John H. Fournelle

Effects of pseudowollastonite (CaSiO3) bioceramic on in vitro activity of human mesenchymal stem cells

We report the effects of two pseudowollastonite (beta-CaSiO(3)) substrates on the attachment, viability, proliferation and osteogenic differentiation of human mesenchymal stem cells (hMSCs), and provide detailed mechanistic links of surface texture, soluble factors and culture media to cell activities. Cell attachment and viability were lower for psWf (fine-grained, roughness 0.74 microm) than for psWc (coarse-grained, roughness 1.25 microm) surface, and were ascribed to the greater specific area of the finer psWf particles resulting in higher release rate of Si, which is cytotoxic at high levels. Interestingly, proliferation was greater on psWf. Osteogenic differentiation occurred on both surfaces, indicated by calcium phosphate bone nodule formation and by osteocalcin, osteopontin and core-binding factor alpha-1 gene expression. Gene levels were lower on psWf than on psWc at day 8 in growth medium, explained by differences in Ca and/or Si concentrations between the two surfaces. Similar gene expression on both surfaces at day 16 in both growth and osteogenic induction media was attributed to pro-osteogenic effects of Ca and P at specific concentrations and complementary Ca and P levels on the two surfaces. In summary, soluble factors from substrates may be more important for osteogenic differentiation in growth medium than small surface roughness variations within a factor of 2. Optimum concentration ranges exist for individual soluble factors to balance cell toxicity/growth versus osteogenic differentiation, and soluble factors together have complex, cooperative or opposing, effects on a given cell activity.

Two populations of carbonate in ALH84001: geochemical evidence for discrimination and genesis

We present major and trace-element, oxygen isotope, textural, and structural data for carbonates and related phases in the SNC meteorite ALH84001. These data document the existence of at least two distinct carbonate populations: one composed of finely zoned, chemically and isotopically heterogeneous concretions of magnesio-siderite with distinct white magnesite rims, and a second composed of relatively homogeneous, isotopically and compositionally simple domains of ankeritic carbonate and intimately intergrown glass and fine-grained pyroxene. We suggest on the basis of textural evidence and geochemical systematics that the first population consists of low-temperature aqueous precipitates, and the second is produced by shock melting of the first. Values of δ^(18)O and Sr/Ca ratios are correlated with one another in magnesio-siderite concretions; the trend formed by these data is consistent with the predicted relationship for inorganic precipitation of carbonate from a solution of constant composition between temperatures of ∼190°C (for concretion cores) to 20°C (for magnesite-rich concretion rims). Given the assumptions inherent in this temperature estimate, the aqueous fluid parental to carbonate concretions is constrained to have a δ^(18)O of −5‰ VSMOW (significantly mass fractionated compared with expected juvenile martian volatiles) and minor-element abundances broadly similar to terrestrial seawater.

X-ray absorption spectroscopy of silicates for in situ, sub-micrometer mineral identification

Abstract We present X-ray absorption near-edge structure (XANES) spectroscopy of 11 silicate and aluminosilicate minerals and two glasses at the SiK and SiL2,3, and OK edges. The similar nearestneighbor environments lead to similar spectral lineshapes at each edge, but the fine-structure differences allow individual and groups of structurally similar minerals to be distinguished. By combining spectra and their first energy derivative from three absorption edges, we show that every mineral studied is distinguishable with XANES. This background work, combined with X-ray PhotoElectron Emission spectroMicroscopy (X-PEEM), allows non-destructive in situ, sub-micrometer (to 35 nm) X-ray analysis of materials, including silicate inclusions, which has not been possible previously. Images and spectra from a 7 μm × 3.5 μm quartz inclusion in zircon are presented as a test of this novel technique in geology.

