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At least 1,189 records · Page 66

Getting to the root of the problem: Soil carbon and microbial responses to root inputs within a buried paleosol along an eroding hillslope in southwestern Nebraska, USA

Large quantities of soil carbon (C) can persist within paleosols for millennia due to burial and subsequent isolation from plant-derived inputs, atmospheric conditions, and microbial activity at the modern surface. Erosion exposes buried soils to modern root-derived C influx via root exudation and root turnover, thus stimulating microbial activity leading to SOC decomposition and accumulation through organo-mineral stabilization of modern C. With this study we aim to quantify how modern root-derived C inputs impact paleosol C decomposition and stabilization across varying degrees of isolation from modern surface conditions in southwestern Nebraska, USA, where hillslope erosion is bringing a buried Late-Pleistocene-early Holocene paleosol (the “Brady Soil”) closer to the modern surface. We collected Brady Soil samples from 0.2m, 0.4m, and 1.2m below the modern surface and conducted two lab-based incubations. Soils were amended with either (1) a lab-synthesized mixture of low molecular weight compounds (12 atom% 13 C), or (2) 13 C enriched root residues (92 atom% 13 C), in 30-day and 240-day incubation experiments, respectively. Here we determined microbial responses to synthetic root exudates and residues by partitioning the 13 C label from Brady Soil C, including measurements of total, root, and primed C respiration, microbial biomass C (MBC), microbial C use efficiency (CUE). To assess the capacity of isolated paleosols to accrue modern plant C, we used Nano-scale Secondary Ion Mass Spectrometry imaging. We found that: (1) adding root-derived C inputs primed Brady Soil C across all depths, and was mediated by depth and composition of root additions; (2) root-derived C inputs stimulated microbial biomass C (MBC) growth similarly across depths, but the magnitude of CUE and MBC varied by chemistry of root-derived additions; (3) new particulate organic matter was incorporated into mineral-associated pools over time; (4) material from the added root residues was found in association with bacterial cells and fungal hyphae as well as with soil aggregate and mineral surfaces. Our study shows that paleosols defy expectations of C content and reactivity with depth, and changes in land cover and climate will expose buried paleosols to modern surface conditions, increasing respired C. This work highlights the importance of evaluating the role resurfacing buried soils through landscape change plays in C cycle feedbacks to the climate system.

54 ENVIRONMENTAL SCIENCES↗

Pyrolysis of polyolefins for increasing the yield of monomers' recovery

Highlights: Black-Right-Pointing-Pointer Thermal and catalytic pyrolysis of mixed polyolefins in fluidized bed has been studied. Black-Right-Pointing-Pointer We tested applicability of a commercial Ziegler-Natta catalyst (Z-N: TiCl{sub 4}/MgCl{sub 2}). Black-Right-Pointing-Pointer The catalyst has a strong influence on product distribution, increasing gas fraction. Black-Right-Pointing-Pointer At 650 Degree-Sign C the monomer generation increased by 55% when the catalyst was used. Black-Right-Pointing-Pointer We showed the concept of treatment of mixed polyolefins without a need of separation. - Abstract: Pyrolysis of plastic waste is an alternative way of plastic recovery and could be a potential solution for the increasing stream of solid waste. The objective of this work was to increase the yield the gaseous olefins (monomers) as feedstock for polymerization process and to test the applicability of a commercial Ziegler-Natta (Z-N): TiCl{sub 4}/MgCl{sub 2} for cracking a mixture of polyolefins consisted of 46% wt. of low density polyethylene (LDPE), 30% wt. of high density polyethylene (HDPE) and 24% wt. of polypropylene (PP). Two sets of experiments have been carried out at 500 and 650 Degree-Sign C via catalytic pyrolysis (1% of Z-N catalyst) and at 650 and 730 Degree-Sign C via only-thermal pyrolysis. These experiments have been conducted in a lab-scale, fluidized quartz-bed reactor of a capacity of 1-3 kg/h at Hamburg University. The results revealed a strong influence of temperature and presence of catalyst on the product distribution. The ratios of gas/liquid/solid mass fractions via thermal pyrolysis were: 36.9/48.4/15.7% wt. and 42.4/44.7/13.9% wt. at 650 and 730 Degree-Sign C while via catalytic pyrolysis were: 6.5/89.0/4.5% wt. and 54.3/41.9/3.8% wt. at 500 and 650 Degree-Sign C, respectively. At 650 Degree-Sign C the monomer generation increased by 55% up to 23.6% wt. of total pyrolysis products distribution while the catalyst was added. Obtained yields of olefins were compared with the naphtha steam cracking process and other potentially attractive processes for feedstock generation. The concept of closed cycle material flow for polyolefins has been discussed, showing the potential benefits of feedstock recycling in a plastic waste management.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Experimental and Computational Interrogation of Fast SCR Mechanism and Active Sites on H-Form SSZ-13

