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At least 811 records · Page 45

Effect of adsorbed chlorine and oxygen on the shear strength of iron and copper junctions

Static-friction experiments were performed in ultrahigh vacuum at room temperature on copper, iron, and steel contacts selectively contaminated with oxygen and chlorine in submonolayer amounts. The concentration of the adsorbates was determined with Auger electron spectroscopy and was measured relative to the saturation concentration of oxygen on iron (concentration, 1.0). The coefficient of static friction decreased with increasing adsorbate concentration; however, it was independent of the type of metal and the adsorbate species. The results compared satisfactorily with an extension of the junction growth theory to heterogeneous interfaces. The reduction in interfacial shear strength was measured by the ratio of the shear strength of the interface with an adsorbate concentration of 1.0 and the strength of the clean metal interface. This ratio was about 0.835 for all the systems tested.

Wheeler, D. R.↗

The concentration and isotopic composition of carbon in basaltic glasses from the Juan de Fuca Ridge, Pacific Ocean

The abundance and C-13/C-12 ratios of carbon were analyzed in basaltic glass from twenty locations along the Juan de Fuca Ridge using a 3-step combustion/extraction technique. Carbon released during the first two combustion steps at 400-500 C and 600-650 C is interpreted to be secondary, and only the carbon recovered during a final combustion step at about 1200 C is thought to be indigenous to the samples. For carbon released at about 1200 C, glasses analyzed as 1-2 mm chips contained 23-146 ppm C with delta C-13 values of -4.8 to -9.3 per mil, whereas samples crushed to 38-63 microns or 63-90 microns yielded 56-103 ppm C with delta C-13 values of -6.1 to -9.2 per mil. The concentrations and isotopic compositions of the primary carbon dissolved in the glasses and present in the vesicles are similar to those previously reported for other ocean-ridge basalts. The Juan de Fuca basaltic magmas were not in equilibrium with respect to carbon when they erupted and quenched on the sea floor. Evidence of disequilibrium includes (1) a large range of carbon contents among glasses collected at similar depths, (2) a highly variable calculated carbon isotopic fractionation between melt and vapor determined by comparing crushed and uncrushed splits of the same sample, and (3) a lack of correlation between vesicle abundance, carbon concentration, and depth of eruption. Variations in carbon concentration and delta C-13 ratios along the ridge do not correlate with major element chemistry. The observed relationship between carbon concentrations and delta C-13 values may be explained by late-stage, variable degrees of open-system (Rayleigh-like) degassing.

Blank, Jennifer G.↗

Observed particle evolution in the polar stratospheric cloud of January 24, 1989

Particle-size distributions measured from the NASA ER-2 with the new Forward Scattering Spectrometer Probe 300 in a type I polar stratospheric cloud (PSC) on January 24, 1989 show a volume mode near 0.8 micron in diameter. The large increase in particle concentration and volume after cloud entry did not occur until the apparent saturation ratio of nitric acid with respect to nitric acid trihydrate reached 10, but at ratios near 1 subtle changes in the size distribution suggest some type I particles were present. Particle concentrations in cloud of 15-17/cu cm were greater than the CN concentrations of 5-7/cu cm just outside of cloud, suggesting nucleation on more than just sulfate particles. Some particles greater than 4 microns in diameter were observed in a region which was saturated with respect to ice.

Dye, J. E.↗

Calculated mineral precipitation upon evaporation of a model Martian groundwater near 0 C

Previously, the effect of weathering a basalt of Shergotty meteorite composition with pure water buffered at martian atmospheric values of CO2 and O2, to place constraints upon the composition of martian groundwater, and to determine possible equilibrium mineral assemblages was calculated. A revised calculation of the composition of the aqueous phase in the weathering reaction as a function of the amount of basalt titrated into the solution is shown. The concentrations of sulfate and chloride ions increase in the solution from high water/rock ratios (w/r) on the left to low water/rock ratios on the right, until at w/r = 1, where 1 kg of basalt has been titrated, sulfate concentration is 1564 ppm and chloride is 104 ppm. This resulting fluid is dominated by sulfate and sodium, with bicarbonate and chloride at about the same concentration. This solution was evaporated in an attempt to determine if the resulting evaporite can explain the Viking XRF data. The program CHILLER was used to evaporate this solution at 0.1 C.

