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At least 235 records · Page 13

Can we achieve atmospheric chemical environments in the laboratory? An integrated model-measurement approach to chamber SOA studies

Secondary organic aerosol (SOA), atmospheric particulate matter formed from low-volatility products of volatile organic compound (VOC) oxidation, affects both air quality and climate. Current 3D models, however, cannot reproduce the observed variability in atmospheric organic aerosol. Because many SOA model descriptions are derived from environmental chamber experiments, our ability to represent atmospheric conditions in chambers directly affects our ability to assess the air quality and climate impacts of SOA. Here, we develop an approach that leverages global modeling and detailed mechanisms to design chamber experiments that mimic the atmospheric chemistry of organic peroxy radicals (RO 2 ), a key intermediate in VOC oxidation. Drawing on decades of laboratory experiments, we develop a framework for quantitatively describing RO 2 chemistry and show that no previous experimental approaches to studying SOA formation have accessed the relevant atmospheric RO 2 fate distribution. We show proof-of-concept experiments that demonstrate how SOA experiments can access a range of atmospheric chemical environments and propose several directions for future studies.

Science & Technology - Other Topics↗

Metallic and Insulating Oxide Interfaces Controlled by Electronic Correlations

The formation of two-dimensional electron gases (2DEGs) at complex oxide interfaces is directly influenced by the oxide electronic properties. We investigated how local electron correlations control the 2DEG by inserting a single atomic layer of a rare-earth oxide (RO) [RO is lanthanum (La), praseodymium (Pr), neodymium (Nd), samarium (Sm), or yttrium (Y)] into an epitaxial strontium titanate oxide (SrTiO{sub 3}) matrix using pulsed-laser deposition with atomic layer control. We find that structures with La, Pr, and Nd ions result in conducting 2DEGs at the inserted layer, whereas the structures with Sm or Y ions are insulating. Our local spectroscopic and theoretical results indicate that the interfacial conductivity is dependent on electronic correlations that decay spatially into the SrTiO{sub 3} matrix. Such correlation effects can lead to new functionalities in designed heterostructures.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Photocatalytic C–H activation and the subtle role of chlorine radical complexation in reactivity

A complex role for chlorine radicals Radicals are atoms or molecules that are highly reactive because they have an unpaired electron. A common means of investigating whether they are involved in a particular reaction is to try to trap them with an acceptor compound. Yang et al. reinvestigated a photoinduced alkane oxidation reaction for which a trapping study had previously implicated alkoxy radicals. Their spectroscopic, kinetic, and isotopic labeling studies revealed that chlorine, rather than alkoxy, was the key radical intermediate; the prior trapping results had stemmed from its complexation with alcohols. Science , abd8408, this issue p. 847

Science & Technology - Other Topics↗

Magnetic Convection in a Nonuniformly Rotating Electroconducting Medium

We study the stability of a convective flow in a nonuniformly rotating plasma layer in an axially uniform magnetic field. The stationary and oscillating regimes of magnetic convection are considered depending on the angular velocity profile (Rossby number Ro) of the electroconducting medium. Using the Galerkin method for describing the weakly nonlinear stage of evolution of convection, we have obtained a nonlinear dynamic system of Lorentz-type equations. Numerical analysis of these equations has revealed the chaotic behavior of convective flows. The criteria for the emergence of chaotic flows are obtained depending on parameters of convection (Rayleigh number Ra), magnetic field (Chandrasekhar number Q), and rotation (Taylor number Ta) for the Rayleigh (Ro = –1) and Kepler (Ro = –3/4) angular velocity profiles of the medium.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Insights into ENSO Diversity from an Intermediate Coupled Model. Part I: Uniqueness and Sensitivity of the ENSO Mode

