Canyon Diablo lonsdaleite is a nanocomposite containing c/h stacking disordered diamond and diaphite.

In 1967, a diamond polymorph was reported from hard, diamond-like grains of the Canyon Diablo iron meteorite and named lonsdaleite. This mineral was defined and identified by powder X-ray diffraction (XRD) features that were indexed with a hexagonal unit cell. Since 1967, several natural and synthetic diamond-like materials with XRD data matching lonsdaleite have been reported and the name lonsdaleite was used interchangeably with hexagonal diamond. Its hexagonal structure was speculated to lead to physical properties superior to cubic diamond, and as such has stimulated attempts to synthesize lonsdaleite. Despite numerous reports, several recent studies have provided alternative explanations for the XRD, transmission electron microscopy and Raman data used to identify lonsdaleite. Here, we show that lonsdaleite from the Canyon Diablo diamond-like grains are a nanocomposite material dominated by subnanometre-scale cubic/hexagonal stacking disordered diamond and diaphite domains. These nanostructured elements are intimately intergrown, giving rise to structural features erroneously associated with h diamond. Our data suggest that the diffuse scattering in XRD and the hexagonal features in transmission electron microscopy images reported from various natural and laboratory-prepared samples that were previously used for lonsdaleite identification, in fact arise from cubic/hexagonal stacking disordered diamond and diaphite domains. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.

Seasonal formation of ikaite in slime flux jelly on an infected tree (Populus fremontii) wound from the Sonoran Desert.

Ikaite is the calcium carbonate hexahydrate (CaCO3·6H2O), which precipitates below ~ 7 °C, first identified from Ikka Fjord in southwest Greenland and subsequently more widely reported. Here is described the serendipitous discovery of ikaite on a tree (Populus fremontii) wound from the hot Sonoran Desert, which precipitates during short cold periods in the winter, whereas monohydrocalcite forms through most of the year. The tree wound consists of infected wood, called wetwood that exudes a nutrient-rich water on which a jelly-like slime flux forms. Ikaite, along with alpha sulfur, precipitates in and on the bacterial slime flux jelly. Each tree wound occurs as an island of mineralization: all the elements for the mineral formation are supplied through the xylem sap expressed from the wetwood infection. The P. fremontii wetwood is capped and surrounded by a hard mineralized zone dominated by ikaite/monohydrocalcite, alpha sulfur, and a range of carbonates and sulfates, on which the slime flux jelly occurs. Water oozing from the wetwood is modestly alkaline (pH = 8.34), with elevated concentrations of K+ (5554.7 ppm) and S as SO42- (1662.9 ppm), with Ca2+ (151.9 ppm) and Mg2+ (270.3 ppm). This water chemistry favors the precipitation of ikaite/monohydrocalcite, both within and below the jelly. The ikaite is temperature sensitive, though the laboratory results show that it can persist for several days at room temperature in the sulfur-rich jelly. The ikaite, and associated mineralization within and around the slime flux jelly, illustrates a new, and likely, global form of bio-mediated mineralization.

Shock-formed carbon materials with intergrown sp3- and sp2-bonded nanostructured units.

Studies of dense carbon materials formed by bolide impacts or produced by laboratory compression provide key information on the high-pressure behavior of carbon and for identifying and designing unique structures for technological applications. However, a major obstacle to studying and designing these materials is an incomplete understanding of their fundamental structures. Here, we report the remarkable structural diversity of cubic/hexagonally (c/h) stacked diamond and their association with diamond-graphite nanocomposites containing sp3-/sp2-bonding patterns, i.e., diaphites, from hard carbon materials formed by shock impact of graphite in the Canyon Diablo iron meteorite. We show evidence for a range of intergrowth types and nanostructures containing unusually short (0.31 nm) graphene spacings and demonstrate that previously neglected or misinterpreted Raman bands can be associated with diaphite structures. Our study provides a structural understanding of the material known as lonsdaleite, previously described as hexagonal diamond, and extends this understanding to other natural and synthetic ultrahard carbon phases. The unique three-dimensional carbon architectures encountered in shock-formed samples can place constraints on the pressure-temperature conditions experienced during an impact and provide exceptional opportunities to engineer the properties of carbon nanocomposite materials and phase assemblages.

