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DePaolo, Donald J.

Publications and source records attributed to DePaolo, Donald J..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Concurrent measurement of strain and chemical reaction rates in a calcite grain pack undergoing pressure solution: Evidence for surface-reaction controlled dissolution

Pressure solution is inferred to be a significant contributor to sediment compaction and lithification, especially in carbonate sediments. For a sediment deforming primarily by pressure solution, the compaction rate should be directly related to the rate of calcite dissolution, transport along grain contacts, and calcite reprecipitation. Previous experimental work has shown that there is evidence that deformation in wet calcite grain packs is consistent with control by pressure solution, but considerable ambiguity remains regarding the rate limiting mechanism. We present the results of laboratory compaction experiments designed to directly measure calcite dissolution and precipitation rates (recrystallization rates) concurrently with strain rate to test whether measured rates are consistent with predicted rates both in absolute magnitude and time evolution. Recrystallization rates are measured using trace element chemistry (Sr/Ca, Mg/Ca) and isotopes (87Sr/86Sr) of fluids flowing slowly through a compacting grain pack as it is being triaxially compressed. Imaging techniques are used to characterize the grain contacts and strain effects in the post-experiment grain pack. Our data show that calcite recrystallization rates calculated from all three geochemical parameters are in approximate agreement and that the rates closely track strain rate. The geochemically inferred rates are close to predicted rates in absolute magnitude. Uncertainty in grain contact dimensions makes distinguishing between surface reaction control and diffusion control difficult. Measured reaction rates decrease faster than predicted from standard pressure solution creep flow laws. This inconsistency may indicate that calcite dissolution rates at grain contacts are more complex, and more time-dependent, than suggested by geometric models designed to predict grain contact stresses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Thermo-Hydro-Chemical Simulation of Mid-Ocean Ridge Hydrothermal Systems: Static 2D Models and Effects of Paleo-Seawater Chemistry

Decades of research have resulted in characterization of the ocean floor manifestations of mid-ocean ridge (MOR) hydrothermal systems, yet numerical models accounting for the connections between heat transfer, hydrology and geochemistry have been slow to develop. The Thermo-hydro-chemical code ToughReact can be used to describe the coupled effects of fluid flow, heat transfer, and fluid-rock chemical interactions that occur in MOR systems. We describe the results of 2-dimensional simulations of steady state flow in fractured diabase with mineral-fluid chemical reactions. Basal heating and specified permeability yield maximum temperature of 400°C. Total fluid flux and high fracture flow velocities are in accord with observations. Fluid chemistry, mineralogical changes and 87 Sr/ 86 Sr ratios can be compared to observations to assess and calibrate models. Simulated high temperature fracture fluids have Mg and SO 4 near zero, elevated Ca and 87 Sr/ 86 Sr of about 0.7040. Total alteration is 10%–50% for simple models of spreading. Anhydrite forms mainly near the base of the upwelling zone and results in substantial local fracture porosity reduction. A calibrated model is used to predict how Sr isotopes and other features of altered oceanic crust would be different in the Cretaceous (95 Ma) early Proterozoic (1,800 Ma) and Archean (3,800 Ma), when seawater may have had high Ca and Sr concentrations, lower pH, higher temperature, and lower Na, Mg, and SO 4 . The simulations are offered as a start on what ultimately may require a longer-term community effort to better understand the role of MOR thermo-hydro-chemical systems in Earth evolution.

