Partial Equilibration Research Articles

Hyperosmolar environment and intestinal epithelial cells: impact on mitochondrial oxygen consumption, proliferation, and barrier function in vitro

The aim of the present study was to elucidate the in vitro short-term (2-h) and longer-term (24-h) effects of hyperosmolar media (500 and 680 mOsm/L) on intestinal epithelial cells using the human colonocyte Caco-2 cell line model. We found that a hyperosmolar environment slowed down cell proliferation compared to normal osmolarity (336 mOsm/L) without inducing cell detachment or necrosis. This was associated with a transient reduction of cell mitochondrial oxygen consumption, increase in proton leak, and decrease in intracellular ATP content. The barrier function of Caco-2 monolayers was also transiently affected since increased paracellular apical-to-basal permeability and modified electrolyte permeability were measured, allowing partial equilibration of the trans-epithelial osmotic difference. In addition, hyperosmotic stress induced secretion of the pro-inflammatory cytokine IL-8. By measuring expression of genes involved in energy metabolism, tight junction forming, electrolyte permeability and intracellular signaling, different response patterns to hyperosmotic stress occurred depending on its intensity and duration. These data highlight the potential impact of increased luminal osmolarity on the intestinal epithelium renewal and barrier function and point out some cellular adaptive capacities towards luminal hyperosmolar environment.

Impact of Molecular Partitioning and Partial Equilibration on the Estimation of Diffusion Coefficients from Release Experiments.

The present work addresses the effect of partial equilibration and molecular partitioning on the interpretation of release experiments. In this regard, it is shown how release profiles and the values of extracted transport parameters are affected by the time protocol chosen for sample collection by considering a series of experiments where the latter is systematically varied. Caffeine is investigated as a main model drug because of its similar affinity for water and lipids, while monolinolein-based lipid cubic phases are chosen as host matrices because of their wide employment in release studies. Our findings point to a progressive decline in diffusion rate upon increasing the time step, that is, the gap in time between two consecutive pickups, which is a signature of increasing equilibration of caffeine concentration between the lipidic mesophase and the water phase. Furthermore, the amount of released molecules at the first pickup displays negligible changes for large time steps, indicating complete equilibration in such cases. A model is introduced based on Fick's diffusion which goes beyond the assumption of perfect-sink conditions, a common feature of the typical theoretical approaches hitherto developed. The model is shown to account quantitatively for the experimental data and is subsequently employed to clarify the interplay of the adopted release protocol with the various transport parameters in determining the final outcome of the release process. Particularly, two additional molecular drugs are considered, namely glucose and proflavine, which are, respectively, more hydrophilic and hydrophobic than caffeine, thus allowing elucidating the role of molecular partitioning.

Partial equilibration of integer and fractional edge channels in the thermal quantum Hall effect

Since the charged mode is much faster than the neutral modes on quantum Hall edges at large filling factors, the edge may remain out of equilibrium in thermal conductance experiments. This sheds light on the observed imperfect quantization of the thermal Hall conductance at $\nu=8/3$ and can increase the observed thermal conductance by two quanta at $\nu=8/5$. Under certain unlikely but not impossible assumptions, this might also reconcile the observed thermal conductance at $\nu=5/2$ with not only the PH-Pfaffian order but also the anti-Pfaffian order.

The partial equilibration of garnet porphyroblasts in pelitic schists and its control on prograde metamorphism, Glen Roy, Scotland

