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DOE OSTI2010

Observation of new neutron-rich isotopes at the NSCL

Recently, increased primary beam intensities at the National Superconducting Cyclotron Laboratory (NSCL) at Michigan State University and advances in experimental techniques allowed probing further into unknown regions of the table of the isotopes with fragmentation and in-flight fission reactions. Recent measurements at the NSCL have demonstrated that primary beams of {sup 48}Ca at 141 MeV/u and {sup 76}Ge at 132 MeV/u can be used to produce new isotopes {sup 40}Mg, {sup 42,43}Al, {sup 44}Si, {sup 52}Ar, {sup 50}Cl, {sup 52,53}Ar, {sup 55,56}K, {sup 57,58}Ca, {sup 59,60,61}Sc, {sup 62,63}Ti, {sup 65,66}V, {sup 68}Cr, {sup 70}Mn in the proximity of the neutron dripline. Also, experiments with {sup 238}U(81 MeV/u) and {sup 208}Pb(86 MeV/u) beams in order to measure production yields and possibly observe several neutron rich isotopes in the first time have recently been performed at the NSCL. A search for new neutron-rich isotopes with {sup 48}Ca and {sup 76}Ge beams was carried out using the recently developed two-stage fragment separator technique.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2010

Production of neutron-rich Ca, Sn, and Xe isotopes in transfer-type reactions with radioactive beams

The production cross sections of neutron-rich isotopes {sup 52,54,56,58,60}Ca, {sup 136,138,140,142}Sn, and {sup 146,148,150,152}Xe are predicted for future experiments in the diffusive multinucleon transfer reactions {sup 86,90,92,94}Kr, {sup 124,130,132,134}Sn, {sup 136,140,142,146}Xe, and {sup 138,144,146}Ba+{sup 48}Ca with stable and radioactive beams at incident energies close to the Coulomb barrier. Because of the small cross sections, the production of neutron-rich isotopes requires the optimal choice of projectile-target combinations and bombarding energies.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2010

Nuclear Data Sheets for A = 58

The evaluated spectroscopic data are presented for known nuclides of mass 58 (Ca,Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn). Excited-state data are nonexistent for {sup 58}Ca, {sup 58}Sc, and {sup 58}Zn; and very scarce for {sup 58}Ti and {sup 58}V, with only one tentative level in each case. Except for half-lives, no other radioactive decay data are available for the decay of {sup 58}Sc and {sup 58}Ti. The radioactive decays of {sup 58}V, {sup 58}Cr and {sup 58}Zn are not considered as well established. Superdeformed structures are known in {sup 58}Ni (two bands) and in {sup 58}Cu (one band). Prompt proton decay of high-spin states in 58Ni for eight levels and prompt {alpha} decay for two states have been identified. In {sup 58}Cu, one high-spin state decays by prompt proton emission. Very complex high-spin structures are now known for {sup 58}Ni from the work by 2009Jo03.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2013

Dynamic and impact contact mechanics of geologic materials: Grain-scale experiments and modeling

High fidelity treatments of the generation and propagation of seismic waves in naturally occurring granular materials is becoming more practical given recent advancements in our ability to model complex particle shapes and their mechanical interaction. Of particular interest are the grain-scale processes that are activated by impact events and the characteristics of force transmission through grain contacts. To address this issue, we have developed a physics based approach that involves laboratory experiments to quantify the dynamic contact and impact behavior of granular materials and incorporation of the observed behavior indiscrete element models. The dynamic experiments do not involve particle damage and emphasis is placed on measured values of contact stiffness and frictional loss. The normal stiffness observed in dynamic contact experiments at low frequencies (e.g., 10 Hz) are shown to be in good agreement with quasistatic experiments on quartz sand. The results of impact experiments - which involve moderate to extensive levels of particle damage - are presented for several types of naturally occurring granular materials (several quartz sands, magnesite and calcium carbonate ooids). Implementation of the experimental findings in discrete element models is discussed and the results of impact simulations involving up to 5 Multiplication-Sign 105 grains are presented.