58 GEOSCIENCES↗
DOE OSTI2022

New insights into Mn 2+ and Mg 2+ inhibition of calcite growth

Impurity ion and isotope partitioning into carbonate minerals provide a window into the molecular processes occurring at the fluid-mineral interface during crystal growth. Here, we employ calcium isotope fractionation together with process-based modeling to elucidate the mechanisms by which two divalent cations with starkly contrasting compatibility, magnesium and manganese, inhibit calcite growth and incorporate into the mineral lattice. Calcite growth inhibition by Mg 2+ is log-linear and K Mg is on the order of 0.02–0.03 throughout the range of {Mg 2+ }/{Ca 2+ } studied here (0.01–2.6). Mn 2+ exhibits much stronger log-linear growth rate inhibition at low Mn 2+ concentrations (fluid {Mn 2+ }/{Ca 2+ } = 0.001–0.02). Mn 2+ is readily incorporated into the calcite lattice to form a calcite-rhodochrosite solid solution, with large partition coefficients (K Mn 4.6–15.6) inversely correlated to growth rate. For both Mn 2+ and Mg 2+ , calcium isotope fractionation is found to be invariant with {Me 2+ }/{Ca 2+ } despite more than an order of magnitude decline in growth rate. This invariant Δ 44/40 Ca suggests that the presence of Mn 2 + or Mg 2+ does not significantly change the relative rates of Ca 2+ attachment and detachment at kink sites during growth, indicative of a dominantly kink blocking inhibition mechanism. Because the partitioning behavior dictates that Mn 2+ must attach to the surface significantly faster than Ca 2+ , attachment of Mn 2+ is likely to be as a non-monomer species such as an ion pair or possibly a larger polynuclear cluster. We propose that calcite growth rate inhibition by Mn is determined by the kinetics of carbonate attachment at Mn-occupied kink sites, potentially due to slow re-orientation kinetics of carbonate ions that have formed an inner-sphere complex with Mn 2+ at the surface but must reorient to incorporate into the lattice. We demonstrate that patterns in Mg 2+ partitioning and inhibition behavior are broadly consistent with growth inhibition driven by slow Mg 2+ -aquo complex dehydration relative to Ca 2+ but argue that this mechanism likely represents one endmember scenario, seen in Mg-calcite growth at low supersaturations and net precipitation rates. During growth at faster net precipitation rates, some portion of Mg 2+ is likely incorporated as a partially hydrated or otherwise complexed species, but calcite growth remains significantly inhibited by the kinetics of CO 3 2- attachment at Mg 2+ kink sites. These findings suggest a hybrid classical/nonclassical growth mechanism whereby Ca 2+ incorporates largely as a free ion at kink sites while Mn 2+ and some portion of Mg 2+ are incorporated via non-monomer attachment. This pattern may be generalizable; trace constituent cations with aquo-complex desolvation rates significantly slower than the mineral growth rate preferentially incorporate as a non-monomer species during otherwise classical crystal growth.

58 GEOSCIENCES↗
DOE OSTI2021

External Review Committee Report on the California Geological Survey

In May and June of 2021, the External Review Committee (ERC) assessed the activities and major programs of the California Geological Survey (CGS). The ERC reviewed materials from the five CGS program areas and upper management, as well as online presentations from program leaders and the California Department of Conservation (DOC), which oversees CGS.

58 GEOSCIENCES↗
DOE OSTI2021

Isotopic fractionation accompanying CO 2 hydroxylation and carbonate precipitation from high pH waters at The Cedars, California, USA

The Cedars ultramafic block hosts alkaline springs (pH > 11) in which calcium carbonate forms upon uptake of atmospheric CO 2 and at times via mixing with surface water. Here, these processes lead to distinct carbonate morphologies with “floes” forming at the atmosphere-water interface, “snow” of fine particles accumulating at the bottom of pools and terraced constructions of travertine. Floe material is mainly composed of aragonite needles despite CaCO 3 precipitation occurring in waters with low Mg/Ca (<0.01). Precipitation of aragonite is likely promoted by the high pH (11.5–12.0) of pool waters, in agreement with published experiments illustrating the effect of pH on calcium carbonate polymorph selection.

