Aerosol Absorption: Progress Towards Global and Regional Constraints

Purpose of ReviewSome aerosols absorb solar radiation, altering cloud properties, atmospheric stability and circulation dynamics, and the water cycle. Here we review recent progress towards global and regional constraints on aerosol absorption from observations and modeling, considering physical properties and combined approaches crucial for understanding the total (natural and anthropogenic) influences of aerosols on the climate.Recent FindingsWe emphasize developments in black carbon absorption alteration due to coating and ageing, brown carbon characterization, dust composition, absorbing aerosol above cloud, source modeling and size distributions, and validation of high-resolution modeling against a range of observations.SummaryBoth observations and modeling of total aerosol absorption, absorbing aerosol optical depths and single scattering albedo, as well as the vertical distribution of atmospheric absorption, still suffer from uncertainties and unknowns significant for climate applications. We offer a roadmap of developments needed to bring the field substantially forward.

Related papers:

title: Aerosol light absorption and its measurement: A review
abstract: Light absorption by aerosols contributes to solar radiative forcing through absorption of solar radiation and heating of the absorbing aerosol layer. Besides the direct radiative effect, the heating can evaporate clouds and change the atmospheric dynamics. Aerosol light absorption in the atmosphere is dominated by black carbon (BC) with additional, significant contributions from the still poorly understood brown carbon and from mineral dust. Sources of these absorbing aerosols include biomass burning and other combustion processes and dust entrainment. For particles much smaller than the wavelength of incident light, absorption is proportional to the particle volume and mass. Absorption can be calculated with Mie theory for spherical particles and with more complicated numerical methods for other particle shapes. The quantitative measurement of aerosol light absorption is still a challenge. Simple, commonly used filter measurements are prone to measurement artifacts due to particle concentration and modification of particle and filter morphology upon particle deposition, optical interaction of deposited particles and filter medium, and poor angular integration of light scattered by deposited particles. In situ methods measure particle absorption with the particles in their natural suspended state and therefore are not prone to effects related to particle deposition and concentration on filters. Photoacoustic and refractive index-based measurements rely on the heating of particles during light absorption, which, for power-modulated light sources, causes an acoustic signal and modulation of the refractive index in the air surrounding the particles that can be quantified with a microphone and an interferometer, respectively. These methods may suffer from some interference due to light-induced particle evaporation. Laser-induced incandescence also monitors particle heating upon absorption, but heats absorbing particles to much higher temperatures to quantify BC mass from the thermal radiation emitted by the heated particles. Extinction-minus-scattering techniques have limited sensitivity for measuring aerosol light absorption unless the very long absorption paths of cavity ring-down techniques are used. Systematic errors can be dominated by truncation errors in the scattering measurement for large particles or by subtraction errors for high single scattering albedo particles. Remote sensing techniques are essential for global monitoring of aerosol light absorption. While local column-integrated measurements of aerosol light absorption with sun and sky radiometers are routinely done, global satellite measurements are so far largely limited to determining a semi-quantitative UV absorption index.

title: Modeling the mineralogy of atmospheric dust sources
abstract: The variability of atmospheric dust mineralogy influences the impact of desert dust on the Earth's radiative budget and biogeochemical cycles. Until now, atmospheric transport models have assumed that dust was a constant homogeneous mixture, hence neglecting this variability. The lack of mineralogical data in arid areas prevented a better description of the atmospheric dust composition, and we propose here a new formulation to estimate the mineral content of arid surfaces on a global scale. First, we collect a Database of Arid Soil Surface Mineralogy for eight major minerals: quartz, feldspar, calcite, gypsum, illite, kaolinite, smectite, and hematite, both for the clay and silt fraction. On the basis of this, we formulate a Mean Mineralogical Table that relates classical soil types to surface mineralogy. We use this table and the geographical distribution of soil types given in the Food and Agriculture Organization Soil Map of the World to obtain the mineralogy of arid surfaces globally. In order to validate these results, we present a compilation of measured mineralogical composition of dust samples with identified sources. The correlation between observed dust mineralogy and those inferred from soil types in corresponding areas is between 0.70 and 0.94. We then calculate the maps of the single scattering albedo and of the ratio of infrared extinction to visible extinction for the erodible fraction of arid areas. Mineralogical maps presented here will be used in future studies with an emission scheme in a global transport model.

title: Incorporation of mineralogical composition into models of the radiative properties of mineral aerosol from UV to IR wavelengths
abstract: We describe a technique to model the radiative properties of mineral aerosols which accounts for their composition. We compile a data set of refractive indices of major minerals and employ it, along with data on mineralogical composition of dust from various locations, to calculate spectral optical and radiative properties of mineral aerosol mixtures. Such radiative properties are needed for climate modeling and remote sensing applications. We consider external mixtures of individual minerals, as well as mixtures of aggregates. We demonstrate that an external mixture of individual minerals must contain unrealistically high amounts of hematite to have a single scattering albedo lower than 0.9 at 500 nm wavelength. In contrast, aggregation of hematite with quartz or clays can strongly enhance absorption by dust at solar wavelengths. We also simulate the daily mean net (solar + infrared) forcing by dust of varying compositions. We found that, for a given composition and under similar atmospheric conditions, a mixture of aggregates can cause the positive radiative forcing while a mixture of individual minerals gives the negative forcing.

title: Evidence that the spectral dependence of light absorption by aerosols is affected by organic carbon
abstract: The wavelength dependence of light absorption by aerosols collected on filters is investigated throughout the near-ultraviolet to near-infrared spectral region. Measurements were made using an optical transmission method. Aerosols produced by biomass combustion, including wood and savanna burning, and by motor vehicles, including diesel trucks, are included in the analysis. These aerosol types were distinguished by different wavelength (λ) dependences in light absorption. Light absorption by the motor vehicle aerosols exhibited relatively weak wavelength dependence; absorption varied approximately as λ−1, indicating that black carbon (BC) was the dominant absorbing aerosol component. By contrast, the biomass smoke aerosols had much stronger wavelength dependence, approximately λ−2. The stronger spectral dependence was the result of enhanced light absorption at wavelengths shorter than 600 nm and was largely reduced when much of the sample organic carbon (OC) was extracted by dissolution in acetone. This indicates that OC in addition to BC in the biomass smoke aerosols contributed significantly to measured light absorption in the ultraviolet and visible spectral regions and that OC in biomass burning aerosols may appreciably absorb solar radiation. Estimated absorption efficiencies and imaginary refractive indices are presented for the OC extracted from biomass burning samples and the BC in motor vehicle-dominated aerosol samples. The uncertainty of these constants is discussed. Overall, results of this investigation show that low-temperature, incomplete combustion processes, including biomass burning, can produce light-absorbing aerosols that exhibit much stronger spectral dependence than high-temperature combustion processes, such as diesel combustion.

title: Spectral absorption properties of atmospheric aerosols
abstract: We have determined the solar spectral absorption optical depth of atmospheric aerosols for specific case studies during several field programs (three cases have been reported previously; two are new results). We combined airborne measurements of the solar net radiant flux density and the aerosol optical depth with a detailed radiative transfer model for all but one of the cases. The field programs (SAFARI 2000, ACE Asia, PRIDE, TARFOX, INTEX-A) contained aerosols representing the major absorbing aerosol types: pollution, biomass burning, desert dust and mixtures. In all cases the spectral absorption optical depth decreases with wavelength and can be approximated with a power-law wavelength dependence (Absorption Angstrom Exponent or AAE). We compare our results with other recent spectral absorption measurements and attempt to briefly summarize the state of knowledge of aerosol absorption spectra in the atmosphere. We discuss the limitations in using the AAE for calculating the solar absorption. We also discuss the resulting spectral single scattering albedo for these cases.

title: Characterizing elemental, equivalent black, and refractory black carbon aerosol particles: a review of techniques, their limitations and uncertainties
abstract: Elemental-, equivalent black- and refractory black-carbon are terms that have been defined in order to dissect the more general term, black carbon, into its component parts related to its specific chemical and optical properties and its impact on climate and health. Recent publications have attempted to clarify the meaning of these terms with respect to their environmental impact, particularly on climate. Here, we focus on the measurement aspects, reviewing the most commonly implemented techniques for the direct and indirect derivation of black carbon properties, their strengths, limitations, and uncertainties, and provide a non-exhaustive bibliography where the reader can find more detailed information. This review paper is designed as a guide for those wishing to learn about the current state of black carbon measurement instrumentation, how calibration is carried out, when one instrument may have the advantage over another, and where new techniques are needed to fill important knowledge gaps.

title: Historical (1850–2000) gridded anthropogenic and biomass burning emissions of reactive gases and aerosols: methodology and application
abstract: We present and discuss a new dataset of gridded emissions covering the historical period (1850–2000) in decadal increments at a horizontal resolution of 0.5° in latitude and longitude. The primary purpose of this inventory is to provide consistent gridded emissions of reactive gases and aerosols for use in chemistry model simulations needed by climate models for the Climate Model Intercomparison Program #5 (CMIP5) in support of the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (AR5). Our best estimate for the year 2000 inventory represents a combination of existing regional and global inventories to capture the best information available at this point; 40 regions and 12 sectors are used to combine the various sources. The historical reconstruction of each emitted compound, for each region and sector, is then forced to agree with our 2000 estimate, ensuring continuity between past and 2000 emissions. Simulations from two chemistry-climate models is used to test the ability of the emission dataset described here to capture long-term changes in atmospheric ozone, carbon monoxide and aerosol distributions. The simulated long-term change in the Northern mid-latitudes surface and mid-troposphere ozone is not quite as rapid as observed. However, stations outside this latitude band show much better agreement in both present-day and long-term trend. The model simulations indicate that the concentration of carbon monoxide is underestimated at the Mace Head station; however, the long-term trend over the limited observational period seems to be reasonably well captured. The simulated sulfate and black carbon deposition over Greenland is in very good agreement with the ice-core observations spanning the simulation period. Finally, aerosol optical depth and additional aerosol diagnostics are shown to be in good agreement with previously published estimates and observations.

title: Radiative forcing of the direct aerosol effect from AeroCom Phase II simulations
abstract: We report on the AeroCom Phase II direct aerosol effect (DAE) experiment where 16 detailed global aerosol models have been used to simulate the changes in the aerosol distribution over the industrial era. All 16 models have estimated the radiative forcing (RF) of the anthropogenic DAE, and have taken into account anthropogenic sulphate, black carbon (BC) and organic aerosols (OA) from fossil fuel, biofuel, and biomass burning emissions. In addition several models have simulated the DAE of anthropogenic nitrate and anthropogenic influenced secondary organic aerosols (SOA). The model simulated all-sky RF of the DAE from total anthropogenic aerosols has a range from −0.58 to −0.02 Wm−2, with a mean of −0.27 Wm−2 for the 16 models. Several models did not include nitrate or SOA and modifying the estimate by accounting for this with information from the other AeroCom models reduces the range and slightly strengthens the mean. Modifying the model estimates for missing aerosol components and for the time period 1750 to 2010 results in a mean RF for the DAE of −0.35 Wm−2. Compared to AeroCom Phase I (Schulz et al., 2006) we find very similar spreads in both total DAE and aerosol component RF. However, the RF of the total DAE is stronger negative and RF from BC from fossil fuel and biofuel emissions are stronger positive in the present study than in the previous AeroCom study. We find a tendency for models having a strong (positive) BC RF to also have strong (negative) sulphate or OA RF. This relationship leads to smaller uncertainty in the total RF of the DAE compared to the RF of the sum of the individual aerosol components. The spread in results for the individual aerosol components is substantial, and can be divided into diversities in burden, mass extinction coefficient (MEC), and normalized RF with respect to AOD. We find that these three factors give similar contributions to the spread in results.

title: The Community Earth System Model: A Framework for Collaborative Research
abstract: The Community Earth System Model (CESM) is a flexible and extensible community tool used to investigate a diverse set of Earth system interactions across multiple time and space scales. This global coupled model significantly extends its predecessor, the Community Climate System Model, by incorporating new Earth system simulation capabilities. These comprise the ability to simulate biogeochemical cycles, including those of carbon and nitrogen, a variety of atmospheric chemistry options, the Greenland Ice Sheet, and an atmosphere that extends to the lower thermosphere. These and other new model capabilities are enabling investigations into a wide range of pressing scientific questions, providing new foresight into possible future climates and increasing our collective knowledge about the behavior and interactions of the Earth system. Simulations with numerous configurations of the CESM have been provided to phase 5 of the Coupled Model Intercomparison Project (CMIP5) and are being analyzed by the broad com...

title: Recommendations for diagnosing effective radiative forcing from climate models for CMIP6
abstract: The usefulness of previous Coupled Model Intercomparison Project (CMIP) exercises has been hampered by a lack of radiative forcing information. This has made it difficult to understand reasons for differences between model responses. Effective radiative forcing (ERF) is easier to diagnose than traditional radiative forcing in global climate models (GCMs) and is more representative of the eventual temperature response. Here we examine the different methods of computing ERF in two GCMs. We find that ERF computed from a fixed sea-surface temperature (SST) method (ERF_fSST) has much more certainty than regression based methods. Thirty-year integrations are sufficient to reduce the 5-95% confidence interval in global ERF_fSST to 0.1 W m-2. For 2xCO2 ERF, 30 year integrations are needed to ensure that the signal is larger than the local confidence interval over more than 90% of the globe. Within the ERF_fSST method there are various options for prescribing SSTs and sea-ice. We explore these and find that ERF is only weakly dependent on the methodological choices. Prescribing the monthly-averaged seasonally varying model’s preindustrial climatology is recommended for its smaller random error and easier implementation. As part of CMIP6, the Radiative Forcing Model Intercomparison Project (RFMIP) asks models to conduct 30-year ERF_fSST experiments using the model’s own preindustrial climatology of SST and sea-ice. The Aerosol and Chemistry Model Intercomparison Project (AerChemMIP) will also mainly use this approach. We propose this as a standard method for diagnosing ERF and recommend that it be used across the climate modelling community to aid future comparisons.

title: Fast and slow precipitation responses to individual climate forcers: a PDRMIP multimodel study.
abstract: Precipitation is expected to respond differently to various drivers of anthropogenic climate change. We present the first results from the Precipitation Driver and Response Model Intercomparison Project (PDRMIP), where nine global climate models have perturbed CO2, CH4, black carbon, sulfate, and solar insolation. We divide the resulting changes to global mean and regional precipitation into fast responses that scale with changes in atmospheric absorption and slow responses scaling with surface temperature change. While the overall features are broadly similar between models, we find significant regional intermodel variability, especially over land. Black carbon stands out as a component that may cause significant model diversity in predicted precipitation change. Processes linked to atmospheric absorption are less consistently modeled than those linked to top-of-atmosphere radiative forcing. We identify a number of land regions where the model ensemble consistently predicts that fast precipitation responses to climate perturbations dominate over the slow, temperature-driven responses.

title: Rapid adjustments cause weak surface temperature response to increased black carbon concentrations.
abstract: We investigate the climate response to increased concentrations of black carbon (BC), as part of the Precipitation Driver Response Model Intercomparison Project (PDRMIP). A tenfold increase in BC is simulated by 9 global coupled-climate models, producing a model-median effective radiative forcing (ERF) of 0.82 (ranging from 0.41 to 2.91) Wm-2, and a warming of 0.67 (0.16 to 1.66) K globally and 1.24 (0.26 to 4.31) K in the Arctic. A strong positive instantaneous radiative forcing (median of 2.10 Wm-2 based on five of the models) is countered by negative rapid adjustments (-0.64 Wm-2 for the same five models), which dampen the total surface temperature signal. Unlike other drivers of climate change, the response of temperature and cloud profiles to the BC forcing is dominated by rapid adjustments. Low-level cloud amounts increase for all models, while higher-level clouds are diminished. The rapid temperature response is particularly strong above 400 hPa, where increased atmospheric stabilization and reduced cloud cover contrast the response pattern of the other drivers. In conclusion, we find that this substantial increase in BC concentrations does have considerable impacts on important aspects of the climate system. However, some of these effects tend to offset one another, leaving a relatively small global warming of 0.47 K per Wm-2 - about 20 % lower than the response to a doubling of CO2. Translating the tenfold increase in BC to the present-day impact of anthropogenic BC (given the emissions used in this work) would leave a warming of merely 0.07 K.

title: Optical properties of soot–water drop agglomerates: An experimental study
abstract: Black carbon (BC) and organic carbon (OC) are the largest contributors to the aerosol absorption in the atmosphere, yet the absorption cross sections of BC and OC per unit mass are subject to a large uncertainty due to morphology, physicochemical properties, and the mixing state of carbonaceous particles. Theoretical studies suggest the possibility of an enhanced absorption by soot–cloud drop agglomerates; however, the magnitude of the effect has never been measured directly and remains highly uncertain. This study is a laboratory experiment aimed at the modeling of direct radiation forcing due to soot-water interaction in the presence of glutaric acid, a water-soluble OC. Specifically, we generate, in the laboratory, hydrophobic soot (acetylene soot) and hydrophilic soot (mixture of acetylene soot and glutaric acid) and investigate the structural and optical properties of hydrophobic and hydrophilic soot particles in dry and water-saturated air. Hydrophobic soot (HBS) particles do not exhibit any structural or morphological differences under dry and saturated conditions, whereas hydrophilic soot (HLS) particles, i.e., BC with a monolayer of glutaric acid, collapse into globules when relative humidity (RH) is increased to saturation. The optical properties of HBS show very little dependence on RH while HLS scattering and absorption coefficient increase markedly with RH. For the cases considered here, the maximum enhancement in absorption for a soot–water drop mixture was as much as a factor of 3.5, very similar to theoretical predictions. The data provided in this study should advance the treatment of polluted cloud layers in climate models.

title: Light Absorption by Carbonaceous Particles: An Investigative Review
abstract: The optical properties of the light-absorbing, carbonaceous substance often called “soot,” “black carbon,” or “carbon black" have been the subject of some debate. These properties are necessary to model how aerosols affect climate, and our review is targeted specifically for that application. We recommend the term light-absorbing carbon to avoid conflict with operationally based definitions. Absorptive properties depend on molecular form, particularly the size of sp 2-bonded clusters. Freshly-generated particles should be represented as aggregates, and their absorption is like that of particles small relative to the wavelength. Previous compendia have yielded a wide range of values for both refractive indices and absorption cross section. The absorptive properties of light-absorbing carbon are not as variable as is commonly believed. Our tabulation suggests a mass-normalized absorption cross section of 7.5 ± 1.2 m2/g at 550 nm for uncoated particles. We recommend a narrow range of refractive indices for strongly-absorbing carbon particles, of which the highest is 1.95–0.79i. Our refractive indices are consistent with most measurements reported in the literature, and values used in present-day climate modeling are in error. Realistic refractive indices underpredict measured absorption by about 30% when used with common theories for spherical particles or aggregates. Field programs since about 1970 have measured quantities relevant to light absorption, but have only recently made enough measurements to isolate the light-absorbing carbonaceous component and determine its absorptive properties.

title: Light absorption by organic carbon from wood combustion
abstract: Carbonaceous aerosols affect the radiative balance of the Earth by absorbing and scattering light. While black carbon (BC) is highly absorbing, some organic carbon (OC) also has significant absorption, especially at near-ultraviolet and blue wavelengths. To the extent that OC absorbs visible light, it may be a non-negligible contributor to positive direct aerosol radiative forcing. Quantification of that absorption is necessary so that radiative-transfer models can evaluate the net radiative effect of OC. In this work, we examine absorption by primary OC emitted from solid fuel pyrolysis. We provide absorption spectra of this material, which can be related to the imaginary refractive index. This material has polar character but is not fully water-soluble: more than 92% was extractable by methanol or acetone, compared with 73% for water and 52% for hexane. Water-soluble OC contributes to light absorption at both ultraviolet and visible wavelengths. However, a larger portion of the absorption comes from OC that is extractable only by methanol. Absorption spectra of water-soluble OC are similar to literature reports. We compare spectra for material generated with different wood type, wood size and pyrolysis temperature. Higher wood temperature is the main factor creating OC with higher absorption; changing wood temperature from a devolatilizing state of 210 °C to a near-flaming state of 360 °C causes about a factor of four increase in mass-normalized absorption at visible wavelengths. A clear-sky radiative transfer model suggests that, despite the absorption, both high-temperature and low-temperature OC result in negative top-of-atmosphere radiative forcing over a surface with an albedo of 0.19 and positive radiative forcing over bright surfaces. Unless absorption by real ambient aerosol is higher than that measured here, it probably affects global average clear-sky forcing very little, but could be important in energy balances over bright surfaces.