An exceptionally stable and widespread hydrated amorphous calcium carbonate precipitated by the dog vomit slime mold Fuligo septica (Myxogastria).

Biogenic amorphous calcium carbonate (ACC) is typically metastable and can rapidly transform through aging, dehydration, and/or heating to crystalline calcium carbonate. Gaining insight into its structure and properties is typically hampered by its tendency to crystallize over short time periods once isolated from the host organism, and also by the small quantities that are usually available for study. Here we describe an exceptionally stable hydrated ACC (HACC) precipitated by the cosmopolitan slime mold Fuligo septica (L.) F.H. Wigg. (1780). A single slime mold can precipitate up to a gram of HACC over the course of one night. Powder x-ray diffraction (XRD) patterns, transmission electron microscopy images, infrared absorption spectra, together with the lack of optical birefringence are consistent with an amorphous material. XRD simulations, supported by thermogravimetric and evolved gas analysis data, are consistent with an intimate association of organic matter with ~ 1-nm-sized ACC units that have monohydrocalcite- and calcite-like nano-structural properties. It is postulated that this association imparts the extreme stability of the slime mold HACC by inhibiting loss of H2O and subsequent crystallization. The composition, structure, and thermal behavior of the HACC precipitated by F. septica collected over 8000 km apart and in markedly different environments, suggests a common structure, as well as similar biochemical and biomineralization mechanisms.

Correlated iron isotopes and silicon contents in aubrite metals reveal structure of their asteroidal parent body.

Iron isotopes record the physical parameters, such as temperature and redox conditions, during differentiation processes on rocky bodies. Here we report the results of a correlated investigation of iron isotope compositions and silicon contents of silicon-bearing metal grains from several aubritic meteorites. Based on their Fe isotopic and elemental Si compositions and thermal modelling, we show that these aubrite metals equilibrated with silicates at temperatures ranging from ~ 1430 to ~ 1640 K and likely sampled different depths within their asteroidal parent body. The highest temperature in this range corresponds to their equilibration at a minimum depth of up to ~ 35 km from the surface of the aubrite parent body, followed by brecciation and excavation by impacts within the first ~ 4 Myr of Solar System history.

Diamond-Graphene Composite Nanostructures.

The search for new nanostructural topologies composed of elemental carbon is driven by technological opportunities as well as the need to understand the structure and evolution of carbon materials formed by planetary shock impact events and in laboratory syntheses. We describe two new families of diamond-graphene (diaphite) phases constructed from layered and bonded sp3 and sp2 nanostructural units and provide a framework for classifying the members of this new class of materials. The nanocomposite structures are identified within both natural impact diamonds and laboratory-shocked samples and possess diffraction features that have previously been assigned to lonsdaleite and postgraphite phases. The diaphite nanocomposites represent a new class of high-performance carbon materials that are predicted to combine the superhard qualities of diamond with high fracture toughness and ductility enabled by the graphitic units and the atomically defined interfaces between the sp3- and sp2-bonded nanodomains.

Terrestrial exposure of a fresh Martian meteorite causes rapid changes in hydrogen isotopes and water concentrations.

Determining the hydrogen isotopic compositions and H2O contents of meteorites and their components is important for addressing key cosmochemical questions about the abundance and source(s) of water in planetary bodies. However, deconvolving the effects of terrestrial contamination from the indigenous hydrogen isotopic compositions of these extraterrestrial materials is not trivial, because chondrites and some achondrites show only small deviations from terrestrial values such that even minor contamination can mask the indigenous values. Here we assess the effects of terrestrial weathering and contamination on the hydrogen isotope ratios and H2O contents of meteoritic minerals through monitored terrestrial weathering of Tissint, a recent Martian fall. Our findings reveal the rapidity with which this weathering affects nominally anhydrous phases in extraterrestrial materials, which illustrates the necessity of sampling the interiors of even relatively fresh meteorite falls and underlines the importance of sample return missions.