Silician magnetite from the Dales Gorge Member of the Brockman Iron Formation, Hamersley Group, Western Australia

Abstract We report silician magnetite from banded iron formation (BIF) in the Dales Gorge Member of the Brockman Iron Formation, Hamersley Group, Western Australia. Magnetite mesobands typically consisting of individual ~100 μm microlaminae are revealed to be composed of silician magnetite overgrowths on magnetite. Silician magnetite overgrowths contain from 1 to 3 wt% SiO2, whereas (low-Si) magnetite domains contain less than 1 wt% SiO2. Silicon solid solution is present in the magnetite crystal lattice as determined by in situ micro-X-ray diffraction and high-resolution transmission electron microscopy. Three textures are distinguished in magnetite mesobands: (1) magnetite sub-microlaminae with silician magnetite overgrowths, (2) recrystallized magnetite fragments with silician magnetite overgrowths, and (3) a complex intergrowth of magnetite and silician magnetite. All three textures are found in magnetite mesobands from the BIF4-5 and BIF12-16 macrobands of the Dales Gorge type-section drill core DDH-47A from Wittenoom, Western Australia. Magnetite domains contain numerous submicrometer-to-micrometer inclusions of quartz, carbonate, stilpnomelane, and apatite, whereas silician magnetite overgrowths are devoid of mineral inclusions. The presence of mineral inclusions in magnetite indicates the BIF oxide precipitate was not chemically pure iron oxyhydroxide/oxide. Magnetite domains display textures formed during soft sediment deformation that are the earliest and best preserved relict sedimentary structures in this BIF. Silician magnetite is the dominant iron oxide in the Dales Gorge BIF and is present in many other sub-greenschist facies BIFs worldwide. We suggest the former presence of organic matter creates reducing conditions necessary to stabilize silician magnetite. Thus, silician magnetite is a potential biosignature in BIFs.

High-resolution calibration of Eocene strata : 40Ar/39Ar geochronology of biotite in the Green River Formation

The Sixth tuff of the Wilkins Peak Member of the Green River Formation is an important potential calibration point for magnetic stratigraphy, mammalian evolution, and lacustrine processes. However, two recent 40 Ar/ 39 Ar ages based on laser fusion of biotite from this important bed are not in agreement with one other. Most large, euhedral biotite from the basal 1 cm give concordant age spectra when incrementally heated. However, some crystals yield discordant age spectra and have plateau and integrated ages that are scattered toward both older and younger apparent ages. Electron-probe microanalysis indicates that intergrown alteration phases occur in a small fraction of Sixth tuff biotite crystals, and likely contributed to open-system processes that led to the observed discordance and age scatter. A new age of 49.62 ± 0.10 Ma is obtained from 22 concordant incremental-heating experiments. This age agrees with a new 49.78 ± 0.08 Ma age for the sanidine from the Layered tuff, which is stratigraphically 24 m below the Sixth tuff.

Water contents, temperatures and diversity of the magmas of the catastrophic eruption of Nevado del Ruiz, Colombia, November 13, 1985

Abstract The petrology of the highly phyric two-pyroxene andesitic to dacitic pyroclastic rocks of the November 13, 1985 eruption of Nevado del Ruiz, Colombia, reveals evidence of: (1) increasingly fractionated bulk compositions with time; (2) tapping of a small magma chamber marginally zoned in regard to H 2 O contents (1 to 4%), temperature (960–1090°C), and amount of residual melt (35 to 65%); (3) partial melting and assimilation of degassed zones in the hotter less dense interior of the magma chamber; (4) probable heating, thermal disruption and mineralogic and compositional contamination of the magma body by basaltic magma “underplating”; and (5) crustal contamination of the magmas during ascent and within the magma chamber. Near-crater fall-back or “spill-over” emitted in the middle of the eruptive sequence produced a small pyroclastic flow that became welded in its central and basal portions because of ponding and thus heat conservation on the flat glaciated summit near the Arenas crater. The heterogeneity of Ruiz magmas may be related to the comparatively small volume (0.03 km 3 ) of the eruption, nearly ten times less than the 0.2 km 3 of the Plinian phase of Mount St. Helens, and probable steep thermal and P H 2 O gradients of a small source magma chamber, estimated at 300 m long and 100 m wide for an assumed ellipsoidal shape.

Anhydrite in Nevado del Ruiz November 1985 pumice: relevance to the sulfur problem

Abstract The purpose of this letter is to document the occurrence of anhydrite within a pumice phenocryst, and to determine the sulfur contents of the quenched melts in this pumice and to consider if the anhydrite could have crystallized from the magma. Additionally, the presence is noted in the Central Cordillera, potentially below Nevado del Ruiz, of sulfide- and sulfate-bearing deposits of possible relevance to this problem.

Vanadate and acetate biostimulation of contaminated sediments decreases diversity, selects for specific taxa, and decreases aqueous V5+ concentration.

