Evaluation of Alternative Sources of Proteins and Other Nutrients with Potential Applications in Fish Nutrition.

The European Union's (EU) agricultural self-sufficiency is challenged by its reliance on imported plant proteins, particularly soy from the Americas, contributing to deforestation and greenhouse gas emissions. Addressing the EU's protein deficit, this study evaluates alternative protein sources for aquaculture, focusing on their nutritional value, elemental content, and polycyclic aromatic hydrocarbons (PAHs). Protein flours from gastropods (Helix pomatia, Arion lusitanicus, Arion vulgaris) and their hepatopancreas, along with plant-based proteins from food industry by-products (oilcakes, coffee grounds, spent brewer's yeast), were analyzed. Results revealed that snail flour contained the highest protein content at 59.09%, significantly outperforming hepatopancreas flour at 42.26%. Plant-based proteins demonstrated substantial nutritional value, with coffee grounds flour exhibiting a remarkable protein content of 71.8% and spent brewer's yeast flour at 57.9%. Elemental analysis indicated high levels of essential minerals such as magnesium in hepatopancreas flour (5719.10 mg/kg) and calcium in slug flour (48,640.11 mg/kg). However, cadmium levels in hepatopancreas flour (11.45 mg/kg) necessitate caution due to potential health risks. PAH concentrations were low across all samples, with the highest total PAH content observed in hepatopancreas flour at 0.0353 µg/kg, suggesting minimal risk of PAH-related toxicity. The analysis of plant-based protein sources, particularly oilcakes derived from sunflower, hemp, flax, and pumpkin seeds, revealed that these by-products not only exhibit high protein contents but present a promising avenue for enhancing the nutritional quality of feed. This study underscores the potential of utilizing gastropod and plant-based by-products as sustainable and nutritionally adequate alternatives to conventional feeds in aquaculture, contributing to the EU's environmental sustainability goals.

Impact of Low Lithium Concentrations on the Fatty Acids and Elemental Composition of Salvinia natans.

The photosynthetic pigments, protein, macro and microelements concentrations, and fatty acids composition of Salvinia natans, a free-floating aquatic plant, were analyzed after exposure to Hoagland nutrient solution containing 1, 3, and 5 mg/L Li. The Li content of Salvinia natans grew exponentially with the Li concentration in the Hoagland nutrient solution. The exposure to Li did not induce significant changes in Na, Mg, K, Cu, and Zn content but enhanced the Ba, Cr, Mn, Ni and Mo absorption in Salvinia natans. The most abundant fatty acids determined in oils extracted from Salvinia natans were C16:0, C18:3(n6), C18:2(n6), and C18:3(n3). The photosynthetic pigments did not change significantly after exposure to Li. In contrast, chlorophyll and protein content decreased, whilst monounsaturated and polyunsaturated fatty acids content increased after the exposure to 1 mg/L Li. The results indicated that Salvinia natans exposed to low Li concentrations may be a good source of minerals, omega 6 and omega 3.

Lithological distribution of rare earth elements in soils in the As-Sb-Tl Allchar mining area, North Macedonia.

Despite the growing interest, the information available on rare earth elements (REEs) in the last two decades is relatively premature and sparse. The importance of these elements as indicators of soil and physiological processes and responses have contributed to the increased interest in these previously less considered elements in the environmental sciences. This study provides an overview of the content and distribution of rare earth elements in the soil in the vicinity of the hydrothermal volcanogenic As-Sb-Tl deposit of Allchar, North Macedonia. Elemental contents were determined by inductively coupled plasma mass spectrometry (ICP-MS). The light rare earth elements (LREEs) content in the study area ranges from 8.92 to 188 mg/kg, while the heavy rare earth elements (HREEs) content ranges from 1.95 to 42.7 mg/kg. It can be concluded that there is some enrichment of light REEs in the volcanic intrusive rocks of the Allchar mine area, including latite, quartz-latite, trachyte and occasionally andesite and dacite. The spatial distribution of HREEs is closely related to the lithology of the region, especially the sandstone and claystone, followed by layered and massive carbonate rocks (limestone, dolomite, marble) that occurred in the Middle and Upper Triassic.