title: Color of brown carbon : A model for ultraviolet and visible light absorption by organic carbon aerosol
abstract: We recommend ultraviolet and visible absorption spectra to represent particular types of atmospheric organic particles. Spectra of liquids and particles can be compared using the absorption coefficient of bulk material divided by material density. Reported absorption by absorbing organic aerosol from combustion is greater than that of organic material isolated by humic acid extraction. We examine ultraviolet and visible spectra of 200 organic compounds, concluding that visible absorption may be attributable to n → π* electronic transitions in a small fraction of oxygenated compounds. Absorption spectra can be communicated using the band-gap and Urbach relationships instead of the absorption Angstrom exponent. Water-soluble atmospheric aerosol has a band-gap of about 2.5 eV; insoluble aerosol may have a lower band-gap and higher absorption. Although different types of organic carbon may exhibit a continuum in absorption, there is a sharp distinction between the most-absorbing organic carbon and black carbon.

title: Remote sensing of soot carbon – Part 1: Distinguishing different absorbing aerosol species
abstract: We describe a method of using the Aerosol Robotic Network (AERONET) size distributions and complex refractive indices to retrieve the relative proportion of carbonaceous aerosols and free iron minerals (hematite and goethite). We assume that soot carbon has a spectrally flat refractive index and enhanced imaginary indices at the 440 nm wavelength are caused by brown carbon or hematite. Carbonaceous aerosols can be separated from dust in imaginary refractive index space because 95 % of biomass burning aerosols have imaginary indices greater than 0.0042 at the 675–1020 nm wavelengths, and 95 % of dust has imaginary refractive indices of less than 0.0042 at those wavelengths. However, mixtures of these two types of particles can not be unambiguously partitioned on the basis of optical properties alone, so we also separate these particles by size. Regional and seasonal results are consistent with expectations. Monthly climatologies of fine mode soot carbon are less than 1.0 % by volume for West Africa and the Middle East, but the southern African and South American biomass burning sites have peak values of 3.0 and 1.7 %. Monthly averaged fine mode brown carbon volume fractions have a peak value of 5.8 % for West Africa, 2.1 % for the Middle East, 3.7 % for southern Africa, and 5.7 % for South America. Monthly climatologies of free iron volume fractions show little seasonal variability, and range from about 1.1 to 1.7 % for coarse mode aerosols in all four study regions. Finally, our sensitivity study indicates that the soot carbon retrieval is not sensitive to the component refractive indices or densities assumed for carbonaceous and free iron aerosols, and the retrieval differs by only 15.4 % when these parameters are altered from our chosen baseline values. The total uncertainty of retrieving soot carbon mass is  ∼ 50 % (when uncertainty in the AERONET product and mixing state is included in the analysis).

title: Comparison of the radiative properties and direct radiative effect of aerosols from a global aerosol model and remote sensing data over ocean
abstract: A global aerosol transport model (Oslo CTM2) with main aerosol components included is compared to five satellite retrievals of aerosol optical depth (AOD) and one data set of the satellite-derived radiative effect of aerosols. The model is driven with meteorological data for the period November 1996 to June 1997 which is the time period investigated in this study. The modelled AOD is within the range of the AOD from the various satellite retrievals over oceanic regions. The direct radiative effect of the aerosols as well as the atmospheric absorption by aerosols are in both cases found to be of the order of 20 Wm -2 in certain regions in both the satellite-derived and the modelled estimates as a mean over the period studied. Satellite and model data exhibit similar patterns of aerosol optical depth, radiative effect of aerosols, and atmospheric absorption of the aerosols. Recently published results show that global aerosol models have a tendency to underestimate the magnitude of the clear-sky direct radiative effect of aerosols over ocean compared to satellite-derived estimates. However, this is only to a small extent the case with the Oslo CTM2. The global mean direct radiative effect of aerosols over ocean is modelled with the Oslo CTM2 to be –5.5 Wm -2 and the atmospheric aerosol absorption 1.5 Wm -2 .

title: Physical and optical properties of mineral dust aerosol during the Dust and Biomass-burning Experiment
abstract: We present aircraft measurements of dust aerosol during the Dust and Biomass-burning Experiment (DABEX), a project affiliated with the African Monsoon Multidisciplinary Analysis. DABEX took place between 13 January and 3 February 2006 in Sahelian west Africa, with the aircraft based at Niamey, Niger. The data set is augmented with Aerosol Robotic Network (AERONET) data. A mineral dust layer below 1–2 km (sourced from the north) and an overlying biomass burning (BB) layer (sourced from anthropogenic fires to the south) was observed on all days, although variability was observed in both layers. There is evidence of ozone loss within the dust, but with CO levels between 140 and 170 ppbv some history of combustion has occurred. Size distribution of the dust is compared with that of the BB aerosol and with dust measured near Senegal, during the Dust Outflow and Deposition to the Ocean (DODO-1) experiment. For accurate representation of the optical properties, five log-normals to the size distribution across sizes 0.05–5 μm are required, although two log-normals are adequate. The single scattering albedo was almost purely scattering, with values of 0.99 ± 0.01. During the strongest dust events the dust contribution to the column optical depth was 75–80%, compared to a DABEX mean of 50%. The aircraft-derived optical depth varied between 0.19 and 1.07, with the dust-only contribution between 0.07 and 0.81. AERONET optical depth trends are in good agreement with aircraft during DABEX, albeit with a bias to higher aircraft values. Retrieved AERONET aerosol size distributions show variable agreement with the aircraft. Differences between Versions 1 and 2 of the AERONET algorithm are highlighted.

title: Measurement of the mixing state, mass, and optical size of individual black carbon particles in urban and biomass burning emissions
abstract: In situ measurements of the mass, mixing state, and optical size of individual black-carbon (BC) particles in the fine mode (90–600 nm) have been made in fresh emissions from urban and biomass burning sources with an airborne single-particle soot photometer. Contrasts between the two sources are significant and consistent. Urban BC tends to smaller sizes, fewer coated particles, thinner coatings, and less absorption per unit mass than biomass-burning BC. This suggests that urban BC may have a longer lifetime in the atmosphere and a different impact on BC radiative forcing in the first indirect effect than biomass-burning BC. These measurements bound the likely variability in the microphysical state of BC emissions from typical continental processes, and provide direct measurements of the size distribution and coating state of fine-mode BC for use in constraining climate and aerosol models. These results highlight the need for the integration of source-specific information into such models.

title: Remote sensing of soot carbon – Part 2: Understanding the absorption Ångström exponent
abstract: Recently, some authors have suggested that the absorption Angstrom exponent (AAE) can be used to deduce the component aerosol absorption optical depths (AAODs) of carbonaceous aerosols in the AERONET database. This AAE approach presumes that AAE ≪ 1 for soot carbon, which contrasts the traditional small particle limit of AAE = 1 for soot carbon. Thus, we provide an overview of the AERONET retrieval, and we investigate how the microphysics of carbonaceous aerosols can be interpreted in the AERONET AAE product. We find that AAE ≪ 1 in the AERONET database requires large coarse mode fractions and/or imaginary refractive indices that increase with wavelength. Neither of these characteristics are consistent with the current definition of soot carbon, so we explore other possibilities for the cause of AAE ≪ 1. AAE is related to particle size, and coarse mode particles have a smaller AAE than fine mode particles for a given aerosol mixture of species. We also note that the mineral goethite has an imaginary refractive index that increases with wavelength, is very common in dust regions, and can easily contribute to AAE ≪ 1. We find that AAE ≪ 1 can not be caused by soot carbon, unless soot carbon has an imaginary refractive index that increases with wavelength throughout the visible and near-infrared spectrums. Finally, AAE is not a robust parameter for separating carbonaceous absorption from dust aerosol absorption in the AERONET database.

title: The absorption Ångström exponent of black carbon: from numerical aspects
abstract: The absorption Angstrom exponent (AAE) is an important aerosol
optical parameter used for aerosol characterization and apportionment
studies. The AAE of black carbon (BC) particles is widely accepted to be 1.0,
although observational estimates give quite a wide range of
0.6–1.3. With considerable uncertainties
related to observations, a numerical study is a powerful method, if not the
only one, to provide a better and more accurate understanding on BC AAE. This
study calculates BC AAE using realistic particle geometries based on fractal
aggregate and an accurate numerical optical model (namely the multiple-sphere
T-matrix method), and considers
bulk properties of an ensemble of BC particles following lognormal size
distributions. At odds with the expectations, BC AAE is not 1.0, even when BC
is assumed to have small sizes and a wavelength-independent refractive index.
With a wavelength-independent refractive index, the AAE of fresh BC is
approximately 1.05 and relatively insensitive to particle size. For BC with
geometric mean diameters larger than 0.12  µ m, BC AAE becomes
smaller when BC particles are aged (compact structures or coated by other
non-absorptive materials). For coated BC, we prescribe the coating fraction
variation based on a laboratory study, where smaller BC cores are shown to
develop larger coating fractions than those of bigger BC cores. For both compact and coated BC, the AAE is highly
sensitive to particle size distribution, ranging from approximately 0.8 to
even over 1.4 with wavelength-independent refractive index. When the
refractive index is allowed to vary with wavelength, a feature with
observational backing, the BC AAE may show an even wider range. For different
BC morphologies, we derive simple empirical equations on BC AAE based on our
numerical results, which can serve as a guide for the response of BC AAE to
BC size and refractive index. Due to its complex influences, the effects of
BC geometry is better to be discussed at certain BC properties, i.e., known
size and refractive index.

title: Carbonaceous aerosol over the Indian Ocean: OC/EC fractions and selected specifications from size‐segregated onboard samples
abstract: Concentrations and mass fractions of organic carbon, elemental carbon, and numerous organic species have been determined for submicrometer and supermicrometer particles in the Indian Ocean on the cruise of the R/V Ron Brown during INDOEX in February/March 1999. The total carbon (TC) concentration was low for air masses originating from the southern hemisphere of the Indian Ocean, where only small amounts of organic carbon (OC) could be detected in supermicrometer (sea salt) particles. The OC concentration was typically more than one order of magnitude higher in the northern Indian Ocean, where continental air masses were encountered, both for submicrometer and supermicrometer particles. Elemental carbon (EC) was mostly found in submicrometer particles, increasing up to more than two orders of magnitude in the northern part compared to the southern part of the Indian Ocean. The mass fraction of carbonaceous material was in the range of 6–15% and 2–12% for submicrometer and supermicrometer particles, respectively, with the higher values for more polluted air masses. A high degree of mixing with light scattering material is the main reason for high-absorption coefficients. The absorption efficiency is higher for lower mass fractions of EC. Various short-chain dicarboxylic and hydroxylated dicarboxylic acids have been determined. Dicarboxylic acids were mostly found in supermicrometer particles, whereas hydroxylated dicarboxylic acids showed up mainly in submicrometer particles. Alkanes and polycyclic aromatic hydrocarbons have been found in small amounts, leading to the conclusion that an important part of the organic material is of secondary origin. This is confirmed by the good correlation of the sum of carboxylic acids with OC, nitrate with a less pronounced correlation with sulfate. However, low OC/EC ratios indicate the existence of primary OC.

title: The dependence of the specific attenuation cross-section on black carbon mass fraction and particle size
abstract: The specific attenuation cross-section σATN which relates the attenuation of light by a particleloaden quartz fiber filter to the black carbon (BC) content of deposited fine dust is the most important parameter far optical BC determination using an aethalometer. A simple model is presented to describe the effects of light scattering particles on the specific attenuation cross-section. It is found that σATN varies with the BC fraction of total mass f according to δATN = σabs + (f−1 − 1)σscat The average specific scattering cross-section σscat depends on the light scattering dry fraction of fine dust particles, while the specific absorption cross-section σabs is determined by the light absorbing BC particles. The application of the model to an externally mixed BC-NaCl aerosol shows excellent agreement between the proposed theory and our experiments. The suitability of the outlined model is confirmed by analyses of attenuation data sets obtained from several measuring sites in Germany. For the examined data sets the average attenuation cross-section σATN of ambient BC varies between 8 m2 g−1 (rural sites) and 19 m2 g−1 (street crossing). These variations can be explained by assuming a site-independent BC absorption cross-section σabs = 4 m2 g−1 which is derived from experiments with a BC test aerosol, and by varying the σscat value from 0.45 m2 g−1 (rural sites) to 1.2–1.4 m2 g−1 (urban areas). Finally, the particle size dependence of the specific absorption cross-section σabs is examined for a particle size range from 0.05 μm to 1.1 μm. As it is suggested by the fractal nature of BC particles no size dependence of σabs with respect to the used BC test aerosol is found.

title: Radiative absorption enhancement from coatings on black carbon aerosols.
abstract: The radiative absorption enhancement of ambient black carbon (BC), by light-refractive coatings of atmospheric aerosols, constitutes a large uncertainty in estimates of climate forcing. The direct measurements of radiative absorption enhancement require the experimentally-removing the coating materials in ambient BC-containing aerosols, which remains a challenge. Here, the absorption enhancement of the BC core by non-absorbing aerosol coatings was quantified using a two-step removal of both inorganic and organic matter coatings of ambient aerosols. The mass absorption cross-section (MAC) of decoated/pure atmospheric BC aerosols of 4.4±0.8m(2)g(-1) was enhanced to 9.6±1.8m(2)g(-1) at 678-nm wavelength for ambiently-coated BC aerosols at a rural Northern China site. The enhancement of MAC (EMAC) rises from 1.4±0.3 in fresh combustion emissions to ~3 for aged ambient China aerosols. The three-week high-intensity campaign observed an average EMAC of 2.25±0.55, and sulfates were primary drivers of the enhanced BC absorption.

title: Absorption coefficient and site-specific mass absorption efficiency of elemental carbon in aerosols over urban, rural, and high-altitude sites in India.
abstract: Temporal and spatial variability in the absorption coefficient (b(abs), Mm(-1)) and mass absorption efficiency (MAE, sigma(abs), ) of elemental carbon (EC) in atmospheric aerosols studied from urban, rural, and high-altitude sites is reported here. Ambient aerosols, collected on tissuquartz filters, are analyzed for EC mass concentration using thermo-optical EC-OC analyzer, wherein simultaneously measured optical-attenuation (ATN, equivalent to initial transmittance) of 678 nm laser source has been used for the determination of MAE and absorption coefficient. At high-altitude sites, measured ATN and surface EC loading (EC(s), microg cm(-2)) on the filters exhibit linear positive relationship (R(2) = 0.86-0.96), suggesting EC as a principal absorbing component. However, relatively large scatter in regression analyses for the data from urban sites suggests contribution from other species. The representative MAE of EC, during wintertime (Dec 2004), at a rural site (Jaduguda) is 6.1 +/- 2.0 m(2)g(-1). In contrast, MAE at the two high-altitude sites is 14.5 +/- 1.1 (Manora Peak) and 10.4 +/- 1.4 (Mt. Abu); and that at urban sites is 11.1 +/- 2.6 (Allahabad) and 11.3 +/- 2.2 m(2)g(-1) (Hisar). The long-term average MAE at Manora Peak (February 2005 to June 2007) is 12.8 +/- 2.9 m(2)g(-1) (range: 6.1-19.1 m(2)g(-1)). These results are unlike the constant conversion factor used for MAE in optical instruments for the determination of BC mass concentration. The absorption coefficient also shows large spatiotemporal variability; the lower values are typical of the high-altitude sites and higher values for the urban and rural atmosphere. Such large variability documented for the absorption parameters suggests the need for their suitable parametrization in the assessment of direct aerosol radiative forcing on a regional scale.

title: Quantifying black carbon from biomass burning by means of levoglucosan - A one-year time series at the Arctic observatory Zeppelin
abstract: Levoglucosan, a highly specific tracer of partic- ulate matter from biomass burning, has been used to study the influence of residential wood burning, agricultural waste burning and Boreal forest fire emissions on the Arctic atmo- sphere black carbon (BC) concentration. A one-year time series from March 2008 to March 2009 of levoglucosan has been established at the Zeppelin observatory in the Eu- ropean Arctic. Elevated concentrations of levoglucosan in winter (mean: 1.02 ng m 3 ) compared to summer (mean: 0.13 ng m 3 ) were observed, resembling the seasonal vari- ation seen for e.g. sulfate and BC. The mean concentration in the winter period was 2-3 orders of magnitude lower than typical values reported for European urban areas in winter, and 1-2 orders of magnitude lower than European rural back- ground concentrations. Episodes of elevated levoglucosan concentration lasting from 1 to 6 days were more frequent in winter than in summer and peak values were higher, ex- ceeding 10 ng m 3 at the most. Concentrations of elemental carbon from biomass burn- ing (ECbb) were obtained by combining measured concen- trations of levoglucosan and emission ratios of levoglucosan and EC for wildfires/agricultural fires and for residential wood burning. Neglecting chemical degradation by OH pro- vides minimum levoglucosan concentrations, corresponding to a mean ECbb concentration of 3.7± 1.2 ng m 3 in win- ter (October-April) and 0.8± 0.3 ng m 3 in summer (May- September), or 8.8± 4.5 % of the measured equivalent black carbon (EBC) concentration in winter and 6.1± 3.4 % in summer. When accounting for chemical degradation of lev- oglucosan by OH, an upper estimate of 31-45 % of EBC could be attributed to EC bb (ECbb adjusted for chemical degradation) in winter, whereas no reliable (< 100 %) upper estimate could be provided for summer for the degradation rates applied. Hence, fossil fuel sources appear to dominate the European Arctic BC concentrations in winter, whereas the very wide range obtained for summer does not allow us to conclude upon this for the warm season. Calculations using the Lagrangian particle dispersion model FLEXPART show that the seasonal variation of the modeled ECbb (ECbb,m) concentration compared relatively well with observationally derived ECbb from agricultural fires/wildfires during summer, and residential wood burning in winter. The model overestimates by a factor of 2.2 in win- ter and 4.4 in summer when compared to the observationally derived mean ECbb concentration, which provides the mini- mum estimate, whereas it underestimates by a factor of 2.3- 3.3 in winter and a factor of 4.5 in summer when compared to EC bb , which provides the upper estimate. There are indi- cations of too-low emissions of residential wood burning in northern Russia, a region of great importance with respect to observed concentrations of BC in the European Arctic.

title: A European aerosol phenomenology-5 : Climatology of black carbon optical properties at 9 regional background sites across Europe
abstract: A reliable assessment of the optical properties of atmospheric black carbon is of crucial importance for an accurate estimation of radiative forcing. In this study we investigated the spatio-temporal variability of the mass absorption cross-section (MAC) of atmospheric black carbon, defined as light absorption coefficient (σap) divided by elemental carbon mass concentration (mEC). σap and mEC have been monitored at supersites of the ACTRIS network for a minimum period of one year. The 9 rural background sites considered in this study cover southern Scandinavia, central Europe and the Mediterranean. σap was determined using filter based absorption photometers and mEC using a thermal-optical technique. Homogeneity of the data-set was ensured by harmonization of all involved methods and instruments during extensive intercomparison exercises at the European Center for Aerosol Calibration (ECAC). Annual mean values of σap at a wavelength of 637 nm vary between 0.66 and 1.3 Mm−1 in southern Scandinavia, 3.7–11 Mm−1 in Central Europe and the British Isles, and 2.3–2.8 Mm−1 in the Mediterranean. Annual mean values of mEC vary between 0.084 and 0.23 μg m−3 in southern Scandinavia, 0.28–1.1 in Central Europe and the British Isles, and 0.22–0.26 in the Mediterranean. Both σap and mEC in southern Scandinavia and Central Europe have a distinct seasonality with maxima during the cold season and minima during summer, whereas at the Mediterranean sites an opposite trend was observed. Annual mean MAC values were quite similar across all sites and the seasonal variability was small at most sites. Consequently, a MAC value of 10.0 m2 g−1 (geometric standard deviation = 1.33) at a wavelength of 637 nm can be considered to be representative of the mixed boundary layer at European background sites, where BC is expected to be internally mixed to a large extent. The observed spatial variability is rather small compared to the variability of values in previous literature, indicating that the harmonization efforts resulted in substantially increased precision of the reported MAC. However, absolute uncertainties of the reported MAC values remain as high as ± 30–70% due to the lack of appropriate reference methods and calibration materials. The mass ratio between elemental carbon and non-light-absorbing matter was used as a proxy for the thickness of coatings around the BC cores, in order to assess the influence of the mixing state on the MAC of BC. Indeed, the MAC was found to increase with increasing values of the coating thickness proxy. This provides evidence that coatings do increase the MAC of atmospheric BC to some extent, which is commonly referred to as lensing effect.

