Oxygen and Sulfur Isotope Systematics of Dissolved Sulfate in a Nonvolcanic Geothermal System: Sulfate Source, Evolution and Impact on Geothermometers

Dual isotopes of sulfate (δ³⁴S_SO4 and δ¹⁸O_SO4), along with isotopes in water and trace elements of geothermal waters, are systematically investigated to quantitatively elucidate sulfate sources and oxygen and sulfur isotopic behaviors during deep groundwater circulation and to constrain reservoir temperatures in the Jimo nonvolcanic geothermal system on the eastern coast of China. The results show that δ³⁴S_SO4 and δ¹⁸O_SO4 values in geothermal waters ranged from −21.0 to 5.7‰ and from 1.1 to 8.8‰, respectively. An increase in SO₄ concentrations (140–796 mg/L) with a systematic decrease in δ³⁴S_SO4 and δ¹⁸O_SO4 values was observed along the flow path from the central to eastern and western parts. The sulfate in the Middle Group was predominantly from atmospheric deposition, with sulfide oxidation contributions of <27%. In contrast, 80–85% of SO₄ in the Eastern Group is derived from pyrite oxidation. In the Western Group, the oxidation of multiple metal sulfides contributed 43–66% of SO₄. Sulfate oxidation and mixing of shallow groundwater caused reservoir temperatures to be underestimated by 9 ± 6–14 ± 16% using silica and K-Mg geothermometers but overestimated by up to 52–62% using sulfate–water oxygen isotope geothermometers. The estimated average target reservoir temperature was 144 ± 8 °C, with geothermal waters circulating to depths of 3.6–4.6 km. This study offers new insights into the significant impact of sulfate-related processes on geothermometric estimates, a factor often overlooked when using aqueous geothermometers. It also provides valuable guidance for accurately estimating target geothermal reservoir temperatures and advancing exploration in nonvolcanic geothermal systems.