Items

Advanced search

Impact of emission changes on secondary inorganic aerosol episodes across Germany

In this study, the response of secondary inorganic aerosol (SIA) concentrations to changes in precursor emissions during high PM10 episodes over central Europe in spring 2009 was investigated with the Eulerian Chemistry Transport Model (CTM) REM-Calgrid (RCG). The model performed well in capturing the temporal variation of PM10 and SIA concentrations and was used to analyse the different origin, development and characteristics of the selected high PM10 episodes. SIA concentrations, which contribute to about 50% of the PM10 concentration in northwestern Europe, have been studied by means of several model runs for different emission scenarios. SO2, NOx and NH3 emissions have been varied within a domain covering Germany and within a domain covering Europe. It was confirmed that the response of sulfate, nitrate and ammonium concentrations and deposition fluxes of S and N to SO2, NOx and NH3 emission changes is non-linear. The deviation from linearity was found to be lower for total deposition fluxes of S and N than for SIA concentrations. Furthermore, the study has shown that incorporating explicit cloud chemistry in the model adds non-linear responses to the system. It significantly modifies the response of modelled SIA concentrations and S and N deposition fluxes to changes in precursor emissions. The analysis of emission reduction scenario runs demonstrates that next to European-wide emission reductions additional national NH3 measures in Germany are more effective in reducing SIA concentrations and deposition fluxes than additional national measures on SO2 and NOx.
Reactivity of chlorine radical with submicron palmitic acid particles: kinetic measurements and product identification

The heterogeneous reaction of Cl&bullet; radicals with submicron palmitic acid (PA) particles was studied in an aerosol flow tube in the presence or in the absence of O2. Fine particles were generated by homogeneous condensation of PA vapours and introduced into the reactor, where chlorine atoms were produced by photolysis of Cl2 using UV lamps surrounding the reactor. The effective reactive uptake coefficient (γ) has been determined from the rate loss of PA measured by gas chromatography–mass spectrometer (GC/MS) analysis of reacted particles as a function of the chlorine exposure. In the absence of O2, γ = 14 ± 5 indicates efficient secondary chemistry involving Cl2. GC/MS analysis has shown the formation of monochlorinated and polychlorinated compounds in the oxidized particles. Although the PA particles are solid, the complete mass can be consumed. In the presence of oxygen, the reaction is still dominated by secondary chemistry but the propagation chain length is smaller than in the absence of O2, which leads to an uptake coefficient γ = 3 ± 1. In the particulate phase, oxocarboxylic acids and dicarboxylic acids were identified by GC/MS. The formation of alcohols and monocarboxylic acids is also suspected. A reaction pathway for the main products and more functionalized species is proposed. All these results show that solid organic particles could be efficiently oxidized by gas-phase radicals not only on their surface but also in bulk by mechanisms which are still unclear. They help to understand the aging of primary tropospheric aerosol containing fatty acids.
Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase

In the atmosphere, one important class of reactions occurs in the aqueous phase in which organic compounds are known to undergo oxidation towards a number of radicals, among which OH radicals are the most reactive oxidants. In 2008, Monod and Doussin have proposed a new structure–activity relationship (SAR) to calculate OH-oxidation rate constants in the aqueous phase. This estimation method is based on the group-additivity principle and was until now limited to alkanes, alcohols, acids, bases and related polyfunctional compounds. In this work, the initial SAR is extended to carbonyl compounds, including aldehydes, ketones, dicarbonyls, hydroxy carbonyls, acidic carbonyls, their conjugated bases, and the hydrated form of all these compounds. To do so, only five descriptors have been added and none of the previously attributed descriptors were modified. This extension leads now to a SAR which is based on a database of 102 distinct compounds for which 252 experimental kinetic rate constants have been gathered and reviewed. The efficiency of this updated SAR is such that 58% of the rate constants could be calculated within ±20% of the experimental data and 76% within ±40% (respectively 41 and 72% for the carbonyl compounds alone).
Liquid–liquid phase separation in particles containing organics mixed with ammonium sulfate, ammonium bisulfate, ammonium nitrate or sodium chloride

As the relative humidity varies from high to low values in the atmosphere, particles containing organic species and inorganic salts may undergo liquid–liquid phase separation. The majority of the laboratory work on this subject has used ammonium sulfate as the inorganic salt. In the following we studied liquid–liquid phase separation in particles containing organics mixed with the following salts: ammonium sulfate, ammonium bisulfate, ammonium nitrate and sodium chloride. In each experiment one organic was mixed with one inorganic salt and the liquid–liquid phase separation relative humidity (SRH) was determined. Since we studied 23 different organics mixed with four different salts, a total of 92 different particle types were investigated. Out of the 92 types, 49 underwent liquid–liquid phase separation. For all the inorganic salts, liquid–liquid phase separation was never observed when the oxygen-to-carbon elemental ratio (O : C) &geq; 0.8 and was always observed for O : C < 0.5. For 0.5 &leq; O : C < 0.8, the results depended on the salt type. Out of the 23 organic species investigated, the SRH of 20 organics followed the trend: (NH4)2SO4 &geq; NH4HSO4 &geq; NaCl &geq; NH4NO3. This trend is consistent with previous salting out studies and the Hofmeister series. Based on the range of O : C values found in the atmosphere and the current results, liquid–liquid phase separation is likely a frequent occurrence in both marine and non-marine environments.
Estimation of nocturnal222Rn soil fluxes over Russia from TROICA measurements

