Thermal alteration of labile elements in carbonaceous chondrites
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Alessondra Springmann↗
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Highly labile elements
Certain elements of high lability are very responsive to thermal processes, being either highly volatile during primary nebular condensation or highly mobile by postaccretionary metamorphic or shock heating. Data for highly labile elements indicate that different thermal processes were important in the genesis of each of the chondritic groups and a discussion of each is given. Contents of highly labile elements in a given group of contemporary falls differ from those of the same group that fell in Antarctica more than 0.1 Myr ago. This difference is due either to a time-dependent change in meteorite sources or, less likely, orbital variation of the meteorite flux to Earth.
Lipschutz, Michael E.↗
Multivariate statistical analysis: Principles and applications to coorbital streams of meteorite falls
Multivariate statistical analysis techniques (linear discriminant analysis and logistic regression) can provide powerful discrimination tools which are generally unfamiliar to the planetary science community. Fall parameters were used to identify a group of 17 H chondrites (Cluster 1) that were part of a coorbital stream which intersected Earth's orbit in May, from 1855 - 1895, and can be distinguished from all other H chondrite falls. Using multivariate statistical techniques, it was demonstrated that a totally different criterion, labile trace element contents - hence thermal histories - or 13 Cluster 1 meteorites are distinguishable from those of 45 non-Cluster 1 H chondrites. Here, we focus upon the principles of multivariate statistical techniques and illustrate their application using non-meteoritic and meteoritic examples.
Wolf, S. F.↗
An H chondrite stream - Identification and confirmation
Fall data indicate that a significant, elongate cluster of co-orbital H chondrite falls in May between 1855 and 1895 (H Cluster 1) records encounters with two or three closely spaced and probably related meteoroid stream components, each of which was met near its perihelion. Although meteorites included in the cluster vary widely in petrographic type, shock facies, and Ne-21 exposure age, they have a distinct labile trace element signature that confirms a common thermal history and, thus, a common source region within an H chondrite parent body. Hence, meteorites selected by one criterion (fall parameters) as distinguishable from all other H chondrites, are distinguished from them by another completely different criterion (contents of labile trace elements).
Dodd, Robert T.↗
Node Distortion as a Tunable Mechanism for Negative Thermal Expansion in Metal–Organic Frameworks
Chemically functionalized series of metal–organic frameworks (MOFs), with subtle differences in local structure but divergent properties, provide a valuable opportunity to explore how local chemistry can be coupled to long-range structure and functionality. Using in situ synchrotron X-ray total scattering, with powder diffraction and pair distribution function (PDF) analysis, we investigate the temperature dependence of the local- and long-range structure of MOFs based on NU-1000, in which Zr 6 O 8 nodes are coordinated by different capping ligands (H 2 O/OH, Cl – ions, formate, acetylacetonate, and hexafluoroacetylacetonate). We show that the local distortion of the Zr 6 nodes depends on the lability of the ligand and contributes to a negative thermal expansion (NTE) of the extended framework. Using multivariate data analyses, involving non-negative matrix factorization (NMF), we demonstrate a new mechanism for NTE: progressive increase in the population of a smaller, distorted node state with increasing temperature leads to global contraction of the framework. The transformation between discrete node states is noncooperative and not ordered within the lattice, i.e., a solid solution of regular and distorted nodes. Density functional theory calculations show that removal of ligands from the node can lead to distortions consistent with the Zr···Zr distances observed in the experiment PDF data. Control of the node distortion imparted by the nonlinker ligand in turn controls the NTE behavior. Furthermore, these results reveal a mechanism to control the dynamic structure of MOFs based on local chemistry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Crystallographic Evidence of Size-Dependent Bond Flexibility in Metal–Organic Framework Nanocrystals
Size-dependent electronic, magnetic, and optical behavior suggests that metal–organic frameworks become softer materials as their particle sizes decrease, but direct evidence is lacking. Here, we report variable-temperature powder X-ray diffraction data of Fe(1,2,3-triazolate)2 particles that offer crystallographic insight into size-dependent bond flexibility. Rietveld refinement reveals size-dependent positive thermal expansion upon downsizing the crystalline domains from 178 to 9 nm, with a 6-fold increase from 16 MK –1 to 96 MK –1 . Here, this behavior occurs in tandem with size-dependent elongation of metal–ligand bonds and increasing thermal displacement parameters, consistent with pronounced metal-linker bond lability. We propose that these effects, as well as size-dependent annealing of crystallite sizes, originate from the high charge density and surface stress of smaller particles. Taken together, these results provide structural evidence that size reduction serves as a synthetic route to controlling the dynamic response of materials to external stimuli.
