Reconciling early Deccan Traps CO2 outgassing and pre-KPB global climate.

A 2 to 4 °C warming episode, known as the Latest Maastrichtian warming event (LMWE), preceded the Cretaceous-Paleogene boundary (KPB) mass extinction at 66.05 ± 0.08 Ma and has been linked with the onset of voluminous Deccan Traps volcanism. Here, we use direct measurements of melt-inclusion CO2 concentrations and trace-element proxies for CO2 to test the hypothesis that early Deccan magmatism triggered this warming interval. We report CO2 concentrations from NanoSIMS and Raman spectroscopic analyses of melt-inclusion glass and vapor bubbles hosted in magnesian olivines from pre-KPB Deccan primitive basalts. Reconstructed melt-inclusion CO2 concentrations range up to 0.23 to 1.2 wt% CO2 for lavas from the Saurashtra Peninsula and the Thakurvadi Formation in the Western Ghats region. Trace-element proxies for CO2 concentration (Ba and Nb) yield estimates of initial melt concentrations of 0.4 to 1.3 wt% CO2 prior to degassing. Our data imply carbon saturation and degassing of Deccan magmas initiated at high pressures near the Moho or in the lower crust. Furthermore, we find that the earliest Deccan magmas were more CO2 rich, which we hypothesize facilitated more efficient flushing and outgassing from intrusive magmas. Based on carbon cycle modeling and estimates of preserved lava volumes for pre-KPB lavas, we find that volcanic CO2 outgassing alone remains insufficient to account for the magnitude of the observed latest Maastrichtian warming. However, accounting for intrusive outgassing can reconcile early carbon-rich Deccan Traps outgassing with observed changes in climate and atmospheric pCO2.

Gigantic C120 Fullertubes: Prediction and Experimental Evidence for Isomerically Purified Metallic [5,5] C120-D5d(1) and Nonmetallic [10,0] C120-D5h(10766).

We report the first experimental characterization of isomerically pure and pristine C120 fullertubes, [5,5] C120-D5d(1) and [10,0] C120-D5h(10766). These new molecules represent the highest aspect ratio fullertubes isolated to date; for example, the prior largest empty cage fullertube was [5,5] C100-D5d(1). This increase of 20 carbon atoms represents a gigantic leap in comparison to three decades of C60-C90 fullerene research. Moreover, the [10,0] C120-D5d(10766) fullertube has an end-cap derived from C80-Ih and is a new fullertube whose C40 end-cap has not yet been isolated experimentally. Theoretical and experimental analyses of anisotropic polarizability and UV-vis assign C120 isomer I as a [5,5] C120-D5d(1) fullertube. C120 isomer II matches a [10,0] C120-D5h(10766) fullertube. These structural assignments are further supported by Raman data showing metallic character for [5,5] C120-D5d(1) and nonmetallic character for C120-D5h(10766). STM imaging reveals a tubular structure with an aspect ratio consistent with a [5,5] C120-D5d(1) fullertube. With microgram quantities not amenable to crystallography, we demonstrate that DFT anisotropic polarizability, augmented by long-accepted experimental analyses (HPLC retention time, UV-vis, Raman, and STM) can be synergistically used (with DFT) to down select, predict, and assign C120 fullertube candidate structures. From 10 774 mathematically possible IPR C120 structures, this anisotropic polarizability paradigm is quite favorable to distinguish tubular structures from carbon soot. Identification of isomers I and II was surprisingly facile, i.e., two purified isomers for two possible structures of widely distinguishing features. These metallic and nonmetallic C120 fullertube isomers open the door to both fundamental research and application development.

Semiconducting and Metallic [5,5] Fullertube Nanowires: Characterization of Pristine D5h(1)-C90 and D5d(1)-C100.

