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87 records · Page 5

Coccolithophorid blooms in the global ocean

The global distribution pattern of coccolithophrid blooms was mapped in order to ascertain the prevalence of these blooms in the world's oceans and to estimate their worldwide production of CaCO3 and dimethyl sulfide (DMS). Mapping was accomplished by classifying pixels of 5-day global composites of coastal zone color scanner imagery into bloom and nonbloom classes using a supervised, multispectral classification scheme. Surface waters with the spectral signature of coccolithophorid blooms annually covered an average of 1.4 x 10(exp 6) sq km in the world oceans from 1979 to 1985, with the subpolar latitudes accounting for 71% of this surface area. Classified blooms were most extensive in the Subartic North Atlantic. Large expanses of the bloom signal were also detected in the North Pacific, on the Argentine shelf and slope, and in numerous lower latitude marginal seas and shelf regions. The greatest spatial extent of classified blooms in subpolar oceanic regions occurred in the months from summer to early autumn, while those in lower latitude marginal seas occurred in midwinter to early spring. Though the classification scheme was effcient in separating bloom and nonbloom classes during test simulations, and biogeographical literature generally confirms the resulting distribution pattern of blooms in the subpolar regions, the cause of the bloom signal is equivocal in some geographic areas, particularly on shelf regions at lower latitudes. Standing stock estimates suggest that the presumed Emiliania huxleyi blooms act as a significant source of calcite carbon and DMS sulfur on a regional scale. On a global scale, however, the satellite-detected coccolithophorid blooms are estimated to play only a minor role in the annual production of these two compounds and their flux from the surface mixed layer.

Brown, Christopher W.↗

An intercomparison of aircraft instrumentation for tropospheric measurements of sulfur dioxide

As part of the NASA Tropospheric Chemistry Program, a series of field intercomparisons have been conducted to evaluate the state-of-the art for measuring key tropospheric species. One of the objectives of the third intercomparison campaign in this series, Chemical Instrumentation Test and Evaluation 3 (CITE 3), was to evaluate instrumentation for making reliable tropospheric aircraft measurements of sulfur dioxide, dimethyl sulfide, hydrogen sulfide, carbon disulfide, and carbonyl sulfide. This paper reports the results of the intercomparisons of five sulfur dioxide measurement methods ranging from filter techniques, in which samples collected in flight are returned to the laboratory for analyses (chemiluminescent or ion chromatographic), to near real-time, in-flight measurements via gas chromatographic, mass spectrometric, and chemiluminescent techniques. All techniques showed some tendency to track sizeable changes in ambient SO2 such as those associated with altitude changes. For SO2 mixing ratios in the range of 200 pptv to a few ppbv, agreement among the techniques varies from about 30% to several orders of magnitude, depending upon the pair of measurements intercompared. For SO2 mixing ratios less than 200 pptv, measurements from the techniques are uncorrelated. In general, observed differences in the measurement of standards do not account for the flight results. The CITE 3 results do not unambiguously identify one or more of the measurement techniques as providing valid or invalid SO2 measurements, but identify the range of 'potential' uncertainty in SO2 measurements reported by currently available instrumentation and as measured under realistic aircraft environments.

Gregory, Gerald L.↗

Saharan Dust Aerosols Change Deep Convective Cloud Prevalence, Possibly by Inhibiting Marine New Particle Formation

Deep convective clouds (DCCs) are important to global climate, atmospheric chemistry, and precipitation. Dust, a dominant aerosol type over the tropical North Atlantic, has potentially large microphysical impacts on DCCs over this region. However, dust effects are difficult to identify, being confounded by co-varying meteorology and other factors. Here, a method is developed to quantify DCC responses to dust and other aerosols at large spatial and temporal scales despite these uncertainties. Over 7 million tropical North Atlantic cloud, aerosol, and meteorological profiles from CloudSat satellite data and MERRA-2 reanalysis products are used to stratify cloud observations into meteorological regimes, objectively select a priori assumptions, and iteratively test uncertainty sensitivity. Dust is robustly associated with a 54% increase in DCC prevalence. However, marine aerosol proxy concentrations are five times more predictive of dust-associated increases in DCC prevalence than the dust itself, or any other aerosol or meteorological factor. Marine aerosols are also the most predictive factor for the even larger increases in DCC prevalence (61-87%) associated with enhanced dimethyl sulfide and combustion and sulfate aerosols. Dust-associated increases in DCC prevalence are smaller at high dust concentrations than at low concentrations. These observations suggest that not only is dust a comparatively ineffective CCN source, but it may also act as a condensation/coagulation sink for chemical precursors to CCN, reducing total CCN availability over large spatial scales by inhibiting new particle formation from marine emissions. These observations represent the first time this rocess, previously predicted by models, is supported and quantified by measurements.

