The reaction Cl + H2CO yields HCl + HCO: Decreased sensitivity of stratospheric ozone to chlorine perturbations

The absolute rate constant for the reaction Cl + H2CO yields HCl + HCO was determined by the flash-photolysis resonance fluorescence method to be 7.5 plus or minus 0.9 (2 sigma) times 10 to the minus 11th power cu cm/molecule sec at 298 K and to have a negligible temperature dependence. This rate which is more than 2000 times faster than the rate of Cl + CH4 indicates that formaldehyde (H2CO) will compete significantly with methane (CH4) for the conversion of active chlorine in the stratosphere to the inactive reservoir HCl. Chlorine will thus be a less efficient destroyer of stratosphere ozone than previously believed. Ambient stratospheric ozone will depend less on the ambient chlorine amount and the predicted response to chlorine perturbations will be lessened. One-dimensional eddy-diffusion photochemical model calculations indicate a factor of 1.1 less sensitivity to chlorine than recently reported. For a steady-state CFM release at 1975 rates (750,000 tons/year) the eventual ozone depletion is now calculated to be 14%

Trends in stratospheric minor constituents

Photochemical models predict that increasing source gas concentrations are also expected to lead to changes in the concentrations of both catalytically active radical species (such as NO2, ClO, and OH) and inactive reservoir species (such as HNO3, HCl, and H2O). For simplicity, we will refer to all these as trace species. Those species that are expected to have increasing concentration levels are investigated. Additionally, the trace species concentration levels are monitored for unexpected changes on the basis of the measure increase in source gases. Carrying out these investigations is difficult due to the limited data base of measurements of stratospheric trace species. In situ measurements are made only infrequently, and there are few satelliteborne measurements, most over a time space insufficient for trend determination. Instead, ground-based measurements of column content must be used for many species, and interpretation is complicated by contributions from the troposphere or mesosphere or both. In this chapter, we examine existing measurements as published or tabulated

Examination of the material removal mechanisms during the lapping process of advanced ceramic rolling elements

Two types of HIPed Si3N4 bearing ball blanks with different surface hardness and fracture toughness were lapped under various loads, speeds, and lubricants using a novel eccentric lapping machine. The lapped surfaces were examined by optical microscope and SEM. The experimental results show that the material removal rate for type I ball blanks were 3-4-fold of type 2 in most cases. Different lapping fluids affected the material removal rate at lower lapping loads, but they had much less influence on the material removal rate at higher lapping loads. The SEM micrographs reveal that the grain pullout prevailed on the lapped surface of type I ball blanks, and the surface of type 2 featured bulk material removal by microcracking. Under extreme high lapping load, surface cracks and damages were found, and SEM with EDX disclosed steel from the lapping plate had transferred to the ceramic ball surface. The preliminary conclusion is that the material removal mechanism during the lapping process of silicon nitride balls using this eccentric lapping machine is mainly mechanical abrasive wear. Lawn and Wilshaw's indentation model on brittle materials is used to explain the difference in material removal rate for the two types of ball blanks

Potential of Virginia Mallow as an Energy Feedstock

This study aims to compare the potential of Virginia mallow to other high yielding perennial grasses and hardwoods by characterising and comparing fast pyrolysis product yields. Feedstocks selected for this study include miscanthus (Miscanthus x giganteus), Virginia mallow (Sida hermaphrodita), willow short rotation coppice (SRC) (Salix viminalis) and oak (Quercus robur). The experimental work was split into two sections: analytical (Py–GC–MS) and laboratory-scale processing using a 300 g h−1 continuous bubbling fluidised bed reactor. Pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS) has been used to quantify pyrolysis products from these feedstocks by simulating fast pyrolysis heating rates using a CDS 5200 pyrolyser closed coupled to a PerkinElmer Clarus 680 GC–MS. High bio-oil yields were achieved for Virginia mallow, willow SRC and oak (65.36, 62.55 and 66.43 wt% respectively), but miscanthus only produced a yield of 53.46 wt% due to increased feedstock ash content. The water content in the bio-oil is highest from miscanthus (17.64 wt%) and relatively low in the Virginia mallow and hardwoods willow SRC and oak (12.49, 13.88 and 14.53 wt%). Similar high yields of bio-oil and low yields of char and non-condensable gas compared to willow SRC make Virginia mallow an attractive feedstock for fast pyrolysis processing. Graphic Abstract: [Figure not available: see fulltext.]

