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Using a combined power law and log-normal distribution model to simulate particle formation and growth in a mobile aerosol chamber

We present the combined power law and log-normal distribution (PL+LN) model, a computationally efficient model to be used in simulations where the particle size distribution cannot be accurately represented by log-normal distributions, such as in simulations involving the initial steps of aerosol formation, where new particle formation and growth occur simultaneously, or in the case of inverse modeling. The model was evaluated against highly accurate sectional models using input parameter values that reflect conditions typical to particle formation occurring in the atmosphere and in vehicle exhaust. The model was tested in the simulation of a particle formation event performed in a mobile aerosol chamber at Mäkelänkatu street canyon measurement site in Helsinki, Finland. The number, surface area, and mass concentrations in the chamber simulation were conserved with the relative errors lower than 2 % using the PL+LN model, whereas a moment-based log-normal model and sectional models with the same computing time as with the PL+LN model caused relative errors up to 17 and 79 %, respectively.
Aerosol water parameterisation: a single parameter framework

We introduce a framework to efficiently parameterise the aerosol water uptake for mixtures of semi-volatile and non-volatile compounds, based on the coefficient, νi. This solute-specific coefficient was introduced in Metzger et al. (2012) to accurately parameterise the single solution hygroscopic growth, considering the Kelvin effect – accounting for the water uptake of concentrated nanometer-sized particles up to dilute solutions, i.e. from the compounds relative humidity of deliquescence (RHD) up to supersaturation (Köhler theory). Here we extend the νi parameterisation from single to mixed solutions. We evaluate our framework at various levels of complexity, by considering the full gas–liquid–solid partitioning for a comprehensive comparison with reference calculations using the E-AIM, EQUISOLV II and ISORROPIA II models as well as textbook examples. We apply our parameterisation in the EQuilibrium Simplified Aerosol Model V4 (EQSAM4clim) for climate simulations, implemented in a box model and in the global chemistry–climate model EMAC. Our results show (i) that the νi approach enables one to analytically solve the entire gas–liquid–solid partitioning and the mixed solution water uptake with sufficient accuracy, (ii) that ammonium sulfate mixtures can be solved with a simple method, e.g. pure ammonium nitrate and mixed ammonium nitrate and (iii) that the aerosol optical depth (AOD) simulations are in close agreement with remote sensing observations for the year 2005. Long-term evaluation of the EMAC results based on EQSAM4clim and ISORROPIA II will be presented separately.
Exploring an approximation for the homogeneous freezing temperature of water droplets

In this work, based on the well-known formulae of classical nucleation theory (CNT), the temperature TNc = 1 at which the mean number of critical embryos inside a droplet is unity is derived from the Boltzmann distribution function and explored as an approximation for homogeneous freezing temperature of water droplets. Without including the information of the applied cooling rate γcooling and the number of observed droplets Ntotal_droplets in the calculation, the approximation TNc = 1 is able to reproduce the dependence of homogeneous freezing temperature on drop size V and water activity aw of aqueous drops observed in a wide range of experimental studies for droplet diameter > 10 µm and aw > 0.85, suggesting the effect of γcooling and Ntotal_droplets may be secondary compared to the effect of V and aw on homogeneous freezing temperatures in these size and water activity ranges under realistic atmospheric conditions. We use the TNc = 1 approximation to argue that the distribution of homogeneous freezing temperatures observed in the experiments may be partly explained by the spread in the size distribution of droplets used in the particular experiment. It thus appears that the simplicity of this approximation makes it potentially useful for predicting homogeneous freezing temperatures of water droplets in the atmosphere.
Characterization of polar organosulfates in secondary organic aerosol from the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal

