Characterization of the inhalable fraction (< 10 µm) of soil from highly urbanized and industrial environments: magnetic measurements, bioaccessibility, Pb isotopes and health risk assessment.

Soil in urban and industrial areas is one of the main sinks of pollutants. It is well known that there is a strong link between metal(loid)s bioaccessibility by inhalation pathway and human health. The critical size fraction is < 10 µm (inhalable fraction) since these particles can approach to the tracheobronchial region. Here, soil samples (< 10 µm) from a highly urbanized area and an industrialized city were characterized by combining magnetic measurements, bioaccessibility of metal(loids) and Pb isotope analyses. Thermomagnetic analysis indicated that the main magnetic mineral is impure magnetite. In vitro inhalation analysis showed that Cd, Mn, Pb and Zn were the elements with the highest bioaccessibility rates (%) for both settings. Anthropogenic sources that are responsible for Pb accumulation in < 10 µm fraction are traffic emissions for the highly urbanized environment, and Pb related to steel emissions and coal combustion in cement plant for the industrial setting. We did not establish differences in the Pb isotope composition between pseudo-total and bioaccessible Pb. The health risk assessment via the inhalation pathway showed limited non-carcinogenic risks for adults and children. The calculated risks based on pseudo-total and lung bioaccessible concentrations were identical for the two areas of contrasting anthropogenic pressures. Carcinogenic risks were under the threshold levels (CR < 10-4), with Ni being the dominant contributor to risk. This research contributes valuable insights into the lung bioaccessibility of metal(loids) in urban and industrial soils, incorporating advanced analytical techniques and health risk assessments for a comprehensive understanding.

Geochemistry and origin of inorganic contaminants in soil, river sediment and surface water in a heavily urbanized river basin.

Understanding the geochemistry and contamination of rivers affected by anthropogenic activities is paramount to water resources management. The Asopos river basin in central Greece is facing environmental quality deterioration threats due to industrial, urban and agricultural activities. Here, the geochemistry of river sediments and adjacent soil in terms of major and trace elements (Al, Ca, Mg, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and the geochemical composition of surface water in terms of major ions, trace elements and nutrients along the Asopos river basin were determined. In addition, this study characterized potential nitrate sources through the analysis of stable isotope composition of NO3- (δ15Ν-ΝΟ3- and δ18Ο-ΝΟ3-). Results indicated that specific chemical constituents including nutrients (NO2-, NH4+, PO43-) and major ions (Na+, Cl-) were highest in the urban, industrialized and downstream areas. On the other hand, nitrate (NO3-) concentration in river water (median 7.9 mg/L) showed a decreasing trend from the upstream agricultural sites to the urban area and even more in the downstream of the urban area sites. Ionic ratios (NO3-/Cl-) and δ15Ν-ΝΟ3- values (range from +10.2 ‰ to +15.7 ‰), complemented with a Bayesian isotope mixing model, clearly showed the influence of organic wastes from septic systems and industries operating in the urban area on river nitrate geochemistry. The interpretation of geochemical data of soil and river sediment samples demonstrated the strong influence of local geology on Cr, Fe, Mn and Ni content, with isolated samples showing elevated concentrations of Cd, Cu, Pb and Zn, mostly within the industrialized urban environment. The calculation of enrichment factors based on the national background concentrations provided limited insights into the origin of geogenic metals. Overall, this study highlighted the need for a more holistic approach to assess the impact of the geological background and anthropogenic activities on river waters and sediments.

Enhanced Gastric/Lung Arsenic Bioaccessibility from Lignite Fly Ashes: Comparing Bioaccessibility Rates with Multiple Environmental Matrices.

