Internally Mixed Research Articles

On Effective Radiative Forcing of Partial Internally and Externally Mixed Aerosols and Their Effects on Global Climate

AbstractThe total effective radiative forcing (ERF) due to partial internally mixed (PIM) and externally mixed (EM) anthropogenic aerosols, as well as their climatic effects since the year of 1850, was evaluated and compared using the aerosol‐climate online coupled model of BCC_AGCM2.0_CUACE/Aero. The influences of internal mixing (IM) on aerosol hygroscopicity parameter, optical properties, and concentration were considered. Generally, IM could markedly weaken the negative ERF and cooling effects of anthropogenic aerosols. The global annual mean ERF of EM anthropogenic aerosols from 1850 to 2010 was −1.87 W m−2, of which the aerosol‐radiation interactive ERF (ERFari) and aerosol‐cloud interactive ERF (ERFaci) were −0.49 and −1.38 W m−2, respectively. The global annual mean ERF due to PIM anthropogenic aerosols from 1850 to 2010 was −1.23 W m−2, with ERFari and ERFaci of −0.23 and −1.01 W m−2, respectively. The global annual mean surface temperature and water evaporation and precipitation were reduced by 1.74 K and 0.14 mm d−1 for EM scheme and 1.28 K and 0.11 mm d−1 for PIM scheme, respectively. However, the relative humidity near the surface was slightly increased for both mixing cases. The Intertropical Convergence Zone was southwardly shifted for both EM and PIM cases but was less southwardly shifted in PIM scheme due to the less reduction in atmospheric temperature in the midlatitude and low latitude of the Northern Hemisphere.

Mechanism of SOA formation determines magnitude of radiative effects

Secondary organic aerosol (SOA) nearly always exists as an internal mixture, and the distribution of this mixture depends on the formation mechanism of SOA. A model is developed to examine the influence of using an internal mixing state based on the mechanism of formation and to estimate the radiative forcing of SOA in the future. For the present day, 66% of SOA is internally mixed with sulfate, while 34% is internally mixed with primary soot. Compared with using an external mixture, the direct effect of SOA is decreased due to the decrease in total aerosol surface area and the increase of absorption efficiency. Aerosol number concentrations are sharply reduced, and this is responsible for a large decrease in the cloud albedo effect. Internal mixing decreases the radiative effect of SOA by a factor of >4 compared with treating SOA as an external mixture. The future SOA burden increases by 24% due to CO2 increases and climate change, leading to a total (direct plus cloud albedo) radiative forcing of -0.05 W m-2 When the combined effects of changes in climate, anthropogenic emissions, and land use are included, the SOA forcing is -0.07 W m-2, even though the SOA burden only increases by 6.8%. This is caused by the substantial increase of SOA associated with sulfate in the Aitken mode. The Aitken mode increase contributes to the enhancement of first indirect radiative forcing, which dominates the total radiative forcing.

Metrics to quantify the importance of mixing state for CCN activity

Abstract. It is commonly assumed that models are more prone to errors in predicted cloud condensation nuclei (CCN) concentrations when the aerosol populations are externally mixed. In this work we investigate this assumption by using the mixing state index (χ) proposed by Riemer and West (2013) to quantify the degree of external and internal mixing of aerosol populations. We combine this metric with particle-resolved model simulations to quantify error in CCN predictions when mixing state information is neglected, exploring a range of scenarios that cover different conditions of aerosol aging. We show that mixing state information does indeed become unimportant for more internally mixed populations, more precisely for populations with χ larger than 75 %. For more externally mixed populations (χ below 20 %) the relationship of χ and the error in CCN predictions is not unique and ranges from lower than −40 % to about 150 %, depending on the underlying aerosol population and the environmental supersaturation. We explain the reasons for this behavior with detailed process analyses.

