Search NASA⌕ Search

Engineering topics

Vali, Hojatollah

Publications and source records attributed to Vali, Hojatollah.

Focused Ion Beam Microscopy of ALH84001 Carbonate Disks

Our aim is to understand the mechanism(s) of formation of carbonate assemblages in ALH84001. A prerequisite is that a detailed characterization of the chemical and physical properties of the carbonate be established. We present here analyses by transmission electron microscopy (TEM) of carbonate thin sections produced by both focused ion beam (FIB) sectioning and ultramicrotomy. Our results suggest that the formation of ALH84001 carbonate assemblages were produced by considerably more complex process(es) than simple aqueous precipitation followed by partial thermal decomposition as proposed by other investigators [e.g., 1-3].

Thomas-Keprta, Kathie L.↗

Determination of the Three-Dimensional Morphology of ALH84001 and Biogenic MV-1 Magnetite: Comparison of Results from Electron Tomography and Classical Transmission Electron Microscopy

Dated at approximately 3.9 billion years of age, carbonate disks, found within fractures of the host rock of Martian meteorite ALH84001, have been interpreted as secondary minerals that formed at low temperature in an aqueous medium. Heterogeneously distributed within these disks are magnetite nanocrystals that are of Martian origin. Approximately one quarter of these magnetites have morphological and chemical similarities to magnetite particles produced by magnetotactic bacteria strain MV-1, which are ubiquitous in aquatic habitats on Earth. Moreover, these types of magnetite particles are not known or expected to be produced by abiotic means either through geological processes or synthetically in the laboratory. The remaining three quarters of the ALH84001 magnetites are likely products of multiple processes including, but not limited to, precipitation from a hydrothermal fluid, thermal decomposition of the carbonate matrix in which they are embedded, and extracellular formation by dissimilatory Fe-reducing bacteria. We have proposed that the origins of magnetites in ALH84001 can be best explained as the products of multiple processes, one of which is biological. Recently the three-dimensional (3-D) external morphology of the purported biogenic fraction of the ALH84001 magnetites has been the subject of considerable debate. We report here the 3-D geometry of biogenic magnetite crystals extracted from MV-1 and of those extracted from ALH84001 carbonate disks using a combination of high resolution classical and tomographic transmission electron microscopy (TEM). We focus on answering the following questions: (1) which technique provides adequate information to deduce the 3-D external crystal morphology?; and, (2) what is the precise 3-D geometry of the ALH84001 and MV-1 magnetites?

Thomas-Keprta, Kathie L.↗

Three-Dimensional Morphological Analysis of ALH84001 Magnetite Using Electron Tomography

We report here the crystal morphologies of MV-1 and ALH84001 magnetites as calculated by back-projection using electron tomography. In the present study, we used a 300 keV TEM with a field emission gun (Tecnai F-30 from FEI Inc.), equipped with a 2048 x 2048 pixel CCD camera from Gatan Inc. to image magnetite crystals over tilt ranges of approx. +/- 72 deg in 2 deg tilt intervals. The images were aligned for back-projection, either manually, or through the use of fiducial 5 nm Au spheres affixed to the specimen prior to microscopy. Three-dimensional (3-D) reconstructions were computed using weighted back-projection of the tilted views. The tomograms were viewed and analyzed as a series of slices 1.0 nm thick, taken parallel to the specimen-supporting grid, using the IMOD software package. The shape of each magnetite crystal was determined by defining the external contour of a given magnetite in each slice and assembling a stack of these contours in 3-D. To aid in visualization, the stacked contour array was reduced to an optimal mesh by Delaunay triangulation. The surface normal to each of the triangles in the mesh was calculated and the triangle faces colored according to the orientation of that surface normal relative to the principal crystallographic axis of magnetite. Green surfaces correspond to {111} orientations, blue surfaces to {100} orientations, and red surfaces to {110} orientations. Triangles whose surface normal did not correspond to one of the principal axes were colored gray. Within the experimental and numerical uncertainties of the deconvolution, the tomographic reconstruction of both MV-1 and ALH84001 magnetites are equivalent and correspond to a truncated hexa-octahedral morphology.

