Abiotic Sedimentary Dolomite Formation: from Nano- to Macro-scale

Abiotic Sedimentary Dolomite Formation: from Nano- to Macro-scale
Author: Yihang Fang
Publisher:
Total Pages: 0
Release: 2022
Genre:
ISBN:

With over centuries of effort to understand the formation mechanism of dolomite, a common mineral in sedimentary rocks, the geologic community still struggles to formulate a universal mechanism to explain the origin of massive deposition of sedimentary dolomite. Understanding the exact mechanism for dolomite formation at Earth's surface conditions is crucial for investigating economic reservoirs, interpreting sedimentary environments, reconstructing secular seawater variations, assessing potential carbon sequestration reservoirs, and understanding biominerlization processes.One of the main obstacles for dolomite nucleation and growth is the high water affinity of magnesium and the subsequent kinetic energy barrier for surface Mg2+-water complex to dehydrate. Polysaccharides, exopolymeric substances (EPS), and hydrogen sulfides demonstrate the capability to overcome the kinetic barriers and catalyze dolomite growth, which supports the hypothesis that sedimentary dolomite has a microbial origin. However, not all dolomite are formed by microbial life as dolomite is much more abundant in earlier Earth history when microbial activity levels are lower compare to nowadays, and an abiotic mechanism is needed to explain massive dolomite formation. This work applied laboratory and synchrotron X-ray diffraction, high-resolution TEM imaging, Z-contract imaging, and electron microprobe analysis on low-temperature synthesized and natural samples to understand abiotic controls on surface Mg2+-water complex dehydration and dolomite precipitation. Several focused studies were conducted toward exploring this topic, including: (1) Using ethanol-water mixtures to validate the hypothesis that low-dipole moment materials induce the surface Mg2+-water complex dehydrate, thus allowing disordered dolomite precipitation; (2) Demonstrating that dissolved silica, a low dipole moment molecule, in naturally available concentrations can promote disordered dolomite growth; (3) Applying a dissolved silica catalyzed dolomite growth model to decipher Marinoan cap carbonate formation with coupled Ca, Mg Si, and C cycles; (4) Testing dissolved silica driven dolomite growth in modern hypersaline settings (i.e., the Great Salt Lake, UT); (5) Examining the effect of dissolved silica toward catalyzing dolomite formation in Early Silurian dolomite. Results from this research demonstrate that dissolved silica may be a dominating abiotic control for dolomite precipitation in early Earth history, when dissolved silica in seawater is significantly higher prior to the appearance of silica-consuming microorganisms, and modern hypersaline environments. This abiotic mechanism would allow the reconstruction of solution chemistry changes based on abundances, textures, and associated minerals of dolomite. Changes in dolomite abundances might also contain information on weathering intensities, sea level variations, and Wilson cycles both locally and globally from changes in dissolved silica concentration.

Investigation of the Role of Anaerobic Microorganisms in Sedimentary Dolomite Formation

