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Direct Surface and Droplet Microsampling for Electrospray Ionization Mass Spectrometry Analysis with an Integrated Dual-Probe Microfluidic Chip

Ambient mass spectrometry (MS) has revolutionized the way of MS analysis and broadened its application in various fields. This paper describes the use of microfluidic techniques to simplify the setup and improve the functions of ambient MS by integrating the sampling probe, electrospray emitter probe, and online mixer on a single glass microchip. Two types of sampling probes, including a parallel-channel probe and a U-shaped channel probe, were designed for dryspot and liquid-phase droplet samples, respectively. We demonstrated that the microfabrication techniques not only enhanced the capability of ambient MS methods in analysis of dry-spot samples on various surfaces, but also enabled new applications in the analysis of nanoliter-scale chemical reactions in an array of droplets. The versatility of the microchip-based ambient MS method was demonstrated in multiple different applications including evaluation of residual pesticide on fruit surfaces, sensitive analysis of low-ionizable analytes using postsampling derivatization, and high-throughput screening of Ugi-type multicomponent reactions.

Huang, Cong-Min↗

Efficient sampling over rough energy landscapes with high barriers: A combination of metadynamics with integrated tempering sampling

In order to efficiently overcome high free energy barriers embedded in a complex energy landscape and calculate overall thermodynamics properties using molecular dynamics simulations, we developed and implemented a sampling strategy by combining the metadynamics with (selective) integrated tempering sampling (ITS/SITS) method. The dominant local minima on the potential energy surface (PES) are partially exalted by accumulating history-dependent potentials as in metadynamics, and the sampling over the entire PES is further enhanced by ITS/SITS. With this hybrid method, the simulated system can be rapidly driven across the dominant barrier along selected collective coordinates. Then, ITS/SITS ensures a fast convergence of the sampling over the entire PES and an efficient calculation of the overall thermodynamic properties of the simulation system. To test the accuracy and efficiency of this method, we first benchmarked this method in the calculation of ϕ − ψ distribution of alanine dipeptide in explicit solvent. We further applied it to examine the design of template molecules for aromatic meta-C—H activation in solutions and investigate solution conformations of the nonapeptide Bradykinin involving slow cis-trans isomerizations of three proline residues.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetic resonance imaging of DNP enhancements in a rotor spinning at the magic angle

Simulations performed on model, static, samples have shown that the microwave power is non-uniformly distributed in the magic angle spinning (MAS) rotor when using conventional dynamic nuclear polarization (DNP) instrumentation. Here, we applied the stray-field magic angle spinning imaging (STRAFI–MAS) experiment to generate a spatial map of the DNP enhancements in a full rotor, which is spun at a low rate in a commercial DNP–MAS NMR system. Notably, we observed that the enhancement factors produced in the center of the rotor can be twice as large as those produced at the top of the rotor. Surprisingly, we observed that the largest enhancement factors are observed along the axis of the rotor as opposed to against its walls, which are most directly irradiated by the microwave beam. We lastly observed that the distribution of enhancement factors can be moderately improved by degassing the sample and increasing the microwave power. The inclusion of dielectric particles greatly amplifies the enhancement factors throughout the rotor. Furthermore, the STRAFI–MAS approach can provide useful guidance for optimizing the access of microwave power to the sample, and thereby lead to further increases in sensitivity of DNP–MAS NMR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Subtask 1.1 – Advanced Characterization of Unconventional Oil and Gas Reservoirs to Enhance CO2 Storage Resource Estimates