Simulated effects of internal mixing of anthropogenic aerosols on the aerosol–radiation interaction and global temperature

ABSTRACTA partial internal mixing (PIM) treatment of black carbon (BC), organic carbon (OC), and sulphate was examined, and the core‐shell model was used to represent the internally mixed aerosols with BC as the core and sulphate or OC as the shell. The influences of PIM treatment on the effective radiative forcing due to aerosol–radiative interaction (ERFari) and global temperature were examined and compared to those of external mixing (EM) treatment using an aerosol‐climate online coupled model of BCC_AGCM2.0_CUACE/Aero. Radiative forcing due to aerosol–radiation interaction (RFari) of the anthropogenic aerosols since the preindustrial era was −0.34 W m−2 for EM and −0.23 W m−2 for PIM, respectively. The global annual mean ERFari of anthropogenic aerosols since the preindustrial era was −0.42 W m−2 for EM and −0.34 W m−2 for PIM, respectively. The change in global annual mean surface temperature increased accordingly from −0.18 K in the EM case to −0.125 K in the PIM case. Well geographic consistence between the change in low‐level cloud amount and the change in temperature can be found. The atmospheric temperature in the troposphere was markedly less reduced in the PIM case than in the EM case. The RFari/ERFari for 50% and 100% were −0.11/–0.07 and 0.13/0.14 W m−2, respectively. RFari, ERFari, and surface temperature changed approximately linearly with the internal mixing proportion.

Impact of mixing state and hygroscopicity on CCN activity of biomass burning aerosol in Amazonia

Abstract. Smoke aerosols prevail throughout Amazonia because of widespread biomass burning during the dry season, and external mixing, low variability in the particle size distribution and low particle hygroscopicity are typical. There can be profound effects on cloud properties. This study uses an adiabatic cloud model to simulate the activation of smoke particles as cloud condensation nuclei (CCN) for three hypothetical case studies, chosen as to resemble biomass burning aerosol observations in Amazonia. The relative importance of variability in hygroscopicity, mixing state, and activation kinetics for the activated fraction and maximum supersaturation is assessed. For a population with κp = 0.04, an overestimation of the cloud droplet number concentration Nd for the three selected case studies between 22.4 ± 1.4 and 54.3 ± 3.7 % was obtained when assuming a hygroscopicity parameter κp = 0.20. Assuming internal mixing of the aerosol population led to overestimations of up to 20 % of Nd when a group of particles with medium hygroscopicity was present in the externally mixed population cases. However, the overestimations were below 10 % for external mixtures between very low and low-hygroscopicity particles, as seems to be the case for Amazon smoke particles. Kinetic limitations were significant for medium- and high-hygroscopicity particles, and much lower for very low and low-hygroscopicity particles. When particles were assumed to be at equilibrium and to respond instantly to changes in the air parcel supersaturation, the overestimation of the droplet concentration was up to ∼ 100 % in internally mixed populations, and up to ∼ 250 % in externally mixed ones, being larger for the higher values of hygroscopicity. In addition, a perceptible delay between the times when maximum supersaturation and maximum aerosol activated fraction are reached was noticed and, for aerosol populations with effective hygroscopicity κpeff higher than a certain threshold value, the delay in particle activation was such that no particles were activated at the time of maximum supersaturation. Considering internally mixed populations, for an updraft velocity W = 0.5 m s−1 this threshold of no activation varied between κpeff = 0.35 and κpeff = 0.5 for the different case studies. However, for low hygroscopicity, kinetic limitations played a weaker role for CCN activation of particles, even when taking into account the large aerosol mass and number concentrations. For the very low range of hygroscopicities, the overestimation of the droplet concentration due to the equilibrium assumption was lowest and the delay between the times when maximum supersaturation and maximum activated fraction were reached was greatly reduced or no longer observed (depending on the case study). These findings on uncertainties and sensitivities provide guidance on appropriate simplifications that can be used for modeling of smoke aerosols within general circulation models. The use of medium values of hygroscopicity representative of smoke aerosols for other biomass burning regions on Earth can lead to significant errors compared to the use of low hygroscopicity for Amazonia (between 0.05 and 0.13, according to available observations). Also in this region, consideration of the biomass burning population as internally mixed will lead to small errors in the droplet concentration, while significantly increasing the computational burden. Regardless of the large smoke aerosol loads in the region during the dry season, kinetic limitations are expected to be low.