Crystals↗
Accessing pluripotent materials through tempering of dynamic covalent polymer networks
Pluripotency, which is defined as a system not fixed as to its developmental potentialities, is typically associated with biology and stem cells. Here, inspired by this concept, we report synthetic polymers that act as a single “pluripotent” feedstock and can be differentiated into a range of materials that exhibit different mechanical properties, from hard and brittle to soft and extensible. To achieve this, we have exploited dynamic covalent networks that contain labile, dynamic thia-Michael bonds, whose extent of bonding can be thermally modulated and retained through tempering, akin to the process used in metallurgy. In addition, we show that the shape memory behavior of these materials can be tailored through tempering and that these materials can be patterned to spatially control mechanical properties.
36 MATERIALS SCIENCE↗
Synthesis and evaluation of polymers for use in early warning fire alarm devices
Conjugated polyacetylene polymers and one condensation polyene, all containing a high degree of conjugated unsaturation, were synthesized. These polymers were characterized by chemical analysis and by thermogravimetric analysis, as well as for their film-forming capability and gas/polymer interactions. It was found that those that had a high degree of conjugated unsaturation and had resonance - stabilizing groups were very thermally stable to 200 C, e.g., poly(dicyanoacetylene), poly(ethynylferrocene) and poly(phenylacetylene); while those with labile moieties, such as poly(p-formamidophenylacetylene), among others, suffered some degradation when heated in air. When subjected to gas/polymer interaction effects, the greatest change in electrical conductance was observed when ammonia was used as the gas and poly(p-nitrophenylacetylene) was the detector. Other polymers showed similar behavior. For example, poly(ethynylcarborane), considered to be an electron acceptor also showed a change in electrical conductance when exposed to ammonia, while poly(ethynylpyridine) and poly(ethylidenepyridazine) responded to carbon monoxide. However, for "fire gases" (gases from smoldering cotton), poly(ethynylferrocene) was the most responsive. Thus, the concept of polymers with different electronegativities forming charge-transfer complexes with different gases was found to be operable.
Byrd, N. R.↗
Undercoolability and the exposure of metastable structures
The thermodynamic conditions for exposing metastable states are established by deenergizing a material, as in melt quenching, condensation, etc. When these conditions are met, metastable states may appear because they are kinetically preferred. The understanding of these kinetic preferences is reviewed. Formation of metastable structures by melt quenching requires high resistance to crystal nucleation to deep undercooling through the labile regime between the liquidus and configurational freezing temperature, Tg. Further, the growth of the most stable phase must be thermally activated (and therefore quench-suppressible) if the metastable state is to persist at T less than Tg. In metal systems, selective alloying is often crucial to the provision of the nucleation and/or growth resistance requisite to forming various metastable structures. These alloying effects are surveyed and interpreted.