In TROICA (TRanscontinental Observations Into the Chemistry of the Atmosphere) campaigns (1999–2008), the simultaneous observations of near surface 222Rn concentrations and atmospheric boundary layer thermal structure were performed along the Trans-Siberian Railway across northern Eurasia from Moscow to Vladivostok, including central, southern and far eastern parts of Russia. The data on 222Rn and temperature vertical distribution are used to estimate 222Rn regional scale soil fluxes based on calculations of nocturnal 222Rn accumulation rates in the surface layer under inversion conditions. An effect of seasonal soil thawing on 2–4 times surface 222Rn concentration increase from summer 1999 to autumn 2005 is observed. The estimated 222Rn regional averaged fluxes vary over Russia from 29 ± 8 mBq m−2 s−1 in its so-called European territory to 95 ± 51 mBq m−2 s−1 in the southern area of Siberia. The highest 222Rn fluxes are derived in the regions of high tectonic activity and orogenic belts of central and eastern Siberia and in far eastern Russia. The observed high 222Rn flux variations in specific events show a strong effect of both soil and atmospheric conditions on 222Rn near-surface abundance and the derived seasonal patterns over the continent.
Quantification of waves in lidar observations of noctilucent clouds at scales from seconds to minutes

We present small-scale structures and waves observed in noctilucent clouds (NLC) by lidar at an unprecedented temporal resolution of 30 s or less. The measurements were taken with the Rayleigh/Mie/Raman lidar at the ALOMAR observatory in northern Norway (69° N) in the years 2008–2011. We find multiple layer NLC in 7.9% of the time for a brightness threshold of δ β = 12 × 10−10 m−1 sr−1. In comparison to 10 min averaged data, the 30 s dataset shows considerably more structure. For limited periods, quasi-monochromatic waves in NLC altitude variations are common, in accord with ground-based NLC imagery. For the combined dataset, on the other hand, we do not find preferred periods but rather significant periods at all timescales observed (1 min to 1 h). Typical wave amplitudes in the layer vertical displacements are 0.2 km with maximum amplitudes up to 2.3 km. Average spectral slopes of temporal altitude and brightness variations are −2.01 ± 0.25 for centroid altitude, −1.41 ± 0.24 for peak brightness and −1.73 ± 0.25 for integrated brightness. Evaluating a new single-pulse detection system, we observe altitude variations of 70 s period and spectral slopes down to a scale of 10 s. We evaluate the suitability of NLC parameters as tracers for gravity waves.
Water uptake is independent of the inferred composition of secondary aerosols derived from multiple biogenic VOCs

We demonstrate that the water uptake properties derived from sub- and super-saturated measurements of chamber-generated biogenic secondary organic aerosol (SOA) particles are independent of their degree of oxidation, determined using both online and offline methods. SOA particles are formed from the photooxidation of five structurally different biogenic VOCs, representing a broad range of emitted species and their corresponding range of chemical reactivity: α-pinene, β-caryophyllene, limonene, myrcene and linalool. The fractional contribution of mass fragment 44 to the total organic signal (f44) is used to characterise the extent of oxidation of the formed SOA as measured online by an aerosol mass spectrometer. Results illustrate that the values of f44 are dependent on the precursor, the extent of photochemical ageing as well as on the initial experimental conditions. SOA generated from a single biogenic precursor should therefore not be used as a general proxy for biogenic SOA. Similarly, the generated SOA particles exhibit a range of hygroscopic properties, depending on the precursor, its initial mixing ratio and photochemical ageing. The activation behaviour of the formed SOA particles show no temporal trends with photochemical ageing. The average κ values derived from the HTDMA and CCNc are generally found to cover the same range for each precursor under two different initial mixing ratio conditions. A positive correlation is observed between the hygroscopicity of particles of a single size and f44 for α-pinene, β-caryophyllene, linalool and myrcene, but not for limonene SOA. The investigation of the generality of this relationship reveals that α-pinene, limonene, linalool and myrcene are all able to generate particles with similar hygroscopicity (κHTDMA ~0.1) despite f44 exhibiting a relatively wide range of values (~4 to 11%). Similarly, κCCN is found to be independent of f44. The same findings are also true when sub- and super-saturated water uptake properties of SOA are compared to the averaged carbon oxidation state (OSC) determined using an offline method. These findings do not necessarily suggest that water uptake and chemical composition are not related. Instead, they suggest that either f44 and OSC do not represent the main dominant composition-related factors controlling water uptake of SOA particles, or they may emphasise the possible impact of semi-volatile compounds on limiting the ability of current state-of-the-art techniques to determine the chemical composition and water uptake properties of aerosol particles.
Impacts of seasonal and regional variability in biogenic VOC emissions on surface ozone in the Pearl River delta region, China