title: Radiative Absorption Enhancements Due to the Mixing State of Atmospheric Black Carbon
abstract: Dark Forcing Soot, or black carbon, is a ubiquitous atmospheric pollutant whose warming effect might be second only to carbon dioxide. When black carbon is emitted, it combines with other aerosols to form heterogeneous mixtures. Models have predicted that internal mixing of black carbon with other materials can double the amount of radiation absorbed. Cappa et al. (p. 1078) report that in situ measurements of the enhancement of radiation absorption by these mixed black carbon–containing particles in the atmosphere show a much smaller effect. Thus, many climate models may be overestimating the amount of warming caused by black carbon emissions. Direct measurements show that ambient atmospheric particulate black carbon absorbs less solar radiation than theory suggested. Atmospheric black carbon (BC) warms Earth’s climate, and its reduction has been targeted for near-term climate change mitigation. Models that include forcing by BC assume internal mixing with non-BC aerosol components that enhance BC absorption, often by a factor of ~2; such model estimates have yet to be clearly validated through atmospheric observations. Here, direct in situ measurements of BC absorption enhancements (Eabs) and mixing state are reported for two California regions. The observed Eabs is small—6% on average at 532 nm—and increases weakly with photochemical aging. The Eabs is less than predicted from observationally constrained theoretical calculations, suggesting that many climate models may overestimate warming by BC. These ambient observations stand in contrast to laboratory measurements that show substantial Eabs for BC are possible.

title: Absorption Enhancement of Coated Absorbing Aerosols: Validation of the Photo-Acoustic Technique for Measuring the Enhancement
abstract: A photo-acoustic absorption spectrometer (PAS) and a cavity ring down aerosol extinction spectrometer (CRD-AES) were used, in conjunction with Mie Theory, to measure the refractive index (RI) of absorbing polystyrene spheres (APSS). The PAS and CRD-AES were also used to measure the absorption and extinction enhancement after these APSS were coated in oleic acid. The experimental enhancements were then compared to predictions from coated-sphere Mie Theory. The measured absorption and extinction enhancements both agreed with modeled enhancements to within an average of 5%. A filter-based absorption technique (particle soot absorption photometer, PSAP) was also used to measure the absorption by the APSS and showed a significant size-dependent bias, as evidenced by the filter-based method measuring significantly lower absorption for both uncoated and coated APSS compared to the PAS. These results suggest the validity of applying photo-acoustics to measure the absorption enhancement created by semi-volatile atmospheric species coating absorbing particles.

title: Variability in morphology, hygroscopicity, and optical properties of soot aerosols during atmospheric processing
abstract: The atmospheric effects of soot aerosols include interference with radiative transfer, visibility impairment, and alteration of cloud formation and are highly sensitive to the manner by which soot is internally mixed with other aerosol constituents. We present experimental studies to show that soot particles acquire a large mass fraction of sulfuric acid during atmospheric aging, considerably altering their properties. Soot particles exposed to subsaturated sulfuric acid vapor exhibit a marked change in morphology, characterized by a decreased mobility-based diameter but an increased fractal dimension and effective density. These particles experience large hygroscopic size and mass growth at subsaturated conditions (<90% relative humidity) and act efficiently as cloud-condensation nuclei. Coating with sulfuric acid and subsequent hygroscopic growth enhance the optical properties of soot aerosols, increasing scattering by ≈10-fold and absorption by nearly 2-fold at 80% relative humidity relative to fresh particles. In addition, condensation of sulfuric acid is shown to occur at a similar rate on ambient aerosols of various types of a given mobility size, regardless of their chemical compositions and microphysical structures. Representing an important mechanism of atmospheric aging, internal mixing of soot with sulfuric acid has profound implications on visibility, human health, and direct and indirect climate forcing.

title: Relative importance of black carbon, brown carbon, and absorption enhancement from clear coatings in biomass burning emissions
abstract: A wide range of globally significant biomass fuels were burned during the fourth Fire Lab at Missoula Experiment (FLAME-4). A multi-channel photoacoustic absorption spectrometer (PAS) measured dry absorption at 405, 532, and 660 nm and thermally denuded (250 °C) absorption at 405 and 660 nm. Absorption coefficients were broken into contributions from black carbon (BC), brown carbon (BrC), and lensing following three different methodologies, with one extreme being a method that assumes the thermal denuder effectively removes organics and the other extreme being a method based on the assumption that black carbon (BC) has an Angstrom exponent of unity. The methodologies employed provide ranges of potential importance of BrC to absorption but, on average, there was a difference of a factor of 2 in the ratio of the fraction of absorption attributable to BrC estimated by the two methods. BrC absorption at shorter visible wavelengths is of equal or greater importance to that of BC, with maximum contributions of up to 92 % of total aerosol absorption at 405 nm and up to 58 % of total absorption at 532 nm. Lensing is estimated to contribute a maximum of 30 % of total absorption, but typically contributes much less than this. Absorption enhancements and the estimated fraction of absorption from BrC show good correlation with the elemental-carbon-to-organic-carbon ratio (EC ∕ OC) of emitted aerosols and weaker correlation with the modified combustion efficiency (MCE). Previous studies have shown that BrC grows darker (larger imaginary refractive index) as the ratio of black to organic aerosol (OA) mass increases. This study is consistent with those findings but also demonstrates that the fraction of total absorption attributable to BrC shows the opposite trend: increasing as the organic fraction of aerosol emissions increases and the EC ∕ OC ratio decreases.

title: Light absorption of black carbon aerosol and its enhancement by mixing state in an urban atmosphere in South China
abstract: 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 PM 2.5 mass concentration. The PM 2.5 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 PM 2.5 in visual spectrum (AAE 405–781 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 m 2  g −1 during the campaign, with an average of 6.5 ± 0.5 m 2  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.

title: Markedly enhanced absorption and direct radiative forcing of black carbon under polluted urban environments
abstract: Although black carbon (BC) represents a key short-lived climate forcer, its direct radiative forcing remains highly uncertain. The available results from available studies of absorption enhancement of BC particles during atmospheric aging are conflicting. Using a novel environmental chamber method, we have, for the first time to our knowledge, quantified the aging and variation in the optical properties of BC particles under ambient urban conditions representative of developed and developing countries. Our results indicate that BC under polluted urban environments could contribute significantly to both pollution development and large positive radiative forcing, implying that reduction of BC emissions under polluted environments achieves a cobenefit in simultaneously controlling air pollution and protecting climate, especially for developing countries. Black carbon (BC) exerts profound impacts on air quality and climate because of its high absorption cross-section over a broad range of electromagnetic spectra, but the current results on absorption enhancement of BC particles during atmospheric aging remain conflicting. Here, we quantified the aging and variation in the optical properties of BC particles under ambient conditions in Beijing, China, and Houston, United States, using a novel environmental chamber approach. BC aging exhibits two distinct stages, i.e., initial transformation from a fractal to spherical morphology with little absorption variation and subsequent growth of fully compact particles with a large absorption enhancement. The timescales to achieve complete morphology modification and an absorption amplification factor of 2.4 for BC particles are estimated to be 2.3 h and 4.6 h, respectively, in Beijing, compared with 9 h and 18 h, respectively, in Houston. Our findings indicate that BC under polluted urban environments could play an essential role in pollution development and contribute importantly to large positive radiative forcing. The variation in direct radiative forcing is dependent on the rate and timescale of BC aging, with a clear distinction between urban cities in developed and developing countries, i.e., a higher climatic impact in more polluted environments. We suggest that mediation in BC emissions achieves a cobenefit in simultaneously controlling air pollution and protecting climate, especially for developing countries.

title: Jury is still out on the radiative forcing by black carbon
abstract: Peng et al. (1) conclude that a fast increase in the mass absorption cross-section (MAC) of black carbon (BC) in urban environments leads to significantly increased estimates of the BC radiative forcing (RF). Their chamber measurements are highly valuable and complement observations performed in ambient conditions, but their “enhancement factor” relative to an unspecified baseline may not be directly comparable to values used or simulated in global aerosol models. MAC, a key parameter in our understanding of the net BC climate impact, is indeed a more relevant quantity to examine. A fast MAC enhancement in polluted environments as the BC gets coated with organic and inorganic species is consistent with recent findings (2, 3). Global models used in AeroCom [table S1 in Peng et al. (1), ref. 4] have an average MAC of ∼8 m2 … 

[↵][1]1To whom correspondence should be addressed.  olivier.boucher{at}lmd.jussieu.fr.

 : #xref-corresp-1-1

title: Black carbon absorption at the global scale is affected by particle-scale diversity in composition
abstract: Atmospheric black carbon (BC) exerts a strong, but uncertain, warming effect on the climate. BC that is coated with non-absorbing material absorbs more strongly than the same amount of BC in an uncoated particle, but the magnitude of this absorption enhancement (Eabs) is not well constrained. Modelling studies and laboratory measurements have found stronger absorption enhancement than has been observed in the atmosphere. Here, using a particle-resolved aerosol model to simulate diverse BC populations, we show that absorption is overestimated by as much as a factor of two if diversity is neglected and population-averaged composition is assumed across all BC-containing particles. If, instead, composition diversity is resolved, we find Eabs=1−1.5 at low relative humidity, consistent with ambient observations. This study offers not only an explanation for the discrepancy between modelled and observed absorption enhancement, but also demonstrates how particle-scale simulations can be used to develop relationships for global-scale models.

title: Black-carbon absorption enhancement in the atmosphere determined by particle mixing state
abstract: Mixing with non-black carbon can enhance the radiative effect of black-carbon aerosols. Lab and field measurements of aerosol properties reveal that the mass ratio of black to non-black carbon determines the amount of enhancement.

title: Historical emissions of black and organic carbon aerosol from energy-related combustion, 1850-2000 - article no. GB2018
abstract: We present an emission inventory of primary black carbon (BC) and primary organic carbon (OC) aerosols from fossil fuel and biofuel combustion between 1850 and 2000. We reconstruct fossil fuel consumption and represent changes in technology on a national and sectoral basis. Our estimates rely on new estimates of biofuel consumption, and updated emission factors for old technologies. Emissions of black carbon increase almost linearly, totaling about 1000 Gg in 1850, 2200 Gg in 1900, 3000 Gg in 1950, and 4400 Gg in 2000. Primary organic carbon shows a similar pattern, with emissions of 4100 Gg, 5800 Gg, 6700 Gg, and 8700 Gg in 1850, 1900, 1950, and 2000, respectively. Biofuel is responsible for over half of BC emission until about 1890, and dominates energy-related primary OC emission throughout the entire period. Coal contributes the greatest fraction of BC emission between 1880 and 1975, and is overtaken by emissions from biofuel around 1975, and by diesel engines around 1990. Previous work suggests a rapid rise in BC emissions between 1950 and 2000. This work supports a more gradual increase between 1950 and 2000, similar to the increase between 1850 and 1925; implementation of clean technology is a primary reason.

title: Estimating global black carbon emissions using a top‐down Kalman Filter approach
abstract: Black carbon (BC) is an important aerosol constituent in the atmosphere and climate forcer. A good understanding of the radiative forcing of BC and associated climate feedback and response is critical to minimize the uncertainty in predicting current and future climate influenced by anthropogenic aerosols. One reason for this uncertainty is that current emission inventories of BC are mostly obtained from the so-called bottom-up approach, an approach that derives emissions based on categorized emitting sources and emission factors used to convert burning mass to emissions. In this work, we provide a first global-scale top-down estimation of global BC emissions, as well as an estimated error range, by using a Kalman Filter. This method uses data of both column aerosol absorption optical depth and surface concentrations from global and regional networks to constrain our fully coupled climate-aerosol-urban model and thus to derive an optimized estimate of BC emissions as 17.8 ± 5.6 Tg/yr, a factor of more than 2 higher than commonly used global BC emissions data sets. We further perform 22 additional optimization simulations that incorporate the known uncertain ranges of various important physical, model, and measurement parameters and still yield an optimized value within the above given range, from a low of 14.6 Tg/yr to a high of 22.2 Tg/yr. Furthermore, we show that the emissions difference between our optimized and a priori estimation is not uniform, with East Asia, Southeast Asia, and Eastern Europe underestimated, while North America is overestimated in the a priori inventory.

title: Estimation of global black carbon direct radiative forcing and its uncertainty constrained by observations
abstract: Black carbon (BC) contributes to global warming by absorbing sunlight. However, the size of this contribution, namely, the direct radiative forcing (RF), ranges from +0.1 to +1.0 W m A2 , largely due to differences between bottom-up and observation-based estimates. Current global models systematically underestimate BC radiation absorption relative to observations, which is often attributed to the underestimation of BC emissions. Several studies that adjusted emissions to correct biases of global aerosol models resulted in a revised upward estimate of the BC RF. However, the BC RF was never optimized against observations in a rigorous mathematical manner. Here we simulated the absorption of solar radiation by BC from all sources at the 10 km resolution by combining a highly disaggregated emission inventory with a nested aerosol climate model and a downscaling method. As a result, the normalized mean bias in BC radiation absorption was reduced from A56% to A5% in Asia and from A71% to A46% elsewhere. We applied a Bayesian method that makes the best account of all model, representativeness, and observational uncertainties to estimate the BC RF and its uncertainty. Using the new emission inventory and high-resolution model reduces uncertainty in BC RF from A109%/+172% to A77%/+78% over Asia and from A83%/+114% to A64%/+70% over other continental regions. Finally, we derived an observationally constrained BC RF of 0.53 Wm A2 (0.14 to 1.19 as 90% confidence) as our best estimate, less than previous estimates. Our estimate implies that reduction in BC emissions would contribute to slow down global warming, but the contribution could be less than previously thought.

title: Brown carbon and internal mixing in biomass burning particles
abstract: Biomass burning (BB) contributes large amounts of black carbon (BC) and particulate organic matter (POM) to the atmosphere and contributes significantly to the earth’s radiation balance. BB particles can be a complicated optical system, with scattering and absorption contributions from BC, internal mixtures of BC and POM, and wavelength-dependent absorption of POM. Large amounts of POM can also be externally mixed. We report on the unique ability of multi-wavelength photo-acoustic measurements of dry and thermal-denuded absorption to deconstruct this complicated wavelength-dependent system of absorption and mixing. Optical measurements of BB particles from the Four Mile Canyon fire near Boulder, Colorado, showed that internal mixtures of BC and POM enhanced absorption by up to 70%. The data supports the assumption that the POM was very weakly absorbing at 532 nm. Enhanced absorption at 404 nm was in excess of 200% above BC absorption and varied as POM mass changed, indicative of absorbing POM. Absorption by internal mixing of BC and POM contributed 19( ± 8)% to total 404-nm absorption, while BC alone contributed 54( ± 16)%. Approximately 83% of POM mass was externally mixed, the absorption of which contributed 27( ± 15)% to total particle absorption (at 404 nm). The imaginary refractive index and mass absorption efficiency (MAE) of POM at 404 nm changed throughout the sampling period and were found to be 0.007 ± 0.005 and 0.82 ± 0.43 m2 g-1, respectively. Our analysis shows that the MAE of POM can be biased high by up to 50% if absorption from internal mixing of POM and BC is not included.

title: Biomass burning dominates brown carbon absorption in the rural southeastern United States
abstract: Brown carbon aerosol consists of light-absorbing organic particulate matter with wavelength-dependent absorption. Aerosol optical extinction, absorption, size distributions, and chemical composition were measured in rural Alabama during summer 2013. The field site was well located to examine sources of brown carbon aerosol, with influence by high biogenic organic aerosol concentrations, pollution from two nearby cities, and biomass burning aerosol. We report the optical closure between measured dry aerosol extinction at 365 nm and calculated extinction from composition and size distribution, showing agreement within experiment uncertainties. We find that aerosol optical extinction is dominated by scattering, with single-scattering albedo values of 0.94 ± 0.02. Black carbon aerosol accounts for 91 ± 9% of the total carbonaceous aerosol absorption at 365 nm, while organic aerosol accounts for 9 ± 9%. The majority of brown carbon aerosol mass is associated with biomass burning, with smaller contributions from biogenically derived secondary organic aerosol.

title: Investigation of black and brown carbon multiple-wavelength-dependent light absorption from biomass and fossil fuel combustion source emissions.
abstract: Quantification of the black carbon (BC) and brown carbon (BrC) components of source emissions is critical to understanding the impact combustion aerosols have on atmospheric light absorption. Multiple-wavelength absorption was measured from fuels including wood, agricultural biomass, coals, plant matter, and petroleum distillates in controlled combustion settings. Filter-based absorption measurements were corrected and compared to photoacoustic absorption results. BC absorption was segregated from the total light extinction to estimate the BrC absorption from individual sources. Results were compared to elemental carbon (EC)/organic carbon (OC) concentrations to determine composition's impact on light absorption. Multiple-wavelength absorption coefficients, Angstrom exponent (6.9 to 0.9 OC/TC), source emissions have variable absorption spectra, and nonbiomass combustion sources can be significant contributors to BrC.

title: Radiative forcing of organic aerosol in the atmosphere and on snow: Effects of SOA and brown carbon
abstract: Organic aerosols (OA) play an important role in climate change. However, very few calculations of global OA radiative forcing include secondary organic aerosol (SOA) or the light-absorbing part of OA (brown carbon). Here we use a global model to assess the radiative forcing associated with the change in primary organic aerosol (POA) and SOA between present-day and preindustrial conditions in both the atmosphere and the land snow/sea ice. Anthropogenic emissions are shown to substantially influence the SOA formation rate, causing it to increase by 29 Tg/yr (93%) since preindustrial times. We examine the effects of varying the refractive indices, size distributions for POA and SOA, and brown carbon fraction in SOA. The increase of SOA exerts a direct forcing ranging from −0.12 to −0.31 W m−2 and a first indirect forcing in warm-phase clouds ranging from −0.22 to −0.29 W m−2, with the range due to different assumed SOA size distributions and refractive indices. The increase of POA since preindustrial times causes a direct forcing varying from −0.06 to −0.11 W m−2, when strongly and weakly absorbing refractive indices for brown carbon are used. The change in the total OA exerts a direct forcing ranging from −0.14 to −0.40 W m−2. The atmospheric absorption from brown carbon ranges from +0.22 to +0.57 W m−2, which corresponds to 27%~70% of the black carbon (BC) absorption predicted in the model. The radiative forcing of OA deposited in land snow and sea ice ranges from +0.0011 to +0.0031 W m−2 or as large as 24% of the forcing caused by BC in snow and ice simulated by the model.

title: Molecular characterization of brown carbon (BrC) chromophores in secondary organic aerosol generated from photo-oxidation of toluene.
abstract: Atmospheric brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365 nm = 0.78 m(2) g(-1)) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene < 1/300). Fifteen compounds, most of which are nitrophenols, are identified as major BrC chromophores responsible for the enhanced light absorption of Tol-SOA material produced in the presence of NOx. The integrated absorbance of these fifteen chromophores accounts for 40-60% of the total light absorbance by Tol-SOA at wavelengths between 300 nm and 500 nm. The combination of tandem LC-UV/Vis-ESI/HRMS measurements provides an analytical platform for predictive understanding of light absorption properties by BrC and their relationship to the structure of individual chromophores. General trends in the UV/Vis absorption by plausible isomers of the BrC chromophores were evaluated using theoretical chemistry calculations. The molecular-level understanding of BrC chemistry is helpful for better understanding the evolution and behavior of light absorbing aerosols in the atmosphere.

