Micro- and nano-size hydrogrossular-like clusters in pyrope crystals from ultra-high-pressure rocks of the Dora-Maira Massif, western Alps

The supracrustal metamorphic rocks of the Dora-Maira Massif, western Alps, have been intensively studied. Certain ultra-high-pressure lithologies contain coesite and nearly end-member composition pyrope, Mg₃Al₂Si₃O₁₂, making this locality petrologically and mineralogically unique. Structural OH⁻, loosely termed “water”, in pyrope crystals of different composition has been investigated numerous times, using different experimental techniques, by various researchers. However, it is not clear where the minor OH⁻ is located in them. IR single-crystal spectra of two pyropes of composition {Mg_(2.79),Fe²⁺_(0.15),Ca_(0.04)}_(Σ2.98)[Al]_(2.02)(Si)_(2.99)O₁₂ and {Mg_(2.90),Fe²⁺_(0.04),Ca_(0.02)}_(Σ2.96)[Al]_(2.03)(Si)₃O₁₂ were recorded at room temperature (RT) and 80 K. The spectra show five distinct OH⁻ bands located above 3600 cm⁻¹ at RT and seven narrow bands at 80 K and additional fine structure. The spectra were curve fit and the OH⁻ stretching modes analyzed and assigned. It is argued that OH⁻ is located in microscopic- and nano-size Ca₃Al₂H₁₂O₁₂-like clusters. The basic substitution mechanism is the hydrogarnet one, where (H₄O₄)⁴⁻ ⇔ (SiO₄)⁴⁻, and various local configurations containing different numbers of (H₄O₄)⁴⁻ groups define the cluster type. The amounts of H₂O range between 5 and 100 ppm by weight, depending on the IR calibration adopted, and are variable among crystals. Hydrogrossular-like clusters are also present in a synthetic pyrope with a minor Ca content grown hydrothermally at 900 °C and 20 kbar, as based on its IR spectra at RT and 80 K. Experiment and nature are in agreement, and OH⁻ groups are partitioned into various barely nano-size hydrogrossular-like clusters. This proposal is new and significant mineralogical, petrological, and geochemical implications result. Ca and proton ordering occur. Hypothetical “defect” and/or coupled-substitution mechanisms to account for structural OH⁻ are not needed to interpret experimental results. OH⁻ incorporation in pyrope of different generations at Dora-Maira is discussed and OH- could potentially be used as an indicator of changing P_(H₂O)(a_(H₂O)) – T conditions in a metamorphic cycle. Published experimental hydration, dehydroxylation, and hydrogen diffusion results on Dora-Maira pyropes can now be interpreted atomistically

Heavy resonance production in high energy nuclear collisions

We estimate freezeout conditions for $s$, $c$, and $b$ quarks in high energy nuclear collisions. Freezeout is due either to loss of thermal contact, or to particles ``wandering'' out of the region of hot matter. We then develop a thermal recombination model in which both single-particle (quark and antiquark) and two-particle (quark-antiquark) densities are conserved. Conservation of two-particle densities is necessary because quarks and antiquarks are always produced in coincidence, so that the local two-particle density can be much larger than the product of the single-particle densities. We use the freezeout conditions and recombination model to discuss heavy resonance production at zero baryon density in high energy nuclear collisions.Comment: revtex, 15 pages, no figures, KSUCNR-009-9

Heat capacity and entropy behavior of andradite: a multi-sample and −methodological investigation

Andradite, ideal end-member formula Ca_3 Fe^(3+)_2Si_3O_(12), is one of the common rock-forming garnets found in the Earth's crust. There are several outstanding questions regarding andradite's thermodynamic and physical property behavior. Three issues are: i) Could there be differences in the thermodynamic properties, namely heat capacity, C_p , between synthetic and natural andradite crystals, as observed in the Ca-garnet grossular, Ca_3Al_2Si_3O_(12)? ii) What is the thermal nature of the low-temperature magnetic-phasetransition behavior of andradite? and iii) How quantitative are older published calorimetric (i. e., adiabatic and DSC) heat-capacity results? In this work, four natural nearly end-member single crystals and two synthetic polycrystalline andradite samples were carefully characterized by optical microscope examination, X-ray powder diffraction, microprobe analysis, and IR and UV/VIS single-crystal spectroscopy. The IR spectra of the different samples commonly show a main intense OH stretching band located at 3563 cm^(-1), but other OH bands can sometimes be observed as well. Structural OH concentrations, calculated from the IR spectra, vary from about 0.006 to 0.240 wt% H_2O. The UV/VIS spectra indicate that there can be slight, but not fully understood, differences in the electronic state between synthetic and natural andradite crystals. The C_p behavior was determined by relaxation calorimetry between 2 and 300 K and by differential scanning calorimetry (DSC) methods between 150/300 and 700/950 K, employing the same andradite samples that were used for the other characterization measurements. The low-temperature C_p results show a magnetic phase transition with a Néel temperature of 11.3 ± 0.2 K, which could be slightly affected by the precise electronic state of Fe^(2+/3+) in the crystals. The published adiabatic calorimetry results on andradite do not provide a full and correct thermal description of this magnetic transition. The calorimetric Cp measurements give a best estimate for the standard third-law entropy at 298.15 K for andradite of S^o ≈ 324 ± 2 J/mol · K vs. the value of 316.4 ± 2.0 J/mol · K, as given in an early adiabatic investigation. Both natural and synthetic crystals give similar S o values within experimental uncertainty of about 1.0%, but one natural andradite, richer in OH, may have a very slightly higher value around S^o≈ 326 J/mol·K. Low-temperature DSC measurements made below 298 K agree excellently with those from relaxation calorimetry. The DSC measurements above 298 K show a similarity in C_p behavior among natural and synthetic andradites. A C_p polynomial for use above room temperature to approximately 1000 K was calculated from the data on synthetic andradite giving: C_p (J/mol·K) = 599.09 (±14) 2709.5 (±480)· T^(0.5) 1.3866 (±0.26)· 10^7 · T^2 + 1.6052 (±0.42) · 10^9 · T^3

