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Aerosol ageing in an urban plume – implication for climate

The climate effects downwind of an urban area resulting from gaseous and particulate emissions within the city are as yet inadequately quantified. The aim of this work was to estimate these effects for Malmö city in southern Sweden (population 280 000). The chemical and physical particle properties were simulated with a model for Aerosol Dynamics, gas phase CHEMistry and radiative transfer calculations (ADCHEM) following the trajectory movement from upwind of Malmö, through the urban background environment and finally tens and hundreds of kilometers downwind of Malmö. The model results were evaluated using measurements of the particle number size distribution and chemical composition. The total particle number concentration 50 km (~ 3 h) downwind, in the center of the Malmö plume, is about 3700 cm−3 of which the Malmö contribution is roughly 30%. Condensation of nitric acid, ammonium and to a smaller extent oxidized organic compounds formed from the emissions in Malmö increases the secondary aerosol formation with a maximum of 0.7–0.8 μg m−3 6 to 18 h downwind of Malmö. The secondary mass contribution dominates over the primary soot contribution from Malmö already 3 to 4 h downwind of the emission sources and contributes to an enhanced total surface direct or indirect aerosol shortwave radiative forcing in the center of the urban plume ranging from −0.3 to −3.3 W m−2 depending on the distance from Malmö, and the specific cloud properties.
Global multi-year O3-CO correlation patterns from models and TES satellite observations

The correlation between measured tropospheric ozone (O3) and carbon monoxide (CO) has been used extensively in tropospheric chemistry studies to explore the photochemical characteristics of different regions and to evaluate the ability of models to capture these characteristics. Here, we present the first study that uses multi-year, global, vertically resolved, simultaneous and collocated O3 and CO satellite (Tropospheric Emission Spectrometer) measurements, to determine this correlation in the middle/lower free troposphere for two different seasons, and to evaluate two chemistry-climate models. We find results that are fairly robust across different years, altitudes and timescales considered, which indicates that the correlation maps presented here could be used in future model evaluations. The highest positive correlations (around 0.8) are found in the northern Pacific during summer, which is a common feature in the observations and the G-PUCCINI model. We make quantitative comparisons between the models using a single-figure metric (C), which we define as the correlation coefficient between the modeled and the observed O3-CO correlations for different regions of the globe. On a global scale, the G-PUCCINI model shows a good performance in the summer (C=0.71) and a satisfactory performance in the winter (C=0.52). It captures midlatitude features very well, especially in the summer, whereas the performance in regions like South America or Central Africa is weaker. The UKCA model (C=0.46/0.15 for July–August/December–January on a global scale) performs better in certain regions, such as the tropics in winter, and it captures some of the broad characteristics of summer extratropical correlations, but it systematically underestimates the O3-CO correlations over much of the globe. It is noteworthy that the correlations look very different in the two models, even though the ozone distributions are similar. This demonstrates that this technique provides a powerful global constraint for understanding modeled tropospheric chemical processes. We investigated the sources of the correlations by performing a series of sensitivity experiments. In these, the sign of the correlation is, in most cases, insensitive to removing different individual emissions, but its magnitude changes downwind of emission regions when applying such perturbations. Interestingly, we find that the O3-CO correlation does not solely reflect the strength of O3 photochemical production, as often assumed by earlier studies, but is more complicated and may reflect a mixture of different processes such as transport.
A reanalysis of MODIS fine mode fraction over ocean using OMI and daily GOCART simulations

Using daily Goddard Chemistry Aerosol Radiation and Transport (GOCART) model simulations and columnar retrievals of 0.55 μm aerosol optical thickness (AOT) and fine mode fraction (FMF) from the Moderate Resolution Imaging Spectroradiometer (MODIS), we estimate the satellite-derived aerosol properties over the global oceans between June 2006 and May 2007 due to black carbon (BC), organic carbon (OC), dust (DU), sea-salt (SS), and sulfate (SU) components. Using Aqua-MODIS aerosol properties embedded in the CERES-SSF product, we find that the mean MODIS FMF values for each aerosol type are SS: 0.31 ± 0.09, DU: 0.49 ± 0.13, SU: 0.77 ± 0.16, and (BC + OC): 0.80 ± 0.16. We further combine information from the ultraviolet spectrum using the Ozone Monitoring Instrument (OMI) onboard the Aura satellite to improve the classification process, since dust and carbonate aerosols have positive Aerosol Index (AI) values >0.5 while other aerosol types have near zero values. By combining MODIS and OMI datasets, we were able to identify and remove data in the SU, OC, and BC regions that were not associated with those aerosol types. The same methods used to estimate aerosol size characteristics from MODIS data within the CERES-SSF product were applied to Level 2 (L2) MODIS aerosol data from both Terra and Aqua satellites for the same time period. As expected, FMF estimates from L2 Aqua data agreed well with the CERES-SSF dataset from Aqua. However, the FMF estimate for DU from Terra data was significantly lower (0.37 vs. 0.49) indicating that sensor calibration, sampling differences, and/or diurnal changes in DU aerosol size characteristics were occurring. Differences for other aerosol types were generally smaller. Sensitivity studies show that a difference of 0.1 in the estimate of the anthropogenic component of FMF produces a corresponding change of 0.2 in the anthropogenic component of AOT (assuming a unit value of AOT). This uncertainty would then be passed along to any satellite-derived estimates of anthropogenic aerosol radiative effects.
Thin and subvisible cirrus and contrails in a subsaturated environment