AbstractGarnet porphyroblasts in sillimanite‐bearing pelitic schists contain complex textural and compositional zoning, with considerable variation both within and between adjacent samples. The sillimanite‐bearing schists locally occur in regional Barrovian garnet zone assemblages and are indicative of a persistent lack of equilibrium during prograde metamorphism. Garnet in these Dalradian rocks from the Scottish Highlands preserves evidence of a range of metamorphic responses including initial growth and patchy coupled dissolution–reprecipitation followed by partial dissolution. Individual porphyroblasts each have a unique and variable response to prograde metamorphism and garnet with mainly flat compositional profiles co‐exists with those containing largely unmodified characteristic bell‐shaped Mn profiles. This highlights the need for caution in applying traditional interpretations of effective volume diffusion eliminating compositional variation. Cloudy garnet with abundant fluid inclusions is produced during incomplete modification of the initial porphyroblasts and these porous garnet are then particularly prone to partial replacement in sillimanite‐producing reactions. The modification of garnet via a dissolution–reprecipitation process releases Ca into the effective whole‐rock composition, displacing the pressure–temperature positions of subsequent isograd reactions. This represents the first report of internal metasomatism controlling reaction pathways. The behaviour of garnet highlights the importance of kinetic factors, especially deformation and fluids, in controlling reaction progress and how the resulting variability influences subsequent prograde history. The lack of a consistent metamorphic response, within and between adjacent schists, suggests that on both local and regional scales these rocks have largely not equilibrated at peak metamorphic conditions.

Kinetic effects during the experimental transition of aragonite to calcite in aqueous solution: Insights from clumped and oxygen isotope signatures

Abstract Paleoenvironmental reconstructions based on the clumped isotopes (Δ47) and traditional isotope (δ13C or δ18O) techniques are often problematic for carbonates that have undergone diagenetic alteration. One of the most common types of diagenesis is the transition between polymorphs, such as the replacement of aragonite by calcite. The isotope fractionation during such transitions in aqueous solutions remains unclear. We conducted a series of aragonite-to-calcite transition experiments in aqueous solutions of varying salinity and experiment durations at 25 °C and 90 °C to examine the variations of δ13C, δ18O, and Δ47 values for carbonates at varying degrees of the transition. The results confirm the retarding effect of Mg2+ and the catalytic effect of Na+ and Ca2+ on the transition, which are consistent with previous findings. Compared with the results from the transitions at 25 °C, the 90 °C experiments show a greater transition to calcite and a more depleted oxygen isotope composition. However, both clumped and carbon isotope values show no significant variation in the various experiments, suggesting that they are unaffected by mineralogical transition. Based on published equilibrium calibrations for δ18O and Δ47, the results demonstrate that kinetic effects in isotope systems are controlled primarily by the rate of polymorph transition, but there is a significant kinetic difference between the clumped isotope bond (13C 18O) reordering and the 18O exchange within the dissolved inorganic carbon pool. This kinetic difference results in partial equilibration in δ18O with no significant reordering in Δ47 toward their equilibriums, which can be accounted for by the difference of equilibration rates between the oxygen isotopes bound to 12C and those bound to 13C. This study provides a clear observation of the response of isotope systems to carbonate polymorph transitions and sheds light on their reliability as paleoenvironmental proxies.

Re-Os systematics in petroleum during water-oil interaction: The effects of oil chemistry

Abstract The Re-Os geochronometer can be applied to date petroleum, which is the end product of complex natural processes. Improved interpretation of natural Re-Os datasets requires identification of key controlling factors for Re-Os systematics and their isotopic imprint in oils. Here, we focus on the role of water in (re)setting the Re-Os geochronometer in oils, as formation waters and oils often coexist in basinal systems. To quantify Re-Os systematics during water-oil interaction, we performed a series of equilibration experiments between different oils and dilute aqueous solutions doped with Re and Os. The investigated parameters include the oil composition, water to oil ratio, interaction time and the initial Re-Os content in the aqueous solution. In experiments performed across a high concentration gradient, the oils fully homogenized with respect to their Os isotopic composition but had variable 187Re/188Os ratios. This indicates that the Re-Os geochronometer has been reset during water-oil interaction. However, in experiments investigating partial isotopic overprint, the crude oil and its maltene and asphaltene fractions preserved their isochron-derived age. Thus, the Re-Os radiometric clock of a single crude oil sample remains intact, even during partial equilibration of the 187Os/188Os ratio. These experimental findings provide a new foundation for interpretation of Re-Os systematics in natural water-hydrocarbon systems.