Assessment of natural and anthropogenic factors on the distribution of chemical elements in soil from the Skopje region, North Macedonia.

The main objective of this study is to present the distribution of different chemical elements in soil samples from the Skopje region, North Macedonia. To determine the level of presence of chemical elements, soil samples are collected from a total of 60 locations. From each location, from an area of 5 × 5 km2 samples of soil are collected: topsoil (0-5 cm) and subsoil (20-30 cm). The soil samples were analyzed for 69 elements by using two instrumental methods: inductively coupled plasma-atomic emission spectrometry (ICP-AES) for macro-elements and inductively coupled plasma-mass spectrometry (ICP-MS) for trace elements. A factor analysis was applied to analyze the factors affecting the linear combination variables grouped at the same factor. Spatial distribution maps of each factor as well as distribution maps for the analyzed elements were prepared by universal kriging interpolation. It was found that the distribution of most elements follows the lithology of the examined area, except for some elements (Cd, Cu, Fe, Hg, Mn, Pb, and Zn) whose higher contents are found in the area of the city of Skopje as a result of urban and industrial activities (traffic, metal processing, fossil fuel combustion for heating).

Moss biomonitoring of air pollution with potentially toxic elements in the Kumanovo Region, North Macedonia.

A study was carried out to investigate air deposition and to explore the natural distribution and contamination with potentially toxic elements (PTEs) in the Kumanovo Region, North Macedonia, by using moss samples as biomonitors for air pollution. The distribution of 51 elements was detected in 42 moss samples collected from this area. Moss samples were analyzed following microwave digestion by inductively coupled plasma-atomic emission spectrometry (ICP-AES) and inductively coupled plasma-mass spectrometry (ICP-MS). It was found that the atmospheric deposition for some PTEs in the moss samples in specific parts of the study area is influenced by anthropogenic and urban activities. R-mode factor analysis was used to identify and characterize element associations, and six associations of elements were determined. Four factors were separated from the group of macroelements determined by ICP-AES: Factor 1 (Al, Cr, Fe, Li, Ni, V, and Zn), F2 (K, Mg, and P), F3 (Ba and Sr), and F4 (Cd, Pb, and Zn); and two associations were separated from the group of trace elements determined by ICP-MS: Factor 1 (As, Co, Cs, Ga, Ge, Sc, Ti, Y, Zr, and rare earth elements-REEs) and Factor 2 (Bi, Br, Hg, I, Sb, Sn, and W).

Application of Inductively Coupled Plasma Spectrometric Techniques and Multivariate Statistical Analysis in the Hydrogeochemical Profiling of Caves-Case Study Cloșani, Romania.

The aim of the study was to develop the hydrogeochemical profiling of caves based on the elemental composition of water and silty soil samples and a multivariate statistical analysis. Major and trace elements, including rare earths, were determined in the water and soil samples. The general characteristics of water, anions content, inorganic and organic carbon fractions and nitrogen species (NO3- and NH4+) were also considered. The ANOVA-principal component analysis (PCA) and two-way joining analysis were applied on samples collected from Cloșani Cave, Romania. The ANOVA-PCA revealed that the hydrogeochemical characteristics of Ca2+-HCO3- water facies were described by five factors, the strongest being associated with water-carbonate rock interactions and the occurrence of Ca, Mg and HCO3- (43.4%). Although organic carbon fractions have a lower influence (20.1%) than inorganic ones on water characteristics, they are involved in the chemical processes of nitrogen and of the elements involved in redox processes (Fe, Mn, Cr and Sn). The seasonal variability of water characteristics, especially during the spring, was observed. The variability of silty soil samples was described by four principal components, the strongest influence being attributed to rare earth elements (52.2%). The ANOVA-PCA provided deeper information compared to Gibbs and Piper diagrams and the correlation analysis.

Long-term Geochemical Evolution of Lithogenic Versus Anthropogenic Distribution of Macro and Trace Elements in Household Attic Dust.