Investigation of the Role of Anaerobic Microorganisms in Sedimentary Dolomite Formation
Author:
Publisher:
Total Pages: 0
Release: 2013
Genre:
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The objective of this study is to systematically investigate the role of anaerobic microorganisms in sedimentary dolomite formation. My results showed that dissolved sulfide, which can be one of the major products of bacterial sulfate reduction, can significantly enhance the Mg incorporation into the calcitic structure, and promote the crystallization of disordered dolomite. In situ atomic force microscopy observations of Ca-Mg carbonate {104} surface growing from supersaturated solutions showed that dissolved sulfide greatly enhanced both the 1-D step nucleation and step growth which had been retarded by Mg2+ ions. These data offer a mechanism by which sulfate-reducing bacteria (SRB) induce dolomite precipitation. The effect of polysaccharides, which can be a major component of extracellular polymeric substances (EPS), was also tested on dolomite precipitation. Both model polysaccharides, carboxymethyl cellulose and agar, were showed to induce disordered dolomite crystallization. The connection between anaerobes and dolomite precipitation was further explored by characterizing the effect of EPS on dolomite crystallization. EPS secreted by a natural consortium of halophilic anaerobes consisted of fermentative bacteria and SRB was extracted and purified for synthesis experiments. EPS was showed to catalyze disordered dolomite precpitation, while dead cells without EPS only induced hydrous Mg-carbonates. Furthermore, inactive biomass from model strains of both fermentative bacteria and SRB was showed to promote dolomite precipitation, which therefore found a new link between fermentative bacteria and dolomite formation. In addition, EPS secreted by a model methanogen which generally inhabit freshwater environments showed similar catalytic effect. Total polysaccharides analyses showed the existence of significant amounts of polysaccharides in EPS. I suggest that these polysaccharides in EPS served as catalysts for dolomite precipitation. I propose that dissolved sulfide and polysaccharides may adsorb on carbonate surfaces through hydrogen bonding between the H in HS-/H2S or the OH group of polysaccharides and the O in CO32- on carbonate surfaces to weaken the rigid Mg2+ hydration shell, resulting in enhanced Mg incorporation and dolomite crystallization. These findings provide insight into the long-standing "dolomite problem" and suggest a fundamental role for microbial processes in the formation of dolomite across a wide range of environmental conditions from freshwater to hypersaline.

Dolomitization

Dolomitization
Author: Lynton Stuart Land
Publisher: American Association of Petroleum Geologists
Total Pages: 30
Release: 1983
Genre: Science
ISBN:

The Effects of Catalysts in Dolomite Growth at Low Temperature and the Structures of Nano-precipitates in Sedimentary Dolomite

The Effects of Catalysts in Dolomite Growth at Low Temperature and the Structures of Nano-precipitates in Sedimentary Dolomite
Author:
Publisher:
Total Pages: 0
Release: 2015
Genre:
ISBN:

Laboratory syntheses of dolomite at low temperatures cannot be successful without catalysts. The rate-limiting step in the dolomite growth is most likely to be the dehydration of surface Mg2+. We have applied molecular dynamics simulations (MD) and density functional theory (DFT) simulations to study the effects of catalysts in the dolomite growth. There are two hypotheses regarding the role(s) of catalysts in the dehydration of surface magnesium. One hypothesis is that catalysts can be strongly adsorbed onto crystal surface replacing surface water. To test this hypothesis DFT simulations were carried out to study the thermodynamics of competitive adsorption of hydrogen sulfide and water on dolomite (104) surfaces from solution. We find that water is thermodynamically more stable on the surface than hydrogen sulfide. However, hydrogen sulfide adsorbed on the surface increases the nearby Mg2+-H2O distances. Another hypothesis is that catalysts can lower the dehydration barrier of surface Mg2+. Potential of mean force (PMF) calculations have been performed for water molecules leaving the first two hydration layers above dolomite (104) surface in the following three conditions: without catalyst, with mannose and with tri-mannose (three units of mannose). We fitted the force field for the interactions between -OH groups of sugar and surface cations of dolomite. The simulations have shown that a bridge shaped configuration of oligosaccharide lying relatively flat on the surface is able to decrease the dehydration barrier by 0.7~1.1 kcal/mol. The hydrophobic space near the surface created by the non-polar-CH groups of the oligosaccharide is the reason for the observed reduction of dehydration barrier. The fine-scale cation ordering and metastable Ca-Mg carbonates indicate the diagenetic processes of sedimentary dolomites from disordered metastable sediments to hard rocks. Therefore, we studied "c" and "d" superstructures in sedimentary dolomite by using scanning transmission electron microscopy (STEM). STEM images of Wisconsin Ordovician dolomite show that the "c"--Reflections could be the result of multiple diffractions between the host dolomite and twinned Mg-calcite nano-lamellae. Z-contrast images of Proterozoic dolomite demonstrate that the "d" superstructure has a cation ordering sequence of Ca-Ca-Mg-Ca-Ca-Mg along the c direction