Size-dependent chemical ageing of oleic acid aerosol under dry and humidified conditions

Abstract. A chemical reaction chamber system has been developed for the processing of oleic acid aerosol particles with ozone under two relative humidity conditions: dry and humidified to 65 %. The apparatus consists of an aerosol flow tube, in which the ozonolysis occurs, coupled to a scanning mobility particle sizer (SMPS) and an aerosol time-of-flight mass spectrometer (ATOFMS) which measure the evolving particle size and composition. Under both relative humidity conditions, ozonolysis results in a significant decrease in particle size and mass which is consistent with the formation of volatile products that partition from the particle to the gas phase. Mass spectra derived from the ATOFMS reveal the presence of the typically observed reaction products: azelaic acid, nonanal, oxononanoic acid and nonanoic acid, as well as a range of higher molecular weight products deriving from the reactions of reaction intermediates with oleic acid and its oxidation products. These include octanoic acid and 9- and 10-oxooctadecanoic acid, as well as products of considerably higher molecular weight. Quantitative evaluation of product yields with the ATOFMS shows a marked dependence upon both particle size association (from 0.3 to 2.1 µm diameter) and relative humidity. Under both relative humidity conditions, the percentage residual of oleic acid increases with increasing particle size and the main lower molecular weight products are nonanal and oxononanoic acid. Under dry conditions, the percentage of higher molecular weight products increases with increasing particle size due to the poorer internal mixing of the larger particles. Under humidified conditions, the percentage of unreacted oleic acid is greater, except in the smallest particle fraction, with little formation of high molecular weight products relative to the dry particles. It is postulated that water reacts with reactive intermediates, competing with the processes which produce high molecular weight products. Whilst the oleic acid model aerosol system is of limited relevance to complex internally mixed atmospheric aerosol, the generic findings presented in this paper give useful insights into the nature of heterogeneous chemical processes.

Simulation of particle diversity and mixing state over Greater Paris: a model-measurement inter-comparison.

Air quality models are used to simulate and forecast pollutant concentrations, from continental scales to regional and urban scales. These models usually assume that particles are internally mixed, i.e. particles of the same size have the same chemical composition, which may vary in space and time. Although this assumption may be realistic for continental-scale simulations, where particles originating from different sources have undergone sufficient mixing to achieve a common chemical composition for a given model grid cell and time, it may not be valid for urban-scale simulations, where particles from different sources interact on shorter time scales. To investigate the role of the mixing state assumption on the formation of particles, a size-composition resolved aerosol model (SCRAM) was developed and coupled to the Polyphemus air quality platform. Two simulations, one with the internal mixing hypothesis and another with the external mixing hypothesis, have been carried out for the period 15 January to 11 February 2010, when the MEGAPOLI winter field measurement campaign took place in Paris. The simulated bulk concentrations of chemical species and the concentrations of individual particle classes are compared with the observations of Healy et al. (Atmos. Chem. Phys., 2013, 13, 9479-9496) for the same period. The single particle diversity and the mixing-state index are computed based on the approach developed by Riemer et al. (Atmos. Chem. Phys., 2013, 13, 11423-11439), and they are compared to the measurement-based analyses of Healy et al. (Atmos. Chem. Phys., 2014, 14, 6289-6299). The average value of the single particle diversity, which represents the average number of species within each particle, is consistent between simulation and measurement (2.91 and 2.79 respectively). Furthermore, the average value of the mixing-state index is also well represented in the simulation (69% against 59% from the measurements). The spatial distribution of the mixing-state index shows that the particles are not mixed in urban areas, while they are well mixed in rural areas. This indicates that the assumption of internal mixing traditionally used in transport chemistry models is well suited to rural areas, but this assumption is less realistic for urban areas close to emission sources.

Single-particle speciation of alkylamines in ambient aerosol at five European sites.

