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Authors: Censi, Valentina* 
Zuddas, Pierpaolo* 
Sposito, Fabio* 
Cangemi, Marianna* 
Inguaggiato, Claudio* 
Piazzese, Daniela* 
Title: Boron and lithium behaviour in river waters under semiarid climatic conditions
Journal: Chemosphere 
Series/Report no.: /306 (2022)
Publisher: Elsevier
Issue Date: Nov-2022
DOI: 10.1016/j.chemosphere.2022.135509
Keywords: B/Li ratio; Ionic strength; Mine drainage; Mn-oxyhydroxides; Salt minerals
Abstract: 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.
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