We show in the present study that the unsaturated aldehydes 2-E-pentenal, 2-E-hexenal, and 3-Z-hexenal are biogenic volatile organic compound (BVOC) precursors for polar organosulfates with molecular weights (MWs) 230 and 214, which are also present in ambient fine aerosol from a forested site, i.e., K-puszta, Hungary. These results complement those obtained in a previous study showing that the green leaf aldehyde 3-Z-hexenal serves as a precursor for MW 226 organosulfates. Thus, in addition to isoprene, the green leaf volatiles (GLVs) 2-E-hexenal and 3-Z-hexenal, emitted due to plant stress (mechanical wounding or insect attack), and 2-E-pentenal, a photolysis product of 3-Z-hexenal, should be taken into account for secondary organic aerosol and organosulfate formation. Polar organosulfates are of climatic relevance because of their hydrophilic properties and cloud effects. Extensive use was made of organic mass spectrometry (MS) and detailed interpretation of MS data (i.e., ion trap MS and accurate mass measurements) to elucidate the chemical structures of the MW 230, 214 and 170 organosulfates formed from 2-E-pentenal and indirectly from 2-E-hexenal and 3-Z-hexenal. In addition, quantum chemical calculations were performed to explain the different mass spectral behavior of 2,3-dihydroxypentanoic acid sulfate derivatives, where only the isomer with the sulfate group at C-3 results in the loss of SO3. The MW 214 organosulfates formed from 2-E-pentenal are explained by epoxidation of the double bond in the gas phase and sulfation of the epoxy group with sulfuric acid in the particle phase through the same pathway as that proposed for 3-sulfooxy-2-hydroxy-2-methylpropanoic acid from the isoprene-related α,β-unsaturated aldehyde methacrolein in previous work (Lin et al., 2013). The MW 230 organosulfates formed from 2-E-pentenal are tentatively explained by a novel pathway, which bears features of the latter pathway but introduces an additional hydroxyl group at the C-4 position. Evidence is also presented that the MW 214 positional isomer, 2-sulfooxy-3-hydroxypentanoic acid, is unstable and decarboxylates, giving rise to 1-sulfooxy-2-hydroxybutane, a MW 170 organosulfate. Furthermore, evidence is obtained that lactic acid sulfate is generated from 2-E-pentenal. This chemistry could be important on a regional and local scale where GLV emissions such as from grasses and cereal crops are substantial.
Vertical profiling of aerosol hygroscopic properties in the planetary boundary layer during the PEGASOS campaigns

Vertical profiles of the aerosol particles hygroscopic properties, their mixing state as well as chemical composition were measured above northern Italy and the Netherlands. An aerosol mass spectrometer (AMS; for chemical composition) and a white-light humidified optical particle spectrometer (WHOPS; for hygroscopic growth) were deployed on a Zeppelin NT airship within the PEGASOS project. This allowed one to investigate the development of the different layers within the planetary boundary layer (PBL), providing a unique in situ data set for airborne aerosol particles properties in the first kilometre of the atmosphere. Profiles measured during the morning hours on 20 June 2012 in the Po Valley, Italy, showed an increased nitrate fraction at ∼  100 m above ground level (a.g.l.) coupled with enhanced hygroscopic growth compared to ∼  700 m a. g. l. This result was derived from both measurements of the aerosol composition and direct measurements of the hygroscopicity, yielding hygroscopicity parameters (κ) of 0.34  ± 0.12 and 0.19  ± 0.07 for 500 nm particles, at ∼  100 and ∼  700 m a. g. l., respectively. The difference is attributed to the structure of the PBL at this time of day which featured several independent sub-layers with different types of aerosols. Later in the day the vertical structures disappeared due to the mixing of the layers and similar aerosol particle properties were found at all probed altitudes (mean κ ≈ 0.18  ± 0.07). The aerosol properties observed at the lowest flight level (100 m a. g. l.) were consistent with parallel measurements at a ground site, both in the morning and afternoon. Overall, the aerosol particles were found to be externally mixed, with a prevailing hygroscopic fraction. The flights near Cabauw in the Netherlands in the fully mixed PBL did not feature altitude-dependent characteristics. Particles were also externally mixed and had an even larger hygroscopic fraction compared to the results in Italy. The mean κ from direct measurements was 0.28 ± 0.10, thus considerably higher than κ values measured in Italy in the fully mixed PBL.
Canopy-scale flux measurements and bottom-up emission estimates of volatile organic compounds from a mixed oak and hornbeam forest in northern Italy