Alkylamines are associated with both natural and anthropogenic sources and have been detected in ambient aerosol in a variety of environments. However, little is known about the ubiquity or relative abundance of these species in Europe. In this work, ambient single-particle mass spectra collected at five sampling sites across Europe have been analysed for their alkylamine content. The aerosol time-of-flight mass spectrometer (ATOFMS) data used were collected in Ireland (Cork), France (Paris, Dunkirk and Corsica) and Switzerland (Zurich) between 2008 and 2013. Each dataset was queried for mass spectral marker ions associated with the following ambient alkylamines: dimethylamine (DMA), trimethylamine (TMA), diethylamine (DEA), triethylamine (TEA), dipropylamine (DPA) and tripropylamine (TPA). The fraction of ambient particles that contained detectable alkylamines ranged from 1 to 17% depending on location, with the highest fractions observed in Paris and Zurich in the winter months. The lowest fractions were observed at coastal sites, where the influence of animal husbandry-related alkylamine emissions is also expected to be lowest. TMA was the most ubiquitous particle phase alkylamine detected and was observed at all locations. Alkylamines were found to be internally mixed with both sulphate and nitrate for each dataset, suggesting that aminium salt formation may be important at all sites investigated. Interestingly, in Corsica, all alkylamine particles detected were also found to be internally mixed with methanesulphonic acid (MSA), indicating that aminium methanesulphonate salts may represent a component of marine ambient aerosol in the summer months. Internal mixing of alkylamines with sea salt was not observed, however. Alkylamine-containing particle composition was found to be reasonably homogeneous at each location, with the exception of the Corsica and Dunkirk sites, where two and four distinct mixing states were observed, respectively.

Stochastic parameterization for light absorption by internally mixed BC/dust in snow grains for application to climate models

A stochastic approach has been developed to model the positions of BC (black carbon)/dust internally mixed with two snow grain types: hexagonal plate/column (convex) and Koch snowflake (concave). Subsequently, light absorption and scattering analysis can be followed by means of an improved geometric-optics approach coupled with Monte Carlo photon tracing to determine BC/dust single-scattering properties. For a given shape (plate, Koch snowflake, spheroid, or sphere), the action of internal mixing absorbs substantially more light than external mixing. The snow grain shape effect on absorption is relatively small, but its effect on asymmetry factor is substantial. Due to a greater probability of intercepting photons, multiple inclusions of BC/dust exhibit a larger absorption than an equal-volume single inclusion. The spectral absorption (0.2–5 µm) for snow grains internally mixed with BC/dust is confined to wavelengths shorter than about 1.4 µm, beyond which ice absorption predominates. Based on the single-scattering properties determined from stochastic and light absorption parameterizations and using the adding/doubling method for spectral radiative transfer, we find that internal mixing reduces snow albedo substantially more than external mixing and that the snow grain shape plays a critical role in snow albedo calculations through its forward scattering strength. Also, multiple inclusion of BC/dust significantly reduces snow albedo as compared to an equal-volume single sphere. For application to land/snow models, we propose a two-layer spectral snow parameterization involving contaminated fresh snow on top of old snow for investigating and understanding the climatic impact of multiple BC/dust internal mixing associated with snow grain metamorphism, particularly over mountain/snow topography.

Single particle diversity and mixing state measurements

Abstract. A newly developed framework for quantifying aerosol particle diversity and mixing state based on information-theoretic entropy is applied for the first time to single particle mass spectrometry field data. Single particle mass fraction estimates for black carbon, organic aerosol, ammonium, nitrate and sulfate, derived using single particle mass spectrometer, aerosol mass spectrometer and multi-angle absorption photometer measurements are used to calculate single particle species diversity (Di). The average single particle species diversity (Dα) is then related to the species diversity of the bulk population (Dγ) to derive a mixing state index value (χ) at hourly resolution. The mixing state index is a single parameter representation of how internally/externally mixed a particle population is at a given time. The index describes a continuum, with values of 0 and 100% representing fully external and internal mixing, respectively. This framework was applied to data collected as part of the MEGAPOLI winter campaign in Paris, France, 2010. Di values are low (~ 2) for fresh traffic and wood-burning particles that contain high mass fractions of black carbon and organic aerosol but low mass fractions of inorganic ions. Conversely, Di values are higher (~ 4) for aged carbonaceous particles containing similar mass fractions of black carbon, organic aerosol, ammonium, nitrate and sulfate. Aerosol in Paris is estimated to be 59% internally mixed in the size range 150–1067 nm, and mixing state is dependent both upon time of day and air mass origin. Daytime primary emissions associated with vehicular traffic and wood-burning result in low χ values, while enhanced condensation of ammonium nitrate on existing particles at night leads to higher χ values. Advection of particles from continental Europe containing ammonium, nitrate and sulfate leads to increases in Dα, Dγ and χ. The mixing state index represents a useful metric by which to compare and contrast ambient particle mixing state at other locations globally.