58 GEOSCIENCES↗
DOE OSTI2018

Kinetics of D/H isotope fractionation between molecular hydrogen and water

At equilibrium, the D/H isotope fractionation factor between H 2 and H 2 O (α H 2 O-H 2 (eq) ) is a sensitive indicator of temperature, and has been used as a geothermometer for natural springs and gas discharges. However, δD H 2 measured in spring waters may underestimate subsurface temperatures of origin due to partial isotopic re-equilibration during ascent and cooling. In this work, we present new experimental data on the kinetics of D–H exchange for H 2 dissolved in liquid water at temperatures below 100 °C. Comparing these results with published exchange rates obtained from gas phase experiments (100–400 °C), we derive a consistent activation energy of 52 kJ/mol, and the following rate expressions; ln k =9.186 - 6298/ T and k 1 = 9764.61[H 2 O] e-6298/ T where T is absolute temperature (K), k is the universal rate constant ([L/mol]/hr), and k 1 is a pseudo-first-order constant (hr -1 ) applicable to water-dominated terrestrial systems by constraining [H 2 O] as the density of H 2 O (in mol/L) at the P-T of interest. The density-dependent rate constant accounts for the kinetic disparity of D–H exchange with H 2 when dissolved in liquid H 2 O relative to a gas/steam phase, exemplifed by 1/ k 1 at 100 °C of ~2 days in liquid, versus ~7 yrs in saturated steam. This difference may explain the high variability of δDH 2 observed in fumarolic gases. Fluids convecting in the crust frequently reach T > 225 °C, where isotopic equilibrium is rapidly attained (<1 hr). We compare fractionation factors measured in natural fluids (α OBS ) with values expected for equilibrium at the T of acquisition. Where these values differ, we use kinetic models to estimate cooling rates during upward advection that account for the observed disequilibrium. Models fit to fluids from Yellowstone Park and the Lost City (deep-sea) vent field, both recovered at ~90 °C, require respective transit times of ~7 hrs and ~11 days between higher temperature reaction zones and the surface. Using estimates of subsurface depths of origin, however, suggests similar mean fluid flow rates (10 s of meters/hr). Additional complications must be considered when interpreting the δDH 2 of lower-temperature effluent. When applied to data from deep-sea hydrothermal systems, our kinetic models indicate microbial catalysis accelerates D–H exchange once fluids cool below ~60 °C. The H 2 measured in both continental alkaline springs and fracture fluids from Precambrian shield rock is likely produced at T < 100 °C, through processes such as serpentinization. In these settings, δDH 2 values appear closer to equilibrium with H 2 O than those from geothermal systems. Considering kinetic isotope effects may yield H 2 that is out of equilibrium when generated at lower temperatures, we calculate maximum (isothermal) times to apparent isotopic equilibrium of 1.3 yrs at 50 °C, 9 yrs at 25 °C, and 35 yrs at 10 °C. A similar calculation applied to Antarctic brines (-13 °C), where measured δDH 2 is far from equilibrium, yields ~350 yrs. This time is shorter than the fluids have been isolated (2.8 ka), suggesting kinetic isotope effects associated with H 2 destruction or loss via diffusion may also be possible.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Potassium and Calcium Isotopic Fractionation by Plants (Soybean [Glycine max], Rice [Oryza sativa], and Wheat [Triticum aestivum])

Here, we conducted hydroponic experiments growing soybean (Glycine max), rice (Oryza sativa), and wheat (Triticum aestivum) under K and Ca replete conditions to establish the degree of K isotopic fractionation by plants, and compare the isotopic fractionation of Ca and K. Each of the test plants displays fractionation relative to the growth solution favoring the light isotopes of K and Ca. The average δ 41 K values of the roots from the three plant species were similar, and have an overall average of -0.55 ± 0.24‰ 2s, while the overall average δ 44 Ca for roots is -0.67 ± 0.44. For leaves, the overall average of δ 41 K is -0.97 ± 0.4‰, compared to an overall average leaf δ 44 Ca of -0.83 ± 0.09‰. In the case of the soybean plants, the lightest K and Ca occurs in the stems with average δ 41 K of -1.31 ± 0.40‰ 2s and average δ 44 Ca of -1.20 ± 0.19 ‰ 2s. We present a simple box model involving the relative fluxes of K and its isotopic fractionation that reproduces our K isotopic observations and suggests a fractionation of ~0.8‰ with K uptake from solution by roots. Finally, directly comparing the per amu fractionation of K and Ca reveals an average factor of 2.05 ± 0.50 2s greater fractionation of K isotopes which may reflect their different roles and behaviors in plants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Authigenic carbonate formation rates in marine sediments and implications for the marine δ 13 C record