Although fullerenes were discovered nearly 35 years ago, scientists still struggle to isolate "single molecule" tubular fullerenes larger than C90. In similar fashion, there is a paucity of reports for pristine single-walled carbon nanotubes (SWNTs). In spite of Herculean efforts, the isolation and properties of pristine members of these carbonaceous classes remain largely unfulfilled. For example, the low abundance of spherical and tubular higher fullerenes in electric-arc extracts (<0.01-0.5%) and multiplicity of structural isomers remain a major challenge. Recently, a new isolation protocol for highly tubular fullerenes, also called f ullertubes, was reported. Herein, we describe spectroscopic characterization including 13C NMR, XPS, and Raman results for purified [5,5] fullertube family members, D5h-C90 and D5d-C100. In addition, DFT computational HOMO-LUMO gaps, polarizability indices, and electron density maps were also obtained. The Raman and 13C NMR results are consistent with semiconducting and metallic properties for D5h-C90 and D5d-C100, respectively. Our report suggests that short [5,5] fullertubes with aspect ratios of only ∼1.5-2 are metallic and could exhibit unique electronic properties.

Elucidating the Role of InGaAs and InAlAs Buffers on Carrier Dynamics of Tensile-Strained Ge Double Heterostructures.

Extensive research efforts of strained germanium (Ge) are currently underway due to its unique properties, namely, (i) possibility of band gap and strain engineering to achieve a direct band gap, thus exhibiting superior radiative properties, and (ii) higher electron and hole mobilities than Si for upcoming technology nodes. Realizing lasing structures is vital to leveraging the benefits of tensile-strained Ge (ε-Ge). Here, we use a combination of different analytical tools to elucidate the effect of the underlying InGaAs/InAlAs and InGaAs overlaying heterostructures on the material quality and strain state of ε-Ge grown by molecular beam epitaxy. Using X-ray analysis, we show the constancy of tensile strain in sub-50 nm ε-Ge in a quantum-well (QW) heterostructure. Further, effective carrier lifetime using photoconductive decay as a function of buffer type exhibited a high (low) defect-limited carrier lifetime of ∼68 ns (∼13 ns) in 0.61% (0.66%) ε-Ge grown on an InGaAs (InAlAs) buffer. These results correspond well with the measured surface roughness of 1.289 nm (6.303 nm), consistent with the surface effect of the ε-Ge/III-V heterointerface. Furthermore, a reasonably high effective lifetime of ∼78 ns is demonstrated in a QW of ∼30 nm 1.6% ε-Ge, a moderate reduction from ∼99 ns in uncapped ε-Ge, alluding to the surface effect of the overlying heterointerface. Thus, the above results highlight the prime quality of ε-Ge that can be achieved via III-V heteroepitaxy and paves a path for integrated Ge photonics.

GeSn-on-GaAs with photoconductive carrier lifetime >400 ns: role of substrate orientation and atomistic simulation.

Group IV GeSn quantum material finds application in electronics and silicon-compatible photonics. Synthesizing these materials with low defect density and high carrier lifetime is a potential challenge due to lattice mismatch induced defects and tin segregation at higher growth temperature. Recent advancements in the growth of these GeSn materials on Si, Ge, GaAs, and with substrate orientations, demonstrated different properties using epitaxial and chemical deposition methods. This article addresses the effect of GaAs substrate orientation and misorientation on the materials' properties and carrier lifetimes in epitaxial Ge0.94Sn0.06 layers. With starting GaAs substrates of (100)/2°, (100)/6°, (110) and (111)A orientations, Ge0.94Sn0.06 epitaxial layers were grown with an intermediate Ge buffer layer by molecular beam epitaxy and analyzed by several analytical tools. X-ray analysis displayed good crystalline quality, and Raman spectroscopy measurements showed blue shifts in phonon wavenumber due to biaxial compressive strain in Ge0.94Sn0.06 epilayers. Cross-sectional transmission electron microscopy analysis confirmed the defect-free heterointerface of Ge0.94Sn0.06/Ge/GaAs heterostructure. Minority carrier lifetimes of the unintentionally doped n-type Ge0.94Sn0.06 epilayers displayed photoconductive carrier lifetimes of >400 ns on (100)/6°, 319 ns on (100)/2°, and 434 ns on (110) GaAs substrate at 1500 nm excitation wavelength. On the other hand, Ge0.94Sn0.06 layer showed poor carrier lifetime on (111)A GaAs substrate. The observed differences in carrier lifetimes were correlated with the formation energy of the Ge on (100)/6° and (100)/2° GaAs heterointerface using Stillinger-Weber interatomic potential model-based atomistic simulation with different heterointerfacial bonding by Synopsys QuantumATK tool. Total energy computation of 6280-atom Ge/GaAs supercell on (100)/6° leads to lower formation energy than (100)/2°, making it more thermodynamically stable. Hence, the growth of the GeSn/III-V material system using misoriented (100) substrates that are more thermodynamically stable will enhance the performances of optoelectronic devices.

