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.

Sabella spallanzanii mucus bacterial agglutinating activity after arsenic exposure. The equilibrium between predation safety and immune response stability.

We report the Sabella spallanzanii mucus bacterial agglutination response after inorganic arsenic (As) exposure. As is actively adsorbed from the surrounding environment and accumulated at high concentrations in tissues as an anti-predatory strategy. Here we investigated the effect of high As concentrations on its immunobiological response. It may act on mucus lectins and on its ability to agglutinate bacteria. We concluded that As at high concentrations leads to the inhibition of pathogen recognition. Nevertheless, although its biological activity is significant reduced in winter, responses to As concentrations are very similar, and below a certain threshold do not induce alterations, supporting the hypothesis of adaptation to high As concentrations related to involvement in predation defence.

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.

The ascidian Styela plicata hemocytes as a potential biomarker of marine pollution: In vitro effects of seawater and organic mercury.

Toxic metals, such as mercury, contribute substantially to anthropogenic pollution in many estuarine environments. Animals living in those environments, particularly invertebrate filter feeders like tunicates, can be used as bioindicators. In an attempt to identify cellular markers for revealing pollution, this study examined in vitro the effects of different concentrations of methyl mercury on Styela plicata hemocytes. The harvested hemocytes from S. plicata that were exposed to the metal had a significant mortality, cellular count and morphometric alterations. These findings provided evidence of MeHg immunotoxic effects on S. plicata, resulting in hemocyte death and morphological changes induced by cytoskeleton alterations. Thus, a morphometric cellular parameter, such as spreading ability, was used as a complementary method for differentiation between hemocytes treated with a marine solution (as a negative control) and hemocytes incubated with methylmercury and/or Sicilian seawater samples.

Binding of acrylic and sulphonic polyanions by open-chain polyammonium cations.

The interactions between some acrylic and sulphonic polyanions and some protonated amines (diamines NH(2)-(CH(2))(x)-NH(2), x=2,...,10; linear tri-, tetra-, penta- and hexa-amines) were studied potentiometrically in aqueous solution, at 25 degrees C. For both types of polyanions AL(2)H(i) (L(-), monomer of polyanion, A, amine) species are formed, with i=1,...,n (n=number of amino groups in the amine). The stability of these species is strictly dependent on the polyammonium cation charge, and fairly independent of the type of amine (in diamine species maximum stability is observed for x=4, 5). Acrylic and sulphonic polyanion complexes are considerably stronger than analogous species formed by low molecular weight anions. Mean stability can be expressed as logK=2.87zeta(2/3), for polyacrylic anions and logK=2.42zeta(2/3) for polysulphonic anions (zeta=absolute value for charge product of reactants).