Ozone decomposition kinetics on alumina: effects of ozone partial pressure, relative humidity and state of film oxidation

International audienceThe room temperature kinetics of gas-phase ozone loss via heterogeneous interactions with thin alumina films has been studied in real-time using 254 nm absorption spectroscopy to monitor ozone concentrations. The films were prepared from dispersions of fine alumina powder in methanol and their surface areas were determined by an in situ procedure using adsorption of krypton at 77 K. The alumina was found to lose reactivity with increasing ozone exposure. However, some of the lost reactivity could be recovered over timescales of days in an environment free of water, ozone and carbon dioxide. From multiple exposures of ozone to the same film it was found that the number of active sites is large, greater than 1.4×1014 active sites per cm2 of surface area, or comparable to the total number of surface sites. The films maintain some reactivity at this point, which is consistent with there being some degree of active site regeneration during the experiment and with ozone loss being catalytic to some degree. The initial uptake coefficients on fresh films were found to be inversely dependent on the starting ozone concentration varying from roughly 10?6 for ozone concentrations of 1014 molecules/cm3 to 10?5 at 1013 molecules/cm3. The initial uptake coefficients were not dependent on the relative humidity, up to 75%, within the precision of the experiment. The reaction mechanism is discussed, as well as the implications these results have for assessing the effect of mineral dust on atmospheric oxidant levels

Ozone decomposition kinetics on alumina: effects of ozone partial pressure, relative humidity and repeated oxidation cycles

International audienceThe room temperature kinetics of gas-phase ozone loss via heterogeneous interactions with thin alumina films has been studied in real-time using 254nm absorption spectroscopy to monitor ozone concentrations. The films were prepared from dispersions of fine alumina powder in methanol and their surface areas were determined by an in situ procedure using adsorption of krypton at 77K. The alumina was found to lose reactivity with increasing ozone exposure. However, some of the lost reactivity could be recovered over timescales of days in an environment free of water, ozone and carbon dioxide. From multiple exposures of ozone to the same film, it was found that the number of active sites is large, greater than 1.4x1014 active sites per cm2 of surface area or comparable to the total number of surface sites. The films maintain some reactivity at this point, which is consistent with there being some degree of active site regeneration during the experiment and with ozone loss being catalytic to some degree. The initial uptake coefficients on fresh films were found to be inversely dependent on the ozone concentration, varying from roughly 10-6 for ozone concentrations of 1014 molecules/cm3 to 10-5 at 1013 molecules/cm3. The initial uptake coefficients were not dependent on the relative humidity, up to 75%, within the precision of the experiment. The reaction mechanism is discussed, as well as the implications these results have for assessing the effect of mineral dust on atmospheric oxidant levels

Ozone decomposition kinetics on alumina: effects of ozone partial pressure, relative humidity and repeated oxidation cycles

The room temperature kinetics of gas-phase ozone loss via heterogeneous interactions with thin alumina films has been studied in real-time using 254nm absorption spectroscopy to monitor ozone concentrations. The films were prepared from dispersions of fine alumina powder in methanol and their surface areas were determined by an in situ procedure using adsorption of krypton at 77K. The alumina was found to lose reactivity with increasing ozone exposure. However, some of the lost reactivity could be recovered over timescales of days in an environment free of water, ozone and carbon dioxide. From multiple exposures of ozone to the same film, it was found that the number of active sites is large, greater than 1.4x1014 active sites per cm2 of surface area or comparable to the total number of surface sites. The films maintain some reactivity at this point, which is consistent with there being some degree of active site regeneration during the experiment and with ozone loss being catalytic to some degree. The initial uptake coefficients on fresh films were found to be inversely dependent on the ozone concentration, varying from roughly 10-6 for ozone concentrations of 1014 molecules/cm3 to 10-5 at 1013 molecules/cm3. The initial uptake coefficients were not dependent on the relative humidity, up to 75%, within the precision of the experiment. The reaction mechanism is discussed, as well as the implications these results have for assessing the effect of mineral dust on atmospheric oxidant levels

Denying humanness to victims: How gang members justify violent behavior

The high prevalence of violent offending amongst gang-involved youth has been established in the literature. Yet the underlying psychological mechanisms that enable youth to engage in such acts of violence remain unclear. 189 young people were recruited from areas in London, UK, known for their gang activity. We found that gang members, in comparison to non-gang youth, described the groups they belong to as having recognized leaders, specific rules and codes, initiation rituals, and special clothing. Gang members were also more likely than non-gang youth to engage in violent behavior and endorse moral disengagement strategies (i.e., moral justification, euphemistic language, advantageous comparison, displacement of responsibility, attribution of blame, and dehumanization). Finally, we found that dehumanizing victims partially mediated the relationship between gang membership and violent behavior. These findings highlight the effects of groups at the individual level and an underlying psychological mechanism that explains, in part, how gang members engage in violence

The Role of Sulfur Dioxide in Stratospheric Aerosol Formation Evaluated by Using in situ Measurements in the Tropical Lower Stratosphere