The Energy & Environmental Research Center (EERC) developed methods and approaches for advanced characterization of unconventional oil and gas reservoirs to enhance CO2 storage resource estimates using samples collected from organic-rich shales of the Bakken Formation. The project was funded under U.S. Department of Energy (DOE) Cooperative Agreement No. DE-FE0024233, with nonfederal cost share provided by Hitachi High Technologies America. The project participants included the EERC, Hitachi High Technologies America, the team at the National Energy Technology Laboratory’s (NETL’s) computed tomography (CT) scanning laboratory in Morgantown, West Virginia, and several NETL staff who have worked on CO2 storage resource estimation. Investigations on the use of subsurface geologic formations for CO2 storage have been ongoing for many years. In the last decade, improvements in directional drilling technology and hydraulic fracturing of organic-rich shale and other tight rock formations have opened new opportunities for CO2 storage, with the potential cobenefit of enhancing gas and oil recovery. Gas-bearing, organic-rich shales have been of particular interest as a carbon storage target because their ability to store large volumes of CO2 is implied by their ability to store methane; however, estimating the CO2 storage resource of organic-rich shales and other unconventional reservoirs is challenging because of the lack of detailed geologic and petrophysical data that are needed to develop improved volumetric equations. According to NETL’s method for estimating regional-scale CO2 storage resources, the key factors that control CO2 storage in geologic formations include void space within induced fractures, natural fractures and matrix pores, as well as the occurrence and distribution of organic matter (OM) and clay minerals. A key goal of this effort was to use field emission scanning electron microscopy (FESEM) analysis of fine-grain unconventional reservoir rocks coupled with advanced image analysis and machine learning techniques to quantify the occurrence and distribution of porosity, OM, and clay minerals. By better understanding the potential migration pathways of CO2 within tight rocks and quantifying the occurrence of sorptive components (OM and clays) along potential flow pathways, methods to estimate the CO2 storage resource of such rocks can be refined. The Bakken petroleum system (Bakken) was used as the source of rock samples for this effort because it includes organic-rich shales with contrasting degrees of thermal maturity as well as tight, nonshale clastic rocks with varying clay mineral content. To better understand the key components of interest in tight rock samples, the EERC worked closely with Hitachi to optimize the FESEM settings necessary to resolve the sample mineralogy, porosity and OM content at micro- to nanoscale resolution. The EERC also worked closely with Hitachi to apply and improve its advanced mineral identification and characterization system (AMICS) software so that it is better suited for mineral identification at the high resolution necessary to resolve features of interest in fine-grained rocks such as organic-rich shales. The EERC also applied advanced image analysis software packages, including Ilastik, to classify and quantify the key components of interest within the samples using FESEM imagery. These advanced techniques allowed for quantification and differentiation of the void space within fractures, pores and OM, as well as a technique to determine and quantify the key mineral and OM components surrounding pore spaces. Being able to better quantify the void space and the potential accessibility of CO2 to sorptive minerals or OM within tight rocks allows for improved estimation of the CO2 storage resource potential of organic-rich shales and other unconventional formations. The information derived from the image analysis techniques was used to refine NETL’s method for estimating regional-scale CO2 storage resources in collaboration with staff from NETL. An additional goal of this work was to better understand rates of CO2 permeation, flow pathways, and sorption in organic-rich shales and nonshale reservoir rocks and to evaluate potential changes in CO2 flow over time. The EERC conducted long-duration (several weeks) CO2 flow-through testing at reservoir conditions using Bakken shale and nonshale samples to assess CO2 permeation rates and retention/sorption within core plugs to represent bulk matrix behavior. Conventional isothermal adsorption testing over a range of pressure conditions was also performed on pulverized Bakken samples to better assess potential maximum sorptive capacity of the samples. The results of this testing illustrated the higher sorptive capacity of the Bakken shales when compared to the sorptive capacity of the nonshale reservoir rock, which contains very little OM when compared to the Bakken shales. The results also illustrate the differences in permeation behavior as a function of fracture flow versus matrix flow. In an attempt to visualize CO2 permeation and flow behavior in Bakken shale samples over time, the EERC collaborated with NETL’s CT Lab in Morgantown, West Virginia. A variety of tests were performed at the NETL lab on unfractured and fractured samples of the Bakken shale. The unfractured Bakken shale samples did not result in CO2 migration within the samples over the testing duration; thus imagery of CO2 migration pathways within the matrix of Bakken samples was not obtained. The results of the flow-through testing within fractured samples illustrate changes in CO2 permeation rates over time, with a trend of decreasing CO2 flow over time. The results of this effort suggest that FESEM analysis coupled with advanced image analysis and machine learning techniques are effective in characterizing and quantifying the mineralogy, porosity, fractures, and OM content of 2-D imagery at the high resolution needed to identify features of interest in tight rocks. In addition, the image analysis techniques allow for identification and quantification of different porosity types as well as the key mineral components and/or OM that CO2 would contact in the reservoir as it migrates through pores and fracture networks. This is key information needed to better estimate the CO2 storage resource potential of organic-rich shales and other tight reservoirs. Additional work is needed to determine the sorptive capacity of the individual sample components (OM and clay minerals) at reservoir conditions so that this approach and the refined CO2 storage resource equation can be applied to other shale and unconventional reservoirs. In addition, subsequent work should be performed to better understand the number of images needed to use stereological approaches to estimate the volume of sample components using 2-D imagery, to explore machine learning techniques to differentiate between induced vs. natural fractures, and to estimate the connectivity of pores and fracture networks using 2-D imagery. Being able to derive this information at the microscale would facilitate scaling up of the sample characterization data used for reservoir modeling and simulation to estimate the CO2 storage resource potential of tight formations.