This study investigated the impacts of seasonal and regional variability in biogenic volatile organic compounds (BVOCs) on surface ozone over the Pearl River delta (PRD) region in southern China in 2010 with the WRF–Chem/MEGAN (Weather Research and Forecasting coupled with Chemistry/Model of Emissions of Gases and Aerosols from Nature) modeling system. Compared to observations in the literature and this study, MEGAN tends to predict reasonable BVOC emissions in summer, but may overestimate isoprene emissions in autumn, even when the local high-resolution land-cover data and observed emission factors of BVOCs from local plant species are combined to constrain the MEGAN BVOC emissions model. With the standard MEGAN output, it is shown that the impact of BVOC emissions on the surface ozone peak is ~3 ppb on average with a maximum of 24.8 ppb over the PRD region in autumn, while the impact is ~10 ppb on average, with a maximum value of 34.0 ppb in summer. The areas where surface ozone is sensitive to BVOC emissions are different in autumn and in summer, which is primarily due to the change of prevailing wind over the PRD; nevertheless, in both autumn and summer, the surface ozone is most sensitive to the BVOC emissions in the urban area because the area is usually VOC-limited. Three additional experiments concerning the sensitivity of surface ozone to MEGAN input variables were also performed to assess the sensitivity of surface ozone to MEGAN drivers, and the results reveal that land cover and emission factors of BVOCs are the most important drivers and have large impacts on the predicted surface ozone.
Glyoxal and methylglyoxal in Atlantic seawater and marine aerosol particles: method development and first application during the Polarstern cruise ANT XXVII/4

An analytical method for the determination of the alpha dicarbonyls glyoxal (GLY) and methylglyoxal (MGLY) from seawater and marine aerosol particles is presented. The method is based on derivatization with o-(2,3,4,5,6-Pentafluorobenzyl)-hydroxylamine (PFBHA) reagent, solvent extraction and GC-MS (SIM) analysis. The method showed good precision (RSD < 10%), sensitivity (detection limits in the low ng L−1 range), and accuracy (good agreement between external calibration and standard addition). The method was applied to determine GLY and MGLY in oceanic water sampled during the Polarstern cruise ANT XXVII/4 from Capetown to Bremerhaven in spring 2011. GLY and MGLY were determined in the sea surface microlayer (SML) of the ocean and corresponding bulk water (BW) with average concentrations of 228 ng L−1 (GLY) and 196 ng L−1 (MGLY). The results show a significant enrichment (factor of 4) of GLY and MGLY in the SML. Furthermore, marine aerosol particles (PM1) were sampled during the cruise and analyzed for GLY (average concentration 0.19 ng m−3) and MGLY (average concentration 0.15 ng m−3). On aerosol particles, both carbonyls show a very good correlation with oxalate, supporting the idea of a secondary formation of oxalic acid via GLY and MGLY. Concentrations of GLY and MGLY in seawater and on aerosol particles were correlated to environmental parameters such as global radiation, temperature, distance to the coastline and biological activity. There are slight hints for a photochemical production of GLY and MGLY in the SML (significant enrichment in the SML, higher enrichment at higher temperature). However, a clear connection of GLY and MGLY to global radiation as well as to biological activity cannot be concluded from the data. A slight correlation between GLY and MGLY in the SML and in aerosol particles could be a hint for interactions, in particular of GLY, between seawater and the atmosphere.
Evaluating global emission inventories of biogenic bromocarbons

Emissions of halogenated very short-lived substances (VSLS) are poorly constrained. However, their inclusion in global models is required to simulate a realistic inorganic bromine (Bry) loading in both the troposphere, where bromine chemistry perturbs global oxidising capacity, and in the stratosphere, where it is a major sink for ozone (O3). We have performed simulations using a 3-D chemical transport model (CTM) including three top-down and a single bottom-up derived emission inventory of the major brominated VSLS bromoform (CHBr3) and dibromomethane (CH2Br2). We perform the first concerted evaluation of these inventories, comparing both the magnitude and spatial distribution of emissions. For a quantitative evaluation of each inventory, model output is compared with independent long-term observations at National Oceanic and Atmospheric Administration (NOAA) ground-based stations and with aircraft observations made during the NSF (National Science Foundation) HIAPER Pole-to-Pole Observations (HIPPO) project. For CHBr3, the mean absolute deviation between model and surface observation ranges from 0.22 (38%) to 0.78 (115%) parts per trillion (ppt) in the tropics, depending on emission inventory. For CH2Br2, the range is 0.17 (24%) to 1.25 (167%) ppt. We also use aircraft observations made during the 2011 Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere (SHIVA) campaign, in the tropical western Pacific. Here, the performance of the various inventories also varies significantly, but overall the CTM is able to reproduce observed CHBr3 well in the free troposphere using an inventory based on observed sea-to-air fluxes. Finally, we identify the range of uncertainty associated with these VSLS emission inventories on stratospheric bromine loading due to VSLS (BryVSLS). Our simulations show BryVSLS ranges from ~4.0 to 8.0 ppt depending on the inventory. We report an optimised estimate at the lower end of this range (~4 ppt) based on combining the CHBr3 and CH2Br2 inventories which give best agreement with the compilation of observations in the tropics.