Determining gypsum growth temperatures using monophase fluid inclusions-Application to the giant gypsum crystals of Naica, Mexico

Determining the formation temperature of minerals using fluid inclusions is a crucial step in understanding rock-forming scenarios. Unfortunately, fluid inclusions in minerals formed at low temperature, such as gypsum, are commonly in a metastable monophase liquid state. To overcome this problem, ultra-short laser pulses can be used to induce vapor bubble nucleation, thus creating a stable two-phase fluid inclusion appropriate for subsequent measurements of the liquid-vapor homogenization temperature, T-h. In this study we evaluate the applicability of T-h data to accurately determine gypsum formation temperatures. We used fluid inclusions in synthetic gypsum crystals grown in the laboratory at different temperatures between 40 degrees C and 80 degrees C under atmospheric pressure conditions. We found an asymmetric distribution of the T-h values, which are systematically lower than the actual crystal growth temperatures, T-g; this is due to (1) the effect of surface tension on liquid-vapor homogenization, and (2) plastic deformation of the inclusion walls due to internal tensile stress occurring in the metastable state of the inclusions. Based on this understanding, we have determined growth temperatures of natural giant gypsum crystals from Naica (Mexico), yielding 47 +/- 1.5 degrees C for crystals grown in the Cave of Swords (120 m below surface) and 54.5 +/- 2 degrees C for giant crystals grown in the Cave of Crystals (290 m below surface). These results support the earlier hypothesis that the population and the size of the Naica crystals were controlled by temperature. In addition, this experimental method opens a door to determining the growth temperature of minerals forming in low-temperature environments.

Diesel spray mixing limited vaporization with non-ideal and multi-component fuel thermophysical property effects

Internal combustion engines are, and will continue to be, a primary mode of power generation for ground transportation. Challenges exist in meeting fuel consumption regulations and emission standards while upholding performance, as fuel prices rise, and resource depletion and environmental impacts are of increasing concern. Diesel engines are advantageous due to their inherent efficiency advantage over spark ignition engines; however, their NOx and soot emissions can be difficult to control and reduce due to an inherent tradeoff. Diesel combustion is spray and mixing controlled providing an intrinsic link between spray and emissions, motivating detailed, fundamental studies on spray, vaporization, mixing, and combustion characteristics under engine relevant conditions. An optical combustion vessel facility has been developed at Michigan Technological University for these studies, with detailed tests and analysis being conducted. In this combustion vessel facility a preburn procedure for thermodynamic state generation is used, and validated using chemical kinetics modeling both for the MTU vessel, and institutions comprising the Engine Combustion Network international collaborative research initiative. It is shown that minor species produced are representative of modern diesel engines running exhaust gas recirculation and do not impact the autoignition of n-heptane. Diesel spray testing of a high-pressure (2000 bar) multi-hole injector is undertaken including non-vaporizing, vaporizing, and combusting tests, with sprays characterized using Mie back scatter imaging diagnostics. Liquid phase spray parameter trends agree with literature. Fluctuations in liquid length about a quasi-steady value are quantified, along with plume to plume variations. Hypotheses are developed for their causes including fuel pressure fluctuations, nozzle cavitation, internal injector flow and geometry, chamber temperature gradients, and turbulence. These are explored using a mixing limited vaporization model with an equation of state approach for thermopyhysical properties. This model is also applied to single and multi-component surrogates. Results include the development of the combustion research facility and validated thermodynamic state generation procedure. The developed equation of state approach provides application for improving surrogate fuels, both single and multi-component, in terms of diesel spray liquid length, with knowledge of only critical fuel properties. Experimental studies are coupled with modeling incorporating improved thermodynamic non-ideal gas and fuel

Development of one-dimensional and two-dimensional computational tools that simulate steady internal condensing flows in terrestrial and zero-gravity environments