58 GEOSCIENCES↗

DOE OSTI2020

Semiquantitative Estimates of Rainfall Variability During the 8.2 kyr Event in California Using Speleothem Calcium Isotope Ratios

A multiproxy record from a fast-growing stalagmite reveals variable hydroclimate on the California coast across the 8.2 kyr event and a precursor event likely caused by initial drainage of proglacial Lake Agassiz. Using speleothem δ 44 Ca, we develop the first semiquantitative estimates of paleorainfall variability for California through calibration with measurements of the modern climate and cave environment. We find that the magnitude of rainfall variability during the 8.2 kyr event approached the multiyear variability observable in the recent past (1950–2019) and the magnitude of variability during the precursor event likely exceeded this range. Additionally, we observe other instances of multidecadal variability comparable in magnitude to the precursor event during the record. Finally, our work suggests that speleothem calcium isotope ratios are a powerful semiquantitative means to reconstruct paleorainfall, although numerous factors must be assessed in each cave system before applying this approach.

58 GEOSCIENCES↗

DOE OSTI2011

Ion exchange phenomena

Ion exchange phenomena involve the population of readily exchangeable ions, the subset of adsorbed solutes that balance the intrinsic surface charge and can be readily replaced by major background electrolyte ions (Sposito, 2008). These phenomena have occupied a central place in soil chemistry research since Way (1850) first showed that potassium uptake by soils resulted in the release of an equal quantity of moles of charge of calcium and magnesium. Ion exchange phenomena are now routinely modeled in studies of soil formation (White et al., 2005), soil reclamation (Kopittke et al., 2006), soil fertilitization (Agbenin and Yakubu, 2006), colloidal dispersion/flocculation (Charlet and Tournassat, 2005), the mechanics of argillaceous media (Gajo and Loret, 2007), aquitard pore water chemistry (Tournassat et al., 2008), and groundwater (Timms and Hendry, 2007; McNab et al., 2009) and contaminant hydrology (Chatterjee et al., 2008; van Oploo et al., 2008; Serrano et al., 2009).

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2011

Framboidal iron oxide: Chondrite-like material from the black mat, Murray Springs, Arizona

At the end of the Pleistocene a Younger Dryas black mat was deposited on top of the Pleistocene sediments inmany parts of North America. A study of themagnetic fraction ({approx}10,900 50 B.P.) fromthe basal section of the black mat at Murray Springs, AZ revealed the presence of amorphous iron oxide framboids in a glassy iron-silica matrix. These framboids are very similar in appearance and chemistry to those reported from several types of carbonaceous chondrites. The glass contains iron, silicon, oxygen, vanadium and minor titanium, while the framboidal particles contain calcium as well. The major element chemistry of both the spherules and the glass matrix are consistent with the chemistry of material associated with meteorite impact sites and meteorites. Electron microscopy confirms that the glassy material is indeed amorphous, and also shows that what appear to be individual oxide particles are amorphous as well. The latter appears consistent with their overall morphology that, while euhedral, typically shows significant fracture. Based on these data, we argue that these particles are the product of a hypervelocity impact.

58 GEOSCIENCES↗

DOE OSTI2011

Geophysical Monitoring and Reactive Transport Modeling of Ureolytically-Driven Calcium Carbonate Precipitation

