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Permeability, porosity, and mineral surface area changes in basalt cores induced by reactive transport of CO 2 -rich brine

Four reactive flow–through laboratory experiments (two each at 0.1 mL/min and 0.01 mL/min flow rates) at 150°C and 150 bar (15 MPa) are conducted on intact basalt cores to assess changes in porosity, permeability, and surface area caused by CO 2 –rich fluid–rock interaction. Permeability decreases slightly during the lower flow rate experiments and increases during the higher flow rate experiments. At the higher flow rate, core permeability increases by more than one order of magnitude in one experiment and less than a factor of two in the other due to differences in preexisting flow path structure. X–ray computed tomography (XRCT) scans of pre– and post–experiment cores identify both mineral dissolution and secondary mineralization, with a net decrease in XRCT porosity of ~0.7%–0.8% for the larger pores in all four cores. (Ultra) small–angle neutron scattering ((U)SANS) data sets indicate an increase in both (U)SANS porosity and specific surface area (SSA) over the ~1 nm to 10 µm scale range in post–experiment basalt samples, with differences due to flow rate and reaction time. Net porosity increases from summing porosity changes from XRCT and (U)SANS analyses are consistent with core mass decreases. (U)SANS data suggest an overall preservation of the pore structure with no change in mineral surface roughness from reaction, and the pore structure is unique in comparison to previously published basalt analyses. Altogether, these data sets illustrate changes in physical parameters that arise due to fluid–basalt interaction in relatively low pH environments with elevated CO 2 concentration, with significant implications for flow, transport, and reaction through geologic formations.

(ultra) small‐angle neutron scattering ((U)SANS)↗

Measuring the Internal Structure and Physical Conditions in Star and Planet Forming Clouds Cores: Towards a Quantitative Description of Cloud Evolution

This grant funds a research program to use infrared extinction measurements to probe the detailed structure of dark molecular cloud cores and investigate the physical conditions which give rise to star and planet formation. The goals of this program are to acquire, reduce and analyze deep infrared and molecular-line observations of a carefully selected sample of nearby dark clouds in order to determine the detailed initial conditions for star formation from quantitative measurements of the internal structure of starless cloud cores and to quantitatively investigate the evolution of such structure through the star and planet formation process.

Lada, Charles J.↗

Diamond as a solid state micro-fission chamber for thermal neutron detection at the VR-1 research reactor

