Variability assessment of metals distributions due to anthropogenic and geogenic impact in the lead-zinc mine and flotation „Zletovo” environs (moss biomonitoring)

Moss species (Hypnum cupressiforme, Scleropodium purum and Campthotecium lutescens) wereused as suitable sampling media for biomonitoring the origin of heavy metal pollution in the lead–zinc mine and flotationenviron near the town of Probištip. The 21 metals contents were determined by atomic emission spectrometrywith inductively coupled plasma (ICP–AES). Data processing was applied with combinations of multivariate statisticalmethods: factor analysis, principal component analysis and cluster analysis. The main anthropogenic markersin the investigated area were Pb and Zn (maximal values of 200 and 186 mg kg–1, respectively). The factor analysissingled out (in the increasing scale) the following associations: F1/D1: Fe < Mo < Pb < Na < Cd < Mg < Zn < Ag <Cu and F2/D2: Mn < Ni < K < P < Ba < Sr < Ca < As < Cr < Al < V < Li. The anthropogenic elements contents varyindependent from the moss species, but depending on the distancing from the pollution source, there are positive correlation.Long distance distribution from the emission source doesn’t occur

Approach to detect possible genotoxic effects of metals in plants

During the intensive research in past decades, the scientific community and regulatory agencies also, focused their interest on measuring contaminant levels in tissues and environmental samples and on understanding the mechanisms of toxicity of different and pervasive contaminants. Among them, metals were always in focus because of possible detrimental and long lasting effects on living organisms. The current study was designed to assess the effects of long term, high metal exposition (cadmium, lead, copper, nickel and zinc) on DNA damage

Comparison of response of moss, lichens and attic dust to geology and atmospheric pollution from copper mine

Abstract Different sampling media (moss, lichen and attic dust) were used for monitoring the distribution of 15 elements, including certain trace elements, in the vicinity of an intensively exploited copper mine in the east of the Republic of Macedonia. Moss species (Hypnum cupressiforme and Campothecium lutescens), epiphytic lichens (Hypogymnia physodes and Evernia prunastri) and attic dust were collected for comparative analysis for monitoring air pollution. In both cases (lithological and anthropogenic affected areas) for the distribution of elements, the sampling media follows the expression capabilities: attic dust > moss > lichens. Enrichment factors M/L—moss vs. lichen, for plant response to elements distribution and D/L—attic dust vs. lichen, for historical response of elements distribution were significant for Cu and Ni, which were singled out as the main markers for anthropogenic and geogenic distribution. The factor analysis highlighted geogenic (F1: Ni-Cr-Cd-Fe-Al-K-Mn-Zn) and anthropogenic (F2: As-Cu-Pb) association of elements from three types of media samples. For anthropogenic affected areas, T value and F value for Cu content were significant at p < 0.05 and higher enrichment factors were obtained for lichen, moss and attic dust media (3.8, 5.0 and 5.7, respectively). Spatial distribution for element deposition (with emphasis on Cu and Ni) is not disturbed by the significant differences in the sampling media matrix. Treated sample materials (attic dust, moss, lichen) are shown to be useful in determining an anthropogenic impact, as well as the chemical properties or geological background on orographic diverse terrain in the presence of complex geological structure

Assessment of Heavy Metal Pollution in R. Macedonia Using a Plant Assay

Different plant organs (leaves, flowers, stems, or roots) from four plant species—Urtica dioica L. (Urticaceae), Robinia pseudoacacia L. (Fabaceae), Taraxacum officinale (Asteraceae), and Matricaria recutita (Asteraceae)—were evaluated as possible bioindicators of heavy-metal pollution in Republic of Macedonia. Concentrations of Pb, Cu, Cd, Mn, Ni, and Zn were determined in unwashed plant parts collected from areas with different degrees of metal pollution by ICP-AES

Application of principal component analysis in the assessment of essential and toxic metals in vegetable and soil from polluted and referent areas