Retention characteristics of some antibiotic and anti-retroviral compounds in hydrophilic interaction chromatography using isocratic elution, and gradient elution with repeatable partial equilibration

The separation of some zwitterionic, basic and neutral antibiotic and antiretroviral compounds was studied using hydrophilic interaction chromatography (HILIC) on bare silica, bonded amide and urea superficially porous phases. The differences in the selectivity and retentivity of these stationary phases were evaluated for compounds with widely different physicochemical properties (logD −3.43 to 2.41 at wwpH 3.0). The mobile phase was acetonitrile-ammonium formate buffered at low wwpH. Compounds containing quinolone and serine groups showed poor peak shapes on all columns, attributed to metal-oxide interactions with system metals. Peak shapes were improved by addition of citrate buffers. Gradient elution, particularly with regard to column equilibration, was also studied due to the large differences in retention factors observed under isocratic conditions. Full equilibration in HILIC was slow for both ionogenic and neutral solutes, requiring as much as ∼40 column volumes. However, highly repeatable partial equilibration, suitable for gradient elution, was achieved in only a few minutes. Pronounced selectivity differences in the separations were shown dependent on the partial equilibration time.

O, Mg, and Si isotope distributions in the complex ultrarefractory CAI Efremovka 101.1: Assimilation of ultrarefractory, FUN, and regular CAI precursors

Oxygen, magnesium, and silicon isotopic compositions in the mineralogically complex, ultrarefractory (UR) calcium-aluminum-rich inclusion (CAI) E101.1 from the reduced CV3 chondrite Efremovka confirm that E101.1 is a compound CAI composed of several lithological units that were once individual CAIs, free-floating in the solar protoplanetary disk. Each precursor unit was found to have had its own thermal history prior to being captured and incorporated into the partially molten host CAI.Four major lithological units can be distinguished on the basis of their isotopic compositions. (1) Al-diopside-rich sinuous fragments, hereafter sinuous pyroxene, are 16O-rich (Δ17O ≤ −20‰) and have light Mg and Si isotopic compositions with mass fractionation down to −3.5‰/amu for both isotopic systems. We attribute these peculiar isotopic compositions to kinetic effects during condensation out of thermal equilibrium. (2) Spinel clusters are 16O-rich (Δ17O ∼ −22‰) and have Mg isotope systematics consistent with extensive equilibration with the host melt. This includes (i) δ25Mg values varying between + 2.6‰ and + 6.5‰ close to the typical value of host melilite at ∼+5‰, and (ii) evidence for exchange of radiogenic 26Mg with adjacent melilite as indicated by Al/Mg systematics. The spinel clusters may represent fine-grained spinel-rich proto-CAIs captured, partially melted, and recrystallized in the host melt. Al/Mg systematics indicate that both the sinuous pyroxene fragments and spinel clusters probably had canonical or near-canonical 26Al contents before partial equilibration. (3) The main CAI host (Δ17O ≤ −2‰) had a complex thermal history partially obscured by subsequent capture and assimilation events. Its formation, referred to as the “cryptic” stage, could have resulted from the partial melting and crystallization of a 16O-rich precursor that underwent 16O-depletion and a massive evaporation event characteristic of F and FUN CAIs (Fractionated with Unknown Nuclear effects). Alternatively, a 16O-rich UR precursor may have coagulated with a 16O-poor FUN CAI having 48Ca anomalies, as indicated by perovskite, before subsequent extensive melting. The Al/Mg systematics (2.4 × 10−5 ≤ (26Al/27Al)0′ ≤ 5.4 × 10−5, where (26Al/27Al)0′ is a model initial 26Al/27Al ratio per analysis spot) are best understood if the FUN component was 26Al-poor, as are many FUN CAIs. (4) A complete Wark-Lovering rim (WLR) surrounds E101.1. Its Mg and Si isotopic compositions indicate that it formed by interaction of the evaporated interior CAI with an unfractionated 16O-rich condensate component. Heterogeneities in 26Al content in WLR spinels (3.7 × 10−5 ≤ (26Al/27Al)0′ ≤ 5.7 × 10−5) suggest that the previously reported age difference of as much as 300,000 years between interior CAIs and their WLRs may be an artifact resulting from Mg isotopic perturbations, possibly by solid state diffusion or mixing between the interior and condensate components.The isotopic systematics of E101.1 imply that 16O-rich and 16O-poor reservoirs co-existed in the earliest solar protoplanetary disk and that igneous CAIs experienced a 16O-depletion in an early high temperature stage. The coagulation of various lithological units in E101.1 and their partial assimilation supports models of CAI growth by competing fragmentation and coagulation in a partially molten state. Our results suggest that chemical and isotopic heterogeneities of unclear origin in regular CAIs may result from such a complex aggregation history masked by subsequent melting and recrystallization.