title: Sources, composition and absorption Ångström exponent of light-absorbing organic components in aerosol extracts from the Los Angeles Basin.
abstract: We investigate the sources, chemical composition, and spectral properties of light-absorbing organic aerosol extracts (i.e., brown carbon, or BrC) in the Los Angeles (LA) Basin during the CalNex-2010 field campaign. Light absorption of PM2.5 water-soluble components at 365 nm (Abs365), used as a proxy for water-soluble BrC, was well correlated with water-soluble organic carbon (WSOC) (r(2) = 0.55-0.65), indicating secondary organic aerosol (SOA) formation from anthropogenic emissions was the major source of water-soluble BrC in this region. Normalizing Abs365 to WSOC mass yielded an average solution mass absorption efficiency (MAE365) of 0.71 m(2) g(-1) C. Detailed chemical speciation of filter extracts identified eight nitro-aromatic compounds that were correlated with Abs365. These compounds accounted for ∼4% of the overall water-soluble BrC absorption. Methanol-extracted BrC in LA was approximately 3 and 21 times higher than water-soluble BrC at 365 and 532 nm, respectively, and had a MAE365 of 1.58 m(2) g(-1) C (Abs365 normalized to organic carbon mass). The water-insoluble BrC was strongly correlated with ambient elemental carbon concentration, suggesting similar sources. Absorption Ångström exponent (Å(a)) (fitted between 300 and 600 nm wavelengths) was 3.2 (±1.2) for the PILS water-soluble BrC measurement, compared to 4.8 (±0.5) and 7.6 (±0.5) for methanol- and water-soluble BrC from filter extracts, respectively. These results show that fine particle BrC was prevalent in the LA basin during CalNex, yet many of its properties and potential impacts remain unknown.

title: Optical, physical, and chemical properties of tar balls observed during the Yosemite Aerosol Characterization Study
abstract: The Yosemite Aerosol Characterization Study of summer 2002 (YACS) occurred during an active fire season in the western United States and provided an opportunity to investigate many unresolved issues related to the radiative effects of biomass burning aerosols. Single particle analysis was performed on field-collected aerosol samples using an array of electron microscopy techniques. Amorphous carbon spheres, or “tar balls,” were present in samples collected during episodes of high particle light scattering coefficients that occurred during the peak of a smoke/haze event. The highest concentrations of light-absorbing carbon from a dual-wavelength aethalometer (λ = 370 and 880 nm) occurred during periods when the particles were predominantly tar balls, indicating they do absorb light in the UV and near-IR range of the solar spectrum. Closure experiments of mass concentrations and light scattering coefficients during periods dominated by tar balls did not require any distinct assumptions of organic carbon molecular weight correction factors, density, or refractive index compared to periods dominated by other types of organic carbon aerosols. Measurements of the hygroscopic behavior of tar balls using an environmental SEM indicate that tar balls do not exhibit deliquescence but do uptake some water at high (∼83%) relative humidity. The ability of tar balls to efficiently scatter and absorb light and to absorb water has important implications for their role in regional haze and climate forcing.

title: Brown Carbon Spheres in East Asian Outflow and Their Optical Properties
abstract: Atmospheric aerosols play a substantial role in climate change through radiative forcing. Combustion-produced carbonaceous particles are the main light-absorbing aerosols; thus, quantifying their optical properties is essential for determining the magnitude of direct forcing. By using the electron energy-loss spectrum in the transmission electron microscope, we quantified the optical properties of individual, submicrometer amorphous carbon spheres that are ubiquitous in East Asian–Pacific outflow. The data indicate that these common spheres are brown, not black, with a mean refractive index of 1.67 – 0.27i (where i = \batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \(\sqrt{1}\) \end{document}) at a wavelength of 550 nanometers. The results suggest that brown carbon aerosols should be explicitly included in radiative forcing models.

title: Atmospheric tar balls from biomass burning in Mexico
abstract: Atmospheric tar balls (TBs) are spherical, organic aerosol particles that occur in smoke from biomass burning (BB). They absorb sunlight and thereby cause warming of the atmosphere. This study reports a transmission electron microscope (TEM) study of TBs from BB smoke samples collected within minutes to hours from emission in a tropical area of Mexico. Their spherical shapes as seen in both scanning electron microscope images and with electron tomography indicate that they were solid when collected. They consist of C and minor O, S, K, and N. The hygroscopic growth factor for our relatively fresh TBs is 1.09 ± 0.04 at a relative humidity of 100%. In samples 1.6 km from the fire, an average of ∼1 and 14%, respectively, of particles with aerodynamic diameter from 50 to 300 nm consisted of TBs. For the latter, more aged samples, the total volume was roughly double that of soot, and their total calculated light absorption at a wavelength of 550 nm was between 74 and 96% that of soot, with the exact amount depending on the size, shape, and coating of the soot. In general, the TBs that we analyzed were similar to those from North America, southern Africa, and Europe in terms of size, external mixing, relative freedom of inclusions, and composition. This and previous studies show that TBs result from a range of biomass fuels. Their distribution from various regions across the globe, combined with their optical properties, suggests they have important effects on regional and perhaps global climate.

title: Individual aerosol particles from biomass burning in southern Africa: 1. Compositions and size distributions of carbonaceous particles
abstract: Individual aerosol particles in smoke plumes from biomass fires and in regional hazes in southern Africa were studied using analytical transmission electron microscopy (TEM), which allowed detailed characterization of carbonaceous particle types in smoke and determination of changes in particle properties and concentrations during smoke aging. Based on composition, morphology, and microstructure, three distinct types of carbonaceous particles were present in the smoke: organic particles with inorganic (K-salt) inclusions, ‘‘tar ball’’ particles, and soot. The relative number concentrations of organic particles were largest in young smoke, whereas tar balls were dominant in a slightly aged (1 hour) smoke from a smoldering fire. Flaming fires emitted relatively more soot particles than smoldering fires, but soot was a minor constituent of all studied plumes. Further aging caused the accumulation of sulfate on organic and soot particles, as indicated by the large number of internally mixed organic/sulfate and soot/sulfate particles in the regional haze. Externally mixed ammonium sulfate particles dominated in the boundary layer hazes, whereas organic/sulfate particles were the most abundant type in the upper hazes. Apparently, elevated haze layers were more strongly affected by biomass smoke than those within the boundary layer. Based on size distributions and the observed patterns of internal mixing, we hypothesize that organic and soot particles are the cloudnucleating constituents of biomass smoke aerosols. Sea-salt particles dominated in the samples taken in stratus clouds over the Atlantic Ocean, off the coast of Namibia, whereas a distinct haze layer above the clouds consisted of aged biomass smoke particles.  Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0315 Atmospheric Composition and Structure: Biosphere/atmosphere interactions; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry;  biomass burning, carbonaceous aerosol, individual particles, TEM

title: Hygroscopic behavior of aerosol particles from biomass fires using environmental transmission electron microscopy
abstract: We used both a conventional transmission electron microscope and an environmental transmission electron microscope (ETEM) to determine morphology, composition, and water uptake of 80 individual aerosol particles collected from the young smoke of flaming and smoldering fires during SAFARI-2000, a comprehensive air quality campaign in southern Africa. Six representative carbonaceous particle types are described, including soot, tar balls, and heterogeneously internally mixed particles containing C with S-, K-, Mg- or Na-rich inorganic phases. The hygroscopic behavior of these particles over the range 0–100% relative humidity (RH) was studied in detail. Soot and tar balls did not take up water, whereas the mixed organic–inorganic particles took up water between 55 and 100% RH, the exact value depending on the composition of their water-soluble phases. The inorganic phase appeared to determine the hygroscopic properties of all mixed organic–inorganic particles. Thus, incorporation of inorganic plant material or reactions with inorganic atmospheric components can dramatically alter the hygroscopic properties of carbonaceous particles in smoke plumes. The fraction of these mixed organic–inorganic particles plausibly increases with time, which will modulate the effects of smoke on radiative budgets.

title: Sources of uncertainties in modelling black carbon at the global scale
abstract: Our understanding of the global black carbon (BC) cycle is essentially qualitative due to uncertainties in our knowledge of its properties. This work investigates two source of uncertainties in modelling black carbon: those due to the use of different schemes for BC ageing and its removal rate in the global Transport-Chemistry model TM5 and those due to the uncertainties in the definition and quantification of the observations, which propagate through to both the emission inventories, and the measurements used for the model evaluation. The schemes for the atmospheric processing of black carbon that have been tested with the model are (i) a simple approach considering BC as bulk aerosol and a simple treatment of the removal with fixed 70% of in-cloud black carbon concentrations scavenged by clouds and removed when rain is present and (ii) a more complete description of microphysical ageing within an aerosol dynamics model, where removal is coupled to the microphysical properties of the aerosol, which results in a global average of 40% in-cloud black carbon that is scavenged in clouds and subsequently removed by rain, thus resulting in a longer atmospheric lifetime. This difference is reflected in comparisons between both sets of modelled results and the measurements. Close to the sources, both anthropogenic and vegetation fire source regions, the model results do not differ significantly, indicating that the emissions are the prevailing mechanism determining the concentrations and the choice of the aerosol scheme does not influence the levels. In more remote areas such as oceanic and polar regions the differences can be orders of magnitude, due to the differences between the two schemes. The more complete description reproduces the seasonal trend of the black carbon observations in those areas, although not always the magnitude of the signal, while the more simplified approach underestimates black carbon concentrations by orders of magnitude. The sensitivity to wet scavenging has been tested by varying in-cloud and below-cloud removal. BC lifetime increases by 10% when large scale and convective scale precipitation removal efficiency are reduced by 30%, while the variation is very small when below-cloud scavenging is zero. Since the emission inventories are representative of elemental carbon-like substance, the model output should be compared to elemental carbon measurements and if known, the ratio of black carbon to elemental carbon mass should be taken into account when the model is compared with black carbon observations.

title: Inferring absorbing organic carbon content from AERONET data
abstract: Black carbon, light-absorbing organic carbon (of- ten called "brown carbon") and mineral dust are the ma- jor light-absorbing aerosols. Currently the sources and formation of brown carbon aerosol in particular are not well understood. In this study we estimated the amount of light-absorbing organic carbon and black carbon from AERONET measurements. We find that the columnar ab- sorbing organic carbon (brown carbon) levels in biomass burning regions of South America and Africa are relatively high (about 15-20 mg m 2 during biomass burning season), while the concentrations are significantly lower in urban ar- eas in US and Europe. However, we estimated significant ab- sorbing organic carbon amounts from the data of megacities of newly industrialized countries, particularly in India and China, showing also clear seasonality with peak values up to 30-35 mg m 2 during the coldest season, likely caused by the coal and biofuel burning used for heating. We also com- pared our retrievals with the modeled organic carbon by the global Oslo CTM for several sites. Model values are higher in biomass burning regions than AERONET-based retrievals, while the opposite is true in urban areas in India and China.

title: Observationally constrained estimates of carbonaceous aerosol radiative forcing
abstract: Carbonaceous aerosols (CA) emitted by fossil and biomass fuels consist of black carbon (BC), a strong absorber of solar radiation, and organic matter (OM). OM scatters as well as absorbs solar radiation. The absorbing component of OM, which is ignored in most climate models, is referred to as brown carbon (BrC). Model estimates of the global CA radiative forcing range from 0 to 0.7 Wm-2, to be compared with the Intergovernmental Panel on Climate Change’s estimate for the pre-Industrial to the present net radiative forcing of about 1.6 Wm-2. This study provides a model-independent, observationally based estimate of the CA direct radiative forcing. Ground-based aerosol network data is integrated with field data and satellite-based aerosol observations to provide a decadal (2001 through 2009) global view of the CA optical properties and direct radiative forcing. The estimated global CA direct radiative effect is about 0.75 Wm-2 (0.5 to 1.0). This study identifies the global importance of BrC, which is shown to contribute about 20% to 550-nm CA solar absorption globally. Because of the inclusion of BrC, the net effect of OM is close to zero and the CA forcing is nearly equal to that of BC. The CA direct radiative forcing is estimated to be about 0.65 (0.5 to about 0.8) Wm-2, thus comparable to or exceeding that by methane. Caused in part by BrC absorption, CAs have a net warming effect even over open biomass-burning regions in Africa and the Amazon.

title: Aerosol forcing in the Climate Model Intercomparison Project (CMIP5) simulations by HadGEM2‐ES and the role of ammonium nitrate
abstract: The latest Hadley Centre climate model, HadGEM2-ES, includes Earth system components such as interactive chemistry and eight species of tropospheric aerosols. It has been run for the period 1860–2100 in support of the fifth phase of the Climate Model Intercomparison Project (CMIP5). Anthropogenic aerosol emissions peak between 1980 and 2020, resulting in a present-day all-sky top of the atmosphere aerosol forcing of −1.6 and −1.4 W m−2 with and without ammonium nitrate aerosols, respectively, for the sum of direct and first indirect aerosol forcings. Aerosol forcing becomes significantly weaker in the 21st century, being weaker than −0.5 W m−2 in 2100 without nitrate. However, nitrate aerosols become the dominant species in Europe and Asia and decelerate the decrease in global mean aerosol forcing. Considering nitrate aerosols makes aerosol radiative forcing 2–4 times stronger by 2100 depending on the representative concentration pathway, although this impact is lessened when changes in the oxidation properties of the atmosphere are accounted for. Anthropogenic aerosol residence times increase in the future in spite of increased precipitation, as cloud cover and aerosol-cloud interactions decrease in tropical and midlatitude regions. Deposition of fossil fuel black carbon onto snow and ice surfaces peaks during the 20th century in the Arctic and Europe but keeps increasing in the Himalayas until the middle of the 21st century. Results presented here confirm the importance of aerosols in influencing the Earth's climate, albeit with a reduced impact in the future, and suggest that nitrate aerosols will partially replace sulphate aerosols to become an important anthropogenic species in the remainder of the 21st century.

title: A global simulation of brown carbon: Implications for photochemistry and direct radiative effect
abstract: Recent observations suggest that a certain fraction of organic carbon (OC) aerosol effectively absorbs solar radiation, which is also known as brown carbon (BrC) aerosol. Despite much observational evidence of its presence, very few global modelling studies have been conducted because of poor understanding of global BrC emissions. Here we present an explicit global simulation of BrC in a global 3-D chemical transport model (GEOS-Chem), including global BrC emission estimates from primary (3.9 ± 1.7 and 3.0 ± 1.3 TgC yr−1 from biomass burning and biofuel) and secondary (5.7 TgC yr−1 from aromatic oxidation) sources. We evaluate the model by comparing the results with observed absorption by water-soluble OC in surface air in the United States, and with single scattering albedo observations at Aerosol Robotic Network (AERONET) sites all over the globe. The model successfully reproduces the seasonal variations of observed light absorption by water-soluble OC, but underestimates the magnitudes, especially in regions with high secondary source contributions. Our global simulations show that BrC accounts for 21 % of the global mean surface OC concentration, which is typically assumed to be scattering. We find that the global direct radiative effect of BrC is nearly zero at the top of the atmosphere, and consequently decreases the direct radiative cooling effect of OC by 16 %. In addition, the BrC absorption leads to a general reduction of NO2 photolysis rates, whose maximum decreases occur in Asia up to −8 % (−17 %) on an annual (spring) mean basis. The resulting decreases of annual (spring) mean surface ozone concentrations are up to −6 % (−13 %) in Asia, indicating a non-negligible effect of BrC on photochemistry in this region.

title: Global budget and radiative forcing of black carbon aerosol: Constraints from pole-to-pole (HIPPO) observations across the Pacific
abstract: We use a global chemical transport model (GEOS-Chem) to interpret aircraft curtain observations of black carbon (BC) aerosol over the Pacific from 85°N to 67°S during the 2009–2011 HIAPER (High-Performance Instrumented Airborne Platform for Environmental Research) Pole-to-Pole Observations (HIPPO) campaigns. Observed concentrations are very low, implying much more efficient scavenging than is usually implemented in models. Our simulation with a global source of 6.5 Tg a−1 and mean tropospheric lifetime of 4.2 days (versus 6.8 ± 1.8 days for the Aerosol Comparisons between Observations and Models (AeroCom) models) successfully simulates BC concentrations in source regions and continental outflow and captures the principal features of the HIPPO data but is still higher by a factor of 2 (1.48 for column loads) over the Pacific. It underestimates BC absorbing aerosol optical depths (AAODs) from the Aerosol Robotic Network by 32% on a global basis. Only 8.7% of global BC loading in GEOS-Chem is above 5 km, versus 21 ± 11% for the AeroCom models, with important implications for radiative forcing estimates. Our simulation yields a global BC burden of 77 Gg, a global mean BC AAOD of 0.0017, and a top-of-atmosphere direct radiative forcing (TOA DRF) of 0.19 W m−2, with a range of 0.17–0.31 W m−2 based on uncertainties in the BC atmospheric distribution. Our TOA DRF is lower than previous estimates (0.27 ± 0.06 W m−2 in AeroCom, 0.65–0.9 W m−2 in more recent studies). We argue that these previous estimates are biased high because of excessive BC concentrations over the oceans and in the free troposphere.

title: Important fossil source contribution to brown carbon in Beijing during winter
abstract: Organic aerosol (OA) constitutes a substantial fraction of fine particles and affects both human health and climate. It is becoming clear that OA absorbs light substantially (hence termed Brown Carbon, BrC), adding uncertainties to global aerosol radiative forcing estimations. The few current radiative-transfer and chemical-transport models that include BrC primarily consider sources from biogenic and biomass combustion. However, radiocarbon fingerprinting here clearly indicates that light-absorbing organic carbon in winter Beijing, the capital of China, is mainly due to fossil sources, which contribute the largest part to organic carbon (OC, 67 ± 3%) and its sub-constituents (water-soluble OC, WSOC: 54 ± 4%, and water-insoluble OC,  73 ± 3%). The dual-isotope (Δ14C/δ13C) signatures, organic molecular tracers and Beijing-tailored emission inventory identify that this fossil source is primarily from coal combustion activities in winter, especially from the residential sector. Source testing on Chinese residential coal combustion provides direct evidence that intensive coal combustion could contribute to increased light-absorptivity of ambient BrC in Beijing winter. Coal combustion is an important source to BrC in regions such as northern China, especially during the winter season. Future modeling of OA radiative forcing should consider the importance of both biomass and fossil sources.

title: Top-of-atmosphere radiative forcing affected by brown carbon in the upper troposphere
abstract: Carbonaceous aerosols affect the global radiative balance by absorbing and scattering radiation, which leads to warming or cooling of the atmosphere, respectively. Black carbon is the main light-absorbing component. A portion of the organic aerosol known as brown carbon also absorbs light. The climate sensitivity to absorbing aerosols rapidly increases with altitude, but brown carbon measurements are limited in the upper troposphere. Here we present aircraft observations of vertical aerosol distributions over the continental United States in May and June 2012 to show that light-absorbing brown carbon is prevalent in the troposphere, and absorbs more short-wavelength radiation than black carbon at altitudes between 5 and 12 km. We find that brown carbon is transported to these altitudes by deep convection, and that in-cloud heterogeneous processing may produce brown carbon. Radiative transfer calculations suggest that brown carbon accounts for about 24% of combined black and brown carbon warming effect at the tropopause. Roughly two-thirds of the estimated brown carbon forcing occurs above 5 km, although most brown carbon is found below 5 km. The highest radiative absorption occurred during an event that ingested a wildfire plume. We conclude that high-altitude brown carbon from biomass burning is an unappreciated component of climate forcing. Brown carbon absorbs light, but its climate impacts in the upper troposphere are not well known. A series of aircraft observations in the US reveals that convection lofts brown carbon to high altitudes, causing greater warming than at lower altitudes.