Volumetrics of CO2 storage in deep saline formations.

Concern about the role of greenhouse gases in global climate change has generated interest in sequestering CO(2) from fossil-fuel combustion in deep saline formations. Pore space in these formations is initially filled with brine, and space to accommodate injected CO(2) must be generated by displacing brine, and to a lesser extent by compression of brine and rock. The formation volume required to store a given mass of CO(2) depends on the storage mechanism. We compare the equilibrium volumetric requirements of three end-member processes: CO(2) stored as a supercritical fluid (structural or stratigraphic trapping); CO(2) dissolved in pre-existing brine (solubility trapping); and CO(2) solubility enhanced by dissolution of calcite. For typical storage conditions, storing CO(2) by solubility trapping reduces the volume required to store the same amount of CO(2) by structural or stratigraphic trapping by about 50%. Accessibility of CO(2) to brine determines which storage mechanism (structural/stratigraphic versus solubility) dominates at a given time, which is a critical factor in evaluating CO(2) volumetric requirements and long-term storage security.

CO2 sorption to subsingle hydration layer montmorillonite clay studied by excess sorption and neutron diffraction measurements.

Geologic storage of CO(2) requires that the caprock sealing the storage rock is highly impermeable to CO(2). Swelling clays, which are important components of caprocks, may interact with CO(2) leading to volume change and potentially impacting the seal quality. The interactions of supercritical (sc) CO(2) with Na saturated montmorillonite clay containing a subsingle layer of water in the interlayer region have been studied by sorption and neutron diffraction techniques. The excess sorption isotherms show maxima at bulk CO(2) densities of ≈ 0.15 g/cm(3), followed by an approximately linear decrease of excess sorption to zero and negative values with increasing CO(2) bulk density. Neutron diffraction experiments on the same clay sample measured interlayer spacing and composition. The results show that limited amounts of CO(2) are sorbed into the interlayer region, leading to depression of the interlayer peak intensity and an increase of the d(001) spacing by ca. 0.5 Å. The density of CO(2) in the clay pores is relatively stable over a wide range of CO(2) pressures at a given temperature, indicating the formation of a clay-CO(2) phase. At the excess sorption maximum, increasing CO(2) sorption with decreasing temperature is observed while the high-pressure sorption properties exhibit weak temperature dependence.

Spatially resolved CO2 carbon stable isotope analyses at the microscale using Raman spectroscopy.