This dissertation presents an effective quasi one-dimensional (1-D) computational simulation tool and a full two-dimensional (2-D) computational simulation methodology for steady annular/stratified internal condensing flows of pure vapor. These simulation tools are used to investigate internal condensing flows in both gravity as well as shear driven environments. Through accurate numerical simulations of the full two dimensional governing equations, results for laminar/laminar condensing flows inside mm-scale ducts are presented. The methodology has been developed using MATLAB/COMSOL platform and is currently capable of simulating film-wise condensation for steady (and unsteady flows). Moreover, a novel 1-D solution technique, capable of simulating condensing flows inside rectangular and circular ducts with different thermal boundary conditions is also presented. The results obtained from the 2-D scientific tool and 1-D engineering tool, are validated and synthesized with experimental results for gravity dominated flows inside vertical tube and inclined channel; and, also, for shear/pressure driven flows inside horizontal channels. Furthermore, these simulation tools are employed to demonstrate key differences of physics between gravity dominated and shear/pressure driven flows. A transition map that distinguishes shear driven, gravity driven, and “mixed” driven flow zones within the non-dimensional parameter space that govern these duct flows is presented along with the film thickness and heat transfer correlations that are valid in these zones. It has also been shown that internal condensing flows in a micro-meter scale duct experiences shear driven flow, even in different gravitational environments. The full 2-D steady computational tool has been employed to investigate the length of annularity. The result for a shear driven flow in a horizontal channel shows that in absence of any noise or pressure fluctuation at the inlet, the onset of non-annularity is partly due to insufficient shear at the liquid-vapor interface. This result is being further corroborated/investigated by R. R. Naik with the help of the unsteady simulation tool. The condensing flow results and flow physics understanding developed through these simulation tools will be instrumental in reliable design of modern micro-scale and spacebased thermal systems.

Preservation of high resolution protein structure by cryo-electron microscopy of vitreous sections

We have quantitated the degree of structural preservation in cryo-sections of a vitrified biological specimen. Previous studies have used sections of periodic specimens to assess the resolution present, but preservation before sectioning was not assessed and so the damage due particularly to cutting was not clear. In this study large single crystals of lysozyme were vitrified and from these X-ray diffraction patterns extending to better than 2.1A were obtained. The crystals were high pressure frozen in 30% dextran, and cryo-sectioned using a diamond knife. In the best case, preservation to a resolution of 7.9A was shown by electron diffraction, the first observation of sub-nanometre structural preservation in a vitreous section.

A gamma-glutamyl peptide isolated from onion (Allium cepa L.) by bioassay-guided fractionation inhibits resorption activity of osteoclasts

One gram of onion added to the food of rats inhibits significantly (p < 0.05) bone resorption as assessed by the urinary excretion of tritium released from bone of 9-week-old rats prelabeled with tritiated tetracycline from weeks 1 to 6. To isolate and identify the bone resorption inhibiting compound from onion, onion powder was extracted and the extract fractionated by column chromatography and medium-pressure liquid chromatography. A single active peak was finally obtained by semipreparative high-performance liquid chromatography. The biological activity of the various fractions was tested in vitro on the activity of osteoclasts to form resorption pits on a mineralized substrate. Medium, containing the various fractions or the pure compound, was added to osteoclasts of new-born rats settled on ivory slices. After 24 h of incubation, the tartrate-resistant acid phosphatase positive multinucleated cells, that is, osteoclasts, were counted. Subsequently, the number of resorption pits was determined. Activity was calculated as the ratio of resorption pits/osteoclasts and was compared to a negative control, that is, medium containing 10% fetal bovine serum only and to calcitonin (10(-12) M) as a positive control. Finally, a single peak inhibited osteoclast activity significantly (p < 0.05). The structure of this compound was elucidated with high-performance liquid chromatography-electrospray ionization-mass spectrometry, time-of-flight electrospray ionization mass spectrometry, and nuclear magnetic resonance spectroscopy. The single peak was identified as gamma-L-glutamyl-trans-S-1-propenyl-L-cysteine sulfoxide (GPCS). It has a molecular mass of 306 Da and inhibits dose-dependently the resorption activity of osteoclasts, the minimal effective dose being approximately 2 mM. As no other peak displayed inhibitory activity, it likely is responsible for the effect of onion on bone resorption.

Multiplex Liquid Chromatography-Tandem Mass Spectrometry Assay for Simultaneous Therapeutic Drug Monitoring of Ribavirin, Boceprevir, and Telaprevir

