Zirconium–hafnium and rare earth element signatures discriminating the effect of atmospheric fallout from hydrothermal input in volcanic lake water

Abstract

Geochemical behaviour of rare earth elements (REE), Zr, andHfwas investigated in CO2-richwaters circulating in Pantelleria Island also including ‘Specchio di Venere’ Lakewithin a calderic depression. A wide range of total dissolved REE concentrationswas found (2.77–12.07 nmol L−1),with the highest contents in the lake. Themain REE complexes in the CO2-rich waters are [REE(CO3)2]− and [REECO3]+, showing changeable proportions as a function of pH. The REE normalized to post-Archean Australian Shale (PAAS) showed similar features with heavy REE (HREE) enrichments in CO2-rich waters collected from springs and wells, whereas a different REE pattern was found in the ‘Specchio di Venere’ Lake water with middle REE (MREE) enrichments. The PAAS normalized concentration ratios (LREE/HREE)N and (MREE/HREE)N in waters are b1, except for the lake water in which (MREE/HREE)N N 1. Positive Eu anomalies were found in the investigated waters owing to water–rock interactions with less evolved host rocks. Ce anomalies as a function of Eh values were recognized, with the highest Ce anomaly occurring in the lake water with respect to the CO2-rich waters. The Y/Ho and Zr/Hf molar ratios are higher in the investigated waters (except for lake water) than that in the local rocks, with values ranging from 35.4 to 77.9 and from 76.3 to 299, respectively. The precipitation of authigenic phases was considered to be responsible for the increase in the Y/Ho and Zr/Hf ratios owing to enhanced Hf and Ho removal with respect to Zr and Y. The REE patterns in the lake water show a similar shape (MREE-enriched and a positive Ce anomaly) as those found in the settling dust and in the desert varnish coating of the rocks in arid environments,which mainly contain Fe- and Mn-oxyhydroxides and clay minerals. Similarly, Y/Ho and Zr/Hf ratios in the ‘Specchio di Venere’ Lake (35.4 and 76.3, respectively) show a desert varnish signature. These data, coupled with the presence of iron oxyhydroxides and phyllosilicates in the shallowest water layer of the ‘Specchio di Venere’ Lake, verify the aeolian input from the Sahara Desert