A counterexample to the first Zassenhaus conjecture

Hans J. Zassenhaus conjectured that for any unit u of finite order in the integral group ring of a finite group G there exists a unit a in the rational group algebra of G such that a−1· u · a = ±g for some g ∈ G. We disprove this conjecture by first proving general results that help identify counterexamples and then providing an infinite number of examples where these results apply. Our smallest example is a metabelian group of order 27·32·5·72·192 whose integral group ring contains a unit of order 7 · 19 which, in the rational group algebra, is not conjugate to any element of the form ±g

The Measurement of Sulfur Oxidation Products and Their Role in Homogeneous Nucleation

The loss rate of H2SO4 vapor onto submicron particles was measured for three different particle substrates. The experimental technique involved direct flow tube measurements of H2SO4 decay rates onto a polydisperse aerosol using chemical ionization mass spectroscopic detection. The aerosols of this study were partially hydrated crystalline salts with diameters in the size range of 20 to 400 nm. The mass accommodation coefficients, a, were calculated from the first-order rate constants for H2SO4 loss to be 0.73 + 0.21 and 0.79 + 0.23 for loss onto (NH4)2SO4 and NaCl, respectively. Measurements of the loss rate of H2SO4 onto a NaCl aerosol coated with stearic acid resulted in lower mass accommodation coefficients with values of 0.31 and 0.19 for aerosol with high and low stearic acid coverage, respectively. The observed decrease in a on an aerosol with a hydrocarbon coating suggests that aerosol composition is a key factor in H2SO4 adsorption on to a particle surface

An Experimental Study of Atmospheric Homogeneous Nucleation: Cluster Growth and Gas-Particle Reactions of H2SO4

The work proposed on this project included both field and laboratory studies. The laboratory studies were to consist of measurements of H2SO4 uptake and evaporation from aerosols of varying chemical composition, while the field component would include measurements of H2SO4 and other compounds which would be conducted as part of a large field campaign. By chance, the opportunity to conduct such an H2SO4/aerosol/ultrafine particle study in conjunction with an OH intercomparison/photochemistry study became available very early in this project (September 1993). This study was conducted at Caribou, Colorado in conjunction with several other groups from NCAR, NOAA and a number of universities. Our group measured OH, H2SO4, SO2, and H20, while Dr. McMurfy's group measured ultrafine particles, and total particle number and size distribution. In addition measurements of HO2/RO2, O3, NO, NO2, NO(y) CO, hydrocarbons, CH2O, and other chemical compounds and meteorological parameters were performed by the other participants and a new laser oblation/mass spectrometry technique was also employed by the NOAA Aeronomy Laboratory to study aerosol composition. The study of aerosol production and growth in conjunction with photochemical measurements is highly advantageous because particle growth precursors such as H2SO4.or MSA are formed by OH initiated sulfur oxidation. The large number of hydrocarbon measurements included in this study were also important in understanding particle growth

Baryon stopping and strange baryon/antibaryon production at SPS energies

The amount of proton stopping in central Pb+Pb collisions from 20-160 AGeV as well as hyperon and antihyperon rapidity distributions are calculated within the UrQMD model in comparison to experimental data at 40, 80 and 160 AGeV taken recently from the NA49 collaboration. Furthermore, the amount of baryon stopping at 160 AGeV for Pb+Pb collisions is studied as a function of centrality in comparison to the NA49 data. We find that the strange baryon yield is reasonably described for central collisions, however, the rapidity distributions are somewhat more narrow than the data. Moreover, the experimental antihyperon rapidity distributions at 40, 80 and 160 AGeV are underestimated by up to factors of 3 - depending on the annihilation cross section employed - which might be addressed to missing multi-meson fusion channels in the UrQMD model.Comment: 18 pages, including 7 eps figures, to be published in Phys. Rev.