Inorganic arsenic (As), a carcinogenic element to humans, is among the most dangerous and flammable substances that coal-burning plants could release. When coal is burned, large portions of arsenic are captured on fly-ash (FA) particles, but it could also contribute significantly to stack emissions of fine fly-ash particles. The aim of this study was to evaluate the oral and respiratory bioaccessibility of arsenic in lignite fly-ash (LFA) samples, and their contribution to total As exposure. Arsenic bioaccessibility fractions via ingestion and inhalation showed significant differences, suggesting the presence of highly soluble As-bearing phases in the studied LFA samples. The bioaccessible As fractions (BAF%) in the simulated gastric fluids (UBM protocol, ISO 17924:2018) showed a range of 45-73%, while the pulmonary bioaccessibility rates in the simulated lung fluid (artificial lung fluid (ALF)) exhibited significantly enhanced levels ranging from 86% to 95%. The obtained arsenic bioaccessibility rates were compared with previous data for multiple environmental matrices such as soil and dust-related materials, revealing that LFA exhibited significantly higher bioaccessibility (%) for the inhalation pathway.

Assessment of natural and anthropogenic contamination sources in a Mediterranean aquifer by combining hydrochemical and stable isotope techniques.

The Atalanti basin is an intensively cultivated area in central Greece, facing groundwater quality deterioration threats due to natural and anthropogenic-related contamination sources. A combination of statistical and hydrogeochemical techniques, and stable isotope compositions (δ2H-H2O and δ18Ο-Η2Ο, δ15Ν-ΝΟ3- and δ18Ο-ΝΟ3-, δ34S-SO42- and δ18O-SO42-) were applied to elucidate the origin of salinity and nitrate contamination, and shed light on the potential associations between geogenic Cr(VI) and NO3- sources and transformations. Nitrate and Cr(VI) concentrations reached up to 337 mg L-1 and 76.1 µg L-1, respectively, exceeding WHO threshold values in places. The cluster of samples with the high salinity was mostly influenced by irrigation return flow and marine aerosols, and less by seawater intrusion, as evidenced by the ionic ratios (e.g., Na+/Cl-) and the stable isotopes of oxygen and hydrogen in water, and sulphur and oxygen in sulphates. The δ15Ν-ΝΟ3- and δ18O-NO3- values ranged from +2.0 ‰ to +14.5 ‰ and + 0.3 ‰ to +11.0 ‰, respectively. We found that the dominant sources of NO3- in groundwater were fertilizers in the central part of the area and sewage waste in the northern part around the residential area of Livanates. The occurrence of denitrification was evident in the northern part of the basin, where the DO levels were lowest (≤ 2.2 mg L-1), whereas nitrification of NH4+-fertilizers prevailed in the central part. Elevated Cr(VI) values (≥ 20 µg/l) were associated with the lowest deviation of the measured from the theoretical nitrification δ18Ο-NO3- values, whereas the lowest Cr(VI) values were observed in the denitrified water samples. Our isotope findings revealed the strong influence of redox conditions on the biogeochemical transformations of N species and the mobilization of Cr(VI) that will help improve the understanding of the fate of these contaminants from the unsaturated zone to the groundwater in areas of agricultural and urban land use.

Estimating remobilization of potentially toxic elements in soil and road dust of an industrialized urban environment.

The mobility of potentially toxic elements (PTEs) is of paramount concern in urban settings, particularly those affected by industrial activities. Here, contaminated soils and road dusts of the medium-size, industrialized city of Volos, Central Greece, were subjected to single-step extractions (0.43 M HNO3 and 0.5 M HCl) and the modified BCR sequential extraction procedure. This approach will allow for a better understanding of the geochemical phase partitioning of PTEs and associated risks in urban environmental matrices. Based on single extraction procedures, Pb and Zn exhibited the highest remobilization potential. Of the non-residual phases, the reducible was the most important for Pb, and the oxidizable for Cu and Zn in both media. On the other hand, mobility of Ni, Cr, and Fe was low, as inferred by their dominance into the residual fraction. Interestingly, we found a significant increase of the residual fraction in the road dust samples compared to soils. Carbonate content and organic matter controlled the extractabilities of PTEs in the soil samples. By contrast, for the road dust, magnetic susceptibility exerted the main control on the geochemical partitioning of PTEs. We suggest that anthropogenic particles emitted by heavy industries reside in the residual fraction of the SEP, raising concerns about the assessment of this fraction in terms of origin of PTEs and potential environmental risks. Conclusively, the application of sequential extraction procedures should be complemented with source identification of PTEs with the aim to better estimate the remobilization of PHEs in soil and road dust influenced by industrial emissions.