Diamond exhibits a combination of properties which makes it attractive for neutron detection in hostile conditions. In the particular case of detection in a nuclear reactor, it is resilient to radiation, exhibits a natural low sensitivity to gamma rays, and its small size (as compared with that of gas ionisation chambers) enables fluency monitoring with a high position resolution. We report here on the use of synthetic CVD diamond as a solid state micro-fission chamber with U-235 converting material for in-core thermal neutron monitoring. Two types of thin diamond detectors were developed for this application. The first type of detector is fabricated using thin diamond membrane obtained by etching low-cost commercially available single crystal CVD intrinsic diamond, so called 'optical grade' material. Starting from a few hundred of micrometre thick samples, the sample is sliced with a laser and then plasma etched down to a few tenths of micrometre. Here we report the result obtained with a 17 μm thick device. The detection surface of this detector is equal to 1 mm{sup 2}. Detectors with surfaces up to 1 cm{sup 2} can be fabricated with this technique. The second type of detector is fabricated by growing successively two thin films of diamond, by the microwave enhanced chemical vapour deposition technique, on HPHT single crystal diamond. A first, a film of boron doped (p+) single crystal diamond, a few microns thick, is deposited. Then a second film of intrinsic diamond with a thickness of a few tens of microns is deposited. This results in a P doped, Intrinsic, Metal structure (PIM) structure in which the intrinsic volume id the active part of the detector. Here we report the results obtained with a 20 μm thick intrinsic whose detection surface is equal to 0.5 mm{sup 2}, with the possibility to enlarge the surface of the detector up to 1 cm{sup 2}. These two types of detector were tested at the VR-1 research reactor at the Czech Technical University in Prague. The Training Reactor VR-1 is a pool type (light water) reactor based on UO{sub 2} low enriched uranium. It has a nominal power of 1 kW, and can be operated for a short period up to 5 kW. The arrangement of the reactor pool reactor facilitates access to the core, setting and removal of various experimental samples and detectors, and safe and easy handling of fuel assemblies. The reactor is equipped with two horizontal channels (radial and tangential) and 10 vertical channels, of varying diameters, which can be loaded into various core positions, and one pneumatic transfer system. It is also equipped with several specifically designed educational instrumentation systems that can be used to supply complementary measurements and characterization around the reactor. The reactor is operated by the Department of Nuclear Reactors of the Faculty of Nuclear Sciences and Physical Engineering of the Czech Technical University in Prague. The two detectors were placed in-core through one of the vertical insertion channel. They were coupled to remote placed (5 m BNC cable) classical nuclear charge sensitive electronics. Detection properties of both sensors, including: pulse height spectra of U-235 fission fragments (response linearity with neutron flux, count rate, gamma background, were evaluated varying the power of the reactor from 0.005 W to 500 W. The evolution of the counting rate of the thinned optical grade detector as a function of counting rate of a gas ionization chamber used currently for reactor monitoring shows the very good linearity of the detector over the 5 decades. Similar results were obtained with the PIM detector. Additionally fast transient current signals of the detectors were recorded on a digital storage oscilloscope (DSO) using broad-band amplifier and with a simple bias-T, showing potential use of such sensors for neutron counting with no need of an amplification stage, since non-amplified signals from fission fragments exceeded 4 mV in amplitude. Therefore, one can think of simple neutron counting system by feeding diamond detectors signals directly to the low threshold discriminators. The results obtained on the VR1 will be described and discussed in detail in the paper and associated presentation. The results demonstrate that diamond micro-fission chambers can be used for in-core neutron monitoring, where robust, simple and compact devices are required.