title: Effect of solar radiation on the optical properties and molecular composition of laboratory proxies of atmospheric brown carbon.
abstract: Sources, optical properties, and chemical composition of atmospheric brown carbon (BrC) aerosol are uncertain, making it challenging to estimate its contribution to radiative forcing. Furthermore, optical properties of BrC may change significantly during its atmospheric aging. We examined the effect of photolysis on the molecular composition, mass absorption coefficient, and fluorescence of secondary organic aerosol (SOA) prepared by high-NOx photooxidation of naphthalene (NAP SOA). Our experiments were designed to model photolysis processes of NAP SOA compounds dissolved in cloud or fog droplets. Aqueous solutions of NAP SOA were observed to photobleach (i.e., lose their ability to absorb visible radiation) with an effective half-life of ∼15 h (with sun in its zenith) for the loss of near-UV (300-400 nm) absorbance. The molecular composition of NAP SOA was significantly modified by photolysis, with the average SOA formula changing from C14.1H14.5O5.1N0.085 to C11.8H14.9O4.5N0.023 after 4 h of irradiation. However, the average O/C ratio did not change significantly, suggesting that it is not a good metric for assessing the extent of photolysis-driven aging in NAP SOA (and in BrC in general). In contrast to NAP SOA, the photobleaching of BrC material produced by the reaction of limonene + ozone SOA with ammonia vapor (aged LIM/O3 SOA) was much faster, but it did not result in a significant change in average molecular composition. The characteristic absorbance of the aged LIM/O3 SOA in the 450-600 nm range decayed with an effective half-life of <0.5 h. These results emphasize the highly variable and dynamic nature of different types of atmospheric BrC.

title: Modeling investigation of light-absorbing aerosols in the Amazon Basin during the wet season
abstract: We use a global chemical transport model (GEOS-Chem) to interpret observed light-absorbing aerosols in Amazonia during the wet season. Observed aerosol properties, including black carbon (BC) concentration and light absorption, at the Amazon Tall Tower Observatory (ATTO) site in the central Amazon have relatively low background levels but frequently show high peaks during the study period of January–April 2014. With daily temporal resolution for open fire emissions and modified aerosol optical properties, our model successfully captures the observed variation in fine/coarse aerosol and BC concentrations as well as aerosol light absorption and its wavelength dependence over the Amazon Basin. The source attribution in the model indicates the important influence of open fire on the observed variances of aerosol concentrations and absorption, mainly from regional sources (northern South America) and from northern Africa. The contribution of open fires from these two regions is comparable, with the latter becoming more important in the late wet season. The analysis of correlation and enhancement ratios of BC versus CO suggests transport times of  1.8). Uncertainty analysis shows that accounting for absorption due to secondary organic aerosol (SOA) and primary biogenic aerosol (PBA) particles could result in differences of

title: Solar absorption by elemental and brown carbon determined from spectral observations
abstract: Black carbon (BC) is functionally defined as the absorbing component of atmospheric total carbonaceous aerosols (TC) and is typically dominated by soot-like elemental carbon (EC). However, organic carbon (OC) has also been shown to absorb strongly at visible to UV wavelengths and the absorbing organics are referred to as brown carbon (BrC), which is typically not represented in climate models. We propose an observationally based analytical method for rigorously partitioning measured absorption aerosol optical depths (AAOD) and single scattering albedo (SSA) among EC and BrC, using multiwavelength measurements of total (EC, OC, and dust) absorption. EC is found to be strongly absorbing (SSA of 0.38) whereas the BrC SSA varies globally between 0.77 and 0.85. The method is applied to the California region. We find TC (EC + BrC) contributes 81% of the total absorption at 675 nm and 84% at 440 nm. The BrC absorption at 440 nm is about 40% of the EC, whereas at 675 nm it is less than 10% of EC. We find an enhanced absorption due to OC in the summer months and in southern California (related to forest fires and secondary OC). The fractions and trends are broadly consistent with aerosol chemical-transport models as well as with regional emission inventories, implying that we have obtained a representative estimate for BrC absorption. The results demonstrate that current climate models that treat OC as nonabsorbing are underestimating the total warming effect of carbonaceous aerosols by neglecting part of the atmospheric heating, particularly over biomass-burning regions that emit BrC.

title: Exploring the observational constraints on the simulation of brown carbon
abstract: Organic aerosols (OA) that strongly absorb solar radiation in the near-UV are referred to as brown carbon (BrC). The sources, evolution, and optical properties of BrC remain highly uncertain and contribute significantly to uncertainty in the estimate of the global direct radiative effect (DRE) of aerosols. Previous modeling studies of BrC optical properties and DRE have been unable to fully evaluate model performance due to the lack of direct measurements of BrC absorption. In this study, we develop a global model simulation (GEOS-Chem) of BrC and test it against BrC absorption measurements from two aircraft campaigns in the continental US (SEAC4RS and DC3). To the best of our knowledge, this is the first study to compare simulated BrC absorption with direct aircraft measurements. We show that BrC absorption properties estimated based on previous laboratory measurements agree with the aircraft measurements of freshly emitted BrC absorption but overestimate aged BrC absorption. In addition, applying a photochemical scheme to simulate bleaching/degradation of BrC improves model skill. The airborne observations are therefore consistent with a mass absorption coefficient (MAC) of freshly emitted biomass burning OA of 1.33 m2 g−1 at 365 nm coupled with a 1-day whitening e-folding time. Using the GEOS-Chem chemical transport model integrated with the RRTMG radiative transfer model, we estimate that the top-of-the-atmosphere all-sky direct radiative effect (DRE) of OA is −0.344 Wm−2, 10 % higher than that without consideration of BrC absorption. Therefore, our best estimate of the absorption DRE of BrC is +0.048 Wm−2. We suggest that the DRE of BrC has been overestimated previously due to the lack of observational constraints from direct measurements and omission of the effects of photochemical whitening.

title: Climate response to externally mixed black carbon as a function of altitude
abstract: The climate response to the presence of black carbon (BC) aerosol at a given altitude in the atmosphere is investigated using a global circulation model. The vertical dependence of the efficiency with which BC exerts radiative forcing (RF) through the direct aerosol effect has previously been extensively studied. Here we use the Community Atmosphere Model version 4 atmospheric component of the National Center for Atmospheric Research Community Earth System model version 1.03 to calculate the three-dimensional response to a BC layer inserted at various altitudes. Simulations have been performed both for fixed sea surface temperatures and using a slab ocean setup to include the surface temperature response. We investigate the vertical profiles of RF exerted per gram of externally mixed BC due to both the direct and semidirect aerosol effects. Associated changes in cloud cover, relative humidity, and precipitation are discussed. The precipitation response to BC is decomposed into a fast, stability-related change and a slow, temperature-driven component. We find that while the efficiency of BC to exert positive RF due to the direct effect strengthens with altitude, as in previous studies, it is strongly offset by a negative semidirect effect. The net radiative perturbation of BC at top of atmosphere is found to be positive everywhere below the tropopause and negative above. The global, annual mean precipitation response to BC, after equilibration of a slab ocean, is found to be positive between the surface and 900 hPa but negative at all other altitudes.

title: Detection and Inventory of Intense Pyroconvection in Western North America using GOES-15 Daytime Infrared Data
abstract: AbstractIntense wildfires occasionally generate fire-triggered storms, known as pyrocumulonimbus (pyroCb), that can inject smoke particles and trace gases into the upper troposphere and lower stratosphere (UTLS). This study develops the first pyroCb detection algorithm using three infrared (IR) channels from the imager on board GOES-West (GOES-15). The algorithm first identifies deep convection near active fires via the longwave IR brightness temperature, distinguishing between midtropospheric and UTLS injections. During daytime, unique pyroCb microphysical properties are characterized by a medium-wave brightness temperature that is significantly larger than that in the longwave, allowing for separation of pyroCb from other deep convection. A cloud-opacity test reduces potential false detections. Application of this algorithm to 88 intense wildfires observed during the 2013 fire season in western North America resulted in successful detection of individual intense events, pyroCb embedded within traditiona...

title: Contribution of particulate brown carbon to light absorption in the rural and urban Southeast US
abstract: Measurements of wavelength dependent aerosol light absorption coefficients were carried out as part of the Southern Oxidant and Aerosol Study (SOAS) during the summer of 2013 to determine the contribution of light absorbing organic carbon (BrC) to total aerosol light absorption in a rural location (Centreville, AL) and an urban area (Atlanta, GA). The light absorption coefficients in the near UV and visible wavelengths were measured for both ambient air, as well as ambient air heated in a thermal denuder to 200 °C to remove the semi-volatile organic compounds. Atlanta measurements show dominance of semi-volatile brown carbon with an average absorption angstrom exponent (AAE) of 1.4 before heating and about 1.0 after heating. In urban Atlanta, a decrease of about ∼35% in the light absorption coefficient at 370 nm after heating indicates that light absorbing organic compounds are a substantial fraction of the light absorption budget. Furthermore, a considerable increase in the fraction of light absorption by the semi-volatile aerosol occurs during the daytime, likely linked with photochemistry. Measurements at rural Centerville, on the other hand, do not show any major change in AAE with values before and after heating of 0.99 and 0.98, respectively. Overall the results suggest that photochemical aged urban emissions result in the presence of light absorbing BrC, while at rural locations which are dominated by aged aerosol and local biogenic emissions (based on measurements of Angstrom exponents) BrC does not significantly contribute to light absorption.

title: Deriving brown carbon from multiwavelength absorption measurements: method and application to AERONET and Aethalometer observations
abstract: The radiative impact of organic aerosols (OA) is a large source of uncertainty in estimating the global direct radiative effect (DRE) of aerosols. This radiative impact includes not only light scattering but also light absorption from a subclass of OA referred to as brown carbon (BrC). However, the absorption properties of BrC are poorly understood, leading to large uncertainties in modeling studies. To obtain observational constraints from measurements, a simple absorption Angstrom exponent (AAE) method is often used to separate the contribution of BrC absorption from that of black carbon (BC). However, this attribution method is based on assumptions regarding the spectral dependence of BC that are often violated in the ambient atmosphere. Here we develop a new AAE method which improves upon previous approaches by using the information from the wavelength-dependent measurements themselves and by allowing for an atmospherically relevant range of BC properties, rather than fixing these at a single assumed value. We note that constraints on BC optical properties and mixing state would help further improve this method. We apply this method to multiwavelength absorption aerosol optical depth (AAOD) measurements at AERONET sites worldwide and surface aerosol absorption measurements at multiple ambient sites. We estimate that BrC globally contributes up to 40 % of the seasonally averaged absorption at 440 nm. We find that the mass absorption coefficient of OA (OA-MAC) is positively correlated with the BC ∕ OA mass ratio. Based on the variability in BC properties and BC ∕ OA emission ratio, we estimate a range of 0.05–1.5 m2 g−1 for OA-MAC at 440 nm. Using the combination of AERONET and OMI UV absorption observations we estimate that the AAE388∕440 nm for BrC is generally  ∼ 4 worldwide, with a smaller value in Europe (

title: Strong spectral variation of biomass smoke light absorption and single scattering albedo observed with a novel dual-wavelength photoacoustic instrument
abstract: A dual-wavelength photoacoustic instrument operating at 405 and 870 nm was used during the 2006 Fire Lab at Missoula Experiment to measure light scattering and absorption by smoke from the combustion of a variety of biomass fuels. Simultaneous measurements of aerosol light scattering by reciprocal nephelometry within the instrument's acoustic resonator accompany photoacoustic aerosol light absorption measurements. Single scattering albedo values at 405 nm ranging from 0.37 to 0.95 were measured for different fuel types, and the spectral dependence of absorption was quantified using the Angstrom exponent of absorption. An absorption Angstrom exponent near unity is commonly observed for motor vehicle emission-generated black carbon aerosol. For biomass smoke, Angstrom exponents as high as 3.5 were found in association with smoke having single scattering albedo near unity. The measurements strongly suggest that light-absorbing organic material is present in wood smoke. A second single-wavelength photoacoustic instrument with reciprocal nephelometry was used to quantify aerosol scattering and absorption at 532 nm. Absorption Angstrom exponents calculated using 532 and 870 nm data were as large as 2.5 for smoke with single scattering albedos near unity. The spectral variation in optical properties provides insight into the differentiation of aerosols from mobile or industrial sources versus those from biomass burning. Optical properties of biomass smokes could be classified by general fuel type such as flowering shrubs versus pine needle litter.

title: Analysis and quantification of the diversities of aerosol life cycles within AeroCom
abstract: Simulation results of global aerosol models have been assembled in the framework of the AeroCom intercomparison exercise. In this paper, we analyze the life cycles of dust, sea salt, sulfate, black carbon and particulate organic matter as simulated by sixteen global aerosol models. The differences among the results (model diversities) for sources and sinks, burdens, particle sizes, water uptakes, and spatial dispersals have been established. These diversities have large consequences for the calculated radiative forcing and the aerosol concentrations at the surface. Processes and parameters are identified which deserve further research. The AeroCom all-models-average emissions are dominated by the mass of sea salt (SS), followed by dust (DU), sulfate (SO 4 ), particulate organic matter (POM), and finally black carbon (BC). Interactive parameterizations of the emissions and contrasting particles sizes of SS and DU lead generally to higher diversities of these species, and for total aerosol. The lower diversity of the emissions of the fine aerosols, BC, POM, and SO 4 , is due to the use of similar emission inventories, and does therefore not necessarily indicate a better understanding of their sources. The diversity of SO 4 -sources is mainly caused by the disagreement on depositional loss of precursor gases and on chemical production. The diversities of the emissions are passed on to the burdens, but the latter are also strongly affected by the model-specific treatments of transport and aerosol processes. The burdens of dry masses decrease from largest to smallest: DU, SS, SO 4 , POM, and BC. The all-models-average residence time is shortest for SS with about half a day, followed by SO 4 and DU with four days, and POM and BC with six and seven days, respectively. The wet deposition rate is controlled by the solubility and increases from DU, BC, POM to SO 4 and SS. It is the dominant sink for SO 4 , BC, and POM, and contributes about one third to the total removal of SS and DU species. For SS and DU we find high diversities for the removal rate coefficients and deposition pathways. Models do neither agree on the split between wet and dry deposition, nor on that between sedimentation and other dry deposition processes. We diagnose an extremely high diversity for the uptake of ambient water vapor that influences the particle size and thus the sink rate coefficients. Furthermore, we find little agreement among the model results for the partitioning of wet removal into scavenging by convective and stratiform rain. Large differences exist for aerosol dispersal both in the vertical and in the horizontal direction. In some models, a minimum of total aerosol concentration is simulated at the surface. Aerosol dispersal is most pronounced for SO 4 and BC and lowest for SS. Diversities are higher for meridional than for vertical dispersal, they are similar for the individual species and highest for SS and DU. For these two components we do not find a correlation between vertical and meridional aerosol dispersal. In addition the degree of dispersals of SS and DU is not related to their residence times. SO 4 , BC, and POM, however, show increased meridional dispersal in models with larger vertical dispersal, and dispersal is larger for longer simulated residence times.

title: Smaller desert dust cooling effect estimated from analysis of dust size and abundance
abstract: Desert dust aerosols a ect Earth’s global energy balance through direct interactions with radiation, and through indirect interactions with clouds and ecosystems. But the magnitudes of these e ects are so uncertain that it remains unclear whether atmospheric dust has a netwarming or cooling e ect on global climate. Consequently, it is still uncertainwhether large changes in atmospheric dust loading over the past century have slowed or accelerated anthropogenic climate change, orwhat the e ects of potential future changes in dust loading will be. Here we present an analysis of the size and abundance of dust aerosols to constrain the direct radiative e ect of dust. Using observational data on dust abundance, in situmeasurements of dust optical properties and size distribution, and climate and atmospheric chemical transport model simulations of dust lifetime, we find that the dust found in the atmosphere is substantially coarser than represented in current global climate models. As coarse dust warms the climate, the global dust direct radiative e ect is likely to be less cooling than the∼−0.4Wm estimated by models in a current global aerosol model ensemble. Instead, we constrain the dust direct radiative e ect to a range between −0.48 and+0.20Wm, which includes the possibility that dust causes a net warming of the planet.

title: Spectral- and size-resolved mass absorption efficiency of mineral dust aerosols in the shortwave spectrum: a simulation chamber study
abstract: This paper presents new laboratory measurements of the mass absorption efficiency (MAE) between 375 and 850 nm for 12 individual samples of mineral dust from different source areas worldwide and in two size classes: PM10. 6 (mass fraction of particles of aerodynamic diameter lower than 10.6 µm) and PM2. 5 (mass fraction of particles of aerodynamic diameter lower than 2.5 µm). The experiments were performed in the CESAM simulation chamber using mineral dust generated from natural parent soils and included optical and gravimetric analyses. The results show that the MAE values are lower for the PM10. 6 mass fraction (range 37–135  ×  10−3 m2 g−1 at 375 nm) than for the PM2. 5 (range 95–711  ×  10−3 m2 g−1 at 375 nm) and decrease with increasing wavelength as λ−AAE, where the Angstrom absorption exponent (AAE) averages between 3.3 and 3.5, regardless of size. The size independence of AAE suggests that, for a given size distribution, the dust composition did not vary with size for this set of samples. Because of its high atmospheric concentration, light absorption by mineral dust can be competitive with black and brown carbon even during atmospheric transport over heavy polluted regions, when dust concentrations are significantly lower than at emission. The AAE values of mineral dust are higher than for black carbon (∼ 1) but in the same range as light-absorbing organic (brown) carbon. As a result, depending on the environment, there can be some ambiguity in apportioning the aerosol absorption optical depth (AAOD) based on spectral dependence, which is relevant to the development of remote sensing of light-absorbing aerosols and their assimilation in climate models. We suggest that the sample-to-sample variability in our dataset of MAE values is related to regional differences in the mineralogical composition of the parent soils. Particularly in the PM2. 5 fraction, we found a strong linear correlation between the dust light-absorption properties and elemental iron rather than the iron oxide fraction, which could ease the application and the validation of climate models that now start to include the representation of the dust composition, as well as for remote sensing of dust absorption in the UV–vis spectral region.

title: Dominance of goethite over hematite in iron oxides of mineral dust from Western Africa: Quantitative partitioning by X‐ray absorption spectroscopy
abstract: This paper reports on the X-ray absorption analysis of samples of mineral dust emitted from or transported to Western Africa. We found that iron oxides account, by mass, for 38% to 72% of the total elemental iron. They are composed of minerals in the Fe(III) oxidation state: goethite (FeO·OH) and hematite (Fe2O3). The apparent fraction of iron oxide attributed to goethite is higher than hematite regardless of the source region from which the dust originated. The goethite percent content of iron oxides is in the range 52–78% (by mass), the highest values being measured for dust originating in the Sahel. The limited number of samples analyzed and the sample-to-sample variability prevent us from concluding firmly on the regional variability of the goethite-to-hematite ratio. Based on the experimental data on mineralogical composition and on concurrent measurements of the number size distribution, the optical properties of mineral dust have been calculated in a Mie approximation for homogeneous spherical particles. At 550 nm, the single-scattering albedo ω0 ranges between 0.89 and 0.93, the asymmetry factor g ranges between 0.76 and 0.8 and the mass extinction efficiency kext varies between 0.5 and 1.1 m2 g−1; these values are all in the range of those from independent direct measurements. Neglecting the partitioning between hematite and goethite and the assimilation of iron oxides by hematite, as it is often done with models, lowers the single-scattering albedo and increases the asymmetry factor in the UV-visible spectral region below 550 nm. The mass extinction efficiency is insensitive to the nature of the iron oxides but rather responds to variations in the number size distribution. The mineralogy of iron oxides should therefore be taken into account when assessing the effect of mineral dust on climate and atmospheric chemistry, in particular via interactions involving photolysis.

title: Recent progress in understanding physical and chemical properties of African and Asian mineral dust
abstract: This paper presents a review of recently acquired knowledge on the physico-chemical properties of mineral dust from Africa and Asia based on data presented and discussed during the Third International Dust Workshop, held in Leipzig (Germany) in September 2008. Various regional field experiments have been conducted in the last few years, mostly close to source regions or after short-range transport. Although significant progress has been made in characterising the regional variability of dust properties close to source regions, in particular the mineralogy of iron and the description of particle shape and mixing state, difficulties remain in estimating the range of variability of those properties within one given source region. As consequence, the impact of these parameters on aerosol properties like optical properties, solubility, hygroscopicity, etc. – determining the dust impact on climate – is only partly understood. Long-term datasets in remote regions such as the dust source regions remain a major desideratum. Future work should also focus on the evolution of dust properties during transport. In particular, the prediction of the mineral dust size distribution at emission and their evolution during transport should be considered as a high-priority. From the methodological point of view, a critical assessment and standardisation of the experimental and analytical techniques is highly recommended. Techniques to characterize the internal state of mixing of dust particles, particularly with organic material, should be further developed.