Abstract The basic dynamics of the spatiotemporal diversity for El Niño–Southern Oscillation (ENSO) has been the subject of extensive research and, while several hypotheses have been proposed, remains elusive. One promising line of studies suggests that the observed eastern Pacific (EP) and central Pacific (CP) ENSO may originate from two coexisting leading ENSO modes. We show that the coexistence of unstable EP-like and CP-like modes in these studies arises from contaminated linear stability analysis due to unnoticed numerical scheme caveats. In this two-part study, we further investigate the dynamics of ENSO diversity within a Cane–Zebiak-type model. We first revisit the linear stability issue to demonstrate that only one ENSO-like linear leading mode exists under realistic climate conditions. This single leading ENSO mode can be linked to either a coupled recharge-oscillator (RO) mode favored by the thermocline feedback or a wave-oscillator (WO) mode favored by the zonal advective feedback at the weak air–sea coupling end. Strong competition between the RO and WO modes for their prominence in shaping this ENSO mode into a generalized RO mode makes it sensitive to moderate changes in these two key feedbacks. Modulations of climate conditions yield corresponding modulations in spatial pattern, amplitude, and period associated with this ENSO mode. However, the ENSO behavior undergoing this linear climate condition modulations alone does not seem consistent with the observed ENSO diversity, suggesting the inadequacy of linear dynamics in explaining ENSO diversity. A nonlinear mechanism for ENSO diversity will be proposed and discussed in Part II.

Geng, Licheng↗

Characterization of Fish Passage Conditions through a Francis Turbine and Regulating Outlet at Cougar Dam, Oregon, Using Sensor Fish, 2009–2010

Fish passage conditions through a Francis turbine and a regulating outlet (RO) at Cougar Dam on the south fork of the McKenzie River in Oregon were evaluated by Pacific Northwest National Laboratory for the U.S. Army Corps of Engineers, Portland District, using Sensor Fish devices. The objective of the study was to describe and compare passage exposure conditions, identifying potential fish injury regions encountered during passage via specific routes. The RO investigation was performed in December 2009 and the turbine evaluation in January 2010, concurrent with HI-Z balloon-tag studies by Normandeau Associates, Inc. Sensor Fish data were analyzed to estimate 1) exposure conditions, particularly exposure to severe collision, strike, and shear events by passage route sub-regions; 2) differences in passage conditions between passage routes; and 3) relationships to live-fish injury and mortality data estimates. Comparison of the three passage routes evaluated at Cougar Dam indicates that the RO passage route through the 3.7-ft gate opening was relatively the safest route for fish passage under the operating conditions tested; turbine passage was the most deleterious. These observations were supported also by the survival and malady estimates obtained from live-fish testing. Injury rates were highest for turbine passage. Compared to mainstem Columbia River passage routes, none of the Cougar Dam passage routes as tested are safe for juvenile salmonid passage.

54 ENVIRONMENTAL SCIENCES↗

DOE SBIR 2014 Topic 2.C – Phase I Final Report

Freshwater is a vital resource for human survival as well as a key component of a wide range of industrial and agricultural needs. However, only 0.65% of the world’s water resources are available as freshwater, and the demand on the world’s water reserves continues to increase, with the demand beginning to outpace the supply in many areas. A water-energy nexus is being reached that requires low –cost and –energy solutions for various degrees of treated water. In a 2012 survey, 88% of Americans were concerned about potential water shortages and approximately two-thirds of the world’s population will be suffering a water shortage over the next few years. Seawater and other saline water materials make up around 98% of the available water, representing an almost unlimited supply of water. The energy, cost and maintenance to remove salts and other unwanted compounds is a barrier to widespread implementation of salt-to-freshwater facilities. These facilities most commonly use reverse osmosis (RO) systems. Due to the high required pressures and moving parts these facilities consume much grid energy and require constant maintenance leading to high capital and operational costs. RO also generates highly concentrated brine that is costly to safely return to the ocean. Capacitive desalination (or capacitive deionization [CDI]) has no moving parts (aside from a low pressure pump and valves), operates at low pressure and does not generate brine that is hazardous to marine life. Not only can the capacitive charge/discharge be cycled almost indefinitely but the system uses low energy and capacitive discharge electrical current can be co-generated back to the system. However, CDI has not seen widespread use for large- or small- scale desalination because electrode efficiency limits the extraction rate below what is useful for most applications. Mainstream Engineering Corporation (MEC) has demonstrated an innovative new electrode structure for the high efficiency desalination of brackish water by capacitive deionization. Electrode manufacturing (nanomanufacturing) is a highly scalable and low-cost electrochemical self-assembly method using a templated process that Mainstream has pioneered and leveraged for several energy technologies over the last decade. The primary accomplishment for Phase I is the fabrication and demonstration of CDI electrode structures are: • Demonstrating the linear scalability of templated approach to the fabrication scaling the electrode structure. • Demonstrated the ability to tune the fabrication of the electrode structures to produce electrodes with a highly controllable aligned nanopore diameter and nanopore depth. • Demonstrated the efficient removal of a sodium chloride salt from brackish water with a 60 times improvement in mg-salt removed/g-carbon compared to a commercial system under the same conditions. • Demonstrated good reproducibility and stability of the electrode structure under realistic CDI operating conditions. • Demonstrated charge efficiency as high as 93% with an expected system level energy requirement of 0.7 to 1.5 kWh/m3 of water; significantly lower than the 2.9 to 3.7 kWh/m3 observed for RO systems Based on the performance characteristics of the electrodes, Mainstream was able to propose a modular and scalable capacitive deionization design that can be adapted to a wide range of conditions providing energy efficient desalination of brackish water.

