Size-frequency distributions and physical properties of chondrules from x-ray computed microtomography and digital data extraction.

Within this work, we present the first true three-dimensional (3D) analysis of chondrule size. Knowledge about the physical properties of chondrules is important for validating astrophysical theories concerning chondrule formation and their aggregation into the chondritic meteorites (known as chondrites) that contain them. The classification of chondrites into chemical groups also relies on chondrule properties, including their dimensions. Within this work, we quantify the diameters of chondrules in five ordinary chondrites (OCs; comprised of the H, L, and LL chondrites) and one low-iron enstatite (EL) chondrite. To extract the chondrule size data, we use x-ray computed microtomography to image small (~1-2 cm3 ) chondrite samples followed by manual digital segmentation to isolate chondrules within the volumes or subvolumes. Our data yield true 3D results without stereographic corrections necessary for two-dimensional (2D) or petrographic thin section-based determinations of chondrule sizes. Our results are completely novel, but are consistent with previous surface analysis (2D) data for OCs. Within our OC chondrule diameter data, we find the trend of mean chondrule diameters increasing in the order H < L < LL. We also present the first detailed EL chondrite chondrule size-frequency distribution. Finally, we examine the shapes and collective orientations of the chondrules within the chondrites and show that chondrite petrofabrics can be explored with our methodology. Chondrule shape-preferred orientations are identical to the orientations of the metal and sulfide grains in the chondrites and this is likely due to impact-related compaction. HIGHLIGHTS: We present a first true three-dimensional analysis of chondrule size. Our ordinary chondrite chondrule diameter data demonstrate the trend of mean chondrule diameters increasing in the order H chondrites < L chondrites < LL chondrites. We also present the first detailed low-iron enstatite chondrite chondrule size-frequency distribution. We examine the shapes and collective orientations of the chondrules and show that chondrite petrofabrics can be explored with our methodology.

An early chondrichthyan and the evolutionary assembly of a shark body plan.

Although relationships among the major groups of living gnathostomes are well established, the relatedness of early jawed vertebrates to modern clades is intensely debated. Here, we provide a new description of Gladbachus, a Middle Devonian (Givetian approx. 385-million-year-old) stem chondrichthyan from Germany, and one of the very few early chondrichthyans in which substantial portions of the endoskeleton are preserved. Tomographic and histological techniques reveal new details of the gill skeleton, hyoid arch and jaws, neurocranium, cartilage, scales and teeth. Despite many features resembling placoderm or osteichthyan conditions, phylogenetic analysis confirms Gladbachus as a stem chondrichthyan and corroborates hypotheses that all acanthodians are stem chondrichthyans. The unfamiliar character combination displayed by Gladbachus, alongside conditions observed in acanthodians, implies that pre-Devonian stem chondrichthyans are severely under-sampled and strongly supports indications from isolated scales that the gnathostome crown group originated at the latest by the early Silurian (approx. 440 Ma). Moreover, phylogenetic results highlight the likely convergent evolution of conventional chondrichthyan conditions among earliest members of this primary gnathostome division, while skeletal morphology points towards the likely suspension feeding habits of Gladbachus, suggesting a functional origin of the gill slit condition characteristic of the vast majority of living and fossil chondrichthyans.

Local structure of liquid gallium under pressure.

In situ high energy X-ray pair distribution function (PDF) measurements, microtomography and reverse Monte Carlo simulations were used to characterize the local structure of liquid gallium up to 1.9 GPa. This pressure range includes the well-known solid-solid phase transition from Ga-I to Ga-II at low temperature. In term of previous research, the local structure of liquid gallium within this domain was suggested a mixture of two local structures, Ga I and Ga II, based on fitting experimental PDF to known crystal structure, with a controversy. However, our result shows a distinctly different result that the local structure of liquid gallium resembles the atomic arrangement of both gallium phase II and III (the high pressure crystalline phase). A melting mechanism is proposed for Ga, in which the atomic structure of phase Ι breaks up at the onset of melting, providing sufficient free volume for atoms to rearrange, to form the melt.

High Pressure Single Crystal Diffraction at PX2.