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Spatially Resolved, In Situ Carbon Isotope Analysis of Archean Organic Matter

Spatiotemporal variability in the carbon isotope composition of sedimentary organic matter (OM) preserves information about the evolution of the biosphere and of the exogenic carbon cycle as a whole. Primary compositions, and imprints of the post-depositional processes that obscure them, exist at the scale of individual sedimentary grains (mm to micron). Secondary ion mass spectrometry (SIMS) (1) enables analysis at these scales and in petrographic context, (2) permits morphological and compositional characterization of the analyte and associated minerals prior to isotopic analysis, and (3) reveals patterns of variability homogenized by bulk techniques. Here we present new methods for in situ organic carbon isotope analysis with sub-permil precision and spatial resolution to 1 micron using SIMS, as well as new data acquired from a suite of Archean rocks. Three analytical protocols were developed for the CAMECA ims1280 at WiscSIMS to analyze domains of varying size and carbon concentration. Average reproducibility (at 2SD) using a 6 micron spot size with two Faraday cup detectors was 0.4 %, and 0.8 % for analyses using 1 micron and 3 micron spot sizes with a Faraday cup (for C-12) and an electron multiplier (for C-13). Eight coals, two ambers, a shungite, and a graphite were evaluated for micron-scale isotopic heterogeneity, and LCNN anthracite (delta C-13 = -23.56 +/- 0.1 %, 2SD) was chosen as the working standard. Correlation between instrumental bias and H/C was observed and calibrated for each analytical session using organic materials with H/C between 0.1 and 1.5 (atomic), allowing a correction based upon a C-13H/C-13 measurement included in every analysis. Matrix effects of variable C/SiO2 were evaluated by measuring mm to sub-micron graphite domains in quartzite from Bogala mine, Sri Lanka. Apparent instrumental bias and C-12 count rate are correlated in this case, but this may be related to a crystal orientation effect in graphite. Analyses of amorphous Archean OM suggest that instrumental bias is consistent for 12C count rates as low as 10% relative to anthracite. Samples from the ABDP-9 (n=3; Mount McRae Shale, approximately 2.5 Ga), RHDH2a (n=2; Carrawine Dolomite and Jeerinah Fm, approximately 2.6 Ga), WRL1 (n=3; Wittenoom Fm, Marra Mamba Iron Formation, and Jeerinah Fm, approximately 2.6 Ga), and SV1 (n=1; Tumbiana Fm, approximately 2.7 Ga) drill cores, each previously analyzed for bulk organic carbon isotope composition, yielded 100 new, in situ data from Neoarchean sedimentary OM. In these samples, delta C-13 varies between -53.1 and -28.3 % and offsets between in situ and bulk compositions range from -8.3 to 18.8%. In some cases, isotopic composition and mode of occurrence (e.g. morphology and mineral associations) are statistically correlated, enabling the identification of distinct reservoirs of OM. Our results support previous evidence for gradients of oxidation with depth in Neoarchean environments driven by photosynthesis and methane metabolism. The relevance of these findings to questions of bio- and syngenicity as well as the alteration history of previously reported Archean OM will be discussed.

