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A low bias in carbon monoxide (CO) at northern high and mid-latitudes is a common feature of chemistry climate models (CCMs) that may indicate or contribute to a high bias in simulated OH and corresponding low bias in methane lifetime. We use simulations with CO tagged by source type to investigate the sensitivity of the CO bias to CO emissions, transport, global mean OH, and the hemispheric asymmetry of OH. We also investigate how each of these possible contributors to the CO bias affects the methane lifetime. We find that the use of specified meteorology alters the distribution of CO compared to a free-running CCM simulation, improving the comparison with surface observations in summer. Our results also show that reducing the hemispheric asymmetry of OH improves the agreement of simulated CO with observations. We use simulations with parameterized OH to quantify the impact of known model biases on simulated OH. Removing biases in ozone and water vapor as well as reducing Northern Hemisphere NO<sub><i>x</i></sub> does not remove the hemispheric asymmetry in OH, but it reduces global mean OH by 18 %, bringing the simulated methane lifetime into agreement with observation-based estimates.
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The vertical columns of formaldehyde (HCHO) retrieved from two satellite instruments, the Global Ozone Monitoring Instrument-2 (GOME-2) on Metop-A and the Ozone Monitoring Instrument (OMI) on Aura, are used to constrain global emissions of HCHO precursors from open fires, vegetation and human activities in the year 2010. To this end, the emissions are varied and optimized using the adjoint model technique in the IMAGESv2 global CTM (chemical transport model) on a monthly basis and at the model resolution. Given the different local overpass times of GOME-2 (09:30 LT) and OMI (13:30 LT), the simulated diurnal cycle of HCHO columns is investigated and evaluated against ground-based optical measurements at seven sites in Europe, China and Africa. The modeled diurnal cycle exhibits large variability, reflecting competition between photochemistry and emission variations, with noon or early afternoon maxima at remote locations (oceans) and in regions dominated by anthropogenic emissions, late afternoon or evening maxima over fire scenes, and midday minima in isoprene-rich regions. The agreement between simulated and ground-based columns is generally better in summer (with a clear afternoon maximum at mid-latitude sites) than in winter, and the annually averaged ratio of afternoon to morning columns is slightly higher in the model (1.126) than in the ground-based measurements (1.043). <br><br> The anthropogenic VOC (volatile organic compound) sources are found to be weakly constrained by the inversions on the global scale, mainly owing to their generally minor contribution to the HCHO columns, except over strongly polluted regions, like China. The OMI-based inversion yields total flux estimates over China close to the bottom-up inventory (24.6 vs. 25.5 TgVOC yr<sup>−1</sup> in the a priori) with, however, pronounced increases in the northeast of China and reductions in the south. Lower fluxes are estimated based on GOME-2 HCHO columns (20.6 TgVOC yr<sup>−1</sup>), in particular over the northeast, likely reflecting mismatches between the observed and the modeled diurnal cycle in this region. <br><br> The resulting biogenic and pyrogenic flux estimates from both optimizations generally show a good degree of consistency. A reduction of the global annual biogenic emissions of isoprene is derived, of 9 and 13 % according to GOME-2 and OMI, respectively, compared to the a priori estimate of 363 Tg in 2010. The reduction is largest (up to 25–40 %) in the Southeastern US, in accordance with earlier studies. The GOME-2 and OMI satellite columns suggest a global pyrogenic flux decrease by 36 and 33 %, respectively, compared to the GFEDv3 (Global Fire Emissions Database) inventory. This decrease is especially pronounced over tropical forests, such as in Amazonia, Thailand and Myanmar, and is supported by comparisons with CO observations from IASI (Infrared Atmospheric Sounding Interferometer). In contrast to these flux reductions, the emissions due to harvest waste burning are strongly enhanced over the northeastern China plain in June (by ca. 70 % in June according to OMI) as well as over Indochina in March. Sensitivity inversions showed robustness of the inferred estimates, which were found to lie within 7 % of the standard inversion results at the global scale.
