetic resonance”, Analytica Chimica Acta, 2014, vol. 513, no. 1, pp. 277–282.

29) Kostic,D, Mitic, S, Miletic, G, Despotovic, S, Zarubica, A., “The concentrations of Fe, Cu and Zn in selected wines from South-East Serbia”, Journal of Serb Chemistry Society, 2010, vol. 75(12), pp. 1701–1709.

30) di Paola-Naranjo Romina D., Baroni María V., Podio Natalia S., Rubinstein H.R., Fabani María P., Badini R.G., Inga Marcela, Ostera H. A., Cagnoni Mariana, Gallegos E., Gautier E., García Pilar Peral, Hoogewerff H and Wunderlin D.A., „Fingerprints for main varieties of Argentinean wines: Terroir differentiation by inorganic, organic, and stable isotopic analyses coupled to chemometrics“, Journal Agricultural and Food Chemistry, 2011, 59, 7854–7865, dx.doi.org/10.1021/jf2007419

31) Petropulos, Violeta Ivanova, Wiltsche, H., Stafilov, T., Stefova, Marina, Motter H., Lankmayr, E., „Multielement analysis of Macedonian wines by inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-optical emission spectrometry (ICP-OES) for their classification“, Macedonian Journal of Chemistry and Chemical Engineering, 2013, Vol. 32, No. 2, pp. 265–281

32) Regmi, U., Palma, M. and Barroso, C.G, “Direct determination of organic acids in wine and wine-derived products by Fourier transform infrared spectroscopy and chemometric techniques”, Analytica Chimica Acta, 2012, vol. 732, pp. 137–144

33) Serrano-Lourido D, Saurina, J, Hernández-Cassou, S. and Checa, A., “Classification and characterisation of Spanish red wines according to their appellation of origin based on chromatographic profiles and chemometric data analysis”, Food Chemistry, 2012, vol. 135, no. 3, pp. 1425–1431.

34) Tariba B. “Metals in wine-impact on wine quality and health outcomes”, Biol Trace Elem Res, 2011, vol.144, pp.143–56

35) Tuzen, M, Soylak, M., “Evaluation of trace element contents in canned foods marketed from Turkey”, Food Chem, 2007, vol. 102, pp. 1089–1095.

36) Toti M., Dumitru M., Vlad V., Calciu, Irina. 2017. Solul – element de bază al conceptului ”Terroir”, Ed. Terra Nostra, Iași

37) Zava, A., Sebastião, P. J., Catarino, S., “Wine traceability and authenticity: Approaches for geographical origin, variety and vintage assessment”, Journal of Ciência e Técnica Vitivinícola, 2020, vol. 35(2), pp. 133-147. https://www.researchgate.net/publication

38) Woldemariam, D.M. and Chandravanshi, B.S., “Concentration levels of essential and non-essential elements in selected Ethiopian wines”, Bulletin Chemistry Society Ethiopian, 2011, 25(2), 169-180.

Volume 05 Issue 02 February 2022