36 MATERIALS SCIENCE↗

Flue-Gas Desulfurization Effluent Management using an Innovative Low-Energy Biosorpotion Treatment System to Remove Key Contaminants

Among the most critical water contaminants of concern affecting wide geographical regions and a number of industries and natural systems is selenium. Selenium found in surface, ground and wastewater in originates from natural sources, as well as industrial sources such as petroleum refineries, electronics manufacturing, pesticides, and coal power plants and mining also contribute to selenium contamination in water in the US. At high concentrations, selenium is toxic to human and wildlife. There are a number of technologies that have been used to treat selenium and other similar contaminants in water. Biological treatment of selenium has been used in the past to reduce soluble SeVI and/or SeIV to insoluble Se0, which is then filtered in the same vessel. The insoluble selenium (Se0) is then backwashed from the system and solids are separated for subsequent disposal, if they meet the leaching and water content criteria. In order to promote biological reduction to insoluble Se0, heating of bioreactor is needed in some applications, and excess food source (electron donor) is added so that all selenium can be filtered. An additional disadvantage of these systems is the significant amount of water lost due to extensive and frequent backwash and rinse cycles. When comparing the advantages and energy requirements of the various treatment technologies, RO membrane filtration immediately stands out due to the excessive energy expenditure needed to pump water across the membrane although RO is an effective way to remove selenium. In addition, RO requires extensive pretreatment, such as MF membrane, and frequent maintenance, rendering it an expensive option that may be out of reach for certain applications. In fact, although the performance was good during the pilot testing by the NSMP Working Group for treatment naturally occurring selenium in the surface water, the high electricity requirements and significant reject water stream made it an infeasible alternative. While conventional ion exchange maybe an effective treatment option, it requires frequent regeneration of the resin when applied to highly contaminated water, which leads to several tons of contaminant-laden, high-salinity brine that needs to be disposed off-site each day. One of the water systems in the west coast currently uses ion exchange for selenium treatment and has been trucking selenium laden hazardous brine waste weekly in the last several years. Pneumatic pumping and rinse water pumping required for ion exchange also increase the energy usage. In comparison, adsorption process is a passive treatment system where contaminated water comes in contact with an adsorption media in a vessel. Typically, there is no mixing, backwash, or recycle pumping required, thus significantly reducing the energy usage. A passive single-use adsorption system does not require backwash, thereby generating small amount of process waste, and producing the highest water yield among the alternatives. The energy and water efficiencies, and applicability for SeVI and SeIV are summarized in Table 1. Despite these benefits though, adsorption typically does not work for the most oxidized form of selenium (SeVI). The innovative biosorption process integrates both process to increase the treatment efficiency while minimizing energy, chemical, and time required to treat both SeVI and SeIV. Additional advantages include simple partial biological reduction with reduced on-site waste generation, which lead to water and electricity savings, and less operational need compared to biological treatment alone. This makes biosorption especially suitable for remote areas, where liquid backwash and brine disposal may be cost prohibitive or infeasible.

20 FOSSIL-FUELED POWER PLANTS↗

Recent Advances of PyROS: A Pyomo Solver for Nonconvex Two-Stage Robust Optimization in Process Systems Engineering

This poster highlights uncertainty and technical risk reduction capabilities in CCSI2, with a focus on robust optimization. It presents recent advances of the two-stage robust optimization (RO) solver PyROS and applications to advanced energy systems optimization. To demonstrate the computational performance and reliability of PyROS, a benchmarking study on a library of over 8,500 small-scale RO problems is presented. Further, PyROS is used to obtain robust system designs of a MEA-based CO2 absorber under uncertainty in the thermodynamic property models for a variety of CO2 capture rate threshold requirements. Overall, the results demonstrate that the PyROS solver, including recent extensions to multi-stage RO settings, provides a reliable avenue to optimize the design and operation of advanced energy systems subject to various sources of parametric uncertainty.