03 NATURAL GAS↗

Unusual phonon density of states and response to superconducting transition in In-doped topological crystalline insulator Pb 0.5 Sn 0.5 Te

Here, we present inelastic neutron scattering results of phonons in (Pb 0.5 Sn 0.5 ) 1–x In x Te powders, with x = 0, and 0.3.The x = 0 sample is a topological crystalline insulator, and the x = 0 . 3 sample is a superconductor with a bulk superconducting transition temperature T c of 4.7 K. In both samples, we observe unexpected van Hove singularities in the phonon density of states at energies of 1– 2.5 meV, suggestive of local modes. On cooling the superconducting sample through T c , there is an enhancement of these features for energies below twice the superconducting-gap energy. We further note that the superconductivity in (Pb 0.5 Sn 0.5 ) 1–x In x Te occurs in samples with normal-state resistivities of order 10 mΩ cm, indicative of bad-metal behavior. Calculations based on density functional theory suggest that the superconductivity is easily explainable in terms of electron-phonon coupling; however, they completely miss the low-frequency modes and do not explain the large resistivity. While the bulk superconducting state of (Pb 0.5 Sn 0.5 ) 0.7 In 0.3 Te appears to be driven by phonons, a proper understanding will require ideas beyond simple BCS theor

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Growth and characterization of Hg(1-x)Zn(x)Se

Hg sub 1-xZn sub xSe alloys of composition x=0.10 were grown in a Bridgman-Stockbarger growth furnace at translation rates of 0.3 and 0.1 micron sec. The axial and radial composition profiles were determined using precision density measurements and IR transmission-edge-mapping, respectively. A more radially homogeneous alloy was produced at the slower growth rate, while the faster growth rate produced more axially homogeneous alloys. A determination of the electrical properties of the Hg sub 1-xZn sub xSe samples in the temperature range 300K-20K was also made. Typical carrier concentrations were on the order of magnitude of 10 to the 18th power cu/cm, and remained fairly constant as a function of temperature. A study was also made of the temperature dependence of the resistivity and Hall mobility. The effect of annealing in a selenium vapor on both the IR transmission and the electrical properties was determined. Annealing was effective in reducing the number of native donor defects and at the resulting lower carrier concentrations, charge carrier concentration was shown to be a function of temperature. Annealing caused the mobility to increase, primarily at the lower temperature, and the room temperature resistivity to increase. Annealing was also observed to greatly enhance the % IR transmittance of the samples. This was due primarily to the effect of annealing on decreasing the charge carrier concentration.