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Solid aerosol particles have long been proposed as an alternative to sulfate aerosols for solar geoengineering. Any solid aerosol introduced into the stratosphere would be subject to coagulation with itself, producing fractal aggregates, and with the natural sulfate aerosol, producing liquid-coated solids. Solid aerosols that are coated with sulfate and/or have formed aggregates may have very different scattering properties and chemical behavior than uncoated non-aggregated monomers do. We use a two-dimensional (2-D) chemistry–transport–aerosol model to capture the dynamics of interacting solid and liquid aerosols in the stratosphere. As an example, we apply the model to the possible use of alumina and diamond particles for solar geoengineering. For 240 nm radius alumina particles, for example, an injection rate of 4 Tg yr<sup>−1</sup> produces a global-average shortwave radiative forcing of −1.2 W m<sup>−2</sup> and minimal self-coagulation of alumina although almost all alumina outside the tropics is coated with sulfate. For the same radiative forcing, these solid aerosols can produce less ozone loss, less stratospheric heating, and less forward scattering than sulfate aerosols do. Our results suggest that appropriately sized alumina, diamond or similar high-index particles may have less severe technology-specific risks than sulfate aerosols do. These results, particularly the ozone response, are subject to large uncertainties due to the limited data on the rate constants of reactions on the dry surfaces.
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Soot particles are the most strongly light-absorbing particles commonly found in the atmosphere. They are major contributors to the radiative budget of the Earth and to the toxicity of atmospheric pollution. Atmospheric aging of soot may change its health- and climate-relevant properties by oxidizing the primary black carbon (BC) or organic particulate matter (OM) which, together with ash, comprise soot. This atmospheric aging, which entails the condensation of secondary particulate matter as well as the oxidation of the primary OM and BC emissions, is currently poorly understood. <br><br> In this study, atmospheric aging of wood-stove soot aerosols was simulated in a continuous-flow reactor. The composition of fresh and aged soot particles was measured in real time by a dual-vaporizer aerosol-particle mass spectrometer (SP-AMS). The dual-vaporizer SP-AMS provided information on the OM and BC components of the soot as well as on refractory components internally mixed with BC. By switching the SP-AMS laser vaporizer off and using only the AMS thermal vaporizer (at 600 °C), information on the OM component only was obtained. In both modes, OM appeared to be generated largely by cellulose and/or hemicellulose pyrolysis and was only present in large amounts when new wood was added to the stove. In SP-AMS mode, BC signals otherwise dominated the mass spectrum. These signals consisted of ions related to refractory BC (rBC, C<sub>1-5</sub><sup>+</sup>), oxygenated carbonaceous ions (CO<sub>1-2</sub><sup>+</sup>), potassium (K<sup>+</sup>), and water (H<sub>2</sub>O<sup>+</sup> and related fragments). The C<sub>4</sub><sup>+</sup> : C<sub>3</sub><sup>+</sup> ratio, but not the C<sub>1</sub><sup>+</sup> : C<sub>3</sub><sup>+</sup> ratio, was consistent with the BC-structure trends of Corbin et al. (2015c). The CO<sub>1-2</sub><sup>+</sup> signals likely originated from BC surface groups: upon aging, both CO<sup>+</sup> and CO<sub>2</sub><sup>+</sup> increased relative to C<sub>1-3</sub><sup>+</sup> while CO<sub>2</sub><sup>+</sup> simultaneously increased relative to CO<sup>+</sup>. Factor analysis (positive matrix factorization) of SP-AMS and AMS data, using a modified error model to address peak-integration uncertainties, indicated that the surface composition of the BC was approximately constant across all stages of combustion for both fresh and aged samples. These results represent the first time-resolved measurements of in situ BC surface aging and suggest that the surface of beech-wood BC may be modelled as a single chemical species.
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Extreme particulate matter (PM) air pollution of January 2013 in China was found to be associated with an anomalous eastward extension of the Siberian High (SH). We developed a Siberian High position index (SHPI), which depicts the mean longitudinal position of the SH, as a new indicator of the large-scale circulation pattern that controls wintertime air quality in China. This SHPI explains 58 % (correlation coefficient of 0.76) of the interannual variability of wintertime aerosol optical depth (AOD) retrieved by MODIS over North China (NC) during 2001–2013. By contrast, the intensity-based conventional Siberian High index (SHI) shows essentially no skill in predicting this AOD variability. On the monthly scale, some high-AOD months for NC are accompanied with extremely high SHPIs; notably, extreme PM pollution of January 2013 can be explained by the SHPI value exceeding 2.6 times the standard deviation of the 2001–2013 January mean. When the SH extends eastward, thus higher SHPI, prevailing northwesterly winds over NC are suppressed not only in the lower troposphere but also in the middle troposphere, leading to reduced southward transport of pollution from NC to South China (SC). The SHPI hence exhibits a significantly negative correlation of −0.82 with MODIS AOD over SC during 2001–2013, although the robustness of this correlation depends on that of satellite-derived AOD. The suppressed northwesterly winds during high-SHPI winters also lead to increased relative humidity (RH) over NC. Both the wind and RH changes are responsible for enhanced PM pollution over NC during the high-SHPI winters.