The aim of the paper is to assess the 23 elements distribution in agricultural soil and vegetables [garlic (Allium sativum), onion (Allium cepa) and parsley (Petroselinum crispum)] widely used as food in areas contaminated with toxic metals due to long-lasting copper mining activities in the Republic of Macedonia. Principal components analysis (PCA) models were computed with different variables: elements contents in vegetables and soil samples collected from contaminated and uncontaminated areas and the bioaccumulation and transferring factors for hazardously metals. Bioaccumulation and mobility of the elements were determined with three soil extraction methods: in 0.1 M HCl; in H2O and in a mixed buffered solution of diethylenetriaminepentaacetic acid, CaCl2 and triethanolamine (DTPA-CaCl2-TEA). Inductively coupled plasma - atomic emission spectrometry (ICP-AES) was applied to determine the contents of the analyzed elements content in the vegetables, soils and soil extracts. The total contents in soil were found above the European standards for As, Cd, Cu and Pb in urban and mines environ, while the vegetables were enriched with Pb and Cd in polluted areas. The PCs plant and soil models (PCA1, PCA2 and PCA3 models) were very useful in determination the relation/correlation of the elements contents in soil (total and extractable contents) and vegetable species. Significant extraction efficiency was obtained for HCl extraction agent (for Ag, Al, Ba, Ca, Cr, K, Li, Mg, Mn, Mo, Na, Ni, P, V and Zn) and for DTPA-CaCl2-TEA (for Cd, Cu, partially Ni, and Pb). Parsley, onion and garlic showed higher translocation efficiency for As, Cd, Cu and Pb in urban area and mines polluted areas (TF > 1)

Bioavailability and bioaccumulation characterization of essential and heavy metals contents in R. acetosa, S. oleracea and U. dioica from copper polluted and referent areas

Background: Bioavailability of metals occurring in soil is the basic source of its accumulation in vegetables and herbs. The impact of soil pollution (due to urban and mining areas) on the food chain presents a challenge for many investigations. Availability of metals in a potentially polluted soil and their possible transfer and bioaccumulation in sorrel (Rumex acetosa), spinach (Spinacia oleracea) and common nettle (Urtica dioica), were examined. Methods: Microwave digestion was applied for total digestion of the plant tissues, while on the soil samples open wet digestion with a mixture of acids was applied. Three extraction methods were implemented for the bioavailable metals in the soil. Atomic emission spectrometry with inductively coupled plasma was used for determination of the total contents of 21 elements. Results: Significant enrichments in agricultural soil for As, Pb and Zn (in urban area), Cd, Cu and Ni (in a copper mine area), compared with the respective values from European standards were detected. On the basis of three different extraction methods, higher availability was assumed for both lithogenic and anthropogenic elements. Translocation values >1 were obtained for As, Cd, Cu, Ni, Pb and Zn. Higher bioconcentrating value was obtained only for Cd, while the bioaccumulation values vary from 0.17 for Cd to 0.82 for Zn. Conclusions: The potential availability of hazardous metals in urban and mining soils is examined using DTPA-TEA-CaCl2 (urban) and HCl (Cu-mines areas). Our results suggested that S. oleracea and R. acetosa have a phytostabilization potential for Cd, Cu, Ni and Pb, while U. dioica only for Cu. R. acetosa has a potential for phytoextraction of Cd in urban and copper polluted areas

Moss biomonitoring of air pollution with heavy metals in zinc and lead mine environ

