Chronometry and formation pathways of gypsum using Electron Spin Resonance and Fourier Transform Infrared Spectroscopy

Gypsum is an authigenic precipitate that forms under periods of accentuated aridity and occurs widely in arid zones. However its use in quantitative paleoclimatology has been limited due to the absence of a method to determine the timing of its formation. We present here the results of a feasibility study that demonstrates that the timing of the formation event of gypsum can be estimated using Electron Spin Resonance (ESR) analysis. We used well documented samples from White Sands in New Mexico, USA, the Thar Desert, India and lakes in the Simpson Desert and Mallee Region, Australia and found that ESR ages could be obtained using radiation sensitive SO4-, SO3- radicals and a photobleachable signal O3-. ESR signals were consistent with control ages based on contextual information. These suggest that the dating signals (SO4-, SO3-) are stable over time scales >100 ka. We propose that this stability of the SO4- signals over geological time scales arises due to hydrogen bonding between the water proton and the SO4- radical and that the suitability of these radiation-induced radicals comes from their being a part of the host matrix. Further, ESR along with Fourier Transform Infrared (FT-IR) Spectroscopy methods additionally inform on the geochemical pathways for gypsum formation and help elucidate complex formation processes even in samples that appeared unambiguous gypsum precipitates. Thus, the presence of Hannebachite (CaSO3.1/2H2O) and Mn2+ in Thar and Australian samples suggested a reducing environment such that low valence sulfur reacted with CaCO3 to form hannebachite and eventually gypsum. The presence of sulfur, partially as sulfite in Thar gypsum samples suggested that redox cycles were mediated by microbial activity. Absence of these features in White Sands samples suggested oxic conditions during gypsum precipitation

Structural Probe of a Glass Forming Liquid: Generalized Compressibility

We introduce a new quantity to probe the glass transition. This quantity is a linear generalized compressibility which depends solely on the positions of the particles. We have performed a molecular dynamics simulation on a glass forming liquid consisting of a two component mixture of soft spheres in three dimensions. As the temperature is lowered (or as the density is increased), the generalized compressibility drops sharply at the glass transition, with the drop becoming more and more abrupt as the measurement time increases. At our longest measurement times, the drop occurs approximately at the mode coupling temperature $T_C$. The drop in the linear generalized compressibility occurs at the same temperature as the peak in the specific heat. By examining the inherent structure energy as a function of temperature, we find that our results are consistent with the kinetic view of the glass transition in which the system falls out of equilibrium. We find no size dependence and no evidence for a second order phase transition though this does not exclude the possibility of a phase transition below the observed glass transition temperature. We discuss the relation between the linear generalized compressibility and the ordinary isothermal compressibility as well as the static structure factor.Comment: 18 pages, Latex, 26 encapsulated postscript figures, revised paper is shorter, to appear in Phys. Rev.

Jamming at Zero Temperature and Zero Applied Stress: the Epitome of Disorder

We have studied how 2- and 3- dimensional systems made up of particles interacting with finite range, repulsive potentials jam (i.e., develop a yield stress in a disordered state) at zero temperature and applied stress. For each configuration, there is a unique jamming threshold, $\phi_c$, at which particles can no longer avoid each other and the bulk and shear moduli simultaneously become non-zero. The distribution of $\phi_c$ values becomes narrower as the system size increases, so that essentially all configurations jam at the same $\phi$ in the thermodynamic limit. This packing fraction corresponds to the previously measured value for random close-packing. In fact, our results provide a well-defined meaning for "random close-packing" in terms of the fraction of all phase space with inherent structures that jam. The jamming threshold, Point J, occurring at zero temperature and applied stress and at the random close-packing density, has properties reminiscent of an ordinary critical point. As Point J is approached from higher packing fractions, power-law scaling is found for many quantities. Moreover, near Point J, certain quantities no longer self-average, suggesting the existence of a length scale that diverges at J. However, Point J also differs from an ordinary critical point: the scaling exponents do not depend on dimension but do depend on the interparticle potential. Finally, as Point J is approached from high packing fractions, the density of vibrational states develops a large excess of low-frequency modes. All of these results suggest that Point J may control behavior in its vicinity-perhaps even at the glass transition.Comment: 21 pages, 20 figure

Dynamics of the frustrated Ising lattice gas

The dynamical properties of a three dimensional model glass, the frustrated Ising lattice gas (FILG) are studied by Monte Carlo simulations. We present results of compression experiments, where the chemical potential is either slowly or abruptly changed, as well as simulations at constant density. One time quantities like density and two time ones like correlations, responses and mean square displacements are measured, and the departure from equilibrium clearly characterized. The aging scenario, particularly in the case of density autocorrelations is reminiscent of spin glass phenomenology with violations of the Fluctuation-dissipation theorem, typical of systems with one replica symmetry breaking. The FILG, as a valid on-lattice model of structural glasses can be described with tools developed in spin glass theory and, being a finite dimensional model, can open the way for a systematic study of activated processes in glasses.Comment: to appear in Phys. Rev. E, november (2000

The kinetic fragility of liquids as manifestation of the elastic softening

We show that the fragility $m$, the steepness of the viscosity and relaxation time close to the vitrification, increases with the degree of elastic softening, i.e. the decrease of the elastic modulus with increasing temperature, in universal way. This provides a novel connection between the thermodynamics, via the modulus, and the kinetics. The finding is evidenced by numerical simulations and comparison with the experimental data of glassformers with widely different fragilities ($33 \le m \le 115$), leading to a fragility-independent elastic master curve extending over eighteen decades in viscosity and relaxation time. The master curve is accounted for by a cavity model pointing out the roles of both the available free volume and the cage softness. A major implication of our findings is that ultraslow relaxations, hardly characterised experimentally, become predictable by linear elasticity. As an example, the viscosity of supercooled silica is derived over about fifteen decades with no adjustable parameters.Comment: 7 pages, 6 figures; Added new results, improved the theoretical sectio

Ammonium Dithionate – a New Material for Highly Sensitive EPR Dosimetry

Polycrystalline ammonium dithionate has been examined for its radiation response in the low dose range (< 5 Gy) using EPR technique. The •SO3- radical ion was detected as a single EPR line with a peak-to-peak derivative width of ca. 0.44 mT in irradiated samples and its intensity was found to vary linearly with dose. At equal and moderate settings of microwave power and modulation amplitude ammonium dithionate was at least 7 times more sensitive than L-alanine which is the most common EPR dosimeter standard. Pulse experiments were performed on the powder samples to obtain the longitudinal relaxation time. These and microwave saturation experiments served to indicate the optimal microwave power to be applied during measurements as an EPR dosimeter for best sensitivity of this material. It is thus claimed that ammonium dithionate has excellent potential to become an EPR dosimeter with a low limit of the measurable dose for cases where tissue equivalence is not required or can be corrected for.Original publication: M. Danilczuka, H. Gustafsson, M.D. Sastry, E. Lund and A. Lund, Ammonium Dithionate – a New Material for Highly Sensitive EPR Dosimetry, 2008, Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, (69), 1, 18-21. http://dx.doi.org/ 10.1016/j.saa.2007.03.001. Copyright: Copyright: Elsevier B.V., http://www.elsevier.com