Debraal, J. D.↗

Concentration-Discharge Relationships in the Six Largest Arctic Rivers, 2003-2019

This dataset provides the results of the analysis of the relationship of dissolved analyte concentrations and river discharges in the six largest Arctic rivers across the global panarctic region (see Figure 1 in documentation file *.pdf). Long-term measurements of dissolved analyte concentrations and river discharge have been collected for each of the Kolyma, Lena, Mackenzie, Ob, Yenisey, and Yukon rivers by the Arctic Great Rivers Observatory (ArcticGRO) project from ~2003-present (Shiklomanov, 2021). The relationship of dissolved analyte concentrations and discharges in each river was characterized by statistical analysis of the slope of the log(concentration) vs log(discharge) (b), the coefficient of variation ratio (CVc/CVq), the 2.5% and 97.5% confidence intervals of b, and assigning a chemostatic, flushing, diluting, or non-systematic behavior category according to Koger (2018). The summary of these analyses for all six rivers is provided in one .csv file. The concentrations of 20 dissolved analytes and discharge measurement data for the individual Kolyma, Lena, Mackenzie, Ob, Yenisey, and Yukon rivers are also provided with this dataset. There are seven *.csv files; one for each river plus the statistical summary. These public ArcticGRO data at "https://www.arcticgreatrivers.org" (Shiklomanov, 2021) were downloaded on Feb 13, 2020, but each river has different measurement dates over the sampling and analysis period. The ArcticGRO metadata document (*.pdf) downloaded on Feb 13, 2020 is also included in this dataset. The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗

Stannous chloride as a tool for mercury stripping in contaminated streams: Experimental assessment of toxicity in an invertebrate model species

In this work, the chronic toxicity of an innovative Hg water treatment system using tin (Sn) (II) chloride (SnCl 2 ) followed by air stripping was assessed through measurements of survival, growth, and reproduction rate in the freshwater cladoceran Ceriodaphnia dubia, a model species for toxicity testing. We first calculated the concentrations of Hg causing 25% reduction in survival and reproduction (Lethal or Inhibition Concentrations, or LC 25 and IC 25 , for survival and reproduction, respectively) through exposure to aqueous Hg at concentrations ranging from 0 to 25,000 ng L -1 . Then, we treated media (DMW and natural stream water) contaminated with Hg at LC 25 and IC 25 concentrations with SnCl 2 at a Sn:Hg stoichiometric ratio of 8:1 and air stripping and exposed C. dubia to this Sn-amended media. Our results showed that Hg significantly affected survival, reproduction rates and impaired growth. SnCl 2 -treatment removed 100% of the Hg from the media at all concentrations tested with no deleterious effects on survival, growth and reproduction. Our results confirmed the efficacy of SnCl 2 in removing aqueous Hg from stream water and showed that the added Sn did not impact C. dubia at the concentrations tested, supporting the suitability of SnCl 2 -based treatments in appropriate Hg-contaminated environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stress-concentration factors for finite orthotropic laminates with a circular hole and uniaxial loading

Stresses were calculated for finite-width orthotropic laminates with a circular hole and remote uniaxial loading using a two-dimensional finite element analysis with both uniform stress and uniform displacement boundary conditions. Five different laminates were analyzed. Computed results are presented for selected combinations of hole diameter/sheet-width ratio d/w and length-to-width ratio L/w. For small L/w values, the stress-concentration factors K sub tn were significantly different for the uniform stress and uniform displacement boundary conditions. Typically, for the uniform stress condition, the K sub tn values were much larger than for the infinite strip reference condition; however, for the uniform displacement condition, they were only slightly smaller than for this reference. The results for long strips are also presented as width correction factors. For d/w less or = 0.33, these width correction factors are nearly equal for all five laminates.