Distribution of 22 elements in the air, including certain heavy metals, in the vicinity of lead and zinc mine “Sasa” near the city of Makedonska Kamenica, Republic of Macedonia, was studied by moss biomonitoring. The anthropogenic introducing of certain heavy metals in mine environ was expected, due to continually distribution of higher amounts of heavy metals, which occurs because of winds caring out the fine particles into the atmosphere. Moss samples (Hypnum cupressiforme and Campothecium lutescens) were used as plant species for heavy metals biomonitoring. The contents of the analysed elements (Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V and Zn) were determinate by atomic emission spectrometry with inductively coupled plasma (ICP-AES). The obtained values for the content of the elements in moss samples were statistically processed using basic descriptive statistics. Moss species were demonstrated as highly tolerant to higher contents of Pb and Zn. The results show obvious anthropogenic influence of the mine activities as well as the existence of the flotation tailings dump site. Thus, the median values for Pb and Zn in the wider area were 8.5 and 26.1 mg kg-1 while for the mine environ they were 26.9 and 36.2 mg kg-1, respectively. Maximum values obtained from the investigated area for these certain heavy metals were ~450 mg kg-1

Comparison of different sampling media (moss, lichen, attic dust) for determination of air pollution with heavy metals in the vicinity of copper mine

Moss and lichen species and attic dust samples were used for monitoring distribution of heavy metals and other trace elements in the vicinity of intensively exploited copper mine. Hypnum cupressiforme, Campothecium lutescens and Homolothecium sericium were collected as characteristic moss species and Hypogymnia physodes, Pseudevernia furfuracea and Evernia prunastri were collected as characteristic lichens species for comparative analysis [1, 2]. Attic dust samples were collected from the same region in order of historical record for metals distribution [3]. The analysis of 17 elements (Al, Ba, Ca, Co, Cr, Cu, Li, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, V and Zn) was performed by atomic emission spectrometry with inductively coupled plasma (ICP-AES). As and Cd were analyzed by electrothermal atomic absorption spectrometry (ETAAS). The comparative analysis between elements content from mosses and lichens showed: (a) collected species were very tolerant to high content of Cu, Pb, Fe (>0.01%, >0.01% and 1% respectively); (b) moss species accumulate higher amounts of lithophile elements (Al, Ba Cr, Fe, Mn, Na, Ni, Sr) and lichen more easily accumulates atmophile elements ( Pb, V, Zn); (c) mosses and lichens cannot be used interchangeably as biomonitors of metals in areas with Cu mineral deposits and ore processing. Attic dust samples enabled recording the historical emission of heavy metals in air with emphasis of Cu, where was found that there is a deposition of large amount of copper. The highest values for copper were obtained from lichen, moss and attic dust (134, 198 and 415 mg kg-1 respectively) samples collected very close to the mine. The ultimate effect is that spatial distribution for element deposition (with emphasis on heavy metals) is not disturbed with the significant differences in sampling media matrix. Using of different types of environmental samples unable covering deficiencies one with another in order of monitoring long term and long distance metal distribution and it deposition in the environment

Distribution of chemical elements in attic dust as reflection of their geogenic and anthropogenic sources in the vicinity of the copper mine and flotation plant

The main aim of this article was to assess the atmospheric pollution with heavy metals due to copper mining Bucim near Radovis, the Republic of Macedonia. The open pit and mine waste and flotation tailings are continually exposed to open air, which leads to winds carrying the fine particles into the atmosphere. Samples of attic dust were examined as historical archives of mine emissions, with the aim of elucidating the pathways of pollution. Dust was collected from the attics of 29 houses, built between 1920 and 1970. Nineteen elements (Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Li, Fe, K, Mg, Mn,Na, Ni, Pb, Sr, and Zn)were analyzed by atomic emission spectrometry with inductively coupled plasma. The obtained values of the investigated elements in attic dust samples were statistically processed using nonparametric and parametric analysis. Factor analysis revealed three factors governing the source of individual chemical elements. Two of them grouping Ca, Li, Mg, Mn, and Sr (Factor 1) and Co, Cr, and Ni (Factor 2) can be characterized as geogenic. The third factor grouping As, Cu, and Pb is anthropogenic and mirrors dust fallout from mining operation and from flotation tailings. Maps of areal deposition were prepared for this group of elements, from which correlation of these anthropogenic born elements was confirmed