A study of column equilibration time in hydrophilic interaction chromatography

The time taken to achieve full column equilibration for isocratic analysis of acidic, basic, and neutral solutes in hydrophilic interaction liquid chromatography (HILIC) was compared using the mobile phase disturbance method, column efficiency measurements and retention time stability. Full equilibration, which could take up to an hour, was best measured by the last procedure and was found to depend on the nature of the stationary phase, the pre-equilibrium (e.g. storage) solvent and the flow rate. While longer equilibration times are a relatively minor inconvenience in isocratic analysis, they are surprisingly not a barrier to the use of gradient elution in HILIC. A repeatable partial equilibration giving retention time stability equivalent to that in isocratic analysis was demonstrated for an equilibration time of only ∼5 min, using as few as 2 preliminary conditioning runs on a column that had taken the longest time to achieve full equilibration. Due to selectivity changes that occur dependent on the equilibration time, it is necessary to use identical gradient conditions in a series of analyses, which however appears to be facile on a modern HPLC instrument.

A Subsolidus Olivine Water Solubility Equation for the Earth's Upper Mantle

AbstractThe pressure and temperature sensitivity of the two most important point hydrous defects in mantle olivine involving Si vacancies (associated to trace amounts of titanium [TiChu‐PD] or exclusively to Si vacancies [Si]) was investigated at subsolidus conditions in a fluid‐saturated natural peridotite from 0.5 to 6 GPa (approximately 20–200 km depth) at 750 to 1050°C. Water contents in olivine were monitored in sandwich experiments with a fertile serpentine layer in the middle and olivine and pyroxene sensor layers at the border. Textures and mineral compositions provide evidence that olivine completely recrystallized during the weeklong experiments, whereas pyroxenes displayed only partial equilibration. A site‐specific water solubility law for olivine has been formulated based on the experiments reconciling previous contradictory results from low‐ and high‐pressure experiments. The site‐specific solubility laws permit to constrain water incorporation into olivine in the subducting slab and the mantle wedge, as these are rare locations on Earth where fluid‐present conditions exist. Chlorite dehydration in the hydrated slab is roughly parallel to the isopleth of 50 ± 20 ppm wt H2O in olivine, a value which is independent of the pressure and temperature trajectory followed by the slab. Hydrous defects are dominated by [Si] under the relevant conditions for the mantle wedge affected by fluids coming from the slab dehydration (slab‐adjacent low viscosity/seismic low‐velocity channel, P > 3 GPa). In cold subduction zones at 5.5 km from the slab surface the storage capacity of the mantle wedge at depths of 100–250 km ranges from 400 to 2,000 ppm wt H2O.

