Medium-range order in molecular materials: fluctuation electron microscopy for detecting fullerenes in disordered carbons.

During a fluctuation electron microscopy (FEM) study of disordered carbons, we found that samples containing C(60) exhibit a normalized variance peak at 7.1 nm(-1) that appears to be a unique indicator of tight curvature in layered materials. This peak is associated with the characteristic in-plane carbon-carbon bond distance of approximately 0.14 nm in graphene. Diffraction from this spacing is normally forbidden in planar graphene (and graphite), but becomes allowed when the layer structure is interrupted. Such interruptions arise at the edges of graphite fragments and also when 5-rings are incorporated into a layer. We show that the curvature induced by a high density of 5-rings, such as that in C(60), can dominate the variance peak at 7.1 nm(-1). FEM simulations reveal that the variance peak at approximately 7.1 nm(-1), which we label F(1), is one of several fullerene-signature peaks, with others occurring at Q values of 10.6 nm(-1) (F(2)) and 12.4 nm(-1) (F(3)). We conclude that FEM is a sensitive method for detecting dilute quantities of highly curved pentagon-rich fullerenes, such as C(60), when dispersed within disordered graphitic carbon.

Ozonolysis of mixed oleic-acid/stearic-acid particles: reaction kinetics and chemical morphology.

The ozonolysis of mixed oleic-acid/stearic-acid (OL/SA) aerosol particles from 0/100 to 100/0 wt % composition is studied. The magnitude of the divergence of the particle beam inside an aerosol mass spectrometer shows that, in the concentration range 100/0 to 60/40, the mixed OL/SA particles are liquid prior to reaction. Upon ozonolysis, particles having compositions of 75/25 and 60/40 change shape, indicating that they have solidified during reaction. Transmission electron micrographs show that SA(s) forms needles. For particles having compositions of 75/25, 60/40, and greater SA content, the reaction kinetics exhibit an initial fast decay of OL for low O(3) exposure with no further loss of OL at higher O(3) exposures. For compositions from 50/50 to 10/90, the residual OL concentration remains at 28 +/- 2% of its initial value. The initial reactive uptake coefficient for O(3), as determined by OL loss, decreases linearly from 1.25 (+/-0.2) x 10(-3) to 0.60 (+/-0.15) x 10(-3) for composition changes of 100/0 to 60/40. At 50/50 composition, the uptake coefficient drops abruptly to 0.15 (+/-0.1) x 10(-3), and there are no further changes with increased SA content. These observations can be explained with a combination of three postulates: (1) Unreacted mixed particles remain as supersaturated liquids up to 60/40 composition, and the OL in this form rapidly reacts with O(3). (2) SA, as it solidifies, locks into its crystal structure a significant amount of OL, and this OL is completely inaccessible to O(3). (3) Accompanying crystallization, some stearic acid molecules connect as a filamentous network to form a semipermeable gel containing liquid OL but with a reduced uptake coefficient because of the decrease in molecular diffusivity in the gel. An individual particle of 50/50 to 90/10 is hypothesized as a combination of SA crystals having OL impurities (postulate 2) that are partially enveloped by an SA/OL gel (postulate 3) to explain (a) the abrupt drop in the uptake coefficient from 60/40 to 50/50 and (b) the residual OL content even after high ozone exposure. The results of this study, pointing out the important effects of particle phase, composition, and morphology on chemical reactivity, contribute to an improved understanding of the aging processes of atmospheric aerosol particles.

Comparison of intensity distributions in tomograms from BF TEM, ADF STEM, HAADF STEM, and calculated tilt series.

The three-dimensional (3D) morphology of a nanometer-sized object can be obtained using electron tomography. Variations in composition or density of the object cause variations in the reconstructed intensity. When imaging homogeneous objects, variations in reconstructed intensity are caused by the imaging technique, imaging conditions, and reconstruction. In this paper, we describe data acquisition, image processing, and 3D reconstruction to obtain and compare tomograms of magnetite crystals from bright field (BF) transmission electron microscopy (TEM), annular dark-field (ADF) scanning transmission electron microscopy (STEM), and high-angle annular dark field (HAADF) STEM tilt series. We use histograms, which plot the number of volume elements (voxels) at a given intensity vs. the intensity, to measure and quantitatively compare intensity distributions among different tomograms. In combination with numerical simulations, we determine the influence of maximum tilt angle, tilt increment, contrast changes with tilt (diffraction contrast), and the signal-to-noise ratio (SNR) as well as the choice of the reconstruction approach (weighted backprojection (WB) and sequential iterative reconstruction technique (SIRT)) on the histogram. We conclude that because ADF and HAADF STEM techniques are less affected by diffraction, and because they have a higher SNR than BF TEM, they are better suited for tomography of nanometer-sized crystals.

