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

The geochemical behaviour of Rare Earth Elements, Zr and Hf was investigated in the thermal waters of Nevado del Ruiz volcano system. A wide range of pH, between 1.0 and 8.8, characterizes these fluids. The acidicwaters are sulphate dominatedwith different Cl/SO4 ratios. The important role of the pH and the ionic complexes for the distribution of REE, Zr a nd Hf in the aqueous phase was evidenced. The pH rules the precipitation of authigenic Fe and Al oxyhydroxides producing changes in REE, Zr, Hf amounts and strong anomalies of Cerium. The precipitation of alunite and jarosite removes LREE from the solution, changing the REE distribution in acidic waters. Y-Ho and Zr-Hf (twin pairs) have a different behaviour in strong acidic waterswith respect to the water with pH near-neutral. Yttrium and Ho behave as Zr and Hf in waters with pH near neutral-to-neutral, showing superchondritic ratios. The twin pairs showed to be sensitive to the co-precipitation and/or adsorption onto the surface of authigenic particulate (Fe-, Al-oxyhydroxides), suggesting an enhanced scavenging of Ho and Hf with respect to Y and Zr, leading to superchondritic values. In acidic waters, a different behaviour of twin pairs occurs with chondritic Y/Ho ratios and sub-chondritic Zr/Hf ratios. For the first time, Zr and Hf were investigated in natural acidic fluids to understand the behaviour of these elements in extreme acidic conditions and different major anion chemistry. Zr/Hf molar ratio changes from 4.75 to 49.29 in water with pH < 3.6. In strong acidic waters the fractionation of Zr and Hf was recognized as function of major anion contents (Cl and SO4), suggesting the formation of complexes leading to sub-chondritic Zr/Hf molar ratios.