The oceanic magnesium budget is important to our understanding of Earth's carbon cycle, because similar processes control both (e.g., weathering, volcanism, and carbonate precipitation). However, dolomite sedimentation and low-temperature hydrothermal circulation remain enigmatic oceanic Mg sinks. In recent years, magnesium isotopes (δ26Mg) have provided new constraints on the Mg cycle, but the lack of data for the low-temperature hydrothermal isotope fractionation has hindered this approach. Here we present new δ26Mg data for low-temperature hydrothermal fluids, demonstrating preferential 26Mg incorporation into the oceanic crust, on average by εsolid-fluid ≈ 1.6‰. These new data, along with the constant seawater δ26Mg over the past ~20 Myr, require a significant dolomitic sink (estimated to be 1.5-2.9 Tmol yr-1; 40-60% of the oceanic Mg outputs). This estimate argues strongly against the conventional view that dolomite formation has been negligible in the Neogene and points to the existence of significant hidden dolomite formation.
Abstract Gypsum ( CaSO 4 ·2 H 2 O ), alunite ( KAl 3 ( SO 4 ) 2 ( OH ) 6 ), and rare phosphate–sulphate sanjuanite Al 2 ( PO 4 )( SO 4 )( OH ) 9( H 2 O ) and rossiantonite ( Al 3 ( PO 4 )( SO 4 ) 2( OH ) 2 ( H 2 O ) 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 H 2 S 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.
Dolomite is an important constituent of many economically important gas and oil reservoir rocks. Studies conducted in modern environments combined with microbiological laboratory experiments have shown that microbes and their extracellular polymeric substances (EPS) play an important role for the formation of primary dolomite at Earth's surface conditions. These studies showed that, at low temperature, Mg is incorporated into the carbonate mineral exclusively in the presence of specific organic molecules. However, because the organic molecules involved in the mineralization process rarely survive metamorphism and are usually not preserved in the carbonate mineral, identifying microbial dolomite in ancient rocks represents a challenging task. It remains, as yet, unclear what percentage of sedimentary dolomite is a primary microbially mediated precipitate vs. a secondary replacement product that formed during diagenesis or at high temperatures during metamorphism. A useful approach for evaluating the microbial origin of ancient dolomite is that of searching for microfossils and other microstructures of biological origin associated with the dolomite crystals. Here, we present the results of scanning electron microscopy (SEM) investigations of various ancient sedimentary dolomites. Several investigated samples include abundant filamentous microstructures that we interpret to be mineralized EPS. In some cases, these filaments form a well-structured alveolar pattern, whose architecture appears too complex to be the result of an abiotic process. In order to reinforce our interpretation, we also investigated modern biofilms, which include microstructures of EPS that are morphologically identical to the mineralized and preserved EPS in ancient dolomites. In some rare cases, we also found microfossils (i.e. mineralized cells) in close spatial association with the dolomite crystals. These occurrences are remarkable, considering that it is commonly thought that only chert has the potential of preserving the soft tissues constituting microbial cells. Although we cannot prove conclusively that the fossilized cells and EPS mediated the formation of the adjacent dolomite crystals, our results indicate that dolomite formation took place in environments where microorganisms and biofilms were an important component of the depositional setting. The "microbial factor", which has been proven to be essential for the precipitation of dolomite at low temperature in modern environments, may, therefore, have also been active during the formation of these ancient carbonates.
Abstract Dolomite is globally present in past geological records, but rare in modern environments. The mechanisms favouring its precipitation under ambient conditions remain highly debated. This study investigates sediments, containing high concentrations of early diagenetic calcian dolomite, from alkaline Lake Van (Republic of Türkiye, formally Turkey) dating back to 252 ka bp . Powder X‐ray diffraction and scanning electron microscopy evidence suggests that dolomite formation is associated with prior dissolution of aragonite and low‐Mg calcite and a subsequent co‐precipitation with, and/or partial transformation of, high‐Mg calcite into dolomite. The infrequent presence of diatom frustules encapsulated by dolomite suggests, for Lake Van, unusually low pore‐water pH at the time of dolomite formation. Conditions facilitating the preservation of silica, as well as dissolution and subsequent reprecipitation of carbonate phases, could result from periodic reventilations of Lake Van's deep water and an advection of pore fluids with contrasting redox potential and chemical concentration gradients. This continental analogue of the coastal ‘mixing‐zone’ dolomitization model argues that not overcoming a single specific hydrochemical threshold, but highly dynamic and fluctuating conditions trigger dolomite formation in Lake Van.
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