The frequency of occurrence of cirrus clouds and contrails, their life time, ice crystal size spectra and thus their radiative properties depend strongly on the ambient distribution of the relative humidity with respect to ice (RHice). Ice clouds do not form below a certain supersaturation and both cirrus and contrails need at least saturation conditions to persist over a longer period. Under subsaturated conditions, cirrus and contrails should dissipate. During the mid-latitude aircraft experiment CONCERT 2008 (CONtrail and Cirrus ExpeRimenT), RHice and ice crystals were measured in cirrus and contrails. Here, we present results from 2.3/1.7 h of observation in cirrus/contrails during 6 flights. Thin and subvisible cirrus with contrails embedded therein have been detected frequently in a subsaturated environment. Nevertheless, ice crystals up to radii of 50 μm and larger, but with low number densities were often observed inside the contrails as well as in the cirrus. Analysis of the meteorological situation indicates that the crystals in the contrails were entrained from the thin/subvisible cirrus clouds, which emerged in frontal systems with low updrafts. From model simulations of cirrus evaporation times it follows that such thin/subvisible cirrus can exist for time periods of a couple of hours and longer in a subsaturated environment and thus may represent a considerable part of the cirrus coverage.
Development and evaluation of the aerosol dynamics and gas phase chemistry model ADCHEM

The aim of this work was to develop a model suited for detailed studies of aerosol dynamics, gas and particle phase chemistry within urban plumes, from local scale (1 × 1 km2) to regional scale. This article describes and evaluates the trajectory model for Aerosol Dynamics, gas and particle phase CHEMistry and radiative transfer (ADCHEM). The model treats both vertical and horizontal dispersion perpendicular to an air mass trajectory (2-space dimensions). The Lagrangian approach enables a more detailed representation of the aerosol dynamics, gas and particle phase chemistry and a finer spatial and temporal resolution compared to that of available regional 3D-CTMs. These features make it among others well suited for urban plume studies. The aerosol dynamics model includes Brownian coagulation, dry deposition, wet deposition, in-cloud processing, condensation, evaporation, primary particle emissions and homogeneous nucleation. The organic mass partitioning was either modeled with a 2-dimensional volatility basis set (2D-VBS) or with the traditional two-product model approach. In ADCHEM these models consider the diffusion limited and particle size dependent condensation and evaporation of 110 and 40 different organic compounds respectively. The gas phase chemistry model calculates the gas phase concentrations of 61 different species, using 130 different chemical reactions. Daily isoprene and monoterpene emissions from European forests were simulated separately with the vegetation model LPJ-GUESS, and included as input to ADCHEM. ADCHEM was used to simulate the ageing of the urban plumes from the city of Malmö in southern Sweden (280 000 inhabitants). Several sensitivity tests were performed concerning the number of size bins, size structure method, aerosol dynamic processes, vertical and horizontal mixing, coupled or uncoupled condensation and the secondary organic aerosol formation. The simulations show that the full-stationary size structure gives accurate results with little numerical diffusion when more than 50 size bins are used between 1.5 and 2500 nm, while the moving-center method is preferable when only a few size bins are selected. The particle number size distribution in the center of the urban plume from Malmö was mainly affected by dry deposition, coagulation and vertical dilution. The modeled PM2.5 mass was dominated by organic material, nitrate, sulfate and ammonium. If the condensation of HNO3 and NH3 was treated as a coupled process (pH independent) the model gave lower nitrate PM2.5 mass than if considering uncoupled condensation. Although the time of ageing from that SOA precursors are emitted until condensable products are formed is substantially different with the 2D-VBS and two product model, the models gave similar total organic mass concentrations.
Evaluation of cloud convection and tracer transport in a three-dimensional chemical transport model