This paper reports the fluxes and mixing ratios of biogenically emitted volatile organic compounds (BVOCs) 4 m above a mixed oak and hornbeam forest in northern Italy. Fluxes of methanol, acetaldehyde, isoprene, methyl vinyl ketone + methacrolein, methyl ethyl ketone and monoterpenes were obtained using both a proton-transfer-reaction mass spectrometer (PTR-MS) and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS) together with the methods of virtual disjunct eddy covariance (using PTR-MS) and eddy covariance (using PTR-ToF-MS). Isoprene was the dominant emitted compound with a mean daytime flux of 1.9 mg m−2 h−1. Mixing ratios, recorded 4 m above the canopy, were dominated by methanol with a mean value of 6.2 ppbv over the 28-day measurement period. Comparison of isoprene fluxes calculated using the PTR-MS and PTR-ToF-MS showed very good agreement while comparison of the monoterpene fluxes suggested a slight over estimation of the flux by the PTR-MS. A basal isoprene emission rate for the forest of 1.7 mg m−2 h−1 was calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN) isoprene emission algorithms (Guenther et al., 2006). A detailed tree-species distribution map for the site enabled the leaf-level emission of isoprene and monoterpenes recorded using gas-chromatography mass spectrometry (GC–MS) to be scaled up to produce a bottom-up canopy-scale flux. This was compared with the top-down canopy-scale flux obtained by measurements. For monoterpenes, the two estimates were closely correlated and this correlation improved when the plant-species composition in the individual flux footprint was taken into account. However, the bottom-up approach significantly underestimated the isoprene flux, compared with the top-down measurements, suggesting that the leaf-level measurements were not representative of actual emission rates.
Tropospheric column ozone response to ENSO in GEOS-5 assimilation of OMI and MLS ozone data

We use GEOS-5 analyses of Ozone Monitoring Instrument (OMI) and Microwave Limb Sounder (MLS) ozone observations to investigate the magnitude and spatial distribution of the El Niño Southern Oscillation (ENSO) influence on tropospheric column ozone (TCO) into the middle latitudes. This study provides the first explicit spatially resolved characterization of the ENSO influence and demonstrates coherent patterns and teleconnections impacting the TCO in the extratropics. The response is evaluated and characterized by both the variance explained and sensitivity of TCO to the Niño 3.4 index. The tropospheric response in the tropics agrees well with previous studies and verifies the analyses. A two-lobed response symmetric about the Equator in the western Pacific/Indonesian region seen in some prior studies and not in others is confirmed here. This two-lobed response is consistent with the large-scale vertical transport. We also find that the large-scale transport in the tropics dominates the response compared to the small-scale convective transport. The ozone response is weaker in the middle latitudes, but a significant explained variance of the TCO is found over several small regions, including the central United States. However, the sensitivity of TCO to the Niño 3.4 index is statistically significant over a large area of the middle latitudes. The sensitivity maxima and minima coincide with anomalous anti-cyclonic and cyclonic circulations where the associated vertical transport is consistent with the sign of the sensitivity. Also, ENSO related changes to the mean tropopause height can contribute significantly to the midlatitude response. Comparisons to a 22-year chemical transport model simulation demonstrate that these results from the 9-year assimilation are representative of the longer term. This investigation brings insight to several seemingly disparate prior studies of the El Niño influence on tropospheric ozone in the middle latitudes.
Derivation of physical and optical properties of mid-latitude cirrus ice crystals for a size-resolved cloud microphysics model

Single-crystal images collected in mid-latitude cirrus are analyzed to provide internally consistent ice physical and optical properties for a size-resolved cloud microphysics model, including single-particle mass, projected area, fall speed, capacitance, single-scattering albedo, and asymmetry parameter. Using measurements gathered during two flights through a widespread synoptic cirrus shield, bullet rosettes are found to be the dominant identifiable habit among ice crystals with maximum dimension (Dmax) greater than 100 µm. Properties are therefore first derived for bullet rosettes based on measurements of arm lengths and widths, then for aggregates of bullet rosettes and for unclassified (irregular) crystals. Derived bullet rosette masses are substantially greater than reported in existing literature, whereas measured projected areas are similar or lesser, resulting in factors of 1.5–2 greater fall speeds, and, in the limit of large Dmax, near-infrared single-scattering albedo and asymmetry parameter (g) greater by ∼  0.2 and 0.05, respectively. A model that includes commonly imaged side plane growth on bullet rosettes exhibits relatively little difference in microphysical and optical properties aside from ∼ 0.05 increase in mid-visible g primarily attributable to plate aspect ratio. In parcel simulations, ice size distribution, and g are sensitive to assumed ice properties.
Urban increments of gaseous and aerosol pollutants and their sources using mobile aerosol mass spectrometry measurements