Williford, Kenneth H.↗

Thermodynamic and Diffusion Model Estimates on Metamorphic Temperatures and Timescales for Basaltic Eucrite GRA 98098

Introduction: HED meteorites are thought to rep-resent igneous rocks from Vesta’s basaltic crust and preserve evidence of early crustal metamorphism. Determining the temperatures and timescales of thermal metamorphism is important for reconstructing crustal evolution in the early solar system. Here, we study basaltic eucrite Graves Nunataks (GRA) 98098, which has been identified as a highly metamorphosed eucrite [1]. We present new estimates on metamorphic temperatures determined via thermodynamic modeling as well as the initial results from diffusion models constraining timescales of thermal metamorphism. Sample Description: GRA 98098 is an unbrecciated eucrite with a granoblastic plagioclase and pyroxene mineralogy. Millimeter to cm-long lathes of tridymite cross-cut and poikilitically enclose plagioclase and pyroxene [1,this work]. Pyroxene grains have exsolved into Ca-rich (~Wo38En29Fs33) and Ca-poor (~Wo4.5En36Fs59.5) lamellae. Both unzoned and zoned plagioclase grains are observed. Unzoned plagioclase grains are found solely with tridymite laths. These grains have ~An92 compositions. The cores of the zoned plagioclase grains have the same composition and thin, relatively sodic rims (~An67), (Fig. 1). The bulk sample is unusually enriched in highly in-compatible elements and has one of the most fractionated REE patterns reported [1]. Maximum metamorphic temperatures of 985±78°C have been estimated using two-pyroxene thermometry [2]. Methods: Thermodynamic modeling. Thermodynamic models were constructed using the software Perple_X, which employs a Gibbs free energy minimization in order to determine the most stable phase assemblage for a given bulk rock composition [3]. Bulk composition was calculated using mineral com-positions acquired via EMPA (this study) and the observed abundancies present in the thin section. Two bulk compositions were estimated; 1) includes all phases present in the thin section, (assumes that all phases are present during metamorphism), 2) excludes tridymite from the bulk calculation (assumes that tridymite was not present during metamorphism). In order to determine whether metamorphic equilibria was achieved and estimate temperatures of metamorphism, we compared measured pyroxene compositions with thermodynamically predicted compositions [4, Fig. 2]. Diffusion Modeling. Several time-temperature de-pendent diffusion profiles were calculated in order to determine the best match for XAn chemical profiles observed at the edges of the zoned plagioclase (Fig. 3). We assumed that the start condition was a stepwise gradient at the plagioclase/pyroxene interface. We also assumed an average diffusion coefficient (D) and a constant temperature using the equation in [5]. D was determined for two temperatures (T = 1060ºC; near eucrite solidus [6] and T = 985ºC; metamorphism reported in [4]) and then XAn was calculated as a function of distance from plagioclase core to rim using an error function solution to Fick’s second law. Results: Thermodynamic model results are summarized in Fig. 2. For a bulk composition that includes all phases in the thin section, pyroxene endmember compositions plot in the following temperature ranges: Fs ~660-860ºC, En~1000ºC & 1150ºC, and Wo~760-900ºC (Fig. 2a). For a bulk composition that excludes tridymite from the peak metamorphic assemblage (i.e., the bulk composition minus the contribution from tridymite), a temperature range could not be determined for the Fs component of pyroxene. For Wo, T~760-900ºC and En, T~1000ºC & 1150ºC (Fig. 2b). Fig. 3 summarizes the diffusion model results. For T = 1060°C & 985°C, the most appropriate time interval was estimated based on which diffusion curve most matched (solid lines, Fig. 3) the EMPA data. For T = 1060°C, the best looking match was t = 500 ka. For T = 985°C, the best match was t = 7 Ma. Discussion and future work: Temperature estimates from thermodynamic models are not conclusive because the temperature ranges determined for pyroxene endmember stability do not overlap (colored fields in Fig. 2), thus implying that there is disequilibrium between pyroxene crystals and the bulk composition considered [4]. Thus, additional exploration is needed to define a metamorphically equilibrated do-main that accurately records peak temperature. The utility of defining metamorphically equilibrated do-mains to improve the accuracy and level of detail elucidated regarding the petrogenetic history of metamorphose samples has been demonstrated previously [4,7]. We suggest that in the case of Fig. 2a, the thin section composition is not representative of the length scales over which metamorphic equilibrium was achieve and in the case of Fig. 2b, the assumption that tridymite was not present during metamorphism was incorrect. However, results from thermodynamic models can provide insight into the relative timing of mineral and compositional textures. For example from texture alone, it is unclear whether tridymite was igneous in origin and represents the last bits of melt in a crystallizing magma chamber, or if it formed during (and possibly initiated) open system thermal metamorphism. The latter could be consistent with a partial melt hypothesis [8,9] while the former implies that simple fractional crystallization can yield the textures present in GRA 98098. The lack of coincidence be-tween pyroxene endmember compositions in Fig. 2b suggest that the bulk composition minus tridymite was not the assemblage in equilibrium with the pyroxene, suggesting that tridymite was present during metamorphism and formed during igneous crystallization. We conclude that the development of the Na-rich plagioclase rims likely occurred during or immediately after peak thermal metamorphism, because eucrites of similar metamorphic grade and texture have unzoned plagioclase (~An92) [2,4,8], and Na zoning is only observed in the plagioclase not included in the tridymite. This suggests that the zoning formed after tridymite formation, and therefore after igneous crystallization. Thus, the timescales calculated via diffusion modeling possibly represent the time interval over which thermal metamorphism occurred. Cooling rates approximated for the Vestan crust predict that the crust cooled below 300°C around 35-40 Ma after formation[10]. This is consistent with our modeling results that predict formation of the Na rich plagioclase rims occurring at higher temperatures over a period of 0.5 to 7 Ma years. Future work. Additional thermodynamic modeling work will focus on selecting an equilibrated bulk rock domain in which to elucidate metamorphic conditions. Diffusion models currently provide a minimum time-scale, since diffusion slows down as the system cools. Future work with will focus on integrating cooling into the diffusion models and constraining the depth at which thermal metamorphism occurs because it could be used to determine whether the range of time-scales calculated for thermal metamorphism are consistent with the geologic environment.