Ureolytically-driven calcium carbonate precipitation is the basis for a promising in-situ remediation method for sequestration of divalent radionuclide and trace metal ions. It has also been proposed for use in geotechnical engineering for soil strengthening applications. Monitoring the occurrence, spatial distribution, and temporal evolution of calcium carbonate precipitation in the subsurface is critical for evaluating the performance of this technology and for developing the predictive models needed for engineering application. In this study, we conducted laboratory column experiments using natural sediment and groundwater to evaluate the utility of geophysical (complex resistivity and seismic) sensing methods, dynamic synchrotron x-ray computed tomography (micro-CT), and reactive transport modeling for tracking ureolytically-driven calcium carbonate precipitation processes under site relevant conditions. Reactive transport modeling with TOUGHREACT successfully simulated the changes of the major chemical components during urea hydrolysis. Even at the relatively low level of urea hydrolysis observed in the experiments, the simulations predicted an enhanced calcium carbonate precipitation rate that was 3-4 times greater than the baseline level. Reactive transport modeling results, geophysical monitoring data and micro-CT imaging correlated well with reaction processes validated by geochemical data. In particular, increases in ionic strength of the pore fluid during urea hydrolysis predicted by geochemical modeling were successfully captured by electrical conductivity measurements and confirmed by geochemical data. The low level of urea hydrolysis and calcium carbonate precipitation suggested by the model and geochemical data was corroborated by minor changes in seismic P-wave velocity measurements and micro-CT imaging; the latter provided direct evidence of sparsely distributed calcium carbonate precipitation. Ion exchange processes promoted through NH4+ production during urea hydrolysis were incorporated in the model and captured critical changes in the major metal species. The electrical phase increases were potentially due to ion exchange processes that modified charge structure at mineral/water interfaces. Our study revealed the potential of geophysical monitoring for geochemical changes during urea hydrolysis and the advantages of combining multiple approaches to understand complex biogeochemical processes in the subsurface.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Thermally Insulating, Thermal Shock Resistant Calcium Aluminate Phosphate Cement Composites for Reservoir Thermal Energy Storage

This paper presents the use of hydrophobic silica aerogel (HSA) and hydrophilic fly ash cenosphere (FCS) aggregates for improvements in the thermal insulating and mechanical properties of 100- and 250 °C-autoclaved calcium aluminate phosphate (CaP) cement composites reinforced with micro-glass (MGF) and micro-carbon (MCF) fibers for deployment in medium- (100 °C) and high-temperature (250 °C) reservoir thermal energy storage systems. The following six factors were assessed: (1) Hydrothermal stability of HSA; (2) Pozzolanic activity of the two aggregates and MGF in an alkali cement environment; (3) CaP cement slurry heat release during hydration and chemical reactions; (4) Composite phase compositions and phase transitions; (5) Mechanical behavior; (6) Thermal shock (TS) resistance at temperature gradients of 150 and 225 °C. The results showed that hydrophobic trimethylsilyl groups in trimethylsiloxy-linked silica aerogel structure were susceptible to hydrothermal degradation at 250 °C. This degradation was followed by pozzolanic reactions (PR) of HSA, its dissolution, and the formation of a porous microstructure that caused a major loss in the compressive strength of the composites at 250 °C. The pozzolanic activities of FCS and MGF were moderate, and they offered improved interfacial bonding at cement-FCS and cement-MGF joints through a bridging effect by PR products. Despite the PR of MGF, both MGF and MCF played an essential role in minimizing the considerable losses in compressive strength, particularly in toughness, engendered by incorporating weak HSA. As a result, a FCS/HSA ratio of 90/10 in the CaP composite system was identified as the most effective hybrid insulating aggregate composition, with a persistent compressive strength of more than 7 MPa after three TS tests at a 150 °C temperature gradient. This composite displayed thermal conductivity of 0.28 and 0.35 W/mK after TS with 225 and 150 °C thermal gradients, respectively. These values, below the TC of water (TC water = 0.6 W/mK), were measured under water-saturated conditions for applications in underground reservoirs. However, considering the hydrothermal disintegration of HSA at 250 °C, these CaP composites have potential applications for use in thermally insulating, thermal shock-resistant well cement in a mid-temperature range (100 to 175 °C) reservoir thermal energy storage system.

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↗

DOE OSTI2025

Sulfate Promotes Compact CaCO 3 Formation and Protects Portland Cement from Supercritical CO 2 Attack

