Laboratory kinetic studies of the reactions of Cl atoms with species of biogenic origin: δ3-Carene, isoprene, methacrolein and methyl vinyl ketone

The rate coefficients for the reaction between atomic chlorine and a number of naturally occurring species have been measured at ambient temperature and atmospheric pressure using the relative rate technique. The values obtained were (4.0 ± 0.8) × 10-10, (2.1 ± 0.5) × 10-10, (3.2 ± 0.5) × 10-10, and (4.9 ± 0.5) × 10-10 cm3 molecule-1 s-1, for reactions with isoprene, methyl vinyl ketone, methacrolein and δ3-carene, respectively. The value obtained for isoprene compares favourably with previously reported values. No values have been reported to date for the rate constants of the other reactions.

Biogenic nitric oxide emissions from soils: impact on NOx and ozone over West Africa during AMMA (African Monsoon Multidisciplinary Analysis) - observational study

Chemical and meteorological parameters measured on board the Facility for Airborne Atmospheric Measurements (FAAM) BAe 146 Atmospheric Research Aircraft during the African Monsoon Multidisciplinary Analysis (AMMA) campaign are presented to show the impact of NOx emissions from recently wetted soils in West Africa. NO emissions from soils have been previously observed in many geographical areas with different types of soil/vegetation cover during small scale studies and have been inferred at large scales from satellite measurements of NOx. This study is the first dedicated to showing the emissions of NOx at an intermediate scale between local surface sites and continental satellite measurements. The measurements reveal pronounced mesoscale variations in NOx concentrations closely linked to spatial patterns of antecedent rainfall. Fluxes required to maintain the NOx concentrations observed by the BAe-146 in a number of cases studies and for a range of assumed OH concentrations (1×106 to 1×107 molecules cm−3) are calculated to be in the range 8.4 to 36.1 ng N m−2 s−1. These values are comparable to the range of fluxes from 0.5 to 28 ng N m−2 s−1 reported from small scale field studies in a variety of non-nutrient rich tropical and sub-tropical locations reported in the review of Davidson and Kingerlee (1997). The fluxes calculated in the present study have been scaled up to cover the area of the Sahel bounded by 10 to 20 N and 10 E to 20 W giving an estimated emission of 0.03 to 0.30 Tg N from this area for July and August 2006. The observed chemical data also suggest that the NOx emitted from soils is taking part in ozone formation as ozone concentrations exhibit similar fine scale structure to the NOx, with enhancements over the wet soils. Such variability can not be explained on the basis of transport from other areas. Delon et al. (2008) is a companion paper to this one which models the impact of soil NOx emissions on the NOx and ozone concentration over West Africa during AMMA. It employs an artificial neural network to define the emissions of NOx from soils, integrated into a coupled chemistry-dynamics model. The results are compared to the observed data presented in this paper. Here we compare fluxes deduced from the observed data with the model-derived values from Delon et al. (2008).

Biogenic nitric oxide emissions from soils: impact on NOx and ozone over West Africa during AMMA (African Monsoon Multidisciplinary Analysis) - Modelling study

Nitrogen oxide biogenic emissions from soils are driven by soil and environmental parameters. The relationship between these parameters and NO fluxes is highly non linear. A new algorithm, based on a neural network calculation, is used to reproduce the NO biogenic emissions linked to precipitations in the Sahel on the 6 August 2006 during the AMMA campaign. This algorithm has been coupled in the surface scheme of a coupled chemistry dynamics model (MesoNH Chemistry) to estimate the impact of the NO emissions on NOx and O3 formation in the lower troposphere for this particular episode. Four different simulations on the same domain and at the same period are compared: one with anthropogenic emissions only, one with soil NO emissions from a static inventory, at low time and space resolution, one with NO emissions from neural network, and one with NO from neural network plus lightning NOx. The influence of NOx from lightning is limited to the upper troposphere. The NO emission from soils calculated with neural network responds to changes in soil moisture giving enhanced emissions over the wetted soil, as observed by aircraft measurements after the passing of a convective system. The subsequent enhancement of NOx and ozone is limited to the lowest layers of the atmosphere in modelling, whereas measurements show higher concentrations above 1000 m. The neural network algorithm, applied in the Sahel region for one particular day of the wet season, allows an immediate response of fluxes to environmental parameters, unlike static emission inventories. Stewart et al (2008) is a companion paper to this one which looks at NOx and ozone concentrations in the boundary layer as measured on a research aircraft, examines how they vary with respect to the soil moisture, as indicated by surface temperature anomalies, and deduces NOx fluxes. In this current paper the model-derived results are compared to the observations and calculated fluxes presented by Stewart et al (2008).