J S Gorce↗

Early-type galaxy core phase densities

Early-type galaxies have projected central density brightness profile logarithmic slopes, γ', ranging from about 0 to 1. We show that γ' is strongly correlated, r = 0.83, with the coarse grain phase density of the galaxy core, Q {sub 0} ≡ ρ/σ{sup 3}. The luminosity-γ' correlation is much weaker, r = –0.51. Q {sub 0} also serves to separate the distribution of steep core profiles, γ' > 0.5, from shallow profiles, γ' < 0.3, although there are many galaxies of intermediate slope, at intermediate Q {sub 0}, in a volume-limited sample. The transition phase density separating the two profile types is approximately 0.003 M {sub ☉} pc{sup –3} km{sup –3} s{sup 3}, which is also where the relation between Q {sub 0} and core mass shows a change in slope, the rotation rate of the central part of the galaxy increases, and the ratio of the black hole to core mass increases. These relations are considered relative to the globular cluster inspiral core buildup and binary black hole core scouring mechanisms for core creation and evolution. Mass-enhanced globular cluster inspiral models have quantitative predictions that are supported by data, but no single model yet completely explains the correlations.

79 ASTRONOMY AND ASTROPHYSICS↗

Facile synthesis and microwave absorbability of C@Ni–NiO core–shell hybrid solid sphere and multi-shelled NiO hollow sphere

We reported the preparation of C@Ni–NiO core–shell hybrid solid spheres or multi-shelled NiO hollow spheres by combining a facile hydrothermal route with a calcination process in H{sub 2} or air atmosphere, respectively. The synthesized C@Ni–NiO core–shell solid spheres with diameters of approximately 2–6 μm were in fact built from dense NiO nanoparticles coated by random two-dimensional metal Ni nanosheets without any visible pores. The multi-shelled NiO hollow spheres were built from particle-like ligaments and there are a lot of pores with size of several nanometers on the surface. Combined Raman spectra with X-ray photoelectron spectra (XPS), it suggested that the defects in the samples play a limited role in the dielectric loss. Compared with the other samples, the permeability of the samples calcined in H{sub 2} and air was increased slightly and the natural resonance frequency shifted to higher frequency (7, 11 and 14 GHz, respectively), leading to an enhancement of microwave absorption property. For the sample calcined in H{sub 2}, an optimal reflection loss less than − 10 was obtained at 7 GHz with a matching thickness of 5.0 mm. Our study demonstrated the potential application of C@Ni–NiO core–shell hybrid solid sphere or multi-shelled NiO hollow sphere as a more efficient electromagnetic (EM) wave absorber. - Highlights: • C@Ni–NiO core–shell hybrid solid sphere was synthesized by a facile method. • Multi-shelled NiO hollow sphere was synthesized by a facile method. • It suggested that the defects in the samples play a limited role in dielectric loss. • The permeability of the samples calcined in H{sub 2} and air was increased. • Microwave absorbability of C@Ni–NiO core–shell hybrid solid sphere was investigated.

36 MATERIALS SCIENCE↗

The Gamma-Ray Emitting Radio-Loud Narrow-Line Seyfert 1 Galaxy PKS 2004-447 II. The Radio View

Context. gamma-ray-detected radio-loud narrow-line Seyfert 1 (gamma-NLS1) galaxies constitute a small but interesting sample of the gamma-ray-loud AGN. The radio-loudest gamma-NLS1 known, PKS2004447, is located in the southern hemisphere and is monitored in the radio regime by the multiwavelength monitoring programme TANAMI. Aims. We aim for the first detailed study of the radio morphology and long-term radio spectral evolution of PKS2004447, which are essential for understanding the diversity of the radio properties of gamma-NLS1s. Methods. The TANAMI VLBI monitoring program uses the Australian Long Baseline Array (LBA) and telescopes in Antarctica, Chile, New Zealand, and South Africa to monitor the jets of radio-loud active galaxies in the southern hemisphere. Lower resolution radio flux density measurements at multiple radio frequencies over four years of observations were obtained with the Australia Telescope Compact Array (ATCA). Results. The TANAMI VLBI image at 8.4GHz shows an extended one-sided jet with a dominant compact VLBI core. Its brightness temperature is consistent with equipartition, but it is an order of magnitude below other gamma-NLS1s with the sample value varying over two orders of magnitude. We find a compact morphology with a projected large-scale size 11 kpc and a persistent steep radio spectrum with moderate flux-density variability. Conclusions. PKS2004447 appears to be a unique member of the gamma-NLS1 sample. It exhibits blazar-like features, such as a flat featureless X-ray spectrum and a core-dominated, one-sided parsec-scale jet with indications for relativistic beaming. However, the data also reveal properties atypical for blazars, such as a radio spectrum and large-scale size consistent with compact-steep-spectrum (CSS) objects, which are usually associated with young radio sources. These characteristics are unique among all gamma-NLS1s and extremely rare among gamma-ray-loud AGN.