Calibration of projector lens distortions.

The distortions introduced into high-resolution transmission electron microscope (HRTEM) images by the projector lens system are an important source of systematic error for quantitative displacement and strain determination. Using geometric phase analysis of images of perfect crystals, we measured these errors for two different transmission electron microscopes. Local magnification varies by as much as 5%, and rotation can reach 2 degrees across a typical image. Our experimental results are compared with theory, and optical pincushion and spiral distortion coefficients are determined. A method for calibrating and removing these distortions is presented that enables quantification to 0.1% strain and 0.1 degrees rotation across the whole field of view. This calibration is also critical for the accurate measurement of local lattice parameters from HRTEM images.

Magnetite morphology and life on Mars.

Nanocrystals of magnetite (Fe(3)O(4)) in a meteorite from Mars provide the strongest, albeit controversial, evidence for the former presence of extraterrestrial life. The morphological and size resemblance of the crystals from meteorite ALH84001 to crystals formed by certain terrestrial bacteria has been used in support of the biological origin of the extraterrestrial minerals. By using tomographic and holographic methods in a transmission electron microscope, we show that the three-dimensional shapes of such nanocrystals can be defined, that the detailed morphologies of individual crystals from three bacterial strains differ, and that none uniquely match those reported from the Martian meteorite. In contrast to previous accounts, we argue that the existing crystallographic and morphological evidence is inadequate to support the inference of former life on Mars.

The structure of ferritin cores determined by electron nanodiffraction.

Electron nanodiffraction, with a 100-keV electron beam less than 1 nm in diameter, has been used to obtain single-crystal diffraction patterns from individual iron-containing cores of ferritin molecules. We show that, while a majority of the cores have a hexagonal structure somewhat similar to the major phase in the mineral ferrihydrite, as previously assumed, several minor phases are present including some that are similar in structure to the iron oxides magnetite and hematite and also some composed of highly disordered material. In general, each core consists of one single crystal of one phase.

Magnetite biomineralization and ancient life on Mars.

Certain chemical and mineral features of the Martian meteorite ALH84001 were reported in 1996 to be probable evidence of ancient life on Mars. In spite of new observations and interpretations, the question of ancient life on Mars remains unresolved. Putative biogenic, nanometer magnetite has now become a leading focus in the debate.

Airborne minerals and related aerosol particles: effects on climate and the environment.

Aerosol particles are ubiquitous in the troposphere and exert an important influence on global climate and the environment. They affect climate through scattering, transmission, and absorption of radiation as well as by acting as nuclei for cloud formation. A significant fraction of the aerosol particle burden consists of minerals, and most of the remainder- whether natural or anthropogenic-consists of materials that can be studied by the same methods as are used for fine-grained minerals. Our emphasis is on the study and character of the individual particles. Sulfate particles are the main cooling agents among aerosols; we found that in the remote oceanic atmosphere a significant fraction is aggregated with soot, a material that can diminish the cooling effect of sulfate. Our results suggest oxidization of SO2 may have occurred on soot surfaces, implying that even in the remote marine troposphere soot provided nuclei for heterogeneous sulfate formation. Sea salt is the dominant aerosol species (by mass) above the oceans. In addition to being important light scatterers and contributors to cloud condensation nuclei, sea-salt particles also provide large surface areas for heterogeneous atmospheric reactions. Minerals comprise the dominant mass fraction of the atmospheric aerosol burden. As all geologists know, they are a highly heterogeneous mixture. However, among atmospheric scientists they are commonly treated as a fairly uniform group, and one whose interaction with radiation is widely assumed to be unpredictable. Given their abundances, large total surface areas, and reactivities, their role in influencing climate will require increased attention as climate models are refined.

Reaction sequence of iron sulfide minerals in bacteria and their use as biomarkers.

Some bacteria form intracellular nanometer-scale crystals of greigite (Fe3S4) that cause the bacteria to be oriented in magnetic fields. Transmission electron microscope observations showed that ferrimagnetic greigite in these bacteria forms from nonmagnetic mackinawite (tetragonal FeS) and possibly from cubic FeS. These precursors apparently transform into greigite by rearrangement of iron atoms over a period of days to weeks. Neither pyrrhotite nor pyrite was found. These results have implications for the interpretation of the presence of pyrrhotite and greigite in the martian meteorite ALH84001.