Air pollution is one of the main environmental concerns in urban areas, where anthropogenic emissions strongly affect air quality. This work presents the first spatially resolved detailed characterization of PM2.5 (particulate matter with aerodynamic equivalent diameter daero  ≤  2.5 µm) in two major Estonian cities, Tallinn and Tartu. The measurements were performed in March 2014 using a mobile platform. In both cities, the non-refractory (NR)-PM2.5 was characterized by a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) using a recently developed lens which increases the transmission of super-micron particles. Equivalent black carbon (eBC) and several trace gases including carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4) were also measured. The chemical composition of PM2.5 was found to be very similar in the two cities. Organic aerosol (OA) constituted the largest fraction, explaining on average about 52 to 60 % of the PM2.5 mass. Four sources of OA were identified using positive matrix factorization (PMF): hydrocarbon-like OA (HOA, from traffic emissions), biomass burning OA (BBOA, from biomass combustion), residential influenced OA (RIOA, probably mostly from cooking processes with possible contributions from waste and coal burning), and oxygenated OA (OOA, related to secondary aerosol formation). OOA was the major OA source during nighttime, explaining on average half of the OA mass, while during daytime mobile measurements the OA was affected by point sources and dominated by the primary fraction. A strong increase in the secondary organic and inorganic components was observed during periods with transport of air masses from northern Germany, while the primary local emissions accumulated during periods with temperature inversions. Mobile measurements offered the identification of different source regions within the urban areas and the assessment of the extent to which pollutants concentrations exceeded regional background levels (urban increments). HOA, eBC, CO2, and CO showed stronger enhancements on busy roads during the morning and evening traffic rush hours; BBOA had its maximum enhancement in the residential areas during the evening hours and RIOA was enhanced in both the city center (emissions from restaurants) and in the residential areas (emissions from residential cooking). In contrast, secondary components (OOA, sulfate (SO4), nitrate (NO3), ammonium (NH4), and chloride (Cl)) had very homogeneous distributions in time and space. We were able to determine a total PM2.5 urban increment in Tartu of 6.0 µg m−3 over a regional background concentration of 4.0 µg m−3 (i.e., a factor of 2.5 increase). Traffic exhaust emissions were identified as the most important source of this increase, with eBC and HOA explaining on average 53.3 and 20.5 % of the total increment, respectively.
Precipitation and microphysical processes observed by three polarimetric X-band radars and ground-based instrumentation during HOPE

This study presents a first analysis of precipitation and related microphysical processes observed by three polarimetric X-band Doppler radars (BoXPol, JuXPol and KiXPol) in conjunction with a ground-based network of disdrometers, rain gauges and vertically pointing micro rain radars (MRRs) during the High Definition Clouds and Precipitation for advancing Climate Prediction (HD(CP)2) Observational Prototype Experiment (HOPE) during April and May 2013 in Germany. While JuXPol and KiXPol were continuously observing the central HOPE area near Forschungszentrum Jülich at a close distance, BoXPol observed the area from a distance of about 48.5 km. MRRs were deployed in the central HOPE area and one MRR close to BoXPol in Bonn, Germany. Seven disdrometers and three rain gauges providing point precipitation observations were deployed at five locations within a 5 km  ×  5 km region, while three other disdrometers were collocated with the MRR in Bonn. The daily rainfall accumulation at each rain gauge/disdrometer location estimated from the three X-band polarimetric radar observations showed very good agreement. Accompanying microphysical processes during the evolution of precipitation systems were well captured by the polarimetric X-band radars and corroborated by independent observations from the other ground-based instruments.