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The formulation of the background error covariances represented in the spectral space is discussed in the context of univariate assimilation relying on a grid point model, leaving out all the aspects of balances between the different control variables needed in meteorological assimilation. The spectral transform operations are discussed in the case of a spherical harmonics basis and we stress that there is no need for an inverse spectral transform and of a Gaussian grid. The analysis increments are thus produced directly on the model grid. The practice of producing analysis increments on a horizontal Gaussian grid and then interpolating to an equally spaced grid is also shown to produce a degradation of the analysis. The method discussed in this paper allows the implementation of separable and non-separable spatial correlations. The separable formulation has been implemented in the Belgian Assimilation System for Chemical ObsErvations (BASCOE) and its impact on the assimilation of O<sub>3</sub> observed by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) is shown. To promote the use of this method by other non-meteorological variational systems and in particular chemistry, the Fortran code developed is made available to the community.
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The biosphere emits volatile organic compounds (BVOCs) which, after oxidation in the atmosphere, can partition on the existing aerosol population or even form new particles. The large quantities emitted provide means for a large potential impact on both aerosol direct and indirect effects. Biogenic responses to atmospheric temperature change can establish feedbacks even in rather short timescales. However, due to the complexity of organic aerosol partitioning, even the sign of these feedbacks is of large uncertainty. We use the global aerosol-climate model ECHAM5.5-HAM2 to explore the effect of BVOC emissions on new particle formation, clouds and climate. Two BVOC emission models, MEGAN2 and LPJ-GUESS, are used. MEGAN2 shows a 25% increase while LPJ-GUESS shows a slight decrease in global BVOC emission between years 2000 and 2100. The change of shortwave cloud forcing from year 1750 to 2000 ranges from −1.4 to −1.8 W m<sup>−2</sup> with 5 different nucleation mechanisms. We show that the change in shortwave cloud forcing from the year 2000 to 2100 ranges from 1.0 to 1.5 W m<sup>−2</sup>. Although increasing future BVOC emissions provide 3–5% additional CCN, the effect on the cloud albedo change is modest. Due to simulated decreases in future cloud cover, the increased CCN concentrations from BVOCs can not provide significant additional cooling in the future.
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Chemical processes occurring on snow and ice surfaces play an important role in controlling the oxidative capacity of the overlying atmosphere. However, efforts to gain a better, mechanistic understanding of such processes are impeded by our poor understanding of the chemical nature of the air-ice interface. Here we use glancing-angle laser induced fluorescence in conjunction with harmine – a surface-active, pH-sensitive fluorescent dye – to investigate how the nature of the ice, whether frozen freshwater, salt water or seawater, influences pH changes at the surface. Deposition of HCl(g) leads to a very different pH response at the frozen freshwater surface than at the frozen salt water surface indicating that these two surfaces present different chemical environments. Importantly, the sea ice surface is buffered against pH changes arising from deposition of gas phase species. These results have important implications for understanding pH-sensitive processes occurring at the air-ice boundary, such as bromine activation.
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This study investigates the causes of elevated PM<sub>2.5</sub> episodes and potential exceedences of the US National Ambient Air Quality Standards (NAAQS) in Truckee Meadows, Nevada, an urban valley of the Western US, during winter 2009/2010, an unusually cold and snowy winter. Continuous PM<sub>2.5</sub> mass and time-integrated chemical speciation data were acquired from a central valley monitoring site, along with meteorological measurements from nearby sites. All nine days with PM<sub>2.5</sub> > 35 μg m<sup>−3</sup> showed 24-h average temperature inversion of 1.5–4.5 °C and snow cover of 8–18 cm. Stagnant atmospheric conditions limited wind ventilation while highly reflective snow cover reduced daytime surface heating creating persistent inversion. Elevated ammonium nitrate (NH<sub>4</sub>NO<sub>3</sub>) and water associated with it are found to be main reasons for the PM<sub>2.5</sub> exceedances. An effective-variance chemical mass balance (EV-CMB) receptor model using locally-derived geological profiles and inorganic/organic markers confirmed secondary NH<sub>4</sub>NO<sub>3</sub> (27–37%), residential wood combustion (RWC; 11–51%), and diesel engine exhaust (7–22%) as the dominant PM<sub>2.5</sub> contributors. Paved road dust and de-icing materials were minor, but detectable contributors. RWC is a more important source than diesel for organic carbon (OC), but vice versa for elemental carbon (EC). A majority of secondary NH<sub>4</sub>NO<sub>3</sub> is also attributed to RWC and diesel engines (including snow removal equipment) through oxides of nitrogen (NO<sub>x</sub>) emissions from these sources. Findings from this study may apply to similar situations experienced by other urban valleys.
