The impact of air pollutant and methane emission controls on tropospheric ozone and radiative forcing: CTM calculations for the period 1990-2030

To explore the relationship between tropospheric ozone and radiative forcing with changing emissions, we compiled two sets of global scenarios for the emissions of the ozone precursors methane (CH₄), carbon monoxide (CO), non-methane volatile organic compounds (NMVOC) and nitrogen oxides (NO_x) up to the year 2030 and implemented them in two global Chemistry Transport Models. The 'Current Legislation' (CLE) scenario reflects the current perspectives of individual countries on future economic development and takes the anticipated effects of presently decided emission control legislation in the individual countries into account. In addition, we developed a 'Maximum technically Feasible Reduction' (MFR) scenario that outlines the scope for emission reductions offered by full implementation of the presently available emission control technologies, while maintaining the projected levels of anthropogenic activities. Whereas the resulting projections of methane emissions lie within the range suggested by other greenhouse gas projections, the recent pollution control legislation of many Asian countries, requiring introduction of catalytic converters for vehicles, leads to significantly lower growth in emissions of the air pollutants NO_x, NMVOC and CO than was suggested by the widely used and more pessimistic IPCC (Intergovernmental Panel on Climate Change) SRES (Special Report on Emission Scenarios) scenarios (Nakicenovic et al., 2000), which made Business-as-Usual assumptions regarding emission control technology. With the TM3 and STOCHEM models we performed several long-term integrations (1990-2030) to assess global, hemispheric and regional changes in CH₄, CO, hydroxyl radicals, ozone and the radiative climate forcings resulting from these two emission scenarios. Both models reproduce broadly the observed trends in CO, and CH₄ concentrations from 1990 to 2002. <P style='line-height: 20px;'> For the 'current legislation' case, both models indicate an increase of the annual average ozone levels in the Northern Hemisphere by 5ppbv, and up to 15ppbv over the Indian sub-continent, comparing the 2020s (2020-2030) with the 1990s (1990-2000). The corresponding higher ozone and methane burdens in the atmosphere increase radiative forcing by approximately 0.2 Wm^-2. Full application of today's emissions control technologies, however, would bring down ozone below the levels experienced in the 1990s and would reduce the radiative forcing of ozone and methane to approximately -0.1 Wm^-2. This can be compared to the 0.14-0.47 Wm^-2 increase of methane and ozone radiative forcings associated with the SRES scenarios. While methane reductions lead to lower ozone burdens and to less radiative forcing, further reductions of the air pollutants NO_x and NMVOC result in lower ozone, but at the same time increase the lifetime of methane. Control of methane emissions appears an efficient option to reduce tropospheric ozone as well as radiative forcing

Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds

Kinetic and mechanistic data relevant to the tropospheric degradation of volatile organic compounds (VOC), and the production of secondary pollutants, have previously been used to define a protocol which underpinned the construction of a near-explicit Master Chemical Mechanism. In this paper, an update to the previous protocol is presented, which has been used to define degradation schemes for 107 non-aromatic VOC as part of version 3 of the Master Chemical Mechanism (MCM v3). The treatment of 18 aromatic VOC is described in a companion paper. The protocol is divided into a series of subsections describing initiation reactions, the reactions of the radical intermediates and the further degradation of first and subsequent generation products. Emphasis is placed on updating the previous information, and outlining the methodology which is specifically applicable to VOC not considered previously (e.g. <font face='Symbol' >a</font>- and <font face='Symbol' >b</font>-pinene). The present protocol aims to take into consideration work available in the open literature up to the beginning of 2001, and some other studies known by the authors which were under review at the time. Application of MCM v3 in appropriate box models indicates that the representation of isoprene degradation provides a good description of the speciated distribution of oxygenated organic products observed in reported field studies where isoprene was the dominant emitted hydrocarbon, and that the <font face='Symbol' >a</font>-pinene degradation chemistry provides a good description of the time dependence of key gas phase species in <font face='Symbol' >a</font>-pinene/NO_X photo-oxidation experiments carried out in the European Photoreactor (EUPHORE). Photochemical Ozone Creation Potentials (POCP) have been calculated for the 106 non-aromatic non-methane VOC in MCM v3 for idealised conditions appropriate to north-west Europe, using a photochemical trajectory model. The POCP values provide a measure of the relative ozone forming abilities of the VOC. Where applicable, the values are compared with those calculated with previous versions of the MCM

Atmospheric chemistry regimes in intercontinental air traffic corridors:Ozone versus NOx sensitivity

This study focusses on the environmental consequences of aircraft NOx emissions and their role and impact on ozone formation in the upper troposphere and lower stratosphere (UTLS). We use a global chemistry transport/box model approach to quantify the impacts of NOx on UTLS ozone over time scales of hours and over distance scales appropriate to air traffic corridors and aircraft flight paths. An important feature of our study has been to provide a marked contrast to the coarse spatial resolution of the global model studies typically employed to assess the impacts of aviation NOx on UTLS ozone. Real operational aviation routing data are used to quantify the NOx impacts on ozone at 235 locations on 21 flight paths. The NOx impact on ozone in the intercontinental air traffic corridors is strongest in the great circle routes from North America and Europe into Asia and weakest in the trans-polar routes. The NOx impacts identified with the CTM/box model combination are significantly smaller compared with those identified in the current global models typically used to assess aviation NOx impacts. Further research is required to confirm our assessment of those flight paths that appear to show greatest NOx – O3 impacts and those the least and extend our analyses into the tropics and southern hemisphere

Acid-yield measurements of the gas-phase ozonolysis of ethene as a function of humidity using Chemical Ionisation Mass Spectrometry (CIMS)

