PhD: Distribution of heavy metals in environmental samples in the Allchar mine and its environ

Katerina Bačeva
Institute of Chemistry, Faculty of Natural Sciences and Mathematics, Ss. Cyril and Methodius University, Skopje, Macedonia
October, 2013


The results from the investigation of the anthropogenic and geogenic influence of the presence of heavy metals in the Allchar locality, Republic of Macedonia are presented in this PhD thesis, as well as characterization of the possible influence to the human health and living organisms by the pollution with some toxic elements. The region’s wider area, which is of interest in this investigation, is characterized by complex volcanic occurrences within the Kožuf massif in Vardar’s geological zone. Although a number of geological and mineralogical investigations on the Allchar’s region have been made, there have not been any detailed investigations of As, Sb, Tl and other toxic metals’ possible influence over the pollution of the environment. This investigation includes the analysis of a significant number of soil samples, river sediments, water samples, and for the investigation of the air pollution, certain species of moss, and various floral endemic species from the investigated region have been used. During this investigation, 62 elements were analyzed (Ag, Al, As, Ba, Be, Bi, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Hg, Ho, I, In, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, P, Pb, Pd, Pr, Pt, Rb, Rh, S, Sb, Sc, Sm, Sn, Sr, Ta, Tb, Te, Th, Tl, Tm, V, W, Y, Yb, Zn and Zr) in soil, water, sediments and moss samples. In order to achieve this, atomic emission spectrometry with inductively coupled plasma (AES-ICP) and mass spectrometry with inductively coupled plasma (ICP-MS) were applied. The obtained results were processed with specialized statistical analysis software and corresponding distribution maps were developed for various sampling media for each investigated element.

The results from the soil survey were processed by the method of multivariate factor analysis and six associations of elements were determined: Rb-Ta-K-Nb-Ga-Sn-Ba-Bi-Li-Be-(La-Eu)-Hf-Zr-Zn-In-Pd-Ag-Pt-Mg; Tl-As-Sb-Hg; Te-S-Ag-Pt-Al-Sc-(Gd-Lu)-Y; Fe-Cu-V-Ge-Co-In; Pd-Zr-Hf-W-Be and Ni-Mn-Co-Cr-Mg. For all analyzed elements and geochemical associations, distribution maps were prepared. The geochemical association of the As, Sb and Tl indicates mainly natural enrichment, but some high-values for Sb were result of former mining activity in the studied area. Anthropogenic influence to the distribution of Sb is also reflected in the river sediments as well.

Atmospheric pollution with certain toxic and heavy elements was measured using the moss biomonitoring technique in Allchar and its environ. By application of multivariate cluster and R-mode factor analysis, five geochemical associations were determined: F1 (Co, Cr, Fe, Sc, Li, V, Ga, Y, Ni, Mn, Al, La-Lu, Cu, Ge, Be, Bi and Hf); F2 (As, Tl, Sb and Mg); F3 (Rb, Cs and Mo); F4 (Sr, Ba, Hf, Zr, La-Lu and Bi) and F5 (Cd, Zn, Ag and Cu). The data from the samples around the Allchar mine and the rest of the Allchar area show that their source is mainly from natural phenomena. The comparison between the results from the samples around the Allchar mine and the rest of the Allchar area shows highest median values for As, Sb and Tl in the vicinity of the mine.

Within this thesis, an investigation for establishing the accumulation of some toxic elements in relation to its mobility in some local endemic plant species from this locality, Viola allchariensis G. Beck, Viola arsenica G. Beck, Viola macedonica Boiss. & Heldr., Onobrychis degenii Dörfler, Thymus alsarensis Ronn. and Centaurea leucomalla Bornm, was also carried out. The results showed that all studied endemic species are able to hyperaccumulate heavy metals in their roots, stems, leaves, flowers and seeds.