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Five years of PM<sub>10</sub> and PM<sub>2.5</sub> ambient air measurements at a roadside, an urban, and a regional background site in Leipzig (Germany) were analyzed for violations of the legal PM<sub>10</sub> limit value (EC, 1999). The annual mean PM<sub>10</sub> concentrations at the three sites were well below the legal threshold of 40 μg m<sup>−3</sup> (32.6, 22.0 and 21.7 μg m<sup>−3</sup>, respectively). At roadside, the daily maximum value of 50 μg m<sup>−3</sup> was exceeded on 232 days (13% of all days) in 2005–2009, which led to a violation of the EC directive in three out of five years. We analysed the meteorological factors and local source contributions that eventually led to the exceedances of the daily limit value. As noted in other urban environments before, most exceedance days were observed in the cold season. Exceedance days were most probable under synoptic situations characterised by stagnant winds, low temperatures and strong temperature inversions in winter time. However, these extreme situations accounted for only less than half of the exeedance days. We also noticed a significant number of exceedance days that occurred in the cold season under south-westerly winds, and in the warm season in the presence of easterly winds. Our analysis suggests that local as well as regional sources of PM are equally responsible for exceedances days at the roadside site. The conclusion is that a combined effort of local, national and international reduction measures appears most likely to avoid systematic exceedances of the daily limit value in the future.
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The impact of climate change and changes in ozone precursor emission on summer surface ozone in Europe was studied using a regional CTM over the period 1990 to 2100. Two different climate simulations under the SRES A1B scenario together with ozone precursor emission changes from the RCP4.5 scenario were used as model input. In southern Europe regional climate change leads to increasing surface ozone concentrations during April–September, but projected emission reductions in Europe have a stronger effect, resulting in net reductions of surface ozone concentrations. In northern Europe regional climate change decreases surface O<sub>3</sub> and reduced European emissions acts to further strengthen this trend also when including increasing hemispheric background concentrations. The European O<sub>3</sub> precursor emission reductions in RCP4.5 are substantial and it remains to be seen if these reductions can be achieved. There is substantial decadal variability in the simulations forced by climate variability which is important to consider when looking at changes in surface O<sub>3</sub> concentrations, especially until the first half of the 21st century. In order to account for changes in background O<sub>3</sub> future regional model studies should couple global (hemispheric) and regional CTMs forced by a consistent set of meteorological and precursor emission data.
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Biogenic volatile organic compounds (BVOCs) can react in the atmosphere to form organic nitrates, which serve as NO<sub>x</sub> (NO + NO<sub>2</sub>) reservoirs, impacting ozone and secondary organic aerosol production, the oxidative capacity of the atmosphere, and nitrogen availability to ecosystems. To examine the contributions of biogenic emissions and the formation and fate of organic nitrates in a forest environment, we simulated the oxidation of 57 individual BVOCs emitted from a rural mixed forest in northern Michigan. Key BVOC-oxidant reactions were identified for future laboratory and field investigations into reaction rate constants, yields, and speciation of oxidation products. Of the total simulated organic nitrates, monoterpenes contributed ~70% in the early morning at ~12 m above the forest canopy when isoprene emissions were low. In the afternoon, when vertical mixing and isoprene nitrate production were highest, the simulated contribution of isoprene-derived organic nitrates was greater than 90% at all altitudes, with the concentration of secondary isoprene nitrates increasing with altitude. Notably, reaction of isoprene with NO<sub>3</sub> leading to isoprene nitrate formation was found to be significant (~8% of primary organic nitrate production) during the daytime, and monoterpene reactions with NO<sub>3</sub> were simulated to comprise up to ~83% of primary organic nitrate production at night. Lastly, forest succession, wherein aspen trees are being replaced by pine and maple trees, was predicted to lead to increased afternoon concentrations of monoterpene-derived organic nitrates. This further underscores the need to understand the formation and fate of these species, which have different chemical pathways and oxidation products compared to isoprene-derived organic nitrates and can lead to secondary organic aerosol formation.