Gas-phase ethene ozonolysis experiments were conducted at room temperature to determine formic acid yields as a function of relative humidity (RH) using the integrated EXTreme RAnge chamber-Chemical Ionisation Mass Spectrometry technique, employing a CH&lt;sub&gt;3&lt;/sub&gt;I ionisation scheme. RHs studied were &lt;1, 11, 21, 27, 30 % and formic acid yields of (0.07±0.01) and (0.41±0.07) were determined at &lt;1 % RH and 30 % RH respectively, showing a strong water dependence. It has been possible to estimate the ratio of the rate coefficient for the reaction of the Criegee biradical, CH&lt;sub&gt;2&lt;/sub&gt;OO with water compared with decomposition. This analysis suggests that the rate of reaction with water ranges between 1×10&lt;sup&gt;−12&lt;/sup&gt;–1×10&lt;sup&gt;−15&lt;/sup&gt; cm&lt;sup&gt;3&lt;/sup&gt; molecule&lt;sup&gt;−1&lt;/sup&gt; s&lt;sup&gt;−1&lt;/sup&gt; and will therefore dominate its loss with respect to bimolecular processes in the atmosphere. Global model integrations suggest that this reaction between CH&lt;sub&gt;2&lt;/sub&gt;OO and water may dominate the production of HC(O)OH in the atmosphere

Application of ¹⁴C analyses to source apportionment of carbonaceous PM_2.5 in the UK

Determination of the radiocarbon (&lt;sup&gt;14&lt;/sup&gt;C) content of airborne particulate matter yields insight into the proportion of the carbonaceous material derived from fossil and contemporary carbon sources. Daily samples of PM&lt;sub&gt;2.5&lt;/sub&gt; were collected by high-volume sampler at an urban background site in Birmingham, UK, and the fraction of &lt;sup&gt;14&lt;/sup&gt;C in both the total carbon, and in the organic and elemental carbon fractions, determined by two-stage combustion to CO&lt;sub&gt;2&lt;/sub&gt;, graphitisation and quantification by accelerator mass spectrometry. OC and EC content was also determined by Sunset Analyzer. The mean fraction contemporary TC in the PM&lt;sub&gt;2.5&lt;/sub&gt; samples was 0.50 (range 0.27–0.66, n = 26). There was no seasonality to the data, but there was a positive trend between fraction contemporary TC and magnitude of SOC/TC ratio and for the high values of these two parameters to be associated with air-mass back trajectories arriving in Birmingham from over land. Using a five-compartment mass balance model on fraction contemporary carbon in OC and EC, the following average source apportionment for the TC in these PM&lt;sub&gt;2.5&lt;/sub&gt; samples was derived: 27% fossil EC; 20% fossil OC; 2% biomass EC; 10% biomass OC; and 41% biogenic OC. The latter category will comprise, in addition to BVOC-derived SOC, other non-combustion contemporary carbon sources such as biological particles, vegetative detritus, humic material and tyre wear. The proportion of total PM&lt;sub&gt;2.5&lt;/sub&gt; at this location estimated to derive from BVOC-derived secondary organic aerosol was 9–29%. The findings from this work are consistent with those from elsewhere in Europe and support the conclusion of a significant and ubiquitous contribution from non-fossil biogenic sources to the carbon in terrestrial aerosol

Chemical nonlinearities in relating intercontinental ozone pollution to anthropogenic emissions

Model studies typically estimate intercontinental influence on surface ozone by perturbing emissions from a source continent and diagnosing the ozone response in the receptor continent. Since the response to perturbations is non-linear due to chemistry, conclusions drawn from different studies may depend on the magnitude of the applied perturbation. We investigate this issue for intercontinental transport between North America, Europe, and Asia with sensitivity simulations in three global chemical transport models. In each region, we decrease anthropogenic emissions of NOx and nonmethane volatile organic compounds (NMVOCs) by 20% and 100%. We find strong nonlinearity in the response to NOx perturbations outside summer, reflecting transitions in the chemical regime for ozone production. In contrast, we find no significant nonlinearity to NOx perturbations in summer or to NMVOC perturbations year-round. The relative benefit of decreasing NOx vs. NMVOC from current levels to abate intercontinental pollution increases with the magnitude of emission reductions

Structural learning difficulties implicate altered hippocampal functioning in adults with Autism Spectrum Disorder

Structural learning is fundamental to the formation of cognitive maps that are necessary for learning, memory, and spatial navigation. It also enables successful navigation of the social world, which is something that individuals with autism spectrum disorder (ASD) find particularly difficult. To master these situations, a person needs to bind pieces of information to one another and to consider the context in which experiences happen. Such binding is a capacity of the hippocampus. Although altered hippocampal function has for long been suspected to play a role in the etiology of ASD, the relevant evidence has remained inconclusive because few behavioral tests that are known to specifically necessitate preserved hippocampal function have been employed in studies of ASD. To address this gap in the literature, a total sample of 57 pairs of age and ability matched ASD and comparison participants was divided into 3 subsamples who were asked either to complete structural learning, or 1 of 2 configural learning control tasks (biconditional discrimination and transverse patterning) drawn from animal research. As predicted, ASD adults demonstrated specific difficulty with structural learning but not with other forms of configural learning. These differences were not attributable to decreased attentional shifting or increased perseveration, which would have indicated atypical frontal modulation of hippocampal processes. Instead, the observations implicate atypical hippocampal functioning as the source of structural learning difficulties in ASD. The data suggest that disturbances in domain-general cognitive processes such as structural learning, caused by altered hippocampal function, play a critical role in the etiology of ASD