Experiment and density functional theory (DFT) models are combined to develop a unified, quantitative model of the mechanism and kinetics of fast selective catalytic reduction (SCR) of NO/NO2 mixtures over H-SSZ-13 zeolite. Rates, rate orders, and apparent activation energies collected under differential conditions reveal two distinct kinetic regimes. First-principles thermodynamics simulations are used to determine the relative coverages of free Brønsted sites, chemisorbed NH4+ and physisorbed NH3 as a function of reaction conditions. First-principles metadynamics calculations show that all three sites can contribute to the rate-limiting N-N bond forming step in fast SCR. The results are used to parameterize a kinetic model that encompasses the full range of reaction conditions and recovers observed rate orders and apparent activation energies. Observed kinetic regimes are related to changes in most-abundant surface intermediates. Financial support was provided by the National Science Foundation GAOLI program under award number 1258690-CBET. We thank the Center for Research Computing at Notre

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microwave-based laboratory experiments for internally-heated mantle convection

The thermal evolution of terrestrial planets is mainly controlled by the amount of radioactive heat sources in their mantle, and by the geometry and efficiency of solid state thermo-chemical convection within. So far, these systems have been studied using numerical methods only and cross validation by laboratory analogous experiments has not been conducted yet. To fill this gap we perform the first laboratory experiments of mantle convection driven by microwave-generated internal heating. We use a 30×30×5 cm{sup 3} experimental tank filled with 0.5 % Natrosol in water mixture (viscosity 0.6 Pa.s at 20°C). The fluid is heated from within by a microwave device that delivers a uniform volumetric heating from 10 to 70 kW/m{sup 3}; the upper boundary of the fluid is kept at constant temperature, whereas the lower boundary is adiabatic. The velocity field is determined with particle image velocimetry and the temperature field is measured using thermochromic liquid crystals which enable us to charaterize the geometry of the convective regime as well as its bulk thermal evolution. Numerical simulations, conducted using Stag-3D in 3D cartesian geometry, reproduce the experimental setup (i.e., boundary conditions, box aspect ratio, temperature dependence of physical parameters, internal heating rate). The successful comparison between the experimental and numerical results validates our approach of modelling internal heating using microwaves.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of silver nanoparticles by chemical reduction at various fraction of MSA and their structure characterization

Nanosilver is currently one of the most common engineered nanomaterials and is used in many applications that lead to the release of silver nanoparticles and silver ions into aqueous systems. Nanosilver also possesses enhanced antimicrobial activity and bioavailability that may less environmental risk compared with other manufactured nanomaterials. Described in this research are the synthesis of silver nanoparticle produced by chemical reduction from silver nitrate (AgNO{sub 3}) solution. As a reducing agent, Sodium Borohydride (NaBH{sub 4}) was used and mercaptosuccinic Acid (MSA) as stabilizer to prevent the nanoparticle from aglomerating. It was also used two kinds of solvent, they are water and methanol. In typical experiment MSA was dissolve in methanol with a number of variation of molarity i.e. 0,03 M, 0,06 M, 0,12 M, 0,15 M, and the mixture was kept under vigorous stirring in an ice bath. A solution of silver nitrate of 340 mg in 6,792 ml water was added. A freshly prepared aqueous solution of sodium borohydride (756,6 mL in 100 mL of water) was added drop wisely. The solution was kept for half an hour for stirring and were allowed to settle down in methanol. The obtained samples then characterized by means of x-ray diffractometer, and scanning electron microscopy, as well as transmission electron microscopy to obtain their structures of silver nanoparticles, morphology, and sizes. It is shown that diameter of silver nanoparticle sized about 24.3 nm (Ag@MSA 0.03 M), 20.4 nm (Ag@MSA 0.06 M), 16.8 nm (Ag@MSA 0.12 M), 16.9 nm (Ag@MSA 0.15 M) which was calculated by Scherrer formula by taking the FWHM from fitting to Gaussian. The phases and lattice parameter showed that there is no significant change in its volume by increasing molarity of stabilizer. In contrast, the size of particles is decreasing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