Andrews, R. N.↗

Mission Design Overview for Mars 2003/2005 Sample Return Mission

In May 2003, a new and exciting chapter in Mars exploration will begin with the launch of the first of three spacecraft that will collectively contribute toward the goal of delivering samples from the Red Planet to Earth. This mission is called Mars Sample Return (MSR) and will utilize both the 2003 and 2005 launch opportunities with an expected sample return in October 2008. NASA and CNES are major partners in this mission. The baseline mission mode selected for MSR is Mars orbit rendezvous (MOR), analogous in concept to the lunar orbit rendezvous (LOR) mode used for Apollo in the 1960s. Specifically, MSR will employ two NASA-provided landers of nearly identical design and one CNES-provided orbiter carrying a NASA payload of rendezvous sensors, orbital capture mechanisms, and an Earth entry vehicle (EEV). The high-level concept is that the landers will launch surface samples into Mars orbit, and the orbiter will retrieve the samples in orbit and then carry them back to Earth. The first element to depart for Mars will be one of the two landers. Currently, it is proposed that an intermediate class launch vehicle, such as the Boeing Delta 3 or Lockheed Martin Atlas 3A, will launch this 1800-kg lander from Cape Canaveral during the May 2003 opportunity. The lander will utilize a Type-1 transfer trajectory with an arrival at Mars in mid-December 2003. Landing will be aided by precision approach navigation and a guided hypersonic entry to achieve a touchdown accuracy of 10 km or better. Although the exact landing site has not yet been determined, it is estimated that lander resource constraints will limit the site to between 15 degrees north and south latitudes. Following touchdown, the lander will deploy a six-wheeled, 60-kg rover carrying an extensive suite of instruments designed to aid in the analysis of the local terrain and collection of core samples from selected rocks. The surface mission is currently designed around a concept called the surface traverse. Each traverse will involve the rover exploring a selected area of terrain up to 100 meters from the lander, the collection of rock core samples, and the delivery of the samples from the traverse back to a sample canister on the lander. Planning estimates indicate that up to three traverses may be possible during the expected 90-sol lifetime of the lander. The canister that will receive the samples from the rover will be attached to the top stage of a small solid-fueled rocket mounted to the deck of the lander. This rocket is called the Mars Ascent Vehicle (MAV) and consists of three stages weighing a total of about 140 kg. After the conclusion of the surface mission, the MAV will lift-off and insert the sample canister into a near-circular orbit with an altitude of about 600 km and inclination of 45 degrees. The sample canister will wait in this orbit until it is retrieved by the orbiter sometime in early 2007. In August 2005, the second lander and a CNES-provided orbiter weighing 2700 kg will depart for Mars. Currently, it is proposed that a single Ariane 5 provided by CNES will launch both of these two elements onto a Type-2 transfer trajectory. Although the orbiter and lander will be launched together, they will separate shortly after injection and will fly to Mars as two independent spacecraft. However, both spacecraft will perform a maneuver between 10 and 15 days after launch so that their arrival times at Mars differ by between 12 and 24 hours. This scheme will reduce the operational complexity at the encounter date. A set of four 60-kg surface probes will ride piggyback on the orbiter to Mars. These CNES-provided probes are called Netlanders and will serve as surface stations for scientific investigations independent of the Mars Sample Return goals. Starting approximately one month prior to arrival at Mars, the orbiter will begin to release the Netlanders one at a time. Each release cycle will take several days, and will include time for precision navigation to execute one or two maneuvers that will target the Netlanders to their proper landing site. All four deployment cycles will be completed prior to 10 days before arrival. Both the orbiter and lander will arrive in late-July 2006. Upon arrival, the lander will perform a precision landing and surface mission similar in concept to the one that was executed during the 2003 opportunity. Although the landing site for the 2005 opportunity has not been selected, it is expected to be different from the 2003 site to enhance the diversity of the collected samples. The orbiter's arrival at Mars will be highlighted by the first use of aerocapture to insert a spacecraft into a capture orbit around another planet. The choice of aerocapture, as opposed to a propulsive orbit insertion, was considered mission enabling due to a reduction of over 2000 m/s in mission AV. Aerocapture will be targeted to produce a 250 km x 1400 km capture orbit with an inclination of 45 degrees. Current analysis indicates that achieving this goal will require approximately six minutes of flight deep in the atmosphere with a targeted periapsis of approach of about 43 km. After factoring into account the penalty for carrying a heat shield to survive aerocapture, the net savings compared to a propulsive orbital insertion amounts to several hundred kilograms.