Vapor-Deposited Glasses with Long-Range Columnar Liquid Crystalline Order

Anisotropic molecular packing, particularly in highly ordered liquid crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized glassy solids of discotic liquid crystalline systems. Using grazing incidence X-ray scattering, atomic force microscopy, and UV–vis spectroscopy, we compare three systems: a rectangular columnar liquid crystal, a hexagonal columnar liquid crystal, and a nonmesogen. The packing motifs accessible by vapor deposition are highly organized for the liquid crystalline systems with columns propagating either in-plane or out-of-plane depending upon the substrate temperature during deposition. The structures formed at a given substrate temperature can be understood as resulting from partial equilibration toward the structure of the equilibrium liquid crystal surface during the deposition process.

Constraining seasonal active layer dynamics and chemical weathering reactions occurring in North Slope Alaskan watersheds with major ion and isotope (δ34SSO4, δ13CDIC, 87Sr/86Sr, δ44/40Ca, and δ44/42Ca) measurements

Rising air temperatures in the Arctic may destabilize a large pool of organic carbon stored in permafrost, thereby causing a positive feedback to global climate warming. Permafrost thaw could also deepen hydrologic flow paths and expose previously frozen rock and mineral fragments to chemical weathering. Future shifts in the inorganic solute geochemistry of Arctic rivers may signal changes in soil processes that also affect organic carbon storage. Tracing permafrost thaw with dissolved riverine loads requires understanding the spatial and seasonal variation of chemical weathering reactions and other biogeochemical phenomena that affect elemental mass-transport. To help identify connections between mineral weathering and active layer processes, we studied the major ion and isotope (δ34SSO4, δ13CDIC, 87Sr/86Sr, δ44/40Ca, and δ44/42Ca) geochemistry of five streams draining the North Slope of Alaska. Continuous permafrost underlies all streams, but the Atigun River, Roche Moutonnée Creek, and Trevor Creek primarily drain bare bedrock outcrops in the Brooks Range, while the Upper Kuparuk River and Imnavait Creek primarily drain tundra. In total, we collected 546 water samples spanning the spring freshet through fall freeze-up in 2009 and 2010. We also analyzed snow, rock, sediment, soil, and plant samples.Major ion ratios and δ13CDIC values point to the overall dominance of carbonate weathering by carbonic and sulfuric acids, with additional influences from atmospheric deposition, plant decay, sulfate salt dissolution, and silicate weathering by carbonic acid. δ13CDIC values may also reflect partial equilibration with soil and atmospheric CO2. All streams display large seasonal variations in major ion ratios and δ13CDIC values that are consistent with progressive deepening of the seasonally thawed zone over the summer. In the mountain watersheds, carbonate weathering dominates during the spring and summer, while sulfate salt (primarily CaSO4 and MgSO4) dissolution dominates during the fall. Riverine δ34SSO4 values reveal that the sulfate salts are secondary precipitates. We propose a conceptual model where cryoconcentration in soils during the late fall and winter causes secondary mineral formation at depth and re-exposure during subsequent thaw seasons produces the observed geochemical signals in rivers. The tundra streams lack definitive evidence for sulfate salt dissolution, presumably because thick peat soils limit the exposure and weathering of underlying glacial sediment where the salts are expected to form and dissolve. Appearance of a sulfate salt dissolution signal in tundra streams may correlate with future permafrost degradation. Carbonate weathering dominates riverine 87Sr/86Sr ratios, but the compositional heterogeneity of bedrock limits interpretation of the data. All rivers have higher δ44/40Ca values compared to bedrock, likely due to plant uptake of lighter Ca isotopes. In the tundra watersheds, freshet δ44/40Ca values were 0.10–0.20‰ lower than summer and fall values. These trends likely reflect contributions from plant decay, as comparison between δ44/40Ca and δ44/42Ca values suggests that all isotopic variation is mass-dependent with minimal radiogenic 40Ca inputs from the weathering of old silicate minerals with high K/Ca ratios.

Influence of Molecular Shape on the Thermal Stability and Molecular Orientation of Vapor-Deposited Organic Semiconductors.