THE EFFECT OF BROADBAND SOFT X-RAYS IN SO{sub 2}-CONTAINING ICES: IMPLICATIONS ON THE PHOTOCHEMISTRY OF ICES TOWARD YOUNG STELLAR OBJECTS

We investigate the effects produced mainly by broadband soft X-rays up to 2 keV (plus fast (∼keV) photoelectrons and low-energy (∼eV) induced secondary electrons) in the ice mixtures containing H{sub 2}O:CO{sub 2}:NH{sub 3}:SO{sub 2} (10:1:1:1) at two different temperatures (50 and 90 K). The experiments are an attempt to simulate the photochemical processes induced by energetic photons in SO{sub 2}-containing ices present in cold environments in the ices surrounding young stellar objects (YSO) and in molecular clouds in the vicinity of star-forming regions, which are largely illuminated by soft X-rays. The measurements were performed using a high-vacuum portable chamber from the Laboratório de Astroquímica e Astrobiologia (LASA/UNIVAP) coupled to the spherical grating monochromator beamline at the Brazilian Synchrotron Light Source (LNLS) in Campinas, Brazil. In situ analyses were performed by a Fourier transform infrared spectrometer. Sample processing revealed the formation of several organic molecules, including nitriles, acids, and other compounds such as H{sub 2}O{sub 2}, H{sub 3}O{sup +}, SO{sub 3}, CO, and OCN{sup −}. The dissociation cross section of parental species was on the order of (2–7) × 10{sup −18} cm{sup 2}. The ice temperature does not seem to affect the stability of SO{sub 2} in the presence of X-rays. Formation cross sections of new species produced were also determined. Molecular half-lives at ices toward YSOs due to the presence of incoming soft X-rays were estimated. The low values obtained employing two different models of the radiation field of YSOs (TW Hydra and typical T-Tauri star) reinforce that soft X-rays are indeed a very efficient source of molecular dissociation in such environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High resolution spectroscopic study of Be Λ 10

Spectroscopy of a $^{10}_{\Lambda}$Be hypernucleus was carried out at JLab Hall C using the $(e,e^{\prime}K^{+})$ reaction. A new magnetic spectrometer system (SPL+HES+HKS), specifically designed for high resolution hypernuclear spectroscopy, was used to obtain an energy spectrum with a resolution of 0.78 MeV (FWHM). The well-calibrated spectrometer system of the present experiment using the $p(e,e^{\prime}K^{+})\Lambda,\Sigma^{0}$ reactions allowed us to determine the energy levels, and the binding energy of the ground state peak (mixture of 1$^{-}$ and 2$^{-}$ states) was obtained to be B$_{\Lambda}$=8.55$\pm$0.07(stat.)$\pm$0.11(sys.) MeV. Furthermore, the result indicates that the ground state energy is shallower than that of an emulsion study by about 0.5 MeV which provides valuable experimental information on charge symmetry breaking effect in the $\Lambda N$ interaction.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

IC W13_fephases Highlight:Solid-Solid Phase Boundary in Fe

Temperature of the fcc-bcc (face-centered cubic – body-centered cubic) solid-solid phase transition in Fe calculated as Teq = Tinst ΔEfcc-bcc/ΔEbcc-m. (where m. stands for martensitic mixture that bcc-Fe converts into at Tinst) maps out a curve which is consistent with the line of the fast recrystallization threshold observed in the recent experiments on Fe at ESRF.

36 MATERIALS SCIENCE↗

Astrophysical Dynamics in the Laboratory: Mach Stems and Magnetized Shock Waves. Final Report DE-N0002037 R18200

The work for this grant focused around two major themes: (1) study of the phenomena that occur when two strong shock waves intersect, and (2) understanding the effects that magnetic fields have on gas in the postshock region, especially when the gas exhibits strong cooling. Both of these themes had a laboratory, numerical, and astronomical observational component. The emphasis on new astrophysical observations to accompany the experimental work has been a signature of our previous programs, and this interdisciplinary approach continued to yield a host of new discoveries and insights as evidenced by the large number of refereed papers in major journals. This document summarizes briefly how the published work fits in with the two major themes. The eclectic mixture of observational, experimental, and numerical present in our efforts is self-evident from the titles of the papers in most cases. Connecting the observations to the experiments in a meaningful way has long been a major challenge in this field, and we are one of very few groups to do this successfully.