Electromagnetic heating in the early solar nebula and the formation of chondrules.

Certain opaque inclusions within primitive meteorites exhibit textures that suggest chondrules formed during intense, short-duration radiative heating episodes in the early solar system. Experimental support for this interpretation is provided by the textures produced when chondrule-like assemblages are heated with visible laser light. Computer simulations of radiative heating provide additional evidence for the role of electromagnetic energy in heating nebular solids by offering an explanation for the size distributions of chondrules and the presence of dusty chondrule rims. Nebular lightning and magnetic reconnection flares are possible sources of electromagnetic energy for these transient heating events.

Fullerenes from a fulgurite.

Peaks at 720 and 840 atomic mass units were identified by mass spectrometry in a sample extracted from a fulgurite, which is a glassy rock that forms where lightning strikes the ground. The peaks are interpreted as arising from C(60) and C(70) and the associated peaks as produced from other fullerenes. The intense conditions generated by the lightning not only melted the rock it struck and fused the associated soil but also allowed fullerenes to form, presumably from the organic debris in the soil.

Fullerenes from the geological environment.

By means of high-resoluton transmission electron microscopy, both C(60) and C(70) fullerenes have been found in a, carbon-rich Precambrian rock from Russia The fullerenes were confirmed by Fourier transform mass spectrometry with both laser desorption and thermal desorption/electron-capture methods to verify that the fullerenes were indeed present in the geological sample and were not generated by the laser ionization event. The mass spectra were measured under conditions sufficient to resolve the (13)C/(12)C isotopic ratios for C(60) and C(70) and indicate that these ratios correspond to the normal range of isotopic values.

Calcic micas in the allende meteorite: evidence for hydration reactions in the early solar nebula.

Two calcic micas, clintonite and margarite, have been identified in alteration products in a calcium- and aluminum-rich inclusion (CAI) in the Allende meteorite. Clintonite replaces grossular in alteration veins, and margarite occurs as lamellae in anorthite. Their occurrence suggests that, in addition to undergoing high-temperature alteration by a volatile and iron-rich vapor that produced the grossular and anorthite, some CAIs underwent alteration at moderate temperatures (

Hematite nanospheres of possible colloidal origin from a precambrian banded iron formation.

Exceptionally small spheres (nanospheres) of hematite (diameters between 120 and 200 nanometers) occur in the Marra Mamba Iron Formation of the Hamersley Basin, Australia. The nanospheres are clustered into small aggregates and may have formed by structural ordering and dehydration of colloidal iron hydroxide particles. Individual spheres consist of numerous thin, curved hematite platelets surrounding a central void that is approximately half the diamter of the sphere; this texture suggests that they formed by a volume reduction of the original colloidal particles by approximately 12.5%. The occurrence of hematite nanospheres supports the hypothesis that some ofthe iron was deposited colloidally during the development ofbanded iron formations, approximately 2.5 billion years ago.

Spatially resolved organic analysis of the allende meteorite.

The distribution of polycyclic aromatic hydrocarbons(PAHs) in the Allende meteorite has been probed with two-step laser desorption/laser multiphoton ionization mass spectrometry. This method allows direct in situ analysis with a spatial resolution of 1 square millimeter or better of selected organic molecules. Spectra from freshly fractured interior surfaces of the meteorite show that PAH concentrations are locally high compared to the average concentrations found by wet chemical analysis of pulverized samples. The data suggest that the PAHs are primarily associated with the fine-grained matrix, where the organic polymer occurs. In addition, highly substituted PAH skeletons were observed. Interiors of individual chondrules were devoid of PAHs at our detection limit(about 0.05 parts per million).

Direct observation of dissociated dislocations in garnet.

Dislocation core structures in garnet [grossularite (Ca(2.9)Fe(II)(0.1))(Al(1.9)Fe(III)(0.1)Si(3.0)O(12)] have been examined with near atomic resolution transmission electron microscopy. Dissociated dislocations have been observed as parallel a/4<111> partial dislocations that are separated by stacking faults. The partial dislocations have narrow cores ( approximately 3 burgers vectors), and the stacking fault zone between the narrow partial dislocations is apparently a low-energy configuration that results from the occupancy of previously unfilled dodecahedral and tetrahedral sites. Previous studies of garnet dislocations suggested that dissociation involves departures from garnet stoichiometry (that is, trace amounts of impurities), but evidence of detectable amounts of impurities has not been found even in the highest resolution images. These results have implications for mantle mineral rheology and transformations as well as for ceramics of material science interest.