Methane Emissions in a Chemistry-Climate Model: Feedbacks and Climate Response.

Understanding the past, present, and future evolution of methane remains a grand challenge. Here we have used a hierarchy of models, ranging from simple box models to a chemistry-climate model (CCM), UM-UKCA, to assess the contemporary and possible future atmospheric methane burden. We assess two emission data sets for the year 2000 deployed in UM-UKCA against key observational constraints. We explore the impact of the treatment of model boundary conditions for methane and show that, depending on other factors, such as CO emissions, satisfactory agreement may be obtained with either of the CH4 emission data sets, highlighting the difficulty in unambiguous choice of model emissions in a coupled chemistry model with strong feedbacks. The feedbacks in the CH4-CO-OH system, and their uncertainties, play a critical role in the projection of possible futures. In a future driven by large increases in greenhouse gas forcing, increases in tropospheric temperature drive, an increase in water vapor, and, hence, [OH]. In the absence of methane emission changes this leads to a significant decrease in methane compared to the year 2000. However, adding a projected increase in methane emissions from the RCP8.5 scenario leads to a large increase in methane abundance. This is modified by changes to CO and NOx emissions. Clearly, future levels of methane are uncertain and depend critically on climate change and on the future emission pathways of methane and ozone precursors. We highlight that further work is needed to understand the coupled CH4-CO-OH system in order to understand better future methane evolution.

A world avoided: impacts of changes in anthropogenic emissions on the burden and effects of air pollutants in Europe and North America.

Emissions from anthropogenic activity are known to have deleterious impacts on human and ecosystem health and as such a significant amount of time, effort and money has been spent developing legislation to minimise their effects. Here we use a state of the art coupled chemistry-climate model HadGEM2-ES, with extended tropospheric chemistry, to assess the impacts that changes in emissions from anthropogenic activity have had on the burden and impacts of air pollutants over the last three decades. We use HadGEM2-ES to assess an alternative trajectory in air pollutant emissions to that which we have seen, with a regional focus on the contiguous United States and areas of Western Europe. This alternative trajectory can be considered to reflect a world avoided. In this world avoided, the significant levels of air pollution legislation imposed over the last three decades are simulated to not have come into effect in the contiguous United States and Western Europe. Rather a business as usual emission scenario is followed from 1970 to the present day. By combining the results of simulations of the world avoided with a base case present day atmosphere our model runs demonstrate that as a result of air pollution legislation, over 500 000 early mortalities a year have been mitigated owing to extensive reduction in sulfate aerosol and up to 8000 early mortalities a year have been mitigated as a result of improvements in ozone and nitrogen dioxide pollution. These results highlight the important role of legislation in reducing air pollution related mortality in these areas of the globe and highlight a compelling case for developing regions to follow.

Determination of the photolysis rate coefficient of monochlorodimethyl sulfide (MClDMS) in the atmosphere and its implications for the enhancement of SO2 production from the DMS + Cl2 reaction.

In this work, the photolysis rate coefficient of CH3SCH2Cl (MClDMS) in the lower atmosphere has been determined and has been used in a marine boundary layer (MBL) box model to determine the enhancement of SO2 production arising from the reaction DMS + Cl2. Absorption cross sections measured in the 28000-34000 cm(-1) region have been used to determine photolysis rate coefficients of MClDMS in the troposphere at 10 solar zenith angles (SZAs). These have been used to determine the lifetimes of MClDMS in the troposphere. At 0° SZA, a photolysis lifetime of 3-4 h has been obtained. The results show that the photolysis lifetime of MClDMS is significantly smaller than the lifetimes with respect to reaction with OH (≈ 4.6 days) and with Cl atoms (≈ 1.2 days). It has also been shown, using experimentally derived dissociation energies with supporting quantum-chemical calculations, that the dominant photodissocation route of MClDMS is dissociation of the C-S bond to give CH3S and CH2Cl. MBL box modeling calculations show that buildup of MClDMS at night from the Cl2 + DMS reaction leads to enhanced SO2 production during the day. The extra SO2 arises from photolysis of MClDMS to give CH3S and CH2Cl, followed by subsequent oxidation of CH3S.

The impact of local surface changes in Borneo on atmospheric composition at wider spatial scales: coastal processes, land-use change and air quality.

We present results from the OP3 campaign in Sabah during 2008 that allow us to study the impact of local emission changes over Borneo on atmospheric composition at the regional and wider scale. OP3 constituent data provide an important constraint on model performance. Treatment of boundary layer processes is highlighted as an important area of model uncertainty. Model studies of land-use change confirm earlier work, indicating that further changes to intensive oil palm agriculture in South East Asia, and the tropics in general, could have important impacts on air quality, with the biggest factor being the concomitant changes in NO(x) emissions. With the model scenarios used here, local increases in ozone of around 50 per cent could occur. We also report measurements of short-lived brominated compounds around Sabah suggesting that oceanic (and, especially, coastal) emission sources dominate locally. The concentration of bromine in short-lived halocarbons measured at the surface during OP3 amounted to about 7 ppt, setting an upper limit on the amount of these species that can reach the lower stratosphere.