79 ASTRONOMY AND ASTROPHYSICS↗

Estimating normal mixture parameters from the distribution of a reduced feature vector

A FORTRAN computer program was written and tested. The measurements consisted of 1000 randomly chosen vectors representing 1, 2, 3, 7, and 10 subclasses in equal portions. In the first experiment, the vectors are computed from the input means and covariances. In the second experiment, the vectors are 16 channel measurements. The starting covariances were constructed as if there were no correlation between separate passes. The biases obtained from each run are listed.

Guseman, L. F.↗

Rate constant for the OH + CO reaction - Pressure dependence and the effect of oxygen

The effect of pressure on the rate constant of the OH + CO reaction has been measured for Ar, N2, and SF6 over the pressure range 200-730 torr. All experiments were at room temperature. The method involved laser-induced fluorescence to measure steady-state OH concentrations in the 184.9 nm photolysis of H2O-CO mixtures in the three carrier gases, combined with supplementary measurements of the CO depletion in these same carrier gases in the presence and absence of competing reference reactants. The effect of O2 on the pressure effect was determined. A pressure enhancement of the rate constant was observed for N2 and SF6, but not for Ar, within an experimental error of about 10 percent. The pressure effect for N2 was somewhat lower than previous literature reports, being about 40 percent at 730 torr. For SF6 a factor of two enhancement was seen at 730 torr. In each case it was found that O2 had no effect on the pressure enhancement. The roles of the radical species HCO and HOCO were evaluated.

Demore, W. B.↗

Mars, clays and the origins of life

To detect life in the Martian soil, tests were designed to look for respiration and photosynthesis. Both tests (labeled release, LR, and pyrolytic release, PR) for life in the Martian soils were positive. However, when the measurement for organic molecules in the soil of Mars was made, none were found. The interpretation given is that the inorganic constituents of the soil of Mars were responsible for these observations. The inorganic analysis of the soil was best fitted by a mixture of minerals: 60 to 80 percent clay, iron oxide, quartz, and soluble salts such as halite (NaCl). The minerals most successful in simulating the PR and LR experiments are iron-rich clays. There is a theory that considers clays as the first organisms capable of replication, mutation, and catalysis, and hence of evolving. Clays are formed when liquid water causes the weathering of rocks. The distribution of ions such as aluminum, magnesium, and iron play the role of bases in the DNA. The information was stored in the distribution of ions in the octahedral and tetrahedral molecules, but that they could, like RNA and DNA, replicate. When the clays replicated, each sheet of clay would be a template for a new sheet. The ion substitutions in one clay sheet would give rise to a complementary or similar pattern on the clay synthesized on its surface. It was theorized that it was on the surface of replicating iron-rich clays that carbon dioxide would be fixed in the light into organic acids such as formic or oxalic acid. If Mars had liquid water during a warm period in its past, clay formation would have been abundant. These clays would have replicated and evolved until the liquid water was removed due to cooling of Mars. It is entirely possible that the Viking mission detected life on Mars, but it was clay life that awaits the return of water to continue its evolution into life based on organic molecules.

Hartman, Hyman↗

Mars brine formation experiment

The presence of water-soluble cations and anions in the Martian regolith has been the subject of speculation for some time. Viking lander data provided evidence for salt-cemented crusts on the Martian surface. If the crusts observed at the two Viking landing sites are, in fact, cemented by salts, and these crusts are globally widespread, as IRTM-derived thermal inertia studies of the Martian surface seem to suggest, then evaporite deposits, probably at least in part derived from brines, are a major component of the Martian regolith. The composition of liquid brines in the subsurface, which not only may be major agents of physical weathering but may also presently constitute a major deep subsurface liquid reservoir, is currently unconstrained by experimental work. A knowledge of the chemical identity and rate of production of Martian brines is a critical first-order step toward understanding the nature of both these fluids and their precipitated evaporites. Laboratory experiments are being conducted to determine the identity and production rate of water-soluble ions that form in initially pure liquid water in contact with Mars-mixture gases and unaltered Mars-analog minerals.