New directly acting antivirals (DAAs) that inhibit hepatitis C virus (HCV) replication are increasingly used for the treatment of chronic hepatitis C. A marked pharmacokinetic variability and a high potential for drug-drug interactions between DAAs and numerous drug classes have been identified. In addition, ribavirin (RBV), commonly associated with hemolytic anemia, often requires dose adjustment, advocating for therapeutic drug monitoring (TDM) in patients under combined antiviral therapy. However, an assay for the simultaneous analysis of RBV and DAAs constitutes an analytical challenge because of the large differences in polarity among these drugs, ranging from hydrophilic (RBV) to highly lipophilic (telaprevir [TVR]). Moreover, TVR is characterized by erratic behavior on standard octadecyl-based reversed-phase column chromatography and must be separated from VRT-127394, its inactive C-21 epimer metabolite. We have developed a convenient assay employing simple plasma protein precipitation, followed by high-performance liquid chromatography coupled to tandem mass spectrometry (HPLC-MS/MS) for the simultaneous determination of levels of RBV, boceprevir, and TVR, as well as its metabolite VRT-127394, in plasma. This new, simple, rapid, and robust HPLC-MS/MS assay offers an efficient method of real-time TDM aimed at maximizing efficacy while minimizing the toxicity of antiviral therapy.

Metamorphic and geochronogical study of the Triassic El Oro metamorphic complex, Ecuador: Implications for high-temperature metamorphism in a forearc zone

In the forearc of the Andean active margin in southwest Ecuador, the El Oro metamorphic complex exhibits a well exposed tilted forearc section partially migmatized. We used Raman spectroscopy on carbonaceous matter (RSCM) thermometry and pseudosections coupled with mineralogical and textural studies to constrain the pressure–temperature (P–T) evolution of the El Oro metamorphic complex during Triassic times. Our results show that anatexis of the continental crust occurred by white-mica and biotite dehydration melting along a 10 km thick crustal domain (from 4.5 to 8 kbar) with increasing temperature from 650 to 700 °C. In the biotite dehydration melting zone, temperature was buffered at 750–820 °C in a 5 km thick layer. The estimated average thermal gradient during peak metamorphism is of 30 °C/km within the migmatitic domain can be partitioned into two apparent gradients parts. The upper part from surface to 7 km depth records a 40–45 °C/km gradient. The lower part records a quasi-adiabatic geotherm with a 10 °C/km gradient consistent with an isothermal melting zone. Migmatites U–Th–Pb geochronology yielded zircon and monazite ages of 229.3 ± 2.1 Ma and 224.5 ± 2.3 Ma, respectively. This thermal event generated S-type magmatism (the Marcabeli granitoid) and was immediately followed by underplating of the high-pressure low-temperature (HP-LT) Arenillas–Panupalí unit at 225.8 ± 1.8 Ma. The association of high-temperature low-pressure (HT-LP) migmatites with HP-LT unit constitutes a new example of a paired metamorphic belt along the South American margin. We propose that in addition to crustal thinning, underplating of the Piedras gabbroic unit before 230 Ma provided the heat source necessary to foster crustal anatexis. Furthermore, its MORB signature shows that the asthenosphere was involved as the source of the heat anomaly. S-type felsic magmatism is widespread during this time and suggests that a large-scale thermal anomaly affected a large part of the South American margin during the late Triassic. We propose that crustal anatexis is related to an anomaly that arose during subduction of the Panthalassa ocean under the South American margin. Slab verticalization or slab break-off can be invoked as the origin of the upwelling of the asthenosphere.

A new sensitive method for the quantification of glyoxal and methylglyoxal in snow and ice by stir bar sorptive extraction and liquid desorption-HPLC-ESI-MS

In this study, the development of a new sensitive method for the analysis of alpha-dicarbonyls glyoxal (G) and methylglyoxal (MG) in environmental ice and snow is presented. Stir bar sorptive extraction with in situ derivatization and liquid desorption (SBSE-LD) was used for sample extraction, enrichment, and derivatization. Measurements were carried out using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). As part of the method development, SBSE-LD parameters such as extraction time, derivatization reagent, desorption time and solvent, and the effect of NaCl addition on the SBSE efficiency as well as measurement parameters of HPLC-ESI-MS/MS were evaluated. Calibration was performed in the range of 1–60 ng/mL using spiked ultrapure water samples, thus incorporating the complete SBSE and derivatization process. 4-Fluorobenzaldehyde was applied as internal standard. Inter-batch precision was <12 % RSD. Recoveries were determined by means of spiked snow samples and were 78.9 ± 5.6 % for G and 82.7 ± 7.5 % for MG, respectively. Instrumental detection limits of 0.242 and 0.213 ng/mL for G and MG were achieved using the multiple reaction monitoring mode. Relative detection limits referred to a sample volume of 15 mL were 0.016 ng/mL for G and 0.014 ng/mL for MG. The optimized method was applied for the analysis of snow samples from Mount Hohenpeissenberg (close to the Meteorological Observatory Hohenpeissenberg, Germany) and samples from an ice core from Upper Grenzgletscher (Monte Rosa massif, Switzerland). Resulting concentrations were 0.085–16.3 ng/mL for G and 0.126–3.6 ng/mL for MG. Concentrations of G and MG in snow were 1–2 orders of magnitude higher than in ice core samples. The described method represents a simple, green, and sensitive analytical approach to measure G and MG in aqueous environmental samples.