galaxies: active / galaxies: individual: PKS 2004-↗

Synthesis and Characterization of Core-Shell Cu-Ru, Cu-Rh, and Cu-Ir Nanoparticles

Optimizing the use of expensive precious metals is critical to developing sustainable and low-cost processes for heterogeneous catalysis or electrochemistry. Here, we report a synthesis method that yields core-shell Cu-Ru, Cu-Rh, and Cu-Ir nanoparticles with the platinum-group metals segregated on the surface. The synthesis of Cu-Ru, Cu-Rh, and Cu-Ir particles allows maximization of the surface area of these metals and improves catalytic performance. Furthermore, the Cu core can be selectively etched to obtain nanoshells of the platinum-group metal components, leading to a further increase in the active surface area. Characterization of the samples was performed with X-ray absorption spectroscopy, X-ray powder diffraction, and ex situ and in situ transmission electron microscopy. CO oxidation was used as a reference reaction: the three core-shell particles and derivatives exhibited promising catalyst performance and stability after redox cycling. Furthermore, these results suggest that this synthesis approach may optimize the use of platinum-group metals in catalytic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mineralogy, fabric and deformation domains in D" across the southwestern border of the African LLSVP

Recent advances in seismic anisotropy studies that jointly use reflections and shear wave splitting have proven to place tight constraints on the plausible anisotropic and deformation scenarios in the D" region. We apply this novel methodology to a large area of the D" region beneath the South Atlantic, in proximity to and within the African large low seismic velocity province (LLSVP). This area of the mantle is characterized by a transition from fast to slow seismic velocity anomalies and it is thought to be the location of deep-seated plumes responsible for hotspot volcanism. Attempting to probe mantle composition and deformation along the LLSVP borders may provide key information on mantle dynamics. By analysing seismic phases sampling this region, we detect a D" discontinuity over a large area beneath the South Atlantic, with inferred depth ranges ~170 to ~240 km above the core–mantle boundary. We find evidence for a D" reflector within the area of the LLSVP. Shear wave splitting observations suggest that anisotropy is present in this region of the mantle, in agreement with previous studies that partially sampled this region. We model the observations considering lattice- and shape-preferred orientation of materials expected in the D" region. A regional variation of mineralogy, phase transition boundaries, and deformation direction is required to explain the data. We infer two distinct domains of mineralogy and deformation: aligned post-perovskite outside the LLSVP and aligned bridgmanite within the LLSVP. Finally, the scenario depicted by this study agrees well with the current hypotheses for the composition of the LLSVP and with the prevalence of vertical deformation directions expected to occur along the LLSVPs borders.

58 GEOSCIENCES↗

Dynamic strength of iron under pressure-temperature conditions of Earth’s inner core

Iron (Fe) is a primary constituent of terrestrial planetary cores, yet its rheological properties under extreme conditions remain uncertain. Here we present direct measurements of Fe strength at 310-430 GPa pressures and 3700-5800 K temperatures, obtained using Rayleigh-Taylor (RT) instability experiments at the National Ignition Facility. Single-crystal α-Fe samples with [001] and [111] orientations are shock-ramp compressed past the α-ε transition along paths approaching Earth’s inner core conditions. We find that ε-Fe derived from [001] α-Fe is consistently stronger (11-20 GPa) than that from [111] α-Fe (8-18 GPa), contrary to the trend at ambient conditions. Large-scale molecular dynamics simulations reproduce this atypical strength anisotropy and attribute it to microstructural evolution during the phase transition and subsequent ε-phase plasticity. Ripple growth analysis further constrains viscosities of 100-170 Pa·s under the driven conditions. Our results provide experimental benchmarks for Fe rheology at inner-core conditions, with implications for seismic anisotropy and the geodynamo.