Attic dusts were examined as historical archives of anthropogenic emissions, with the goal of elucidating the enrichment pathways associated with hydrothermal exploitation of Cu, Pb, and Zn minerals in the Bregalnica River basin in the eastern part of the Republic of Macedonia. Dust samples were collected from 84 settlements. Atomic emission spectrometry and mass spectrometry with inductively coupled plasma were applied as analytical techniques for the determination of 69 element contents. Multivariate analysis was applied for the extraction of dominant geochemical markers. The lithogenic distribution was simplified to six dominant geochemical markers: F1: Ga-Nb-Ta-Y-(La-Gd)-(Eu-Lu); F2: Be-Cr-Li-Mg-Ni; F3: Ag-Bi-Cd-Cu-In-Mn-Pb-Sb-Te-W-Zn; F4: Ba-Cs-Hf-Pd-Rb-Sr-Tl-Zr; F5: As-Co-Ge-V; and F6: К-Na-Sc-Ti. The anthropogenic effects on the air pollution were marked by a dominance of F3 and secondary dominance of F5. The fifth factor also was determined as a lithogenic marker for the occurrence of the very old Rifeous shales. The first factor also presents a very unique association that despite the heterogeneity relays on natural phenomena of tracking the deposition in areas of Proterosoic gneisses; related to the distribution of fine particles was associated with carbonate-silicate volcanic rocks. Intensive poly-metallic dust depositions were recorded only in the surroundings of localities where the hydrothermal extractions are implemented. Long-term deposition can be considered as pollution indexes for these hot spots. This mainly affects the Cd, Pb, and Zn deposition that is as high as 25, 3900, and 3200 mg/kg, respectively.

Geochemical hunting of lithogenic and anthropogenic impacts on polymetallic distribution (Bregalnica river basin, Republic of Macedonia).

The main subject of this investigation was the assessment of the lithogenic and anthropogenic distribution of 69 elements in the sediments and fluvisol in the Bregalnica river basin. Alluvial soil and fluvisol samples were collected from the total of eighteen locations along the course of the Bregalnica river and additional thirteen samples were collected from its tributaries. The matrix elements accumulation patterns followed the order: Fe > Na > Al > Ca > Mg > K > Ti > P. The potentially toxic elements, such as As, Cd, Pb, and Zn, have enriched content in the sediments in the medium course of the river, where the main anthropogenic introduction activities occurred. By multivariate analysis the dominant geochemical associations were extracted, as follows: F1: Y-Eu-Lu-Cr-V-La-Gd-Nb-Co-Hf-Zr-Ga-Mg-Fe-Sr-Ta-Sn-Li-Na-Rb-Ni-Ge-Be-Cs; F2: As-W-Ba-Ag-Cu-Tl-Zn-Sb-Mo-In-Cd-Te-Bi-Pb and F3: I-Sc-Br-K. Lead and zinc contents were strongly correlated with the hydrothermal exploitations, especially in the area of Neogene clastite and vulcanite. These elements occur as dominant geochemical markers of the anthropogenic impacts of polymetallic enrichments due to the hydrothermal ore exploitation (Factor 2). The impact of Oligocene volcanism (Kratovo-Zletovo region) was observed in the lithological enrichments of Pb, Zn, Cu, As, Sb, Mo and Bi. Despite the natural distribution along the course of the Bregalnica river, an exceptional anomaly in the iron distribution of the old polymetallic unused mineralization was detected in Zone 1 (Berovo region).

Distribution of trace elements in sediment and soil from river Vardar Basin, Macedonia/Greece.

A systematic study was carried out to investigate the distribution of 59 elements in the sediment and soil samples collected from the river Vardar (Republic of Macedonia and Greece) and its major tributaries. The samples were collected from 28 sampling sites. Analyses were performed by inductively coupled plasma-mass spectrometry. R-mode factor analysis (FA) was used to identify and characterise element associations. Seven associations of elements were determined by the method of multivariate statistics. Every factor (Factors 1-3 and 6 and 7 as geogenic and Factors 4 and 5 as anthropogenic associations of elements) are examined and explained separately. The distribution of various elements showed that there is a presence of anthropogenic elements (Ag, Cd, Cu, Ge, Pb, Sn and Zn) introduced in the river sediments and soils from the mining, metallurgical, industrial and agricultural activities in Vardar River Basin, which covers most of the Republic of Macedonia and Central-northern part of Greece.