Aerosol-cloud interactions↗

Missing OH Reactivity in the Global Marine Boundary Layer

The hydroxyl radical (OH) reacts with thousands of chemical species in the atmosphere, initiating their removal and the chemical reaction sequences that produce ozone, secondary aerosols, and gas-phase acids. OH reactivity, which is the inverse of OH lifetime,influences the OH abundance and the ability of OH to cleanse the atmosphere. The NASA Atmospheric Tomography (ATom) campaign used instruments on the NASA DC-8 aircraft to measure OH reactivity and more than 100 trace chemical species. ATom presented a unique opportunity to test the completeness of the OH reactivity calculated from the chemical species measurements by comparing it to the measured OH reactivity over two oceans across four seasons. Although, throughout much of the free troposphere, the calculated OH reactivity was below the limit-of-detection for the ATom instrument used to measure OH reactivity, the instrument was able to measure the OH reactivity in and just above the marine boundary layer. The mean measured value of OH reactivity in the marine boundary layer across all latitudes and all ATom deployments was 1.9 s-1, which is 0.5 s-1larger than the mean calculated OH reactivity. The missing OH reactivity, the difference between the measured and calculated OH reactivity, varied between 0 s-1to 3.5 s-1, with the highest values over the Northern Hemisphere Pacific Ocean. Correlations of missing OH reactivity with formaldehyde, dimethyl sulfide, butanal, and sea surface temperature suggest the presence of unmeasured or unknown volatile organic compounds or oxygenated volatile organic compounds associated with ocean emissions.

NASA Atmospheric Tomography (ATom)↗

Next-generation wildlife tracking devices and integrated sensors for measuring species-environment interactions and advancing conservation

Global land use and climate change have magnified the importance of collecting accurate animal movement and environmental data to improve our ability to model species interactions with the environment and promote effective conservation. Advanced animal tracking devices that couple cutting-edge technologies with our expanding need for ecological information is critical. In addition to further optimizing device size to monitor small, sensitive species, new paradigms for collecting, storing, and transmitting data about animals and their environments will propel wildlife tracking devices forward. Advanced telemetry capabilities will increase our ability to pair location and sensor data from tagged wildlife with remote sensing data. The USGS Western Ecological Research Center, NASA Ames Research Center, and collaborators have been developing new wildlife tracking devices and integrated environmental sensors to address these challenges. We describe a new, miniaturized solar GPS-enabled Globalstar satellite transmitter with accelerometer capability that is 20% lighter and 25% less expensive than existing commercially available tags. We also introduce a novel peer-to-peer, solar-powered network tag that uses long-range, low-power, wireless platform technology. Concurrently, we began adapting a carbon nanotube (CNT) sensor to detect dimethyl sulfide (DMS), a trace gas relevant to marine ecology and climate studies. CNT sensors offer a small, lightweight, and low-power technology that can detect changes in resistance across carbon nanotubes coated with adsorbent selected to specifically bind with a variety of reactive trace gasses. We flew a prototype sensor in a small UAS and sampled an apparent increase in DMS concentration consistent with a well-defined marine frontal boundary. Currently we are integrating project components to create a hybridized architecture of networked peer-to-peer and satellite tags with integrated CNT and additional on-board and remote sensors to advance animal tracking and to provide information for next generation wildlife conservation.

Ian G. Brosnan↗

A nitrogenase-like enzyme system catalyzes methionine, ethylene, and methane biogenesis

Bacterial production of gaseous hydrocarbons like ethylene and methane affect soil environments and atmospheric climate. We demonstrate that biogenic methane and ethylene from terrestrial and freshwater bacteria are directly produced by a previously unknown methionine biosynthesis pathway. This pathway, present in numerous species, employs a nitrogenase-like reductase that is distinct from known nitrogenases and nitrogenase-like reductases. It specifically functions in C-S bond breakage to reduce ubiquitous and significant volatile organic sulfur compounds such as dimethyl sulfide. Liberated methanethiol serves as the immediate precursor to methionine, while ethylene or methane is released into the environment. Anaerobic ethylene production by this pathway apparently explains the origin and long- standing observation of ethylene accumulation in oxygen-depleted soils. Methane production bolsters the accumulating evidence that methanogenesis is not exclusively archaeal.