IR spectroscopy and OH^– in silicate garnet: The long quest to document the hydrogarnet substitution

There has been much research undertaken on structural OH^– in various nominally anhydrous minerals including the common silicate garnets (i.e., X_3Y_2Si_3O_(12), where X = Mg, Fe^(2+), Mn^(2+), and Ca and Y = Al, Fe^(3+), and Cr^(3+)). However, it is still largely not understood where small concentrations of H atoms are incorporated in the garnet crystal structure. In this work, the IR single-crystal spectra of end-member or approaching end-member composition andradite, pyrope, and almandine are measured. Both a natural and synthetic andradite sample show a broad, asymmetric OH^–-stretching mode at 3563 cm^(–1) that splits into two narrower modes at lower temperatures. They are located at 3575 and 3557 cm^(–1) at 80 K with the higher wavenumber mode being considerably more intense compared to that at lower energy. These results are analyzed together with published IR spectra of synthetic end-member katoite, pyrope, and almandine also recorded at low temperature. These garnets show similar IR behavior with a broad OH^– band at room temperature that splits into two narrower bands at lower temperatures and with a similar intensity relationship as shown by andradite. This behavior is indicative of the hydrogarnet substitution. The measured IR spectra of natural almandine- and pyrope-rich (Dora Maira, Italy) crystals, on the other hand, show different spectroscopic features with several OH^– modes that are not consistent with the hydrogarnet mechanism. An analysis of the energy of the OH^–-stretching mode is made for various composition hydrogarnet clusters [i.e., X_3Y_2(O_4H_4)_3, where X = Mg, Fe^(2+), Mn^(2+) and Ca and Y = Al and Fe^(3+)] in terms of crystal-chemical properties and local atomic configurations. The OH^– mode energy, which lies roughly between 3660 and 3550 cm^(–1) at RT for various end-member garnets, is a function of the mass of the X- and Y-cations due to mode coupling and/or mixing. In addition, the strength of the chemical bonding between the X- and Y-cations and the O^2–anion of the OH^– dipole plays a role in affecting the wavenumber of the OH^–-stretching vibration. OH^– mode broadening, observed in the spectra of end-member garnets, is primarily a result of thermal anharmonic disorder, especially with regard to the light H cation. OH mode broadening in intermediate solid-solution composition garnets is a function of both thermal effects and variations in local cation configurations around the OH^– dipole(s). Published IR spectra of certain high-pressure pyrope-rich garnets, both synthetic and natural, are analyzed and arguments made that OH^– can often be incorporated as the hydrogarnet or hydropyrope substitution. IR spectra similar in appearance, having multiple relatively narrow OH^– modes that are distinct from those indicating the hydrogarnet substitution, can be observed for certain synthetic end-member and various composition natural pyropes from Dora Maira and some natural spessartines. This indicates that other common OH^– substitution mechanisms, which have yet to be determined, can also occur in different silicate garnets

Heat capacity and entropy behavior of andradite: a multi-sample and −methodological investigation

