Understanding zinc isotopic signatures in volcanic lakes

Abstract

Magmatic activity can be monitored through the chemical variations of volcanic lakes. While those lakes can be influenced by direct magmatic input, water-rock interaction processes in hydrothermal system also have a large influence. Disentangling those effects is critical to use crater lakes for volcanic activity monitoring purposes. Zinc is a volatile metal that is easily degassed and can be incorporated into fluid circulation. During degassing, Zn isotopes can be fractionated and can thus be a potential tracer of magmatic input. Here we present a novel approach using stable Zn isotopic systems to understand how dissolution/precipitation processes affect isotopic compositions of volcanic lakes and if they can be used as tracers of magmatic activity. We investigate Zn isotopes expressed as δ66Zn for four volcanic lakes ranging from hyperacidic to neutral waters. Two of them, Kawah Ijen (Indonesia) and Santa Ana (El Salvador) volcanic lakes have been sampled from 2010 to 2012 and 2000–2002, respectively, and show a clear magmatic input with extremely low pH [0.1–1]. Taal (Philippines, pH ≈ 3) and Kelud (Indonesia, pH ≈ 6.5) volcanic lakes were sampled from 2017 to 2019 and 2003–2007 respectively, and are dominated by hydrothermal rather than magmatic inputs. Hyper-acidic lakes show minimal isotopic variation over the investigated time ranges, with δ66Zn values similar to their basalt-andesitic host rocks (0.26 ± 0.08 ‰). In contrast, we observe large δ66Zn fractionation for the Taal waters (0.4 ± 0.01 ‰) compared to their basalt-andesitic host rocks but no δ66Zn temporal variations. Kelud waters show significant δ66Zn (−0.08 ± 0.06 ‰ to 0.43 ± 0.06 ‰) temporal variation. This could be related to an evolution of the lake water chemistry as the sampling period occurred between two increases in lake temperature culminating into a lava dome eruption in 2007. For Taal and Kelud volcanic lakes, enrichment factors (EF) and PHREEQc modelling indicate that Zn is depleted and suggest that Zn could precipitate in the hydrothermal system, hence fractionating Zn isotopes during these precipitation processes. This contrasts to Zn elemental and isotope values from Kawah Ijen and Santa Ana with an EF ≈ 1 suggesting that Zn is derived from host rock dissolution, in agreement with their δ66Zn. These data are still limited and a longer observation is needed in the future to highlight significant geochemical changes in volcanic lakes and their relation to volcanic activity.