Measuring the carbon stable isotope ratio (13C/12C, expressed as δ13CCO2) in geogenic CO2 fluids is a crucial geochemical tool for studying Earth's degassing. Carbon stable isotope analysis is traditionally performed by bulk mass spectrometry. Although Raman spectroscopy distinguishes 12CO2 and 13CO2 isotopologue bands in spectra, using this technique to determine CO2 isotopic signature has been challenging. Here, we report on in-situ non-destructive analyses of the C stable isotopic composition of CO2, applying a novel high-resolution Raman configuration on 42 high-density CO2 fluid inclusions in mantle rocks from the Lake Tana region (Ethiopia) and El Hierro (Canary Islands). We collected two sets of three spectra with different acquisition times at high spectral resolution in each fluid inclusion. Among the 84 sets of spectra, 58 were characterised by integrated 13CO2/12CO2 band area ratios with reproducibility better than 4‰. Our results demonstrate the determination of δ13CCO2 by Raman spectroscopy in individual fluid inclusions with an error better than 2.5 ‰, which satisfactorily matches bulk mass spectrometry analyses in the same rock samples, supporting the accuracy of the measurements. We thus show that Raman Spectroscopy can provide a fundamental methodology for non-destructive, site-specific, and spatially resolved carbon isotope labelling at the microscale.

Mapping the Interfacial Electronic Structure of Strain-Engineered Epitaxial Germanium Grown on In x Al1-x As Stressors.

The indirect nature of silicon (Si) emission currently limits the monolithic integration of photonic circuitry with Si electronics. Approaches to circumvent the optical shortcomings of Si include band structure engineering via alloying (e.g., Si x Ge1-x-y Sn y ) and/or strain engineering of group IV materials (e.g., Ge). Although these methods enhance emission, many are incapable of realizing practical lasing structures because of poor optical and electrical confinement. Here, we report on strong optoelectronic confinement in a highly tensile-strained (ε) Ge/In0.26Al0.74As heterostructure as determined by X-ray photoemission spectroscopy (XPS). To this end, an ultrathin (∼10 nm) ε-Ge epilayer was directly integrated onto the In0.26Al0.74As stressor using an in situ, dual-chamber molecular beam epitaxy approach. Combining high-resolution X-ray diffraction and Raman spectroscopy, a strain state as high as ε ∼ 1.75% was demonstrated. Moreover, high-resolution transmission electron microscopy confirmed the highly ordered, pseudomorphic nature of the as-grown ε-Ge/In0.26Al0.74As heterostructure. The heterointerfacial electronic structure was likewise probed via XPS, revealing conduction- and valence band offsets (ΔE C and ΔE V) of 1.25 ± 0.1 and 0.56 ± 0.1 eV, respectively. Finally, we compare our empirical results with previously published first-principles calculations investigating the impact of heterointerfacial stoichiometry on the ε-Ge/In x Al1-x As energy band offset, demonstrating excellent agreement between experimental and theoretical results under an As0.5Ge0.5 interface stoichiometry exhibiting up to two monolayers of heterointerfacial As-Ge diffusion. Taken together, these findings reveal a new route toward the realization of on-Si photonics.

Biogenic formation of amorphous carbon by anaerobic methanotrophs and select methanogens.

Elemental carbon exists in different structural forms including graphite, diamond, fullerenes, and amorphous carbon. In nature, these materials are produced through abiotic chemical processes under high temperature and pressure but are considered generally inaccessible to biochemical synthesis or breakdown. Here, we identified and characterized elemental carbon isolated from consortia of anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB), which together carry out the anaerobic oxidation of methane (AOM). Two different AOM consortia, ANME-1a/HotSeep-1 and ANME-2a/c/Seep-SRB, produce a black material with similar characteristics to disordered graphite and amorphous carbon. Stable isotope probing studies revealed that the carbon is microbially generated during AOM. In addition, we found that select methanogens also produce amorphous carbon with similar characteristics to the carbon from AOM consortia. Biogenic amorphous carbon may serve as a conductive element to facilitate electron transfer, or redox active functional groups associated with the carbon could act as electron donors and acceptors.

Ultrastructural and geochemical characterization of Archean-Paleoproterozoic graphite particles: implications for recognizing traces of life in highly metamorphosed rocks.

