The origin of jarosite associated with a gossan on Archean gneiss in Southwest Greenland

The mineral Jarosite [KFe3(SO4)2(OH)6] since its discovery, by Opportunity rover at Meridiani Planum on Mars, has been the subject of intense geochemical and environmental study over the last 5-10 years. Jarosite requires highly acidic, K-enriched, and oxidizing aqueous conditions for formation. Stable isotopes of O, H, and S of jarosite have the ability to record the temperatures of formation, environments of deposition, fluids, and fluid/atmospheric interactions. Therefore, the origin of jarosite is important for understanding present and past environmental conditions on Mars. Unfortunately, the origin of jarosite on Mars remains unclear. Jarosite is commonly found on Earth in the weathering zones of pyrite-bearing ore deposits, near-surface playa sediments in acid-saline lakes, or epithermal environments and hot springs. Here, we report the occurrence of jarosite in association with a gossan overlying weathered Archean gneiss and Paleoproterozoic mafic dikes at the ice-free margin of southwestern Greenland. In our 2012 field campaign, we excavated soil pits to a depth of 40 cm with a high vertical sampling resolution. No visible pyrite was found in the nearby outcroppings of gneiss in the field. XRD data show that all samples were composed of anorthite, quartz, albite, jarosite, muscovite, and microcline. Jarosite was the only sulfur-bearing mineral identified by XRD, with abundance of jarosite increasing with depth (up to 8.4 wt. %) in the soil pits. Water soluble and acid soluble sulfate were sequentially extracted using 10% NaCl and 2N HCl solutions, respectively. Pyrite was then subsequently extracted from insoluble residues by a chromium reduction method. The average abundance of water soluble sulfate, acid soluble sulfate, and pyrite were 100 ppm, 7 wt. %, and 10 ppm, respectively. The δ34S values of water soluble sulfate, acid soluble sulfate, and pyrite range from -0.7‰ to 3.1‰ (average= 1.5‰), -1.2 to 1.5‰ (average= 0.7‰), and 0.3‰ to 6.7‰ (average= 2.6‰) respectively. δ34S values of all water soluble sulfate and pyrite, were higher than acid soluble sulfate. δ34S values of pyrite were higher than all water soluble sulfate except the surficial sample (0-10 cm depth). The δ34S values of water soluble sulfate and acid soluble sulfate did not change with depth while δ34S values of pyrite increased with depth from 2.4‰ to 6.7 ‰ (peak at 10-15 cm) and dropped to 2.0‰. Preliminary data indicate that the acid soluble sulfate was dominated by jarosite while the water soluble sulfate fraction may have been a mixture of leached jarosite and other sulfate sources, such as atmospheric sulfate. Jarosite formation may result from the oxidative weathering of pyrite inferred to originate from localized, stratiform, hydrothermal mineralization. To constrain the origin of jarosite, a new profile containing soil, permafrost, and bedrock was collected at the same location during the summer 2013 field campaign by drilling ~ 1.0 meter into the permafrost zone. We will employ multiple sulfur isotope and triple oxygen isotope of sulfate and pyrite, which can define the source of sulfur and oxygen. A greater understanding of the formation of jarosite on this ice-free margin of Greenland will provide an insightful potential analogue for jarosite formation and on Mars.