Hong, C. S.↗

Raman lidar measurements of Pinatubo aerosols over southeastern Kansas during November-December 1991

Raman lidar measurements over southeastern Kansas of stratospheric aerosols produced by the June 1991 eruptions of Mt. Pinatubo were made on 10 nights during November and December 1991. Both aerosol backscattering and extinction profiles were derived simultaneously from the lidar data since this system detects Raman scattering from nitrogen and oxygen as well as the backscattered light from aerosols and molecules. Aerosols scattering ratios greater than 3(at 351 nm) were measured on several nights. Peak aerosol concentrations were located between 19-22 km and varied significantly from night to night. Aerosol extinction/backscatter ratios computed from the lidar data and averaged over the altitude region of enhanced aerosol scattering between 15-25 km varied between 18-28 sr. Mie computations show these values to be consistent with scattering by aerosol particles with mode radii between 0.3 to 0.5 micron and that the ratios would increase to 40-65 sr at 694 nm. Aerosol optical thicknesses derived from the lidar extinction measurements at 351 nm varied between 0.04 and 0.06.

Ferrare, R. A.↗

Products of the Strecker Synthesis as Indicators of Parent Body Conditions of the Murchison Meteorite

The Strecker synthesis, R2C=O + HCN + NH3 yields R2C(NH2)CN + H2O yields R2C(NH2)CO2H has been proposed as a source of amino acids in meteorites. The detection of carbonlyl compounds, the precursors of the amino acids in the Strecker synthesis, and a-hydroxy acids, important by-products of the Strecker synthesis, in the Murchison meteorite supports this conjecture. However, the following observations raise questions about the Strecker synthesis as the source of a-amino and a-hydroxy acids in Murchison: a) Imino acetic acids are also important by-products of the Strecker synthesis and have not been reported in Murchison. b) a-aminisobutyric acid (AIBA) is one of the most abundant amino acids in Murchison but the Strecker synthesis conducted at room temperature produced only small amounts of AIBA relative to other amino acids. c) If the a-amino and a-hydroxy acids observed in Murchison arose from a common precursor this ought to be reflected in their relative abundances, but the straight chain a-hydroxy acids appeared to be relatively abundant compared with the analogous a-amino acids. In order to address question a) we have examined a non-hydrolyzed aqueous extract of the Murchison meteorite. Imino di acetic acid, Imino propionic acetic acid and Imino butyric acetic acid (both isomers) have been identified in this fraction. The relative abundances of amino acids and imino acetic acids in this fraction are consistent with a Strecker synthesis at low temperature (263 K) as a origin of both the amino acids and the imino acetic acids found on Murchison. To deal with questions b) and c) we have carried out laboratory simulations of the Strecker synthesis. The starting concentrations for carbonlyl compounds used were based on estimates of what these concentrations might have been on the parent body. for the carbonyl compounds this estimate was determined by the amount of carbonyl compound found on Murchison plus the amounts of the corresponding amino acid and hydroxy acid found on Murchison and the rock to water ratio estimated by Clayton and Mayeda (1984). The cyanide concentration was that estimated by Peltzer et al. (1984). The ammonia concentration and pH were varied. We studied these mixtures at 298 K and 263 K. We found that high relative abundances of AIBA were produced at 263 K but not at 298 K. We only produced a-methyl a-amino hydroxy acids at 263 K with no initial ammonia. The abundances of a-amino acids, a-hydroxy acids and imino acids found on Murchison are consistent with a Strecker synthesis which took place at low temperature and with a low concentration of ammonia.

Lerner, Narcinda R.↗

Removal of As(V) from wastewaters using magnetic iron oxides formed by zero-valent iron electrocoagulation