In this report we describe detailed procedures for carrying out single crystal X-ray diffraction experiments with a diamond anvil cell (DAC) at the GSECARS 13-BM-C beamline at the Advanced Photon Source. The DAC program at 13-BM-C is part of the Partnership for Extreme Xtallography (PX^2) project. BX-90 type DACs with conical-type diamond anvils and backing plates are recommended for these experiments. The sample chamber should be loaded with noble gas to maintain a hydrostatic pressure environment. The sample is aligned to the rotation center of the diffraction goniometer. The MARCCD area detector is calibrated with a powder diffraction pattern from LaB6. The sample diffraction peaks are analyzed with the ATREX software program, and are then indexed with the RSV software program. RSV is used to refine the UB matrix of the single crystal, and with this information and the peak prediction function, more diffraction peaks can be located. Representative single crystal diffraction data from an omphacite (Ca0.51Na0.48)(Mg0.44Al0.44Fe2+0.14Fe3+0.02)Si2O6 sample were collected. Analysis of the data gave a monoclinic lattice with P2/n space group at 0.35 GPa, and the lattice parameters were found to be: a = 9.496 ±0.006 Å, b = 8.761 ±0.004 Å, c = 5.248 ±0.001 Å, ß = 105.06 ±0.03º, α = γ = 90º.

Spatially Resolved Elemental Analysis, Spectroscopy and Diffraction at the GSECARS Sector at the Advanced Photon Source.

X-ray microprobes (XRM) coupled with high-brightness synchrotron X-ray facilities are powerful tools for environmental biogeochemistry research. One such instrument, the XRM at the Geo Soil Enviro Center for Advanced Radiation Sources Sector 13 at the Advanced Photon Source (APS; Argonne National Laboratory, Lemont, IL) was recently improved as part of a canted undulator geometry upgrade of the insertion device port, effectively doubling the available undulator beam time and extending the operating energy of the branch supporting the XRM down to the sulfur K edge (2.3 keV). Capabilities include rapid, high-resolution, elemental imaging including fluorescence microtomography, microscale X-ray absorption fine structure spectroscopy including sulfur K edge capability, and microscale X-ray diffraction. These capabilities are advantageous for (i) two-dimensional elemental mapping of relatively large samples at high resolution, with the dwell times typically limited only by the count times needed to obtain usable counting statistics for low concentration elements, (ii) three-dimensional imaging of internal elemental distributions in fragile hydrated specimens, such as biological tissues, avoiding the need for physical slicing, (iii) spatially resolved speciation determinations of contaminants in environmental materials, and (iv) identification of contaminant host phases. In this paper, we describe the XRM instrumentation, techniques, applications demonstrating these capabilities, and prospects for further improvements associated with the proposed upgrade of the APS.

Protection of soil carbon within macro-aggregates depends on intra-aggregate pore characteristics.

Soil contains almost twice as much carbon (C) as the atmosphere and 5-15% of soil C is stored in a form of particulate organic matter (POM). Particulate organic matter C is regarded as one of the most labile components of the soil C, such that can be easily lost under right environmental settings. Conceptually, micro-environmental conditions are understood to be responsible for protection of soil C. However, quantitative knowledge of the specific mechanisms driving micro-environmental effects is still lacking. Here we combined CO2 respiration measurements of intact soil samples with X-ray computed micro-tomography imaging and investigated how micro-environmental conditions, represented by soil pores, influence decomposition of POM. We found that atmosphere-connected soil pores influenced soil C's, and especially POM's, decomposition. In presence of such pores losses in POM were 3-15 times higher than in their absence. Moreover, we demonstrated the presence of a feed-forward relationship between soil C decomposition and pore connections that enhance it. Since soil hydrology and soil pores are likely to be affected by future climate changes, our findings indicate that not-accounting for the influence of soil pores can add another sizable source of uncertainty to estimates of future soil C losses.

Properties of soil pore space regulate pathways of plant residue decomposition and community structure of associated bacteria.