Sedimentary laminations in the Isheyevo (CH/CBb) carbonaceous chondrite formed by gentle impact-plume sweep-up.

Prominent macroscopic sedimentary laminations, consisting of mm- to cm-thick alternating well-sorted but poorly mixed silicate and metal-rich layers cut by faults and downward penetrating load structures, are prevalent in the Isheyevo (CH/CBb) carbonaceous chondrite. The load structures give the up direction of this sedimentary rock that accumulated from in-falling metal- and silicate-rich grains under near vacuum conditions onto the surface of an accreting planetesimal. The Isheyevo meteorite is the end result of a combination of events and processes that we suggest was initiated by the glancing blow impact of two planetesimals. The smaller impactor was disrupted forming an impact plume downrange of the impact. The components within the plume were aerodynamically size sorted by the nebular gas and swept up by the impacted planetesimal before turbulent mixing within the plume could blur the effects of the sorting. This plume would have contained a range of materials including elementally zoned Fe-Ni metal grains that condensed in the plume to disrupted unaltered material from the crust of the impactor, such as the hydrated matrix lumps. The juxtaposition of hydrated matrix lumps, some of which have not been heated above 150 °C, together with components that formed above 1000 °C, is compelling evidence that they were swept up together. Sweep-up would have occurred as the rotating impactor moved through the plume producing layers of material: the Isheyevo sample thus represents material accumulated while that part of the rotating planetesimal moved into the plume. Vibrations from subsequent impacts helped to form the load structures and induced weak grading within the layers via kinetic sieving. Following sweep-up, the particles were compacted under low static temperatures as evidenced by the preservation of elementally zoned Fe-Ni metal grains with preserved martensite α 2 cores, distinct metal-metal grain boundaries, and metal-deformation microstructures. This meteorite provides evidence of gentle layer-by-layer accretion in the early Solar System, and also extends the terrestrial sedimentary source-to-sink paradigm to a near vacuum environment where neither fluvial nor aeolian processes operate.

Twinning of cubic diamond explains reported nanodiamond polymorphs.

The unusual physical properties and formation conditions attributed to h-, i-, m-, and n-nanodiamond polymorphs has resulted in their receiving much attention in the materials and planetary science literature. Their identification is based on diffraction features that are absent in ordinary cubic (c-) diamond (space group: Fd-3m). We show, using ultra-high-resolution transmission electron microscope (HRTEM) images of natural and synthetic nanodiamonds, that the diffraction features attributed to the reported polymorphs are consistent with c-diamond containing abundant defects. Combinations of {113} reflection and <011> rotation twins produce HRTEM images and d-spacings that match those attributed to h-, i-, and m-diamond. The diagnostic features of n-diamond in TEM images can arise from thickness effects of c-diamonds. Our data and interpretations strongly suggest that the reported nanodiamond polymorphs are in fact twinned c-diamond. We also report a new type of twin (<121> rotational), which can give rise to grains with dodecagonal symmetry. Our results show that twins are widespread in diamond nanocrystals. A high density of twins could strongly influence their applications.

Substantial production of drosophilin A methyl ether (tetrachloro-1,4-dimethoxybenzene) by the lignicolous basidiomycete Phellinus badius in the heartwood of mesquite (Prosopis juliflora) trees.