Supercritical (sc) CO 2 in geologic carbon sequestration (GCS) can chemically and mechanically deteriorate wellbore cement, raising concerns for long-term operations. In contrast to the conventional view of “sulfate attack” on cement, we found that adding 0.15 M sulfate to the acidic brine can significantly reduce the impact of scCO 2 attack on Portland cement, resulting in stronger cement than that found in a sulfate-free system. Scanning electron microscopy revealed a decreased total attack depth in reacted cement in the presence of sulfate. With a newly defined minimum porosity term in reactive transport modeling, our model suggests that sulfate caused CaCO 3 to fill more nanopore spaces in the cement. Small angle X-ray scattering experiments also showed that sulfate can decrease the pore sizes of the carbonate layer. The results suggest that the interactions between sulfate and cement can generate a less porous CaCO 3 layer, which better resists acidic brine. Using this mechanism as a proof-of-concept, we tested the incorporation of sodium sulfate into Portland cement and synthesized new cement composites that show stronger resistance against scCO 2 attacks. Finally, these newly discovered interfacial interactions between CaCO 3 and sulfate provide new insights into engineering mechanically strong and green materials for safer GCS.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2010

Electronic spin and valence states of Fe in CaIrO{sub 3} - type silicate post-perovskite in the earth's lowestmost mantle.

The electronic spin and valence states of Fe in post-perovskite ((Mg{sub 0.75}Fe{sub 0.25})SiO{sub 3}) have been investigated by synchrotron X-ray diffraction, Moessbauer and X-ray emission spectroscopy at 142 GPa and 300 K. Rietveld refinement of the X-ray diffraction patterns revealed that our sample was dominated by CaIrO{sub 3}-type post-perovskite. Combined Moessbauer and X-ray emission results show that Fe in post-perovskite is predominantly Fe{sup 2+} (70%) in the intermediate-spin state with extremely high quadrupole splitting of 3.77(25) mm/s. The remaining 30% Fe can be assigned to two sites. Compared with recent studies, our results indicate that the intermediate-spin Fe{sup 2+} is stabilized in CaIrO{sub 3}-type post-perovskite over a wide range of Fe content, whereas the low-spin Fe{sup 3+} is more dominant in the 2 x 1 kinked post-perovskite structure. The characterization of these structural and compositional effects on the spin and valence states of Fe in post-perovskite can help in understanding the geochemical and geophysical behavior of the core-mantle region.

58 GEOSCIENCES↗

DOE OSTI2022

High-Resolution Transmission Electron Microscopy Study of a Powder River Basin Coal-Derived Fly Ash

Examination of a fly ash derived from the combustion of a low-S, subbituminous Powder River Basin coal by Scanning Electron Microscopy (SEM) and High-resolution Transmission Electron Microscopy (HRTEM), both supplemented by Energy-dispersive X-ray spectroscopy (EDS), showed that the fly ashes were dominated by amorphous phases, Ca-rich plagioclase feldspars, Mg-rich phases, complex Ca-Mg-Al-Si-Ti-Fe grains, and trace amounts of REE-rich particles. Many of the particles were rimmed by a Ca-S, possibly a sulfate. HRTEM-EDS examination of a REE-rich particle proved it to be a mix of light- and heavy-rare earth minerals mixed with amorphous phases.

58 GEOSCIENCES↗

DOE OSTI2012

REACTIVE TRANSPORT MODELING USING A PARALLEL FULLY-COUPLED SIMULATOR BASED ON PRECONDITIONED JACOBIAN-FREE NEWTON-KRYLOV

Systems of multicomponent reactive transport in porous media that are large, highly nonlinear, and tightly coupled due to complex nonlinear reactions and strong solution-media interactions are often described by a system of coupled nonlinear partial differential algebraic equations (PDAEs). A preconditioned Jacobian-Free Newton-Krylov (JFNK) solution approach is applied to solve the PDAEs in a fully coupled, fully implicit manner. The advantage of the JFNK method is that it avoids explicitly computing and storing the Jacobian matrix during Newton nonlinear iterations for computational efficiency considerations. This solution approach is also enhanced by physics-based blocking preconditioning and multigrid algorithm for efficient inversion of preconditioners. Based on the solution approach, we have developed a reactive transport simulator named RAT. Numerical results are presented to demonstrate the efficiency and massive scalability of the simulator for reactive transport problems involving strong solution-mineral interactions and fast kinetics. It has been applied to study the highly nonlinearly coupled reactive transport system of a promising in situ environmental remediation that involves urea hydrolysis and calcium carbonate precipitation.

