Large-scale distributions of tropospheric nitric, formic, and acetic acids over the western Pacific basin during wintertime

We report here measurements of the acidic gases nitric (HNO3), formic (HCOOH), and acetic (CH3COOH) over the western Pacific basin during the February-March 1994 Pacific Exploratory Mission-West (PEM-West B). These data were obtained aboard the NASA DC-8 research aircraft as it flew missions in the altitude range of 0.3–12.5 km over equatorial regions near Guam and then further westward encompassing the entire Pacific Rim arc. Aged marine air over the equatorial Pacific generally exhibited mixing ratios of acidic gases \u3c100 parts per trillion by volume (pptv). Near the Asian continent, discrete plumes encountered below 6 km altitude contained up to 8 parts per billion by volume (ppbv) HNO3 and 10 ppbv HCOOH and CH3COOH. Overall there was a general correlation between mixing ratios of acidic gases with those of CO, C2H2, and C2Cl4, indicative of emissions from combustion and industrial sources. The latitudinal distributions of HNO3 and CO showed that the largest mixing ratios were centered around 15°N, while HCOOH, CH3COOH, and C2Cl4 peaked at 25°N. The mixing ratios of HCOOH and CH3COOH were highly correlated (r2 = 0.87) below 6 km altitude, with a slope (0.89) characteristic of the nongrowing season at midlatitudes in the northern hemisphere. Above 6 km altitude, HCOOH and CH3COOH were marginally correlated (r2 = 0.50), and plumes well defined by CO, C2H2, and C2Cl4 were depleted in acidic gases, most likely due to scavenging during vertical transport of air masses through convective cloud systems over the Asian continent. In stratospheric air masses, HNO3 mixing ratios were several parts per billion by volume (ppbv), yielding relationships with O3 and N2O consistent with those previously reported for NOy

Chemical NOx budget in the upper troposphere over the tropical South Pacific

The chemical NOx budget in the upper troposphere over the tropical South Pacific is analyzed using aircraft measurements made at 6-12 km altitude in September 1996 during the Global Tropospheric Experiment (GTE) Pacific Exploratory Mission (PEM) Tropics A campaign. Chemical loss and production rates of NOx along the aircraft flight tracks are calculated with a photochemical model constrained by observations. Calculations using a standard chemical mechanism show a large missing source for NOx; chemical loss exceeds chemical production by a factor of 2.4 on average. Similar or greater NOx budget imbalances have been reported in analyses of data from previous field studies. Ammonium aerosol concentrations in PEM-Tropics A generally exceeded sulfate on a charge equivalent basis, and relative humidities were low (median 25% relative to ice). This implies that the aerosol could be dry in which case N2O5 hydrolysis would be suppressed as a sink for NOx. Suppression of N2O5 hydrolysis and adoption of new measurements of the reaction rate constants for NO2 + OH + M and HNO3 + OH reduces the median chemical imbalance in the NOx budget for PEM-Tropics A from 2.4 to 1.9. The remaining imbalance cannot be easily explained from known chemistry or long-range transport of primary NOx and may imply a major gap in our understanding of the chemical cycling of NOx in the free troposphere. Copyright 2000 by the American Geophysical Union

Kinetic analysis of a chiral granular motor

We study the properties of a heterogeneous, chiral granular rotor that is capable of performing useful work when immersed in a bath of thermalized particles. The dynamics can be obtained in general from a numerical solution of the Boltzmann-Lorentz equation. We show that a mechanical approach gives the exact mean angular velocity in the limit of an infinitely massive rotor. We examine the dependence of the mean angular velocity on the coefficients of restitution of the two materials composing the motor. We compute the power and efficiency and compare with numerical simulations. We also perform a realistic numerical simulation of a granular rotor which shows that the presence of non uniformity of the bath density within the region where the motor rotates, and that the ratchet effect is slightly weakened, but qualitatively sustained. Finally we discuss the results in connection with recent experiments.Comment: 19 pages, 12 figure

Evolution and chemical consequences of lightning-produced NOx observed in the North Atlantic upper troposphere