Modification of Asian-dust particles transported by different routes – A case study

Two separate Asian dust events occurred before and after the passage of a cold front over Japan on 21 March 2010. According to back trajectories and a model simulation, the two dusty air-masses originated from the same region in Mongoria or northern China and were transported over different routes to Japan. Samples of aerosol particles from both airmasses were collected at Tsukuba and Mt. Haruna and examined by single-particle analysis using a transmission electron microscope and an energy dispersive X-ray analyzer. The mixing properties of mineral aerosol were quite different in the two airmasses and size ranges. In the prefrontal airmass, which were associated with pollution, most of fine (<1 μm) mineral aerosol was internally mixed with sulfate. On the contrary, mineral aerosols in the postfront airmass, which were relatively natural, were mostly externally mixed. In the latter case, the internal mixing was associated with Ca, however in the former case, mixing processes not concerning mineralogy was suggested.

Development of a source oriented version of the WRF/Chem model and its application to the California regional PM&amp;lt;sub&amp;gt;10&amp;lt;/sub&amp;gt; / PM&amp;lt;sub&amp;gt;2.5&amp;lt;/sub&amp;gt; air quality study

Abstract. A source-oriented version of the Weather Research and Forecasting model with chemistry (SOWC, hereinafter) was developed. SOWC separately tracks primary particles with different hygroscopic properties rather than instantaneously combining them into an internal mixture. This approach avoids artificially mixing light absorbing black + brown carbon particles with materials such as sulfate that would encourage the formation of additional coatings. Source-oriented particles undergo coagulation and gas-particle conversion, but these processes are considered in a dynamic framework that realistically "ages" primary particles over hours and days in the atmosphere. SOWC more realistically predicts radiative feedbacks from anthropogenic aerosols compared to models that make internal mixing or other artificial mixing assumptions. A three-week stagnation episode (15 December 2000 to 6 January 2001) in the San Joaquin Valley (SJV) during the California Regional PM10 / PM2.5 Air Quality Study (CRPAQS) was chosen for the initial application of the new modeling system. Primary particles emitted from diesel engines, wood smoke, high-sulfur fuel combustion, food cooking, and other anthropogenic sources were tracked separately throughout the simulation as they aged in the atmosphere. Differences were identified between predictions from the source oriented vs. the internally mixed representation of particles with meteorological feedbacks in WRF/Chem for a number of meteorological parameters: aerosol extinction coefficients, downward shortwave flux, planetary boundary layer depth, and primary and secondary particulate matter concentrations. Comparisons with observations show that SOWC predicts particle scattering coefficients more accurately than the internally mixed model. Downward shortwave radiation predicted by SOWC is enhanced by ~1% at ground level chiefly because diesel engine particles in the source-oriented mixture are not artificially coated with material that increases their absorption efficiency. The extinction coefficient predicted by SOWC is reduced by an average of 0.012 km−1 (4.8%) in the SJV with a maximum reduction of ~0.2 km−1. Planetary boundary layer (PBL) height is increased by an average of 5.2 m (1.5%) with a~maximum of ~100 m in the SJV. Particulate matter concentrations predicted by SOWC are 2.23 μg m−3 (3.8%) lower than the average by the internally mixed version of the same model in the SJV because increased solar radiation at the ground increases atmospheric mixing. The changes in predicted meteorological parameters and particle concentrations identified in the current study stem from the mixing state of black carbon. The source-oriented model representation with realistic aging processes predicts that hydrophobic diesel engine particles remain largely uncoated over the +7 day simulation period, while the internal mixture model representation predicts significant accumulation of secondary nitrate and water on diesel engine particles. Similar results will likely be found in any air pollution stagnation episode that is characterized by significant particulate nitrate production. Future work should consider episodes where coatings are predominantly sulfate and/or secondary organic aerosol.