58 GEOSCIENCES↗

DOE OSTI2010

Hanford 100-N Area In Situ Apatite and Phosphate Emplacement by Groundwater and Jet Injection: Geochemical and Physical Core Analysis

The purpose of this study is to evaluate emplacement of phosphate into subsurface sediments in the Hanford Site 100-N Area by two different technologies: groundwater injection of a Ca-citrate-PO4 solution and water-jet injection of sodium phosphate and/or fish-bone apatite. In situ emplacement of phosphate and apatite adsorbs, then incorporates Sr-90 into the apatite structure by substitution for calcium. Overall, both technologies (groundwater injection of Ca-citrate-PO4) and water-jet injection of sodium phosphate/fish-bone apatite) delivered sufficient phosphate to subsur¬face sediments in the 100-N Area. Over years to decades, additional Sr-90 will incorporate into the apatite precipitate. Therefore, high pressure water jetting is a viable technology to emplace phosphate or apatite in shallow subsurface sediments difficult to emplace by Ca-citrate-PO4 groundwater injections, but further analysis is needed to quantify the relevant areal extent of phosphate deposition (in the 5- to 15-ft distance from injection points) and cause of the high deposition in finer grained sediments.

58 GEOSCIENCES↗

DOE OSTI2018

Mass balance implies Holocene development of a low-relief karst patterned landscape

We constructed mass balances of both calcium and phosphorus for two watersheds in Big Cypress National Preserve in southwest Florida (USA) to evaluate the time scales over which its striking landscape pattern developed. This low-relief carbonate landscape is dotted with evenly spaced, evenly sized, shallow surface depressions that annually fill with surface water and thus support wetland ecosystems (e.g. cypress domes) embedded in a pine-dominated upland matrix with exposed bedrock. Local and landscape scale feedbacks between hydrology, ecological dynamics and limestone dissolution are hypothesized to explain this karst dissolution patterning. This hypothesis requires the region to be wet enough to initiate surface water storage, which constrains landscape formation to interglacial periods. The time scale therefore would be relatively recent if creation of the observed pattern occurred in the current interglacial period (i.e. Holocene), and older time scales could reflect inherited patterns from previous inter-glacial periods, or from other processes of abiotic karstification. We then determined phosphorus stocks across four landscape compartments and estimated the limestone void space (i.e., wetland depression volume) across the landscape to represent cumulative calcium export. We calculated fluxes in (e.g., atmospheric deposition) and out (i.e., solute export) of the landscape to determine landscape denudation rates through mass balance. Comparing stocks and annual fluxes yielded independent estimates of landscape age from the calcium and phosphorus budgets. Our mass balance results indicate that the landscape began to develop in the early-mid Holocene (12,000–5000 ybp). Radiocarbon dating estimates implied similar rates of dissolution (~1 m per 3000–3500 years), and were in agreement with Holocene origin. This supports the hypothesis that ecohydrologic feedbacks between hydrology and vegetation occurring during the present interglacial period are sufficient to shape this landscape into the patterns we see today, and more broadly suggests the potential importance of biota in the development of macro-scale karst features.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2025

Impact of Interfacial Structure on Heterogeneous Nucleation of Amorphous Carbonates

For this work, classical molecular dynamics simulations were performed to provide physical insight into the impact of interfacial structure on the heterogeneous nucleation of amorphous calcium carbonate (ACC, CaCO 3 ·H 2 O) and amorphous magnesium carbonate (AMC, MgCO 3 ·H 2 O) by using α-quartz as a model substrate. Interfacial structure and energies were computed for ACC and AMC in contact with the (100), (001), and (101) α-quartz surfaces. The simulations showed α-quartz surfaces drew water molecules out of the carbonate nuclei to form a partial hydration layer. The formation of a partial hydration layer and its disruption to the ACC/AMC structure meant the α-quartz–ACC/AMC interfaces were not energetically favored relative to separate α-quartz–water and ACC/AMC–water interfaces and, thus, homogeneous ACC/AMC nucleation was favored over heterogeneous nucleation. The CMD simulations hence provided an atomic-level explanation for a reported nonclassical growth mechanism whereby carbonate minerals grow via homogeneous nucleation and subsequent surface attachment of amorphous intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