Airborne observations of NO during the Subsonics Assessment Ozone and Nitrogen Oxides Experiment (SONEX) reveal episodes of high NOx in the upper troposphere believed to be associated with lightning. Linkage to specific periods of lightning activity is possible through back trajectories and data from the National Lightning Detection Network. Lagrangian model calculations are used to explore the evolution of these high NOx plumes over the 1-2 days between their introduction and subsequent sampling by NASA's DC-8 aircraft. Simulations include expected changes in HNO3, H2O2, CH3OOH, HO2, and OH. Depending on the time of injection and dilution rate, initial NOx concentrations are estimated to range from 1 to 7 ppbv. Similar to many previous studies, simulated HNO3 concentrations tend to be greater than observations. Several possible explanations for this difference are explored. H2O2 observations are shown to be consistent with removal in convective activity. While it is possible that upper tropospheric CH3OOH is enhanced by convection, simulations show such increases in CH3OOH can be short-lived (e.g., < 12 hours) with no perceptible trace remaining at the time of sampling. High NO levels further prevent elevated levels of CH3OOH from propagating into increases in H2O2. HO2 is suppressed through reaction with NO in all cases. Simulated increases in OH exceeded a factor of 2 for some cases, but for the highest NOx levels, loss of OH via OH+NO2 offset production from HO2+NO. Additional increases in OH of 30-60% could result from convection of CH3OOH. A final point of discussion concerns how the chemistry within these plumes, their long-range transport, and their potential importance in sustaining background NOx far from source regions present a challenge to global and regional model simulations. Copyright 2000 by the American Geophysical Union

Summertime partitioning and budget of NOycompounds in the troposphere over Alaska and Canada: ABLE 3B

As part of NASA's Arctic Boundary Layer Expedition 3A and 3B field measurement programs, measurements of NO(x) HNO31, PAN, PPN, and NOy were made in the middle to lower troposphere over Alaska and Canada during the summers of 1988 and 1990. These measurements are used to assess the degree of closure within the reactive odd nitrogen (NxOy) budget through the comparison of the values of NOy measured with a catalytic convertor to the sum of individually measured NOy(i) compounds (i.e., Sigma NOy(i) = NOx + HNO3 + PAN + PPN). Significant differences were observed between the various study regions. In the lower 6 km of the troposphere over Alaska and the Hudson Bay lowlands of Canada a significant traction of the NOy budget (30 to 60 per cent) could not be accounted for by the measured Sigma NOy(i). This deficit in the NOy budget is about 100 to 200 parts per trillion by volume (pptv) in the lower troposphere (0.15 to 3 km) and about 200 to 400 pptv in the middle free troposphere (3 to 6.2 km). Conversely, the NOy budget in the northern Labrador and Quebec regions or Canada is almost totally accounted for within the combined measurement uncertainties of NOy and the various NOy(i) compounds. A substantial portion of the NOx budget's 'missing compounds' appears to be coupled to the photochemical and/or dynamical parameters influencing the tropospheric oxidative potential over these regions. A combination of factors are suggested as the causes for the variability observed in the NOy budget. In addition, the apparent stability of compounds represented by the NOy budget deficit in the lower-attitude range questions the ability of these compounds to participate as reversible reservoirs for "active" odd nitrogen and suggest that some portion of the NOy budget may consist of relatively unreactive nitrogencontaining compounds. Bei der Rationalisierung von Kommissioniersystemen besteht bei vielen Unternehmen noch Nachholbedarf. Dies ergab eine Umfrage des Fraunhofer-Instituts für Materialfluss und Logistik in Dortmund bei ca. 800 Unternehmen. Keins der Unternehmen setzt Kommissionierautomaten ein, die Voraussetzungen für durchgehende Automatisierung fehlen

Implications of large scale shifts in tropospheric NOx levels in the remote tropical Pacific

A major observation recorded during NASA's western Pacific Exploratory Mission (PEM-West B) was the large shift in tropical NO levels as a function of geographical location. High-altitude NO levels exceeding 100 pptv were observed during portions of tropical flights 5-8, while values almost never exceeded 20 pptv during tropical flights 9 and 10. The geographical regions encompassing these two flight groupings are here labeled "high" and "low" NOx regimes. A comparison of these two regimes, based on back trajectories and chemical tracers, suggests that air parcels in both were strongly influenced by deep convection. The low NOx regime appears to have been predominantly impacted by marine convection, whereas the high NOx regime shows evidence of having been more influenced by deep convection over a continental land mass. DMSP satellite observations point strongly toward lightning as the major source of NOx in the latter regime. Photochemical ozone formation in the high NOx regime exceeded that for low NOx by factors of 2 to 6, whereas O3 destruction in the low NOx regime exceeded that for high NOx by factors of up to 3. Taking the tropopause height to be 17 km, estimates of the net photochemical effect on the O3 column revealed that the high NOx regime led to a small net production. By contrast, the low NOx regime was shown to destroy O3 at the rate of 3.4% per day. One proposed mechanism for off-setting this projected large deficit would involve the transport of O3 rich midlatitude air into the tropics. Alternatively, it is suggested that O3 within the tropics may be overall near self-sustaining with respect to photochemical activity. This scenario would require that some tropical regions, unsampled at the time of PEM-B, display significant net column O3 production, leading to an overall balanced budget for the "greater" tropical Pacific basin. Details concerning the chemical nature of such regimes are discussed

