Heat capacities of TiO2-bearing silicate liquids: Evidence for anomalous changes in configurational entropy with temperature

The heat capacities of several TiO2-bearing silicate glasses and liquids containing Cs2O, Rb2O, Na2O, K2O, CaO, MgO, or BaO have been measured to 1100 K using a differential scanning calorimeter and to 1800 K using a Setaram HT-1500 calorimeter in step-scanning mode. The results for liquids of M2O-TiO2-2SiO2 composition (M -- Na, K, Cs) are compared to those for liquids of M2O-3SiO2 composition. The presence of TiO2 has a profound influence on the heat capacity of simple three-component silicate liquids over the temperature range 900-1300 K. Specifically, replacement of Si4+ by Ti4+ leads to doubling of the magnitude of the jump in Cp at the glass transion (Tg); this is followed by a progressive decrease in liquid Cp for over 400 K, until Cp eventually becomes constant and similar to that in Ti-free systems. The large heat capacity step at Tg in the TiO2-bearing melts suggests significant configurational rearrangements in the liquid that are not available to TiO2-free silicates. In addition, these "extra" configurational changes apparently saturate as temperature increases, implying the completion of whatever process is responsible for them, or the attainment of a random distribution of structural states. Above 1400 K, however, where the heat capacities of TiO2-bearing and TiO2-free alkali silicate liquids are similar, their configurational entropies differ by ~3.5 J/g.f.w.-K. The larger configurational entropy of the TiO2-bearing alkali silicate liquids relative to the TiO2-free liquids is energetically equivalent to raising the liquid temperature by more than 300 degrees. This result clearly demonstrates the energetic magnitude of the configurational changes apparent in the supercooled liquid region and their impact on the thermodynamic properties of the stable liquid. Consideration of both density measurements on liquids and spectroscopic data on quenched glasses (from the literature) suggests that the anomalous configurational rearrangements may involve the breakdown of alkali and alkaline earth titanate complexes and changes in Ti4+ coordination.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/30728/1/0000377.pd

New density measurements on carbonate liquids and the partial molar volume of the CaCO 3 component

Density measurements on nine liquids in the CaCO 3 –Li 2 CO 3 –Na 2 CO 3 –K 2 CO 3 quaternary system were performed at 1 bar between 555 and 969 °C using the double-bob Archimedean method. Our density data on the end-member alkali carbonate liquids are in excellent agreement with the NIST standards compiled by Janz (1992). The results were fitted to a volume equation that is linear in composition and temperature; this model recovers the measured volumes within experimental error (±0.18% on average, with a maximum residual of ±0.50%). Our results indicate that the density of the CaCO 3 component in natrocarbonate liquids is 2.502 (±0.014) g/cm 3 at 800 °C and 1 bar, which is within the range of silicate melts; its coefficient of thermal expansion is 1.8 (±0.5)×10 −4 K −1 at 800 °C. Although the volumes of carbonate liquids mix linearly with respect to carbonate components, they do not mix linearly with silicate liquids. Our data are used with those in the literature to estimate the value of in alkaline silicate magmas (≥20 cm 3 /mol at 1400 °C and 20 kbar), where CO 2 is dissolved as carbonate in close association with Ca. Our volume measurements are combined with sound speed data in the literature to derive the compressibility of the end-member liquids Li 2 CO 3 , Na 2 CO 3 , and K 2 CO 3 . These results are combined with calorimetric data to calculate the fusion curves for Li 2 CO 3 , Na 2 CO 3 , and K 2 CO 3 to 5 kbar; the calculations are in excellent agreement with experimental determinations of the respective melting reactions.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/47311/1/410_2003_Article_505.pd

A Joint Model for Multistate Disease Processes and Random Informative Observation Times, with Applications to Electronic Medical Records Data

Multistate models are used to characterize individuals\u27 natural histories through diseases with discrete states. Observational data resources based on electronic medical records pose new opportunities for studying such diseases. However, these data consist of observations of the process at discrete sampling times, which may either be pre-scheduled and non-informative, or symptom-driven and informative about an individual\u27s underlying disease status. We have developed a novel joint observation and disease transition model for this setting. The disease process is modeled according to a latent continuous time Markov chain; and the observation process, according to a Markov-modulated Poisson process with observation rates that depend on the individual\u27s underlying disease status. The disease process is observed at informative or non-informative sampling times, with possible misclassification error. We demonstrate that the model is computationally tractable and devise an expectation-maximization algorithm for parameter estimation. Using simulated data, we show how estimates from our joint observation and disease transition model lead to less biased and more precise estimates of the disease rate parameters. We apply the model to a study of secondary breast cancer events, utilizing mammography and biopsy records from a sample of women with a history of primary breast cancer

Multi-technique equation of state for Fe_(2)SiO_4 melt and the density of Fe-bearing silicate melts from 0 to 161 GPa