title: Light scattering by spherical particles with hematite and goethitelike optical properties: Effect of water impregnation
abstract: The interpretation of reflectance spectra (through remote sensing or laboratory research) requires spectral reflectance models that can be inversed to determine the more fundamental physical properties of these surfaces. One of the main hypotheses in reflectance models is that a soil or a powder are generally considered as a collection of particles or aggregates with averaged optical properties. Verification of this hypothesis is of great interest. This paper deals with the study of the scattering and absorption of light by a single mineral particle where diameter ranges from 0.01 to 50 μm. The particles are assumed to be spherical, and their complex refractive index is assumed to be equal to that of hematite or goethite (ordinary indices). These two minerals are responsible for the nonlinear and wavelength-dependent behavior of lateritic soils reflectance spectra upon moistening. The absorption and scattering efficiencies, single scattering albedo, scattering diagram, and opening angle were computed for a single sphere. Different scenarios were considered: first, a sphere in the air, second, a sphere in water, and third, a sphere surrounded by a water layer of different thickness. All the computed spectra (400–700 nm) are classified into three diameter groups (0.01–0.1, 0.1–2, and 2–50 μm). The behavior of the calculated spectra (second and third scenarios) depends both on the particle diameter and the wavelength. A simplified Hapke's model was then used to simulate the reflectance spectra of powders of hematite and goethite. The main result is the existence of an optical elementary arrangement cell which is for the soil what a unit cell is for a crystal.

title: Color Attributes and Mineralogical Characteristics, Evaluated by Radiometry, of Highly Weathered Tropical Soils
abstract: Highly weathered soils are important around the world. Determination of their observed colors and acquisition of spectral curves were used to study their mineralogy. Color was determined through visual comparison with Munsell Soil Color Charts, and soils spectral characterization was made with an infrared intelligent spectroradiometer (IRIS) covering a spectral window from 300 to 3000 nm. The variables of color behaved differently among soils. The Munsell hue was related to hematite content and the hematite/goethite ratio (Hm/Gt), and the Munsell value to organic content of goethitic soils. The Munsell chroma was related to the presence of Fe oxides, giving an idea of relative amounts of either hematite or goethite. Regression equations relating color indices showed that the redness factor (RF) gave the highest determination coefficients to estimate hematite content and Hm/Gt, and reconfirmed that redness saturation occurs with increasing hematite amounts. The typical minerals of these soils showed characteristic absorption bands in their spectral curves. Absorption bands of 450 and 900 nm for Fe oxides, 2200 nm for kaolinite and 2280 for gibbsite, were distinctive features of the main minerals present. Organic matter decreased the intensity of reflectance for most soils and, under its influence, the characteristic bands of goethite practically disappeared while the ones for hematite, kaolinite, and gibbsite were attenuated. High amounts of hematite decreased the reflectance factor strongly as compared with the soil organic matter (SOM). Qualitative mineralogy of highly weathered soils was assessed by radiometry using measurements in the visible and near infrared regions of the electromagnetic spectrum.

title: Impacts on iron solubility in the mineral dust by processes in the source region and the atmosphere: A review
abstract: Mineral dust is a complex entity containing a range of iron minerals including poorly crystalline to crystalline iron oxides to clay minerals. Important progress has been made to characterize iron mineralogical compositions in the dust recently. These include the quantification of the content of crystalline hematite and goethite, which appear to show a regional variation in North Africa as a result of the differences in the degree of chemical weathering. Fractional Fe solubility (dissolved to total iron, FFS) in the atmospheric aerosols has been reported to range from 0.1% to 80%. However, FFS is usually less than 0.5% in the non-atmospherically-processed dust, suggesting that FFS can be enhanced by atmospheric processes. One of the atmospheric processes, gravitational settling of dust, which has been previously hypothesized to cause the abovementioned enhancement of FFS during dust transport has been shown to be insignificant. Cycling of dust particles in the clouds, in which pH is usually higher than 4, and in the aerosol phase, in which pH is usually substantially lower, can significantly affect iron speciation and FFS. Laboratory experiments showed that a significant amount of iron (>0.5%) can only be solubilized in the dust when pH is lower than 4. These laboratory data suggest that acid processing rather than cloud processing might be a prime mechanism to cause an increase in FFS in the dust during transport. Further laboratory studies, field measurements, and modelling are needed to increase the ability of models to quantify the atmospheric processing of iron in the dust.

title: An observationally constrained estimate of global dust aerosol optical depth
abstract: The role of mineral dust in climate and ecosystems has been largely quantified using global climate and chemistry model simulations of dust emission, transport, and deposition. However, differences between these model simulations are substantial, with estimates of global dust aerosol optical depth (AOD) that vary by over a factor of 5. Here we develop an observationally based estimate of the global dust AOD, using multiple satellite platforms, in situ AOD observations and four state-of-the-science global models over 2004–2008. We estimate that the global dust AOD at 550 nm is 0.030 ± 0.005 (1σ), higher than the AeroCom model median (0.023) and substantially narrowing the uncertainty. The methodology used provides regional, seasonal dust AOD and the associated statistical uncertainty for key dust regions around the globe with which model dust schemes can be evaluated. Exploring the regional and seasonal differences in dust AOD between our observationally based estimate and the four models in this study, we find that emissions in Africa are often overrepresented at the expense of Asian and Middle Eastern emissions and that dust removal appears to be too rapid in most models.

title: Global dust model intercomparison in AeroCom phase I
abstract: This study presents the results of a broad intercomparison of a total of 15 global aerosol models within the AeroCom project. Each model is compared to observations related to desert dust aerosols, their direct radiative effect, and their impact on the biogeochemical cycle, i.e., aerosol optical depth (AOD) and dust deposition. Additional comparisons to Angstrom exponent (AE), coarse mode AOD and dust surface concentrations are included to extend the assessment of model performance and to identify common biases present in models. These data comprise a benchmark dataset that is proposed for model inspection and future dust model development. There are large differences among the global models that simulate the dust cycle and its impact on climate. In general, models simulate the climatology of vertically integrated parameters (AOD and AE) within a factor of two whereas the total deposition and surface concentration are reproduced within a factor of 10. In addition, smaller mean normalized bias and root mean square errors are obtained for the climatology of AOD and AE than for total deposition and surface concentration. Characteristics of the datasets used and their uncertainties may influence these differences. Large uncertainties still exist with respect to the deposition fluxes in the southern oceans. Further measurements and model studies are necessary to assess the general model performance to reproduce dust deposition in ocean regions sensible to iron contributions. Models overestimate the wet deposition in regions dominated by dry deposition. They generally simulate more realistic surface concentration at stations downwind of the main sources than at remote ones. Most models simulate the gradient in AOD and AE between the different dusty regions. However the seasonality and magnitude of both variables is better simulated at African stations than Middle East ones. The models simulate the offshore transport of West Africa throughout the year but they overestimate the AOD and they transport too fine particles. The models also reproduce the dust transport across the Atlantic in the summer in terms of both AOD and AE but not so well in winter-spring nor the southward displacement of the dust cloud that is responsible of the dust transport into South America. Based on the dependency of AOD on aerosol burden and size distribution we use model bias with respect to AOD and AE to infer the bias of the dust emissions in Africa and the Middle East. According to this analysis we suggest that a range of possible emissions for North Africa is 400 to 2200 Tg yr−1 and in the Middle East 26 to 526 Tg yr−1.

title: Mineral dust aerosols in the NASA Goddard Institute for Space Sciences ModelE atmospheric general circulation model
abstract: We describe an updated model of the dust aerosol cycle embedded within the NASA Goddard Institute for Space Studies ‘ModelE’ atmospheric general circulation model (AGCM). The model dust distribution is compared to observations ranging from aerosol optical thickness and surface concentration to deposition and size distribution. The agreement with observations is improved compared to previous distributions computed by either an older version of the GISS AGCM or an offline tracer transport model. The largest improvement is in dust transport over the Atlantic due to increased emission over the Sahara. This increase comes from subgrid wind fluctuations associated with dry convective eddies driven by intense summertime heating. Representation of ‘preferred sources’ of soil dust particles is also fundamental to the improvement. The observations suggest that deposition is too efficient in the model, partly due to AGCM rainfall errors.

title: Aerosol single-scattering albedo over the global oceans: Comparing PARASOL retrievals with AERONET, OMI, and AeroCom models estimates
abstract: The aerosol single-scattering albedo (SSA) over the global ocean is evaluated based on polarimetric measurements by the PARASOL (Polarization and Anisotropy of Reflectances for Atmospheric Sciences coupled with Observations from a Lidar) satellite. For the first time, global ocean SSA and Absorption Aerosol Optical Depth (AAOD) from this instrument are shown and evaluated against other observations (the Aerosol Robotic Network, AERONET, and the Ozone Monitoring Instrument, OMI). The observational data sets compare reasonably well, with the majority of the colocated points within 0.05 of the AERONET measurements. PARASOL shows that SSA is characterized by high spatial and seasonal variability, also over the open ocean far from the inland emission regions. The near global coverage in the visible spectral range provided by the PARASOL retrievals represents a unique opportunity to evaluate aerosol optical properties simulated by global aerosol models, as performed in the Aerosol Comparisons between Observations and Models (AeroCom) framework. The SSA (AAOD) estimated by the AeroCom models is generally higher (smaller) than the SSA (AAOD) retrieved from PARASOL. On the other hand, the mean simulated aerosol optical depth is consistent or slightly underestimated compared with observations. An overestimate of the aerosol scattering, compared to absorption, by the models would suggest that these simulate an overly strong aerosol radiative cooling at top of atmosphere, over most of the ocean surfaces. This implies that aerosols have a potentially stronger direct and semidirect impact within the atmosphere than currently simulated.

title: Single-scattering properties of tri-axial ellipsoidal mineral dust aerosols: A database for application to radiative transfer calculations
abstract: This paper presents a user-friendly database software package of the single-scattering properties of individual dust-like aerosol particles for application to radiative transfer calculations in a spectral region from ultraviolet (UV) to far-infrared (far-IR). To expand the degree of morphological freedom of the commonly used spheroidal and spherical models, tri-axial ellipsoids were assumed to be the overall shape of dust-like aerosol particles. A combination of four computational methods, including the Lorenz–Mie theory, the T-matrix method, the discrete dipole approximation, and an improved geometric optics method, was employed to compute the phase matrix, extinction efficiency and single-scattering albedo of ellipsoids with various aspect ratios and sizes. The scattering property database was developed for 42 particle shapes specified in terms of two aspect ratios, 69 refractive indices and 471 size parameters. Additionally, accompanying software, based on interpolation, was developed to provide the single-scattering properties for user-specified aspect ratios, refractive indices and size parameters. The software package allows for the derivation of the bulk optical properties for a given distribution of particle microphysical parameters (i.e., refractive index, size parameter and two aspect ratios). The array-oriented single-scattering property data sets are stored in the NetCDF format.

title: Ability of multiangle remote sensing observations to identify and distinguish mineral dust types: 2. Sensitivity over dark water
abstract: We explore the ability of multiangle, multispectral measurements, such as those from the Multiangle Imaging SpectroRadiometer (MISR), to retrieve mineral dust properties. We first investigate MISR sensitivity theoretically, to a selection of medium-mode particle shapes, to single-scattering albedo (SSA), and to the ratio of medium- to large-mode aerosol optical thickness (AOT). Favorable, but not ideal, viewing conditions over dark water are assumed, and new dust optical models are adopted. This study shows sensitivity to differences in the angular spectral signals of medium-mode shapes when column midvisible AOT is greater than ∼0.15 for components contributing 15–20% or more to the AOT. MISR-like retrievals can also distinguish strongly absorbing (red channel SSA ∼ 0.94) from less absorbing (SSA ∼ 0.98–0.99) dust particles. Bimodal size sensitivity results suggest that MISR can distinguish the ratio of medium to larger components in roughly 20% midvisible AOT increments. For five Saharan dust field events over homogeneous, cloud-free dark water near the Cape Verde AERONET station, MISR research retrieval results were dominated by weakly absorbing medium grains. MISR-retrieved spectral AOT was within 0.02 of the Aerosol Robotic Network (AERONET), except for one spatially heterogeneous AOT > 1 case, and one where AERONET retrieved a significant component <0.1 μm in radius. In two cases where AERONET ran retrievals assuming nonspherical (spheroidal) particles, SSA fell within 0.02 of MISR. When included in the MISR Standard Aerosol Retrieval Algorithm, the new dust optical models improve both the coverage of successful retrievals and the spectral AOT agreement with near-coincident AERONET measurements. Large-mode dust models and available field constraint limitations are being addressed in continuing work.

title: Multi-decadal aerosol variations from 1980 to 2009: a perspective from observations and a global model
abstract: Aerosol variations and trends over different land and ocean regions from 1980 to 2009 are analyzed with the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model and observations from multiple satellite sensors and available ground-based networks. Excluding time periods with large volcanic influence, aerosol optical depth (AOD) and surface concentration over polluted land regions generally vary with anthropogenic emissions, but the magnitude of this association can be dampened by the presence of natural aerosols, especially dust. Over the 30-year period in this study, the largest reduction in aerosol levels occurs over Europe, where AOD has decreased by 40–60% on average and surface sulfate concentrations have declined by a factor of up to 3–4. In contrast, East Asia and South Asia show AOD increases, but the relatively high level of dust aerosols in Asia reduces the correlation between AOD and pollutant emission trends. Over major dust source regions, model analysis indicates that the change of dust emissions over the Sahara and Sahel has been predominantly driven by the change of near-surface wind speed, but over Central Asia it has been largely influenced by the change of the surface wetness. The decreasing dust trend in the North African dust outflow region of the tropical North Atlantic and the receptor sites of Barbados and Miami is closely associated with an increase of the sea surface temperature in the North Atlantic. This temperature increase may drive the decrease of the wind velocity over North Africa, which reduces the dust emission, and the increase of precipitation over the tropical North Atlantic, which enhances dust removal during transport. Despite significant trends over some major continental source regions, the model-calculated global annual average AOD shows little change over land and ocean in the past three decades, because opposite trends in different land regions cancel each other out in the global average, and changes over large open oceans are negligible. This highlights the necessity for regional-scale assessment of aerosols and their climate impacts, as global-scale average values can obscure important regional changes.

title: Characterization of iron oxides in mineral dust aerosols: Implications for light absorption
abstract: We report on measurements that were specifically designed to determine iron oxides in mineral dust aerosols needed for improved optical modeling. Atmospheric dust samples as well as samples generated in a wind tunnel from soils were analyzed by a number of analytical techniques for their total and free iron content (bulk and size resolved), hematite and goethite, mineralogy, and size distribution. These samples are representative of several important dust sources in East Asia and northern Africa. A novel data set generated from these measurements enables us to perform an in-depth modeling study of dust optical properties in the solar spectrum. We modeled the iron oxide–clay aggregates, which are the key light-absorbing species, as well as their mixtures with nonabsorbing minerals. A volume fraction of iron oxide in aggregates was determined from measurements. Significant differences in the single-scattering albedo, ω0, were found between hematite- and goethite-clay aggregates, although these calculations involved several important assumptions about the partition of hematite and goethite in size-resolved aggregates. Furthermore, we found that variability of the free iron content is large enough to cause important differences in ω0 of mineral dust originating from different sources. In contrast, this variability has little effect on the extinction coefficient and optical depth. We demonstrate that for the same size distribution, ω0 calculated from data obtained for Chinese and Tunisian samples show higher values and more distinct wavelength dependence than those of Niger dust. All the above ω0 differ from ones calculated using the refractive indices of Patterson et al. (1977) or the OPAC model (Hess et al., 1998), which are often used in radiative transfer studies. We conclude that information on a size-resolved content of free iron and a fraction of hematite and goethite in aggregates will need to be known on a regional basis to improve the prediction of the single-scattering albedo at solar wavelengths and hence the radiative impact of atmospheric mineral dust.

title: What is the real role of iron oxides in the optical properties of dust aerosols
abstract: Iron oxide compounds constitute an important component of mineral dust aerosols. Several previous studies have shown that these minerals are strong absorbers at visible wavelengths and thus that they play a critical role in the overall climate perturbation caused by dust aerosols. When compiling a database of complex refractive indices of possible mineral species of iron oxides to study their optical properties, we found that uniformly continuous optical constants for a single type of iron oxide in the wavelength range between 0.2 and 50 μm are very scarce, and that the use of hematite to represent all molecular or mineral iron-oxides types is a popular hypothesis. However, the crucial problem is that three continuous data sets for complex refractive indices of hematite are employed in climate models, but there are significant differences between them. Thus, the real role of iron oxides in the optical properties of dust aerosols becomes a key scientific question, and we address this problem by considering different refractive indices, size distributions and more logical weight fractions and mixing states of hematite. Based on the microscopic observations, a semi-external mixture that employs an external mixture between Fe aggregates and other minerals and partly internal mixing between iron oxides and aluminosilicate particles is advised as the optimal approximation. The simulations demonstrate that hematite with a spectral refractive index from Longtin et al. (1988) shows approximately equal absorbing capacity to the mineral illite over the whole wavelength region from 0.55 to 2.5 μm, and only enhances the optical absorption of aerosol mixture at λ

title: Global scale variability of the mineral dust long-wave refractive index: a new dataset of in situ measurements for climate modeling and remote sensing
abstract: Modeling the interaction of dust with long-wave (LW) radiation is still a challenge because of the scarcity of information on the complex refractive index of dust from different source regions. In particular, little is known about the variability of the refractive index as a function of the dust mineralogical composition, which depends on the specific emission source, and its size distribution, which is modified during transport. As a consequence, to date, climate models and remote sensing retrievals generally use a spatially invariant and time-constant value for the dust LW refractive index. In this paper, the variability of the mineral dust LW refractive index as a function of its mineralogical composition and size distribution is explored by in situ measurements in a large smog chamber. Mineral dust aerosols were generated from 19 natural soils from 8 regions: northern Africa, the Sahel, eastern Africa and the Middle East, eastern Asia, North and South America, southern Africa, and Australia. Soil samples were selected from a total of 137 available samples in order to represent the diversity of sources from arid and semi-arid areas worldwide and to account for the heterogeneity of the soil composition at the global scale. Aerosol samples generated from soils were re-suspended in the chamber, where their LW extinction spectra (3–15 µm), size distribution, and mineralogical composition were measured. The generated aerosol exhibits a realistic size distribution and mineralogy, including both the sub- and super-micron fractions, and represents in typical atmospheric proportions the main LW-active minerals, such as clays, quartz, and calcite. The complex refractive index of the aerosol is obtained by an optical inversion based upon the measured extinction spectrum and size distribution. Results from the present study show that the imaginary LW refractive index (k) of dust varies greatly both in magnitude and spectral shape from sample to sample, reflecting the differences in particle composition. In the 3–15 µm spectral range, k is between ∼ 0.001 and 0.92. The strength of the dust absorption at ∼ 7 and 11.4 µm depends on the amount of calcite within the samples, while the absorption between 8 and 14 µm is determined by the relative abundance of quartz and clays. The imaginary part (k) is observed to vary both from region to region and for varying sources within the same region. Conversely, for the real part (n), which is in the range 0.84–1.94, values are observed to agree for all dust samples across most of the spectrum within the error bars. This implies that while a constant n can be probably assumed for dust from different sources, a varying k should be used both at the global and the regional scale. A linear relationship between the magnitude of the imaginary refractive index at 7.0, 9.2, and 11.4 µm and the mass concentration of calcite and quartz absorbing at these wavelengths was found. We suggest that this may lead to predictive rules to estimate the LW refractive index of dust in specific bands based on an assumed or predicted mineralogical composition, or conversely, to estimate the dust composition from measurements of the LW extinction at specific wavebands. Based on the results of the present study, we recommend that climate models and remote sensing instruments operating at infrared wavelengths, such as IASI (infrared atmospheric sounder interferometer), use regionally dependent refractive indices rather than generic values. Our observations also suggest that the refractive index of dust in the LW does not change as a result of the loss of coarse particles by gravitational settling, so that constant values of n and k could be assumed close to sources and following transport. The whole dataset of the dust complex refractive indices presented in this paper is made available to the scientific community in the Supplement.