Vanadium is a commercially important metal that is released into the environment by fossil fuel combustion and mining. Despite its prevalence as a contaminant, the potential for vanadium bioremediation has not been widely studied. Injection of acetate (as a carbon source) directly into an aquifer to biostimulate contaminated sediments in Colorado, United States, resulted in prolonged removal of aqueous vanadium for a period of at least two years. To further investigate this process, we simultaneously added acetate and vanadate (V(5+)) to columns that were packed with aquifer sediment and inserted into groundwater wells installed on the Colorado River floodplain. This allowed evaluation of the microbial response to amendments in columns that received an influx of natural groundwater. Our results demonstrate the removal of up to 99% of the added V(5+)(aq) and suggest microbial mediation. Most probable number measurements demonstrate up to a 50-fold increase in numbers of V(5+)-reducing cells in vanadium-amended columns compared to controls. 16S rRNA gene sequencing indicates decreased diversity and selection for specific taxa in columns that received vanadate compared to those that did not. Overall, our results demonstrate that acetate amendment can be an effective strategy for V removal, and that V bioremediation may be a viable technology.

Precise dating of biotite in distal volcanic ash: Isolating subtle alteration using 40Ar/39Ar laser incremental heating and electron microprobe techniques

Abstract Precise dating of K-rich minerals in volcanic rocks via the 40Ar/39Ar geochronometer has become crucial to resolving many geological problems. In some cases, ash beds containing biotite phenocrysts but lacking sanidine are the only datable horizons at key stratigraphic intervals, necessitating comparison of sanidine and biotite ages within the same chronostratigraphic framework. To assess the integrity of biotite and evaluate the accuracy of ages obtained from this often problematic mineral, incremental heating 40Ar/39Ar experiments were performed on large, millimeter-sized, euhedral biotite crystals from four key Eocene tuffs in the Green River and Wind River Basins and are compared with sanidine 40Ar/39Ar ages. Unaltered biotite crystals with homogenous K-compositions from two tuff beds yielded concordant plateau ages that are indistinguishable from cogenetic sanidine ages. In contrast, biotite crystals from two other tuffs yielded discordant spectra, with relatively young initial steps followed by older, down-stepping apparent ages. Plateau ages from the discordant experiments are older than the sanidine ages by 1 to 14%. Integrated (total fusion) ages from these experiments exhibit scatter toward both younger and older ages that correlate with the degree of spectral discordance. Electron microprobe transects reveal that biotite crystals yielding discordant age spectra contain 1-10 μm thick K-depleted (<8% K2O) alteration zones along internal cleavage planes that are absent in biotite crystals yielding concordant age spectra. We propose that these altered zones promote open-system behavior. Phenomena such as loss of K or 40Ar*, 39ArK recoil into internal K-depleted phases, and 39ArK recoil entirely out of internally corroded biotite crystals are all potential mechanisms that can be related to this alteration. Due to the presence of these multiple potential pathways that promote the gain or loss of isotopes, such altered biotite crystals are unsuitable for high-resolution 40Ar/39Ar dating, comparisons with sanidine ages, or calibration of the geomagnetic polarity timescale.

Low-Voltage Electron-Probe Microanalysis of Fe–Si Compounds Using Soft X-Rays

Conventional electron-probe microanalysis has an X-ray analytical spatial resolution on the order of 1-4 μm width/depth. Many of the naturally occurring Fe-Si compounds analyzed in this study are smaller than 1 μm in size, requiring the use of lower accelerating potentials and nonstandard X-ray lines for analysis. Problems with the use of low-energy X-ray lines (soft X-rays) of iron for quantitative analyses are discussed and a review is given of the alternative X-ray lines that may be used for iron at or below 5 keV (i.e., accelerating voltage that allows analysis of areas of interest <1 μm). Problems include increased sensitivity to surface effects for soft X-rays, peak shifts (induced by chemical bonding, differential self-absorption, and/or buildup of carbon contamination), uncertainties in the mass attenuation coefficient for X-ray lines near absorption edges, and issues with spectral resolution and count rates from the available Bragg diffractors. In addition to the results from the traditionally used Fe Lα line, alternative approaches, utilizing Fe Lβ, and Fe Ll-η lines, are discussed.