Sherman, Jason↗

Recent Advances of PyROS: A Pyomo Solver for Nonconvex Two-Stage Robust Optimization in Process Systems Engineering

This poster highlights uncertainty and technical risk reduction capabilities in CCSI2, with a focus on robust optimization. It presents recent advances of the two-stage robust optimization (RO) solver PyROS and applications to advanced energy systems optimization. To demonstrate the computational performance and reliability of PyROS, a benchmarking study on a library of over 8,500 small-scale RO problems is presented. Further, PyROS is used to obtain robust system designs of a MEA-based CO2 absorber under uncertainty in the thermodynamic property models for a variety of CO2 capture rate threshold requirements. Overall, the results demonstrate that the PyROS solver, including recent extensions to multi-stage RO settings, provides a reliable avenue to optimize the design and operation of advanced energy systems subject to various sources of parametric uncertainty.

Sherman, Jason↗

Mitigation of Acute Ammonia Emissions With Biochar During Swine Manure Agitation Before Pump-Out: Proof-of-the-Concept

Ammonia (NH 3 ) emissions from animal agriculture can cause eutrophication of water ecosystems and are precursors to secondary particulate matter (PM 2 .5 ). NH 3 emissions from stored swine manure represent nutrient loss affecting the fertilizing value of manure. The short-term emission bursts occur when farmers agitate manure before emptying storage and fertilizing fields. There is no proven technology to mitigate gaseous emissions during agitation, while the hazards of acute releases (e.g., H 2 S) are well-known. Biochar mitigates NH 3 emissions from manure over the long-term. The objective of this research was to evaluate the mitigation of acute NH 3 emissions during/after agitation. Two biochars, highly alkaline and porous (HAP from corn stover) and red oak (RO), were tested. The 6 and 12 mm-thick layers of biochar powder were surficial applied followed by 3 min agitation. NH 3 concentrations were measured before/during/after agitation. Mitigation was assessed by comparing: (i) the maximum (peak) flux, (ii) total emission (from agitation start till NH 3 concentration returned to the before-agitation), and (iii) the total emissions during agitation. The 12 mm HAP significantly ( p < 0.05) reduced (i–iii) by 63, 70, and 85%, respectively. The 6 mm HAP significantly reduced (i–iii) by 76, 75, and 78%, respectively. The 12 mm RO significantly reduced (i–iii) by 9, 53, and 57%, respectively. The 6 mm RO significantly reduced (i–iii) by 61, 86, and 63%, respectively. The NH 3 emission kinetics model confirmed that a 6 mm dose was just as effective as the larger dose. More research is needed to optimize and scale-up mitigating emissions and retention of nutrients in manure with biochar.

Chen, Baitong↗

Mitigation of Gaseous Emissions from Swine Manure with the Surficial Application of Biochars

Environmental impact associated with odor and gaseous emissions from animal manure is one of the challenges for communities, farmers, and regulatory agencies. Microbe-based manure additives treatments are marketed and used by farmers for mitigation of emissions. However, their performance is difficult to assess objectively. Thus, comprehensive, practical, and low-cost treatments are still in demand. We have been advancing such treatments based on physicochemical principles. The objective of this research was to test the effect of the surficial application of a thin layer (¼ inches; 6.3 mm) of biochar on the mitigation of gaseous emissions (as the percent reduction, % R) from swine manure. Two types of biochar were tested: highly alkaline and porous (HAP) biochar made from corn stover and red oak (RO), both with different pH and morphology. Three 30-day trials were conducted with a layer of HAP and RO (2.0 & 1.65 kg∙m−2, respectively) applied on manure surface, and emissions of ammonia (NH3), hydrogen sulfide (H2S), greenhouse gases (GHG), and odorous volatile organic compounds (VOCs) were measured. The manure and biochar type and properties had an impact on the mitigation effect and its duration. RO significantly reduced NH3 (19–39%) and p-cresol (66–78%). H2S was mitigated (16~23%), but not significantly for all trials. The phenolic VOCs had relatively high % R in most trials but not significantly for all trials. HAP reduced NH3 (4~21%) and H2S (2~22%), but not significantly for all trials. Significant % R for p-cresol (91~97%) and skatole (74~95%) were observed for all trials. The % R for phenol and indole ranged from (60~99%) and (29~94%) but was not significant for all trials. The impact on GHGs, isobutyric acid, and the odor was mixed with some mitigation and generation effects. However, larger-scale experiments are needed to understand how biochar properties and the dose and frequency of application can be optimized to mitigate odor and gaseous emissions from swine manure. The lessons learned can also be applicable to surficial biochar treatment of gaseous emissions from other waste and area sources.