Toxic organohalogen pollutants produced as by-products of industrial processes, such as chloroform and polychlorinated dibenzo-p-dioxins, also have significant natural sources. A substantial terrestrial source of halogenated organics originates from fungal decay of wood and leaf litter. Here we show that the lignicolous basidiomycete Phellinus badius deposits up to 30,000 mg of the halogenated metabolite drosophilin A methyl ether (DAME, tetrachloro-1,4-dimethoxybenzene) per kilogram of decayed heartwood in the mesquite Prosopis juliflora. DAME occurs as clusters of glassy crystals up to 1 mm long within the decayed heartwood. In addition, the Phellinus badius basidiocarps contain an average of 24,000 mg DAME/kg dried fruiting body, testifying to the significant translocation and accumulation of Cl accompanied by DAME biosynthesis. The high DAME concentrations attest to the substantial Cl content of the heartwood, which averages near 5,000 ppm, with Cl/K near 1:1, consistent with an inorganic chloride precursor. Phellinus badius has a circumglobal distribution in the tropics and subtropics, where it is widely distributed on hardwoods and commonly associated with decay of mesquite. There is the potential for extensive DAME formation within decayed heartwood worldwide given the extensive range of Phellinus badius and its propensity to form DAME within mesquites. Further, DAME production is not limited to Phellinus badius but occurs in a range of lignicolous basidiomycetes, suggesting a significant natural reservoir for this chloroaromatic with potential environmental implications.

NEW INSIGHT INTO THE SOLAR SYSTEM'S TRANSITION DISK PHASE PROVIDED BY THE METAL-RICH CARBONACEOUS CHONDRITE ISHEYEVO.

Many aspects of planet formation are controlled by the amount of gas remaining in the natal protoplanetary disks (PPDs). Infrared observations show that PPDs undergo a transition stage at several megayears, during which gas densities are reduced. Our Solar System would have experienced such a stage. However, there is currently no data that provides insight into this crucial time in our PPD's evolution. We show that the Isheyevo meteorite contains the first definitive evidence for a transition disk stage in our Solar System. Isheyevo belongs to a class of metal-rich meteorites whose components have been dated at almost 5 Myr after formation of Ca, Al-rich inclusions, and exhibits unique sedimentary layers that imply formation through gentle sedimentation. We show that such layering can occur via the gentle sweep-up of material found in the impact plume resulting from the collision of two planetesimals. Such sweep-up requires gas densities consistent with observed transition disks (10-12-10-11 g cm-3). As such, Isheyevo presents the first evidence of our own transition disk and provides new constraints on the evolution of our solar nebula.

Lonsdaleite is faulted and twinned cubic diamond and does not exist as a discrete material.

Lonsdaleite, also called hexagonal diamond, has been widely used as a marker of asteroidal impacts. It is thought to play a central role during the graphite-to-diamond transformation, and calculations suggest that it possesses mechanical properties superior to diamond. However, despite extensive efforts, lonsdaleite has never been produced or described as a separate, pure material. Here we show that defects in cubic diamond provide an explanation for the characteristic d-spacings and reflections reported for lonsdaleite. Ultrahigh-resolution electron microscope images demonstrate that samples displaying features attributed to lonsdaleite consist of cubic diamond dominated by extensive {113} twins and {111} stacking faults. These defects give rise to nanometre-scale structural complexity. Our findings question the existence of lonsdaleite and point to the need for re-evaluating the interpretations of many lonsdaleite-related fundamental and applied studies.

Growth and single-crystal refinement of phase-III potassium nitrate, KNO(3).

Oriented single crystals of the high-temperature phase of KNO(3) (phase III), a ferroelectric compound that may also occur as an atmospheric aerosol particle, were grown at room temperature and pressure by atomizing a solution of KNO(3) in water and allowing droplets to dry on a glass substrate. The crystals are up to 1 mm across and are stable unless mechanically disturbed. There is no evidence of the spontaneous transformation of phase III to the room-temperature stable phase (phase II), even after several months. Single-crystal structure determinations of phase III were obtained at 295 and 123 K. The unit cell regained its room-temperature dimensions after warming from 123 K. The phase-III KNO(3) structure can be viewed as the stacking parallel to the c axis of alternating K atoms and planar NO(3) groups. The NO(3) groups connect the planes of K atoms, where each O is fourfold coordinated to one N and three K. Each K atom has nine O nearest neighbors, with three bonds at 2.813 and six at 2.9092 A. The interatomic K-N-K distance alternates from 5.051 to 3.941 along the c axis. The N-O distances increase from 1.245 (2) A at 295 K to 1.2533 (15) A at 123 K. The nitrate group has a slight non-planarity, with the N atoms 0.011 A above the O plane and directed toward the more distant K of the K-N-K chain.