Turnbull, David↗
Noble gases in presolar diamonds II: Component abundances reflect thermal processing
Using the isotopic compositions derived in Huss and Lewis, 1994a, abundances of the P3, HL, and P6 noble-gas components were determined for 15 diamonds separates from primitive chondrites of 8 chondrite classes. Within a meteorite class, the relative abundances of these components correlate with the petrologic subtype of the host meteorite, indicating that metamorphism is primarily responsible for the variations. Relative abundances of P3, HL, and P6 among diamond samples can be understood in terms of thermal processing of a single mixture of diamonds like those now found in CI and CM2 chondrites. With relatively gentle heating, primitive diamonds first lose their low-temperature P3 gases and a 'labile' fraction of the HL component. Mass loss associated with release of these components produces an increase in the HL and P6 content of the remaining diamond relative to unprocessed diamond. Higher temperatures initiate destruction of the main HL carrier, while the HL content of the surviving diamonds remains essentially constant. At the same time, the P6 carrier begins to preferentially lose light noble gases. Meteorites that have experienced metamorphic temperatures greater than or = 650 C have lost essentially all of their presolar diamond through chemical reactions with surrounding minerals. The P3 abundance seems to be a function only of the maximum temperature experienced by the diamonds and thus is independent of the nature of the surrounding environment. If all classes inherited the same mixture of primitive diamonds, then P3 abundances would tie together the metamorphic scales in different meteorite classes. However, if the P3 abundance indicates a higher temperature than do other thermometers applicable to the host meteorite, then the P3 abundance may contain information about heating prior to accretion. Diamonds in the least metamorphosed EH, CV, and CO chondrites seem to carry a record of pre-accretionary thermal processing.
Huss, Gary R.↗
Chemical studies of differentiated meteorites. I - Labile trace elements in Antarctic and non-Antarctic eucrites
Element contents of Ag, Au, Bi, Cd, Co, Cs, Ga, In, Rb, Sb, Se, Te, Tl, U, and Zn were analyzed, using RNAA, in 25 Antarctic and nine non-Antarctic eucrites to determine whether these two populations differ significantly in thermal history and derive from the same or different eucrite parent body. Data for these 15 elements indicate that basaltic Antarctic and non-Antarctic eucrite populations reflect the same genetic processes and, hence, come from the same parent asteroid.
Paul, Rick L.↗
Polysulfamates as “Macroisosteres” of Polyurethanes with Improved Degradability
Abstract Addressing the environmental persistence of plastics requires the development of next‐generation polymers that combine high performance with enhanced degradability. Progress toward this grand challenge has been impeded, in part, by the absence of a general blueprint for the macromolecular design of such materials. Herein, we introduce a “macroisostere” design strategy, where the carbonyl group (–CO–) in polyurethanes (PUs) is replaced with a sulfonyl group (–SO 2 –), resulting in a virtually unknown family of polymers called polysulfamates. This approach, inspired by the use of bioisosteres in drug discovery, aims to preserve key interchain interactions that contribute to thermomechanical performance while enhancing the hydrolytic lability of the polymer backbone. The optimization of a Sulfur(VI) Fluoride Exchange (SuFEx) polymerization allowed the synthesis of ten polysulfamates structurally analogous to common PUs. Comparative analysis of one PU and its polysulfamate analog showed that this isosteric substitution increases thermal stability, slightly lowers the glass transition temperature, and retains similar hardness and reduced Young's modulus. Notably, the S(VI)‐based polysulfamate demonstrated significantly enhanced hydrolytic degradability. These results highlight the potential of the “macroisostere” approach as a generalizable strategy for designing high‐performance, degradable alternatives to traditional plastics.
Chemistry↗
Microbial responses to long-term warming differ across soil microenvironments
Soil carbon loss is likely to increase due to climate warming, but microbiomes and microenvironments may dampen this effect. In a 30-year warming experiment, physical protection within soil aggregates affected the thermal responses of soil microbiomes and carbon dynamics. In this study, we combined metagenomic analysis with physical characterization of soil aggregates to explore mechanisms by which microbial communities respond to climate warming across different soil microenvironments. Long-term warming decreased the relative abundances of genes involved in degrading labile compounds (e.g. cellulose), but increased those genes involved in degrading recalcitrant compounds (e.g. lignin) across aggregate sizes. These changes were observed in most phyla of bacteria, especially for Acidobacteria, Actinobacteria, Bacteroidetes, Chloroflexi, and Planctomycetes. Microbial community composition was considerably altered by warming, leading to declined diversity for bacteria and fungi but not for archaea. Microbial functional genes, diversity, and community composition differed between macroaggregates and microaggregates, indicating the essential role of physical protection in controlling microbial community dynamics. Our findings suggest that microbes have the capacity to employ various strategies to acclimate or adapt to climate change (e.g. warming, heat stress) by shifting functional gene abundances and community structures in varying microenvironments, as regulated by soil physical protection.