Physical protection of soil carbon (C) is one of the important components of C storage. However, its exact mechanisms are still not sufficiently lucid. The goal of this study was to explore the influence of soil structure, that is, soil pore spatial arrangements, with and without presence of plant residue on (i) decomposition of added plant residue, (ii) CO2 emission from soil, and (iii) structure of soil bacterial communities. The study consisted of several soil incubation experiments with samples of contrasting pore characteristics with/without plant residue, accompanied by X-ray micro-tomographic analyses of soil pores and by microbial community analysis of amplified 16S-18S rRNA genes via pyrosequencing. We observed that in the samples with substantial presence of air-filled well-connected large (>30 µm) pores, 75-80% of the added plant residue was decomposed, cumulative CO2 emission constituted 1,200 µm C g(-1) soil, and movement of C from decomposing plant residue into adjacent soil was insignificant. In the samples with greater abundance of water-filled small pores, 60% of the added plant residue was decomposed, cumulative CO2 emission constituted 2,000 µm C g(-1) soil, and the movement of residue C into adjacent soil was substantial. In the absence of plant residue the influence of pore characteristics on CO2 emission, that is on decomposition of the native soil organic C, was negligible. The microbial communities on the plant residue in the samples with large pores had more microbial groups known to be cellulose decomposers, that is, Bacteroidetes, Proteobacteria, Actinobacteria, and Firmicutes, while a number of oligotrophic Acidobacteria groups were more abundant on the plant residue from the samples with small pores. This study provides the first experimental evidence that characteristics of soil pores and their air/water flow status determine the phylogenetic composition of the local microbial community and directions and magnitudes of soil C decomposition processes.

Atomistic insight into viscosity and density of silicate melts under pressure.

A defining characteristic of silicate melts is the degree of polymerization (tetrahedral connectivity), which dictates viscosity and affects compressibility. While viscosity of depolymerized silicate melts increases with pressure consistent with the free-volume theory, isothermal viscosity of polymerized melts decreases with pressure up to ~3-5 GPa, above which it turns over to normal (positive) pressure dependence. Here we show that the viscosity turnover in polymerized liquids corresponds to the tetrahedral packing limit, below which the structure is compressed through tightening of the inter-tetrahedral bond angle, resulting in high compressibility, continual breakup of tetrahedral connectivity and viscosity decrease with increasing pressure. Above the turnover pressure, silicon and aluminium coordination increases to allow further packing, with increasing viscosity and density. These structural responses prescribe the distribution of melt viscosity and density with depth and play an important role in magma transport in terrestrial planetary interiors.

Method for obtaining silver nanoparticle concentrations within a porous medium via synchrotron X-ray computed microtomography.

Attempts at understanding nanoparticle fate and transport in the subsurface environment are currently hindered by an inability to quantify nanoparticle behavior at the pore scale (within and between pores) within realistic pore networks. This paper is the first to present a method for high resolution quantification of silver nanoparticle (nAg) concentrations within porous media under controlled experimental conditions. This method makes it possible to extract silver nanoparticle concentrations within individual pores in static and quasi-dynamic (i.e., transport) systems. Quantification is achieved by employing absorption-edge synchrotron X-ray computed microtomography (SXCMT) and an extension of the Beer-Lambert law. Three-dimensional maps of X-ray mass linear attenuation are converted to SXCMT-determined nAg concentration and are found to closely match the concentrations determined by ICP analysis. In addition, factors affecting the quality of the SXCMT-determined results are investigated: 1) The acquisition of an additional above-edge data set reduced the standard deviation of SXCMT-determined concentrations; 2) X-ray refraction at the grain/water interface artificially depresses the SXCMT-determined concentrations within 18.1 µm of a grain surface; 3) By treating the approximately 20 × 10(6) voxels within each data set statistically (i.e., averaging), a high level of confidence in the SXCMT-determined mean concentrations can be obtained. This novel method provides the means to examine a wide range of properties related to nanoparticle transport in controlled laboratory porous medium experiments.

X-ray absorption spectroscopy of GeO2 glass to 64 GPa.

