Rare earths release from dissolving atmospheric dust and their accumulation into crystallising halite: The Dead Sea example.

The industrial extraction of Y and lanthanides (hereafter defined as Rare Earth Elements, REE) often requires the achievement of leaching procedures removing these metals from primary rocks and their transfer in aqueous leachates or incorporated in newly forming soluble solids. These procedures are the most dangerous to the environment in relation to the composition of leachates. Hence, the recognition of natural settings where these processes currently occur, represents a worthy challenge for learning how to carry out similar industrial procedures under natural and more eco-friendly conditions. Accordingly, the REE distribution was studied in the brine of Dead Sea, a terminal evaporating basin where brines dissolve atmospheric fallout particles and crystallise halite. Our results indicate that the shale-like fractionation of shale-normalised REE patterns in brines, inherited during the dissolution of atmospheric fallout, changes because of the halite crystallisation. This process leads to crystallising halite mainly enriched in elements from Sm to Ho (medium REE, MREE) and coexisting mother brines enriched in La and some other light REE (LREE). We suggest that the dissolution of atmospheric dust in brines corresponds to the REE extraction from primary silicate rocks, whereas halite crystallisation represents the REE transfer into a secondary more soluble deposit with reduced environmental health outcomes.

Trace element fractionation through halite crystallisation: Geochemical mechanisms and environmental implications.

Halite is an important mineral for industry, agriculture and food production. It crystallises during water evaporation, and the progressive increase of dissolved metal ions in the brine occurs simultaneously. Thus, halite exploitation may deliver metal ions into the environment and the mechanism of this trace element accumulation has to be studied. In this work, we investigate the distribution of lanthanides and Y (hereafter called rare earth elements, REE), Zr and Hf between crystallising halite and brines in the Dead Sea as geochemical tools for recognising the mechanism of metal ion removal from brines and accumulation in halite. Halite forms cubic crystals where octahedral planes sometimes occur under particular thermal gradient conditions. Our findings indicate that crystal morphology influences the mechanism of metal ion removal from brines because octahedral surfaces are polar unlike those that are cubic. Accordingly, octahedra preferentially fractionate aqueous charged species such as [Hf(OH)5]-, compared to neutral species such as [Zr(OH)4]0. Cubic surfaces do not fractionate aqueous species. In crystal cores, positive Eu anomalies occur suggesting Eu substitution for Na in the lattice. This substitution is energetically justified by ab initio calculations. Hf enrichment relative to Zr also occurs in primary halite-rich evaporites. It is not found in cubic halite from saltworks. The results of this study suggest that primary halite kinetically crystallised from brines can concentrate dissolved metal ions onto crystal surfaces where dissolved charged species are adsorbed. Accordingly, the dissolution of halite due to human activity can release these metal ions to the environment.

Zr, Hf and REE distribution in river water under different ionic strength conditions.

The Platani River flowing in south-central Sicily, interacting with evaporite rocks, generates a wide range of ionic strength in the water catchment from 0.1 to 5.0molkg-1. We sampled 38 river sites and analysed the composition for the dissolved fraction filtered through 0.45µm, the truly dissolved fraction obtained through ultrafiltration (10kDa) and the relative included colloidal fraction. This study was focused on the recognition of Zr, Hf and REE behaviour under changing ionic strength conditions, since this is one of parameters responsible for colloid stability in natural waters. In turn, this phenomenon leads to REE release from the colloidal fraction and their scavenging onto surfaces of suspended particles or sediment, or their complexation with dissolved ligands. Our results indicated that in both dissolved and ultra-filtrated fractions REE increases either in the middle (Sm - Dy) or in the heavier (Ho - Lu) part of the PAAS-normalised distribution, while the Zr/Hf ratio value ranges from sub-chondritic to super-chondritic. Scanning Electron Microscopic and Energy Dispersive X-ray Spectrometric (SEM-EDS) analyses and dissolved Mg, Al and Fe concentrations suggested that the studied colloids consist of aggregations of Al-oxyhydroxides, carbonate nanoparticles and clays where organic traces were not found. The studied colloids showed greater affinity with dissolved Zr than Hf determining Zr/Hf values larger than the chondritic values. The largest Zr/Hf values were found in colloidal fractions from waters with ionic strength larger than 0.6molkg-1. These Zr/Hf values up to 280 (w/w) are provided by the faster removal of Hf relative to Zr from coagulating colloids and its preferential scavenging onto authigenic Fe-oxyhydroxides in bottom sediment. Further studies are needed to clarify is this suggested process can represent a suitable starting point for the Zr-Hf decoupling observed in seawater.

Rare earths and trace elements contents in leaves: A new indicator of the composition of atmospheric dust.

The relationship between the trace element distribution in atmospheric particles and leaves of some exposed plants in the environment was recently demonstrated. This indication would suggest that the trace element analysis of leaves in these plants could provide information about the composition, nature and origin of the atmospheric dust dispersed in the environment. In order to corroborate this hypothesis, the distribution of trace elements and Rare Earths were studied in leaves of some endemic plants, in the atmospheric fallout and in soils of rural, urban and industrial ecosystems in Sicily. These elements have been chosen to discriminate the source and nature of different source on atmospheric dust and the larger capability of the composition of the latter materials to influence the metal ion distribution in leaves of studied plants rather than the soil composition. These evidences are related to the recognition both of positive La anomaly and trace element enrichments in studied leaves and to their particular V/Th and Co/Ni signature. On the other hand, some particular normalised REE features recognised in leaves suggest that a limited contribution to the REE budget in studied leaves is provided by the REE migration from roots.