Lee, Wayne J.↗

Novel EBSD preparation method for Cu/Sn microbumps using a focused ion beam

We proposed a novel technique developed from focused ion beam (FIB) polishing for sample preparation of electron backscatter diffraction (EBSD) measurement. A low-angle incident gallium ion beam with a high acceleration voltage of 30 kV was used to eliminate the surface roughness of cross-sectioned microbumps resulting from mechanical polishing. This work demonstrates the application of the FIB polishing technique to solders for a high-quality sample preparation for EBSD measurement after mechanical polishing. - Highlights: Black-Right-Pointing-Pointer The novel FIB technique of sample preparation is fast, effective and low-cost. Black-Right-Pointing-Pointer It can enhance the process precision to the specific area of the sample. Black-Right-Pointing-Pointer It is convenient for analyzing the metallurgy of the microbump in 3DIC packaging. Black-Right-Pointing-Pointer The EBSD image quality can be enhanced by just using a common FIB instrument.

36 MATERIALS SCIENCE↗

Enhancement of perpendicular magnetic anisotropy and spin-orbit torque in Ta/Pt/Co/Ta multi-layered heterostructures through interfacial diffusion

Heavy metal/ferromagnetic metal bi-layered structures that exhibit both strong perpendicular magnetic anisotropy (PMA) and large spin-orbit torque (SOT) efficiency have high potential in high-density, low-power memory, and logic device applications. Here, we report the enhancement of PMA and SOT in Ta/Pt/Co/Ta multi-layered heterostructures through interfacial diffusion. The structures can exhibit PMA fields of 9100 Oe at 300 K and 14100 Oe at 10 K and an effective spin Hall angle (SHA) of 0.61 ± 0.03 at 300 K. These values are larger than the corresponding values reported previously for similar heterostructures. The current-induced magnetization switching was demonstrated. The critical switching current density is on the order of 10 6 A/cm 2 , and the corresponding switching efficiency is higher than that reported for similar structures. X-ray absorption spectroscopy and high-angle annular dark-field scanning transmission electron microscopy analyses suggest a strong correlation between the observed PMA and SOT enhancement and the interfacial diffusion during the sputtering growth of the samples. It is very likely that the interfacial diffusion gives rise to enhanced spin-orbit coupling at the interface, while the latter results in enhancement in the PMA, SHA, and switching efficiency in the structure.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Carbon-enhanced metal-poor stars: CEMP-s and CEMP-no subclasses in the halo system of the Milky Way

We explore the kinematics and orbital properties of a sample of 323 very metal-poor stars in the halo system of the Milky Way, selected from the high-resolution spectroscopic follow-up studies of Aoki et al. and Yong et al. The combined sample contains a significant fraction of carbon-enhanced metal-poor (CEMP) stars (22% or 29%, depending on whether a strict or relaxed criterion is applied for this definition). Barium abundances (or upper limits) are available for the great majority of the CEMP stars, allowing for their separation into the CEMP-s and CEMP-no subclasses. A new method to assign membership to the inner- and outer-halo populations of the Milky Way is developed, making use of the integrals of motion, and applied to determine the relative fractions of CEMP stars in these two subclasses for each halo component. Although limited by small-number statistics, the data suggest that the inner halo of the Milky Way exhibits a somewhat higher relative number of CEMP-s stars than CEMP-no stars (57% versus 43%), while the outer halo possesses a clearly higher fraction of CEMP-no stars than CEMP-s stars (70% versus 30%). Although larger samples of CEMP stars with known Ba abundances are required, this result suggests that the dominant progenitors of CEMP stars in the two halo components were different; massive stars for the outer halo, and intermediate-mass stars in the case of the inner halo.