Micro- and Nanostructural Characteristics of Particles Before and After an Exhaust Gas Recirculation System Scrubber

This work provides insight into the morphology and mixing state of submicron particles in diesel exhaust from a ship engine with an exhaust gas recirculation scrubber. Particles from this low-speed ship engine on test bed were collected using a microinertial impactor with transmission electron microscopy (TEM) grids on two stages. Micro- and nanostructural characteristics of single particles were studied by TEM. Image analysis was carried out on overview and high-resolution images, revealing influence of the exhaust gas treatment (scrubber) on the particle morphology and mixing state. Soot agglomerates were found to be collapsed after scrubber, reflected by their change in fractal dimension (Df ) from 1.88 to 2.13. Soot was predominantly found internally mixed with other components, with a higher degree of internal mixing observed after scrubber. Soot nanostructural characteristics on the near atomic scale such as layer distance, lamella length, and tortuosity were not observed to be influenced by the scr...

Model analysis of influences of aerosol mixing state upon its optical properties in East Asia

The air quality model system RAMS (Regional Atmospheric Modeling System)-CMAQ (Models-3 Community Multi-scale Air Quality) coupled with an aerosol optical/radiative module was applied to investigate the impact of different aerosol mixing states (i.e., externally mixed, half externally and half internally mixed, and internally mixed) on radiative forcing in East Asia. The simulation results show that the aerosol optical depth (AOD) generally increased when the aerosol mixing state changed from externally mixed to internally mixed, while the single scattering albedo (SSA) decreased. Therefore, the scattering and absorption properties of aerosols can be significantly affected by the change of aerosol mixing states. Comparison of simulated and observed SSAs at five AERONET (Aerosol Robotic Network) sites suggests that SSA could be better estimated by considering aerosol particles to be internally mixed. Model analysis indicates that the impact of aerosol mixing state upon aerosol direct radiative forcing (DRF) is complex. Generally, the cooling effect of aerosols over East Asia are enhanced in the northern part of East Asia (Northern China, Korean peninsula, and the surrounding area of Japan) and are reduced in the southern part of East Asia (Sichuan Basin and Southeast China) by internal mixing process, and the variation range can reach ±5 W m−2. The analysis shows that the internal mixing between inorganic salt and dust is likely the main reason that the cooling effect strengthens. Conversely, the internal mixture of anthropogenic aerosols, including sulfate, nitrate, ammonium, black carbon, and organic carbon, could obviously weaken the cooling effect.

Effects of internal mixing and aggregate morphology on optical properties of black carbon using a discrete dipole approximation model

Abstract. According to recent studies, internal mixing of black carbon (BC) with other aerosol materials in the atmosphere alters its aggregate shape, absorption of solar radiation, and radiative forcing. These mixing state effects are not yet fully understood. In this study, we characterize the morphology and mixing state of bare BC and BC internally mixed with sodium chloride (NaCl) using electron microscopy and examine the sensitivity of optical properties to BC mixing state and aggregate morphology using a discrete dipole approximation model (DDSCAT). DDSCAT is flexible in simulating the geometry and refractive index of particle aggregates. DDSCAT predicts a higher mass absorption coefficient (MAC), lower single scattering albedo (SSA), and higher absorption Angstrom exponent (AAE) for bare BC aggregates that are lacy rather than compact. Predicted values of SSA at 550 nm range between 0.16 and 0.27 for lacy and compact aggregates, respectively, in agreement with reported experimental values of 0.25 ± 0.05. The variation in absorption with wavelength does not adhere precisely to a power law relationship over the 200 to 1000 nm range. Consequently, AAE values depend on the wavelength region over which they are computed. The MAC of BC (averaged over the 200–1000 nm range) is amplified when internally mixed with NaCl (100–300 nm in radius) by factors ranging from 1.0 for lacy BC aggregates partially immersed in NaCl to 2.2 for compact BC aggregates fully immersed in NaCl. The SSA of BC internally mixed with NaCl is higher than for bare BC and increases with the embedding in the NaCl. Internally mixed BC SSA values decrease in the 200–400 nm wavelength range, a feature also common to the optical properties of dust and organics. Linear polarization features are also predicted in DDSCAT and are dependent on particle size and morphology. This study shows that DDSCAT predicts complex morphology and mixing state dependent aerosol optical properties that have been reported previously and are relevant to radiative transfer, climate modeling, and interpretation of remote sensing measurements.

