Source and genesis of sulphate and phosphate–sulphate minerals in a quartz‐sandstone cave environment

Abstract

Gypsum (CaSO4·2H2O), alunite (KAl3(SO4)2(OH)6), and rare phosphate–sulphate sanjuanite Al2(PO4)(SO4)(OH) 9(H2O) and rossiantonite (Al3(PO4)(SO4) 2(OH)2(H2O)14) have recently been identified as secondary mineral deposits in different quartz‐sandstone caves in the Gran Sabana region, Venezuela. Due to the extended time scale required for speleogenesis in the hard and barely soluble quartz‐sandstone lithology, these caves are considered to be as old as 20 to 30 My. The study of these peculiar secondary mineral deposits potentially reveals important insights for understanding the interaction between deep, superficial and atmospheric processes over thousands to perhaps millions of years. In this study, chemical and petrographic analyses of potential host rock sources, sulphur and oxygen isotope ratios, and meteorological, hydrological and geographical data are used to investigate the origin of sulphates and phospho–sulphates. The results suggest that the deposition of sulphates in these caves is not linked to the quartz‐sandstone host rock. Rather, these mineral deposits originate from an external atmospheric sulphate source, with potential contributions of marine non‐sea salt sulphates, terrestrial dimethyl sulphide and microbially reduced H2S from the forests or peatbogs within the watershed. Air currents within the caves are the most plausible means of transport for aerosols, driving the accumulation of sulphates and other secondary minerals in specific locations. Moreover, the studied sulphate minerals often co‐occur with silica speleothems of biological origin. Although this association would suggest a possible biogenic origin for the sulphates as well, direct evidence proving that microbes are involved in their formation is absent. Nonetheless, this study demonstrates that these quartz‐sandstone caves accumulate and preserve allogenic sulphates, playing a yet unrecognized role in the sulphur cycle of tropical environments.

Phylotypic Diversity of Bacteria Associated with Speleothems of a Silicate Cave in a Guiana Shield Tepui

“…The Al element present in sample GM1 probably belonged to pyrophyllite, a metamorphic mineral that has been extensively found in tepui bedrock. Sample GM2 also showed S and Ca, which fits with gypsum also reported for other tepui caves [ 27 , 38 , 39 , 40 ].…”

Transition from unclassified Ktedonobacterales to Actinobacteria during amorphous silica precipitation in a quartzite cave environment

“…Among these, the orthoquartzitic Imawarì Yeuta cave represents a non-thermal and mild environment, which hosts a wide variety of unique amorphous silica deposits 10 . This cave is also one of the oldest caves discovered so far (20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30) and is considered a pristine natural place, which is hardly accessible by humans 15,16 . In addition to the absence of light, some areas of the cave are isolated from the external surface, with limited air and water exchanges, determining a general low nutrient availability and low organic carbon sources.…”

Deep seated fault‐related volcanogenic H2S as the key agent of high sinkhole concentration areas

“…It is well known from the literature (Klimchouk et al, 1995(Klimchouk et al, , 1997Forti, 1997, 2004;Bottrell et al, 2001;Forti, 2011a, 2011b;Klimchouk, 2012;Sauro et al, 2014) that this mineral represents a very common phase in speleothem domains. It is well known from the literature (Klimchouk et al, 1995(Klimchouk et al, , 1997Forti, 1997, 2004;Bottrell et al, 2001;Forti, 2011a, 2011b;Klimchouk, 2012;Sauro et al, 2014) that this mineral represents a very common phase in speleothem domains.…”

“…Gypsum is virtually ubiquitous, in PAS, PAG and PSG, yet with different proportions. It is well known from the literature (Klimchouk et al, 1995(Klimchouk et al, , 1997Forti, 1997, 2004;Bottrell et al, 2001;Forti, 2011a, 2011b;Klimchouk, 2012;Sauro et al, 2014) that this mineral represents a very common phase in speleothem domains. If we consider specifically the cave mineral environment, Onac and Forti (2011a and references therein) depicted a series of processes vs mechanisms (and related temperatures) leading to the deposition of different minerals.…”