Thallium in Technosols from Allchar (North Macedonia): isotopic and speciation insights.

Allchar (North Macedonia) mining area is known for anomalous background Tl concentrations. In this study, we combine accurate detection of Tl stable isotope ratios with data on mineralogy/speciation and chemical extraction of Tl in Tl-contaminated Technosol profiles. We demonstrate that Tl in the studied soils varies significantly in both concentration (500 mg/kg-18 g/kg) and isotopic composition (-1.6 and +3.2 ε205Tl, a ∼0.5‰ spread), which is due to changes in the phase chemistry and/or mineralogy of Tl. Moreover, the observed 205Tl/203Tl ratios do not reflect the extent to which individual soils undergo Tl isotopic fractionation during mineral weathering and soil formation. Clearly, they reflect the initial isotopic signal(s) of the primary ore or ore minerals, and thus, the general history or type of their genesis. As the Tl carriers, various types of Tl-Me-arsenates, mixtures of jarosite and dorallcharite and minor Mn-oxides predominated. We revealed intense adsorption of Tl by the identified Mn-oxides (≤6.7 at.%). It is hypothesized that these phases are of key importance in the fractionation of Tl isotopes, meaning at this type of secondary oxide-soil solution interface. However, model studies involving primary/secondary components (sulfides, sulfates, oxides and arsenates) are required to understand the mechanisms that may lead to post-depositional Tl isotopic redistribution in soils, as well as Tl isotope systematics in mining wastes in general.

Assessment of essential and nonessential dietary exposure to trace elements from homegrown foodstuffs in a polluted area in Makedonska Kamenica and the Kocani region (FYRM).

UNLABELLED: The main purpose of the present study is to assess human dietary exposure to essential and non-essential trace elements via consumption of selected homegrown foodstuffs. Twelve essential and non-essential trace elements (Cd, Co, Cu, Cr, Hg, Mo, Ni, Pb, Sb, Se, Zn and As) were detected in various homegrown foodstuffs. Detailed questionnaires were also applied among a sample of the local population to collect information on sociodemographic characteristics. The results of the present study clearly indicate that the majority of the trace elements are at highly elevated levels in the studied foodstuffs, in comparison to international recommendations. The maximum measured levels of ETE and NETE are as follows [µgkg(-1)]: Cd 873, Co 1370, Cu 21700, Cr 59633, Hg 26, Mo 6460, Ni14.5, Pb 11100, Sb 181, Se 0.30, Zn 102 and As 693. Additionally, age, body mass index and gender were significantly associated with levels of dietary exposure. Further research is warranted on the potential health implication of this exposure. CAPSULE ABSTRACT: The study merges the accumulation of ETE and NETE in home-grown foodstuffs and reflects considerably high health risks for inhabitants.

Potentially toxic contamination of sediments, water and two animal species in Lake Kalimanci, FYR Macedonia: relevance to human health.

The objectives of the research were: (1) to examine the concentrations of metals in Vimba melanops and Rana temporaria and (2) to evaluate the potential risks of the contaminated organisms to human health in Makedonska Kamenica region. Analyses identified high levels of Cr, Hg, Ni and Pb in studied animals, which also exceeded their permissible levels in food. In sediment and soil samples, levels of Cd, Cu, Cr, Pb, Zn and As were perceived, while Cd, Cu, Ni, Pb, Se and As were increased in water samples. Results of transfer factor revealed that the examined animals had higher bioaccumulation rate from surrounding waters than from sediments or soils. The accomplished Health Risk Index disclosed that studied animals can have considerably high health risks for inhabitants. Conclusively, they could be considered as highly contaminated with metals and can consequently harm human health, especially children in their early development stages.

Heavy metal characteristics in Kocani Field plant system (Republic of Macedonia).

Heavy metal contamination of soils is widespread and induces a long-term risk to ecosystem health. This research focuses on the heavy metal contamination, transfer values and risk assessment in the Kocani Field plant system (Republic of Macedonia). To identify the heavy metal concentrations in Kocani crops (rice and maize), the geochemical analysis was performed by inductive coupled plasma mass spectrometer and thereupon the transfer factor (TF) and estimated daily intake amount values were calculated. The highest As, Cd, Mo, Pb and Zn values were determined in the rice samples grown in the paddy fields near the Zletovska River. The highest Pb and Mo concentrations measured in the maize samples were from the maize fields near the Zletovska River and Ciflik city. High TF values for Mo, Zn, Cd and Cu revealed a strong accumulation of Mo, Zn and Cd by rice and Mo and Zn by maize crops. The results of the estimated daily intake showed that the regular consumption of rice and maize crops containing the highest Cd, Mo, Pb and Zn concentrations could pose a serious threat to human health, because the daily intake of Cd, Mo, Pb and Zn for crops grown in the fields around the Zletovska River exceeded the recommended provisional tolerable daily intake values. Taking into account the results, the area around Zletovska River is considered as the most anthropogenically impacted part of Kocani Field.

Heavy metal contamination of paddy soils and rice (Oryza sativa L.) from Kocani Field (Macedonia).

This research focuses on the heavy metal contamination of the paddy soils and rice from Kocani Field (eastern Macedonia) resulting from irrigation by riverine water impacted by past and present base-metal mining activities and acid mine drainage. Very high concentrations of As, Cd, Cu, Pb and Zn were found in the paddy soils (47.6, 6.4, 99, 983 and 1,245 microg g(-1)) and the rice (0.53, 0.31, 5.8, 0.5 and 67 microg g(-1)) in the western part of Kocani Field, close to the Zletovska River, which drains the mining facilities of the Pb-Zn mine in Zletovo. In terms of health risk, the observed highest concentrations of these elements in the rice could have an effect on human health and should be the subject of further investigations.

Major and trace elements in paddy soil contaminated by Pb-Zn mining: a case study of Kocani Field, Macedonia.

The objective of this study was to assess the bulk chemical composition as well as the extent and severity of heavy metal contamination in the paddy soil of Kocani Field (eastern Macedonia). The results revealed that the paddy soil of the western part of Kocani Field is severely contaminated with Pb, Zn, As and Cd in the vicinity of the Zletovska River due to irrigation with riverine water that is severely affected by acid mine and tailing effluents from the Pb-Zn mine in Zletovo. The detected total concentrations of these metals are far above the threshold values considered to be phytotoxically excessive for surface soil. The paddy soil in the vicinity of the Zletovska River was also found to exhibit elevated levels of Ba, Th, U, V, W, Mo, Cu, Sb, Bi, Ag, Au, Hg and Tl, with concentrations above their generally accepted median concentration values obtained during this study. A correlation matrix revealed that the Mn and Fe oxides/hydroxides are the most important carrier phase for several trace elements, with the exception of rare earth elements (REEs). These also represent a major sink for the observed heavy metal pollution of the soil. REEs are mostly associated with two phases: light (L)REEs are bound to K-Al, while heavy (H)REEs are bound to Mg-bearing minerals. Although there is no direct evidence of a health risk, the paddy soil in the vicinity of Zletovska River needs further investigation and an assessment should be made of its suitability for agricultural use, particularly in view of the highly elevated concentrations of Pb, Zn, As and Cd.