Kiho Yang

The characterization of CaCo3 in a geothermal environment: A SEM/TEM-EELS study

Mineralization of microbial biomass is a common phenomenon in geothermal habitats, but knowledge of the structure of the minerals formed in these environments is limited. A combination of spectroscopic, microscopic, and stable isotopic methods, as well as the chemical analysis of spring water, were employed in the present study to characterize calcium carbonate minerals deposited in filamentous cyanobacterial mats in different locations of La Duke hot spring, a circumneutral thermal feature near the north entrance of Yellowstone National Park, Montana, USA. Calcite was the primary crystalline mineral phase associated with biofilm-containing deposits closest to the source of the spring and the suspended microbial biomass in a pool further from the source. The carbonate minerals at all sites occurred as aggregated granules, ~2 μm in diameter, in close association with the microbial biomass. Only in the deposits closest to the source were the granules organized as laminated structures interspersed with microbial biomass. The calcium carbonate grains contained two distinct regions: a dense monolithic calcite core and a porous dendritic periphery containing organic matter (OM). Electron energy loss spectroscopy (EELS) indicated that the voids were infilled with OM and carbonates. The EELS technique was employed to distinguish the source of carbon in the organic matter and carbonate mixture. The studies of carbon isotope compositions of the calcium carbonates and the saturation indices for calcite in the spring waters suggest that processes (abiotic vs. biotic) controlling the carbonate formation may vary among the sampling sites.

Quantitative Determination of Fe-oxidation State by Electron Energy Loss Spectroscopy (EELS)

The consequences of microbe-mineral interaction often resulted in the chemical, structural modification, or both in the biologically induced mineral. It is inevitable to utilize the high powered resolution of electron microscopy to investigate the mechanism of biogenic mineral transformation at nano-scale. The applications of transmission electron microscopy (TEM) capable of electron energy loss spectroscopy (EELS) to the study of microbe-mineral interaction were demonstrated for two examples: 1) biogenic illite formation associated with structural Fe(III) reduction in nontronite by Fereducing bacteria; 2) siderite phase formation induced by microbial Fe(III) reduction in magnetite. In particular, quantification of the changes in Fe-oxidation state at nanoscale is essential to understand the dynamic modification of minerals resulted from microbial Fe reduction. The procedure of EELS acquisition and advantages of EELS techniques were discussed.

The formation of Fe-bearing secondary phase minerals from the basalt–sediment interface, South Pacific Gyre: IODP Expedition 329

Alteration of basalt is a ubiquitous process on the vast oceanic crust surface and results in the formation of secondary-phase minerals that include clay minerals and Fe-(oxyhydr)oxides. Thus, this process is a significant consequence of water/rock interactions that could reveal the (bio)geochemical conditions of formation. Core samples at the basalt/sediment interface from a depth of 74.79 m below sea floor (mbsf) were recovered during the International Ocean Discovery Program (IODP) expedition 329 (2010.10.10–2010.12.13) in the South Pacific Gyre (SPG). Two distinct regions of yellow- and red-colored sediment were observed. The mineralogy, elemental composition, Fe oxidation state, and mineral structure of the altered basalt samples were analyzed using transmission electron microscopy (TEM) with selected area electron diffraction (SAED) patterns, energy dispersive spectroscopy (EDS), electron energy loss spectroscopy (EELS), and micro X-ray fluorescence (μ-XRF). In the yellow sediment, K-nontronite and feroxyhyte (δ’-FeO(OH)) were the dominant mineral phases, while Mg-rich smectite (saponite), chlorite, and hematite were found predominantly in the reddish sediment. The appearance of K-nontronite and feroxyhyte mineral assemblages in altered sediment indicated that oxidative conditions prevailed during basalt alteration. Variation in the Fe-oxidation states in the K-nontronite structure, however, may indicate that local reducing conditions persisted throughout the biogeochemical reactions.