59 BASIC BIOLOGICAL SCIENCES↗
Size-Dependent Thermal Shifts to MOF Nanocrystal Optical Gaps Induced by Dynamic Bonding
Conventional semiconductor nanocrystals exhibit wide-ranging optical behavior, whereas the size-dependent photophysical properties of metal–organic framework (MOF) nanocrystals remain an open research frontier. Furthermore, we present size- and temperature-dependent optical absorption spectra of common MOFs with particle sizes ranging from tens of nanometers to several micrometers. All materials exhibit optical gaps that decrease at elevated temperatures, which we attribute to the dynamic nature of MOF metal–linker bonds. Accordingly, whereas the labile titanium–carboxylate bonds of MIL-125 give rise to bandgaps that red-shift by ~600 meV over 300 K, the more rigid zinc–imidazolate bonds of ZIF-8 produce a red-shift of only ~10 meV. Furthermore, smaller particles induce far larger decreases to optical gaps. Taken together, these results suggest MOF bonding becomes more flexible with smaller nanocrystal sizes, offering a powerful tool for manipulating optical behavior through composition, temperature, and dimensionality.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Metamorphism and aqueous alteration in low petrographic type ordinary chondrites
In order to investigate the relative importance of dry metamorphism and aqueous alteration in the history of chondruies, chondruies were hand-picked from the Semarkona (petrographic type 3.0), Bishunpur (3. 1), Chainpur (3.4), Dhajala (3.8) and Allegan (5) chondrites, and matrix samples were extracted from the first three ordinary chondrites. The thermoluminescence (TL) properties of all the samples were measured, and appropriate subsets of the samples were analyzed by electron-microprobe and radiochemical neutron activation and the water and H-isotopic composition determined. The TL data for chondrules from Semarkona and Bishunpur scatter widely showing no unambiguous trends, although group B1 chondrules tend to have lower sensitivities and lower peak temperatures compared with group A5 chondrules. It is argued that these data reflect the variety of processes accompanying chondrule formation. The chondrules show remarkably uniform contents of the highly labile elements, indicating mineralogical control on abundance and volatile loss from silicates and loss and recondensation of mobile chalcophiles and siderophiles in some cases. Very high D/H values (up to approx. 8000% SMOW) are observed in certain Semarkona chondrules, a confirmation of earlier work. With increasing petrographic type, mean TL sensitivities of the chondrules increase, the spread of values within an individual meteorite decreases, and peak temperatures and peak widths show trends indicating that the TL is mainly produced by feldspar and that dry, thermal metamorphism is the dominant secondary process experienced by the chondrules. The TL sensitivities of matrix samples also increase with petrographic type. Chainpur matrix samples show the same spread of peak temperatures and peak widths as Chainpur chondruies, indicating metamorphism-related changes in the feldspar are responsible for the TL of the matrix. The TL data for the Semarkona and Bishunpur matrix samples provide, at best, only weak evidence for aqueous alteration, but the matrix contains H with approximately terrestrial D/H values, even though it contains much water. Secondary processes (probably aqueous alteration) presumably lowered the D/H of the matrix and certain chondrules. While chondrule properties appear to be governed primarily by formation processes and subsequent metamorphism, the matrix of Semarkona has a more complex history involving aqueous alteration as a meteorite-wide process.
Xie, T.↗
Thermal metamorphism of primitive meteorites. VIII - Noble gases, carbon and sulfur in Allende /C3/ meteorite heated at 400-1000 C
Noble gases, C and S, are lost from Allende samples heated for 1 week at temperatures of 400-1000 C in a low pressure environment. In the extreme, losses of He-3 and He-4 are about 100 x while for C, S and Ne, Ar and Kr isotopes and Xe-132 these are less than or equal to 10 x. Except for He, these losses are less severe than those of Bi or Tl from samples heated in the same runs. Significant He, Ne and Ar isotopic fractionation during heating indicates preferential outgassing of specific reservoirs. Next to He, Ar-40 is the most labile of those species considered here but still less so than Bi or Tl. L-group (but not H- or LL-group) chondrites may have lost mobile elements like Tl while being outgassed after late impact-associated heating. A less likely alternative involving a collateral relation between condensation conditions and depth in a parent object may also explain the L-group trend.