Abundant graphite particles occur in amphibolite-grade quartzite of the Archean-Paleoproterozoic Wutai Metamorphic Complex in the Wutaishan area of North China. Petrographic thin section observations suggest that the graphite particles occur within and between quartzite clasts and are heterogeneous in origin. Using HF maceration techniques, the Wutai graphite particles were extracted for further investigation. Laser Raman spectroscopic analysis of a population of extracted graphite discs indicated that they experienced a maximum metamorphic temperature of 513 +/- 50 degrees C, which is consistent with the metamorphic grade of the host rock and supports their indigenicity. Scanning and transmission electron microscopy revealed that the particles bear morphological features (such as hexagonal sheets of graphite crystals) related to metamorphism and crystal growth, but a small fraction of them (graphite discs) are characterized by a circular morphology, distinct marginal concentric folds, surficial wrinkles, and complex nanostructures. Ion microprobe analysis of individual graphite discs showed that their carbon isotope compositions range from -7.4 per thousand to -35.9 per thousand V-PDB (Vienna Pee Dee Belemnite), with an average of -20.3 per thousand, which is comparable to bulk analysis of extracted carbonaceous material. The range of their size, ultrastructures, and isotopic signatures suggests that the morphology and geochemistry of the Wutai graphite discs were overprinted by metamorphism and their ultimate carbon source probably had diverse origins that included abiotic processes. We considered both biotic and abiotic origins of the carbon source and graphite disc morphologies and cannot falsify the possibility that some circular graphite discs characterized by marginal folds and surficial wrinkles represent deflated, compressed, and subsequently graphitized organic-walled vesicles. Together with reports by other authors of acanthomorphic acritarchs from greenschist-amphibolite-grade metamorphic rocks, this study suggests that it is worthwhile to examine carbonaceous materials preserved in highly metamorphosed rocks for possible evidence of ancient life.

Effect of water activity on rates of serpentinization of olivine.

The hydrothermal alteration of mantle rocks (referred to as serpentinization) occurs in submarine environments extending from mid-ocean ridges to subduction zones. Serpentinization affects the physical and chemical properties of oceanic lithosphere, represents one of the major mechanisms driving mass exchange between the mantle and the Earth's surface, and is central to current origin of life hypotheses as well as the search for microbial life on the icy moons of Jupiter and Saturn. In spite of increasing interest in the serpentinization process by researchers in diverse fields, the rates of serpentinization and the controlling factors are poorly understood. Here we use a novel in situ experimental method involving olivine micro-reactors and show that the rate of serpentinization is strongly controlled by the salinity (water activity) of the reacting fluid and demonstrate that the rate of serpentinization of olivine slows down as salinity increases and H2O activity decreases.

Transport Across Heterointerfaces of Amorphous Niobium Oxide and Crystallographically Oriented Epitaxial Germanium.

Because of the high carrier mobility of germanium (Ge) and high dielectric permittivity of amorphous niobium pentoxide (a-Nb2O5), Ge/a-Nb2O5 heterostructures offer several advantages for the rapidly developing field of oxide-semiconductor-based multifunctional devices. To this end, we investigate the growth, structural, band alignment, and metal-insulator-semiconductor (MIS) electrical properties of physical vapor-deposited Nb2O5 on crystallographically oriented (100), (110), and (111)Ge epilayers. The as-deposited Nb2O5 dielectrics were found to be in the amorphous state, demonstrating an abrupt oxide/semiconductor heterointerface with respect to Ge, when examined via low- and high-magnification cross-sectional transmission electron microscopy. Additionally, variable-angle spectroscopic ellipsometry and X-ray photoelectron spectroscopy (XPS) were used to independently determine the a-Nb2O5 band gap, yielding a direct gap value of 4.30 eV. Moreover, analysis of the heterointerfacial energy band alignment between a-Nb2O5 and epitaxial Ge revealed valance band offsets (ΔEV) greater than 2.5 eV, following the relation ΔEV(111) > ΔEV(110) > ΔEV(100). Similarly, utilizing the empirically determined a-Nb2O5 band gap, conduction band offsets (ΔEC) greater than 0.75 eV were found, likewise following the relation ΔEC(110) > ΔEC(100) > ΔEC(111). Leveraging the reduced ΔEC observed at the a-Nb2O5/Ge heterointerface, we also perform the first experimental investigation into Schottky barrier height reduction on n-Ge using a 2 nm a-Nb2O5 interlayer, resulting in a 20× increase in reverse-bias current density and improved Ohmic behavior.