Identification of sources and transformations of nitrate in Cr(VI)-impacted alluvial aquifers by a hydrogeochemical and δ15N-NO3- and δ18O-NO3 - isotopes approach.

A coupled methodology of nitrogen isotopes, hydrogeochemical characterization, multivariate statistical analysis, and SIAR Bayesian modeling has been employed to identify the sources of NO3- and N transformation processes in three alluvial aquifers (Schinos, Thiva, and Central Evia) located in central Greece where geogenic Cr(VI) co-occurs with agricultural activity and rural development. Hexavalent chromium concentrations exceed 50 µg/L in many sampling stations of the studied groundwater bodies, while nitrate contamination is evident in all three study areas with concentrations well over 50 mg/L. The mean δ15N-NO3- and δ18Ο-NO3- values are 6.67 ± 1.77‰ and 2.68 ± 1.77‰ in C. Evia, 8.72 ± 4.74‰ and 3.96 ± 4.57‰ in Schinos and 4.44 ± 1.71‰ and 2.91 ± 1.02‰ in Thiva, respectively. Domestic sewage and N-bearing fertilizers are contributing in various degrees to the observed nitrification which is the dominant transformation process of N in the studied aquifers. Multivariate statistics indicated that the main processes identified in the study areas are salinization, silicate dissolution, and groundwater contamination due to fertilizer use. It is suggested that ultramafic rock-related alluvial aquifers must be closely monitored in terms of nutrient inputs as an effective measure for controlling Cr(VI) release in groundwater.

Tracing the sources of bioaccessible metal(loid)s in urban environments: A multidisciplinary approach.

Understanding the links between sources of magnetic particles and bioaccessibility of metal(loids) in environmental sampling media is crucial for better evaluating human health risks, although relevant information in the scientific literature is scarce. Here, soil, road and house dust samples from a heavy industrial area in Greece were characterized in a multidisciplinary study combining magnetic measurements, SEM/EDS analyses, bioaccessibility measurements and Pb isotopic analyses of bioaccessible Pb. The oral and inhalable bioaccessible fractions of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were assessed by applying simulated gastric and lung solutions. SEM/EDS analysis revealed the abundant presence of anthropogenic Fe-containing spherules of industrial origin in all sampling media, often containing minor contents of Cr, Cu, Mn, Pb and Zn. The inhalation bioaccessibility (%) in all environmental compartments was higher than the oral one for most elements analyzed in the present study. Clear associations between magnetic susceptibility and bioaccessible amounts of most of analyzed elements were encountered for the soil and road dust. The isotopic analyses of bioaccessible Pb showed that there are significant differences in the isotopic ratios between total and bioaccessible Pb. We conclude that Pb solubilized by the simulated gastric and lung extractions is principally anthropogenic, representing a mixture of industrial Pb and Pb related to the past usage of leaded petrol. Low values of 206Pb/207Pb were accompanied by high bioaccessible contents of Cd, Pb and Zn indicating that anthropogenic (mostly industrial) sources exert influence on the bioaccessible forms of these metals. Coupling magnetic and bioaccessibility measurements with stable isotopic technique of bioaccessible Pb is more reliable for determining Pb and other metal sources with high oral and inhalation bioaccessibility.

A DPSIR Approach to Selected Cr(VI) Impacted Groundwater Bodies of Central Greece.