title: Technical note: Mineralogical, chemical, morphological, and opticalinterrelationships of mineral dust re-suspensions
abstract: This paper promotes an understanding of the mineralogical, chemical, and physical interrelationships of re-suspended mineral dusts collected as grab samples from global dust sources. Surface soils were collected from arid regions, including the southwestern USA, Mali, Chad, Morocco, Canary Islands, Cabo Verde, Djibouti, Afghanistan, Iraq, Kuwait, Qatar, UAE, Serbia, China, Namibia, Botswana, Australia, and Chile. The ® membrane and quartz fiber filters for chemical analysis and Nuclepore ® filters for individual particle analysis by scanning electron microscopy (SEM). The   75,

title: Mineral dust emission from the Bodélé Depression, northern Chad, during BoDEx 2005
abstract: Mineral dust in the atmosphere is an important component of the climate system but is poorly quantified. The Bodele depression of Northern Chad stands out as the world’s greatest source region of mineral dust into the atmosphere. Frequent dust plumes are a distinguishing feature of the region’s climate. There is a need for more detailed information on processes of dust emission/transport and dust optical properties to inform model simulations of this source. During the Bodele Dust Experiment (BoDEx) in 2005 instrumentation was deployed to measure dust properties and boundary layer meteorology. Observations indicate that dust emission events are triggered when near surface wind speeds exceed 10ms-1, associated with synoptic scale variability in the large-scale atmospheric circulation. Dust emission pulses in phase with the diurnal cycle of near surface winds. Analysis of dust samples shows that the dust consists predominantly of fragments of diatomite sediment. The particle size distribution of this diatomite dust estimated from sun photometer data, using a modified Aeronet retrieval algorithm, indicate a dominant coarse mode (radius centred on 1-2?m) similar to other Saharan dust observations. Single scattering albedo values are high, broadly in line with other Saharan dust even though the diatomite composition of dust from the Bodele is likely to be unusual. The radiative impact of high dust loadings results in a reduction in surface daytime maximum temperature of around 7°C in the Bodele region. Using optical and physical properties of dust obtained in the field we estimate the total dust flux emitted from the Bodele to be 1.18±0.45Tg per day during a substantial dust event. We speculate that the Bodele depression (~10,800km2) may be responsible for between 6-18% of global dust emission, although the uncertainty in both the Bodele and global estimates remain high.

title: Consistency Between Satellite-Derived and Modeled Estimates of the Direct Aerosol Effect
abstract: Cooling Down Some aerosols, such as sulfates, reflect solar radiation and have a cooling effect on climate, while others, such as black carbon, have a warming effect because they absorb solar radiation. The preponderance of reflective aerosols causes the net effect to be one of cooling, but the amount of cooling is uncertain, owing to a large difference in estimates of the effect of aerosols in global aerosol models compared with estimates based on observations. Myhre (p. 187, published online 18 June; see the Perspective by Quaas) uses a combination of observational data and modeling to reconcile the two approaches, drawing particular attention to relative increases in the aerosol fraction of black carbon. Taken together, the results suggest a best estimate of the cooling effect of aerosols that is 60% of previous reports. Observational data and modeling narrows the large range of uncertainty about how much aerosols influence climate. In the Intergovernmental Panel on Climate Change Fourth Assessment Report, the direct aerosol effect is reported to have a radiative forcing estimate of –0.5 Watt per square meter (W m−2), offsetting the warming from CO2 by almost one-third. The uncertainty, however, ranges from –0.9 to –0.1 W m−2, which is largely due to differences between estimates from global aerosol models and observation-based estimates, with the latter tending to have stronger (more negative) radiative forcing. This study demonstrates consistency between a global aerosol model and adjustment to an observation-based method, producing a global and annual mean radiative forcing that is weaker than –0.5 W m−2, with a best estimate of –0.3 W m−2. The physical explanation for the earlier discrepancy is that the relative increase in anthropogenic black carbon (absorbing aerosols) is much larger than the overall increase in the anthropogenic abundance of aerosols.

title: Global estimate of aerosol direct radiative forcing from satellite measurements
abstract: Atmospheric aerosols cause scattering and absorption of incoming solar radiation. Additional anthropogenic aerosols released into the atmosphere thus exert a direct radiative forcing on the climate system. The degree of present-day aerosol forcing is estimated from global models that incorporate a representation of the aerosol cycles. Although the models are compared and validated against observations, these estimates remain uncertain. Previous satellite measurements of the direct effect of aerosols contained limited information about aerosol type, and were confined to oceans only. Here we use state-of-the-art satellite-based measurements of aerosols and surface wind speed to estimate the clear-sky direct radiative forcing for 2002, incorporating measurements over land and ocean. We use a Monte Carlo approach to account for uncertainties in aerosol measurements and in the algorithm used. Probability density functions obtained for the direct radiative forcing at the top of the atmosphere give a clear-sky, global, annual average of -1.9 W m-2 with standard deviation, ± 0.3 W m-2. These results suggest that present-day direct radiative forcing is stronger than present model estimates, implying future atmospheric warming greater than is presently predicted, as aerosol emissions continue to decline.

title: Reducing the Uncertainties in Direct Aerosol Radiative Forcing
abstract: Direct aerosol radiative forcing (DARF) remains a leading contributor to climate prediction uncertainty. To monitor the spatially and temporally varying global atmospheric aerosol load, satellite remote sensing is required. Despite major advances in observing aerosol amount, type, and distribution from space, satellite data alone cannot provide enough quantitative detail, especially about aerosol microphysical properties, to effect the required improvement in estimates of DARF and the anthropogenic component of DARF. However, the combination of space-based and targeted suborbital measurements, when used to constrain climate models, represents an achievable next step likely to provide the needed advancement.

title: AERONET-a federated instrument network and data archive for aerosol Characterization
abstract: The concept and description of a remote sensing aerosol monitoring network initiated by NASA, developed to support NASA, CNES, and NASDA’s Earth satellite systems under the name AERONET and expanded by national and international collaboration, is described. Recent development of weather-resistant automatic sun and sky scanning spectral radiometers enable frequent measurements of atmospheric aerosol optical properties and precipitable water at remote sites. Transmission of automatic measurements via the geostationary satellites GOES and METEOSATS’ Data Collection Systems allows reception and processing in near real-time from approximately 75% of the Earth’s surface and with the expected addition of GMS, the coverage will increase to 90% in 1998. NASA developed a UNIX-based near real-time processing, display and analysis system providing internet access to the emerging global database. Information on the system is available on the project homepage, http://spamer.gsfc.nasa.gov . The philosophy of an open access database, centralized processing and a user-friendly graphical interface has contributed to the growth of international cooperation for ground-based aerosol monitoring and imposes a standardization for these measurements. The system’s automatic data acquisition, transmission, and processing facilitates aerosol characterization on local, regional, and global scales with applications to transport and radiation budget studies, radiative transfer-modeling and validation of satellite aerosol retrievals. This article discusses the operation and philosophy of the monitoring system, the precision and accuracy of the measuring radiometers, a brief description of the processing system, and access to the database.

title: Exploiting simultaneous observational constraints on mass and absorption to estimate the global direct radiative forcing of black carbon and brown carbon
abstract: Atmospheric black carbon (BC) is a leading climate warming agent, yet uncertainties on the global direct radiative forcing (DRF) remain large. Here we expand a global model simulation (GEOS-Chem) of BC to include the absorption enhancement associated with BC coating and separately treat both the aging and physical properties of fossil-fuel and biomass-burning BC. In addition we develop a global simulation of brown carbon (BrC) from both secondary (aromatic) and primary (biomass burning and biofuel) sources. The global mean lifetime of BC in this simulation (4.4 days) is substantially lower compared to the AeroCom I model means (7.3 days), and as a result, this model captures both the mass concentrations measured in near-source airborne field campaigns (ARCTAS, EUCAARI) and surface sites within 30%, and in remote regions (HIPPO) within a factor of 2. We show that the new BC optical properties together with the inclusion of BrC reduces the model bias in absorption aerosol optical depth (AAOD) at multiple wavelengths by more than 50% at AERONET sites worldwide. However our improved model still underestimates AAOD by a factor of 1.4 to 2.8 regionally, with the largest underestimates in regions influenced by fire. Using the RRTMG model integrated with GEOS-Chem we estimate that the all-sky top-of-atmosphere DRF of BC is +0.13 Wm−2 (0.08 Wm−2 from anthropogenic sources and 0.05 Wm−2 from biomass burning). If we scale our model to match AERONET AAOD observations we estimate the DRF of BC is +0.21 Wm−2, with an additional +0.11 Wm−2 of warming from BrC. Uncertainties in size, optical properties, observations, and emissions suggest an overall uncertainty in BC DRF of −80%/+140%. Our estimates are at the lower end of the 0.2–1.0 Wm−2 range from previous studies, and substantially less than the +0.6 Wm−2 DRF estimated in the IPCC 5th Assessment Report. We suggest that the DRF of BC has previously been overestimated due to the overestimation of the BC lifetime (including the effect on the vertical profile) and the incorrect attribution of BrC absorption to BC.

title: Estimating global black carbon emissions using a top‐down Kalman Filter approach
abstract: Black carbon (BC) is an important aerosol constituent in the atmosphere and climate forcer. A good understanding of the radiative forcing of BC and associated climate feedback and response is critical to minimize the uncertainty in predicting current and future climate influenced by anthropogenic aerosols. One reason for this uncertainty is that current emission inventories of BC are mostly obtained from the so-called bottom-up approach, an approach that derives emissions based on categorized emitting sources and emission factors used to convert burning mass to emissions. In this work, we provide a first global-scale top-down estimation of global BC emissions, as well as an estimated error range, by using a Kalman Filter. This method uses data of both column aerosol absorption optical depth and surface concentrations from global and regional networks to constrain our fully coupled climate-aerosol-urban model and thus to derive an optimized estimate of BC emissions as 17.8 ± 5.6 Tg/yr, a factor of more than 2 higher than commonly used global BC emissions data sets. We further perform 22 additional optimization simulations that incorporate the known uncertain ranges of various important physical, model, and measurement parameters and still yield an optimized value within the above given range, from a low of 14.6 Tg/yr to a high of 22.2 Tg/yr. Furthermore, we show that the emissions difference between our optimized and a priori estimation is not uniform, with East Asia, Southeast Asia, and Eastern Europe underestimated, while North America is overestimated in the a priori inventory.

title: A multiparameter aerosol classification method and its application to retrievals from spaceborne polarimetry
abstract: Classifying observed aerosols into types (e.g., urban-industrial, biomass burning, mineral dust, maritime) helps to understand aerosol sources, transformations, effects, and feedback mechanisms; to improve accuracy of satellite retrievals; and to quantify aerosol radiative impacts on climate. The number of aerosol parameters retrieved from spaceborne sensors has been growing, from the initial aerosol optical depth (AOD) at one or a few wavelengths to a list that now includes AOD, complex refractive index, single scattering albedo (SSA), and depolarization of backscatter, each at several wavelengths, plus several particle size and shape parameters. Making optimal use of these varied data products requires objective, multidimensional analysis methods. We describe such a method, which makes explicit use of uncertainties in input parameters. It treats an N-parameter retrieved data point and its N-dimensional uncertainty as an extended data point, E. It then uses a modified Mahalanobis distance, DEC, to assign an observation to the class (cluster) C that has minimum DEC from the point. We use parameters retrieved from the Aerosol Robotic Network (AERONET) to define seven prespecified clusters (pure dust, polluted dust, urban-industrial/developed economy, urban-industrial/developing economy, dark biomass smoke, light biomass smoke, and pure marine), and we demonstrate application of the method to a 5 year record of retrievals from the spaceborne Polarization and Directionality of the Earth's Reflectances 3 (POLDER 3) polarimeter over the island of Crete, Greece. Results show changes of aerosol type at this location in the eastern Mediterranean Sea, which is influenced by a wide variety of aerosol sources.

title: Comparison of AOD, AAOD and column single scattering albedo from AERONET retrievals and in situ profiling measurements
abstract: Here we present new results comparing aerosol optical depth (AOD), aerosol absorption optical depth (AAOD) and column single scattering albedo (SSA) obtained from in situ vertical profile measurements with AERONET ground-based remote sensing from two rural, continental sites in the US. The profiles are closely matched in time (within ±3 h) and space (within 15 km) with the AERONET retrievals. We have used Level 1.5 inversion retrievals when there was a valid Level 2 almucantar retrieval in order to be able to compare AAOD and column SSA below AERONET's recommended loading constraint (AOD > 0.4 at 440 nm). While there is reasonable agreement for the AOD comparisons, the direct comparisons of in situ-derived to AERONET-retrieved AAOD (or SSA) reveal that AERONET retrievals yield higher aerosol absorption than obtained from the in situ profiles for the low aerosol optical depth conditions prevalent at the two study sites. However, it should be noted that the majority of SSA comparisons for AOD440 > 0.2 are, nonetheless, within the reported SSA uncertainty bounds. The observation that, relative to in situ measurements, AERONET inversions exhibit increased absorption potential at low AOD values is generally consistent with other published AERONET–in situ comparisons across a range of locations, atmospheric conditions and AOD values. This systematic difference in the comparisons suggests a bias in one or both of the methods, but we cannot assess whether the AERONET retrievals are biased towards high absorption or the in situ measurements are biased low. Based on the discrepancy between the AERONET and in situ values, we conclude that scaling modeled black carbon concentrations upwards to match AERONET retrievals of AAOD should be approached with caution as it may lead to aerosol absorption overestimates in regions of low AOD. Both AERONET retrievals and in situ measurements suggest there is a systematic relationship between SSA and aerosol amount (AOD or aerosol light scattering) – specifically that SSA decreases at lower aerosol loading. This implies that the fairly common assumption that AERONET SSA values retrieved at high-AOD conditions can be used to obtain AAOD at low-AOD conditions may not be valid.

title: Multiangle imaging spectroradiometer (MISR) global aerosol optical depth validation based on 2 years of coincident Aerosol Robotic Network (AERONET) observations : Global aerosol system
abstract: Performance of the Multiangle Imaging Spectroradiometer (MISR) early postlaunch aerosol optical thickness (AOT) retrieval algorithm is assessed quantitatively over land and ocean by comparison with a 2-year measurement record of globally distributed AERONET Sun photometers. There are sufficient coincident observations to stratify the data set by season and expected aerosol type. In addition to reporting uncertainty envelopes, we identify trends and outliers, and investigate their likely causes, with the aim of refining algorithm performance. Overall, about 2/3 of the MISR-retrieved AOT values fall within [0.05 or 20% x AOT] of Aerosol Robotic Network (AERONET). More than a third are within [0.03 or 10% x AOT]. Correlation coefficients are highest for maritime stations (∼0.9), and lowest for dusty sites (more than ∼0.7). Retrieved spectral slopes closely match Sun photometer values for Biomass burning and continental aerosol types. Detailed comparisons suggest that adding to the algorithm climatology more absorbing spherical particles, more realistic dust analogs, and a richer selection of multimodal aerosol mixtures would reduce the remaining discrepancies for MISR retrievals over land; in addition, refining instrument low-light-level calibration could reduce or eliminate a small but systematic offset in maritime AOT values. On the basis of cases for which current particle models are representative, a second-generation MISR aerosol retrieval algorithm incorporating these improvements could provide AOT accuracy unprecedented for a spaceborne technique.

title: Absorption properties of Mediterranean aerosols obtained from multi-year ground-based remote sensing observations
abstract: Aerosol absorption properties are of high importance to assess aerosol impact on regional climate. This study presents an analysis of aerosol absorption products obtained over the Mediterranean basin or land stations in the region from multi-year ground-based AERONET observations with a focus on the Absorbing Aerosol Optical Depth (AAOD), Single Scattering Albedo (SSA) and their spectral dependence. The AAOD and Absorption Angstrom Exponent (AAE) dataset is composed of daily averaged AERONET level 2 data from a total of 22 Mediterranean stations having long time series, mainly under the influence of urban-industrial aerosols and/or soil dust. This dataset covers the 17-yr period 1996-2012 with most data being from 2003-2011 (~89% of level-2 AAOD data). Since AERONET level-2 absorption products require a high aerosol load (AOD at 440 nm > 0.4), which is most often related to the presence of desert dust, we also consider level-1.5 SSA data, despite their higher uncertainty, and filter out data with an Angstrom exponent < 1.0 in order to study absorption by carbonaceous aerosols. The SSA dataset includes AERONET level-2 products. Sun-photometer observations show that values of AAOD at 440 nm vary between 0.024 ± 0.01 (resp. 0.040 ± 0.01) and 0.050 ± 0.01 (0.055 ± 0.01) for urban (dusty) sites. Analysis shows that the Mediterranean urban-industrial aerosols appear "moderately" absorbing with values of SSA close to ~0.94-0.95 ± 0.04 (at 440 nm) in most cases except over the large cities of Rome and Athens, where aerosol appears more absorbing (SSA ~0.89-0.90 ± 0.04). The aerosol Absorption Angstrom Exponent (AAE, estimated using 440 and 870 nm) is found to be larger than 1 for most sites over the Mediterranean, a manifestation of mineral dust (iron) and/or brown carbon producing the observed absorption. AERONET level-2 sun-photometer data indicate a possible East-West gradient, with higher values over the eastern basin (AAEEast = 1.39/AAEWest = 1.33). The North-South AAE gradient is more pronounced, especially over the western basin. Our additional analysis of AERONET level-1.5 data also shows that organic absorbing aerosols significantly affect some Mediterranean sites. These results indicate that current climate models treating organics as nonabsorbing over the Mediterranean certainly underestimate the warming effect due to carbonaceous aerosols.

title: Multiangle Imaging SpectroRadiometer global aerosol product assessment by comparison with the Aerosol Robotic Network
abstract: A statistical approach is used to assess the quality of the Multiangle Imaging SpectroRadiometer (MISR) version 22 (V22) aerosol products. Aerosol optical depth (AOD) retrieval results are improved relative to the early postlaunch values reported by [Kahn et al. (2005)], which varied with particle type category. Overall, about 70% to 75% of MISR AOD retrievals fall within 0.05 or 20% × AOD of the paired validation data from the Aerosol Robotic Network (AERONET), and about 50% to 55% are within 0.03 or 10% x AERONET AOD, except at sites where dust or mixed dust and smoke are commonly found. Retrieved particle microphysical properties amount to categorical values, such as three size groupings: "small," "medium," and "large." For particle size, ground-based AERONET sun photometer Angstrom exponents are used to assess statistically the corresponding MISR values, which are interpreted in terms of retrieved size categories. Coincident single-scattering albedo (SSA) and fraction AOD spherical data are too limited for statistical validation. V22 distinguishes two or three size bins, depending on aerosol type, and about two bins in SSA (absorbing vs. nonabsorbing), as well as spherical vs. nonspherical particles, under good retrieval conditions. Particle type sensitivity varies considerably with conditions and is diminished for midvisible AODs below about 0.15 or 0.2. On the basis of these results, specific algorithm upgrades are proposed and are being investigated by the MISR team for possible implementation in future versions of the product.

title: An analysis of global aerosol type as retrieved by MISR
abstract: In addition to aerosol optical depth (AOD), aerosol type is required globally for climate forcing calculations, constraining aerosol transport models and other applications. However, validating satellite aerosol-type retrievals is more challenging than testing AOD results, because aerosol type is a more complex quantity, and ground truth data are far less numerous and generally not as robust. We evaluate the Multiangle Imaging Spectroradiometer (MISR) Version 22 aerosol-type retrievals by assessing product self-consistency on a regional basis and by making comparisons with general expectation and with the Aerosol Robotic Network aerosol-type climatology, as available. The results confirm and add detail to the observation that aerosol-type discrimination improves dramatically where midvisible AOD exceeds about 0.15 or 0.2. When the aerosol-type information content of the observations is relatively low, increased scattering-angle range improves particle-type sensitivity. The MISR standard, operational product discriminates among small, medium, and large particles and exhibits qualitative sensitivity to single-scattering albedo (SSA) under good aerosol-type retrieval conditions, providing a categorical aerosol-type classification. MISR Angstrom exponent deviates systematically from ground truth where particle types missing from the algorithm climatology are present, or where cloud contamination is likely to occur, and SSA tends to be overestimated where absorbing particles are found. We determined that the number of mixtures passing the algorithm acceptance criteria (#SuccMix) represents aerosol-type retrieval quality effectively, providing a useful aerosol-type quality flag.