Herzog, G. F.↗
The formation of peroxonitrites and oxygen on Mars
When Martian regolith samples are moistened with water, a strong oxidant and oxygen gas are released. The many possible oxidants which have been suggested as present, including superoxide (O2(-)) hydrogen peroxide (H2O2(-)), and manganese (IV) oxide (MnO2), as well as peroxonitrite (ONOO(-)), can be distinguished by their ability to account for the numerous observations of the Viking Labelled Release (LR) and Gas Exchange (GEX) experiments. The magnitudes, kinetics, and heat labilities of the LR experiments and the magnitudes and heat labilities of the GEX experiments have been quantitatively replicated with peroxonitrites. Further, it is to be expected from information about the photochemistry of nitrogen in the atmosphere, the calculated fluxes of the NO(x) to the surface, the known reactions of NO(x) with carbonates to produce nitrates and photolysis studies of nitrates, that peroxonitrites are present on Mars. However, considerable uncertainty has existed about the form in which oxygen is stored in photolyzed nitrate crystals. Models have ranged from micropores of O2 to chemically bound oxygen as peroxonitrite (O2NOO(-)), as well as peroxonitrite. Studies of the solution chemistry and solid state photochemistry were completed, which show that much of the oxygen evolved on wetting comes from thermal breakdown of peroxonitrite after it is dissolved. A chemical model is developed for the photochemical processes occurring during UV irradiation of solid nitrates which resolves the several contradictory models discussed in the literature in recent years.
Plumb, Robert C.↗
Organic preservation of vase‐shaped microfossils from the late Tonian Chuar Group, Grand Canyon, Arizona, USA
Abstract Vase‐shaped microfossils (VSMs) are found globally in middle Neoproterozoic (800–730 Ma) marine strata and represent the earliest evidence for testate (shell‐forming) amoebozoans. VSM tests are hypothesized to have been originally organic in life but are most commonly preserved as secondary mineralized casts and molds. A few reports, however, suggest possible organic preservation. Here, we test the hypothesis that VSMs from shales of the lower Walcott Member of the Chuar Group, Grand Canyon, Arizona, contain original organic material, as reported by B. Bloeser in her pioneering studies of Chuar VSMs. We identified VSMs from two thin section samples of Walcott Member black shales in transmitted light microscopy and used scanning electron microscopy to image VSMs. Carbonaceous material is found within the internal cavity of all VSM tests from both samples and is interpreted as bitumen mobilized from Walcott shales likely during the Cretaceous. Energy dispersive X‐ray spectroscopy (EDS) and wavelength dispersive X‐ray spectroscopy (WDS) reveal that VSM test walls contain mostly carbon, iron, and sulfur, while silica is present only in the surrounding matrix. Raman spectroscopy was used to compare the thermal maturity of carbonaceous material within the samples and indicated the presence of pyrite and jarosite within fossil material. X‐ray absorption spectroscopy revealed the presence of reduced organic sulfur species within the carbonaceous test walls, the carbonaceous material found within test cavities, and in the sedimentary matrix, suggesting that organic matter sulfurization occurred within the Walcott shales. Our suite of spectroscopic analyses reveals that Walcott VSM test walls are organic and sometimes secondarily pyritized (with the pyrite variably oxidized to jarosite). Both preservation modes can occur at a millimeter spatial scale within sample material, and at times even within a single specimen. We propose that sulfurization within the Walcott Shales promoted organic preservation, and furthermore, the ratio of iron to labile VSM organic material controlled the extent of pyrite replacement. Based on our evidence, we conclude that the VSMs are preserved with original organic test material, and speculate that organic VSMs may often go unrecognized, given their light‐colored, translucent appearance in transmitted light.
58 GEOSCIENCES↗