Spherical tarball particles form through rapid chemical and physical changes of organic matter in biomass-burning smoke.

Biomass burning (BB) emits enormous amounts of aerosol particles and gases into the atmosphere and thereby significantly influences regional air quality and global climate. A dominant particle type from BB is spherical organic aerosol particles commonly referred to as tarballs. Currently, tarballs can only be identified, using microscopy, from their uniquely spherical shapes following impaction onto a grid. Despite their abundance and potential significance for climate, many unanswered questions related to their formation, emission inventory, removal processes, and optical properties still remain. Here, we report analysis that supports tarball formation in which primary organic particles undergo chemical and physical processing within ∼3 h of emission. Transmission electron microscopy analysis reveals that the number fractions of tarballs and the ratios of N and O relative to K, the latter a conserved tracer, increase with particle age and that the more-spherical particles on the substrates had higher ratios of N and O relative to K. Scanning transmission X-ray spectrometry and electron energy loss spectrometry analyses show that these chemical changes are accompanied by the formation of organic compounds that contain nitrogen and carboxylic acid. The results imply that the chemical changes increase the particle sphericity on the substrates, which correlates with particle surface tension and viscosity, and contribute to tarball formation during aging in BB smoke. These findings will enable models to better partition tarball contributions to BB radiative forcing and, in so doing, better help constrain radiative forcing models of BB events.

Pseudocarbynes: Charge-Stabilized Carbon Chains.

Carbyne is the long-sought linear allotrope of carbon. Despite many reports of solid carbyne, the evidence is unconvincing. A recent report of supposed carbyne shows gold clusters in transmission electron microscopy (TEM) images. In order to determine the effects of such clusters, we performed ab initio calculations of uncapped and capped linear carbon chains and their complexes with gold clusters. The results indicate that gold dramatically alters the electron densities of the C≡C bonds. The resulting charge-stabilization of the carbon chains leads to pseudocarbynes. These findings are corroborated in calculations of the structures of crystals containing isolated carbon chains and those intercalated with gold clusters. Calculated Raman spectra of these pseudocarbynes with gold clusters are in better agreement with experiment than calculated spectra of isolated carbon chains. The current work opens the way toward the design and development of a new class of metal-intercalated carbon compounds.

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.

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.

Light scattering and extinction measurements combined with laser-induced incandescence for the real-time determination of soot mass absorption cross section.

An aerosol albedometer was combined with laser-induced incandescence (LII) to achieve simultaneous measurements of aerosol scattering, extinction coefficient, and soot mass concentration. Frequency doubling of a Nd:YAG laser line resulted in a colinear beam of both λ = 532 and 1064 nm. The green beam was used to perform cavity ring-down spectroscopy (CRDS), with simultaneous measurements of scattering coefficient made through use of a reciprocal sphere nephelometer. The 1064 nm beam was selected and directed into a second integrating sphere and used for LII of light-absorbing kerosene lamp soot. Thermal denuder experiments showed the LII signals were not affected by the particle mixing state when laser peak power was 1.5-2.5 MW. The combined measurements of optical properties and soot mass concentration allowed determination of mass absorption cross section (M.A.C., m(2)/g) with 1 min time resolution when soot concentrations were in the low microgram per cubic meter range. Fresh kerosene nanosphere soot (ns-soot) exhibited a mean M.A.C and standard deviation of 9.3 ± 2.7 m(2)/g while limited measurements on dry ambient aerosol yielded an average of 8.2 ± 5.9 m(2)/g when soot was >0.25 µg/m(3). The method also detected increases in M.A.C. values associated with enhanced light absorption when polydisperse, laboratory-generated ns-soot particles were embedded within or coated with ammonium nitrate, ammonium sulfate, and glycerol. Glycerol coatings produced the largest fractional increase in M.A.C. (1.41-fold increase), while solid coatings of ammonium sulfate and ammonium nitrate produced increases of 1.10 and 1.06, respectively. Fresh, ns-soot did not exhibit increased M.A.C. at high relative humidity (RH); however, lab-generated soot coated with ammonium nitrate and held at 85% RH exhibited M.A.C. values nearly double the low-humidity case. The hybrid instrument for simultaneously tracking soot mass concentration and aerosol optical properties in real time is a valuable tool for probing enhanced absorption by soot at atmospherically relevant concentrations.