The holistic approach of Driver-Pressure-State-Impact-Response (DPSIR) methodology was applied to selected Cr(VI) impacted groundwater bodies of Central Greece. The main driving forces in the study areas are agricultural activities, urban and industrial development as well as tourism. The main pressures induced by the anthropogenic activities are fertilizer use, uncontrolled urban sewage disposal and industrial effluents discharges. Groundwater stress is caused by the qualitative degradation due to Cr(VI), NO3-, Cl- and SO42- contamination. Hexavalent chromium occurrence is attributed to both geogenic and anthropogenic sources. The maximum Cr(VI) concentration (11.7 mg/L) was measured in Oinofyta area. Important impacts are the deterioration of groundwater body chemical status as well as the decline of groundwater use efficiency. Based on the applied DPSIR, a management framework is proposed in order to address the complex environmental issue of Cr(VI) in the study areas.

Metal(loid) and isotopic tracing of Pb in soils, road and house dusts from the industrial area of Volos (central Greece).

This study examines the metal(loid) contents (As, Cd, Cr, Cu, Mn, Ni, Pb, Sb, Tl and Zn) and Pb isotopes in different environmental compartments (soil, road dust, house dust) from the industrial vicinity of Volos, central Greece. The area surrounding two steel factories, a cement plant, an industrial area and the city core were considered as potential hot spots of metal(loid) contamination. Significant anthropogenic enrichments of Cd, Pb and Zn in relation to local baseline were identified for the soil (median Enrichment Factors of 7, 15 and 8, respectively) and road dusts around the steel factory located at Velestino area. The high contents of As, Sb and Tl in the soil and road dust around the cement plant are attributed to natural sources of contamination associated with adjacent mineralization. The soil samples in the city core exhibited moderate enrichments with respect to typical tracers (Pb, Zn) of anthropogenic contamination in urban areas. Anthropogenic influences in terms of metal(loid) concentrations were more pronounced for the road and house dust material. The Pb isotopic ratios of soil (206Pb/207Pb = 1.154 to 1.194), road dust (206Pb/207Pb = 1.144 to 1.174) and house dust (206Pb/207Pb = 1.129 to 1.171) were between those of the local bedrock and anthropogenic Pb sources. Industrial Pb from the steel plant was the predominant anthropogenic Pb source with relative contributions of ~49% for the soil, ~42% for the road dust and ~44% for the house dust samples. For the road and house dust material, the geochemical signature obtained from Pb isotopic compositions and elemental ratios suggests additional contributors from vehicular emissions. The results of this study demonstrate the suitability of soil to trace natural and anthropogenic impacts in industrial areas and the sensitivity of the road and house dust material to record anthropogenic (industrial and vehicular-derived) contamination in such environments.

Tracking the occurrence of anthropogenic magnetic particles and potentially toxic elements (PTEs) in house dust using magnetic and geochemical analyses.

The influence of anthropogenic outdoor sources on the geochemical composition of house dust material in large cities is poorly understood. In this study, we investigate the magnetic signature and the concentrations of potentially toxic elements (PTEs) in randomly selected house dust samples from the metropolitan area of Athens, the most populated city in Greece. Environmental magnetic measurements, including isothermal remanent magnetization and thermomagnetism, indicated that the main magnetic mineral is coarse-grained low-coercivity magnetite. Detailed microscopic observations of the magnetically extracted material revealed the presence of three different kinds of Fe-rich particles deriving from both combustion-related and non-exhaust vehicular sources: irregularly-shaped grains and spherules of Fe-oxides, and particles consisting of metallic Fe. Further study of the morphology of single anthropogenic magnetic spherules (size > 30 µm) identified the presence of magnetite spherical particles, typically formed by industrial combustion processes. Enrichment factors (EFs) for the PTEs calculated against the Athens urban soil showed that the house dusts were very highly enriched in Cd, Cu, Zn and significantly enriched in Pb (median EF values of 34.1, 26.2, 25.4 and 10.3, respectively). The oral bioaccessibility of PTEs in the house dust, evaluated using a simulated gastric solution (0.4 M glycine), was in the order Pb > Zn > Mn > Cd > Ni > Cu > Cr > Fe. Concentrations of Pb increased with the house age. Principal component and cluster analysis demonstrated the close association of anthropogenic Cu, Pb and Zn with the magnetic susceptibility of the house dusts. We conclude that both traffic-related and industrial sources trigger the occurrence of magnetic Fe/PTEs- rich particles in house dust. These results reinforce the use of environmental magnetism determinations for assessing anthropogenic contamination of PTEs in the indoor environment in large cities.