High thermal stability and anisotropic molecular orientation enhance the performance of vapor-deposited organic semiconductors, but controlling these properties is a challenge in amorphous materials. To understand the influence of molecular shape on these properties, vapor-deposited glasses of three disk-shaped molecules were prepared. For all three systems, enhanced thermal stability is observed for glasses prepared over a wide range of substrate temperatures and anisotropic molecular orientation is observed at lower substrate temperatures. For two of the disk-shaped molecules, atomistic simulations of thin films were also performed and anisotropic molecular orientation was observed at the equilibrium liquid surface. We find that the structure and thermal stability of these vapor-deposited glasses results from high surface mobility and partial equilibration toward the structure of the equilibrium liquid surface during the deposition process. For the three molecules studied, molecular shape is a dominant factor in determining the anisotropy of vapor-deposited glasses.

Arrested development – a comparative analysis of multilayer corona textures in high-grade metamorphic rocks

Abstract. Coronas, including symplectites, provide vital clues to the presence of arrested reaction and preservation of partial equilibrium in metamorphic and igneous rocks. Compositional zonation across such coronas is common, indicating the persistence of chemical potential gradients and incomplete equilibration. Major controls on corona mineralogy include prevailing pressure (P), temperature (T) and water activity (aH2O) during formation, reaction duration (t) single-stage or sequential corona layer growth; reactant bulk compositions (X) and the extent of metasomatic exchange with the surrounding rock; relative diffusion rates for major components; and/or contemporaneous deformation and strain. High-variance local equilibria in a corona and disequilibrium across the corona as a whole preclude the application of conventional thermobarometry when determining P–T conditions of corona formation, and zonation in phase composition across a corona should not be interpreted as a record of discrete P–T conditions during successive layer growth along the P–T path. Rather, the local equilibria between mineral pairs in corona layers more likely reflect compositional partitioning of the corona domain during steady-state growth at constant P and T. Corona formation in pelitic and mafic rocks requires relatively dry, residual bulk rock compositions. Since most melt is lost along the high-T prograde to peak segment of the P–T path, only a small fraction of melt is generally retained in the residual post-peak assemblage. Reduced melt volumes with cooling limit length scales of diffusion to the extent that diffusion-controlled corona growth occurs. On the prograde path, the low melt (or melt-absent) volumes required for diffusion-controlled corona growth are only commonly realized in mafic igneous rocks, owing to their intrinsic anhydrous bulk composition, and in dry, residual pelitic compositions that have lost melt in an earlier metamorphic event. Experimental work characterizing rate-limiting reaction mechanisms and their petrogenetic signatures in increasingly complex, higher-variance systems has facilitated the refinement of chemical fractionation and partial equilibration diffusion models necessary to more fully understand corona development. Through the application of quantitative physical diffusion models of coronas coupled with phase equilibria modelling utilizing calculated chemical potential gradients, it is possible to model the evolution of a corona through P–T–X–t space by continuous, steady-state and/or sequential, episodic reaction mechanisms. Most coronas in granulites form through a combination of these endmember reaction mechanisms, each characterized by distinct textural and chemical potential signatures with very different petrogenetic implications. An understanding of the inherent petrogenetic limitations of a reaction mechanism model is critical if an appropriate interpretation of P–T evolution is to be inferred from a corona. Since corona modelling employing calculated chemical potential gradients assumes nothing about the sequence in which the layers form and is directly constrained by phase compositional variation within a layer, it allows far more nuanced and robust understanding of corona evolution and its implications for the path of a rock in P–T–X space.

Non-equilibrium fluctuations and metastability arising from non-additive interactions in dissipative multi-component Rydberg gases

We study the out-of-equilibrium dynamics of dissipative gases of atoms excited to two or more high-lying Rydberg states. This situation bears interesting similarities to classical binary (in general p-ary) mixtures of particles. The effective forces between the components are determined by the inter-level and intra-level interactions of Rydberg atoms. These systems permit to explore new parameter regimes which are physically inaccessible in a classical setting, for example one in which the mixtures exhibit non-additive interactions. In this situation the out-of-equilibrium evolution is characterized by the formation of metastable domains that reach partial equilibration long before the attainment of stationarity. In experimental settings with mesoscopic sizes, this collective behavior may in fact take the appearance of dynamic symmetry breaking.