Geochemical behaviour of rare earths in Vitis vinifera grafted onto different rootstocks and growing on several soils.

The geochemical behaviour of lanthanides and yttrium (Rare Earth Elements, REEs) has been investigated mainly in geological systems where these elements represent the best proxies of processes involving the occurrence of an interface between different media. This behaviour is assessed according to features recorded in sequences of REE concentrations along the REE series normalised with respect to a reference material. In this study, the geochemical behaviour of REE was investigated in different parts of Vitis vinifera specimens grown off-soil, on soils of different nature and grafted onto several rootstocks in order to evaluate effects induced by these changes. The results indicated that roots are the plant organs where REEs are preferentially concentrated, in particular elements from Sm to Ho (middle REE, MREE) whereas Eu enrichments occur in aerial parts. The geochemical behaviour of REE suggests that MREE enrichments in roots are due to preferential MREE interactions with biological membranes or to surface complexation with newly formed phosphates. Eu-positive anomalies suggest that Eu(3+) can form stable organic complexes in place of Ca(2+) in several biological processes in xylem fluids. The possibility that Eu mobility in these fluids can be enhanced by its reductive speciation as Eu(2+) cannot be ruled out. The assessment of the geochemical behaviour of REE according to the theory of the Tetrad Effect carried out confirms that REEs coming from soil are scavenged onto root tissues or mineral surfaces whereas their behaviour in aerial parts of V. vinifera is driven by dissolved complexation.

Relationship between lanthanide contents in aquatic turtles and environmental exposures.

Trace elements released in the environment during agricultural practices can be incorporated and accumulated in biological fluids and tissues of living organisms. The assessment of these exposures were carried out investigating lanthanide distributions in blood and exoskeleton samples collected from Emys trinacris turtle specimens coming from sites with anthropogenic discharge in western and south Sicily, along migration paths of many bird species from Africa to Europe. The data show a significant (Rxy=0.72; Rxy>0.67; α=0.025) linear relationship between the size of turtle specimens and the lanthanide contents in blood lower than 0.4 µg L(-1) whereas this relationship disappears in blood with higher lanthanide contents. Comparative evaluations of normalised concentrations show that lanthanides fractionate between blood and exoskeleton inducing antithetical lanthanide patterns therein. These features are more evident in specimens with high lanthanide contents in blood, suggesting that lanthanide accumulations in the exoskeleton can represent the physiological response of E. trinacris to environmental and the further confirmation of relationship occurring between the environmental and the biological fluids.

Yttrium and lanthanides in human lung fluids, probing the exposure to atmospheric fallout.

Inhalation of airborne particles can produce crystallization of phosphatic microcrysts in intraaveolar areas of lungs, sometimes degenerating into pulmonary fibrosis. Results of this study indicate that these pathologies are induced by interactions between lung fluids and inhaled atmospheric dust in people exposed to volcanic dust ejected from Mount Etna in 2001. Here, the lung solid-liquid interaction is evaluated by the distribution of yttrium and lanthanides (YLn) in fluid bronchoalveolar lavages on selected individuals according the classical geochemical approaches. We found that shale-normalised patterns of yttrium and lanthanides have a 'V shaped' feature corresponding to the depletion of elements from Nd to Tb when compared to the variable enrichments of heavy lanthanides, Y, La and Ce. These features and concurrent thermodynamic simulations suggest that phosphate precipitation can occur in lungs due to interactions between volcanic particles and fluids. We propose that patterns of yttrium and lanthanides can represent a viable explanation of some pathology observed in patients after prolonged exposure to atmospheric fallout and are suitable to become a diagnostic parameter of chemical environmental stresses.

Distribution of rare earth elements in marine sediments from the Strait of Sicily (western Mediterranean Sea): evidence of phosphogypsum waste contamination.

Concentrations of rare earth elements (REE), Y, Th and Sc were recently determined in marine sediments collected using a box corer along two onshore-offshore transects located in the Strait of Sicily (Mediterranean Sea). The REE+Y were enriched in offshore fine-grained sediments where clay minerals are abundant, whereas the REE+Y contents were lower in onshore coarse-grained sediments with high carbonate fractions. Considering this distribution trend, the onshore sediments in front of the southwestern Sicilian coast represent an anomaly with high REE+Y concentrations (mean value 163.4 µg g(-1)) associated to high Th concentrations (mean value 7.9 µg g(-1)). Plot of shale-normalized REE+Y data of these coastal sediments showed Middle REE enrichments relative to Light REE and Heavy REE, manifested by a convexity around Sm-Gd-Eu elements. These anomalies in the fractionation patterns of the coastal sediments were attributed to phosphogypsum-contaminated effluents from an industrial plant, located in the southern Sicilian coast.

Heavy metals in coastal water systems. A case study from the northwestern Gulf of Thailand.

A geochemical survey of the northwestern part of the Thailand Gulf (Inner Gulf) was carried out in order to define concentrations and distribution patterns of selected heavy metals (V, Cr, Co, Ni, Cu, Zn, and U) in the coastal system and estuarine area of the Mae Klong river. The results indicate the presence of two different sources of heavy metals in the studied environment and allowed us to identify a lithogenic component that significantly influences the composition of coastal waters and suspended particulate matter (SPM). Comparison of the normalized heavy metals concentrations both in the studied samples and in those reported for the Sn-W ores present in the surrounding areas suggests an important anthropogenic contribution to the chemistry of the seafloor sediments. Vanadium and nickel enrichment factors (EF) calculated for coastal waters indicate that contamination by hydrocarbons discharge took place in the investigated area.