We have conducted new equation of state measurements on liquid Fe_(2)SiO_4 in a collaborative, multi-technique study. The liquid density (ρ), the bulk modulus (K), and its pressure derivative (K′) were measured from 1 atm to 161 GPa using 1-atm double-bob Archimedean, multi-anvil sink/float, and shock wave techniques. Shock compression results on initially molten Fe_(2)SiO_4 (1573 K) fitted with previous work and the ultrasonically measured bulk sound speed (C_o) in shock velocity (U_S)-particle velocity (u_p) space yields the Hugoniot: U_S = 1.58(0.03) u_p + 2.438(0.005) km/s. Sink/float results are in agreement with shock wave and ultrasonic data, consistent with an isothermal K_T = 19.4 GPa and K′ = 5.33 at 1500°C. Shock melting of initially solid Fe_(2)SiO_4 (300 K) confirms that the Grüneisen parameter (γ) of this liquid increases upon compression where γ = γ_o(ρ_(o)/ρ)^q yields a q value of –1.45. Constraints on the liquid fayalite EOS permit the calculation of isentropes for silicate liquids of general composition in the multicomponent system CaO-MgO-Al_(2)O_3-SiO_2-FeO at elevated temperatures and pressures. In our model a whole mantle magma ocean would first crystallize in the mid-lower mantle or at the base of the mantle were it composed of either peridotite or simplified “chondrite” liquid, respectively. In regards to the partial melt hypothesis to explain the occurrence and characteristics of ultra-low velocity zones, neither of these candidate liquids would be dense enough to remain at the core mantle boundary on geologic timescales, but our model defines a compositional range of liquids that would be gravitationally stable

Multi‐technique equation of state for Fe 2 SiO 4 melt and the density of Fe‐bearing silicate melts from 0 to 161 GPa

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95366/1/jgrb17308.pd

New acoustic velocity measurements on CaO‐MgO‐Al 2 O 3 ‐SiO 2 liquids: Reevaluation of the volume and compressibility of CaMgSi 2 O 6 ‐CaAl 2 Si 2 O 8 liquids to 25 GPa

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95309/1/jgrb15318.pd

Control of telomere length by a trimming mechanism that involves generation of t-circles

Telomere lengths are maintained in many cancer cells by the ribonucleoprotein enzyme telomerase but can be further elongated by increasing telomerase activity through the overexpression of telomerase components. We report here that increased telomerase activity results in increased telomere length that eventually reaches a plateau, accompanied by the generation of telomere length heterogeneity and the accumulation of extrachromosomal telomeric repeat DNA, principally in the form of telomeric circles (t-circles). Telomeric DNA was observed in promyelocytic leukemia bodies, but no intertelomeric copying or telomere exchange events were identified, and there was no increase in telomere dysfunction-induced foci. These data indicate that human cells possess a mechanism to negatively regulate telomere length by trimming telomeric DNA from the chromosome ends, most likely by t-loop resolution to form t-circles. Additionally, these results indicate that some phenotypic characteristics attributed to alternative lengthening of telomeres (ALT) result from increased mean telomere length, rather than from the ALT mechanism itself

Optimum spectral window for imaging of art with optical coherence tomography

Optical Coherence Tomography (OCT) has been shown to have potential for important applications in the field of art conservation and archaeology due to its ability to image subsurface microstructures non-invasively. However, its depth of penetration in painted objects is limited due to the strong scattering properties of artists’ paints. VIS-NIR (400 nm – 2400 nm) reflectance spectra of a wide variety of paints made with historic artists’ pigments have been measured. The best spectral window with which to use optical coherence tomography (OCT) for the imaging of subsurface structure of paintings was found to be around 2.2 μm. The same spectral window would also be most suitable for direct infrared imaging of preparatory sketches under the paint layers. The reflectance spectra from a large sample of chemically verified pigments provide information on the spectral transparency of historic artists’ pigments/paints as well as a reference set of spectra for pigment identification. The results of the paper suggest that broadband sources at ~2 microns are highly desirable for OCT applications in art and potentially material science in general

Is the Closest Facility the One Actually Used? An Assessment of Travel Time Estimation Based on Mammography Facilities

Characterizing geographic access depends on a broad range of methods available to researchers and the healthcare context to which the method is applied. Globally, travel time is one frequently used measure of geographic access with known limitations associated with data availability. Specifically, due to lack of available utilization data, many travel time studies assume that patients use the closest facility. To examine this assumption, an example using mammography screening data, which is considered a geographically abundant health care service in the United States, is explored. This work makes an important methodological contribution to measuring access--which is a critical component of health care planning and equity almost everywhere. We analyzed one mammogram from each of 646,553 women participating in the US based Breast Cancer Surveillance Consortium for years 2005-2012. We geocoded each record to street level address data in order to calculate travel time to the closest and to the actually used mammography facility. Travel time between the closest and the actual facility used was explored by woman-level and facility characteristics