Space charges and defect concentration profiles at complex oxide interfaces

We discuss electronic and ionic defect concentration profiles at the conducting interface between the two wide-band-gap insulators ${\mathrm{LaAlO}}_{3}$ and ${\mathrm{SrTiO}}_{3}$ (STO). The profiles are deduced from a thermodynamic model considering a local space charge layer (SCL) originating from charge transfer to the interface region, thus combining electronic and ionic reconstruction mechanisms. We show that the electrical potential confining the two-dimensional electron gas (2DEG) at the interface modifies the equilibrium defect concentrations in the SCL. For the $n$-conducting interface, positively charged oxygen vacancies are depleted within the SCL, while negatively charged strontium vacancies accumulate. Charge compensation within the SCL is achieved by a mixed ionic-electronic interface reconstruction, while the competition between 2DEG and localized ionic defects is controlled by ambient $p{\mathrm{O}}_{2}$. The concentration of strontium vacancies increases drastically in oxidizing conditions and exhibits a steep depth profile towards the interface. Accounting for the low cation diffusivity in STO, we also discuss kinetic limitations of cation defect formation and the effect of a partial equilibration of the cation sublattice. We discuss the resulting implications for low temperature transport.

Controls on the stable isotope compositions of travertine from hyperalkaline springs in Oman: Insights from clumped isotope measurements

Carbonate formation at hyperalkaline springs is typical of serpentinization in peridotite massifs worldwide. These travertines have long been known to exhibit large variations in their carbon and oxygen isotope compositions, extending from apparent equilibrium values to highly depleted values. However, the exact causes of these variations are not well constrained. We analyzed a suite of well-characterized fresh carbonate precipitates and travertines associated with hyperalkaline springs in the peridotite section of the Samail ophiolite, Sultanate of Oman, and found their clumped isotope compositions vary systematically with formation environments. Based on these findings, we identified four main processes controlling the stable isotope compositions of these carbonates. These include hydroxylation of CO2, partial isotope equilibration of dissolved inorganic carbon, mixing between isotopically distinct carbonate end-members, and post-depositional recrystallization. Most notably, in fresh crystalline films on the surface of hyperalkaline springs and in some fresh carbonate precipitates from the bottom of hyperalkaline pools, we observed large enrichments in Δ47 (up to ∼0.2‰ above expected equilibrium values) which accompany depletions in δ18O and δ13C, yielding about 0.01‰ increase in Δ47 and 1.1‰ decrease in δ13C for every 1‰ decrease in δ18O, relative to expected equilibrium values. This disequilibrium trend, also reflected in preserved travertines ranging in age from modern to ∼40,000years old, is interpreted to arise mainly from the isotope effects associated with the hydroxylation of CO2 in high-pH fluids and agrees with our first-order theoretical estimation. In addition, in some fresh carbonate precipitates from the bottom of hyperalkaline pools and in subsamples of one preserved travertine terrace, we observed additional enrichments in Δ47 at intermediate δ13C and δ18O, consistent with mixing between isotopically distinct carbonate end-members. Our results suggest that carbonate clumped isotope analysis can be a valuable tool for identifying and distinguishing processes not readily apparent from the carbonate bulk stable isotope compositions alone, e.g., kinetic effects or mixing of different carbonate end-members, which can significantly alter both the apparent formation temperatures and apparent radiocarbon ages. The isotope trends observed in these travertine samples could be applied more broadly to identify extinct hyperalkaline springs in terrestrial and extraterrestrial environments, to better constrain the formation conditions and post-depositional alteration of hyperalkaline spring carbonates, and to extract potential paleoclimate information.

