Abstract The Von Damm vent field (VDVF) on the Mid-Cayman Rise in the Caribbean Sea is unique among modern hydrothermal systems in that the chimneys and mounds are almost entirely composed of talc. We analyzed samples collected in 2020 and report that in addition to disordered talc of variable crystallinity, carbonates are a major class of mineral at VDVF. The carbonate minerals include aragonite, calcite, magnesium-rich calcite, and dolomite. Talc and carbonate mineral textures indicate that, rather than replacing volcanic host rock, they precipitate from the mixing of hydrothermal fluids and seawater at the seafloor, occurring in chimneys and surrounding rubble. Alternating precipitation of this mineral assemblage is pervasive, with carbonate minerals typically being succeeded by talc, and with indications that in some cases talc and carbonate minerals replace one another. Stable carbon isotopic data indicate the carbonate minerals originate from the mixing of seawater and hydrothermal fluid, which is supported by U-Th data. Radiocarbon calcite ages and talc 234U-230Th isochron ages indicate mineral ages spanning over thousands to tens of thousands of years. Analyses of these samples illustrate a dynamic system that transitions from carbonate-dominated to Mg-silicate–dominated precipitation over time scales of thousands of years. Our observations raise questions regarding the eventual fate of seafloor precipitates and whether carbonate and silicate minerals in such settings are sequestered and represented in the rock record.
more »
« less
The role of calcite mineral elastic moduli in carbonate rock physics
Rock-physics models for carbonate reservoirs assume that the mineral elastic moduli are known variables. A review of publications reveals a range of values for calcite that are out of date and misleading. We present a robust compilation for future investigations. We subsequently discuss the application of calcite elastic moduli for rock-physics modeling and interpretation of wireline data through a case study data set from an offshore Canada carbonate reservoir. The data set exhibits an offset between the zero-porosity intercept and the calcite elastic moduli values. Our experience indicates that this phenomenon is present in many wireline data sets from carbonate reservoirs around the world. We demonstrate that the data can be reconciled to the mineral elastic moduli through the interpretation of microcracks in the formation (defined by a crack density of 0.06). Understanding the microcrack effect in relatively low-porosity formations is important for the correct calibration of pore microstructure parameters and for fluid-substitution calculations. Results in the case study data set show a relatively high sensitivity to changes in fluid saturation. The sensitivity can be reduced through the use of effective mineral elastic moduli that are derived from the data. We justify the effective mineral elastic moduli as a representation of the mineral moduli plus microcracks. The effective mineral elastic moduli are proposed as a relatively simple method to constrain the fluid substitution calculations in low-porosity formations where microcracks are present.
more »
« less
- Award ID(s):
- 1836852
- PAR ID:
- 10410636
- Date Published:
- Journal Name:
- The Leading Edge
- Volume:
- 42
- Issue:
- 4
- ISSN:
- 1070-485X
- Page Range / eLocation ID:
- 277 to 284
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Mineral precipitation reactions in porous media can change the porosity and permeability of the rock formations. Predicting the rate of reaction and impacts on formation properties is challenging due to a lack of understanding of mineral precipitation reaction kinetics and mechanisms in porous media. This is furthermore challenging due to the highly heterogeneous nature of natural porous media. Here, we aim to develop a novel experimental platform leveraging 3D printing to facilitate replicable mineral precipitation experiments in controlled, heterogenous porous media systems. This requires fundamental understanding of the kinetics of mineral precipitation on the polymer materials used to fabricate the 3D printed porous media. In this work, we manipulate (via sulfonation) material surfaces (high impact polystyrene, HIPS) to promote calcite precipitation from supersaturated solutions to inform the design of synthetic subsurface systems. Calcite precipitation on HIPS films of varied surface sulfonation is confirmed using X-ray diffraction (XRD) analysis and weight-based precipitation experiments where increased precipitation with increased surface functionalization and solution saturation index are observed. This approach is then applied to 3D-printed porous media to enhance understanding of geochemical reactions, specifically calcite precipitation. Three dimensional images of Bentheimer Sandstone are used as the basis for 3D-printed porous media samples. Two 3D-printed samples were functionalized with acid to activate the surface and promote mineral precipitation. Functionalized and unfunctionalized samples underwent calcite precipitation core flooding experiments with oversaturated calcite solutions for 96 hours. Three dimensional X-ray micro-CT imaging revealed calcite growth in functionalized samples, with a calcite volume fraction of approximately 2.6% and a substantial reduction in porosity. Unfunctionalized samples exhibited diminished calcite precipitation and porosity changes. These findings demonstrate that reactive 3D-printed porous media can provide a versatile geochemical modeling and experimentation platform. Functionalizing 3D printed samples enhances reactivity, allowing investigations of mineral precipitation processes in complex porous media. This research highlights the potential for further exploration of 3D-printed media in various geochemical contexts.more » « less
-
