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.

Boron and lithium behaviour in river waters under semiarid climatic conditions.

Boron (B) and Lithium (Li) concentrations were studied in the Platani river, one of the most important catchments of South-Central Sicily which is under semiarid climatic conditions for roughly eight months to a year. In this area, evaporites result in potential B and Li sources for surface waters. Results from river waters have measured ionic strength values between 0.1 and 4.54 M. B and Li distributions in these waters were studied in colloidal (CF, extracted by ultrafiltration from the 0.45 µm filtrate) and total dissolved (TDF) fractions and in fractions extracted from corresponding riverbed sediments, according to changes of the B/Li ratio. In river waters, CF and TDF showed very similar B/Li values, suggesting that only negligible fractionation occurs between Li and B in the aqueous phase. Similar evidence was observed between B/Li values in TDF and the labile sediment fraction, whereas an inverse relationship arose between B/Li values in TDF and in the easily reducible sediment fraction. This relationship indicates that Mn oxy-hydroxides preferentially react with aqueous B species relative to Li at the riverbed sediment interface. The extent of the B-Mn oxy-hydroxide reactions is influenced by the ionic strength, so that only B/Li values below 4 are measured in river waters with ionic strength values above 0.5 M. Comparing B/Li and ionic strength values measured in the Platani river with those from oxic brines worldwide, the same preferential B removal relative to Li is observed. This evidence suggests that B is removed as positively-charged borate ion-pairs, formed in the aqueous phase under higher ionic strength conditions, reacting with negatively charged surfaces of Mn oxy-hydroxides. The observed B reactivity relative to Li could be exploited to bring down the B excess from natural or waste waters, allowing the natural reactions with Mn oxy-hydroxides to take place under natural conditions.

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.

Role of CO2 in low to medium enthalpy geothermal systems in the Central Betic Cordillera (Spain).

There is growing interest in geothermal energy, which is considered as an efficient energy solution to mitigate rising atmospheric CO2. Besides known high enthalpy geothermal systems, increasing attention is paid to low temperature geothermal systems, as they are suitable for local use. Although geothermal production seems to be an environmentally advantageous renewable energy, it might result in significant CO2 emissions. In this study, we investigate the relationship between temperature, fugacity of CO2 (fCO2), and mineral buffers in the reservoir conditions, taking the low- to medium- enthalpy thermal waters in the Central Betic Cordillera as case study. Using geochemical modeling, three main groups of waters have been identified depending on temperature, buffering mineral assemblage, and fCO2 in their reservoir. A group of waters with a reservoir temperature ranging from 70 to 90 °C and located in the intramountain sedimentary basins shows a fCO2 in depth ranging from ~6 × 10-2 and 6 × 10-1. The reservoir chemistry of this water group seems to be mainly controlled by carbonates and evaporites displaying a fCO2 variation between depth and surface (ΔfCO2) of 10-1. Another intermediate group of waters, located in an active extension zone, displays lower temperature (50-60 °C) and fCO2 in the reservoir (from 10-3 to 10-2). Finally, the third group of waters, located on the metamorphic complexes contacts, show the highest estimated temperatures (130-140 °C) and fCO2 in the reservoir (1 to 102). The two latter groups suggest increasing buffering effect of alumino-silicates, in addition to carbonates and quartz. Therefore, we evidenced a strong relationship between temperature and fCO2 in the reservoir as well as the potential mineral buffers. We discussed the potential of geothermal systems as clean energy source based on the estimation of the CO2 emissions generated by the investigated thermal systems for a practical case of household heating.

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.

Nitrogen patterns in subsurface waters of the Yzeron stream: effect of combined sewer overflows and subsurface-surface water mixing.

Urbanization subjects streams to increased nitrogen loads. Therefore studying nitrogen forms at the interface between urban stream and groundwater is important for water resource management. In this study we report results on water δ(18)O and nitrogen forms in subsurface waters of a stream (Yzeron, France). The sites studied were located upstream and downstream of combined sewer overflows (CSO) in a rural area and a periurban area, respectively. Water δ(18)O allowed us to follow the mixing of subsurface water with surface water. Dissolved organic nitrogen and organic carbon of fine sediment increased by 20-30% between rural and periurban subsurface waters in the cold season, under high flow. The highest nitrate levels were observed in rural subsurface waters in the cold season. The lowest nitrate levels were found in periurban subsurface waters in the warm season, under low flow. They corresponded to slow exchange of subsurface waters with channel water. Thus reduced exchange between surface and subsurface waters and organic-matter-rich input seemed to favor nitrate reduction in the downstream, periurban, subsurface waters impacted by CSO.

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.

Mobility of heavy metals from tailings to stream waters in a mining activity contaminated site.

In this paper the results of a recent characterization of Rio Piscinas (SW of Sardinia, Italy) hydrological basin are reported. In such area (about 50 km2), previous mining activities caused a serious heavy metal contamination of surface waters, groundwater, soils and biota. Acid mine drainage phenomena were observed in the area. The main sources of contamination are the tailings stored in mine tunnels and abandoned along fluvial banks. A methodological approach was adopted in order to identify relations between tailings and water contamination. Representative samples of tailings and stream sediments samples were collected. XRD analyses were performed for mineralogical characterization, while acid digestion was carried out for determining metal contents. Batch sequential leaching tests were performed in order to assess metal mobility. Also groundwater and stream water were sampled in specific locations and suitably characterized. All information collected allowed the understanding of the effect of tailings on water contamination, thus contributing to the qualitative prediction of pollution evolution on the basis of metal mobility. Finally, a potential remediation strategy of stream water is proposed.

Heavy metal coprecipitation with hydrozincite [Zn(5)(CO(3))(2)(OH)(6)] from mine waters caused by photosynthetic microorganisms.

An iron-poor stream of nearly neutral pH polluted by mine tailings has been investigated for a natural phenomenon responsible for the polishing of heavy metals in mine wastewaters. A white mineralized mat, which was determined to be hydrozincite [Zn(5)(CO(3))(2)(OH)(6)] by X-ray diffraction analysis, was observed in the stream sediments mainly in spring. The precipitate shows a total organic matter residue of 10% dry weight and contains high concentrations of Pb, Cd, Ni, Cu, and other metals. Scanning electron microscopy analysis suggests that hydrozincite is mainly of biological origin. Dormant photosynthetic microorganisms have been retrieved from 1-year-old dry hydrozincite. The autofluorescent microorganisms were imaged by a scanning confocal laser microscope. A photosynthetic filamentous bacterium, classified as Scytonema sp. strain ING-1, was found associated with microalga Chlorella sp. strain SA1. This microbial community is responsible for the natural polishing of heavy metals in the water stream by coprecipitation with hydrozincite.