Meiirkhanuly, Zhanibek↗

The Impact of Surficial Biochar Treatment on Acute H2S Emissions during Swine Manure Agitation before Pump-Out: Proof-of-the-Concept

Acute releases of hydrogen sulfide (H2S) are of serious concern in agriculture, especially when farmers agitate manure to empty storage pits before land application. Agitation can cause the release of dangerously high H2S concentrations, resulting in human and animal fatalities. To date, there is no proven technology to mitigate these short-term releases of toxic gas from manure. In our previous research, we have shown that biochar, a highly porous carbonaceous material, can float on manure and mitigate gaseous emissions over extended periods (days–weeks). In this research, we aim to test the hypothesis that biochar can mitigate H2S emissions over short periods (minutes–hours) during and shortly after manure agitation. The objective was to conduct proof-of-the-concept experiments simulating the treatment of agitated manure. Two biochars, highly alkaline and porous (HAP, pH 9.2) made from corn stover and red oak (RO, pH 7.5), were tested. Three scenarios (setups): Control (no biochar), 6 mm, and 12 mm thick layers of biochar were surficially-applied to the manure. Each setup experienced 3 min of manure agitation. Real-time concentrations of H2S were measured immediately before, during, and after agitation until the concentration returned to the initial state. The results were compared with those of the Control using the following three metrics: (1) the maximum (peak) flux, (2) total emission from the start of agitation until the concentration stabilized, and (3) the total emission during the 3 min of agitation. The Gompertz’s model for determination of the cumulative H2S emission kinetics was developed. Here, 12 mm HAP biochar treatment reduced the peak (1) by 42.5% (p = 0.125), reduced overall total emission (2) by 17.9% (p = 0.290), and significantly reduced the total emission during 3 min agitation (3) by 70.4%. Further, 6 mm HAP treatment reduced the peak (1) by 60.6%, and significantly reduced overall (2) and 3 min agitation’s (3) total emission by 64.4% and 66.6%, respectively. Moreover, 12 mm RO biochar treatment reduced the peak (1) by 23.6%, and significantly reduced overall (2) and 3 min total (3) emission by 39.3% and 62.4%, respectively. Finally, 6 mm RO treatment significantly reduced the peak (1) by 63%, overall total emission (2) by 84.7%, and total emission during 3 min agitation (3) by 67.4%. Biochar treatments have the potential to reduce the risk of inhalation exposure to H2S. Both 6 and 12 mm biochar treatments reduced the peak H2S concentrations below the General Industrial Peak Limit (OSHA PEL, 50 ppm). The 6 mm biochar treatments reduced the H2S concentrations below the General Industry Ceiling Limit (OSHA PEL, 20 ppm). Research scaling up to larger manure volumes and longer agitation is warranted.

Chen, Baitong (ORCID:0000000266071253)↗

A solar-pumped fluorescence model for line-by-line emission intensities in the B–X, A–X, AND X–X band systems of {sup 12}C{sup 14}N

We present a new quantitative model for detailed solar-pumped fluorescent emission of the main isotopologue of CN. The derived fluorescence efficiencies permit estimation and interpretation of ro-vibrational infrared line intensities of CN in exospheres exposed to solar (or stellar) radiation. Our g-factors are applicable to astronomical observations of CN extending from infrared to optical wavelengths, and we compare them with previous calculations in the literature. The new model enables extraction of rotational temperature, column abundance, and production rate from astronomical observations of CN in the inner coma of comets. Our model accounts for excitation and de-excitation of rotational levels in the ground vibrational state by collisions, solar excitation to the A{sup 2}Π{sub i} and B{sup 2}Σ{sup +} electronically excited states followed by cascade to ro-vibrational levels of X{sup 2}Σ{sup +}, and direct solar infrared pumping of ro-vibrational levels in the X{sup 2}Σ{sup +} state. The model uses advanced solar spectra acquired at high spectral resolution at the relevant infrared and optical wavelengths and considers the heliocentric radial velocity of the comet (the Swings effect) when assessing the exciting solar flux for a given transition. We present model predictions for the variation of fluorescence rates with rotational temperature and heliocentric radial velocity. Furthermore, we test our fluorescence model by comparing predicted and measured line-by-line intensities for X{sup 2}Σ{sup +} (1–0) in comet C/2014 Q2 (Lovejoy), thereby identifying multiple emission lines observed at IR wavelengths.

