Oxygen isotope analyses (δO18) of micas that were artificially depleted in K+ indicate little or no isotope exchange during the transformation. The oxidation of iron in K-depleted, iron-rich micas by H2O2 treatment resulted in 1.6 to 4.6% decrease in SO18 due to the fact that the equilibrium fractionation factor is less than the initial difference between the starting δO18 of the fluid and micas. The oxygen isotope ratio of a saponite formed by the weathering of phlogopite showed a 9.7% increase in δO18 due to authigenic recrystallization. These results suggest that oxygen isotope ratios can be used to determine the nature of chemical transformation during the weathering of mica to vermiculite and/or smectite.

The Madayi clay deposit consists of a thick sequence of residual white kaolinitic clay underlying the sedimentary Warkallai Formation, which includes gray carbonaceous kaolinitic clays, lignite, ferruginous kaolinitic clays, laterite and bauxite with ferricretes. The conditions of clay genesis and the economic significance of the major residual kaolin seam have been investigated. The raw clay and <2 μm fractions were subjected to X-ray diffraction (XRD), chemical analysis, differential thermal analysis (DTA), Fourier transform infrared (FTIR) spectroscopic and scanning electron microscopic (SEM) studies. The firing behavior of the <45 μm fraction of the major residual clay sequence (L), was investigated systematically to determine the potential industrial use of this kaolin.

Geochemical and morphological studies of different strata indicate the following conditions for clay formation. (1) intense lateritized weathering conditions for kaolinization of the residual white clay from parent quartzo-felspathic mica-gneiss. (2) reducing environment for the gray carbonaceous layers; an. (3) oxidizing environment for the uppermost hematite-rich ferruginous clay. Pyrite/marcasite enriched detrital gray carbonaceous clay shows two distinct environments for in situ kaolinite crystallization. (1) within plant fossils influenced by the high organic content and FeS2 leaching; and (2) precipitation from solution.

Incomplete kaolinization of white residual clay is evident from the presence of pyrophyllite, muscovite with lenticular cleavage void and a lower percentage of fines (<2 μm). The plant fossils from the uppermost portion of residual clay show pyrite mineralization. The Hinckley Index, FTIR and rare earth analysis point towards diverse geochemical environments of deposition and technological evaluation indicates its suitability for application in the ceramics industry.

Ice-crystal fabric can induce mechanical anisotropy that significantly affects flow, but ice-flow models generally do not include fabric development or its effect upon flow. Here, we incorporate a new spectral expansion of fabric, and more complete description of its evolution, into the ice-flow model Elmer/Ice. This approach allows us to model the effect of both lattice rotation and migration recrystallization on large-scale ice flow. The fabric evolution is coupled to flow using an unapproximated non-linear orthotropic rheology that better describes deformation when the stress and fabric states are misaligned. These improvements are most relevant for simulating dynamically interesting areas, where recrystallization can be important, tuning data are scarce and rapid flow can lead to misalignment between stress and fabric. We validate the model by comparing simulated fabric to ice-core and phase-sensitive radar measurements on a transect across Dome C, East Antarctica. With appropriately tuned rates for recrystallization, the model is able to reproduce observations of fabric. However, these tuned rates differ from those previously derived from laboratory experiments, suggesting a need to better understand how recrystallization acts differently in the laboratory compared to natural settings.

Most theoretical descriptions of stresses induced by freezing are rooted in the (generalized) Clapeyron equation, which predicts the pressure that a solid can exert as it cools below its melting temperature. This equation is central for topics ranging beyond glaciology to geomorphology, civil engineering, food storage and cryopreservation. However, it has inherent limitations, requiring isotropic solid stresses and conditions near bulk equilibrium. Here, we examine when the Clapeyron equation is applicable by providing a rigorous derivation that details all assumptions. We demonstrate the natural extension for anisotropic stress states, and we show how the temperature and pressure ranges for validity depend on well-defined material properties. Finally, we demonstrate how the range of applicability of the (linear) Clapeyron equation can be extended by adding higher-order terms, yielding results that are in good agreement with experimental data for the pressure melting of ice.

We compare different ways the bulk flow nonlinearity of glacier ice can be captured in an orthotropic rheology. Specifically, we compare the unapproximated orthotropic rheology, derived from plastic potential theory, to existing approximations that assume either the nonlinear viscosity or fluidity is identical to that of Glen's isotropic flow law. We find, overall, a reasonable agreement between the three orthotropic rheologies, and with existing Dye 3 ice-core deformation tests, although assuming Glen's viscosity provides the best approximation to the unapproximated rheology. Our results therefore suggest that previous studies based on either approximation to the orthotropic rheology are on relatively safe ground in the sense that both approximations generally agree with the unapproximated rheology and experimental data. Finally, we provide the forward and inverse analytical forms of all three rheologies for use in future numerical ice-flow modelling.