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coeffcients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic ( alkane) solvent. The droplet was exposed to gas- phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic- like substances, HULIS; a alpha- pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid- phase di. ffusion and reaction are the rate determining steps. Uptake coe. ffcients, g, were found to be ( 1.1 +/- 0.7) x 10(-5), ( 1.5 +/- 0.7) x 10 (-5) and ( 3.0 - 7.5) x 10 (-3) for the reactions of ozone with the fumarate, benzoate and a- pinene containing droplets, respectively. Liquid- phase bimolecular rate coe. cients for reactions of dissolved ozone molecules with fumarate, benzoate and a- pinene were also obtained: k(fumarate) = ( 2.7 +/- 2) x 10 (5), k(benzoate) = ( 3.5 +/- 3) x 10 (5) and k(alpha-pinene) = ( 1-3) x 10(7) dm(3) mol (-1) s (- 1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS- proxies and for the oxidation of a- pinene in pentadecane. The study of the alpha- pinene/ ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha- pinene suggest the formation of new species containing carbonyl groups.

Sensitivity of biogenic isoprene emissions to past, present and future environmental conditions and implications for atmospheric chemistry.

[1] We have implemented a process-based isoprene emission model in the HadGEM2 Earth-system model with coupled atmospheric chemistry in order to examine the feedback between isoprene emission and climate. Isoprene emissions and their impact on atmospheric chemistry and climate are estimated for preindustrial (1860–1869), present-day (2000–2009), and future (2100–2109) climate conditions. The estimate of 460 TgC/yr for present-day global total isoprene emission is consistent with previous estimates. Preindustrial isoprene emissions are estimated to be 26% higher than present-day. Future isoprene emissions using the RCP8.5 scenario are similar to present-day because increased emissions resulting from climate warming are countered by CO2 inhibition of isoprene emissions. The impact of biogenic isoprene emissions on the global O3 burden and CH4 lifetime is small but locally significant, and the impact of changes in isoprene emissions on atmospheric chemistry depends strongly on the state of climate and chemistry.

Evaluation of a photosynthesis-based biogenic isoprene emission scheme in JULES and simulation of isoprene emissions under present-day climate conditions

We have incorporated a semi-mechanistic isoprene emission module into the JULES land-surface scheme, as a first step towards a modelling tool that can be applied for studies of vegetation – atmospheric chemistry interactions, including chemistry-climate feedbacks. Here, we evaluate the coupled model against local above-canopy isoprene emission flux measurements from six flux tower sites as well as satellite-derived estimates of isoprene emission over tropical South America and east and south Asia. The model simulates diurnal variability well: correlation coefficients are significant (at the 95 % level) for all flux tower sites. The model reproduces day-to-day variability with significant correlations (at the 95 % confidence level) at four of the six flux tower sites. At the UMBS site, a complete set of seasonal observations is available for two years (2000 and 2002). The model reproduces the seasonal pattern of emission during 2002, but does less well in the year 2000. The model overestimates observed emissions at all sites, which is partially because it does not include isoprene loss through the canopy. Comparison with the satellite-derived isoprene-emission estimates suggests that the model simulates the main spatial patterns, seasonal and inter-annual variability over tropical regions. The model yields a global annual isoprene emission of 535 ± 9 TgC yr−1 during the 1990s, 78 % of which from forested areas.

BAECC: a field campaign to elucidate the impact of Biogenic Aerosols on Clouds and Climate

Observations obtained during an 8-month deployment of AMF2 in a boreal environment in Hyytiälä, Finland, and the 20-year comprehensive in-situ data from SMEAR-II station enable the characterization of biogenic aerosol, clouds and precipitation, and their interactions. During “Biogenic Aerosols - Effects on Clouds and Climate (BAECC)”, the U.S. Department of Energy’s Atmospheric Radiation Measurement (ARM) Program deployed the ARM 2nd Mobile Facility (AMF2) to Hyytiälä, Finland, for an 8-month intensive measurement campaign from February to September 2014. The primary research goal is to understand the role of biogenic aerosols in cloud formation. Hyytiälä is host to SMEAR-II (Station for Measuring Forest Ecosystem-Atmosphere Relations), one of the world’s most comprehensive surface in-situ observation sites in a boreal forest environment. The station has been measuring atmospheric aerosols, biogenic emissions and an extensive suite of parameters relevant to atmosphere-biosphere interactions continuously since 1996. Combining vertical profiles from AMF2 with surface-based in-situ SMEAR-II observations allow the processes at the surface to be directly related to processes occurring throughout the entire tropospheric column. Together with the inclusion of extensive surface precipitation measurements, and intensive observation periods involving aircraft flights and novel radiosonde launches, the complementary observations provide a unique opportunity for investigating aerosol-cloud interactions, and cloud-to-precipitation processes, in a boreal environment. The BAECC dataset provides opportunities for evaluating and improving models of aerosol sources and transport, cloud microphysical processes, and boundary-layer structures. In addition, numerical models are being used to bridge the gap between surface-based and tropospheric observations.