79 ASTRONOMY AND ASTROPHYSICS↗

Molecular understanding of the suppression of new-particle formation by isoprene

Nucleation of atmospheric vapours produces more than half of global cloud condensation nuclei and so has an important influence on climate. Recent studies show that monoterpene ( C 10 H 16 ) oxidation yields highly oxygenated products that can nucleate with or without sulfuric acid. Monoterpenes are emitted mainly by trees, frequently together with isoprene ( C 5 H 8 ), which has the highest global emission of all organic vapours. Previous studies have shown that isoprene suppresses new-particle formation from monoterpenes, but the cause of this suppression is under debate. Here, in experiments performed under atmospheric conditions in the CERN CLOUD chamber, we show that isoprene reduces the yield of highly oxygenated dimers with 19 or 20 carbon atoms – which drive particle nucleation and early growth – while increasing the production of dimers with 14 or 15 carbon atoms. The dimers (termed C 20 and C 15 , respectively) are produced by termination reactions between pairs of peroxy radicals ( RO 2 • ) arising from monoterpenes or isoprene. Compared with pure monoterpene conditions, isoprene reduces nucleation rates at 1.7 nm (depending on the isoprene / monoterpene ratio) and approximately halves particle growth rates between 1.3 and 3.2 nm. However, above 3.2 nm, C 15 dimers contribute to secondary organic aerosol, and the growth rates are unaffected by isoprene. We further show that increased hydroxyl radical ( OH • ) reduces particle formation in our chemical system rather than enhances it as previously proposed, since it increases isoprene-derived RO 2 • radicals that reduce C 20 formation. RO 2 • termination emerges as the critical step that determines the highly oxygenated organic molecule (HOM) distribution and the corresponding nucleation capability. Species that reduce the C 20 yield, such as NO, HO 2 and as we show isoprene, can thus effectively reduce biogenic nucleation and early growth. Therefore the formation rate of organic aerosol in a particular region of the atmosphere under study will vary according to the precise ambient conditions.

54 ENVIRONMENTAL SCIENCES↗

Peroxy radical measurements with NCAR's chemical amplifier

The present NCAR instrument for HO2/RO2 measurements has been described previously. It is based on the reactions involving HO2, RO2, and HO radicals with CO and NO. Since (HO2) + (RO2) + (HO) is much greater than (HO) for most atmospheres, it is useful as a peroxy radical detector. Operation of the instrument depends on the creation of a chemical chain reaction which is initiated as HO2 and RO2 radicals in ambient air encounter added NO gas; this forms an NO2 molecule and an HO or RO radical: HO2(RO2) + NO yields HO(RO) + NO2. RO radicals react relatively efficiently with O2 to form an HO2 radical, and subsequently an HO-radical, by reaction with NO. CO gas added to the reaction chamber during part of the operating cycle, recycles the HO to HO2; HO + CO (+O2) yields HO2 + CO2. The reaction sequence may form several hundred NO2 molecules per HO2 (RO2) originally present, before chain termination occurs. The added CO is replaced by N2 addition periodically so that the chain reaction is suppressed, and a 'blank' signal resulting from NO2, O3 and possibly other NO2-forming species (non-chain processes) in ambient air is recorded. The difference between the signal with and without CO is proportional to the peroxy radical concentration. The NO2 produced is monitored using a sensitive luminol chemiluminescence detector system. In the NCAR instrument the length of the amplification chain is determined using a stable source of HO2 radicals (H2O2 thermal decomposition); the ratio of the signal seen with CO present to that with N2 present gives the sensitivity of the instrument to HO2 (molecules of NO2 formed/peroxy radical). The instrument is automated to carry out in hourly repeated cycles: (1) chain length determination; (2) NO2 calibration; and (3) linearity check on the response of signals. One minute averages of signals are normally recorded. The sensitivity of the instrument to detect peroxy radicals is in the pptv range. The present instrument has operated continuously (24 hr/day) in the field studies which extended over a period of several weeks. The major advantages of this instrument are as follows: (1) its relative simplicity; (2) low power requirements; and (3) its rapid response to all types of peroxy radicals--HO2, CH3O2 and the higher alkyl and acyl peroxy radicals; however not all RO2 species generate HO2 radicals with perfect efficiency and hence have somewhat lower response/molecule than HO2 radicals.