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The terrestrial biosphere has experienced dramatic changes in recent decades. Estimates of historical trends in land carbon fluxes remain uncertain because long-term observations are limited on the global scale. Here, we use the Yale Interactive terrestrial Biosphere (YIBs) model to estimate decadal trends in land carbon fluxes and emissions of biogenic volatile organic compounds (BVOCs) and to identify the key drivers for these changes during 1982–2011. Driven by hourly meteorology from WFDEI (WATCH forcing data methodology applied to ERA-Interim data), the model simulates an increasing trend of 297 Tg C a<sup>−2</sup> in gross primary productivity (GPP) and 185 Tg C a<sup>−2</sup> in the net primary productivity (NPP). CO<sub>2</sub> fertilization is the main driver for the flux changes in forest ecosystems, while meteorology dominates the changes in grasslands and shrublands. Warming boosts summer GPP and NPP at high latitudes, while drought dampens carbon uptake in tropical regions. North of 30° N, increasing temperatures induce a substantial extension of 0.22 day a<sup>−1</sup> for the growing season; however, this phenological change alone does not promote regional carbon uptake and BVOC emissions. Nevertheless, increases of leaf area index at peak season accounts for ~ 25 % of the trends in GPP and isoprene emissions at the northern lands. The net land sink shows statistically insignificant increases of only 3 Tg C a<sup>−2</sup> globally because of simultaneous increases in soil respiration. Global BVOC emissions are calculated using two schemes. With the photosynthesis-dependent scheme, the model predicts increases of 0.4 Tg C a<sup>−2</sup> in isoprene emissions, which are mainly attributed to warming trends because CO<sub>2</sub> fertilization and inhibition effects offset each other. Using the MEGAN (Model of Emissions of Gases and Aerosols from Nature) scheme, the YIBs model simulates global reductions of 1.1 Tg C a<sup>−2</sup> in isoprene and 0.04 Tg C a<sup>−2</sup> in monoterpene emissions in response to the CO<sub>2</sub> inhibition effects. Land use change shows limited impacts on global carbon fluxes and BVOC emissions, but there are regional contrasting impacts over Europe (afforestation) and China (deforestation).
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There is a large variety of internal structures inside atmospheric dust particles, making them inherently inhomogeneous. Such structures may have a large effect on ground-level and atmospheric radiation. So far, dust particle internal structures and their effect on the light scattering properties have proved to be hard to quantify, in part due to challenges in obtaining information about these structures. Recently, internal structures of individual dust particles were revealed through focused ion beam milling and analyzed. Here, we perform a sensitivity study to evaluate the optical impacts of some of the typical internal structures revealed. To obtain suitable model particles, the first step is to generate inhomogeneous particles with varying internal structures by using an algorithm that is based on three-dimensional Voronoi tessellation. The parameters for the particle generation are obtained from studies of real-world Asian dust particles. The second step is to generate homogeneous versions of the generated particles by using an effective-medium approximation, for comparison. Third, light scattering by both versions of these particles is simulated with discrete dipole approximation code. This allows us to see how different internal structures affect light scattering, and how important it is to account for these structures explicitly. Further, this allows us to estimate the potential inaccuracies caused by using only homogeneous model particles for atmospheric studies and remote-sensing measurements. The results show that the effects vary greatly between different kinds of internal structures and single-scattering quantity considered, but for most structure types the effects are overall notable. Most significantly, hematite inclusions in particles impact light scattering heavily. Furthermore, internal pores and hematite-rich coating both affect some form of light scattering noticeably. Based on this work, it seems that it is exceedingly important that the effects of dust particle internal structures on light scattering are accounted for in a wide variety of applications.