The structural behavior of GeO2 glass has been investigated up to 64 GPa using results from x-ray absorption spectroscopy in a diamond anvil cell combined with previously reported density measurements. The difference between the nearest Ge-O distances of glassy and rutile-type GeO2 disappears at the Ge-O distance maximum at 20 GPa, indicating completion of the tetrahedral-octahedral transition in GeO2 glass. The mean-square displacement σ(2) of the Ge-O distance in the first Ge-O shell increases progressively to a maximum at 10 GPa, followed by a substantial reduction at higher pressures. The octahedral glass is, as expected, less dense and has a higher compressibility than the corresponding crystalline phase, but the differences in Ge-O distance and density between the glass and the crystals are gradually eliminated over the 20-40 GPa pressure range. Above 40 GPa, GeO2 forms a dense octahedral glass with a compressibility similar to that of the corresponding crystalline phase (α-PbO2 type). The EXAFS and XANES spectra show evidence for subtle changes in the dense glass continuing to occur at these high pressures. The Ge-O bond distance shows little change between 45-64 GPa, and this may reflect a balance between bond shortening and a gradual coordination number increase with compression. The density of the glass is similar to that of the α-PbO2-type phase, but the Ge-O distance is longer and is close to that in the higher-coordination pyrite-type phase which is stable above ∼60 GPa. The density data provide evidence for a possible discontinuity and change in compressibility at 40-45 GPa, but there are no major changes in the corresponding EXAFS spectra. A pyrite-type local structural model for the glass can provide a reasonable fitting to the XAFS spectra at 64 GPa.

Timescales of quartz crystallization and the longevity of the Bishop giant magma body.

Supereruptions violently transfer huge amounts (100 s-1000 s km(3)) of magma to the surface in a matter of days and testify to the existence of giant pools of magma at depth. The longevity of these giant magma bodies is of significant scientific and societal interest. Radiometric data on whole rocks, glasses, feldspar and zircon crystals have been used to suggest that the Bishop Tuff giant magma body, which erupted ~760,000 years ago and created the Long Valley caldera (California), was long-lived (>100,000 years) and evolved rather slowly. In this work, we present four lines of evidence to constrain the timescales of crystallization of the Bishop magma body: (1) quartz residence times based on diffusional relaxation of Ti profiles, (2) quartz residence times based on the kinetics of faceting of melt inclusions, (3) quartz and feldspar crystallization times derived using quartz+feldspar crystal size distributions, and (4) timescales of cooling and crystallization based on thermodynamic and heat flow modeling. All of our estimates suggest quartz crystallization on timescales of <10,000 years, more typically within 500-3,000 years before eruption. We conclude that large-volume, crystal-poor magma bodies are ephemeral features that, once established, evolve on millennial timescales. We also suggest that zircon crystals, rather than recording the timescales of crystallization of a large pool of crystal-poor magma, record the extended periods of time necessary for maturation of the crust and establishment of these giant magma bodies.

X-ray diffraction in the pulsed laser heated diamond anvil cell.

We have developed in situ x-ray synchrotron diffraction measurements of samples heated by a pulsed laser in the diamond anvil cell at pressure up to 60 GPa. We used an electronically modulated 2-10 kHz repetition rate, 1064-1075 nm fiber laser with 1-100 µs pulse width synchronized with a gated x-ray detector (Pilatus) and time-resolved radiometric temperature measurements. This enables the time domain measurements as a function of temperature in a microsecond time scale (averaged over many events, typically more than 10,000). X-ray diffraction data, temperature measurements, and finite element calculations with realistic geometric and thermochemical parameters show that in the present experimental configuration, samples 4 µm thick can be continuously temperature monitored (up to 3000 K in our experiments) with the same level of axial and radial temperature uniformities as with continuous heating. We find that this novel technique offers a new and convenient way of fine tuning the maximum sample temperature by changing the pulse width of the laser. This delicate control, which may also prevent chemical reactivity and diffusion, enables accurate measurement of melting curves, phase changes, and thermal equations of state.

The packing of granular polymer chains.

Rigid particles pack into structures, such as sand dunes on the beach, whose overall stability is determined by the average number of contacts between particles. However, when packing spatially extended objects with flexible shapes, additional concepts must be invoked to understand the stability of the resulting structure. Here, we examine the disordered packing of chains constructed out of flexibly connected hard spheres. Using x-ray tomography, we find that long chains pack into a low-density structure whose mechanical rigidity is mainly provided by the backbone. On compaction, randomly oriented, semi-rigid loops form along the chain, and the packing of chains can be understood as the jamming of these elements. Finally, we uncover close similarities between the packing of chains and the glass transition in polymers.