Trends in total column ozone measurements

It is important to ensure the best available data are used in any determination of possible trends in total ozone in order to have the most accurate estimates of any trends and the associated uncertainties. Accordingly, the existing total ozone records were examined in considerable detail. Once the best data set has been produced, the statistical analysis must examine the data for any effects that might indicate changes in the behavior of global total ozone. The changes at any individual measuring station could be local in nature, and herein, particular attention was paid to the seasonal and latitudinal variations of total ozone, because two dimensional photochemical models indicate that any changes in total ozone would be most pronounced at high latitudes during the winter months. The conclusions derived from this detailed examination of available total ozone can be split into two categories, one concerning the quality and the other the statistical analysis of the total ozone record

Theory and observations: Model simulations of the period 1955-1985

The main objective of the theoretical studies presented here is to apply models of stratospheric chemistry and transport in order to understand the processes that control stratospheric ozone and that are responsible for the observed variations. The model calculations are intended to simulate the observed behavior of atmospheric ozone over the past three decades (1955-1985), for which there exists a substantial record of both ground-based and, more recently, satellite measurements. Ozone concentrations in the atmosphere vary on different time scales and for several different causes. The models described here were designed to simulate the effect on ozone of changes in the concentration of such trace gases as CFC, CH4, N2O, and CO2. Changes from year to year in ultraviolet radiation associated with the solar cycle are also included in the models. A third source of variability explicitly considered is the sporadic introduction of large amounts of NO sub x into the stratosphere during atmospheric nuclear tests

Titania aerogels: Preparation and photocatalytic tests

Titania aerogels are suggested as promising photocatalysts [1]. In the present study aerogels were synthesised by sol-gel method combined with supercritical drying. Tetraisopropyl orthotitanate was used as a precursor, anhydrous methanol and isopropanol as solvents. Three aerogels were prepared using different ways of synthesis. Volumes and surface areas of micro- and mesopores of each aerogel were determined. XRD and SEM analyses were carried out. For comparison analyses were also performed for TiO2 P25 Degussa. Aerogels' BET surface areas ranged from 73 to 96 m2g-1. They indicate the crystalline structure of anatase. Finally photocatalytic tests were performed using water solution of p-chlorophenol and 4-hydroxybenzoic acid. Experiments were carried out in the Solar box simulating sun irradiation and on location. Aerogel Z513 prepared using 30% of precursor (tetraisopropyl orthotitanate) in isopropanol as a solvent indicates the best photocatalytic activity towards p-chlorophenol while Z516 prepared using 60% of precursor in methanol towards 4-hydroxybenzoic acid

One Versus Two Handedness: Directional Preference in a Silent-Failure Scenario

This study focused on the direction drivers of a self-driving car will turn to avoid a crash at a T-intersection. We hypothesized that drivers would steer differently when they drive using both hands and when they use their dominant hand only. Specifically, we hypothesized that participants would favor the direction of their dominant hand (if they use their dominant hand only) and that there with be no directional preference if driving with both hands.. To test this hypothesis, we implemented a driving simulator study. We asked the participants to use either both their hands or only their dominant hand to avoid a crash. We are currently analyzing the data. Keywords: one-handed, two-handed, automated vehicle, silent takeover, directional preferenc

Finding the Missing Stratospheric Br(sub y): A Global Modeling Study of CHBr3 and CH2Br2

Recent in situ and satellite measurements suggest a contribution of ~5 pptv to stratospheric inorganic bromine from short-lived bromocarbons. We conduct a modeling study of the two most important short-lived bromocarbons, bromoform (CHBr3) and dibromomethane (CH2Br2), with the Goddard Earth Observing System Chemistry Climate Model (GEOS CCM) to account for this missing stratospheric bromine. We derive a "top-down" emission estimate of CHBr3 and CH2Br2 using airborne measurements in the Pacific and North American troposphere and lower stratosphere obtained during previous NASA aircraft campaigns. Our emission estimate suggests that to reproduce the observed concentrations in the free troposphere, a global oceanic emission of 425 Gg Br yr(exp -1) for CHBr3 and 57 Gg Br yr(exp -l) for CH2Br2 is needed, with 60% of emissions from open ocean and 40% from coastal regions. Although our simple emission scheme assumes no seasonal variations, the model reproduces the observed seasonal variations of the short-lived bromocarbons with high concentrations in winter and low concentrations in summer. This indicates that the seasonality of short-lived bromocarbons is largely due to seasonality in their chemical loss and transport. The inclusion of CHBr3 and CH2Br2 contributes ~5 pptv bromine throughout the stratosphere. Both the source gases and inorganic bromine produced from source gas degradation (Br~SLS) in the troposphere are transported into the stratosphere, and are equally important. Inorganic bromine accounts for half (2.5 pptv) of the bromine from the inclusion of CHBr3 and CHzBr2 near the tropical tropopause and its contribution rapidly increases to ~ 100% as altitude increases. More than 85% of the wet scavenging of Br(sub y)(sup VSLS) occurs in large-scale precipitation below 500 hPa. Our sensitivity study with wet scavenging in convective updrafts switched off suggests that Br(sub y)(sup SLS) in the stratosphere is not sensitive to convection. Convective scavenging only accounts for ~0.2 pptv (4%) difference in inorganic bromine delivered to the stratosphere