Life in extreme environments: survival strategy of the endolithic desert lichen Verrucaria rubrocincta.

Verrucaria rubrocincta Breuss is an endolithic lichen that inhabits caliche plates exposed on the surface of the Sonoran Desert. Caliche surface temperatures are regularly in excess of 60 degrees C during the summer and approach 0 degrees C in the winter. Incident light intensities are high, with photosynthetically active radiation levels typically to 2,600 micromol/m(2) s(-1) during the summer. A cross-section of rock inhabited by V. rubrocincta shows an anatomical zonation comprising an upper micrite layer, a photobiont layer containing clusters of algal cells, and a pseudomedulla embedded in the caliche. Hyphae of the pseudomedulla become less numerous with depth below the rock surface. Stable carbon and oxygen isotopic data for the caliche and micrite fall into two sloping, well-separated arrays on a delta(13)C-delta(18)O plot. The delta(13)C(PDB) of the micrite ranges from 2.1 to 8.1 and delta(18)O(SMOW) from 25.4 to 28.9, whereas delta(13)C(PDB) of the caliche ranges from -4.7 to 0.7 and delta(18)O(SMOW) from 23.7 to 29.2. The isotopic data of the micrite can be explained by preferential fixing of (12)C into the alga, leaving local (13)C enrichment and evaporative enrichment of (18)O in the water. The (14)C dates of the micrite range from recent to 884 years b.p., indicating that "dead" carbon from the caliche is not a significant source for the lichen-precipitated micrite. The endolithic growth is an adaptation to the environmental extremes of exposed rock surfaces in the hot desert. The micrite layer is highly reflective and reduces light intensity to the algae below and acts as an efficient sunscreen that blocks harmful UV radiation. The micrite also acts as a cap to the lichen and helps trap moisture. The lichen survives by the combined effects of biodeterioration and biomineralization. Biodeterioration of the caliche concomitant with biomineralization of a protective surface coating of micrite results in the distinctive anatomy of V. rubrocincta.

Decay of cacti and carbon cycling.

Cacti contain large quantities of Ca-oxalate biominerals, with C derived from atmospheric CO(2). Their death releases these biominerals into the environment, which subsequently transform to calcite via a monohydrocalcite intermediate. Here, the fate of Ca-oxalates released by plants in arid environments is investigated. This novel and widespread form of biomineralization has unexpected consequences on C cycling and calcite accumulation in areas with large numbers of cacti. The magnitude of this mineralization is revealed by studying the large columnar cactus Carnegiea gigantea (Engelm.) Britton and Rose in southwestern Arizona (locally called the saguaro). A large C. gigantea contains on the order of 1 x 10(5) g of the Ca-oxalate weddellite-CaC(2)O(4) x 2H(2)O. In areas with high C. gigantea density, there is an estimated 40 g C(atm) m(-2) sequestered in Ca-oxalates. Following the death of the plant, the weddellite transforms to calcite on the order to 10-20 years. In areas with high saguaro density, there is an estimated release of up to 2.4 g calcite m(-2) year(-1) onto the desert soil. Similar transformation mechanisms occur with the Ca-oxalates that are abundant in the majority of cacti. Thus, the total atmospheric C returned to the soil of areas with a high number density of cacti is large, suggesting that there may be a significant long-term accumulation of atmospheric C in these soils derived from Ca-oxalate biominerals. These findings demonstrate that plant decay in arid environments may have locally significant impacts on the Ca and inorganic C cycles.