Cantrell, Christopher↗

A phyllosilicate-sulfide vein in Kaidun

A fragment of a carbonaceous chondrite (#53.12, maximal dimension about 2 mm) containing a phyllosilicate-sulfide vein was found during an inspection of small pieces of the Kaidun meteorite. Phyllosilicate veins are apparently rare in carbonaceous chondrites and have so far only been reported from the Y82162 CI chondrite. In hand sample the vein was visible on two perpendicular faces. The polished section prepared from one side displays a complex structure. A single vein, 150 microns in width, bifurcates, and each branch narrows toward a large rounded object (RO). The section contains abundant ROs, most of them less than or equal to 100 microns in diameter. The vein has sharp contacts to the surrounding matrix, whereas the RO contacts are diffuse. The phyllosilicate in the main vein has a massive texture along the contact, which becomes platy toward the vein center where the crystals protrude into an open space. The texture of the largest RO resembles that of a barred olivine (BO) chondrule. Some of the smaller ROs also texturally resemble chondrules. The BO chondrule contains rounded sulfide-silicate objects and small metal grains covered by oxides. Phyllosilicates of the main vein consist mainly of serpentine. The phyllosilicate near the contact with the matrix has low contents of minor elements and a high Mg/Fe ratio. The composition changes in a regular manner toward the center: Al, Na, Ca, Ni, and S increase, indicating increasing amounts of sulfates admixed. The phyllosilicate vein could only have formed after a substantial rock was formed. Mechanical stress probably opened a crack that was subsequently filled by phyllosilicate, pyrrhotite, and finally by a (Fe,Mg)-sulfate. The source of the matter mobilized to form the vein could have been within the rock itself or outside. No compositional or mineralogical zoning is apparent at the vein-rock contacts. The nature of the transporting agent (liquid H2O or vapor) must also remain an enigma. M. Zolensky has recently observed similar phyllosilicate-filled veins in dark, wet clasts in the Al Rais CR chondrite.

Ivanov, A. V.↗

Advanced Observation Operators for GPS Radio Occultation: Validation of the 2D Ray Tracing Approach with CHAMP and SAC-C bending angle and refractivity data - Part 1

Global Positioning System (GPS) Radio Occultations (RO) bending angles and refractivity data characterize mostly the vertical structure of the Earth's atmosphere. We answer the question whether proper simulation of GPS RO data for data assimilation can be obtained with one-dimensional vertical operators, or if accounting also for horizontal atmospheric structures via ray-tracing makes a positive difference when compared with real data. We present a detailed implementation of a geometrical optics multi-plane two-dimensional (2D) ray-tracing as an observation operator to simulate GPS RO bending angles and refractivities within the Finite Volume Data Assimilation System (FVDAS). Comparisons of the outputs of that 2D observation operator with those of simpler ID observation operators are used to generate estimates of errors induced by neglecting tangent point drift (TPD) and horizontal gradients (HG). These error estimates are then confronted with errors estimates derived using 6335 real CHAMP and SAC-C occultations. The agreement for TPD-induced (HG-induced) errors is remarkably positive at altitudes 10-30 km (below 10 km). Comparisons in bending angles O - B STD of the outputs of the multi-plane 2D ray-tracer with those of a vertical Abel transform show reductions of about 8% of the usual O - B bending angle STD due to TPD in the stratosphere (3% due to HG, in the troposphere only). In terms of refractivity, the O - B STD reductions are about 1520% for TPD and 3-5% for HG in the same regions. These reductions are obtained using either 6-hour forecasts or analyses as backgrounds, and using Geometrical Optics (GO) or Canonical Transform (CT) data.

Poli, P.↗