Structure and Reactivity of Terrestrial and Extraterrestrial Pyrrhotite

Pyrrhotite (Fe1−xS) is a non-stoichiometric iron monosulfide common in terrestrial rocks, ore deposits, and many extraterrestrial materials. The non-stoichiometry due to metal vacancies relates to a variety of composition-dependent crystallographic superstructures, but little of the existing structural and microstructural complexity has been explored yet. This thesis investigates the occurrences and nature of pyrrhotite superstructures, examines the related nano- and microstructural phenomena, and explores their effects on chemical reactivity. The goal is to comprehend the relations of the nanoscale real structure of pyrrhotite to its physicochemical properties. A central tool in these studies is analytical transmission electron microscopy (TEM), which has been extensively used to study terrestrial and extraterrestrial samples. In three studies, published or submitted as scientific research articles, it is shown that structural complexity of pyrrhotites is a widespread feature in terrestrial and extraterrestrial materials and is strongly interrelated with its physicochemical properties and environments of formation and alteration. A new model based on translation interface modulation is being introduced to provide a realistic description of the structural state of natural NC-pyrrhotites. Novel insights into the thermodynamically stable phase assemblages in the Fe-S system at ambient temperatures are presented and the crystallography and connected thermochemistry of pyrrhotites are deployed to reach new conclusions about the petrogenetic history of chondritic meteorites and the alteration processes they were involved in. Finally, an experimental alteration study reveals for the fist time quantitatively that the vacancy superstructures and anisotropy of pyrrhotites have tremendous effects on their kinetic behaviors during dissolution under acidic and oxidizing conditions. Intrinsic reactivity differences between 4C- and NC-pyrrhotite are clearly resolved and discusses in the framework of the newly established structure model

Upper limits of water contents in olivine and orthopyroxene of equilibrated chondrites and several achondrites

Hydroxyl defects in nominally anhydrous minerals (NAMs) were potential carriers of water in the early Solar System and might have contributed to the accretion of terrestrial water. To better understand this, we have conducted a nanoscale secondary ion mass spectrometry survey of water contents in olivine and orthopyroxene from a set of equilibrated ordinary chondrites of the L and LL groups (Baszkówka, Bensour, Kheneg Ljouâd, and Tuxtuac) and several ultramafic achondrites (Zakłodzie, Dhofar 125, Northwest Africa [NWA] 4969, NWA 6693, and NWA 7317). For calibration, we used terrestrial olivine and orthopyroxene with H2O contents determined by Fourier transform infrared. Our 99.7% (~3SD) detection limits are 3.6–5.4 ppmw H2O for olivine and 7.7–10.9 ppmw H2O for orthopyroxene. None of the meteoritic samples studied consistently shows water contents above the detection limits. A few exceptions slightly above the detection limits are suspected of terrestrial contamination by ferric oxyhydroxides. If the meteorite samples investigated accreted in the presence of small amounts of water ice, the upper limits of water contents provided by our survey suggest that the retention of hydrogen during thermal metamorphism and differentiation was ineffective. We suggest that loss occurred through combinations of low internal pressures, high permeability along grain boundaries, and speciation of hydrogen into reduced compounds such as H2 and methane, which are less soluble in NAMs than in water

Light scattering observations of spin reversal excitations in the fractional quantum Hall regime

Resonant inelastic light scattering experiments access the low lying excitations of electron liquids in the fractional quantum Hall regime in the range $2/5 \geq \nu \geq 1/3$. Modes associated with changes in the charge and spin degrees of freedom are measured. Spectra of spin reversed excitations at filling factor $\nu \gtrsim 1/3$ and at $\nu \lesssim 2/5$ identify a structure of lowest spin-split Landau levels of composite fermions that is similar to that of electrons. Observations of spin wave excitations enable determinations of energies required to reverse spin. The spin reversal energies obtained from the spectra illustrate the significant residual interactions of composite fermions. At $\nu = 1/3$ energies of spin reversal modes are larger but relatively close to spin conserving excitations that are linked to activated transport. Predictions of composite fermion theory are in good quantitative agreement with experimental results.Comment: Submitted to special issue of Solid State Com

The polymict carbonaceous breccia aguas zarcas: A potential analog to samples being returned by the OSIRIS‐REx and hayabusa2 missions