We investigate the performance of cloud convection and tracer transport in a global off-line 3-D chemical transport model. Various model simulations are performed using different meteorological (re)analyses (ERA-40, ECMWF operational and ECMWF Interim) to diagnose the updraft mass flux, convective precipitation and cloud top height. The diagnosed upward mass flux distribution from TOMCAT agrees quite well with the ECMWF reanalysis data (ERA-40 and ERA-Interim) below 200 hPa. Inclusion of midlevel convection improves the agreement at mid-high latitudes. However, the reanalyses show strong convective transport up to 100 hPa, well into the tropical tropopause layer (TTL), which is not captured by TOMCAT. Similarly, the model captures the spatial and seasonal variation of convective cloud top height although the mean modelled value is about 2 km lower than observed. The ERA-Interim reanalyses have smaller archived upward convective mass fluxes than ERA-40, and smaller convective precipitation, which is in better agreement with satellite-based data. TOMCAT captures these relative differences when diagnosing convection from the large-scale fields. The model also shows differences in diagnosed convection with the version of the operational analyses used, which cautions against using results of the model from one specific time period as a general evaluation. We have tested the effect of resolution on the diagnosed modelled convection with simulations ranging from 5.6° × 5.6° to 1° × 1°. Overall, in the off-line model, the higher model resolution gives stronger vertical tracer transport, however, it does not make a large change to the diagnosed convective updraft mass flux (i.e., the model results using the convection scheme fail to capture the strong convection transport up to 100 hPa as seen in the archived convective mass fluxes). Similarly, the resolution of the forcing winds in the higher resolution CTM does not make a large improvement compared to the archived mass fluxes. Including a radon tracer in the model confirms the importance of convection for reproducing observed midlatitude profiles. The model run using archived mass fluxes transports significantly more radon to the upper troposphere but the available data does not strongly discriminate between the different model versions.
Aerosol climatology and planetary boundary influence at the Jungfraujoch analyzed by synoptic weather types

Fourteen years of meteorological parameters, aerosol variables (absorption and scattering coefficients, aerosol number concentration) and trace gases (CO, NOx, SO2) measured at the Jungfraujoch (JFJ, 3580 m a.s.l.) have been analyzed as a function of different synoptic weather types. The Schüepp synoptic weather type of the Alps (SYNALP) classification from the Alpine Weather Statistics (AWS) was used to define the synoptic meteorology over the whole Swiss region. The seasonal contribution of each synoptic weather type to the aerosol concentration was deduced from the aerosol annual cycles while the planetary boundary layer (PBL) influence was estimated by means of the diurnal cycles. Since aerosols are scavenged by precipitation, the diurnal cycle of the CO concentration was also used to identify polluted air masses. SO2 and NOx concentrations were used as precursor tracers for new particle formation and growth, respectively. The aerosol optical parameters and number concentration show elevated loadings during advective weather types during the December–March period and for the convective anticyclonic and convective indifferent weather types during the April–September period. This study confirms the consensus view that the JFJ is mainly influenced by the free troposphere during winter and by injection of air parcels from the PBL during summer. A more detailed picture is, however, drawn where the JFJ is completely influenced by free tropospheric air masses in winter during advective weather types and largely influenced by the PBL also during the night in summer during the subsidence weather type. Between these two extreme situations, the PBL influence at the JFJ depends on both the time of year and the synoptic weather type. The fraction of PBL air transported to the JFJ was estimated by the relative increase of the specific humidity and CO.
Aerosol optical properties in the North China Plain during HaChi campaign: an in-situ optical closure study