Stratospheric aerosols (SAs) are a variable component of the Earth\u27s albedo that may be intentionally enhanced in the future to offset greenhouse gases (geoengineering). The role of tropospheric-sourced sulfur dioxide (SO2) in maintaining background SAs has been debated for decades without in situ measurements of SO2 at the tropical tropopause to inform this issue. Here we clarify the role of SO2 in maintaining SAs by using new in situ SO2 measurements to evaluate climate models and satellite retrievals. We then use the observed tropical tropopause SO2 mixing ratios to estimate the global flux of SO2 across the tropical tropopause. These analyses show that the tropopause background SO2 is about 5 times smaller than reported by the average satellite observations that have been used recently to test atmospheric models. This shifts the view of SO2 as a dominant source of SAs to a near-negligible one, possibly revealing a significant gap in the SA budget. ©2017. American Geophysical Union

The NASA Airborne Tropical TRopopause EXperiment (ATTREX):High-Altitude Aircraft Measurements in the Tropical Western Pacific

The February through March 2014 deployment of the NASA Airborne Tropical TRopopause EXperiment (ATTREX) provided unique in situ measurements in the western Pacific Tropical Tropopause Layer (TTL). Six flights were conducted from Guam with the long-range, high-altitude, unmanned Global Hawk aircraft. The ATTREX Global Hawk payload provided measurements of water vapor, meteorological conditions, cloud properties, tracer and chemical radical concentrations, and radiative fluxes. The campaign was partially coincident with the CONTRAST and CAST airborne campaigns based in Guam using lower-altitude aircraft The ATTREX dataset is being used for investigations of TTL cloud, transport, dynamical, and chemical processes as well as for evaluation and improvement of global-model representations of TTL processes

Distribution of lead in single atmospheric particles

Three independent single particle mass spectrometers measured Pb in individual aerosol particles. These data provide unprecedented sensitivity and statistical significance for the measurement of Pb in single particles. This paper explores the reasons for the frequency of Pb in fine particles now that most gasoline is unleaded. Trace amounts of Pb were found in 5 to 25% of 250 to 3000 nm diameter particles sampled by both aircraft and surface instruments in the eastern and western United States. Over 5% of particles at a mountain site in Switzerland contained Pb. Particles smaller than 100 nm with high Pb content were also observed by an instrument that was only operated in urban areas. Lead was found on all types of particles, including Pb present on biomass burning particles from remote fires. Less common particles with high Pb contents contributed a majority of the total amount of Pb. Single particles with high Pb content often also contained alkali metals, Zn, Cu, Sn, As, and Sb. The association of Pb with Zn and other metals is also found in IMPROVE network filter data from surface sites. Sources of airborne Pb in the United States are reviewed for consistency with these data. The frequent appearance of trace Pb is consistent with widespread emissions of fine Pb particles from combustion sources followed by coagulation with larger particles during long-range transport. Industrial sources that directly emit Pb-rich particles also contribute to the observations. Clean regions of the western United States show some transport of Pb from Asia but most Pb over the United States comes from North American sources. Resuspension of Pb from soil contaminated by the years of leaded gasoline was not directly apparent

Confronting gang membership and youth violence: Intervention challenges and potential futures

Evaluation of approaches and psychological obstacles to tackling youth gang involvement

Design, development and validity testing of the Gang Affiliation Risk Measure (GARM)

This study aimed to create a measure of risk for gang affiliation, for use in the UK. A pilot stage invited gang affiliated and non-gang affiliated participants between the ages of 16–25 years to retrospectively self-report on 58 items of risk exposure at the age of 11 years. Based on performance of these items, a 26-item measure was developed and administered to a main study sample (n=185) of gang affiliated and non-gang affiliated participants. Categorical Principal Component Analysis was applied to data, yielding a single-factor solution (historic lack of safety and current perception of threat). A 15-item gang affiliation risk measure (GARM) was subsequently created. The GARM demonstrated good internal consistency, construct validity and discriminative ability. Items from the GARM were then transformed to read prospectively, resulting in a test measure for predictive purposes (T-GARM). The T-GARM requires further validation regarding its predictive utility and generalisability. However, this study has resulted in the first measure of gang affiliation, with promising results

The Role of Sulfur Dioxide in Stratospheric Aerosol Formation Evaluated Using In Situ Measurements in the Tropical Lower Stratosphere

Stratospheric aerosols (SAs) are a variable component of the Earth's albedo that may be intentionally enhanced in the future to offset greenhouse gases (geoengineering). The role of tropospheric-sourced sulfur dioxide (SO2) in maintaining background SAs has been debated for decades without in-situ measurements of SO2 at the tropical tropopause to inform this issue. Here we clarify the role of SO2 in maintaining SAs by using new in-situ SO2 measurements to evaluate climate models and satellite retrievals. We then use the observed tropical tropopause SO2 mixing ratios to estimate the global flux of SO2 across the tropical tropopause. These analyses show that the tropopause background SO2 is about 5 times smaller than reported by the average satellite observations that have been used recently to test atmospheric models. This shifts the view of SO2 as a dominant source of SAs to a near-negligible one, possibly revealing a significant gap in the SA budget