Condensed-matter physics↗

HST observations of globular clusters in M 31. 1: Surface photometry of 13 objects

We present the initial results of a study of globular clusters in M 31, using the Faint Object Camera (FOC) on the Hubble Space Telescope (HST). The sample of objects consists of 13 clusters spanning a range of properties. Three independent image deconvolution techniques were used in order to compensate for the optical problems of the HST, leading to mutually fully consistent results. We present detailed tests and comparisons to determine the reliability and limits of these deconvolution methods, and conclude that high-quality surface photometry of M 31 globulars is possible with the HST data. Surface brightness profiles have been extracted, and core radii, half-light radii, and central surface brightness values have been measured for all of the clusters in the sample. Their comparison with the values from ground-based observations indicates the later to be systematically and strongly biased by the seeing effects, as it may be expected. A comparison of the structural parameters with those of the Galactic globulars shows that the structural properties of the M 31 globulars are very similar to those of their Galactic counterparts. A candidate for a post-core-collapse cluster, Bo 343 = G 105, has been already identified from these data; this is the first such detection in the M 31 globular cluster system.

Pecci, F. Fusi↗

Bright, Mechanosensitive Upconversion with Cubic-Phase Heteroepitaxial Core–Shell Nanoparticles

Lanthanide-doped nanoparticles are an emerging class of optical sensors, exhibiting sharp emission peaks, high signal-to-noise ratio, photostability, and a ratiometric color response to stress. The same centrosymmetric crystal field environment that allows for high mechanosensitivity in the cubic-phase (α), however, contributes to low upconversion quantum yield (UCQY). In this work, we engineer brighter mechanosensitive upconverters using a core–shell geometry. Sub-25 nm α-NaYF 4 :Yb,Er cores are shelled with an optically inert surface passivation layer of ~4.5 nm thickness. Using different shell materials, including NaGdF 4 , NaYF 4 , and NaLuF 4 , we study how compressive to tensile strain influences the nanoparticles’ imaging and sensing properties. All core–shell nanoparticles exhibit enhanced UCQY, up to 0.14% at 150 W/cm 2 , which rivals the efficiency of unshelled hexagonal-phase (β) nanoparticles. Additionally, strain at the core–shell interface can tune mechanosensitivity. In particular, the compressive Gd shell results in the largest color response from yellow-green to orange or, quantitatively, a change in the red to green ratio of 12.2 ± 1.2% per GPa. For all samples, the ratiometric readouts are consistent over three pressure cycles from ambient to 5 GPa. Furthermore, heteroepitaxial shelling significantly improves signal brightness without compromising the core’s mechano-sensing capabilities and further, promotes core–shell cubic-phase nanoparticles as upcoming in vivo and in situ optical sensors.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A review of imputation strategies for isobaric labeling-based shotgun proteomics

The throughput efficiency and increased depth of coverage provided by isobaric-labeled proteomics measurements have led to increased usage of these techniques. However, the structure of missing data is uniquely different than unlabeled studies. In this review, we compare the efficacy of nine imputation methods on a CPTAC proteomics iTRAQ dataset. Imputation methods were evaluated with regard to accuracy, variability, statistical hypothesis test inference and run time over datasets consisting of varying number of iTRAQ plexes and percentages of missing data. In general, expectation maximization and random forest imputation methods yielded the best performances, and constant-based methods performed poorly consistently across all dataset sizes and percentages of missing values. For datasets with small sample sizes and higher percentages of missing data, results indicate that statistical inference with no imputation may be preferable. Based on the findings in this review, there are core imputation methods that perform higher for isobaric-labeled proteomics data, but great care and consideration as to whether imputation should be used should be given for datasets comprised of a small number of samples, as well as to factors such as computational time and reproducibility of imputation values.