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A theoretical black carbon (BC) aging model is developed to account for three typical evolution stages, namely, freshly emitted aggregates, BC coated by soluble material, and BC particles undergoing further hygroscopic growth. The geometric-optics surface-wave (GOS) approach is employed to compute the BC single-scattering properties at each aging stage, which are subsequently compared with laboratory measurements. Theoretical calculations are consistent with measurements in extinction and absorption cross sections for fresh BC aggregates with different BC sizes (i.e., mobility diameters of 155, 245, and 320 nm), with differences of ≤ 25 %. The measured optical cross sections for BC coated by sulfuric acid and for that undergoing further hygroscopic growth are generally captured (differences < 30 %) by theoretical calculations using a concentric core-shell structure, with an overestimate in extinction and absorption of the smallest BC size and an underestimate in scattering of the largest BC size. We find that the absorption and scattering cross sections of fresh BC aggregates vary by 20–40 and 50–65 %, respectively, due to the use of upper (1.95–0.79<i>i</i>) and lower (1.75–0.63<i>i</i>) bounds of BC refractive index, while the variations are < 20 % in absorption and < 50 % in scattering in the case of coated BC particles. Sensitivity analyses of the BC morphology show that the optical properties of fresh BC aggregates are more sensitive to fractal dimension than primary spherule size. The absorption and scattering cross sections of coated BC particles vary by more than a factor of 2 due to different coating structures. We find an increase of 20–250 % in absorption and a factor of 3–15 in scattering during aging, significantly depending on coating morphology and aging stages. This study suggests that an accurate estimate of BC radiative effects requires the incorporation of a dynamic BC aging process that accounts for realistic coating structures in climate models.
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Idealized large-eddy simulations were performed to investigate the impact of different mountain geometries on daytime pollution transport by thermally driven winds. The main objective was to determine interactions between plain-to-mountain and slope wind systems, and their influence on the pollution distribution over complex terrain. For this purpose, tracer analyses were conducted over a quasi-two-dimensional mountain range with embedded valleys bordered by ridges with different crest heights and a flat foreland in cross-mountain direction. The valley depth was varied systematically. It was found that different flow regimes develop dependent on the valley floor height. In the case of elevated valley floors, the plain-to-mountain wind descends into the potentially warmer valley and replaces the opposing upslope wind. This superimposed plain-to-mountain wind increases the pollution transport towards the main ridge by an additional 20 % compared to the regime with a deep valley. Due to mountain and advective venting, the vertical exchange is 3.6 times higher over complex terrain than over a flat plain. However, the calculated vertical exchange is strongly sensitive to the definition of the convective boundary layer height. In summary, the impact of the terrain geometry on the mechanisms of pollution transport confirms the necessity to account for topographic effects in future boundary layer parameterization schemes.
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Measurements of the hygroscopicity of 15–145 nm particles in a boreal forest environment were conducted using two Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA) systems during the Pan-European Gas-Aerosols-climate interaction Study (PEGASOS) campaign in spring 2013. Measurements of the chemical composition of non-size segregated particles were also performed using a high-resolution aerosol mass spectrometer (HR-AMS) in parallel with hygroscopicity measurements. On average, the hygroscopic growth factor (HGF) of particles was observed to increase from the morning until afternoon. In case of accumulation mode particles, the main reasons for this behavior were increases in the ratio of sulfate to organic matter and oxidation level (O : C ratio) of the organic matter in the particle phase. Using an O : C dependent hygroscopic growth factor of organic matter (HGF<sub>org</sub>), fitted using the inverse Zdanovskii–Stokes–Robinson (ZSR) mixing rule, clearly improved the agreement between measured HGF and that predicted based on HR-AMS composition data. Besides organic oxidation level, the influence of inorganic species was tested when using the ZSR mixing rule to estimate the hygroscopic growth factor of organics in the aerosols. While accumulation and Aitken mode particles were predicted fairly well by the bulk aerosol composition data, the hygroscopicity of nucleation mode particles showed little correlation. However, we observed them to be more sensitive to the gas phase concentration of condensable vapors: the more sulfuric acid in the gas phase, the more hygroscopic the nucleation mode particles were. No clear dependence was found between the extremely low-volatility organics concentration (ELVOC) and the HGF of particles of any size.