Insights into the chemical partitioning of trace metals in roadside and off-road agricultural soils along two major highways in Attica's region, Greece.

We report in this study the magnetic properties and partitioning patterns of selected trace metals (Pb, Zn, Cu, Cd, Ni) in roadside and off-road (>200m distance from the road edge) agricultural soils collected along two major highways in Greece. Sequential extractions revealed that the examined trace metals for the entire data set were predominantly found in the residual fraction, averaging 37% for Cd up to 80% for Cu. Due to the strong influence of lithogenic factors, trace metal pseudototal contents of the roadside soils did not differ significantly to those of the off-road soils. Magnetic susceptibility and frequency dependent magnetic susceptibility determinations showed a magnetic enhancement of soils; however, it was primarily related to geogenic factors and not to traffic-derived magnetic particles. These results highlight that in areas characterized by strong geogenic backgrounds, neither pseudototal trace metal contents nor magnetic properties determinations effectively capture traffic-related contamination of topsoils. The vehicular emission signal was traced by the increased acid-soluble and reducible trace metal contents of the roadside soils compared to their off-road counterparts. In the case of Cu and Zn, changes in the partitioning patterns were also observed between the roadside and off-road soils. Environmental risks associated with agricultural lands extending at the margins of the studied highways may arise from the elevated Ni contents (both pseudototal and potentially mobile), and future studies should investigate Ni levels in the edible parts of plants grown on these agricultural soils.

Metal(loid) distribution and Pb isotopic signatures in the urban environment of Athens, Greece.

Lead concentrations and isotopic compositions of contaminated urban soils and house dusts from Athens, Greece, have been determined to identify possible sources of Pb contamination and examine relationships between these two environmental media. Different soil particle sizes (<2000 µm, <200 µm, <100 µm, <70 µm, <32 µm) and chemical fractions (total, EDTA-extractable and acetic acid-extractable (HAc)) were analyzed for their Pb content and isotopic composition. Metal(loid)s (Pb, Zn, Cu, As, Ni, Cr, Mn, Fe) are significantly enriched in the finest fraction. The Pb isotopic compositions were similar for the different soil particle size fractions and different chemical extractions. The HAc extraction proved to be a useful procedure for tracing anthropogenic Pb in urban soil. The range of (206)Pb/(207)Pb ratios (1.140-1.180) in Athens soil suggests that the Pb content represents an accumulated mixture of Pb deposited from past vehicular emissions and local natural sources. The contribution of anthropogenic Pb to total soil Pb ranged from 36% to 95%. The Pb isotopic composition of vacuum house dusts ((206)Pb/(207)Pb = 1.1.38-1.167) from Athens residents is mostly comparable to that of urban soil suggesting that exterior soil particles are transferred into homes. As a result, anthropogenic Pb in house dust from Athens urban environment principally originated from soil particles containing Pb from automobile emissions (former use of leaded gasoline).

Urban soil geochemistry in Athens, Greece: The importance of local geology in controlling the distribution of potentially harmful trace elements.