Rb–Sr and Sm–Nd study of granite–charnockite association in the Pudukkottai region and the link between metamorphism and magmatism in the Madurai Block

Pudukkottai region in the northeastern part of the Madurai Block exposes the garnetiferous pink granite that intruded the biotite gneiss. Charnockite patches are associated with both the rock types. Rb–Sr biotite and Sm–Nd whole-rock isochron ages indicate a regional uplift and cooling at ∼550 Ma. The initial Nd isotope ratios (\(\varepsilon _{\text {Nd}}^{\mathrm {t}}=-20\) to −22) and Nd depleted-mantle model ages (TDM = 2.25 to 2.79 Ga) indicate a common crustal source for the pink-granite and associated charnockite, while the biotite gneiss and the charnockite within it represent an older crustal source (\(\varepsilon _{\text {Nd}}^{\mathrm {t}}= -29\) and TDM = > 3.2 Ga). The Rb–Sr whole-rock data and initial Sr–Nd isotope ratios also help demonstrate the partial but systematic equilibration of Sr isotope and Rb/Sr ratios during metamorphic mineral-reactions resulting in an ‘apparent whole-rock isochron’. The available geochronological results from the Madurai Block indicate four major periods of magmatism and metamorphism: Neoarchaean–Paleoproterozoic, Mesoproterozoic, mid-Neoproterozoic and late-Neoproterozoic. We suggest that the high-grade and ultrahigh-temperature metamorphism was preceded by magmatism which ‘prepared’ the residual crust to sustain the high P–T conditions. There also appears to be cyclicity in the tectono-magmatic events and an evolutionary model for the Madurai Block should account for the cyclicity in the preserved records.

Substrate temperature controls molecular orientation in two-component vapor-deposited glasses.

Vapor-deposited glasses can be anisotropic and molecular orientation is important for organic electronics applications. In organic light emitting diodes (OLEDs), for example, the orientation of dye molecules in two-component emitting layers significantly influences emission efficiency. Here we investigate how substrate temperature during vapor deposition influences the orientation of dye molecules in a model two-component system. We determine the average orientation of a linear blue light emitter 1,4-di-[4-(N,N-diphenyl)amino]styryl-benzene (DSA-Ph) in mixtures with aluminum-tris(8-hydroxyquinoline) (Alq3) by spectroscopic ellipsometry and IR dichroism. We find that molecular orientation is controlled by the ratio of the substrate temperature during deposition and the glass transition temperature of the mixture. These findings extend recent results for single component vapor-deposited glasses and suggest that, during vapor deposition, surface mobility allows partial equilibration towards orientations preferred at the free surface of the equilibrium liquid.

Shape evolution and collective dynamics of quasifission in the time-dependent Hartree-Fock approach

Background: At energies near the Coulomb barrier, capture reactions in heavy-ion collisions result either in fusion or in quasifission. The former produces a compound nucleus in statistical equilibrium, while the second leads to a reseparation of the fragments after partial mass equilibration without formation of a compound nucleus. Extracting the compound nucleus formation probability is crucial to predict superheavy-element formation cross-sections. It requires a good knowledge of the fragment angular distribution which itself depends on quantities such as moments of inertia and excitation energies which have so far been somewhat arbitrary for the quasifission contribution. Methods: We investigate the evolution of the nuclear density in time-dependent Hartree-Fock (TDHF) calculations leading to quasifission. Our main goal is to extract ingredients of the formula used in the analysis of experimental angular distributions. These include the moment-of-inertia and temperature. We study the dependence of these quantities on various initial conditions of the reaction process. Results: The evolution of the moment of inertia is clearly non-trivial and depends strongly on the characteristics of the collision. The temperature rises quickly when the kinetic energy is transformed into internal excitation. Then, it rises slowly during mass transfer. Conclusions: Fully microscopic theories are useful to predict the complex evolution of quantities required in macroscopic models of quasifission.