Abstract On April 23, 2019, a meteorite fall occurred in Aguas Zarcas, Costa Rica. According to the Meteoritical Bulletin, Aguas Zarcas is a brecciated CM2 chondrite dominated by two lithologies. Our X‐ray computed tomography (XCT) results show many different lithologies. In this paper, we describe the petrographic and mineralogical investigation of five different lithologies of the Aguas Zarcas meteorite. The bulk oxygen isotope compositions of some lithologies were also measured. The Aguas Zarcas meteorite is a breccia at all scales. From two small fragments, we have noted five main lithologies, including (1) Met‐1: a metal‐rich lithology; (2) Met‐2: a second metal‐rich lithology which is distinct from Met‐1; (3) a brecciated CM lithology with clasts of different petrologic subtypes; (4) a C1/2 lithology; and (5) a C1 lithology. The Met‐1 lithology is a new and unique carbonaceous chondrite which bears similarities to CR and CM chondrite groups, but is distinct from both based on oxygen isotope data. Met‐2 also represents a new type of carbonaceous chondrite, but it is more similar to the CM chondrite group, albeit with a very high abundance of metal. We have noted some similarities between the Met‐1 and Met‐2 lithologies and will explore possible genetic relationships. We have also identified a brecciated CM lithology with two primary components: a chondrule‐poor lithology and a chondrule‐rich lithology showing different petrologic subtypes. The other two lithologies, C1 and C1/2, are very altered and possibly related to the CM chondrite group. In this article, we describe all the lithologies in detail and attempt a classification of each in order to understand the origin and the history of formation of the Aguas Zarcas parent body

The question of energy reduction: The problem(s) with feedback

With smart metering initiatives gaining increasing global popularity, the present paper seeks to challenge the increasingly entrenched view that providing householders with feedback about their energy usage, via an in-home-display, will lead them to substantially reduce their energy consumption. Specifically, we draw on existing quantitative and qualitative evidence to outline three key problems with feedback, namely: (a) the limited evidence of efficacy, (b) the need for user engagement, and (c) the potential for unintended consequences. We conclude by noting that, in their current form, existing in-home-displays may not induce the desired energy-reduction response anticipated by smart metering initiatives. Instead, if smart metering is to effectively reduce energy consumption there is a clear need to develop and test innovative new feedback devices that have been designed with user engagement in mind

Fine-mapping of the HNF1B multicancer locus identifies candidate variants that mediate endometrial cancer risk.

Common variants in the hepatocyte nuclear factor 1 homeobox B (HNF1B) gene are associated with the risk of Type II diabetes and multiple cancers. Evidence to date indicates that cancer risk may be mediated via genetic or epigenetic effects on HNF1B gene expression. We previously found single-nucleotide polymorphisms (SNPs) at the HNF1B locus to be associated with endometrial cancer, and now report extensive fine-mapping and in silico and laboratory analyses of this locus. Analysis of 1184 genotyped and imputed SNPs in 6608 Caucasian cases and 37 925 controls, and 895 Asian cases and 1968 controls, revealed the best signal of association for SNP rs11263763 (P = 8.4 × 10(-14), odds ratio = 0.86, 95% confidence interval = 0.82-0.89), located within HNF1B intron 1. Haplotype analysis and conditional analyses provide no evidence of further independent endometrial cancer risk variants at this locus. SNP rs11263763 genotype was associated with HNF1B mRNA expression but not with HNF1B methylation in endometrial tumor samples from The Cancer Genome Atlas. Genetic analyses prioritized rs11263763 and four other SNPs in high-to-moderate linkage disequilibrium as the most likely causal SNPs. Three of these SNPs map to the extended HNF1B promoter based on chromatin marks extending from the minimal promoter region. Reporter assays demonstrated that this extended region reduces activity in combination with the minimal HNF1B promoter, and that the minor alleles of rs11263763 or rs8064454 are associated with decreased HNF1B promoter activity. Our findings provide evidence for a single signal associated with endometrial cancer risk at the HNF1B locus, and that risk is likely mediated via altered HNF1B gene expression

Disentangling sequential and concerted fragmentations of molecular polycations with covariant native frame analysis

Using covariance analysis methods, we study the fragmentation dynamics of multiply ionized 1- and 2-iodopropane. Signatures of isomer-specific nuclear motion occurring during sequential fragmentation pathways are identified.</jats:p

Direct momentum imaging of charge transfer following site-selective ionization

We study ultrafast charge rearrangement in dissociating 2-iodopropane (2−C3H7I) using site-selective core ionization at the iodine atom. Clear signatures of electron transfer between the neutral propyl fragment and multiply charged iodine ions are observed in the recorded delay-dependent ion momentum distributions. The detected charge-transfer pathway is only favorable within a small (few angstroms), charge-state-dependent spatial window located at C-I distances longer than that of the neutral ground-state molecule. These results offer insights into the physics underpinning charge transfer in isolated molecules and pave the way for a different class of time-resolved studies