Thomas-Keprta, Kathie L.↗

A Structural and Molecular Approach for the Study Biomarkers

Investigation of the nucleation and growth of crystals in both abiotic and biotic systems is critical to seemingly diverse disciplines of geology, biology, environmental science, and astrobiology. While there are abundant studies devoted to the determination of the structure and composition of inorganic crystals, as well as to the development of thermodynamic and kinetic models, it is only recently that research efforts have been directed towards understanding mineralization in biological systems (i.e., biomineralization). Biomineralization refers to the processes by which living organisms form inorganic solids. Studies of the processes of biomineralization under low temperature aqueous conditions have focused primarily on magnetite forming bacteria and shell forming marine organisms. Many of the biological building materials consist of inorganic minerals (calcium carbonate, calcium phosphate, silica or iron oxide) intricately combined with organic polymers (like proteins). More recently, efforts have been undertaken to explore the nature of biological activities in ancient rocks. In the absence of well-preserved microorganisms or genetic material required for the polmerase chain reaction (PCR) method in molecular phylogenetic studies, using biominerals as biomarkers offers an alternative approach for the recognition of biogenic activity in both terrestrial and extraterrestrial environments. The primary driving force in biomineralization is the interaction between organic and inorganic phases. Thus, the investigation of the ultrastructure and the nature of reactions at the molecular level occurring at the interface between inorganic and organic phases is essential to understanding the processes leading to the nucleation and growth of crystals. It is recognized that crystal surfaces can serve as the substrate for the organization of organic molecules that lead to the formation of polymers and other complex organic molecules, and in discussions of the origins of life, is referred to as organic synthesis on mineral surfaces. Furthermore, it is suggested that the interaction between mineral surfaces and simple organic molecules resulted in the formation of amino acids, RNA, and perhaps other more complex molecules such as proteins. On the other hand, in natural systems, it is recognized that functional groups on cell walls or membranes of microorganisms serve as sites of nucleation and crystallization. The precise replication of biominerals with controlled structure, morphology, size and texture is not confined to higher organisms as it also occurs in primitive prokaryotic cells such as magnetotactic bacteria and cyanobacteria. This suggests that the principal strategies of biomineralization were established early on in the evolutionary history of organisms. It is critical, therefore, to search for common mechanisms within diverse biological systems. One such common factor is the capability for organization and self-assembly. Organic macromolecules such as proteins and lipids can aggregate and polymerize forming membranes or extracellular matrix. At the organic-inorganic interface, several factors such as lattice geometry, polarity, stereochemistry and topography may act in concert to control nucleation and growth of crystals. Although several models have been proposed that discuss the significance of these factors for biomineralization, no comprehensive experimental data are available. In contrast to crystallization in exclusively inorganic systems, the kinetics of reaction and structural relationships between organic and inorganic phases in biominerals or biomimetic material is poorly understood. For example, it is not clear if the concept of epitactic growth (geometrical matching of unit cells at the interface of a secondary crystal growing on a primary crystal) applies to organic-inorganic systems. In contrast to inorganic templates that often have a smooth and rigid surface that promotes epitactic growth, biological substrates are usually rough and result in a large degree of mismatch. It is apparent that factors controlling the reaction at the crystal-matrix interface are strongly dependent upon the nature of the substrate. Therefore, characterization of the assembled organic surface and surface structure of the inorganic phase is crucial to understanding the processes of biomineralization. The focus of our research is the investigation of the processes leading to the nucleation and growth of crystals on both natural and synthetic systems through an interdisciplinary approach that integrates molecular biology, morphology and mineralogy using advanced preparation and analytical techniques. We have studied run-products, particularly magnetite, siderite and other carbonates, that resulted from extracellular biomineralization by extremophiles isolated from a variety of extreme environments ranging from permafrost to hydrothermal vent systems. The results of this study are critical to recognizing biomarkers in terrestrial and extraterrestrial environments.

Thomas-Keprta, Kathie↗

Search for Past Life on Mars: Possible Relict Biogenic Activity in Martian Meteorite ALH84001

Fresh fracture surfaces of the martian meteorite ALH84001 contain abundant polycyclic aromatic hydrocarbons (PAHs). These fresh fracture surfaces also display carbonate globules. Contamination studies suggest the PAHs are indigenous to the meteorite. High resolution scanning and transmission electron microscopy study of surface textures and internal structures of selected carbonate globules show that the globules contain fine-grained, secondary phases of single-domain magnetite and Fe-monosulfides. The carbonate globules are similar in texture and size to some terrestrial bacterially induced carbonate precipitates. Although inorganic formation is possible, formation of the globules by biogenic processes could explain many of the observed features including the PAHs. The PAHs, the carbonate globules, and their associated secondary mineral phases and textures could thus be fossil remains of a past martian biota.

McKay, David S.↗