Chromium concentrations in seawater are less than 0.5 μg/L, but the Cr(VI) in contaminated coastal groundwater affected by Cr-bearing rocks/ores and/or human activities, coupled with the intrusion of seawater may reach values of hundreds of μg/L. A potential explanation for the stability of the harmful Cr(VI) in contaminated coastal aquifers is still unexplored. The present study is an overview of new and literature data on the composition of coastal groundwater and seawater, aiming to provide potential relationships between Cr(VI) with major components in seawater and explain the elevated Cr(VI) concentrations. It is known that the oxidation of Cr(III) to Cr(VI) and the subsequent back-reduction of Cr(VI) processes, during the transport of the mobilized Cr(VI) in various aquifers, facilitate the natural attenuation process of Cr(VI). Moreover, the presented positive trend between B and Cr(VI) and negative trend between δ53Cr values and B concentration may suggest that seawater components significantly inhibit the Cr(VI) reduction into Cr(III), and provide insights on the role of the borate, [B(OH)4]− ions, a potential buffer, on the stability of Cr(VI) in coastal groundwater. Therefore, efforts are needed toward the prevention and/or minimization of the contamination by Cr(VI) of in coastal aquifers, which are influenced by the intrusion of seawater and are threatened by changes in sea level, due to climate change. The knowledge of the contamination sources, hotspots and monitoring of water salinization processes (geochemical mapping) for every coastal country may contribute to the optimization of agricultural management strategies.
Gallium (Ga) belongs to the group of critical metals and is of noticeable research interest. Although Ga3+ is highly compatible in high-Al spinels a convincing explanation of the positive Ga3+–Al3+ correlation has not yet been proposed. In the present study, spinel-chemistry and geochemical data of high-Al and high-Cr chromitites from Greece, Bulgaria and the Kempirsai Massif (Urals) reveals a strong negative correlation (R ranges from −0.95 to −0.98) between Cr/(Cr + Al) ratio and Ga in large chromite deposits, suggesting that Ga hasn’t been affected by re-equilibration processes. In contrast, chromite occurrences of Pindos and Rhodope massifs show depletion in Ga and Al and elevated Mn, Co, Zn and Fe contents, resulting in changes (sub-solidus reactions), during the evolution of ophiolites. Application of literature experimental data shows an abrupt increase of the inversion parameter (x) of spinels at high temperature, in which the highest values correspond to low-Cr3+ samples. Therefore, key factors controlling the preference of Ga3+ in high-Al chromitites may be the composition of the parent magma, temperature, redox conditions, the disorder degree of spinels and the ability of Al3+ to occupy both octahedral and tetrahedral sites. In contrast, the competing Cr3+ can occupy only octahedral sites (due to its electronic configuration) and the Ga3+ shows a strong preference on tetrahedral sites.
Selenium (Se) is an essential micronutrient for humans and animals, but both Se excess and deficiency can cause various health risks. Since Greece is among the European countries where people have very low Se-serum, the present study is focused on the Se distribution in cultivated and non-cultivated plants and relative soil coming from the Neogene basins of Greece (Assopos-Thiva and Attica), aiming to define potential Se-source/es and factors controlling Se bio-accumulation and enrichment in food. The dry weight Se values are relatively low (0.1–0.9 mg/kg) with the highest Se contents in garlic, beet and lettuce from the Assopos basin, where the translocation percentage [(mplant/msoil) × 100] for Se, P and S is much higher compared to non-cultivated Attica basin. There is a diversity between the Se source in soil and coastal groundwater which is used for irrigation in the cultivated Assopos–Thiva basin. The soil pH and oxidizing conditions (Eh) are considered the main driving force to make Se available for plant uptake. Potential sources for Se in Greece are Fe-Cu-Zn-sulphide ores and peat deposits in northern Greece, with a Se content ranging from decades to hundreds of mg/kg. Application of the leaching testing protocol is necessary to select the most appropriate proportion of additives to improve the Se deficiencies in agricultural soil.
The present study is an integrated approach to the Pt, Pd, and Rh cycling derived from catalytic converters along highway roadsides of the Athens Basin, including their contents, the dispersed Pt- and Pd-bearing nano- and microparticles in dust and bioaccumulation in plants, aiming to assess the auto-catalyst-derived environmental impact to the large city of Athens and the potential human health risk. The determined mean values of 314 Pt, 510 Pd, and 23 Rh (all in μg/kg) in dust samples are much lower than the 2070 μg/kg Pt and 1985 μg/kg Pd contents in gully pots in the Katechaki peripheral highway and higher than the mean values of 230 Pt, 300 Pd, and 13 Rh (all in μg/kg) in the soil samples. With the exception of two samples from gully pots, from 51% to 70% of the samples (for the Pd and Pt, respectively) fall in the range from 100 to 400 μg/kg. The calculated accumulation factors showed means of 3.88 μg/kg Pd and 2.95 μg/kg Pt for plants and tree leaves, but any significant difference (t-test) is lacking, and they are much lower than those reported for roots of plants (literature data). Although the Pt, Pd, and Rh bioaccumulation factors for shoots of plants/crops are relatively low, the increasing number of cars with catalytic converters in Greece and the relatively high bioaccumulation in the food chain may highlight a potential risk for human health and ecosystems, and the need for special attention on their bioaccumulation and bioaccessibility on a global scale.
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