Moore, Jeffrey M.↗

Template properties of oligocytidylates formed in the montmorillonite catalyzed condensation of ImpC

In an attempt to investigate the prebiotic formation of phosphodiester bond in RNA, we have studied the self condensation of 5'-phosphorimidazolide of adenosine (ImpA), in aqueous solutions containing 0.2 M sodium chloride and 0.075 M magnesium chloride at pH 8 using clay minerals as catalyst. In the presence of certain montmorillonites, oligomers containing up to ten monomer units in their chain were formed, while in control experiments, where no catalyst was added, the major product was 5',5'-diadenosine diphosphate, A(sup 5')ppA. In reactions carried out with ImpA: A(sup 5')ppA mixtures at 9:1 mole ratio, oligomers of the type A(sup 5')p(pA)(sub n) and (A(sup 5')p)(sub n)A(sup 5')ppA(pA)(sub n) formed at the expense of (pA)(sub n) type oligomers. Addition of A(sup 5')ppA to the reaction mixture increased the regiospecifity of 3',5'-link formation from 67% to 79%. The condensation of the 5'-phosphorimidazolide of cytidine, ImpC, was also carried out in the presence and absence of A(sup 5')ppA under the same conditions and oligomers containing up to twelve monomer units were obtained.

Ferris, James P.↗

Evaporation Rates of Brine on Mars

While Mars is now largely a dry and barren place, recent data have indicated that water has flowed at specific locations within the last approx. 10(exp 6) y. This had led to a resurgence of interest in theoretical and experimental work aimed at understanding the behavior of water on Mars. There are several means whereby the stability of liquid water on Mars could be increased, one being the presence solutes that would depress the freezing point. Salt water on Earth is about 0.5M NaCl, but laboratory experiments suggest that martian salt water is quite different. We recently began a program of laboratory measurements of the stability of liquid water, ice and ice-dust mixtures under martian conditions and here report measurements of the evaporation rate of 0.25M brine.

Sears, D. W. G.↗

A PdMn Based High Resolution Thermometer for the Temperature Range of 0.7-1 K

Experiments Along the Coexistence near Tricriticality (EXACT) will test exact predictions made by Renormalization Group theory by mapping the phase diagram of liquid He-3 and He-4 mixtures at the tricritical point, Tcp=0.867 K. A PdMn based High Resolution Thermometer (HRT) will be utilized by EXACT to make accurate measurements with a resolution that has never been attained for the temperature range 0.7-1 K. The basic design of this mini high resolution thermometer comprises a sensing element whose magnetic susceptibility changes with temperature, a thermal connector, magnetic shielding, and some permanent magnets to apply a constant magnetic field. In this study, we will quantitatively determine the resolution of possible sensing element candidates of 0.15%, 0.20%, and 0.25% ppm Mn and compare them with an annealed group of PdMn with the corresponding concentrations to see how this processing technique affects sensitivity.

Koo, Peter K.↗

Miniature GC: Minicell ion mobility spectrometer (IMS) for astrobiology planetary missions

Astrobiology flight experiments require highly sensitive instrumentation for in situ analysis of volatile chemical species and minerals present in the atmospheres and surfaces of planets, moons, and asteroids. The complex mixtures encountered place a heavy burden on the analytical instrumentation to detect and identify all species present. The use of land rovers and balloon aero-rovers place additional emphasis on miniaturization of the analytical instrumentation. In addition, smaller instruments, using tiny amounts of consumables, allow the use of more instrumentation and/or longer mission life for stationary landers/laboratories. We describe here the development of a miniature GC - Minicell Ion Mobility Spectrometer (IMS) under development through NASA's Astrobiology Science and Technology Instrument Development (ASTID) Program and NASA's Small Business Innovative Research (SBIR) Program.

Kojiro, Daniel R.↗

APH Experiments: Germination and Seedling Establishment Methods

Plant experiments during ground studies were conducted in the Advanced Plant Habitat (APH) Science Carrier (SC) for ensuring high germination rates and vigorous seedling establishment. The methods constitute a mixture of environmental and planting factors that control moisture and humidity during early seedling establishment. The APH uses granular media that is fertilized with slow release fertilizer pellets. Seeds were sanitized and their germination was tested prior to use in the SC. Seeds were glued in place with guar gum in different wicking materials. It was found that seedlings establishment was reduced if the chamber was too dry or if salt buildup near the seeds was permitted. Thus, germination was carried in media that was flooded and drained, in a chamber held at 80% relative humidity at a low wind speed of 0.3 m/s. After a week the humidity was lowered to 60% RH and wind speed was increased to 0.6 m/s. The germination of different plant species were found to respond differently to germination wicks or to gauze, as well as fertilization rates. Several methods for growing Arabidopsis, wheat, radish and peppers in the APH SC will be presented

O Monje↗