Observation of neutral sulfuric acid-amine containing clusters in laboratory and ambient measurements

Recent ab initio calculations showed that amines can enhance atmospheric sulfuric acid-water nucleation more effectively than ammonia, and this prediction has been substantiated in laboratory measurements. Laboratory studies have also shown that amines can effectively displace ammonia in several types of ammonium clusters. However, the roles of amines in cluster formation and growth at a microscopic molecular scale (from molecular sizes up to 2 nm) have not yet been well understood. Processes that must be understood include the incorporation of amines into sulfuric acid clusters and the formation of organic salts in freshly nucleated particles, which contributes significantly to particle growth rates. We report the first laboratory and ambient measurements of neutral sulfuric acid-amine clusters using the Cluster CIMS, a recently-developed mass spectrometer designed for measuring neutral clusters formed in the atmosphere during nucleation. An experimental technique, which we refer to as Semi-Ambient Signal Amplification (SASA), was employed. Sulfuric acid was added to ambient air, and the concentrations and composition of clusters in this mixture were analyzed by the Cluster CIMS. This experimental approach led to significantly higher cluster concentrations than are normally found in ambient air, thereby increasing signal-to-noise levels and allowing us to study reactions between gas phase species in ambient air and sulfuric acid containing clusters. Mass peaks corresponding to clusters containing four H<sub>2</sub>SO<sub>4</sub> molecules and one amine molecule were clearly observed, with the most abundant sulfuric acid-amine clusters being those containing a C2- or C4-amine (i.e. amines with masses of 45 and 73 amu). Evidence for C3- and C5-amines (i.e. amines with masses of 59 and 87 amu) was also found, but their correlation with sulfuric acid tetramer was not as strong as was observed for the C2- and C4-amines. The formation mechanisms for those sulfuric acid-amine clusters were investigated by varying the residence time in the inlet. It was concluded that the amines react directly with neutral clusters and that ion-induced clustering of sulfuric acid cluster ions with amines was not a dominant process. Results from ambient measurements using the Cluster CIMS without addition of sulfuric acid have shown that the sulfuric acid-amine clusters were reasonably well correlated with sulfuric acid tetramer and consistent with the SASA experiments at the same Boulder sampling site. Also, clusters that contain C2- or C4-amines were more abundant and better correlated with sulfuric acid tetramer than other types of amine containing clusters. However, ambient measurements of sulfuric acid-amine clusters remain difficult and highly uncertain because their concentrations are only slightly above background levels, even during nucleation events

Photochemistry in the arctic free troposphere: Ozone budget and its dependence on nitrogen oxides and the production rate of free radicals

Abstract. Local ozone production and loss rates for the arctic free troposphere (58–85 ◦ N, 1–6 km, February–May) during the Tropospheric Ozone Production about the Spring Equinox (TOPSE) campaign were calculated using a constrained photochemical box model. Estimates were made to assess the importance of local photochemical ozone production relative to transport in accounting for the springtime maximum in arctic free tropospheric ozone. Ozone production and loss rates from our diel steady-state box model constrained by median observations were first compared to two point box models, one run to instantaneous steady-state and the other run to diel steady-state. A consistent picture of local ozone photochemistry was derived by all three box models suggesting that differences between the approaches were not critical. Our model-derived ozone production rates increased by a factor of 28 in the 1–3 km layer and a factor of 7 in the 3–6 km layer between February and May. The arctic ozone budget required net import of ozone into the arctic free troposphere throughout the campaign; however, the transport term exceeded the photochemical production only in the lower free troposphere (1–3 km) between February and March. Gross ozone production rates were calculated to increase linearly with NOx mixing ratios up to ∼300 pptv in February and for NOx mixing ratio

Coupled evolution of BrOx-ClOx-HOx-NOx chemistry during bromine-catalyzed ozone depletion events in the arctic boundary layer

Extensive chemical characterization of ozone (O3) depletion events in the Arctic boundary layer during the TOPSE aircraft mission in March–May 2000 enables analysis of the coupled chemical evolution of bromine (BrOx), chlorine (ClOx), hydrogen oxide (HOx) and nitrogen oxide (NOx) radicals during these events. We project the TOPSE observations onto an O3 chemical coordinate to construct a chronology of radical chemistry during O3 depletion events, and we compare this chronology to results from a photochemical model simulation. Comparison of observed trends in ethyne (oxidized by Br) and ethane (oxidized by Cl) indicates that ClOxchemistry is only active during the early stage of O3 depletion (O3 \u3e 10 ppbv). We attribute this result to the suppression of BrCl regeneration as O3 decreases. Formaldehyde and peroxy radical concentrations decline by factors of 4 and 2 respectively during O3 depletion and we explain both trends on the basis of the reaction of CH2O with Br. Observed NOx concentrations decline abruptly in the early stages of O3 depletion and recover as O3 drops below 10 ppbv. We attribute the initial decline to BrNO3 hydrolysis in aerosol, and the subsequent recovery to suppression of BrNO3 formation as O3 drops. Under halogen-free conditions we find that HNO4 heterogeneous chemistry could provide a major NOx sink not included in standard models. Halogen radical chemistry in the model can produce under realistic conditions an oscillatory system with a period of 3 days, which we believe is the fastest oscillation ever reported for a chemical system in the atmosphere

