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The origin of sulphur in gypsum and dissolved sulphate in the Central Namib Desert,Namibia
Affiliation:1. School of Engineering, RMIT University, GPO Box 2476, Melbourne, Victoria 3001, Australia;2. Centre for Environmental Sustainability and Remediation, RMIT University, Victoria, Australia;3. CDM Smith, Richmond, Victoria, Australia;4. Australian Contaminated Land Consultants Association, Victoria, Australia;5. Centre for Applied Sciences, EPA Victoria, Victoria, Australia;6. School of Science, RMIT University, Victoria, Australia
Abstract:This study investigates the sulphur source of gypsum sulphate and dissolved groundwater sulphate in the Central Namib Desert, home to one of Africa's most extensive gypsum (CaSO4·2H2O) accumulations. It investigates previously suggested sulphate precursors such as bedrock sulphides and decompositional marine biogenic H2S and studies the importance of other potential sources in order to determine the origin of gypsum and dissolved sulphate in the region. An attempt has been made to sample all possible sulphur sources, pathways and types of gypsum accumulations in the Central Namib Desert. We have subjected those samples to sulphur isotopic analyses and have compiled existing results. In addition, ionic ratios of Cl/SO4 are used to determine the presence of non-sea-salt (NSS) sulphur in groundwater and to investigate processes affecting groundwater sulphate. In contrast to previous work, this study proposes that the sulphur cycle, and the formation of gypsum, in the Namib Desert appears to be dominated by the deposition of atmospheric sulphates of phytoplanktonic origin, part of the primary marine production of the Benguela upwelling cells. The aerosol sulphates are subjected to terrestrial storage within the gypsum deposits on the hyper-arid gravel plain and are traceable in groundwater including coastal sabkhas. The hypothesis of decompositional marine biogenic H2S or bedrock sulphide sources, as considered previously for the Namib Desert, cannot account for the widespread accumulation of gypsum in the region. The study area in the Central Namib Desert, between the Kuiseb and Omaruru rivers, features extensive gypsum accumulations in a ca. 50–70 km wide band, parallel to the shore. They consist of surficial or shallow pedogenic gypsum crusts in the desert pavement, hydromorphic playa or sabkha gypsum, as thin isolated pockets on bedrock ridges and as discrete masses of gypsum selenite along some faults. The sulphur isotopic values (δ34S ‰CDT) of these occurrences are between δ34S +13.0 and +18.8‰, with lower values in proximity to sulphuric ore bodies (δ34S +3.1 and +3.4‰). Damaran bedrock sulphides have a wide range from δ34S −4.1 to +13.8‰ but seem to be significant sources on a local scale at the most. Dissolved sulphate at playas, sabkhas, springs, boreholes and ephemeral rivers have an overall range between δ34S +9.8 and +20.8‰. However, they do not show a systematic geographical trend. The Kalahari waters have lower values, between δ34S +5.9 and +12.3‰. Authigenic gypsum from submarine sediments in the upwelling zone of the Benguela Current between Oranjemund and Walvis Bay ranges between δ34S −34.6 to −4.6‰. A single dry atmospheric deposition sample produced a value of δ34S +15.9‰. These sulphur isotopic results, complemented by meteorological, hydrological and geological information, suggest that sulphate in the Namib Desert is mainly derived from NSS sulphur, in particular oxidation products of marine dimethyl sulphide CH3SCH3 (DMS). The hyper-arid conditions prevailing along the Namibian coast since Miocene times favour the overall preservation of the sulphate minerals. However, sporadic and relatively wetter periods have promoted gypsum formation: the segregation of sulphates from the more soluble halite, and the gradual seaward redistribution of sulphate. This study suggests that the extreme productivity of the Benguela Current contributes towards the sulphur budget in the adjacent Namib Desert.
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