Influence of biomass combustion emissions on the distribution of acidic trace gases over the southern Pacific basin during austral springtime

This paper describes the large-scale distributions of HNO3, HCOOH, and CH3COOH over the central and South Pacific basins during the Pacific Exploratory Mission-Tropics (PEM-Tropics) in austral springtime. Because of the remoteness of this region from continental areas, low part per trillion by volume (pptv) mixing ratios of acidic gases were anticipated to be pervasive over the South Pacific basin. However, at altitudes of 2–12 km over the South Pacific, air parcels were encountered frequently with significantly enhanced mixing ratios (up to 1200 pptv) of acidic gases. Most of these air parcels were centered in the 3–7 km altitude range and occurred within the 15°−65°S latitudinal band. The acidic gases exhibited an overall general correlation with CH3Cl, PAN, and O3, suggestive of photochemical and biomass burning sources. There was no correlation or trend of acidic gases with common industrial tracer compounds (e.g., C2Cl4 or CH3CCl3). The combustion emissions sampled over the South Pacific basin were relatively aged exhibiting C2H2/CO ratios in the range of 0.2–2.2 pptv/ppbv. The relationships between acidic gases and this ratio were similar to what was observed in aged air parcels (i.e., \u3e3–5 days since they were over a continental area) over the western North Pacific during the Pacific Exploratory Mission-West Phases A and B (PEM-West A and B). In the South Pacific marine boundary layer a median C2H2/CO ratio of 0.6 suggested that this region was generally not influenced by direct inputs of biomass combustion emissions. Here we observed the lowest mixing ratios of acidic gases, with median values of 14 pptv for HNO3, 19 pptv for HCOOH, and 18 pptv for CH3COOH. These values were coincident with low mixing ratios of NOx(\u3c10 pptv), CO (≈50 parts per billion by volume (ppbv)), O3 (\u3c 20 ppbv), and long-lived hydrocarbons (e.g., C2H6 \u3c300 pptv). Overall, the PEM-Tropics data suggest an important influence of aged biomass combustion emissions on the distributions of acidic gases over the South Pacific basin in austral springtime

Identification and characterization of an imidazolium by-product formed during the synthesis of 4-methylmethcathinone (mephedrone)

4-Methylmethcathinone (2-methylamino-1-(4-methylphenyl)propan-1-one, mephedrone) is a psychoactive substance that has been associated with recreational use worldwide. Analytical data related to mephedrone are abundantly available but the characterization of by-products obtained during organic synthesis remains to be explored. This study presents the identification of a 1,2,3,5-tetramethyl-4-(4-methylphenyl)-1H-imidazol-3-ium salt (TMMPI), which was formed during the synthesis of mephedrone. When diethyl ether was added to the crude reaction product, solid material precipitated from the solution. Analytical characterization of TMMPI employed a range of analytical techniques including chromatographic analysis in combination with various mass spectrometric detection methods, nuclear magnetic resonance spectroscopy, and crystal structure analysis. Additional confirmation was obtained from organic synthesis of the imidazolium by-product. When TMMPI was subjected to analysis by gas chromatography-mass spectrometry (GC-MS), isomerization and degradation into two distinct compounds were observed, which pointed towards thermal instability under GC conditions. A liquid chromatography-mass spectrometry (LC-MS) based investigation into a micro-scale synthesis of mephedrone and three additional analogues revealed that the corresponding TMMPI analogue was formed. Interestingly, storage of mephedrone freebase in a number of organic solvents also gave rise to TMMPI and it appeared that its formation during storage was significantly reduced in the absence of air. The present study aimed to support clandestine forensic investigations by employing analytical strategies that are applicable to manufacturing sites. The imidazolium salts will most likely be found amongst the waste products of any clandestine lab site under investigation rather than with the desired product

Jamming coverage in competitive random sequential adsorption of binary mixture

We propose a generalized car parking problem where cars of two different sizes are sequentially parked on a line with a given probability $q$. The free parameter $q$ interpolates between the classical car parking problem of only one car size and the competitive random sequential adsorption (CRSA) of a binary mixture. We give an exact solution to the CRSA rate equations and find that the final coverage, the jamming limit, of the line is always larger for a binary mixture than for the uni-sized case. The analytical results are in good agreement with our direct numerical simulations of the problem.Comment: 4 pages 2-column RevTeX, Four figures, (there was an error in the previous version. We replaced it (including figures) with corrected and improved version that lead to new results and conclusions