Chemistry and isotopic composition of fumarole discharges of Furnas caldera

Two fumarole grounds at Lagoa das Furnas and Furnas village and a fumarole on the bank of Ribeira dos Tambores are located on a west–east tectonic lineament across the topographic low of the Furnas caldera. The discharge of the fumaroles derives from steam separation from shallow (100–200 m) aquifers at temperatures of about 180°C. As inferred from nitrogen/argon relations and deuterium–oxygen isotope relations the hydrothermal fluid is derived from local precipitation after some 10% steam fractionation in the fumarole conduits. Sulphur isotope ratios of the discharge, being close to those of juvenile rock sulphur, indicate extensive rock-leaching within the aquifers. The carbon isotope composition of the fumarole discharge and carbon dioxide saturated waters encountered across the caldera floor suggests that the source of carbon is regional outgassing of mantle derived juvenile carbon dioxide. Chemistry of the acid gases, carbon dioxide and hydrogen sulphide in the discharge indicates a slight fractionation induced by different boiling in the shallow hydrothermal aquifers. Traces of hydrogen and methane contained in the discharge bear no relation to the low temperature water–steam equilibria of the Furnas fumaroles. Assuming a deeper origin of these gases, a simple model for binary mixtures of methane and hydrogen indicates that these gases are derived from supercritical conditions, presumably equilibrated within hot rocks below the hydrothermal system. The remarkably stable ratios of hydrogen and methane, also considering their inferred deep origin, suggest that these gases might be considered for future chemical monitoring of the fumarole discharge in Furnas.