Electrocoagulation of zero-valent iron has been widely applied to the removal of dissolved arsenic, but the solid-liquid separation of arsenic-containing precipitates remains technically challenging. In this work, zero-valent iron was electrochemically oxidized to magnetic iron oxides for the removal of As(V) from simulated and actual mining wastewaters. The results indicated that lepidocrocite was formed when zero-valent iron was oxidized by dissolved oxygen, but ferrihydrite and green rust were first formed and then transformed to magnetic iron oxides (mainly magnetite and maghemite) in the electrochemical oxidation from 0 to 0.9 V (vs. SCE), which facilitates the adsorption of As(V) and subsequent solid-liquid separation under a magnetic field. In simulated As(V)-containing solution with initial pH 7.0, zero-valent iron was electrochemically oxidized to magnetite and maghemite at 0.6 V (vs. SCE) for 2 h. The As(V) concentration first decreased from 5127.5 to 26.8 μg L -1 with a removal ratio of 99.5%. In actual mining wastewaters, zero-valent iron was electrochemically oxidized to maghemite at 0.6 V (vs. SCE) for 24 h, and the As(V) concentration decreased from 5486.4 to 3.6 μg L -1 with a removal ratio of 99.9%. The removal ratio of As(V) increased slightly with increasing potential, and increased first and then decreased with increasing initial pH. Compared with that of SO 4 2- and NO 3 - , the presence of Cl - significantly enhanced the removal of As(V). This work provides a highly efficient, facile and low-cost technique for the treatment of arsenic-containing wastewaters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reactions of Propyl Radicals: A Shock Tube - VUV Photoionization Mass Spectrometry Study

The pyrolytic reactions of n-propyl and i-propyl radicals and their precursors have been investigated at elevated temperatures and pressures (600 – 900 K and 5 – 8 bar). The studies were performed in a miniature high repetition rate shock tube with synchrotron vacuum ultraviolet photoionization mass spectrometry yielding comprehensive datasets of temporal and photoionization energy dependencies of reagents and products. The propyl radicals were generated by pyrolysis of alkyl nitrites. In addition to the main decomposition path, NO elimination, the mass spectra allowed an alternative minor path via HNO elimination to be identified and quantified. For the n-propyl precursor the HNO elimination route accounted for 9% of the alkyl nitrite while for the i-propyl precursor it was 2.5%. These values are in good agreement with a recent study on i-butyl radicals in the same apparatus at similar conditions. The ratio of disproportionation/recombination was obtained for n- propyl from the relative concentrations of n-hexane and propene and for i-propyl from 2,3-dimethyl butane and propene. For n-propyl the ratio is 0.3 and 1.2 for i-propyl, both are independent of temperature and pressure over the experimental range. The disproportionation/recombination ratios are about a factor of 2 higher than prior evaluations that are based mainly on room temperature data. The experimental results are some of the first from the apparatus used and comments are made about the technique, challenges encountered, and suggestions for future developments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cost/performance of solar reflective surfaces for parabolic dish concentrators

Materials for highly reflective surfaces for use in parabolic dish solar concentrators are discussed. Some important factors concerning performance of the mirrors are summarized, and typical costs are treated briefly. Capital investment cost/performance ratios for various materials are computed specifically for the double curvature parabolic concentrators using a mathematical model. The results are given in terms of initial investment cost for reflective surfaces per thermal kilowatt delivered to the receiver cavity for various operating temperatures from 400 to 1400 C. Although second surface glass mirrors are emphasized, first surface, chemically brightened and anodized aluminum surfaces as well as second surface, metallized polymeric films are treated. Conventional glass mirrors have the lowest cost/performance ratios, followed closely by aluminum reflectors. Ranges in the data due to uncertainties in cost and mirror reflectance factors are given.

Bouquet, F.↗

Frozen storage of proteins: Use of mannitol to generate a homogenous freeze-concentrate

Therapeutic proteins may be subjected to several freeze–thaw cycles throughout manufacturing and storage. The protein solution composition and the freezing conditions may lead to incomplete ice crystallization in the frozen state. This can also result in freeze-concentrate heterogeneity characterized by multiple glass transition temperatures and protein destabilization. The overall objective was to investigate the potential advantages of including a crystallizing excipient (mannitol) along with a sugar (sucrose or trehalose) for frozen storage. Here, this study showed that the addition of mannitol, a readily crystallizing excipient, facilitated ice crystallization. Inclusion of an isothermal hold during cooling (annealing) maximized the mannitol crystallization and resulted in a homogenous freeze-concentrate of a constant composition characterized by a single glass transition temperature. The role of freezing rate and annealing on both mannitol and ice crystallization were discerned using high intensity synchrotron radiation. The addition of sucrose or trehalose, at an appropriate concentration, stabilized the protein. The mannitol to sugar ratio (3:1 or 1:1, 5 % w/v) was optimized to selectively cause maximal crystallization of mannitol while retaining the sugar amorphous. Human serum albumin (1 mg/mL) in these optimized and annealed compositions did not show any meaningful aggregation, even after multiple freeze–thaw cycles. Thus, in addition to a sugar as a stabilizer, the use of a crystallizing excipient coupled with an annealing step can provide an avenue for frozen storage of proteins.