Complex defect in pyrite and its structure model derived from geometric phase analysis.

New methods for defect analysis can lead to improved interpretation of experimental data and thus better understanding of material properties. Although transmission electronmicroscopy (TEM) has been used to study defects for many decades, interpretive ambiguities can arise for cases that seem simple or even trivial.Using geometric phase analysis (GPA), an image processing procedure, we show that an apparent simple line defect in pyrite has an entirely different character. It appears to be a b = ½[100] edge dislocation as viewed in a [001] high-resolution TEM (HRTEM) image, but the measured u(x) and u(y) displacements are asymmetric, which is inconsistent with a simple line dislocation. Instead, the defect is best understood as a terminating {101} marcasite slab in pyrite. The simulated HRTEM image based on this model reproduces the defect contrast and illustrates the power of GPA analysis for (1) avoiding potential pitfalls of misinterpreting apparently simple defects in HRTEM images, (2) detecting differences in elastic properties at the atomic scale, and (3) providing data for the positions of atom columns, thereby facilitating the construction of structure models for complex defects.

Hosted and free-floating metal-bearing atmospheric nanoparticles in Mexico City.

Nanoparticles (NPs) are ubiquitous in the atmosphere. Because of their small sizes, they can travel deeply into the lungs and other parts of the body. Many are highly reactive which, combined with their large surface areas, means they can seriously affect human health. Their occurrences in the atmosphere and their biological effects are not well-understood. We focus on NPs that were either free-floating or hosted within large aerosol particles (aerodynamic diameter 50-300 nm) and consist of or contain transition or post-transition metals (m-NPs). The samples were collected from ambient air above Mexico City (MC). We used transmission electron microscopy to measure their sizes and compositions. More than half of the 572 m-NPs that we analyzed contain two or more metals, and Fe, Pb, or Zn occurs in more than 60%. Hg occurs in 21% and is especially abundant in free-floating m-NPs. We find that m-NPs are common in polluted air such as in the MC area and, by inference, presumably other megacities. The range and variety of compositions of m-NPs that we encountered, whether free-floating or hosted within larger aerosol particles, indicate the complicated occurrences that should be considered when evaluating the health effects of m-NPs in complex urban areas.

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.

Particle formation from pulsed laser irradiation of soot aggregates studied with a scanning mobility particle sizer, a transmission electron microscope, and a scanning transmission x-ray microscope.

We investigated the physical and chemical changes induced in soot aggregates exposed to laser radiation using a scanning mobility particle sizer, a transmission electron microscope, and a scanning transmission x-ray microscope to perform near-edge x-ray absorption fine structure spectroscopy. Laser-induced nanoparticle production was observed at fluences above 0.12 J/cm(2) at 532 nm and 0.22 J/cm(2) at 1064 nm. Our results indicate that new particle formation proceeds via (1) vaporization of small carbon clusters by thermal or photolytic mechanisms, followed by homogeneous nucleation, (2) heterogeneous nucleation of vaporized carbon clusters onto material ablated from primary particles, or (3) both processes.

Crystal habits and magnetic microstructures of magnetosomes in coccoid magnetotactic bacteria

Nós relatamos a aplicação de holografia não-axial e microscopia eletrônica de alta resolução para estudar os hábitos cristalinos de magnetossomos e a microestrutura magnética de dois morfotipos de cocos de bactérias magnetotáticas coletadas em uma lagoa salobra em Itaipu, Brasil. Itaipu-1, o organismo cocóide maior, contémduas cadeias separadas de magnetossomos atipicamente grandes; os cristais dos magnetossomos possuem projeções aproximadamente quadradas, comprimentos deaté 250 nm e são ligeiramente alongados na direção [111] (razão largura/comprimento de aproximadamente 0.9).Os cristais dos magnetossomos em Itaipu-3 possuemcomprimentos até 120 nm, maior alongamento na direção [111] (largura/comprimento ~ 0.6), e proeminentes facetas nas extremidades. Os resultados mostram que os hábitos cristalinos dos magnetossomos em Itaipu-1 eItaipu-3 são relacionados, diferindo apenas nos tamanhos relativos das suas faces cristalinas. Em ambos os casos, os cristais são alinhados com seus eixos de alongamento [111] paralelos à direção da cadeia. Em Itaipu-1, mas não em Itaipu-3, o posicionamento cristalográfico, perpendicular à direção [111], de cristais sucessivos na cadeia de magnetossomos parece estar sobre controlebiológico. Enquanto os magnetossomos grandes em Itaipu-1 são monodomínios magnéticos metaestáveis, em Itaipu-3 eles são monodomínios magnéticos permanentes como na maioria das bactérias.