The search for and analysis of direct samples of early Solar System aqueous fluids.

We describe the current state of the search for direct, surviving samples of early, inner Solar System fluids-fluid inclusions in meteorites. Meteoritic aqueous fluid inclusions are not rare, but they are very tiny and their characterization is at the state of the art for most analytical techniques. Meteoritic fluid inclusions offer us a unique opportunity to study early Solar System brines in the laboratory. Inclusion-by-inclusion analyses of the trapped fluids in carefully selected samples will, in the immediate future, provide us detailed information on the evolution of fluids as they interacted with anhydrous solid materials. Thus, real data can replace calculated fluid compositions in thermochemical calculations of the evolution of water and aqueous reactions in comets, asteroids, moons and the terrestrial planets.This article is part of the themed issue 'The origin, history and role of water in the evolution of the inner Solar System'.

Heterogeneously-Grown Tunable Tensile Strained Germanium on Silicon for Photonic Devices.

The growth, structural and optical properties, and energy band alignments of tensile-strained germanium (ε-Ge) epilayers heterogeneously integrated on silicon (Si) were demonstrated for the first time. The tunable ε-Ge thin films were achieved using a composite linearly graded InxGa1-xAs/GaAs buffer architecture grown via solid source molecular beam epitaxy. High-resolution X-ray diffraction and micro-Raman spectroscopic analysis confirmed a pseudomorphic ε-Ge epitaxy whereby the degree of strain varied as a function of the In(x)Ga(1-x)As buffer indium alloy composition. Sharp heterointerfaces between each ε-Ge epilayer and the respective In(x)Ga(1-x)As strain template were confirmed by detailed strain analysis using cross-sectional transmission electron microscopy. Low-temperature microphotoluminescence measurements confirmed both direct and indirect bandgap radiative recombination between the Γ and L valleys of Ge to the light-hole valence band, with L-lh bandgaps of 0.68 and 0.65 eV demonstrated for the 0.82 ± 0.06% and 1.11 ± 0.03% strained Ge on Si, respectively. Type-I band alignments and valence band offsets of 0.27 and 0.29 eV for the ε-Ge/In(0.11)Ga(0.89)As (0.82%) and ε-Ge/In(0.17)Ga(0.83)As (1.11%) heterointerfaces, respectively, show promise for ε-Ge carrier confinement in future nanoscale optoelectronic devices. Therefore, the successful heterogeneous integration of tunable tensile-strained Ge on Si paves the way for the design and implementation of novel Ge-based photonic devices on the Si technology platform.

The Tissint Martian meteorite as evidence for the largest impact excavation.

High-pressure minerals in meteorites provide clues for the impact processes that excavated, launched and delivered these samples to Earth. Most Martian meteorites are suggested to have been excavated from 3 to 7 km diameter impact craters. Here we show that the Tissint meteorite, a 2011 meteorite fall, contains virtually all the high-pressure phases (seven minerals and two mineral glasses) that have been reported in isolated occurrences in other Martian meteorites. Particularly, one ringwoodite (75 × 140 µm(2)) represents the largest grain observed in all Martian samples. Collectively, the ubiquitous high-pressure minerals of unusually large sizes in Tissint indicate that shock metamorphism was widely dispersed in this sample (~25 GPa and ~2,000 °C). Using the size and growth kinetics of the ringwoodite grains, we infer an initial impact crater with ~90 km diameter, with a factor of 2 uncertainty. These energetic conditions imply alteration of any possible low-T minerals in Tissint.