On the radiative forcing of contrail cirrus contaminated by black carbon

The effects of internal and external mixings of black carbon (BC) (soot) in ice particles on the radiative properties of contrail cirrus are investigated using a simple ice plate model. The internal mixing state absorbs substantially more radiation as compared with its external mixing counterpart due to light absorption enhancement from all directions. The soot absorption effect is largely confined to wavelengths shorter than about 1.4 µm, beyond which ice absorption predominates. For an ice crystal size of 5 µm internally mixed with a soot particle of 0.1 µm radius in contrail cirrus with an optical depth of 0.5, the instantaneous radiative forcings at the top of and within the atmosphere are approximately 0.2 and 0.8 W/m2, respectively. In view of the likelihood of multiple inclusions of soot particles in contrail cirrus, these values are lower limits. Thus, a realistic assessment of the global and regional radiative forcings of contrail cirrus for climate studies must account for the radiative effect induced by soot mixing states associated with the microscopic formation of ice particles.

Organic particle types by single-particle measurements using a time-of-flight aerosol mass spectrometer coupled with a light scattering module

Abstract. Chemical and physical properties of individual ambient aerosol particles can vary greatly, so measuring the chemical composition at the single-particle level is essential for understanding atmospheric sources and transformations. Here we describe 46 days of single-particle measurements of atmospheric particles using a time-of-flight aerosol mass spectrometer coupled with a light scattering module (LS-ToF-AMS). The light scattering module optically detects particles larger than 180 nm vacuum aerodynamic diameter (130 nm geometric diameter) before they arrive at the chemical mass spectrometer and then triggers the saving of single-particle mass spectra. 271 641 particles were detected and sampled during 237 h of sampling in single-particle mode. By comparing timing of the predicted chemical ion signals from the light scattering measurement with the measured chemical ion signals by the mass spectrometer for each particle, particle types were classified and their number fractions determined as follows: prompt vaporization (46%), delayed vaporization (6%), and null (48%), where null was operationally defined as less than 6 ions per particle. Prompt and delayed vaporization particles with sufficient chemical information (i.e., more than 40 ions per particle) were clustered based on similarity of organic mass spectra (using k-means algorithm) to result in three major clusters: highly oxidized particles (dominated by m/z 44), relatively less oxidized particles (dominated by m/z 43), and particles associated with fresh urban emissions. Each of the three organic clusters had limited chemical properties of other clusters, suggesting that all of the sampled organic particle types were internally mixed to some degree; however, the internal mixing was never uniform and distinct particle types existed throughout the study. Furthermore, the single-particle mass spectra and time series of these clusters agreed well with mass-based components identified (using factor analysis) from simultaneous ensemble-averaged measurements, supporting the connection between ensemble-based factors and atmospheric particle sources and processes. Measurements in this study illustrate that LS-ToF-AMS provides unique information about organic particle types by number as well as mass.

Light absorption of black carbon aerosol and its enhancement by mixing state in an urban atmosphere in South China

The effects of black carbon (BC) aerosol on climate warming have been the study focus in the recent decade, and the reduction of BC is now expected to have significant near-term climate change mitigation. Large uncertainties of BC optical properties, however, still exist and seriously restrict the ability to quantify BC's climate effects. In this study, advanced instrumentation (a three-wavelength photoacoustic soot spectrometer (PASS-3) and a single particle soot photometer (SP2)) were used to measure black carbon aerosol and analyze its optical properties in a mega-city in South China, Shenzhen, during the summer of 2011. The results indicated that the average BC mass concentration was 4.0 ± 3.1 μg m−3 during the campaign, accounting for ∼11% of the total PM2.5 mass concentration. The PM2.5 light absorption at 405, 532 and 781 nm was 37.1 ± 28.1, 25.4 ± 19.0 and 17.6 ± 12.9 Mm−1, respectively. The average absorption Angstrom exponent of PM2.5 in visual spectrum (AAE405–781 nm) was 1.1 ± 0.1 during the campaign, indicating that the light absorbing carbon mainly came from vehicular emissions, with little contributions from biomass burning emissions. The mass absorption efficiency (MAE) of BC at 532 nm ranged from 5.0 to 8.5 m2 g−1 during the campaign, with an average of 6.5 ± 0.5 m2 g−1, and showed an obvious diurnal pattern with high values in the daytime. The average percentage of internally mixed BC was 24.3 ± 7.9% during the campaign, showing significant positive correlation relationship with the MAE of BC. More quantitative data analysis indicated that the internally mixed BC would amplify MAE by about 7% during the campaign, which stands in accordance with the new finding of a very recent Science magazine paper (Cappa et al., 2012) that the BC absorption enhancement due to internal mixing in the real atmosphere is relatively low, in apparent contrast to theoretical model predictions.