The vermetidae fossils of Petaloconchus varians, formed by calcium carbonate, associated with their radiocarbon ages, are the most accurate indicators of paleo sea level due to their restricted occupation in the intertidal zone in the rocky shore. However, the recrystallization of minerals can affect these age calculations and, consequently, the interpretation of the data. The aim of this study is to present new indicators of paleo sea-level changes in Southeast Brazil for the last 6000 years contributing to fill the data gap for the late Holocene. The influence of the recrystallization process was successfully resolved using the CarDS protocol, enabling the separation of the original aragonite fraction by density, prior to radiocarbon dating. This avoids the rejuvenation of ages and ensures greater efficiency for data interpretation. Paleo sea-level indicators were able to show a progressive increase in sea level up to the transgressive maximum of 4.15 m in 3700 BP years, followed by a regression to the current zero. This regression seems to have in addition, here we reinforce the reliability of the use of fossil vermetids as indicators of sea-level fluctuations.

Water-filled boreholes in cold ice refreeze in hours to days, and prior attempts to keep them open with antifreeze resulted in a plug of slush effectively freezing the hole even faster. Thus, antifreeze as a method to stabilize hot-water boreholes has largely been abandoned. In the hot-point drilling case, no external water is added to the hole during drilling, so earlier antifreeze injection is possible while the drill continues melting downward. Here, we use a cylindrical Stefan model to explore slush formation within the parameter space representative of hot-point drilling. We find that earlier injection timing creates an opportunity to avoid slush entirely by injecting sufficient antifreeze to dissolve the hole past the drilled radius. As in the case of hot-water drilling, the alternative is to force mixing in the hole after antifreeze injection to ensure that ice refreezes onto the borehole wall instead of within the solution as slush.

Two samples collected from the phosphogypsum deposits of the chemical products industry Elixir Prahovo (Serbia) were subjected to a recrystallization experiment performed over several repeated cycles. In these tests, phosphogypsum was separated into recrystallized (purified) gypsum, insoluble residue and supernatant. Both raw phosphogypsum and recrystallized gypsum were examined using inductively coupled plasma optical emission spectrometry, X-ray diffraction and scanning electron microscopy with energy-dispersive spectrometry. The activity concentrations of 238U, 235U, 226Ra, 210Pb, 232Th and 40K were investigated using γ-ray spectrometry. Based on the activity concentration results, a number of radiometric parameters were calculated for the original and recrystallized phosphogypsum (i.e. radium equivalent activity, γ indices for construction materials, α index and external and internal hazard indices). Raw phosphogypsum samples showed greater mean activity concentration levels of 238U and 226Ra than the international recommended limits, while the recrystallized gypsum demonstrated notably lower activity concentrations for these two isotopes. The activity concentration of 226Ra in recrystallized gypsum is ~6 times lower than in raw phosphogypsum. Therefore, recrystallized gypsum does not present a radiation hazard when used as a building material, while raw phosphogypsum meets the requirements only for road construction materials.

Identifying and tackling recrystallization is a critical factor in the reliable radiocarbon (14C) dating of carbonates, since exogenous carbon can be incorporated and thus mask the real age of the samples. Vermetids are among the most important bioindicators used for paleo sea-level reconstruction, and the accuracy of their chronology can significantly impact sea-level curves. Age differences larger than 1 14C kyr before and after acid etching, combined with X-ray diffraction (XRD) analysis that indicates a significant amount of calcite still remains in the shell, led us to apply the previously developed carbonate density separation protocol (CarDS). Using a solution of sodium polytungstate, with density of 2.80 g/cm3, we successfully separated different carbonate fractions for a set of 10 vermetid samples from the coast of Rio de Janeiro, southeast of Brazil. Each separation was verified by XRD analysis and the 14C concentrations of different fractions were compared. The results show that the calcite fraction in the studied vermetid samples varied from 12 to 63% and aragonite fraction ages are up to 2 14C kyr older than the raw samples, thus confirming the efficacy of CarDS in removing young carbonates and the importance of density separation to vermetids prior to accelerator mass spectrometry (AMS) dating.