59 BASIC BIOLOGICAL SCIENCES↗

Formation of Large (Approximately 100 micrometers) Ice Crystals Near the Tropical Tropopause

Recent high-altitude aircraft measurements with in situ imaging instruments indicated the presence of relatively large (approx.100 microns length), thin (aspect ratios of approx.6:1 or larger) hexagonal plate ice crystals near the tropical tropopause in very low concentrations (<0.01/L). These crystals were not produced by deep convection or aggregation. We use simple growth-sedimentation calculations as well as detailed cloud simulations to evaluate the conditions required to grow the large crystals. Uncertainties in crystal aspect ratio leave a range of possibilities, which could be constrained by knowledge of the water vapor concentration in the air where the crystal growth occurred. Unfortunately, water vapor measurements made in the cloud formation region near the tropopause with different instruments ranged from <2 ppmv to approx.3.5 ppmv. The higher water vapor concentrations correspond to very large ice supersaturations (relative humidities with respect to ice of about 200%). If the aspect ratios of the hexagonal plate crystals are as small as the image analysis suggests (6:1, see companion paper (Lawson et al., 2008)) then growth of the large crystals before they sediment out of the supersaturated layer would only be possible if the water vapor concentration were on the high end of the range indicated by the different measurements (>3 ppmv). On the other hand, if the crystal aspect ratios are quite a bit larger (approx.10:1), then H2O concentrations toward the low end of the measurement range (approx.2-2.5 ppmv) would suffice to grow the large crystals. Gravity-wave driven temperature and vertical wind perturbations only slightly modify the H2O concentrations needed to grow the crystals. We find that it would not be possible to grow the large crystals with water concentrations less than 2 ppmv, even with assumptions of a very high aspect ratio of 15 and steady upward motion of 2 cm/s to loft the crystals in the tropopause region. These calculations would seem to imply that the measurements indicating water vapor concentrations less than 2ppmv are implausible, but we cannot rule out the possibility that higher humidity prevailed upstream of the aircraft measurements and the air was dehydrated by the cloud formation. Simulations of the cloud formation with a detailed model indicate that homogeneous freezing should generate ice concentrations larger than the observed concentrations (20/L), and even concentrations as low as 20/L should have depleted the vapor in excess of saturation and prevented growth of large crystals. It seems likely that the large crystals resulted from ice nucleation on effective heterogeneous nuclei at low ice supersaturations. Improvements in our understanding of detailed cloud microphysical processes require resolution of the water vapor measurement discrepancies in these very cold, dry regions of the atmosphere.

Jensen, E. J.↗

Electron mobility and free-carrier absorption in GaAs - Determination of the compensation ratio

Theoretical calculations of electron mobility and free-carrier absorption in n-type GaAs at room temperature were carried out taking into consideration all major scattering processes. It was found that satisfactory agreement between theoretical and experimental results on free-carrier absorption is obtained only when the effect of compensation is quantitatively taken into account. In conjunction with experimental studies it is shown that the electron mobility (for n greater than 10 to the 15th per cu cm) and free-carrier absorption (for n greater than 10 to the 16th per cu cm) are sufficiently sensitive to the ionized impurity concentration to provide a reliable means for determining the compensation ratio. Convenient procedures are presented for the determination of the compensation ratio from the free-carrier absorption coefficient and from the computed values of room-temperature electron mobility. Values of the compensation ratio obtained by these two procedures are in good agreement provided the carrier-concentration variations in the material are not appreciably greater than 10%.

