Cabbage (Brassica oleracea var. Capitata) as one of the indicators of possible environmental pollution by metals and metalloids in Eastern Croatia

Abstract

Svrha: Nakon biomonitoringa (serum, kosa, urin) lokalnog stanovništva, te okolišnog monitoringa putem uzoraka tla, vode i jestivog samoniklog bilja istočne Hrvatske, u okviru istraživanja opeterećenosti metalima i metaloidima, kao mogućoj posljedici ratnih zbivanja, s područja gdje je poljoprivredna djelatnost ponovo saživjela, izuzimani su uzorci kupusa (zelja), odličnog indikatora taloženja teških metala i metaloida u okolišu. Cilj istraživanja: Hipoteza studije je da su na području istočne Hrvatske, u područjima izloženim borbenim djelovanjima, u okolišu i populaciji, prisutne povećane koncentracije metala i metaloida povezanih s ratnim djelovanjima u odnosu na područja koja su bila pošteđena ratnih djelovanja. Cilj je bio utvrditi postoje li razlike u koncentracijama metala i metaloida uspoređujući lokacije visokog inteziteta borbenih djelovanja (LVIBD) s lokacijama niskog inteziteta borbenih djelovanja (LNIBD). Osim toga pokušala se utvrditi moguća međusobna povezanost kontaminacije s metalima u tlu i kod ljudi, te postoji li podudarnost po pitanju mogućih „vrućih točaka“, mjesta značajno opterećenih metalima. Materijal i metode: Ukupno je s 14 lokacija izuzeto 14 uzoraka kupusa i to 12 uzoraka s lokacija visokog inteziteta borbenih djelovanja (LVIBD), te dva uzorka s lokacija niskog inteziteta borbenih djelovanja (LNIBD) sa 14 lokacija. Koncentracije 20 metala i metaloida (Al, As, B, Ba, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Ni, Pb, Sb, Si, Sr, U, V i Zn), koji se koriste u vojne svrhe, utvrđivane su postupkom induktivno suspregnute plazme i spektrometrije masa ICP-MS. Rezultati: Koncentracije metala obuhvaćane Pravilnikom (As, Cd, Hg i Pb) bile su unutar MDK na svim lokacijama, dok za ostale istraživane elemente nije uočena razlika između LVIBD i LNIBD (p = 0,78; Mann-Whitney U test). Koncentracije metala i metaloida u kupusu nisu značajno korelirale s koncentracijama u uzorcima tla, osim u slučaju Cd, gdje je uočena slaba do umjerena korelacija (Pearsonov koeficijent tlo /kupus = -0,57; p = 0.031; p < 0,05). Analizom glavnih komponenti (PCA) utvrđen je kompaktan središnji klaster (roj), te dva klastera s lokacija Dopsin i Dalj u kojima su koncentracije svih elemenata, osim Hg, bile nešto više. Zaključci: I kupus kao indikator onečišćenja okoliša metalima ukazuje da ukupna opterećenost metalima u istočnoj Hrvatskoj nakon Domovinskog rata nije visoka. Ipak, na primjeru kupusa potvrđeno je mjesto Dalj kao „vruća točka“, sukladno ranije utvrđenim pozitivnim korelacijama Al, Fe, Mg i Ni na istoj lokaciji u kosi, tlu i maslačku, te B, Cu, Si, Sr i Zn u serumu, urinu i vodi, što ukazuje na mogući isti izvor i mehanizam prenošenja metala.Purpose: Within the framework of research on metal and metalloid presence, as a possible consequence of the war, the areas in Eastern Croatia where agricultural activity reestablished biomonitoring (serum, hair, urine) of the local population and environmental monitoring through samples of soil, water and edible wild plants was conducted and samples of cabbage, an indicator for heavy metals and metalloids in the environment, were collected. Aim: The hypothesis of the study is that in areas of Eastern Croatian exposed to combat operations, such as the environment and population, the presence of increased concentrations of metals and metalloids is associated with war activities in relation to the areas that were spared from war. The goal was to determine whether there are differences in the concentrations of metals and metalloids comparing locations of high intensity combat action (HICA) with locations of low intensity combat action (LICA). Besides this, the attempt was to determine the possible interconnection of contamination with metals in the soil and in humans, and whether there was a coincidence in terms of potential "hot spots", places significantly loaded with metals. Materials and Methods: A total of 14 sites included 14 samples of cabbage, where 12 samples from locations of high intensity combat action (HICA) and two (2) samples from locations of low intensity combat action (LICA). The concentrations of 20 metals and metalloids (Al, As, B, Ba, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Ni, Pb, Sb, Si, Sr, In, V, and Zn), which are used for military purposes, were determined by inductive procedure of restrained plasma mass spectrometry ICP-MS. Results: The concentration of metals covered by Regulations (As, Cd, Hg and Pb) were within the MRL on all locations, while in the other investigated elements there was no difference between HICA and LICA (p = 0.78; Mann-Whitney U test). The concentration of metals and metalloids in cabbage was not significantly correlated with the concentration in the soil samples, except in the case of Cd, where the negative correlation (Pearson coefficient soil /cabbage = -0.57; p = 0.031; p < 0.05) was observed. The principal component analysis (PCA) determined a compact central cluster, and two clusters on locations Dopsin and Dalj, where the concentration of all the elements, except for Hg, was higher. Conclusions: Even cabbage, as an indicator of environmental contamination with metals, indicates that after the war the total load of metal in Eastern Croatia is not high. However, the cabbage also confirmed the locality of Dalj as a "hot spot", accordingly to previously established positive correlations of Al, Fe, Mg and Ni in hair, soil and dandelion, and B, Cu, Si, Sr and Zn correlations in serum, urine and water in that same location, indicating a possible common source and mechanism of transferring metals

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