Differences in pipe wall microstructure at various positions throughout the wall thickness of high strength aluminum alloy thick-wall pipes produced by reverse hot extrusion were investigated. The microstructures of the inner wall (IW), outer wall (OW), and half wall (HW) were compared. Further, heterogeneity in the mechanical properties of the pipe throughout the wall thickness was also investigated. Results revealed that the volume fraction of precipitation was highest at the HW position because of the higher Zn and Mg contents. Further, approximately 26% of grains were recrystallized in the OW position due to the greater strain during extrusion, while the recrystallization fractions of the IW and HW positions were 13% and 21%, respectively. The effects of precipitation strengthening and deformation strengthening contribute to the highest ultimate tensile strength and Vickers hardness of the HW position, and to the higher elongation of the IW and OW positions.

In the present work, a β-Ti alloy (Ti–15V–3Sn–3Cr–3Al) was unidirectionally cold rolled to 80% thickness reduction, followed by recrystallization at two temperatures: (i) 1013 K and (ii) 1053 K. The microstructural developments were studied using light optical microscopy, scanning electron microscopy X-ray peak profile analysis, and electron backscattered diffraction. The bulk texture of deformed and fully recrystallized samples was studied using X-ray diffraction. The deformed microstructures showed the presence of high fraction of shear bands, and these bands were preferentially formed in γ-fiber grains than in the grains with other orientations. Cold rolled β-Ti alloy samples were fully recrystallized in 10 min at 1053 K and in 90 min at 1013 K. Strong α- and γ-fibers were formed after 80% cold rolling, while strong discontinuous γ-fiber (with very strong {111}〈112〉 component) was formed after complete recrystallization. Oriented nucleation was found to be the dominant mechanism for the development of recrystallization texture.

Employing atomic-scale simulations, the response of a high-angle grain boundary (GB), the soft/hard GB, against external loading was systematically investigated. Under tensile loading close to the hard orientation, strain-induced dynamic recrystallization was observed to initiate through direct soft-to-hard grain reorientation, which was triggered by stress mismatch, inhibited by surface tension from the soft-hard GB, and proceeded by interface ledges. Such grain reorientation corresponds with expansion and contraction of the hard grain along and perpendicular to the loading direction, respectively, accompanied by local atomic shuffling, providing relatively large normal strain of 8.3% with activation energy of 0.04 eV per atom. Tensile strain and residual dislocations on the hard/soft GB facilitate the initiation of dynamic recrystallization by lowering the energy barrier and the critical stress for grain reorientation, respectively.

Allanite is a common accessory mineral in igneous rocks. Allanite becomes metamict over geological time-scales as a result of the α-decay of radioactive elements in the crystal structure. This study focuses on the recrystallization of metamict allanite from Savvushka, Russia. The structural recovery produced by annealing was investigated by X-ray powder diffraction, single-crystal synchrotron X-ray diffraction and infrared spectroscopy. A kinetic analysis is presented that shows that the recrystallization process proceeds by at least two different mechanisms.

This study describes results from mechanical tests conducted on magnesium single crystals in comparison with polycrystalline magnesium. It was found by impact testing that the magnesium single crystal is highly ductile due to energy absorption by twinning and slip, while the polycrystalline samples fracture easily upon impact. Compressive testing along two orthogonal directions at low plastic strains was also performed. The microstructure studies by electron backscatter diffraction and XRD pole figure analysis revealed profuse ( $10\overline12$ ) twinning when compression is done along the growth plane (72 16 $\overline {88}$ 62). The twinning and interaction between different twin modes resulted in incipient recrystallization at strains as low as 8% at room temperature. Compression along the nearly orthogonal plane (2 2 $\bar{4}$ 15) was marked by a much lower degree of both twinning and recrystallization. The variation in microstructural response with the orientation of loading allows for a wide range for tailoring mechanical properties of pure magnesium single crystals without any need of alloying.

We analyzed the dielectric spectra (0.1 Hz–1 MHz) of 49 firn and ice samples from ice sheets and glaciers to better understand how differing ice formation and evolution affect electrical properties. The dielectric relaxation of ice is well known and its characteristic frequency increases with the concentration of soluble impurities in the ice lattice. We found that meteoric ice and firn generally possess two such relaxations, indicating distinct crystal populations or zonation. Typically, one population is consistent with that of relatively pure ice, and the other is significantly more impure. However, high temperatures (e.g. temperate ice), long residence times (e.g. ancient ice from Mullins Glacier, Antarctica) or anomalously high impurity concentrations favor the development of a single relaxation. These relationships suggest that annealing causes two dielectrically distinct populations to merge into one population. The dielectric response of temperate ice samples indicates increasing purity with increasing depth, suggesting ongoing rejection of impurities from the lattice. Separately, subglacially (lake) frozen samples from the Vostok (Antarctica) 5G ice core possess a single relaxation whose variable characteristic frequency likely reflects the composition of the source water. We conclude that multi-frequency methods are essential to dielectric discrimination between different types of glacier ice.