79 ASTRONOMY AND ASTROPHYSICS↗

Interacting spin and charge density waves in the kagome metal FeGe

Unveiling the interplay between spin density wave (SDW) and charge density wave (CDW) orders in correlated electron materials is important in obtaining a comprehensive understanding of their electronic, structural, and magnetic properties. Kagome lattice materials are interesting because their flat electronic bands, Dirac points, and Van Hove singularities can enable a variety of exotic electronic and magnetic phenomena. The kagome metal FeGe (the B35 phase), which exhibits a CDW order deep within an A-type antiferromagnetic (AFM) phase, was found to respond dramatically to postgrowth annealing—with the ability to tune the CDW repeatedly from long-range order to negligible order. Additionally, neutron scattering studies suggest that incommensurate magnetic peaks that onset at 𝑇 Canting = 𝑇 SDW ≈ 60 K in the system arise from a SDW order instead of the AFM double-cone structure. Here, in this study, we use inelastic neutron scattering to show that two distinct spin excitations exist below 𝑇 Canting corresponding to two coexisting magnetic orders in the system in both sets of annealed samples with and without CDW. While CDW order or negligible order can dramatically affect the onset temperature of 𝑇 Canting and elastic incommensurate magnetic scattering, its impact on low-energy spin fluctuations is more limited. In both samples, a pair of gapless incommensurate spin excitations arising from the SDW order wave vector coexist with gapped commensurate spin waves from the A-type AFM order across 𝑇 Canting . The low-energy spin excitations for both samples couple dynamically to the lattice through enhanced magnetic scattering intensity on cooling below 𝑇 CDW , regardless of the status of the static long-range CDW order. The incommensurate SDW order in the long-range CDW ordered sample also induces a tiny in-plane lattice distortion of the kagome lattice that is absent in the negligible CDW ordered sample, in a way that is different from the previously known SDW and CDW ordering materials.

charge density waves↗

Electron irradiation effects on the optical properties of Hf- and Zn-doped β -Ga 2 O 3

Optical and electrical properties of Hf- and Zn-doped β-Ga 2 O 3 samples, which are n-type and insulating, respectively, were altered via high-energy electron irradiation at 2.5 or 0.5 MeV. The β-Ga 2 O 3 :Hf samples irradiated with 2.5 MeV electrons experienced a color change from blue to yellow and a large drop in conductivity, attributed to the creation of gallium vacancies, which compensate donors. This irradiation resulted in the absence of free carrier absorption and the presence of Cr 3+ photoluminescence (PL). PL mapping prior to irradiation revealed optically active ZnO precipitates that formed during the growth of β-Ga 2 O 3 :Zn. These precipitates have a 384 nm (3.23 eV) stacking fault emission in the core; in the outer shell of the precipitate, the PL blue-shifts to 377 nm (3.29 eV) and a broad defect band is observed. After 0.5 MeV electron irradiation, the defect band broadened and increased in intensity. The blue PL band (435 nm) of β-Ga 2 O 3 was enhanced for both Hf- and Zn-doped samples irradiated with 0.5 MeV. This enhancement is correlated with an increase in oxygen vacancies.

36 MATERIALS SCIENCE↗

Benchmark Analysis on Magnetic and Photoluminescence Properties of Selective Metal Ions Doped ZnS Nanoparticles

The creation of diluted magnetic semiconductors (DMSs) at lower dimensions that exhibit room temperature ferromagnetism (RTFM) has been given immense significance for the fabrication of a new class of spintronic devices through utilizing spin degrees of freedom besides charge nature of electrons. In this view, nanocrystals of ZnS doped with 4% concentration of Fe, Co, Ni, Cr, Mn, Sr, Cu, and Ce have been synthesized at room temperature (RT) by chemical co-precipitation method. The samples were examined by various characterization techniques like energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), and photoluminescence (PL). EDS spectra revealed the existence of parent elements in the prepared samples. XRD characterization disclosed hexagonal structures of nanocrystals, and no secondary phases were observed in all the samples except for Cu and Ni doped ZnS. FTIR data confirmed the proper substitution of dopants in the host lattice as all the graphs have almost same stretchings. The magnetic nature of each sample was evaluated from M-H graphs of VSM, and it corroborated the transition of magnetic properties due to doping. Pristine ZnS showed diamagnetic nature, while Fe and Sr doped ZnS evinced strong ferromagnetic and anti-ferromagnetic properties, respectively. Photoluminescence studies on Ce, Sr and Mn doped ZnS samples revealed strong emission peaks with enhanced luminescence properties compared to bare ZnS. Cu, Cr and Mn doped ZnS exhibited a red shift in emission wavelengths, whereas Co doped ZnS showed emission peak shifted towards the blue region as compared to the host lattice.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Enhancement of acidic gases in biomass burning impacted air masses over Canada

