Behaviour of polythionates in the acid lake of poás volcano: Insights into changes in the magmatic-hydrothermal regime and subaqueous input of volatiles

Abstract

In this chapter, we document an extensive record of concentrations and speciation of polythionates (PTs: S4O62−, S5O62−, and S6O62−), which form in the warm (21–60 °C) and hyper-acidic (pH < 1.8) waters of the crater lake of Poás volcano (Costa Rica) through interaction with gaseous SO2 and H2S of magmatic origin. Our data set, together with earlier published results, covers the period 1980–2006 during which lake properties and behavior were marked by significant variations. Distinct stages of activity can be defined when combining PT distributions with geochemical, geophysical and field observations. Between 1985 and mid-1987, when fumarolic outgassing was centered on-shore, the total concentration of PTs in the lake was consistently high (up to 4,200 mg/kg). Mid-1987 was the start of a 7-year period of vigorous fumarolic activity with intermittent phreatic eruptions from the lake, which then dried out. Concentrations of PTs remained below or close to detection limits throughout this period. After mid-1994, when a new lake formed and fumarolic outgassing shifted to the dome, the total PT concentrations returned to relatively stable intermediate levels (up to 2,800 mg/kg) marking more quiescent conditions. Since early 1995, numerous weak fumarole vents started, opening up at several other locations in the crater area. During short intervals (November 2001–May 2002 and October 2003–March 2005), PTs virtually disappeared. After April 2005, PTs re-appeared in large amounts (up to more than 3,000 mg/kg) until February 2006, one month before the onset of the March 2006–2017 cycle of phreatic eruptions, when concentrations dropped and remained below 100 mg/kg. The observed behavior of PTs records changes in the input and SO2/H2S ratios of subaqueous fumaroles. The prevailing distribution of PTs is S4O62− > S5O62− > S6O62−, which is common for periods when total PT concentrations and SO2/H2S ratios of the gas influx into the lake are relatively high. PTs are virtually absent as a consequence of thermal or sulphitolytic breakdown during periods of strong fumarolic outgassing in response to shallow intrusion of fresh magma or fracturing of the solid envelope around a pre-existing body of cooling magma. They are also low in abundance or undetected during quiescent periods when subaqueous fumarolic output is weak and has low SO2/H2S ratios, resulting in a concentration sequence S5O62− > S4O62− > S6O62−. The onset of phreatic eruptions are preceded by an increase in PT concentrations, accompanied by a change in the dominance from penta- to tetrathionate, and followed by a sharp drop in total PT content, up to several months before. Periods of phreatic eruptive activity that started in 1987 and 2006 followed these PT signals of increased input of sulfur-rich gas, in both cases possibly in response to shallow emplacement of fresh magma or hydrofracturing.