Distribution of chemical elements in soils and stream sediments in the area of abandoned Sb-As-Tl Allchar mine, Republic of Macedonia.

The aim of this study was to investigate the distribution of some toxic elements in topsoil and subsoil, focusing on the identification of natural and anthropogenic element sources in the small region of rare As-Sb-Tl mineralization outcrop and abandoned mine Allchar known for the highest natural concentration of Tl in soil worldwide. The samples of soil and sediments after total digestion were analyzed by inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). Factor analysis (FA) was used to identify and characterize element associations. Six associations of elements were determined by the method of multivariate statistics: 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. The purpose of the assessment was to determine the nature and extent of potential contamination as well as to broadly assess possible impacts to human health and the environment. The results from the analysis of the collected samples in the vicinity of the mine revealed that As and Tl elements have the highest median values. Higher median values for Sb are obviously as a result of the past mining activities and as a result of area surface phenomena in the past.

Applying of factor analyses for determination of trace elements distribution in water from Vardar and its tributaries, Macedonia/Greece.

A systematic study was carried out to investigate the distribution of fifty-six elements in the water samples from river Vardar (Republic of Macedonia and Greece) and its major tributaries. The samples were collected from 27 sampling sites. Analyses were performed by mass spectrometry with inductively coupled plasma (ICP-MS) and atomic emission spectrometry with inductively coupled plasma (ICP-AES). Cluster and R mode factor analysis (FA) was used to identify and characterise element associations and four associations of elements were determined by the method of multivariate statistics. Three factors represent the associations of elements that occur in the river water naturally while Factor 3 represents an anthropogenic association of the elements (Cd, Ga, In, Pb, Re, Tl, Cu, and Zn) introduced in the river waters from the waste waters from the mining and metallurgical activities in the country.

Assessing microbiological and heavy metal pollution in surface waters associated with potential human health risk assessment at fish ingestion exposure.

Fish represent a significant source of nutrients but also cause negative health effects due to their bioaccumulation capacity for pollutants. The aim of this study was to examine the transfer of metals from the water of several rivers (Somes, Tisa, Sasar, Lapus, Lapusel) to fish (Caras sp) tissue (subcutaneous fat, muscles, liver, intestines, kidneys, gills, brain, and eyes) and to identify and assess the carcinogenic and non-carcinogenic health risks of Arsenic (As), Cadmium (Cd), Nickel (Ni), Manganese (Mn), Cooper (Cu), Lead (Pb), Chromium (Cr) and Zinc (Zn) through the ingestion of fish (muscles and subcutaneous fat tissues). The obtained results indicated that a diet consisting of fish is particularly vulnerable, particularly in children compared to adults. The risk assessment results were below the threshold limit, although the fish samples contained heavy metals, with values exceeding the permitted limits of Fe (4.41-1604 mg/kg), Cr (727-4155 µg/kg), Zn (4.72-147 mg/kg), and Ni (333-2194 µg/kg). The studied surface waters are characterized by low and high degrees of pollution with heavy metals, as indicated by the heavy metal pollution index scores (HPI: 12.4-86.4) and the heavy metal evaluation index scores (HEI: 1.06-17.6). The considerable pollution levels are attributed to the high Mn content (0.61-49.7 µg/kg), which exceeded the limit up to fifty times. A consistent set of physico-chemical analysis (pH, electrical conductivity, total hardness, turbidity, chloride, sulphate, nitrate, nitrite, ammonium, Ca, Mg, Na, K) was analysed in water samples as well. Considering the water quality index scores (WQI: 16.0-25.2), the surface waters exhibited good quality. Microbiological results indicated the presence of Listeria monocytogenes and atypical colonies of coagulase-positive staphylococcus in fish. In contrast, the surface waters from which fish samples were collected were positive for Escherichia coli, and coliform bacteria intestinal Enterococci. Based on the study's results, it is recommended to exercise caution in the case of children related to the consumption of fish and using the waters for drinking purposes. This study provides important data of considerable novelty to the riparian population, researchers, and even policy makers on the quality status and potential levels of contamination of river waters, fish and the bioaccumulation of heavy metals in fish that may cause adverse effects on human health if consumed, and similarly the heavy metal pollution degree of waters and the non-carcinogenic risk of heavy metals through ingestion and skin absorption of water in children and adults (the study area is a significant source of fisheries).