Marine latitude/altitude OH distributions: Comparison of Pacific Ocean observations with models

Reported here are tropical/subtropical Pacific basin OH observational data presented in a latitude/altitude geographical grid. They cover two seasons of the year (spring and fall) that reflect the timing of NASA's PEM-Tropics A (1996) and B (1999) field programs. Two different OH sensors were used to collect these data, and each instrument was mounted on a different aircraft platform (i.e., NASA's P-3B and DC-8). Collectively, these chemical snapshots of the central Pacific have revealed several interesting trends. Only modest decreases (factors of 2 to 3) were found in the levels of OH with increasing altitude (0-12 km). Similarly, only modest variations were found (factors of 1.5 to 3.5) when the data were examined as a function of latitude (30° N to 30° S). Using simultaneously recorded data for CO, O3, H2O, NO, and NMHCs, comparisons with current models were also carried out. For three out of four data subsets, the results revealed a high level of correspondence. On average, the box model results agreed with the observations within a factor of 1.5. The comparison with the three-dimensional model results was found to be only slightly worse. Overall, these results suggest that current model mechanisms capture the major photochemical processes controlling OH quite well and thus provide a reasonably good representation of OH levels for tropical marine environments. They also indicate that the two OH sensors employed during the PEM-Tropics B study generally saw similar OH levels when sampling a similar tropical marine environment. However, a modest altitude bias appears to exist between these instruments. More rigorous instrument intercomparison activity would therefore seem to be justified. Further comparisons of model predictions with observations are also recommended for nontropical marine environments as well as those involving highly elevated levels of reactive non-methane hydrocarbons. Copyright 2001 by the American Geophysical Union

Ozone depletion events observed in the high latitude surface layer during the TOPSE aircraft program

During the Tropospheric Ozone Production about the Spring Equinox (TOPSE) aircraft program, ozone depletion events (ODEs) in the high latitude surface layer were investigated using lidar and in situ instruments. Flight legs of 100 km or longer distance were flown 32 times at 30 m altitude over a variety of regions north of 58° between early February and late May 2000. ODEs were found on each flight over the Arctic Ocean but their occurrence was rare at more southern latitudes. However, large area events with depletion to over 2 km altitude in one case were found as far south as Baffin Bay and Hudson Bay and as late as 22 May. There is good evidence that these more southern events did not form in situ but were the result of export of ozone-depleted air from the surface layer of the Arctic Ocean. Surprisingly, relatively intact transport of ODEs occurred over distances of 900–2000 km and in some cases over rough terrain. Accumulation of constituents in the frozen surface over the dark winter period cannot be a strong prerequisite of ozone depletion since latitudes south of the Arctic Ocean would also experience a long dark period. Some process unique to the Arctic Ocean surface or its coastal regions remains unidentified for the release of ozone-depleting halogens. There was no correspondence between coarse surface features such as solid ice/snow, open leads, or polynyas with the occurrence of or intensity of ozone depletion over the Arctic or subarctic regions. Depletion events also occurred in the absence of long-range transport of relatively fresh “pollution” within the high latitude surface layer, at least in spring 2000. Direct measurements of halogen radicals were not made. However, the flights do provide detailed information on the vertical structure of the surface layer and, during the constant 30 m altitude legs, measurements of a variety of constituents including hydroxyl and peroxy radicals. A summary of the behavior of these constituents is made. The measurements were consistent with a source of formaldehyde from the snow/ice surface. Median NOx in the surface layer was 15 pptv or less, suggesting that surface emissions were substantially converted to reservoir constituents by 30 m altitude and that ozone production rates were small (0.15–1.5 ppbv/d) at this altitude. Peroxyacetylnitrate (PAN) was by far the major constituent of NOy in the surface layer independent of the ozone mixing ratio