Autonomy as a protective factor against the detrimental effects of ego depletion on tennis serve accuracy under pressure

It has been repeatedly demonstrated that athletes in a state of ego depletion do not perform up to their capabilities. We assume that autonomous self-control exertion, in contrast to forced self-control exertion, can serve as a buffer against ego depletion effects and can help individuals to show superior performance. In the present study, we applied a between-subjects design to test the assumption that autonomously exerted self-control is less detrimental for subsequent self-control performance in sports than is forced self-control exertion. In a primary self-control task, the level of autonomy was manipulated through specific instructions, resulting in three experimental conditions (autonomy-supportive: n = 19; neutral: n = 19; controlling: n = 19). As a secondary self-control task, participants executed a series of tennis serves under high-pressure conditions, and performance accuracy served as our dependent variable. As expected, a one-way between-groups ANOVA revealed that participants from the autonomy-supportive condition performed significantly better under pressure than did participants from the controlling condition. These results further highlight the importance of autonomy-supportive instructions in order to enable athletes to show superior achievements in high-pressure situations. Practical implications for the coach–athlete relationship are discussed.

Is choking under pressure a consequence of skill-focus or increased distractibility? Results from a tennis serve task

It has been repeatedly demonstrated that athletes often choke in high pressure situations because anxiety can affect attention regulation and in turn performance. There are two competing theoretical approaches to explain the negative anxiety-performance relationship. According to skillfocus theories, anxious athletes’ attention is directed at how to execute the sport-specific movements which interrupts execution of already automatized movements in expert performers. According to distraction theories, anxious athletes are distractible and focus less on the relevant stimuli. We tested these competing assumptions in a between-subject design, as semi-professional tennis players were either assigned to an anxiety group (n = 25) or a neutral group (n = 28), and performed a series of second tennis serves into predefined target areas. As expected, anxiety was negatively related to serve accuracy. However, mediation analyses with the bootstrapping method revealed that this relationship was fully mediated by self-reported distraction and not by skill-focus.

The mammalian central nervous synaptic cleft contains a high density of periodically organized complexes.

Cryo-electron microscopy of vitreous section makes it possible to observe cells and tissues at high resolution in a close-to-native state. The specimen remains hydrated; chemical fixation and staining are fully avoided. There is minimal molecular aggregation and the density observed in the image corresponds to the density in the object. Accordingly, organotypic hippocampal rat slices were vitrified under high pressure and controlled cryoprotection conditions, cryosectioned at a final thickness of approximately 70 nm and observed below -170 degrees C in a transmission electron microscope. The general aspect of the tissue compares with previous electron microscopy observations. The detailed analysis of the synapse reveals that the density of material in the synaptic cleft is high, even higher than in the cytoplasm, and that it is organized in 8.2-nm periodic transcleft complexes. Previously undescribed structures of presynaptic and postsynaptic elements are also described.

The unstable CO2 feedback cycle on ocean planets

Ocean planets are volatile-rich planets, not present in our Solar system, which are thought to be dominated by deep, global oceans. This results in the formation of high-pressure water ice, separating the planetary crust from the liquid ocean and, thus, also from the atmosphere. Therefore, instead of a carbonate-silicate cycle like on the Earth, the atmospheric carbon dioxide concentration is governed by the capability of the ocean to dissolve carbon dioxide (CO2). In our study, we focus on the CO2 cycle between the atmosphere and the ocean which determines the atmospheric CO2 content. The atmospheric amount of CO2 is a fundamental quantity for assessing the potential habitability of the planet's surface because of its strong greenhouse effect, which determines the planetary surface temperature to a large degree. In contrast to the stabilizing carbonate-silicate cycle regulating the long-term CO2 inventory of the Earth atmosphere, we find that the CO2 cycle feedback on ocean planets is negative and has strong destabilizing effects on the planetary climate. By using a chemistry model for oceanic CO2 dissolution and an atmospheric model for exoplanets, we show that the CO2 feedback cycle can severely limit the extension of the habitable zone for ocean planets.