Removal of Cesium and Strontium Ions from Aqueous Solutions by Thermally Treated Natural Zeolite.

The radionuclides of cesium (Cs) and strontium (Sr) are dangerous products of nuclear fission that can be accidentally released into wastewater. In the present work, the capacity of thermally treated natural zeolite (NZ) from Macicasu (Romania) to remove Cs+ and Sr2+ ions from aqueous solutions in batch mode was investigated by contacting different zeolite quantities (0.5, 1, and 2 g) of 0.5-1.25 mm (NZ1) and 0.1-0.5 mm (NZ2) particle size fractions with 50 mL working solutions of Cs+ and Sr2+ (10, 50, and 100 mg L-1 initial concentrations) for 180 min. The concentration of Cs in the aqueous solutions was determined by inductively coupled plasma mass spectrometry (ICP-MS), whereas the Sr concentration was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The removal efficiency of Cs+ varied between 62.8 and 99.3%, whereas Sr2+ ranged between 51.3 and 94.5%, depending on the initial concentrations, the contact time, the amount, and particle size of the adsorbent material. The sorption of Cs+ and Sr2+ was analyzed using the nonlinear form of Langmuir and Freundlich isotherm models and pseudo-first-order (PFO) and pseudo-second-order (PSO) kinetic models. The results indicated that the sorption kinetics of Cs+ and Sr2+ on thermally treated natural zeolite was described by the PSO kinetic model. Chemisorption dominates the retention of both Cs+ and Sr2+ by strong coordinate bonds with an aluminosilicate zeolite skeleton.

Relevance of Soil Heavy Metal XRF Screening for Quality and Landscaping of Public Playgrounds.

Heavy metals have become widespread urban pollutants, exposing vulnerable age groups such as children to potential risk. Specialists need feasible approaches that can routinely assist them in customizing options for sustainable and safer urban playgrounds. The aim of this research was to explore the practical relevance of the X-ray Fluorescence (XRF) method from the perspective of landscaping specialists, and the practical significance of screening for those heavy metals that currently present elevated levels across urban environments Europe-wide. Soil samples from six public children's playgrounds of different typologies from Cluj-Napoca, Romania, were analyzed. The results indicated that this method was sensitive to identifying thresholds stipulated in legislation for the screened elements (V, Cr, Mn, Ni, Cu, Zn, As, and Pb). Coupled with the calculation of pollution indexes, this method can serve as a quick orientation in landscaping options for urban playgrounds. The pollution load index (PLI) for the screened metals showed that three sites displayed baseline pollution with incipient deterioration in soil quality (PLI = 1.01-1.51). The highest contribution to the PLI among the screened elements, depending on the site, was due to Zn, Pb, As, and Mn. The average levels of the detected heavy metals were within admissible limits according to national legislation. Implementable protocols addressed to different categories of specialists could help to transition towards safer playgrounds and more research on accurate cost-effective procedures to overcome the limitations of existing approaches is currently needed.

Moss biomonitoring of air pollution with heavy metals in the vicinity of a ferronickel smelter plant.