Crystal habits and magnetic microstructures of magnetosomes in coccoid magnetotactic bacteria.

We report on the application of off-axis electron holography and high-resolution TEM to study the crystal habits of magnetosomes and magnetic microstructure in two coccoid morphotypes of magnetotactic bacteria collected from a brackish lagoon at Itaipu, Brazil. Itaipu-1, the larger coccoid organism, contains two separated chains of unusually large magnetosomes; the magnetosome crystals have roughly square projections, lengths up to 250 nm and are slightly elongated along [111] (width/length ratio of about 0.9). Itaipu-3 magnetosome crystals have lengths up to 120 nm, greater elongation along [111] (width/length approximately 0.6), and prominent corner facets. The results show that Itaipu-1 and Itaipu-3 magnetosome crystal habits are related, differing only in the relative sizes of their crystal facets. In both cases, the crystals are aligned with their [111] elongation axes parallel to the chain direction. In Itaipu-1, but not Itaipu-3, crystallographic positioning perpendicular to [111] of successive crystals in the magnetosome chain appears to be under biological control. Whereas the large magnetosomes in Itaipu-1 are metastable, single-magnetic domains, magnetosomes in Itaipu-3 are permanent, single-magnetic domains, as in most magnetotactic bacteria.

Void-induced dissolution in molecular dynamics simulations of NaCl and water.

To gain a better understanding of the interaction of water and NaCl at the surface during dissolution, we have used molecular dynamics to simulate the interface with two equal-sized slabs of solid NaCl and liquid water in contact. The introduction of voids in the bulk of the salt, as well as steps or pits on the surface of the NaCl slab results in a qualitative change of system structure, as defined by radial distribution functions (RDFs). As an example, the characteristic Na-Na RDF for the system changes from regularly spaced narrow peaks (corresponding to an ordered crystalline structure), to a broad primary and smaller secondary peak (corresponding to a disordered structure). The change is observed at computationally short time scales of 100 ps, in contrast with a much longer time scale of 1 mus expected for complete mixing in the absence of defects. The void fraction (which combines both bulk and surface defects) required to trigger dissolution varies between 15%-20% at 300 K and 1 atm, and has distinct characteristics for the physical breakdown of the crystal lattice. The void fraction required decreases with temperature. Sensitivity studies show a strong dependence of the critical void fraction on the quantity and distribution of voids on the surface, with systems containing a balanced number of surface defects and a rough surface showing a maximum tendency to dissolve. There is a moderate dependence on temperature, with a 5% decrease in required void fraction with a 100 K increase in temperature, and a weak dependence on water potential model used, with the SPC, SPC/E, TIP4P, and RPOL models giving qualitatively identical results. The results were insensitive to the total quantity of water available for dissolution and the duration of the simulation.

Habits of magnetosome crystals in coccoid magnetotactic bacteria.

High-resolution transmission electron microscopy and electron holography were used to study the habits of exceptionally large magnetite crystals in coccoid magnetotactic bacteria. In addition to the crystal habits, the crystallographic positioning of successive crystals in the magnetosome chain appears to be under strict biological control.

Nanoscale waviness of low-angle grain boundaries.

Low-angle grain boundaries (LAGBs) are ubiquitous in natural and man-made materials and profoundly affect many of their mechanical, chemical, and electrical properties. The properties of LAGBs are understood in terms of their constituent dislocations that accommodate the small misorientations between grains. Discrete dislocations result in a heterogeneous local structure along the boundary. In this article, we report the lattice rotation across a LAGB in olivine (Mg(1.8)Fe(0.2)SiO(4)) measured at the nanometer scale by using quantitative high-resolution transmission electron microscopy. The analysis reveals a grain boundary that is corrugated. Elastic calculations show that this waviness is independent of the host material and thus a general feature of LAGBs. Based on our observations and analysis, we provide equations for the boundary position, local curvature, and the lattice rotation field for any LAGB. These results provide the basis for a reexamination of grain-boundary properties in materials such as high-temperature superconductors, nanocrystalline materials, and naturally deformed minerals.