Walukiewicz, W.↗

Assessing Impacts of Plant Stoichiometric Traits on Terrestrial Ecosystem Carbon Accumulation Using the E3SM Land Model

Carbon (C) enters into the terrestrial ecosystems via photosynthesis and cycles through the system together with other essential nutrients (i.e., nitrogen [N] and phosphorus [P]). Such a strong coupling of C, N, and P leads to the theoretical prediction that limited nutrient availability will limit photosynthesis rate, plant growth, and future terrestrial C dynamics. However, the lack of reliable information about plant tissue stoichiometric constraints remains a challenge for quantifying nutrient limitations on projected global C cycling. In this study, we harmonized observed plant tissue C:N:P stoichiometry from more than 6,000 plant species with the commonly used plant functional type framework in global land models. Using observed C:N:P stoichiometry and the flexibility of these ratios as emergent plant traits, we show that observationally constrained fixed plant stoichiometry does not improve model estimates of present-day C dynamics compared with unconstrained stoichiometry. However, adopting stoichiometric flexibility significantly improves model predictions of C fluxes and stocks. The 21st century simulations with RCP8.5 CO 2 concentrations show that stoichiometric flexibility, rather than baseline stoichiometric ratios, is the dominant controller of plant productivity and ecosystem C accumulation in modeled responses to CO 2 fertilization. The enhanced nutrient limitations and plant P use efficiency mainly explain this result. This study is consistent with the previous consensus that nutrient availability will limit xfuture land carbon sequestration but challenges the idea that imbalances between C and nutrient supplies and fixed stoichiometry limit future land C sinks. We show here that it is necessary to represent nutrient stoichiometric flexibility in models to accurately project future terrestrial ecosystem carbon sequestration.

54 ENVIRONMENTAL SCIENCES↗

Record performance in intrinsic, impurity-free lateral diamond photoconductive semiconductor switches

Photoconductive semiconductor switches (PCSSs) are fabricated on type IIa diamond substrates with varying boron and nitrogen impurity levels (<10 14 –10 16 cm –3 ). The photoresponse of lateral PCSS is reported over the incident laser wavelength range (212–240 nm), energy per pulse (5–65 μJ), and DC bias (–1.2 to +1.2 kV). The PCSS device with the lowest boron and nitrogen impurity concentration achieves the highest normalized responsivity of 9.1 × 10 –8 A-cm/W-V, peak photocurrent of 8.0 A, and on/off ratio of 2.3 × 10 11 at a DC bias of +1.2 kV with the potential for even higher currents at increased DC bias. All PCSS display fast rise times (<3 ns), limited by the laser's rise time. However, photoresponse measurements reveal that higher impurity levels reduce the photocurrent and decrease the on/off ratio. Furthermore, these results highlight the performance advantages of using low background concentration type IIa diamond substrates for PCSS fabrication and present a promising route toward advanced high-power, high-speed diamond-based switches.

42 ENGINEERING↗

Observations on gas exchange and element recycle within a gas-closed algal-mouse system

Life support systems based on bioregeneration rely on the control and manipulation of organisms. Algae are potentially useful for a variety of Closed Ecological Life Support System (CELSS) functions including the revitalization of atmospheres, production of food and for nitrogen fixation. The results of experiments conducted with a gas-closed algal-mouse system designed to investigate gas exchange phenomena under varying algal environmental conditions, and the ability of algae to utilize oxidized mouse solid waste are reported. Inherent instabilities exist between the uptake and release of carbon dioxide (CO2) and oxygen (O2) by the mouse and algae in a gas-closed system. Variations in light intensity and cell density alter the photosynthetic rate of the algae and enable short-term steady-state concentrations of atmospheric CO2 and O2. Different nitrogen sources (urea and nitrate) result in different algal assimilatory quotients (AQ). Combinations of photosynthetic rate and AQ ratio manipulations were examined for their potential in stabilizing atmospheric gas concentrations in the gas-closed algal-mouse system.

Smernoff, D. T.↗