The observable microstructures in ice are the result of many dynamic and competing processes. These processes are influenced by climate variables in the firn. Layers deposited in different climate regimes may show variations in fabric which can persist deep into the ice sheet; fabric may ‘remember’ these past climate regimes. We model the evolution of fabric variations below the firn–ice transition and show that the addition of shear to compressive-stress regimes preserves the modeled fabric variations longer than compression-only regimes, because shear drives a positive feedback between crystal rotation and deformation. Even without shear, the modeled ice retains memory of the fabric variation for 200 ka in typical polar ice-sheet conditions. Our model shows that temperature affects how long the fabric variation is preserved, but only affects the strain-integrated fabric evolution profile when comparing results straddling the thermal-activation-energy threshold (∼−10°C). Even at high temperatures, migration recrystallization does not eliminate the modeled fabric’s memory under most conditions. High levels of nearest-neighbor interactions will, however, eliminate the modeled fabric’s memory more quickly than low levels of nearest-neighbor interactions. Ultimately, our model predicts that fabrics will retain memory of past climatic variations when subject to a wide variety of conditions found in polar ice sheets.

In the deep ice cores drilled at the GRIP, NGRIP and GISP2 sites in Greenland and at Byrd Station and the summit of Law Dome in Antarctica, the mean crystal size increases with depth in the shallow subsurface and reaches steady values at intermediate depth. This behaviour has been attributed to the competition between grain-boundary migration driven crystal growth and crystal polygonization, but the effects of changing crystal dislocation density and non-equiaxed crystal shape in this competition are uncertain. We study these effects with a simple model. It describes how the mean height and width of crystals evolve as they flatten under vertical compression, and as crystal growth and polygonization compete. The polygonization rate is assumed to be proportional to the mean dislocation density across crystals. Migration recrystallization, which can affect crystal growth via strain-induced grain boundary migration but whose impact on the mean crystal size is difficult to quantify for ice at present, is not accounted for. When applied to the five ice-core sites, the model simulates the observed crystal-size profiles well down to the bottom of their steady regions, although the match for Law Dome is less satisfactory. Polygonization rate factors retrieved for the sites range from 10–5 to 10–2 a–1. We conclude that since crystal size and dislocation density evolve in a strongly coupled manner, consistent modelling requires multiple differential equations to track both of these variables. Future ice-core analysis should also determine crystal size in all three principal directions.

The WAIS (West Antarctic Ice Sheet) Divide deep ice core was recently completed to a total depth of 3405 m, ending 50 m above the bed. Investigation of the visual stratigraphy and grain characteristics indicates that the ice column at the drilling location is undisturbed by any large-scale overturning or discontinuity. The climate record developed from this core is therefore likely to be continuous and robust. Measured grain-growth rates, recrystallization characteristics, and grain-size response at climate transitions fit within current understanding. Significant impurity control on grain size is indicated from correlation analysis between impurity loading and grain size. Bubble-number densities and bubble sizes and shapes are presented through the full extent of the bubbly ice. Where bubble elongation is observed, the direction of elongation is preferentially parallel to the trace of the basal (0001) plane. Preferred crystallographic orientation of grains is present in the shallowest samples measured, and increases with depth, progressing to a vertical-girdle pattern that tightens to a vertical single-maximum fabric. This single-maximum fabric switches into multiple maxima as the grain size increases rapidly in the deepest, warmest ice. A strong dependence of the fabric on the impurity-mediated grain size is apparent in the deepest samples.

Understanding physical processes in near-zero accumulation areas can help us to better understand polar ice-core records, particularly during periods when accumulation rates were lower than today. We report measurements from a 5 m firn core from the Allan Hills, Antarctica, which include physical properties using computer tomography, stable isotope ratios δD and δ18O, and 210Pb activity. The core shows a highly metamorphosed firn with homogeneous and stable structure, but with discrete layers near the surface. The observed firn structure is caused by a combination of unique depositional and post-depositional processes. The irregular δD and δ18O signal does not follow the stratigraphic sequence and implies post-depositional modification caused by microscopic pressure gradients in the firn that can result from either forced ventilation over rough surfaces in the presence of wind or alternating temperature-gradients between the firn and the atmosphere. Our results also indicate impact snow deposition under high winds and with a high initial density and air exchange between the atmosphere and the snowpack.210Pb activity below 0.3 m falls below the detection limit, implying that most of the core is more than 100 years old. We conclude that the Allan Hills record provides a unique opportunity to investigate important processes that would have affected ice-core records from glacial periods.