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During April and May 2010 the ash cloud from the eruption of the Icelandic volcano Eyjafjallajökull caused widespread disruption to aviation over northern Europe. The location and impact of the eruption led to a wealth of observations of the ash cloud were being obtained which can be used to assess modelling of the long range transport of ash in the troposphere. The UK FAAM (Facility for Airborne Atmospheric Measurements) BAe-146-301 research aircraft overflew the ash cloud on a number of days during May. The aircraft carries a downward looking lidar which detected the ash layer through the backscatter of the laser light. In this study ash concentrations derived from the lidar are compared with simulations of the ash cloud made with NAME (Numerical Atmospheric-dispersion Modelling Environment), a general purpose atmospheric transport and dispersion model. <br><br> The simulated ash clouds are compared to the lidar data to determine how well NAME simulates the horizontal and vertical structure of the ash clouds. Comparison between the ash concentrations derived from the lidar and those from NAME is used to define the fraction of ash emitted in the eruption that is transported over long distances compared to the total emission of tephra. In making these comparisons possible position errors in the simulated ash clouds are identified and accounted for. <br><br> The ash layers seen by the lidar considered in this study were thin, with typical depths of 550–750 m. The vertical structure of the ash cloud simulated by NAME was generally consistent with the observed ash layers, although the layers in the simulated ash clouds that are identified with observed ash layers are about twice the depth of the observed layers. The structure of the simulated ash clouds were sensitive to the profile of ash emissions that was assumed. In terms of horizontal and vertical structure the best results were obtained by assuming that the emission occurred at the top of the eruption plume, consistent with the observed structure of eruption plumes. However, early in the period when the intensity of the eruption was low, assuming that the emission of ash was uniform with height gives better guidance on the horizontal and vertical structure of the ash cloud. <br><br> Comparison of the lidar concentrations with those from NAME show that 2–5% of the total mass erupted by the volcano remained in the ash cloud over the United Kingdom.
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Atmospheric hydrofluorocarbons (HFCs) and perfluorocarbons (PFCs) were measured in-situ at the Shangdianzi (SDZ) Global Atmosphere Watch (GAW) regional background station, China, from May 2010 to May 2011. The time series for five HFCs and three PFCs showed occasionally high-concentration events while background conditions occurred for 36% (HFC-32) to 83% (PFC-218) of all measurements. The mean mixing ratios during background conditions were 24.5 ppt (parts per trillion, 10<sup>−12</sup>, molar) for HFC-23, 5.86 ppt for HFC-32, 9.97 ppt for HFC-125, 66.0 ppt for HFC-134a, 9.77 ppt for HFC-152a, 79.1 ppt for CF<sub>4</sub>, 4.22 ppt for PFC-116, and 0.56 ppt for PFC-218. The background mixing ratios for the compounds at SDZ are consistent with those obtained at mid to high latitude sites in the Northern Hemisphere. North-easterly winds were associated with negative contributions to atmospheric HFC and PFC loadings (mixing ratio anomalies weighted by time associated with winds in a given sector), whereas south-westerly advection (urban sector) showed positive loadings. Chinese emissions estimated by a tracer ratio method using carbon monoxide as tracer were 3.6 ± 3.2 kt yr<sup>−1</sup> for HFC-23, 4.3 ± 3.6 kt yr<sup>−1</sup> for HFC-32, 2.7 ± 2.3 kt yr<sup>−1</sup> for HFC-125, 6.0 ± 5.6 kt yr<sup>−1</sup> for HFC-134a, 2.0 ± 1.8 kt yr<sup>−1</sup> for HFC-152a, 2.4 ± 2.1 kt yr<sup>−1</sup> for CF<sub>4</sub>, 0.27 ± 0.26 kt yr<sup>−1</sup> for PFC-116, and 0.061 ± 0.095 kt yr<sup>−1</sup> for PFC-218. The lower HFC-23 emissions compared to earlier studies may be a result of the HFC-23 abatement measures taken as part of Clean Development Mechanism (CDM) projects that started in 2005.