North, Justin A.↗

Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters

Abstract Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4‐vinylpyridine) thin films result in the 3D‐nucleation of clusters consistent with a cubane‐type Cd 4 S 4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few‐atom Cd‐based clusters are consistent with electronic and vibrational spectroscopy and grazing‐incidence total X‐ray scattering measurements of 3D‐cluster‐arrays synthesized at 80 °C. The direct synthesis of few‐atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light‐absorbing materials including solar energy harvesting and conversion applications.

Jayaweera, Nuwanthaka P. [Material Science Divisio↗

Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters

Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4-vinylpyridine) thin films result in the 3D-nucleation of clusters consistent with a cubane-type Cd 4 S 4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few-atom Cd-based clusters are consistent with electronic and vibrational spectroscopy and grazing-incidence total X-ray scattering measurements of 3D-cluster-arrays synthesized at 80 °C. The direct synthesis of few-atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light-absorbing materials including solar energy harvesting and conversion applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atmospheric Sulfur Cycle Effects of Carbonyl Sulfide (OCS)

Carbonyl Sulfide(OCS) is considered to be one of the major sources of sulfur appearing in the stratosphere due to its relative inertness, about I to 10 yearsl. However, the roles of OCS as well as other reduced sulfur compounds such as carbon disulfide (CS2), hydrogen sulfide (H2S), and dimethyl disulfide(CH3)2S2, are not completely understood in the atmosphenc sulfur cycle. Consequently vely little information is available about the effect of sulfur compounds in the stratosphere. The ability of OCS to penetrate into the stratosphere makes it an excellent tracer for study of the role of the sulfi r cycle in stratospheric chemistry. Previously techniques such as gas chromatography and whole air sampling have been used to measure OCS analytically. Each technique had its drawbacks however, with both being quite slow, and whole air sampling being somewhat unreliable. With molecular spectroscopy, however, it has been found in recent years that the tunable diode laser absorption spectrometer (TDL) provides a very rapid and accurate method of measuring OCS and other trace gases

McBee, Joshua↗

High-efficiency thin-film GaAs solar cells, phase2

Thin GaAs epi-layers with good crystallographic quality were grown using a (100) Si-substrate on which a thin Ge epi-interlayer was grown by CVD from germane. Both antireflection-coated metal oxide semiconductor (AMOS) and n(+)/p homojunction structures were studied. The AMOS cells were fabricated on undoped-GaAs epi-layers deposited on bulk poly-Ge substrates using organo-metallic CVD film-growth, with the best achieved AM1 conversion efficiency being 9.1%. Both p-type and n(+)-type GaAs growth were optimized using 50 ppm dimethyl zinc and 1% hydrogen sulfide, respectively. A direct GaAs deposition method in fabricating ultra-thin top layer, epitaxial n(+)/p shallow homojunction solar cells on (100) GaAs substrates (without anodic thinning) was developed to produce large area (1 sq/cm) cells, with 19.4% AM1 conversion efficiency achieved. Additionally, an AM1 conversion efficiency of 18.4% (17.5% with 5% grid coverage) was achieved for a single crystal GaAs n(+)/p cell grown by OM-CVD on a Ge wafer.

Yeh, Y. C. M.↗

Magnetic and Impedance Analysis of Fe 2 O 3 Nanoparticles for Chemical Warfare Agent Sensing Applications

A dire need for real-time detection of toxic chemical compounds exists in both civilian and military spheres. In this paper, we demonstrate that inexpensive, commercially available Fe 2 O 3 nanoparticles are capable of selective sensing of chemical warfare agents (CWAs) using frequency-dependent impedance spectroscopy, with additional potential as an orthogonal magnetic sensor. X-ray magnetic circular dichroism analysis shows that Fe 2 O 3 nanoparticles possess moderately lowered moment upon exposure to 2-chloroethyl ethyl sulfide (2-CEES) and diisopropyl methylphosphonate (DIMP) and significantly lowered moment upon exposure to dimethyl methylphosphonate (DMMP) and dimethyl chlorophosphate (DMCP). Associated X-ray absorption spectra confirm a redox reaction in the Fe 2 O 3 nanoparticles due to CWA structural analog exposure, with differentiable energy-dependent features that suggest selective sensing is possible, given the correct method. Impedance spectroscopy performed on samples dosed with DMMP, DMCP, and tabun (GA, chemical warfare nerve agent) showed strong, differentiable, frequency-dependent responses. The frequency profiles provide unique “shift fingerprints” with which high specificity can be determined, even amongst similar analytes. The results suggest that frequency-dependent impedance fingerprinting using commercially available Fe 2 O 3 nanoparticles as a sensor material is a feasible route to selective detection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermoplastic polymers for improved fire safety