Anthropogenic and forest fire pollution aerosol transported to the Arctic: observations from the POLARCAT-France spring campaign

Abstract. During the POLARCAT-France airborne measurement campaign in spring 2008, several pollution plumes transported from mid-latitude regions were encountered. The study presented here focuses on air masses from two different geographic origins (Europe and Asia) and from 2 different source types (anthropogenic pollution and forest fires). A first case study is dedicated to a European air mass, which was repeatedly sampled and analysed during three consecutive days. Thereby, the evolution of the aerosol properties (size distributions, CO mixing ratio) is characterised and related processes are discussed. In particular, the role of coagulation, condensation and cloud processing in the evolution of the Aitken and the accumulation mode particles are contrasted. A second case study focuses on European air masses impacted solely by biomass burning emissions and Asian air masses with contributions from both biomass burning and anthropogenic emissions. The analysis of aerosol modes highlight a similar behaviour for particle originating from biomass burning (from Europe as well as Asia). In comparison to the predominating aged accumulation mode in biomass burning particles, a still larger aerosol accumulation mode related to Asian anthropogenic emissions can be isolated. These findings corroborate the external mixing of such kind of aerosol size distributions. An electron microscopy study (coupled to X-ray elemental analysis) of particles illustrated soot-like inclusions in several samples. Within samples attributed to forest fire sources, the chemical signature is highly associated with the presence of potassium, which is a characteristic tracer element for biomass burning plumes. The single particle images suggest an internal mixing of sampled individual aerosol particles. Thus, particles are found externally mixed as demonstrated from particle size distributions while they appear internally mixed at the particle scale.

Investigating cloud absorption effects: Global absorption properties of black carbon, tar balls, and soil dust in clouds and aerosols

This study examines modeled properties of black carbon (BC), tar ball (TB), and soil dust (SD) absorption within clouds and aerosols to understand better Cloud Absorption Effects I and II, which are defined as the effects on cloud heating of absorbing inclusions in hydrometeor particles and of absorbing aerosol particles interstitially between hydrometeor particles at their actual relative humidity (RH), respectively. The globally and annually averaged modeled 550 nm aerosol mass absorption coefficient (AMAC) of externally mixed BC was 6.72 (6.3–7.3) m2/g, within the laboratory range (6.3–8.7 m2/g). The global AMAC of internally mixed (IM) BC was 16.2 (13.9–18.2) m2/g, less than the measured maximum at 100% RH (23 m2/g). The resulting AMAC amplification factor due to internal mixing was 2.41 (2–2.9), with highest values in high RH regions. The global 650 nm hydrometeor mass absorption coefficient (HMAC) due to BC inclusions was 17.7 (10.6–19) m2/g, ∼9.3% higher than that of the IM‐AMAC. The 650 nm HMACs of TBs and SD were half and 1/190th, respectively, that of BC. Modeled aerosol absorption optical depths were consistent with data. In column tests, BC inclusions in low and mid clouds (CAE I) gave column‐integrated BC heating rates ∼200% and 235%, respectively, those of interstitial BC at the actual cloud RH (CAE II), which itself gave heating rates ∼120% and ∼130%, respectively, those of interstitial BC at the clear‐sky RH. Globally, cloud optical depth increased then decreased with increasing aerosol optical depth, consistent with boomerang curves from satellite studies. Thus, CAEs, which are largely ignored, heat clouds significantly.