Abstract Gibbs free energy, the fundamental thermodynamic potential used to calculate equilibrium mineral assemblages in geological systems, does not apply to non‐hydrostatically stressed solids. Consequently, there is debate over the significance of non‐hydrostatic stress in petrological and geophysical processes. To help resolve this debate, we consider the effects of non‐hydrostatic stress on the polymorph pairs kyanite/sillimanite, graphite/diamond, calcite/aragonite, and quartz/coesite. While these polymorphs are most relevant to metamorphic processes, the concepts developed are applicable to any single‐component solid reaction. We quantitatively show how stress variations normal to an interface alter equilibrium temperatures of polymorph pairs by approximately two orders of magnitude more than stress variations parallel to an interface. Thus, normal stress controls polymorph stability to first order. High‐pressure polymorphs are expected to preferentially nucleate normal to and grow parallel to the maximum stress and low‐pressure polymorphs, the minimum stress. Nonetheless, stress variations parallel to an interface allow for the surprising possibility that a high‐pressure polymorph can become more stable relative to a low‐pressure polymorph as stress decreases. The effects of non‐hydrostatic stress on mineral equilibrium are unlikely to be observed in systems with interconnected, fluid‐filled porosity, as fluid‐mediated reactions yield mineral assemblages at approximately constant pressures. In dry systems, however, reactions can occur directly between elastic solids, facilitating the direct application of non‐hydrostatic thermodynamics. Non‐hydrostatic stress is likely to be important to the evolution of metamorphic systems, as preferential orientations of polymorphic reactions can generate seismicity and may influence fundamental rock properties such as porosity and seismic anisotropy.more » « less
-
null (Ed.)Magnesium (Mg) in natural waters plays a critical role in governing carbonate mineral formation, dissolution, and diagenesis. Previous laboratory experiments show that Mg can strongly inhibit direct calcite precipitation as well as aragonite to calcite diagenetic transformation. Data from natural settings, however, suggest that diagenetic calcite in most Phanerozoic limestones has formed in the shallow marine burial realm in the presence of ample Mg. Thus, the diagenetic conditions under which aragonite-rich sediments convert to calcite-rich limestones are poorly understood. Here, we present data from laboratory experiments whereby aragonite is converted to calcite at 70◦C in Mg-bearing solutions to investigate the effects of fluid:solid ratio (F:S), which varies greatly across diagenetic environments, on Mg inhibition and incorporation in calcite. Our data show that not only can the transformation of aragonite to calcite occur in solutions with higher [Mg] than previously shown possible in laboratory experiments, but that progressively lower F:S increase the rate at which aragonite stabilizes to calcite. For example, in experiments with an F:S of 0.3 mL/g, which corresponds to sediments in a closed system with 50% porosity, aragonite stabilizes to calcite in solution with [Mg]=30 mM (Mg/Ca=5.14) when an initial high degree of undersaturation with respect to aragonite is used and in a solution with [Mg]=20 (Mg/Ca=5.14) when a low degree of undersaturation is used. In contrast, aragonite does not stabilize to calcite after nearly 3000 h in experiments with an F:S of 100 mL/g, which is more typical of an open system, even in a solution with [Mg]=5 mM (Mg/Ca=5.14) regardless of the degree of undersaturation. Our results also show that the amount of Mg incorporated into calcite products increases linearly with the increase of F:S. Collectively, these observations further point to F:S as an important factor in carbonate diagenesis with broad implications. First, the observations that transformation of aragonite to calcite is inhibited at high [Mg] and F:S imply that calcite precipitation is unlikely to occur in marine diagenetic environments that are in direct hydrologic contact with seawater. This leaves aragonite dissolution as the dominant diagenetic process in these environments, which may represent an underrated source of alkalinity to the open ocean. Second, transformation from aragonite-rich sediments to the calcite-rich limestones that dominate the rock record is likely promoted by a decrease in the F:S and the development of a closed system during progressive burial.more » « less
-
Predicting geomechanical properties of rock and other types of porous media is essential to accurate modeling of many important processes, such as wave propagations, seismic events, and underground gas storage, and CO2sequestration, all of which involve deformation of the pore space. We propose a model to predict the porosity dependence of the Young's and bulk moduli in heterogeneous porous media by combining the universal power law, predicted by percolation theory that describes the behavior of elastic moduli near the percolation threshold of the solid skeletons, and the effective‐medium approximation (EMA) for elastic materials that is accurate away from the threshold. The parameters of the model have unambiguous physical meanings, and can, in principle, be measured. We estimate the parameters ‐ the percolation threshold , crossover point between the EMA and percolation power law, the average particle coordination number , and the elastic moduli of the solid skeleton by using experimental data or numerical simulations for a wide variety of porous media in both two and three dimensions. Whenever data are available, the predictions are consistent with them. We then predict the elastic moduli for another 10 porous media using the proposed model and the estimated parameters without adjusting any new parameter. The predictions are in most cases in agreement with the data, hence indicating the accuracy of the approach.more » « less
An official website of the United States government