Biomass-burning impacted air masses sampled over central and eastern Canada during the summer of 1990 as part of ABLE 3B contained enhanced mixing ratios of gaseous HNO3, HCOOH, CH3COOH, and what appears to be (COOH)2. These aircraft-based samples were collected from a variety of fresh burning plumes and more aged haze layers from different source regions. Values of the enhancement factor, delta X/delta CO, where X represents an acidic gas, for combustion-impacted air masses sampled both near and farther away from the fires, were relatively uniform. However, comparison of carboxylic acid emission ratios measured in laboratory fires to field plume enhancement factors indicates significant in-plume production of HCOOH. Biomass-burning appears to be an important source of HNO3, HCOOH, and CH3COOH to the troposphere over subarctic Canada.

Lefer, B. L.↗

Growth and nucleation regimes in boron doped silicon by dynamical x-ray diffraction

The oxygen precipitation of highly (17.5 mΩ cm) and moderately (4.5 Ω cm) boron (B) doped silicon (Si) crystals at 780 °C is investigated by following in-situ the evolution of diffraction Pendellösung oscillations. All samples show an initial diffusion-driven growth process which may change over into Ostwald ripening. For the highly doped sample and involving a nucleation step at 450 °C for 30 h, the precipitate density ρ is enhanced by a factor of 8 as compared to the moderately doped sample. The influence of a high B concentration on ρ is dramatically higher for the samples directly heated to 780 °C, where an enhancement factor of 80 is found. Considering Ostwald ripening as a second growth regime reveals consistent ripening rates and surface energies σ with those found at 900 °C in a previous publication.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

COSMIC EVOLUTION OF STAR FORMATION ENHANCEMENT IN CLOSE MAJOR-MERGER GALAXY PAIRS SINCE z = 1

The infrared (IR) emission of 'M {sub *} galaxies' (10{sup 10.4} {<=} M {sub star} {<=} 10{sup 11.0} M {sub Sun }) in galaxy pairs, derived using data obtained in Herschel (PEP/HerMES) and Spitzer (S-COSMOS) surveys, is compared to that of single-disk galaxies in well-matched control samples to study the cosmic evolution of the star formation enhancement induced by galaxy-galaxy interaction. Both the mean IR spectral energy distribution and mean IR luminosity of star-forming galaxies (SFGs) in SFG+SFG (S+S) pairs in the redshift bin of 0.6 < z < 1 are consistent with no star formation enhancement. SFGs in S+S pairs in a lower redshift bin of 0.2 < z < 0.6 show marginal evidence for a weak star formation enhancement. Together with the significant and strong sSFR enhancement shown by SFGs in a local sample of S+S pairs (obtained using previously published Spitzer observations), our results reveal a trend for the star formation enhancement in S+S pairs to decrease with increasing redshift. Between z = 0 and z = 1, this decline of interaction-induced star formation enhancement occurs in parallel with the dramatic increase (by a factor of {approx}10) of the sSFR of single SFGs, both of which can be explained by the higher gas fraction in higher-z disks. SFGs in mixed pairs (S+E pairs) do not show any significant star formation enhancement at any redshift. The difference between SFGs in S+S pairs and in S+E pairs suggests a modulation of the sSFR by the intergalactic medium (IGM) in the dark matter halos hosting these pairs.