Carbon isotope (δ 13 C) variations measured in carbonates have been attributed to large-scale phenomena throughout Earth history, such as changes in atmospheric oxygen or global glaciations. Additionally, these interpretations follow from a model wherein the δ 13 C of marine dissolved inorganic carbon (DIC) is controlled by the relative sedimentary burial rates of biogenic carbonate (BC) and organic carbon (OC). A new model proposes authigenic carbonate (AC) as a third major sedimentary C pool, implying that δ 13 C anomalies are not necessarily indicative of extreme changes in the global carbon cycle and/or atmospheric oxygen. Two conditions are required for AC formation to significantly alter bulk carbonate δ 13 C: the AC isotopic composition must be at least ~3‰ different from that of BC and the AC/BC ratio must be >0.1. We use pore fluid Ca and Sr concentrations to estimate rates of AC formation in Late Cenozoic marine sediments, then calculate relative fractions of AC, OC, and BC. Today AC is not expected to constitute a significant fraction of total sedimentary carbon (AC+OC+BC) globally; however, there are modern sites where local conditions promote elevated AC/BC and anaerobic metabolisms can alter the δ 13 C of pore fluids. We investigate these sites to determine what conditions might enable AC to alter δ 13 C of marine DIC. Here, we find there is very little net addition of AC relative to BC, but large quantities of AC form today across many settings via recrystallization. In settings where remineralization of organic matter causes recrystallized carbonate to form with modified δ 13 C, AC/BC is generally too low for this recrystallization to significantly shift the δ 13 C of the bulk carbonate. However, exceptions are found in sites with very low BC and extensive methane oxidation, suggesting that this environment type would need to be globally extensive in the past in order for AC formation to change the δ 13 C of marine DIC.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2018

Supercritical CO 2 uptake by nonswelling phyllosilicates

Significance Reliable estimates of geologic carbon storage capacities (needed for policymaking) in both saline aquifers and unconventional gas/oil shales rely on understanding trapping mechanisms. We found that CO 2 uptake by muscovite (a common mineral and a conservative proxy for illite) far exceeds the maximum adsorption capacity of its external surface area. Our measurements using different methods collectively suggest that CO 2 enters muscovite interlayers without bulk interlayer expansion, contrary to the conventional wisdom that only swelling clays take up CO 2 into interlayers. Because the nonswelling illitic clay is the major clay mineral in deep subsurface tight rocks, their excess uptake of CO 2 may significantly contribute to CO 2 storage capacity and warrants further in-depth studies.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2017

Investigating calcite growth rates using a quartz crystal microbalance with dissipation (QCM-D)

Calcite precipitation plays a significant role in processes such as geological carbon sequestration and toxic metal sequestration and, yet, the rates and mechanisms of calcite growth under close to equilibrium conditions are far from well understood. In this study, a quartz crystal microbalance with dissipation (QCM-D) was used for the first time to measure macroscopic calcite growth rates. Calcite seed crystals were first nucleated and grown on sensors, then growth rates of calcite seed crystals were measured in real-time under close to equilibrium conditions (saturation index, SI = log ({Ca 2+ }/{CO 3 2– }/ K sp ) = 0.01–0.7, where {i} represent ion activities and K sp = 10 –8.48 is the calcite thermodynamic solubility constant). At the end of the experiments, total masses of calcite crystals on sensors measured by QCM-D and inductively coupled plasma mass spectrometry (ICP-MS) were consistent, validating the QCM-D measurements. Calcite growth rates measured by QCM-D were compared with reported macroscopic growth rates measured with auto-titration, ICP-MS, and microbalance. Calcite growth rates measured by QCM-D were also compared with microscopic growth rates measured by atomic force microscopy (AFM) and with rates predicted by two process-based crystal growth models. The discrepancies in growth rates among AFM measurements and model predictions appear to mainly arise from differences in step densities, and the step velocities were consistent among the AFM measurements as well as with both model predictions. Using the predicted steady-state step velocity and the measured step densities, both models predict well the growth rates measured using QCM-D and AFM. Furthermore, this study provides valuable insights into the effects of reactive site densities on calcite growth rate, which may help design future growth models to predict transient-state step densities.

