Petra Vrhovnik

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 Kočani 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 Kočani Field plant system (Republic of Macedonia). To identify the heavy metal concentrations in Kočani 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 Kočani Field.

Assessment of essential and nonessential dietary exposure to trace elements from homegrown foodstuffs in a polluted area in Makedonska Kamenica and the Kočani 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.

Geochemical characterization and environmental status of Makirina Bay sediments (northern Dalmatia, Republic of Croatia)

This research focuses on determination of the mineralogical composition, geochemical characteristics and evaluationof pollution status of the Makirina Bay sediments. Calculated enrichment factor (EF) values show no enrichment ( Cd > Pb > Ni > Zn > Cu > As. Principal component analysis (PCA) and correlation analysis confirmed the PTE distribution depends mainly on thegeogenic mineral components and anthropogenic activities in the areas surrounding the bay. Calculated transfer factor(TF) values from sediment to seagrass Cymodocea nodosa (C. nodosa) were < 1, showing that despite the results of thesequential extraction procedure, PTE transfer from sediment to roots was not effective.

Trace Metals in Fish Biominerals as Environmental Indicators: Handheld XRF Analyses

The parts of jawbones and selected teeth (malleolus) of adult marine benthic fish Sparus aurata and Diplodus sargus was collected from different station during east Adriatic coast (Croatia). Biominerals were prepared for three different instrumental analyses: elemental analysis by X-ray Fluorescence (XRF) and inductively coupled plasma spectroscopy (ICP-AES); mineralogical analysis by X-ray diffraction (XRD).The XRF results showed major and traces elements incorporated in the fish teeth. The concentration of zinc (Zn) expressed in mg kg-1 in the enamel - outside part of the malleolus dental surface (teeth crown) varied from 77 up to 1.975 in both fish species. In the root of the same teeth samples of Zn concentration was lower and amounted from 77 - 153 mg kg-1. Contrary, maximal amount of strontium (Sr) was registered in the teeth root from 801 – 1.310 mg kg-1, and in the enamel 476 – 1.104 mg kg-1 respectively. Multivariate statistical analysis based on the Statistica 6.0. PCA has been used to determine differences among elemental composition of the major and trace elements in teeth enamel (crown) and teeth roots, and in examining correlation among incorporated elements and environmental characteristics of the sampling localities.The XRD patterns of both fish jawbones and malleolus teeth showed characteristic hydroxyapatite lines (HAP). The HAP lines of the fish jawbones are broadened and shifted on the higher angles, indicating that mandible and maxilla biominerals are not fully formed and that mineralization of the fish jawbones is a dynamic process that last permanently during organism growth.Selected elements contents Ni, Co, Fe, Cu, and Cr (expressed in mg kg-1) of bulk fishbone samples was determined by ICP-AES analysis. Investigated metals showed higher values in the teeth than in the fish jawbones. The results revealed the distribution of the heavy metals in teeth to be Fe > Cr > Cu > Ni > Co, and in the jaws Fe > Cr > Cu > Ni > Co.The purpose of this study was to investigate the possibility of using XRF for the routine determination of heavy metals in the fish biominerals, in biomonitoring studies and ecological evaluation of the environment. The over-all data obtained indicated that XRF and ICP-AES showed good agreement for the determination of the heavy metals in test samples and that XRF could be used as cost effective method of accurately and precisely determining heavy metals content of the biomineral, while drastically reducing analysis time for initial sample preparation.

Benthic organisms as ecological indicators for the status assessment of coastal ecosystems

The presence of potentially toxic elements (PTE) was determined in different tissues of five selected marine organisms. The As, Cd, Cu, Mn, Mo, Ni, Pb and Zn concentrations were measured in the seagrass Cymodocea nodosa , the green alga Cladophora echinus , the red alga Gelidiella lubrica , the marine topshell Phorcus turbinatus and the littoral crab Carcinus aestuarii , as well as in seawater from Makirina Bay. The levels of As, Cd, Cu, Mn and Zn in the biota were found to exceed those in previously analysed sediments, indicating the bioaccumulation of these PTE. The biota-sediment accumulation factor (BSAF) and concentration factor (CF) varied among different organisms. As regards the five selected species, C. nodosa , C. echinus and G. lubrica proved to be the strongest accumulators of Mn, while P. turbinatus and C. aestuarii showed a high capacity to accumulate As, Cd, Cu and Zn. These species can be considered as good ecological indicators in the assessment of PTE pollution in marine littoral environments.

Environmental Characterization of Lake Ecosystems Located in Serbo Macedonian Massif (FYRM)

This chapter represents the mineralogical, geochemical and isotopic characteristics of recent lacustrine sediments, shells of the Anodonta cygnea and fish species (Rutilus rutilus dojranensis) from the Lake Dojran (FY Republic of Macedonia, southern part of the Serbo-Macedonian Massif (SMM)) which provide indirect evidence regarding biomineralization and calcification processes as well as various geological problems. Environmental pollution can seriously contribute to different biological processes concerning the condition of physiological secretion of carbonate material into the shells. For comparison, sediments and fish species V. melanops from the Lake Kalimanci, located in northern part of the SMM, were also implicated into the study. X-ray powder diffraction (XRD), inductively coupled plasma mass spectrometry (ICP-MS) and C and O stable isotope analyses were performed, and thereupon enrichment factor (EF) values were calculated. The XRD results revealed close association of sediment mineralogy with the prevailing metamorphic, volcanic and igneous rocks of the region surrounding both lakes (Dojran and Kalimanci). According to the EF value results, surficial Lake Dojran sediments are little enriched with Co, Cr, Cu, Pb, and Zn, moderately enriched with Au, Ni and Sb, moderately severely enriched with Au, severely enriched with Sb and very severely enriched with As. This elemental enrichment originates from various geogenic (geological background and polymetallic mineralization) and anthropogenic (tourism, traffic, coatings, untreated wastewater discharge and agrochemicals) sources. Calculated EF revealed that surficial sediments from Lake Kalimanci are extremely severe enriched with Pb, Zn, and Cd, meanwhile As and Cu shows very severe enrichment. Comparing to Lake Dojran, calculated EF is much higher in Lake Kalimanci than in Dojran. Stable isotope signature results showed that Lake Dojran sediments were strongly influenced by evaporation effect. Their δ18O values range from -5.60 to +1.49 ‰ and the δ13CVPDB composition range from -6.45 to -1.65 ‰. Shells Anodonta cygnea are mainly composed from mineral aragonite and their δ18O values varies between 0.43 ‰ and +1.94 ‰, and δ13CVPDB between -2.48 to -1.72 ‰. δ18O signature in shells might be explained by precipitation of the carbonate from isotopically heavier oxygen lake water. The unussualy heavy skeletal oxygen suggested calcification at the elevated temperature and evaporation. Analyses also identified particularly high levels for Cr, Hg, Ni and Pb in fish (V. Melanops) and frog (R. Temporaria) samples from Lake Kalimanci with mean values [µgkg-1]: 1090 – 6.5, 339 – 117, 567 – 5100 and 1127 – 435, respectively. Meanwhile, the contents of Cr, Hg, Ni and Pb in fish samples (R. rutilus dojranensis) from Lake Dojran are a bit lower [µgkg-1]: 2320, 1690, 700 and 50.