A combination of a Drickamer anvil apparatus and monochromatic X-rays for stress and strain measurements under high pressure.

A modified Drickamer anvil apparatus has been developed to combine with monochromatic synchrotron radiation for high-pressure X-ray diffraction and radiography in the GSECARS bending-magnet station, 13-BM-D, at the Advanced Photon Source, Argonne, USA. Using this experimental set-up, deformation experiments can be carried out at pressures in excess of 30 GPa at high temperatures. Differential stresses and total axial strains of polycrystalline platinum and Mg(2)SiO(4) ringwoodite have been measured up to 32 GPa at room temperature using tungsten carbide anvils. The total axial strain of the platinum increases with pressure and reaches about 55% at the highest pressure. A test run using a composite sintered diamond anvil system was performed. The use of X-ray-tranparent anvils enables the entire Debye rings to be observed up to 10 degrees 2theta. With high-energy photons (65-70 keV), this allows a coverage in Q (= 2pi sintheta/lambda) to about 3 A(-1), thus making it possible to evaluate hydrostatic pressure and differential stress in crystalline minerals using diffraction. This, coupled with the ability to determine axial strain, allows deformation studies to be performed to pressures above 30 GPa.

High quality x-ray absorption spectroscopy measurements with long energy range at high pressure using diamond anvil cell.

We describe an approach for acquiring high quality x-ray absorption fine structure (XAFS) spectroscopy spectra with wide energy range at high pressure using diamond anvil cell (DAC). Overcoming the serious interference of diamond Bragg peaks is essential for combining XAFS and DAC techniques in high pressure research, yet an effective method to obtain accurate XAFS spectrum free from DAC induced glitches has been lacking. It was found that these glitches, whose energy positions are very sensitive to the relative orientation between DAC and incident x-ray beam, can be effectively eliminated using an iterative algorithm based on repeated measurements over a small angular range of DAC orientation, e.g., within +/-3 degrees relative to the x-ray beam direction. Demonstration XAFS spectra are reported for rutile-type GeO2 recorded by traditional ambient pressure and high pressure DAC methods, showing similar quality at 440 eV above the absorption edge. Accurate XAFS spectra of GeO2 glass were obtained at high pressure up to 53 GPa, providing important insight into the structural polymorphism of GeO2 glass at high pressure. This method is expected be applicable for in situ XAFS measurements using a diamond anvil cell up to ultrahigh pressures.

Birth and growth of a granular jet.

The interaction between fine grains and the surrounding interstitial gas in a granular bed can lead to qualitatively new phenomena not captured in a simple, single-fluid model of granular flows. This is demonstrated by the granular jet formed by the impact of a solid sphere into a bed of loose, fine sand. Unlike jets formed by impact in fluids, this jet is actually composed of two separate components, an initial thin jet formed by the collapse of the cavity left by the impacting object stacked on top of a second, thicker jet which depends strongly on the ambient gas pressure. This complex structure is the result of an interplay between ambient gas, bed particles, and impacting sphere. Here we present the results of systematic experiments that combine measurements of the jet above the surface varying the release height, sphere diameter, container size, and bed material with x-ray radiography below the surface to connect the changing response of the bed to the changing structure of the jet. We find that the interstitial gas trapped by the low permeability of a fine-grained bed plays two distinct roles in the formation of the jet. First, gas trapped and compressed between grains prevents compaction, causing the bed to flow like an incompressible fluid and allowing the impacting object to sink deep into the bed. Second, the jet is initiated by the gravity driven collapse of the cavity left by the impacting object. If the cavity is large enough, gas trapped and compressed by the collapsing cavity can amplify the jet by directly pushing bed material upwards and creating the thick jet. As a consequence of these two factors, when the ambient gas pressure is decreased, there is a crossover from a nearly incompressible, fluidlike response of the bed to a highly compressible, dissipative response. Compaction of the bed at reduced pressure reduces the final depth of the impacting object, resulting in a smaller cavity and in the demise of the thick jet.

