Spectral and chemical characterization of jarosite in a palaeolacustrine depositional environment in Warkalli Formation in Kerala, South India and its implications

Spectrochim Acta A Mol Biomol Spectrosc. 2016 Nov 5:168:86-97. doi: 10.1016/j.saa.2016.05.035. Epub 2016 May 25.

Abstract

Coastal cliffs fringing the Arabian Sea near Varkala exhibits the Warkalli Formation of the Tertiary sequence of Kerala, South India, with well-marked occurrence of jarosite associated with other hydrous mineral phases of phyllosilicate family in a palaeo-lacustrine depositional environment. Sandy phyllosilicates dominate the mineral assemblage, but jarosite occurs as a prominent secondary phase formed during acid-sulphate alteration of iron sulphide in this area. Here, we discuss about the potentiality of spectroscopic techniques to identify the possible mineral phases in the collected samples. The samples from the coastal cliffs have been characterized by hyperspectral analysis (VIS-NIR-SWIR), X-ray Diffraction (XRD), Fourier Transform Infra-red Reflectance (FTIR), Electron Probe Microanalysis (EPMA) and Laser Raman spectroscopy. The spectral and chemical analyses have confirmed the jarosite as natrojarosite and phyllosilicate as kaolinite. Other accessory phases have also been identified through XRD. FTIR spectroscopy has played a major role in identifying the major hydrous bonds between the minerals. VIS-NIR-SWIR spectra show several optimum spectral features at 910nm, 1470nm, 1849-1864nm (in the form of a doublet), 1940nm and 2270nm, which could be utilised to locate jarosite in the remotely-sensed data. X-ray diffraction peaks helped in the identification of maximum number of minerals (kaolinite, smectite, quartz, feldspar, pyrite, marcasite and hematite) and the variation in jarosite content in the samples. We propose the formation of jarosite in the region by a seasonal, local and temporary development of acidic conditions. Abundance of organic matter in a fluvio-lacustrine environment has developed anaerobic conditions by removing available oxygen through decomposition of organic matter containing sulphur compounds. The sulphur thus liberated combines with hydrogen from water to develop acidic conditions and resulted in the formation of jarosite. The occurrence of jarosite in Warkalli Formation suggests on and off supply of water during diagenesis. Jarosite has been detected as a prominent deposit in several regions on Mars by Mars Exploration rover Opportunity and Mars Reconnaissance Orbiter-Compact Reconnaissance Imaging Spectrometer for Mars (CRISM). This study of jarosite formation in terrestrial environment will influence our understanding on the mineral precipitation, diagenesis and hydration processes on Mars. Additionally, it also shows the importance of spectroscopic techniques like Raman spectrometry to be used in future missions to Mars to further validate the results of orbital spectroscopy.

Keywords: Fluvio-lacustrine; Mars; Natrojarosite; VIS-NIR-SWIR; Warkalli Formation; X-ray diffraction.