The largest uncertainty in the estimation of climate forcing stems from atmospheric aerosols. In early spring and summer of 2009, two periods of in-situ measurements on aerosol physical and chemical properties were conducted within the HaChi (Haze in China) project at Wuqing, a town between Beijing and Tianjin in the North China Plain (NCP). Aerosol optical properties, including the scattering coefficient (σsp), the hemispheric back scattering coefficient (σbsp), the absorption coefficient (σap), as well as the single scattering albedo (ω), are presented. The diurnal and seasonal variations are analyzed together with meteorology and satellite data. The mean values of σsp, 550 nm of the dry aerosol in spring and summer are 280±253 and 379±251 Mm−1, respectively. The average σap for the two periods is respectively 47±38 and 43±27 Mm−1. The mean values of ω at the wavelength of 637 nm are 0.82±0.05 and 0.86±0.05 for spring and summer, respectively. The relative high levels of σsp and σbsp are representative of the regional aerosol pollution in the NCP. Pronounced diurnal cycle of $σsp, σap and ω are found, mainly influenced by the evolution of boundary layer and the accumulation of local emissions during nighttime. The pollutants transported from the southwest of the NCP are more significant than that from the two megacities, Beijing and Tianjin, in both spring and summer. An optical closure experiment is conducted to better understand the uncertainties of the measurements. Good correlations (R>0.98) are found between the values measured by the nephelometer and the values calculated with a modified Mie model. The Monte Carlo simulation shows an uncertainty of about 30 % for the calculations. Considering all possible uncertainties of measurements, calculated σsp and σbsp agree well with the measured values, indicating a stable performance of instruments and thus reliable aerosol optical data.
Investigating the use of secondary organic aerosol as seed particles in simulation chamber experiments

The use of β-caryophyllene secondary organic aerosol particles as seeds for smog chamber simulations has been investigated. A series of experiments were carried out in the Manchester photochemical chamber as part of the Aerosol Coupling in the Earth System (ACES) project to study the effect of seed particles on the formation of secondary organic aerosol (SOA) from limonene photo-oxidation. Rather than use a conventional seed aerosol containing ammonium sulfate or diesel particles, a method was developed to use in-situ chamber generated seed particles from β-caryophyllene photo-oxidation, which were then diluted to a desired mass loading (in this case 4–13 μg m−3). Limonene was then introduced into the chamber and oxidised, with the formation of SOA seen as a growth in the size of oxidised organic seed particles from 150 to 325 nm mean diameter. The effect of the partitioning of limonene oxidation products onto the seed aerosol was assessed using aerosol mass spectrometry during the experiment and the percentage of m/z 44, an indicator of degree of oxidation, increased from around 5 to 8 %. The hygroscopicity of the aerosol also changed, with the growth factor for 200 nm particles increasing from less than 1.05 to 1.25 at 90 % RH. The detailed chemical composition of the limonene SOA could be extracted from the complex β-caryophyllene matrix using two-dimensional gas chromatography (GC × GC) and liquid chromatography coupled to mass spectrometry. High resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS) was used to determine exact molecular formulae of the seed and the limonene modified aerosol. The average O:C ratio was seen to increase from 0.32 to 0.37 after limonene oxidation products had condensed onto the organic seed.
Investigations of primary and secondary particulate matter of different wood combustion appliances with a high-resolution time-of-flight aerosol mass spectrometer

A series of photo-oxidation smog chamber experiments were performed to investigate the primary emissions and secondary aerosol formation from two different log wood burners and a residential pellet burner under different burning conditions: starting and flaming phase. Emissions were sampled from the chimney and injected into the smog chamber leading to primary organic aerosol (POA) concentrations comparable to ambient levels. The composition of the aerosol was measured by an Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS) and black carbon (BC) instrumentation. The primary emissions were then exposed to xenon light to initiate photo-chemistry and subsequent secondary organic aerosol (SOA) production. After correcting for wall losses, the average increase in organic matter (OM) concentrations by SOA formation for the starting and flaming phase experiments with the two log wood burners was found to be a factor of 4.1±1.4 after five hours of aging. No SOA formation was observed for the stable burning phase of the pellet burner. The startup emissions of the pellet burner showed an increase in OM concentration by a factor of 3.3. Including the measured SOA formation potential, average emission factors of BC+POA+SOA, calculated from CO2 emission, were found to be in the range of 0.04 to 3.9 g/kg wood for the stable burning pellet burner and an old log wood burner during startup respectively. SOA contributed significantly to the ion C2H4O2+ at mass to charge ratio m/z 60, a commonly used marker for primary emissions of wood burning. This contribution at m/z 60 can overcompensate for the degradation of levoglucosan leading to an overestimation of the contribution of wood burning or biomass burning to the total OM. The primary organic emissions from the three different burners showed a wide range in O:C atomic ratio (0.19−0.60) for the starting and flaming conditions, which also increased during aging. Primary wood burning emissions have a rather low relative contribution at m/z 43 (f 43) to the total organic mass spectrum. The non-oxidized fragment C3H7+ has a considerable contribution at m/z 43 for the fresh OA with an increasing contribution of the oxygenated ion C2H3O+ during aging. After five hours of aging, the OA has a rather low C2H3O+ signal for a given CO2+ fraction, possibly indicating a higher ratio of acid to non-acid oxygenated compounds in wood burning OA compared to other oxygenated organic aerosol (OOA).