Andradite, ideal end-member formula Ca_3 Fe^(3+)_2Si_3O_(12), is one of the common rock-forming garnets found in the Earth's crust. There are several outstanding questions regarding andradite's thermodynamic and physical property behavior. Three issues are: i) Could there be differences in the thermodynamic properties, namely heat capacity, C_p , between synthetic and natural andradite crystals, as observed in the Ca-garnet grossular, Ca_3Al_2Si_3O_(12)? ii) What is the thermal nature of the low-temperature magnetic-phasetransition behavior of andradite? and iii) How quantitative are older published calorimetric (i. e., adiabatic and DSC) heat-capacity results? In this work, four natural nearly end-member single crystals and two synthetic polycrystalline andradite samples were carefully characterized by optical microscope examination, X-ray powder diffraction, microprobe analysis, and IR and UV/VIS single-crystal spectroscopy. The IR spectra of the different samples commonly show a main intense OH stretching band located at 3563 cm^(-1), but other OH bands can sometimes be observed as well. Structural OH concentrations, calculated from the IR spectra, vary from about 0.006 to 0.240 wt% H_2O. The UV/VIS spectra indicate that there can be slight, but not fully understood, differences in the electronic state between synthetic and natural andradite crystals. The C_p behavior was determined by relaxation calorimetry between 2 and 300 K and by differential scanning calorimetry (DSC) methods between 150/300 and 700/950 K, employing the same andradite samples that were used for the other characterization measurements. The low-temperature C_p results show a magnetic phase transition with a Néel temperature of 11.3 ± 0.2 K, which could be slightly affected by the precise electronic state of Fe^(2+/3+) in the crystals. The published adiabatic calorimetry results on andradite do not provide a full and correct thermal description of this magnetic transition. The calorimetric Cp measurements give a best estimate for the standard third-law entropy at 298.15 K for andradite of S^o ≈ 324 ± 2 J/mol · K vs. the value of 316.4 ± 2.0 J/mol · K, as given in an early adiabatic investigation. Both natural and synthetic crystals give similar S o values within experimental uncertainty of about 1.0%, but one natural andradite, richer in OH, may have a very slightly higher value around S^o≈ 326 J/mol·K. Low-temperature DSC measurements made below 298 K agree excellently with those from relaxation calorimetry. The DSC measurements above 298 K show a similarity in C_p behavior among natural and synthetic andradites. A C_p polynomial for use above room temperature to approximately 1000 K was calculated from the data on synthetic andradite giving: C_p (J/mol·K) = 599.09 (±14) 2709.5 (±480)· T^(0.5) 1.3866 (±0.26)· 10^7 · T^2 + 1.6052 (±0.42) · 10^9 · T^3

Physiology

Contains reports on seven research projects.Bell Laboratories, Inc.Ortho InstrumentsNational Institutes of Health (Grant 5 TO1 EY00090

α5β1 Integrin-Mediated Adhesion to Fibronectin Is Required for Axis Elongation and Somitogenesis in Mice

The arginine-glycine-aspartate (RGD) motif in fibronectin (FN) represents the major binding site for α5β1 and αvβ3 integrins. Mice lacking a functional RGD motif in FN (FNRGE/RGE) or α5 integrin develop identical phenotypes characterized by embryonic lethality and a severely shortened posterior trunk with kinked neural tubes. Here we show that the FNRGE/RGE embryos arrest both segmentation and axis elongation. The arrest is evident at about E9.0, corresponding to a stage when gastrulation ceases and the tail bud-derived presomitic mesoderm (PSM) induces α5 integrin expression and assumes axis elongation. At this stage cells of the posterior part of the PSM in wild type embryos are tightly coordinated, express somitic oscillator and cyclic genes required for segmentation, and form a tapered tail bud that extends caudally. In contrast, the posterior PSM cells in FNRGE/RGE embryos lost their tight associations, formed a blunt tail bud unable to extend the body axis, failed to induce the synchronised expression of Notch1 and cyclic genes and cease the formation of new somites. Mechanistically, the interaction of PSM cells with the RGD motif of FN is required for dynamic formation of lamellipodia allowing motility and cell-cell contact formation, as these processes fail when wild type PSM cells are seeded into a FN matrix derived from FNRGE/RGE fibroblasts. Thus, α5β1-mediated adhesion to FN in the PSM regulates the dynamics of membrane protrusions and cell-to-cell communication essential for elongation and segmentation of the body axis

The general fault in our fault lines

Pervading global narratives suggest that political polarization is increasing, yet the accuracy of such group meta-perceptions has been drawn into question. A recent US study suggests that these beliefs are inaccurate and drive polarized beliefs about out-groups. However, it also found that informing people of inaccuracies reduces those negative beliefs. In this work, we explore whether these results generalize to other countries. To achieve this, we replicate two of the original experiments with 10,207 participants across 26 countries. We focus on local group divisions, which we refer to as fault lines. We find broad generalizability for both inaccurate meta-perceptions and reduced negative motive attribution through a simple disclosure intervention. We conclude that inaccurate and negative group meta-perceptions are exhibited in myriad contexts and that informing individuals of their misperceptions can yield positive benefits for intergroup relations. Such generalizability highlights a robust phenomenon with implications for political discourse worldwide

Genome sequencing analysis identifies new loci associated with Lewy body dementia and provides insights into its genetic architecture

The genetic basis of Lewy body dementia (LBD) is not well understood. Here, we performed whole-genome sequencing in large cohorts of LBD cases and neurologically healthy controls to study the genetic architecture of this understudied form of dementia, and to generate a resource for the scientific community. Genome-wide association analysis identified five independent risk loci, whereas genome-wide gene-aggregation tests implicated mutations in the gene GBA. Genetic risk scores demonstrate that LBD shares risk profiles and pathways with Alzheimer's disease and Parkinson's disease, providing a deeper molecular understanding of the complex genetic architecture of this age-related neurodegenerative condition