Understanding urban soil geochemistry is a challenging task because of the complicated layering of the urban landscape and the profound impact of large cities on the chemical dispersion of harmful trace elements. A systematic geochemical soil survey was performed across Greater Athens and Piraeus, Greece. Surface soil samples (0-10cm) were collected from 238 sampling sites on a regular 1×1km grid and were digested by a HNO3-HCl-HClO4-HF mixture. A combination of multivariate statistics and Geographical Information System approaches was applied for discriminating natural from anthropogenic sources using 4 major elements, 9 trace metals, and 2 metalloids. Based on these analyses the lack of heavy industry in Athens was demonstrated by the influence of geology on the local soil chemistry with this accounting for 49% of the variability in the major elements, as well as Cr, Ni, Co, and possibly As (median values of 102, 141, 16 and 24mg kg(-1) respectively). The contribution to soil chemistry of classical urban contaminants including Pb, Cu, Zn, Sn, Sb, and Cd (medians of 45, 39, 98, 3.6, 1.7 and 0.3mg kg(-1) respectively) was also observed; significant correlations were identified between concentrations and urbanization indicators, including vehicular traffic, urban land use, population density, and timing of urbanization. Analysis of soil heterogeneity and spatial variability of soil composition in the Greater Athens and Piraeus area provided a representation of the extent of anthropogenic modifications on natural element loadings. The concentrations of Ni, Cr, and As were relatively high compared to those in other cities around the world, and further investigation should characterize and evaluate their geochemical reactivity.

Investigating the sources and potential health risks of environmental contaminants in the soils and drinking waters from the rural clusters in Thiva area (Greece).

The present study investigates the possible influence of human activities on metal loadings of topsoil in a typical small rural city in central Greece and the chemical quality of tap water in surrounding villages. Furthermore, the study aimed to examine potential health risks of naturally enriched heavy metals to exposed population taking into account the soil and drinking water as exposure pathways. The mean concentrations of Ni, Cr, Co, Mn, Pb, Cu, Zn and Cd in the soil were 1777, 285, 99, 946, 30, 26, 78 and 0.67 mg/kg respectively. Combination of pollution indexes based on local reference background soils and statistical analyses (correlation analysis, cluster analysis and principal component analysis) revealed that anthropogenic activities have not modified the natural soil chemistry at least in a large scale. High Hazard Quotient (HQ) values for children were estimated for Ni, Cr and Co based on total metal concentrations for the soil ingestion route (9.26E-01, 9.75E-01 and 3.45E+00 respectively). However, evaluation of HQs based on published bioaccessible concentrations suggested that the population groups would not likely experience potential health risks as a result of exposure to contaminated soils. Concentrations of Cr(VI) in tap waters were within the allowable limits. However, the risk assessment model revealed that local residents (adults) of Eleonas and Neochori villages are at some carcinogenic risks considering lifetime ingestion of water (potential cancer risks 2.05E-04 and 1.29E-04 respectively). Despite the uncertainties accompanying these procedures and the great deal of debate regarding the human carcinogenicity of Cr(VI) by the oral route, results of this study drive attention to remediation measures that should include epidemiological studies for the local population.

Evaluation of the sources of contamination in the suburban area of Koropi-Markopoulo, Athens, Greece.

Heavy metal concentrations were monitored in agricultural soils and irrigation groundwaters of Koropi-Markopoulo area, a representative agricultural suburb in Athens, Greece, aiming at the identification of the sources of contaminants. Multivariate analyses of geochemical data demonstrated that agricultural practices and industrial activities considerably affected the quality of both environmental compartments. The levels of Ni, Cr, Co, Mn and Fe in agricultural soils were associated with geological parent materials whereas Pb, Zn and Cu mainly originated from anthropic activities. Referring to groundwaters, individual major anions and cations (K⁺, Na⁺, Ca²âº, Mg²âº, NO3⁻, SO4²â», Cl⁻) were influenced by various natural and anthropogenic factors whereas Ni, Cr, Cu and Zn were controlled by industrial and agronomic activities. The identification of the sources of contaminants in soil and groundwater environments is a valuable basis for encouraging mitigation strategies preventing further quality degradation.

Availability of geogenic heavy metals in soils of Thiva town (central Greece).