79 ASTRONOMY AND ASTROPHYSICS↗

Early Energetic Particle Irradiation of the HED Parent Body Regolith

Previous studies have shown that many individual grains within the dark phase of the Kapoeta howardite were irradiated with energetic particles while residing on the surface of the early HED regolith. Particle tracks in these grains vary in density by more than an order of magnitude and undoubtedly were formed by energetic heavy (Fe) ions associated with early solar flares. Early Irradiation of HED Regolith: Concentrations of excess Ne alone are not sufficient to decide between competing galactic and solar irradiation models. However, from recent studies of depth samples of oriented lunar rocks, we have shown that the cosmogenic 21-Ne/22-Ne ratio produced in feldspar differs substantially between Galactic Cosmic Radiation (GCR) and solar protons, and that this difference is exactly that predicted from cross-section data. Using Ne literature data and new isotopic data we obtained on acid-etched, separated feldspar from both the light and dark phases of Kapoeta, we derive 21-Ne/22-Ne = 0.80 for the recent GCR irradiation and 21-Ne/22-Ne = 0.68 for the early regolith irradiation. This derived ratio indicates that the early Ne production in the regolith occurred by both galactic and solar protons. If we adopt a likely one-component regolith model in which all grains were exposed to galactic protons but individual grains had variable exposure to solar protons, we estimate that this early GCR irradiation lasted for about 3-6 m.y. More complex two-component regolith models involving separate solar and galactic irradiation would permit this GCR age to be longer. Higher-energy solar protons would permit the GCR to be longer. Higher-energy solar protons would permit the GCR age to be shorter. Further, cosmogenic 126(Xe) in Kapoeta dark is no more than a factor of about 2 higher than that observed in Kapoeta light. Because 126(Xe) can only be formed by galactic protons and not solar protons, these data support a short GCR irradiation for the HED regolith. This would also be the maximum time peRiod for the solar irradiation. Various asteroidal regolith models, based on Monte Carlo modeling of impact rates as a function of size and on irradiation features of meteorites, predict surface exposure times of about 0.1 to 10 m.y., and depend on such factors as gravity, rock mechanical properties, and micrometeoroid flux. Because the depth at which solar Fe tracks are produced (is much less than 1 micrometer) is much less than the depth at which Solar Cosmic Rays (SCR) Ne is produced (about 1 cm), for a reasonably well-stirred HED regolith the "surface exposure time" for SCR 21-Ne production should be significantly longer than that for solar tracks and some other surface irradiation features. Enhanced Solar Proton Irradiation: For bulk samples of Kapoeta dark feldspar and a one-component regolith model, the derived ratio of 21-Ne/22-Ne = 0.68 implies that the early production ratio of SCR 21-Ne to GCR 21-Ne was about 0.5-1.5. This ratio is independent of any assumptions about the fraction of dark grains that are irradiated or of the variability in the degree of solar irradiation among grains. The 21-Ne SCR/GCR ratio indirectly derived from bulk Kapoeta pyroxene is somewhat larger, as is the ratio derived for simple two-component regolith models. Individual feldspar grains that were extensively solar irradiated would require even larger 21-Ne SCR/GCR production ratios. In contrast, the theoretical SCR/GCR production ratio for lunar feldspar with 0 g/CM2 shield ing is is less than or equal to 2, and the lowest ratio observed in near-surface samples of lunar anorthosites is less than or equal to 1. Considering the greater solar distance of Vesta (compared to the Moon), the likelihood that SCR 21-Ne was acquired under some shielding where production rates are lower, and the likelihood that the exposure time to galactic protons exceeded the exposure time to solar protons because of their very different penetration depths, the 21-Ne SCR/GCR production ratio on the HED parent body was probably < 0.1. The relatively large difference between the derived 21-Ne SCR/GCR ratio in Kapoeta dark feldspar and the estimated production ratio strongly indicates that the early solar irradiation involved a flux -20-50x the recent solar flux. This enhanced proton flux was probably associated with an overall greater solar activity in the first approximately 10(exp 7) to 10(exp 8) years of solar history.

Bogard, D. D.↗

DeMAID/GA an Enhanced Design Manager's Aid for Intelligent Decomposition

Many companies are looking for new tools and techniques to aid a design manager in making decisions that can reduce the time and cost of a design cycle. One tool is the Design Manager's Aid for Intelligent Decomposition (DeMAID). Since the initial public release of DeMAID in 1989, much research has been done in the areas of decomposition, concurrent engineering, parallel processing, and process management; many new tools and techniques have emerged. Based on these recent research and development efforts, numerous enhancements have been added to DeMAID to further aid the design manager in saving both cost and time in a design cycle. The key enhancement, a genetic algorithm (GA), will be available in the next public release called DeMAID/GA. The GA sequences the design processes to minimize the cost and time in converging a solution. The major enhancements in the upgrade of DeMAID to DeMAID/GA are discussed in this paper. A sample conceptual design project is used to show how these enhancements can be applied to improve the design cycle.

Rogers, J. L.↗