The purpose of this study was to establish the atmospheric deposition of various elements in the Kavadarci region, Republic of Macedonia (known for its ferronickel mining and metallurgical activities) using moss biomonitoring, and to determine whether the deposition is anthropogenic or from geogenic influences. The sampling network includes 31 moss samples evenly distributed over a territory of about 600 km(2). A total of 46 elements (Ag, Al, As, Au, Ba, Be, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hg, Ho, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Rb, Sb, Sm, Sr, Tb, Th, Ti, U, V, Yb, Zn, Zr) were determined by mass spectrometry with inductively coupled plasma (ICP-MS). Based on a distribution pattern of elements determined in moss, two anthropogenic geochemical associations (Co-Cr-Cu-Fe-Mg-Ni and As-Cd-Cu-Hg-Pb-Zn), were detected. The distribution of these elements shows an increased content (especially Ni, Co and Cr) in the moss samples from the surroundings of the smelter plant compared to the rest of the samples. Thus, the median value of Ni in moss samples from the whole region (40 mg kg(-1)) is much higher than the median for Macedonia (5.82 mg kg(-1)). Moreover, the median content of Ni in the moss samples from the polluted area (around the smelter) is 178 mg kg(-1) with an enrichment ratio in the moss samples of almost 5.5 times higher than the unpolluted areas (32 mg kg(-1)). This fact confirms the influence of the dust from the ferronickel plant to the air pollution in this region.

Effect of in vitro simulated gastrointestinal digestion on some nutritional characteristics of several dried fruits.

To provide new information on potential health benefits of dried fruits, the effects of in vitro digestion on minerals, total phenolics, total sugars and the antioxidant capacities were evaluated. For the first time, the bioaccessibility of these compounds during in vitro digestion was assessed by multivariate statistical analysis. Although the amount of all minerals decreased after digestion, moderate bioaccessibility was found, excepting Zn. The highest bioaccessibility of phenolics was obtained in prunes and the lowest in dates and cranberries. Total sugars content increased after in vitro digestion of dates, raisins and coconut, but decreased for cranberries, prunes and banana. The in vitro digestion led to an increase in the antioxidant capacity for the majority of dried fruits. The similarities/dis-similarities in pattern of analyzed parameters during digestion was revealed by heat map. Two-way joining cluster and principal component analysis were used to highlight the most relevant parameters in each digestion phase.

Assessment of Lithium, Macro- and Microelements in Water, Soil and Plant Samples from Karst Areas in Romania.

Lithium is a critical element for the modern society due to its uses in various industrial sectors. Despite its unequal distribution in the environment, Li occurrence in Romania was scarcely studied. In this study a versatile measurement method using ICP-MS technique was optimized for the determination of Li from various matrixes. Water, soil, and plant samples were collected from two important karst areas in the Dobrogea and Banat regions, Romania. The Li content was analyzed together with other macro- and microelement contents to find the relationship between the concentration of elements and their effect on the plants' Li uptake. In Dobrogea region, half of the studied waters had high Li concentration, ranging between 3.00 and 12.2 µg/L in the case of water and between 0.88 and 11.1 mg/kg DW in the case of plants, while the Li content in the soil samples were slightly comparable (from 9.85 to 11.3 mg/kg DW). In the Banat region, the concentration of Li was lower than in Dobrogea (1.40-1.46 µg/L in water, 6.50-9.12 mg/kg DW in soil, and 0.19-0.45 mg/kg DW in plants). Despite the high Li contents in soil, the Li was mostly unavailable for plants uptake and bioaccumulation.

Chemical modeling of groundwater in the Banat Plain, southwestern Romania, with elevated As content and co-occurring species by combining diagrams and unsupervised multivariate statistical approaches.

The study proposes a combined model based on diagrams (Gibbs, Piper, Stuyfzand Hydrogeochemical Classification System) and unsupervised statistical approaches (Cluster Analysis, Principal Component Analysis, Fuzzy Principal Component Analysis, Fuzzy Hierarchical Cross-Clustering) to describe natural enrichment of inorganic arsenic and co-occurring species in groundwater in the Banat Plain, southwestern Romania. Speciation of inorganic As (arsenite, arsenate), ion concentrations (Na+, K+, Ca2+, Mg2+, HCO3-, Cl-, F-, SO42-, PO43-, NO3-), pH, redox potential, conductivity and total dissolved substances were performed. Classical diagrams provided the hydrochemical characterization, while statistical approaches were helpful to establish (i) the mechanism of naturally occurring of As and F- species and the anthropogenic one for NO3-, SO42-, PO43- and K+ and (ii) classification of groundwater based on content of arsenic species. The HCO3- type of local groundwater and alkaline pH (8.31-8.49) were found to be responsible for the enrichment of arsenic species and occurrence of F- but by different paths. The PO43--AsO43- ion exchange, water-rock interaction (silicates hydrolysis and desorption from clay) were associated to arsenate enrichment in the oxidizing aquifer. Fuzzy Hierarchical Cross-Clustering was the strongest tool for the rapid simultaneous classification of groundwaters as a function of arsenic content and hydrogeochemical characteristics. The approach indicated the Na+-F--pH cluster as marker for groundwater with naturally elevated As and highlighted which parameters need to be monitored. A chemical conceptual model illustrating the natural and anthropogenic paths and enrichment of As and co-occurring species in the local groundwater supported by mineralogical analysis of rocks was established.