Potentially toxic metals in the urban chemical environment impose risks to both ecosystem and human health. Here, we evaluate the labile pools and availabilities of non-anthropogenic Ni, Cr, Co and Mn in soil samples from Thiva town (central Greece) and investigate their associations with common soil properties and geochemical data obtained by the aqua regia and single selective dissolutions. Experimental work included the initial application of the sequential extraction protocol proposed by the European Community Bureau of Reference and chemical extractions with ethylenediamine tetraacetic acid solution and a modified physiologically based extraction test with the aim to obtain the operationally defined fractions of plant availability and human bioaccessibility, respectively. The leachate results demonstrated that despite the significant contribution of residual metal species especially for Ni and Cr, the studied serpentine soils provide chemically labile pools for all the considered elements. Nickel was found to be the most available metal with the order being Ni > Cr ∼ Co ∼ Mn for plant uptake and Ni > Cr > Co ∼ Mn for human bioaccessibility. The aqua regia extractable concentrations are not predictors of elemental availabilities except for Ni bioaccessible data interpreting however only a moderate percentage of the total variance. The incorporation of basic soil properties (mostly total organic carbon), geochemical data for the major elements Ca, Mg and Fe and ammonium oxalate extractable Cr significantly improved the estimations for individual elements entailing the strong influence of the chemistry and mineralogy of soil materials to the release of focus metals from the soil matrix. This study provides for the first time bioaccessible data for serpentine-derived soils that are more realistic for evaluating potential adverse effects on the human health.

Hexavalent chromium contamination in groundwaters of Thiva Basin, central Greece.

There is an increasing concern regarding elevated levels of Cr(VI) in the environment due to its higher mobility and toxicity compared to the trivalent form. Anomalous hexavalent chromium concentrations (up to 212 µg/L) were determined in irrigated groundwaters from the wider area of Thiva Basin (central Greece), frequently exceeding the permissible limit for human consumption (50 µg/L for total Cr). Based on the spatial distribution of Cr(VI) values, two groups of groundwater samples were distinguished, possibly reflecting different natural and/or anthropogenic factors that govern the levels of contamination. The first group is spatially located northwards of Thiva town and is consisted of concentrations that range from 13 to 212 µg/L (median 58 µg/L), while the second group is located near Mouriki village and Cr(VI) values range from <9 to 14 µg/L. The Cr(VI) chemical anomalies represent an important social problem because the agricultural products of this region are a major vegetable supply for Greece, bringing up the urgent need to evaluate the health effects associated with Cr(VI) exposure by ingesting the potentially contaminated foods.

Distribution and accumulation of metals in tadpoles inhabiting the metalliferous streams of eastern Chalkidiki, northeast Greece.

The present study investigates the accumulation of heavy metals [copper (Cu), lead (Pb), zinc (Zn), magnesium (Mn), cadmium (Cd), nickel (Ni), and chromium (Cr)] in tadpoles inhabiting the metalliferous streams flowing within the Asprolakkas River basin (northeast Chalkidiki peninsula, Greece) and the effect of potentially harmful elements in stream water and sediment on the corresponding levels in their tissue. Animals were collected from six sampling sites influenced by a wide range of surface water and stream sediment trace element concentrations. The results of the chemical analyses showed that tadpoles accumulated significant levels of all of the examined metals. The range of whole-body mean measured concentrations were (in dry mass) as follows: Cu (46-182 mg/kg), Pb (103-4,490 mg/kg), Zn (494-11,460 mg/kg), Mn (1,620-13,310 mg/kg), Cd (1.2-82 mg/kg), Ni (57-163 mg/kg), and Cr (38-272 mg/kg). The mean concentrations of Pb, Zn, Mn, Ni, Cr, and Cd in Kokkinolakkas stream, which drains a currently active mining area, were the highest ever reported in tadpoles. Our results indicate that whole-body levels of Pb, Zn, Cu, and Cd increase with stream sediment concentrations and that these organisms tend to accumulate metals bound to Fe and Mn oxides. In addition, high dissolved concentrations and significant concentrations associated with more labile geochemical phases of sediments for specific metals were contributing factors determining whole-body levels. Given the observed bioconcentration factors, as well as the correlation with sediment concentrations, it is proposed that these organisms could be considered as bioindicators of environmental contamination and may be used for monitoring purposes within this metal-rich zone and, perhaps, within other rivers affected by metal mining.