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.

Trace element contamination status of surface marine sediments of Greece: an assessment based on two decades (2001-2021) of data.

This study is a first attempt to assess the trace element contamination status in the surface sediments of the Hellenic Seas since the first environmental studies in the country commenced in the mid-1970s. All available trace element data from the last 20 years have been collected and assessed using sediment quality guidelines and application of single- and multielement pollution indices. Although Hellenic marine sediments initially appear as anthropogenically enriched in Cr and As, this enrichment is attributed to the natural background. Central Greece appears more polluted, followed by Northern Greece and lastly Southern Greece. The element pollution indices featured the influence of industrial activities such as mining, steel industry and chemical factories, shipyards, and secondarily the influence of port activities.

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.

Chromium speciation, mobility, and Cr(VI) retention-release processes in ultramafic rocks and Fe-Ni lateritic deposits of Greece.

Water contamination by geogenic hexavalent chromium is an emerging issue in areas developed on ultramafic rocks and their weathering products. In this study, samples of serpentinites, soil, and laterites were collected and analyzed for the levels of Cr species, distribution into phases of different mobility, mineralogy, Cr oxidation capacity, and leaching of Cr(VI). Total chromium (2176-21,929 mg kg-1) was mainly found in Cr spinels (~ 50% wt as Cr2O3) and Fe (hydr)oxides (2.5% wt). Total Cr(VI) contents (0.49-11.5 mg kg-1) increased from the serpentinites to the soil and lateritic deposit, i.e., during the advanced stages of weathering, which were accompanied by increased Cr mobility. Batch experiments of 500-h duration showed that Cr(VI) released in water at rates of 0.25-1.20 nM h-1. Rates were higher in water of pH 5.7 rather than pH 8.5, because more Cr(VI) was formed during the experimental period. Asbolane-type Mn oxides and Mn-bearing crystalline Fe oxides were responsible for Cr(III) oxidation. Most of the generated Cr(VI) (52-79% of total Cr(VI)) remained solid-bound by adsorption and/or precipitation processes. Because all samples had a self-capacity to oxidize Cr(III), it seems that retention processes will ultimately define the extent of geogenic Cr(VI) contamination of aquatic systems.

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.

Dataset on the major and trace elements contents and contamination in the sediments of Saronikos Gulf and Elefsis Bay, Greece.

Coastal marine sediments receive intensive stress from urbanization and industrialization, which is manifested by increased contents of heavy metals and organic pollutants. Saronikos Gulf and the small embayment of Elefsis, stretch along the coast of the greater Athens and Pireaus port, the most urbanized and industrialized areas in Greece. Here we present the data of a 20-year geochemical record on grain-size, organic carbon, and major and trace elements contents of the Saronikos Gulf sediments. A total of 216 sediment samples were collected within the period of 1999-2018 from the four sub-sectors of the gulf, namely, the Elefsis Bay, the Inner, Outer, and Western (Megara and Epidavros basin) Saronikos Gulf. Additionally, at least one core was obtained from each sub-sector. Sediments deposited at pre-industrial periods were recognized by 14C and 210Pb dating, and served for establishing regionalized background levels of metals. Factor analysis was conducted to reveal the inter-parametric relationships, thus their common sources, as well as transport and deposition pathways. Then, Enrichment Factors and the multi-elemental Modified Pollution Index (MPI) were calculated to assess the current environmental status of the sediments. Data of sampling sites with at least a five-year record, were assessed for temporal trends, to explore whether sustained, increasing or decreasing trends of the MPI are observed. The dataset and analyses presented here support the research article entitled Geochemistry of major and trace elements in surface sediments of the Saronikos Gulf (Greece): assessment of contamination between 1999 and 2018 [1].

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.