Nastja Rogan Šmuc

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.

Use of Stable Nitrogen Isotope Signatures of Anthropogenic Organic Matter in the Coastal Environment: The Case Study of the Kosirina Bay (Murter Island, Croatia)

In this study stable nitrogen isotope ratios of particulate matter POM, zooplankton and selected biota such as Mytilus galloprovincialis were used to assess the impact of anthropogenically derived organic matter from the untreated domestic sewage, municipal and industrial effluents on the coastal ecosystem of the Kosirina Bay (Murter Island). The differences in δ15N values observed in POM and organisms collected in Kosirina Bay as compared to POM and biota sampled at unaffected sites from the southern part of the Kornati Island and highly impacted Pirovac Bay revealed only a very minor effects of anthropogenic inputs of nutrients and organic matter which is most probably derived from a sewage outfall south of the Tužbina Island.

The seasonal heavy metal signature and variations in the microbial mat (petola) of the Sečovlje Salina (northern Adriatic)

PurposeThe Sečovlje Salina is a part of Sečovlje Salina Nature Park situated in south-western Slovenia (northern Adriatic). The key element of the centuries-old Slovenian tradition of salt production is the “petola”, i.e. the few-millimetre-thick microbial mat which covers the bottom of the crystallizing salt basins. Petola cultivation proceeds over the whole year, with seasonal variations of petola composition/characteristics. The purpose of this study was to investigate seasonal petola composition variability including heavy metals content.Materials and methodsPetola samples from 2010 (rainy salt production season) and from 2009 (favourable weather conditions) were analyzed for pH, major elements and heavy metals (X-ray fluorescence method) and mineral composition (X-ray powder diffraction). The total organic carbon (TOC) and total nitrogen (TN) content of the petola were determined using a CHNS elemental analyzer. Seasonal variations in temperature, salinity and pH value of the brine were also determined.Results and discussionQuartz, halite, calcite, gypsum, aragonite and clay constitute the major fraction of the petola, while the organic matter content was low. The main mineral composition was associated with the base sediment while gypsum, aragonite and halite formed during crystallization processes. The increase of salinity and the decrease of organic matter were reflected in the elemental composition with highest (Ca, Cl, Mg, S) and lowest (Si, Al, Fe, K) summer concentrations. Similarly, a decrease in heavy metal concentrations (As, Cu, Cr, Mn, Ni, Pb, Zn) was also determined and was related to the lower organic matter and pH values present during this period.ConclusionsBasic sediment composition, the brine salinity gradient, salt production processes, redox conditions and the content of organic matter contribute to seasonal variability of petola composition. These factors favourably affect the petola characteristics that allow manual (seasonal) gathering and contribute to the quality of natural salt from the Sečovlje Salina.

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.

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.

Metal(oid) mobility in a hypersaline salt marsh sediment (Sečovlje Salina, northern Adriatic, Slovenia)

In this research, sediments from the Sečovlje Salina (northern Adriatic, Slovenia) were geochemically investigated in order to decode the mobility of metal(oid)s in the hypersaline environment. The results demonstrated that the concentrations of As, Co, Cu, Mo, Ni, Pb, Sb, Sn and Zn were comparable to those detected in various similar coastal background areas, as well as in the Sečovlje salt marsh core sample. The estimated mobility potential of metal(oid)s in sediment decreases in the following order: Mo > As > Cu > Sb > Sn > Co > Pb > Ni > Zn. Since the hypersaline sediment (e.g. healing mud) is used as a healing factor (it can be applied directly on human skin), the study of metal(oid) bioavailability in an interaction between the hypersaline sediments and the artificial sweat was also performed. It is significant that the metal(oid) contents are leached in very low concentrations and are treated as nontoxic for humans according to international norms for cosmetic products. The study provides information in order to assess the role of metal mobility on the potential health impact of the application of natural healing mud.

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.

Geochemical study of pottery sherds from an archaeological site near Mošnje (Slovenia)

This study is a geochemical analytical approach to the characterization of pottery samples from an archaeological site near Mošnje (Slovenia). Inductively coupled plasma–mass spectrometry and statistical analyses were used to determine detailed geochemical properties of the pottery sherds and to identify potentially individual groups among the samples studied. The geochemical results indicated the existence of four major groups of the pottery sherds: the first and second groups are assembled from eight samples, all generally characterized by their high CaO and TOT/C content; the third group comprised the samples with the highest SiO2 concentrations; and the fourth group is represented by the samples K3, K5 and K13. The principal component analysis and cluster analysis validated the existing groups and revealed a high degree of chemical similarity between these groups. The geochemical and statistical data confirmed the archaeologists’ hypothesis and interpretation of a similar origin/alteration of source material/probable local ceramic production for the majority of the pottery sherds; the imported origin of samples K3 and K13 was recognized, while sample K5 had been intentionally imported as a sample for comparative purposes.