58 GEOSCIENCES↗
DOE OSTI2017

Effect of paleoseawater composition on hydrothermal exchange in midocean ridges

Variations in the Mg, Ca, Sr, and SO 4 concentrations of paleoseawater can affect the chemical exchange between seawater and oceanic basalt in hydrothermal systems at midocean ridges (MOR). Here, we present a model for evaluating the nature and magnitude of these previously unappreciated effects, using available estimates of paleoseawater composition over Phanerozoic time as inputs and 87 Sr/ 86 Sr of ophiolite epidosites and epidote-quartz veins as constraints. The results suggest that modern hydrothermal fluids are not typical due to low Ca and Sr relative to Mg and SO 4 in modern seawater. At other times during the last 500 million years, particularly during the Cretaceous and Ordovician, hydrothermal fluids had more seawater-derived Sr and Ca, a prediction that is supported by Sr isotope data. The predicted 87 Sr/ 86 Sr of vent fluids varies cyclically in concert with ocean chemistry, with some values much higher than the modern value of ~0.7037. The seawater chemistry effects can be expressed in terms of the transfer efficiency of basaltic Ca and Sr to seawater in hydrothermal systems, which varies by a factor of ~1.6 over the Phanerozoic, with minima when seawater Mg and SO 4 are low. This effect provides a modest negative feedback on seawater composition and 87 Sr/ 86 Sr changes. For the mid-Cretaceous, the low 87 Sr/ 86 Sr of seawater requires either exceptionally large amounts of low-temperature exchange with oceanic crust or that the weathering flux of continentally derived Sr was especially small. Lastly, the model also has implications for MOR hydrothermal systems in the Precambrian, when low-seawater SO 4 could help explain low seawater 87 Sr/ 86 Sr.

58 GEOSCIENCES↗
DOE OSTI2017

The influence of seawater carbonate chemistry, mineralogy, and diagenesis on calcium isotope variations in Lower-Middle Triassic carbonate rocks

The geological calcium cycle is linked to the geological carbon cycle through the weathering and burial of carbonate rocks. As a result, calcium (Ca) isotope ratios ( 44 Ca/ 40 Ca, expressed as δ 44/40 Ca) can help to constrain ancient carbon cycle dynamics if Ca cycle behavior can be reconstructed. But, the δ 44/40 Ca of carbonate rocks is influenced not only by the δ 44/40 Ca of seawater but also by diagenetic processes and fractionation associated with carbonate precipitation. In this study, we investigate the dominant controls on carbonate δ 44/40 Ca in Upper Permian to Middle Triassic limestones (ca. 253 to 244 Ma) from south China and Turkey. This time interval is ideal for assessing controls on Ca isotope ratios in carbonate rocks because fluctuations in seawater δ 44/40 Ca may be expected based on several large carbon isotope (δ 13 C) excursions ranging from -2 to + 8‰. Parallel negative δ 13 C and δ 44/40 Ca excursions were previously identified across the end-Permian extinction horizon. Here, we find a second negative excursion in δ 44/40 Ca of ~ 0.2‰ within Lower Triassic strata in both south China and Turkey; however, this excursion is not synchronous between regions and thus cannot be interpreted to reflect secular change in the δ 44/40 Ca of global seawater. Additionally, δ 44/40 Ca values from Turkey are consistently 0.3‰ lower than contemporaneous samples from south China, providing further support for local or regional influences. By measuring δ 44/40 Ca and Sr concentrations ([Sr]) in two stratigraphic sections located at opposite margins of the Paleo-Tethys Ocean, we can determine whether the data represent global conditions (e.g., secular variations in the δ 44/40 Ca of seawater) versus local controls (e.g., original mineralogy or diagenetic alteration). The [Sr] and δ 44/40 Ca data from this study are best described statistically by a log-linear correlation that also exists in many previously published datasets of various geological ages. By using a model of early marine diagenetic water-rock interaction, we illustrate that this general correlation can be explained by the chemical evolution of bulk carbonate sediment samples with different initial mineralogical compositions that subsequently underwent recrystallization. Although early diagenetic resetting and carbonate mineralogy strongly influence the carbonate δ 44/40 Ca values, the relationship between [Sr] and δ 44/40 Ca holds potential for reconstructing first-order secular changes in seawater δ 44/40 Ca composition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