The thermochemical and flammability characteristics of some typical thermoplastic materials currently in use and others being considered for use in aircraft interiors are described. The properties studied included (1) thermomechanical properties such as glass transition and melt temperature, (2) changes in polymer enthalpy by differential scanning calorimetry, (3) thermogravimetric analysis in anaerobic and oxidative environments, (4) oxygen index, (5) smoke evolution, (6) relative toxicity of the volatile products of pyrolysis, and (7) selected physical properties. The generic polymers that were evaluated included: acrylonitrile butadiene styrene, bisphenol A polycarbonate, 9,9 bis (4-hydroxyphenyl) fluorene polycarbonatepoly (dimethyl siloxane) block polymer, phenolphthalein bisphenol A polycarbonate, phenolphthalein polycarbonate, polyether sulfone, polyphenylene oxide, polyphenylene sulfide, polyaryl sulfone, chlorinated polyvinyl chloride homopolymer, polyvinyl fluoride, and polyvinylidene fluoride. Processing parameters, including molding characteristics of some of the advanced polymers, are described. Test results and relative ranking of some of the flammability, smoke, and toxicity properties are presented.

Kourtides, D. A.↗

Evaluating Iodine Immobilization Technologies: Cermets, Polycermets, and Polyhalmets

The work in this report documents the efforts conducted to assess the feasibility of some of the ideas documented in Pacific Northwest National Laboratory invention disclosure reports (IDRs) including: 1) Iodine capture in polyacrylonitrile (PAN)-containing composite sorbents (32451-E). In this work, the composites evaluated included Ag0, Bi0, Cu0, Bi2S3, and Cu2S embedded in PAN. 2) Metal iodide removal from these sorbents through dissolution in dimethyl sulfoxide (DMSO) (32729-E). In this work, PAN dissolution was evaluated for multiple types of sorbents including Ag-Pan, Bi-PAN, Cu-PAN, Bi2S3-PAN, and Cu2S-PAN. 3) Using metal-sulfide sorbents for iodine capture (32647-E). In this work, the composites evaluated under this IDR included Ag2S, Bi2S3, and Cu2S embedded in PAN. 4) Using low-melting metals to immobilize (encapsulate) iodine-loaded and polymer-containing sorbents into polymer-ceramic-metal (called polycermet) or polymer-halide-metal (called polyhalmet) composite waste forms (32625-E). In this work, the iodine-loaded PAN composites included AgI-PAN, BiI-PAN, and CuI-PAN. 5) Ceramic-metal composite waste form synthesis of polymer-containing materials using low-melting metals like bismuth, tin, or bismuth-tin alloys (32537-E). In this work, the metals evaluated included Bi, 58Bi-42Sn eutectic. 6) Cermets for immobilizing commercial sorbents loaded with radioiodine (32806-E). In this work, AgIX (iodine-loaded silver faujasite zeolite) was evaluated in cermet form.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Probing the Mechanism of Cadmium Sulfide Cluster Nucleation and Growth via Sequential Infiltration Synthesis

Few-atom metal chalcogenide clusters may be realized through the sequential infiltration of metal–organic precursors in polymer films. However, the underlying nucleation and growth mechanisms that allow for cluster synthesis with near atomic-scale precision are not fully resolved. The kinetics of the sequential infiltration synthesis (SIS) method that control the nucleation and growth mechanisms of primarily Cd 4 S 4 -core clusters within a poly­(4-vinylpyridine) (P4VP) matrix are probed with in situ UV–visible absorbance spectroscopy. Density functional theory (DFT) calculations that allow simulation of the optical properties of cluster fragments further reveal the thermodynamics that guide cluster growth within the P4VP matrix. Here, we conclude that a reactive capture mechanism for cluster nucleation and growth is dominant, although transient dimethyl cadmium adduction to the polymer backbone may contribute to cluster nucleation under shorter metal–organic purge process conditions. Grazing incidence X-ray diffraction (GI-XRD) and X-ray absorption spectroscopy (XAS) analyses further corroborate the cluster size and atom connectivity throughout the stepwise synthesis.

Jayaweera, Nuwanthaka P. [Argonne National Laborat↗