Multivariate extraction of dominant geochemical markers for deposition of 69 elements in the Bregalnica River basin, Republic of Macedonia (moss biomonitoring).

Atmospheric deposition was investigated using the terrestrial moss species Hypnum cupressiforme (Hedw.) and Homolothecium lutescens (Hedw.) in the Bregalnica River basin, Republic of Macedonia. Long-term emission occurs in this area due to the hydrothermal exploitation of Pb-Zn deposits (Sasa and Zletovo mines) and copper ore exploitation and floatation (Bucim mine). Determination of the chemical elements was conducted using atomic emission spectrometry with inductively coupled plasma (ICP-AES) and mass spectrometry with inductively coupled plasma (ICP-MS). A combination of multivariate techniques (PCA, FA and CA) was applied for data processing and identification of element association with lithogenic/anthropogenic origin. Seven dominant factors were extracted from the total of 69 analysed elements. Spatial distribution maps were constructed for the determination and localisation of smaller areas with higher contents of certain anthropogenic elements. In this way, the influences of selected human activities on local air pollution can be determined. The summarised data show quantification of the element distributions. This not only allows the determination of the distribution of hazardous elements but also presents complete characterisation of element deposition in the environs of mines.

Sediment dynamics and heavy metal pollution history of the Cruhlig Lake (Danube Delta, Romania).

This is the first study reporting recent sedimentation rates data (e.g. the past 120-150 years) for the Cruhlig Lake situated in the Danube Delta. The aim of this study is to analyse the recent sedimentation rates using the (210)Pb dating method and identifying the heavy metal pollutants and their variability in time. Five sediment cores were taken with a gravity corer and - after drying the sliced samples-physical parameters, organic material and inorganic carbon content were determined. The total (210)Pb content was measured via (210)Po by alpha spectrometry, while supported (210)Pb was measured by (226)Ra (trough short life (222)Rn daughters) with HPGe detectors. Heavy metals were determined by ICP-MS; from the 64 measured elements, only exceeding values of Al, As, Cd, Co, Cs, Cr, Cu, Fe, Hg, K, Li, Mg, Mn, Ni, Pb and Zn are discussed. After applying the CRS model, ages and sedimentation rates were calculated. The average sedimentation rate of the Cruhlig Lake is 0.21 ± 0.02 g/cm(2)y, Minimum values (0.05 ± 0.003 g/cm(2)y) are registered along the eastern shoreline of the lake before 1913, while maximum values are recorded due to the flooding in 2006 in the western side (1.34 ± 0.12 g/cm(2)y). Recent sedimentation rates divide the lake into three areas: the secluded eastern near shore part (0.63 ± 0.07 g/cm(2)y), the centre of the lake (0.92 ± 0.05 g/cm(2)y) and the dynamic western area, where most sediment transport takes place (1.13 ± 0.01 g/cm(2)y). The sedimentation pattern proves this lake to be very sensitive to fluvial discharge fluctuations. The building of the Iron Gate dams (1972 and 1985) had a negative impact on the sedimentation decreasing it with 58.74%, while after 1989 these values grew 2.25 times. The lake received a quantity of sediment rich in heavy metals in 1992 ± 3 y, which settled mostly on the eastern part. Values for Cd, Co, Cr, Hg, Pb and Zn are up to five times higher in 1980 ± 5 y in the eastern part of the lake, while Cd, Co, Cr and Ni are twice as high as the values measured for the marine substrate. Values of As show increasing of up to 150% in 2006 ± 2 y throughout the whole surface of the lake.