Bramer, Lisa M.↗

Development and evaluation of a device for simultaneous uniaxial compression and optical imaging of cartilage samples in vitro

In this paper, we present a system that allows imaging of cartilage tissue via optical coherence tomography (OCT) during controlled uniaxial unconfined compression of cylindrical osteochondral cores in vitro. We describe the system design and conduct a static and dynamic performance analysis. While reference measurements yield a full scale maximum deviation of 0.14% in displacement, force can be measured with a full scale standard deviation of 1.4%. The dynamic performance evaluation indicates a high accuracy in force controlled mode up to 25 Hz, but it also reveals a strong effect of variance of sample mechanical properties on the tracking performance under displacement control. In order to counterbalance these disturbances, an adaptive feed forward approach was applied which finally resulted in an improved displacement tracking accuracy up to 3 Hz. A built-in imaging probe allows on-line monitoring of the sample via OCT while being loaded in the cultivation chamber. We show that cartilage topology and defects in the tissue can be observed and demonstrate the visualization of the compression process during static mechanical loading.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

CO Spectral Line Energy Distributions in Galactic Sources: Empirical Interpretation of Extragalactic Observations

The relative populations in rotational transitions of CO can be useful for inferring gas conditions and excitation mechanisms at work in the interstellar medium. We present CO emission lines from rotational transitions observed with Herschel /HIFI in the star-forming cores Orion S, Orion KL, Sgr B2(M), and W49N. Integrated line fluxes from these observations are combined with those from Herschel /PACS observations of the same sources to construct CO spectral line energy distributions (SLEDs) from 5≤ J{sub u} ≤ 48. These CO SLEDs are compared to those reported in other galaxies, with the intention of empirically determining which mechanisms dominate excitation in such systems. We find that CO SLEDs in Galactic star-forming cores cannot be used to reproduce those observed in other galaxies, although the discrepancies arise primarily as a result of beam filling factors. The much larger regions sampled by the Herschel beams at distances of several megaparsecs contain significant amounts of cooler gas, which dominate the extragalactic CO SLEDs, in contrast to observations of Galactic star-forming regions, which are focused specifically on cores containing primarily hot molecular gas.

79 ASTRONOMY AND ASTROPHYSICS↗

Water as the Solvent in the Stober Process for Forming Ultrafine Silica Shells on Magnetite Nanoparticles

Silica coating of magnetite nanoparticles (MNPs) is of great importance since it offers MNPs stability against oxidation, water dispersity, and a tailorable surface for functionalities, allowing a wide range of applications in areas such as water pollutant removal and targeted drug delivery. In this work, a simple and green procedure has been developed using water, instead of traditional alcohols, as the solvent in the Stober method to produce well-dispersed MNPs coated with ultrathin (< 5 nm) silica outer shells. The resultant core-shell structures possess superparamagnetic properties, high magnetization value of 59 emu/g, and excellent resistance to oxidation when exposed to ultrasonic accelerated oxidation. The oxidation stability of the coated 2 MNPs is shown to extend to their functionalized product. All syntheses are carried out under ambient conditions using commonly available chemicals and equipment. In conclusion, the Fe 3 O 4 @SiO 2 core-shell structures are characterized using FTIR-ATR spectroscopy, Transmission Electron Microscopy (TEM), Energy Dispersive X-ray Spectroscopy (EDS), and a Vibrating Sample Magnetometer (VSM).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Detuned synchronized waveform averaging for reducing distortions due to sample interleaving

This invention introduces a method for optimally detuning the ratio of analog-to-digital (ADC) sample rate and trigger rate during waveform averaging to minimize the deleterious effects from sample interleaving. A prescription is described for determining the optimal detuning factor for the ADC or trigger rate in any scenario, depending on the number of ADC cores used and the limited tuning resolution of the clock rates for a specific implementation.

42 ENGINEERING↗