Density measurements of noncrystalline materials at high pressure with diamond anvil cell.

We describe an x-ray absorption method for in situ density measurement of non-crystalline materials in the diamond anvil cell using a monochromatic synchrotron x-ray microbeam. Sample thickness, which is indispensable in the absorption method, can be determined precisely by extrapolating the thickness profile of the gasket obtained by x-ray absorption and diffraction measurements. Diamond deformation across the sample chamber becomes noticeable at high pressures above 10 GPa, which can be monitored with a precision better than 1%, as demonstrated by measurements on crystalline Ag. We have applied the developed method to measure densities of the classic network-forming GeO(2) glass in octahedral form at pressures up to 56 GPa. The fit to the pressure-volume data with the Birch-Murnaghan equation from 13 to 56 GPa gives parameters of V(0)=23.2+/-0.4 cm(3)mol and K=35.8+/-3.0 GPa, assuming that K(')=4. This method could be applicable for in situ determination of the density of liquids and other noncrystalline materials using a diamond anvil cell up to ultrahigh pressures.

Plutonium oxidation and subsequent reduction by Mn(IV) minerals in Yucca Mountain tuff.

Plutonium oxidation state distribution on Yucca Mountain tuff and synthetic pyrolusite (beta-MnO2) suspensions was measured using synchrotron X-ray micro-spectroscopy and microimaging techniques as well as ultrafiltration/solventextraction techniques. Plutonium sorbed to the tuff was preferentially associated with manganese oxides. For both Yucca Mountain tuff and synthetic pyrolusite, Pu(IV) or Pu(V) was initially oxidized to more mobile Pu(V/VI), but over time, the less mobile Pu(IV) became the predominant oxidation state of the sorbed Pu. The observed stability of Pu(IV) on oxidizing surfaces (e.g., pyrolusite), is proposed to be due to the formation of a stable hydrolyzed Pu(IV) surface species. These findings have important implications in estimating the risk associated with the geological burial of radiological waste in areas containing Mn-bearing minerals, such as at the Yucca Mountain or the Hanford Sites, because plutonium will be predominantly in a much less mobile oxidation state (i.e., Pu(IV)) than previously suggested (i.e., Pu(V/VI).

Grain-size control in situ at high pressures and high temperatures in a diamond-anvil cell.

The grain-size distribution and the character of individual grain boundaries in microcrystalline networks play a significant role in material properties, such as melting temperature, diffusion coefficients, resistivity, optical absorption, elastic constants, phase transformation pressure, and so on. In this study, the grain size of NaCl, SiO2 and FeC3 is controlled in situ at high pressures over the entire range of the length scale of crystallinity: single-crystal, micro-/nanocrystalline and amorphous materials within a volume commensurate with the size of the probing X-ray beam. The structure refinement of high-pressure samples from X-ray diffraction data can be significantly improved by controlling grain size by selecting the structure of starting materials and following certain high pressure-temperature-time paths.

Facilities for high-pressure research with the diamond anvil cell at GSECARS.

An overview of facilities for high-pressure research with the diamond anvil cell (DAC) at the GeoSoilEnviroCARS (GSECARS) sector at the Advanced Photon Source (Argonne, Illinois) is presented. There are three operational experimental stations (13-ID-C, 13-ID-D and 13-BM-D) where DAC instrumentation is installed for various types of experiments at high pressure and extreme temperature conditions. A fourth station (13-BM-C) is under construction and will be operational in 2006. While most X-ray diffraction experiments have been undertaken with powder samples so far, there is a growing demand for single-crystal diffraction (SCD) at high pressure. As one of the principal components at GSECARS, SCD is currently under rapid development. Other relevant techniques have also been developed for obtaining complementary information from powder or single-crystal samples at high pressure. For example, an on-line Brillouin system is installed and operational at 13-BM-D for acoustic velocity and single-crystal elasticity determinations. In addition, various X-ray spectroscopy techniques (e.g. X-ray emission and X-ray Raman) are employed for measuring electronic and magnetic properties. Future developments are discussed with the DAC program at GSECARS.