title: MISR research-aerosol-algorithm refinements for dark water retrievals
abstract: We explore systematically the cumulative effect of many assumptions made in the Multi-angle Imaging SpectroRadiometer (MISR) research aerosol retrieval algorithm with the aim of quantifying the main sources of uncertainty over ocean, and correcting them to the extent possible. A total of 1129 coincident, surface-based sun photometer spectral aerosol optical depth (AOD) measurements are used for validation. Based on comparisons between these data and our baseline case (similar to the MISR standard algorithm, but without the "modified linear mixing" approximation), for 558 nm AOD 68% of 558, 672, and 866 nm AOD values fall within the greater of 0.03 or 10%. For the Angstrom exponent (ANG), 67% of 1119 validation cases for AOD > 0.01 fall within 0.275 of the sun photometer values, compared to 49% for the SA. ANG RMSE decreases by 17% compared to the SA, and the median absolute error drops by 36%.

title: Updated MISR Dark Water Research Aerosol Retrieval Algorithm - Part 1: Coupled 1.1 km Ocean Surface Chlorophyll a Retrievals with Empirical Calibration Corrections
abstract: As aerosol amount and type are key factors in the atmospheric correction required for remote-sensing chlorophyll a concentration (Chl) retrievals, the Multi-angle Imaging SpectroRadiometer (MISR) can contribute to ocean color analysis despite a lack of spectral channels optimized for this application. Conversely, an improved ocean surface constraint should also improve MISR aerosol-type products, especially spectral single-scattering albedo (SSA) retrievals. We introduce a coupled, self-consistent retrieval of Chl together with aerosol over dark water. There are time-varying MISR radiometric calibration errors that significantly affect key spectral reflectance ratios used in the retrievals. Therefore, we also develop and apply new calibration corrections to the MISR top-of-atmosphere (TOA) reflectance data, based on comparisons with coincident MODIS (Moderate Resolution Imaging Spectroradiometer) observations and trend analysis of the MISR TOA bidirectional reflectance factors (BRFs) over three pseudo-invariant desert sites. We run the MISR research retrieval algorithm (RA) with the corrected MISR reflectances to generate MISR-retrieved Chl and compare the MISR Chl values to a set of 49 coincident SeaBASS (SeaWiFS Bio-optical Archive and Storage System) in situ observations. Where Chlin situ   0.1). We also compare MODIS–Terra and MISR RA Chl statistically, over much broader regions. With about 1.5 million MISR–MODIS collocations having MODIS Chl The new dark water aerosol/Chl RA can retrieve Chl in low-Chl, case I waters, independent of other imagers such as MODIS, via a largely physical algorithm, compared to the commonly applied statistical ones. At a minimum, MISR's multi-angle data should help reduce uncertainties in the MODIS–Terra ocean color retrieval where coincident measurements are made, while also allowing for a more robust retrieval of particle properties such as spectral single-scattering albedo.

title: Improving satellite-retrieved aerosol microphysical properties using GOCART data
abstract: The Multi-angle Imaging SpectroRadiometer (MISR) aboard the NASA Earth Observing System's Terra satellite can provide more reliable aerosol optical depth (AOD) and better constraints on particle size (Angstrom exponent, or ANG), sphericity, and single-scattering albedo (SSA) than many other satellite instruments. However, many aerosol mixtures pass the algorithm acceptance criteria, yielding a poor constraint, when the particle-type information in the MISR radiances is low, typically at low AOD. We investigate adding value to the MISR aerosol product under these conditions by filtering the list of MISR-retrieved mixtures based on agreement between the mixture ANG and absorbing AOD (AAOD) values, and simulated aerosol properties from the Goddard Chemistry Aerosol Radiation and Transport (GOCART) model. MISR–GOCART ANG difference and AAOD ratio thresholds for applying GOCART constraints were determined based on coincident AOD, ANG, and AAOD measurements from the AErosol RObotic NETwork (AERONET). The results were validated by comparing the adjusted MISR aerosol optical properties over the contiguous USA between 2006 and 2009 with additional AERONET data. The correlation coefficient (r) between the adjusted MISR ANG derived from this study and AERONET improves to 0.45, compared to 0.29 for the MISR Version 22 standard product. The ratio of the adjusted MISR AAOD to AERONET increases to 0.74, compared to 0.5 for the MISR operational retrieval. These improvements occur primarily when AOD

title: The MERRA-2 Aerosol Reanalysis, 1980 Onward. Part II: Evaluation and Case Studies.
abstract: The Modern-Era Retrospective Analysis for Research and Applications, version 2 (MERRA-2), is NASA's latest reanalysis for the satellite era (1980 onward) using the Goddard Earth Observing System, version 5 (GEOS-5), Earth system model. MERRA-2 provides several improvements over its predecessor (MERRA-1), including aerosol assimilation for the entire period. MERRA-2 assimilates bias-corrected aerosol optical depth (AOD) from the Moderate Resolution Imaging Spectroradiometer and the Advanced Very High Resolution Radiometer instruments. Additionally, MERRA-2 assimilates (non bias corrected) AOD from the Multiangle Imaging SpectroRadiometer over bright surfaces and AOD from Aerosol Robotic Network sunphotometer stations. This paper, the second of a pair, summarizes the efforts to assess the quality of the MERRA-2 aerosol products. First, MERRA-2 aerosols are evaluated using independent observations. It is shown that the MERRA-2 absorption aerosol optical depth (AAOD) and ultraviolet aerosol index (AI) compare well with Ozone Monitoring Instrument observations. Next, aerosol vertical structure and surface fine particulate matter (PM2.5) are evaluated using available satellite, aircraft, and ground-based observations. While MERRA-2 generally compares well to these observations, the assimilation cannot correct for all deficiencies in the model (e.g., missing emissions). Such deficiencies can explain many of the biases with observations. Finally, a focus is placed on several major aerosol events to illustrate successes and weaknesses of the AOD assimilation: the Mount Pinatubo eruption, a Saharan dust transport episode, the California Rim Fire, and an extreme pollution event over China. The article concludes with a summary that points to best practices for using the MERRA-2 aerosol reanalysis in future studies.

title: Using the OMI aerosol index and absorption aerosol optical depth to evaluate the NASA MERRA Aerosol Reanalysis
abstract: A radiative transfer interface has been developed to simulate the UV aerosol index (AI) from the NASA Goddard Earth Observing System version 5 (GEOS-5) aerosol assimilated fields. The purpose of this work is to use the AI and aerosol absorption optical depth (AAOD) derived from the Ozone Monitoring Instrument (OMI) measurements as independent validation for the Modern Era Retrospective analysis for Research and Applications Aerosol Reanalysis (MERRAero). MERRAero is based on a version of the GEOS-5 model that is radiatively coupled to the Goddard Chemistry, Aerosol, Radiation, and Transport (GOCART) aerosol module and includes assimilation of aerosol optical depth (AOD) from the Moderate Resolution Imaging Spectroradiometer (MODIS) sensor. Since AI is dependent on aerosol concentration, optical properties and altitude of the aerosol layer, we make use of complementary observations to fully diagnose the model, including AOD from the Multi-angle Imaging SpectroRadiometer (MISR), aerosol retrievals from the AErosol RObotic NETwork (AERONET) and attenuated backscatter coefficients from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation (CALIPSO) mission to ascertain potential misplacement of plume height by the model. By sampling dust, biomass burning and pollution events in 2007 we have compared model-produced AI and AAOD with the corresponding OMI products, identifying regions where the model representation of absorbing aerosols was deficient. As a result of this study over the Saharan dust region, we have obtained a new set of dust aerosol optical properties that retains consistency with the MODIS AOD data that were assimilated, while resulting in better agreement with aerosol absorption measurements from OMI. The analysis conducted over the southern African and South American biomass burning regions indicates that revising the spectrally dependent aerosol absorption properties in the near-UV region improves the modeled-observed AI comparisons. Finally, during a period where the Asian region was mainly dominated by anthropogenic aerosols, we have performed a qualitative analysis in which the specification of anthropogenic emissions in GEOS-5 is adjusted to provide insight into discrepancies observed in AI comparisons.

title: Impact of radiatively interactive dust aerosols in the NASA GEOS-5 climate model: Sensitivity to dust particle shape and refractive index
abstract: The radiative effects of Saharan dust aerosols are investigated in the NASA GEOS-5 atmospheric general circulation model. A sectional aerosol microphysics model (CARMA) is run online in GEOS-5. CARMA treats the dust aerosol lifecycle, and its tracers are radiatively coupled to GEOS-5. A series of AMIP-style simulations are performed, in which input dust optical properties (particle shape and refractive index) are varied. Simulated dust distributions for summertime Saharan dust compare well to observations, with best results found when the most absorbing dust optical properties are assumed. Dust absorption leads to a strengthening of the summertime Hadley cell circulation, increased dust lofting to higher altitudes, and a strengthening of the African easterly jet, resulting in increased dust atmospheric lifetime and farther northward and westward transport. We find a positive feedback of dust radiative forcing on emissions, in contrast with previous studies, which we attribute to our having a relatively strong longwave forcing caused by our simulating larger effective particle sizes. This longwave forcing reduces the magnitude of midday net surface cooling relative to other studies, and leads to a nighttime warming that results in higher nighttime wind speeds and dust emissions. The radiative effects of dust particle shape have only minor impact on transport and emissions, with small (~5%) impact on top of atmosphere shortwave forcing, in line with previous studies, but relatively more pronounced effects on shortwave atmospheric heating and surface forcing (~20% increase in atmospheric forcing for spheroids). Shape effects on longwave heating terms are of order ~10%.

title: Constraining Black Carbon Aerosol over Asia using OMI Aerosol Absorption Optical Depth and the Adjoint of GEOS-Chem
abstract: Accurate estimates of the emissions and distribution of black carbon (BC) in the region referred to here as Southeastern Asia (70–150° E, 11° S–55° N) are critical to studies of the atmospheric environment and climate change. Analysis of modeled BC concentrations compared to in situ observations indicates levels are underestimated over most of Southeast Asia when using any of four different emission inventories. We thus attempt to reduce uncertainties in BC emissions and improve BC model simulations by developing top-down, spatially resolved, estimates of BC emissions through assimilation of OMI (Ozone Monitoring Instrument) observations of aerosol absorption optical depth (AAOD) with the GEOS-Chem (Goddard Earth Observing System – chemistry) model and its adjoint for April and October 2006. Overwhelming enhancements, up to 500 %, in anthropogenic BC emissions are shown after optimization over broad areas of Southeast Asia in April. In October, the optimization of anthropogenic emissions yields a slight reduction (1–5 %) over India and parts of southern China, while emissions increase by 10–50 % over eastern China. Observational data from in situ measurements and AERONET (Aerosol Robotic Network) observations are used to evaluate the BC inversions and assess the bias between OMI and AERONET AAOD. Low biases in BC concentrations are improved or corrected in most eastern and central sites over China after optimization, while the constrained model still underestimates concentrations in Indian sites in both April and October, possibly as a consequence of low prior emissions. Model resolution errors may contribute up to a factor of 2.5 to the underestimation of surface BC concentrations over northern India. We also compare the optimized results using different anthropogenic emission inventories and discuss the sensitivity of top-down constraints on anthropogenic emissions with respect to biomass burning emissions. In addition, the impacts of brown carbon, the formulation of the observation operator, and different a priori constraints on the optimization are investigated. Overall, despite these limitations and uncertainties, using OMI AAOD to constrain BC sources improves model representation of BC distributions, particularly over China.

title: GRASP: a versatile algorithm for characterizing the atmosphere
abstract: GRASP (Generalized Retrieval of Aerosol and Surface Properties) is the first unified algorithm to be developed for characterizing atmospheric properties gathered from a variety of remote sensing observations (an introductory video is available elsewhere1). GRASP is based on a recent algorithm2 created to improve aerosol retrieval from the French Space Agency’s PARASOL3 imager over bright surfaces like deserts where high surface reflectance dwarfs the signal from aerosols. Moreover, GRASP relies on the heritage of retrieval advances4–7 implemented for AERONET,8 a worldwide network of over 200 radiometer sites that generate the data used to validate nearly all satellite observations of atmospheric aerosols. The AERONET retrievals derive detailed aerosol properties,6 including absorption, providing information of vital importance for reducing uncertainty in assessments of climate change. GRASP is based on several generalization principles with the idea of developing a scientifically rigorous, versatile, practically efficient, transparent, and accessible algorithm. There are two main independent modules. The first, numerical inversion, includes general mathematical operations not related to the particular physical nature of the inverted data (in this case, remote sensing observations). The second module, the forward model, was developed to simulate various atmospheric remote sensing observations. Numerical inversion is implemented as a statistically optimized fitting of observations following the multi-term least squares method (LSM) strategy, which combines9 the advantages of a variety of approaches and provides transparency and flexibility in developing algorithms that invert passive and/or active observations and derive several groups of Figure 1. Diagram illustrating the principle of combined synergetic processing of complementary observations using a multi-pixel2 retrieval approach. CALIPSO is a joint lidar mission of NASA and the French Space Agency, which also manages the PARASOL imager. AERONET is a worldwide network of radiometer sites.

title: Absorption of aerosols above clouds from POLDER/PARASOL measurements and estimation of their direct radiative effect
abstract: This study presents an original method to evaluate key parameters for the estimation of the direct radiative effect (DRE) of aerosol above clouds: the absorption of the the cloud albedo. It is based on multi-angle total and polarized radiances both provided by the A-train satellite instrument POLDER – Polarization and Directionality of Earth Reflectances. The sensitivities brought by each kind of measurements are used in a complementary way. Polarization mostly translates scattering processes and is thus used to estimate scattering aerosol optical thickness and aerosol size. On the other hand, total radiances, together with the scattering properties of aerosols, are used to evaluate the absorption optical thickness of aerosols and cloud optical thickness. The retrieval of aerosol and clouds properties (i.e., aerosol and cloud optical thickness, aerosol single scattering albedo and Angstrom exponent) is restricted to homogeneous and optically thick clouds (cloud optical thickness larger than 3). In addition, a procedure has been developed to process the shortwave DRE of aerosols above clouds. Three case studies have been selected: a case of absorbing biomass burning aerosols above clouds over the southeast Atlantic Ocean, a Siberian biomass burning event and a layer of Saharan dust above clouds off the northwest coast of Africa. Besides these case studies, both algorithms have been applied to the southeast Atlantic Ocean and the results have been averaged during August 2006. The mean DRE is found to be 33.5 W m−2 (warming). Finally, the effect of the heterogeneity of clouds has been investigated and reveals that it affects mostly the retrieval of the cloud optical thickness and not greatly the aerosols properties. The homogenous cloud assumption used in both the properties retrieval and the DRE processing leads to a slight underestimation of the DRE.

title: Comparison of aerosol optical properties above clouds between POLDER and AeroCom models over the South East Atlantic Ocean during the fire season
abstract: Aerosol properties above clouds have been retrieved over the South East Atlantic Ocean during the fire season 2006 using satellite observations from POLDER (Polarization and Directionality of Earth Reflectances). From June to October, POLDER has observed a mean Above-Cloud Aerosol Optical Thickness (ACAOT) of 0.28 and a mean Above-Clouds Single Scattering Albedo (ACSSA) of 0.87 at 550 nm. These results have been used to evaluate the simulation of aerosols above clouds in five Aerosol Comparisons between Observations and Models (Goddard Chemistry Aerosol Radiation and Transport (GOCART), Hadley Centre Global Environmental Model 3 (HadGEM3), European Centre Hamburg Model 5-Hamburg Aerosol Module 2 (ECHAM5-HAM2), Oslo-Chemical Transport Model 2 (OsloCTM2), and Spectral Radiation-Transport Model for Aerosol Species (SPRINTARS)). Most models do not reproduce the observed large aerosol load episodes. The comparison highlights the importance of the injection height and the vertical transport parameterizations to simulate the large ACAOT observed by POLDER. Furthermore, POLDER ACSSA is best reproduced by models with a high imaginary part of black carbon refractive index, in accordance with recent recommendations.

title: Retrieval of Aerosol Optical Depth above Clouds from OMI Observations: Sensitivity Analysis and Case Studies
abstract: A large fraction of the atmospheric aerosol load reaching the free troposphere is frequently located above low clouds. Most commonly observed aerosols above clouds are carbonaceous particles generally associated with biomassburningandborealforestfires,andmineralaerosolsoriginatingin aridandsemiaridregionsand transported across large distances, often above clouds. Because these aerosols absorb solar radiation, their role in the radiative transfer balance of the earth‐atmosphere system is especially important. The generally negative (cooling) top-of-the-atmosphere direct effect of absorbing aerosols may turn into warming when the light-absorbing particles are located above clouds. The actual effect depends on the aerosol load and the single scattering albedo, and on the geometric cloud fraction. In spite of its potential significance, the role of aerosols above clouds is not adequately accounted for in the assessment of aerosol radiative forcing effects due to the lack of measurements. This paper discusses the basis of a simple technique that uses near-UV observations to simultaneously derive the optical depth of both the aerosol layer and the underlying cloud for overcast conditions. The two-parameter retrieval method described here makes use of the UV aerosol index andreflectancemeasurementsat 388 nm.Adetailedsensitivityanalysisindicatesthatthemeasuredradiances depend mainly on the aerosol absorption exponent and aerosol‐cloud separation. The technique was applied to above-cloud aerosol events over the southern Atlantic Ocean, yielding realistic results as indicated by indirect evaluation methods. An error analysis indicates that for typical overcast cloudy conditions and aerosol loads, the aerosol optical depth can be retrieved with an accuracy of approximately 54% whereas the cloud optical depth can be derived within 17% of the true value.

title: Quantifying above‐cloud aerosol using spaceborne lidar for improved understanding of cloudy‐sky direct climate forcing
abstract: Estimates of global mean direct climate forcing by absorbing aerosols located above boundary layer clouds are large, uncertain, and almost entirely unconstrained by observations. Spaceborne lidar offers a new opportunity for global constraints. Here we examine techniques for using liquid water clouds as lidar targets, allowing aerosol optical depth and Angstrom exponent to be deduced directly from aerosol effects on light transmission. Two such techniques are examined using data from the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO). The first is a previously reported method based on measurements of cloud depolarization ratio (DR) at 532-nm wavelength. The second is a new method using measurements of cloud color ratio (CR), which is the ratio of the signal from the cloud at 1064 nm to that at 532 nm. Optical depth retrievals from these two methods compare favorably over the eastern tropical Atlantic Ocean during August 2006, when biomass burning aerosols are frequently advected over marine stratiform clouds. The CR technique is mainly sensitive to fine-mode aerosols and essentially insensitive to clouds and coarse-mode dust. Because anthropogenic aerosol is predominantly found in the fine mode, the CR technique can be used to help identify situations where anthropogenic cloudy-sky direct radiative forcing is occurring. We demonstrate this capability using 6 months data over the eastern tropical Atlantic Ocean.

title: A Color Ratio Method for Simultaneous Retrieval of Aerosol and Cloud Optical Thickness of Above-Cloud Absorbing Aerosols From Passive Sensors: Application to MODIS Measurements
abstract: The presence of absorbing aerosols above cloud decks reduces the amount of upwelling ultraviolet (UV), visible (VIS), and shortwave infrared radiation reaching the top of atmosphere. This effect is often referred to as “cloud darkening,” which can be seen by eye in images and quantitatively in the spectral reflectance measurements made by passive sensors such as the Moderate Resolution Imaging Spectroradiometer (MODIS) in the regions where light-absorbing carbonaceous and dust aerosols overlay low-level clouds. Radiative transfer simulations support the observational evidence and further reveal that the reduction in the spectral reflectance and color ratio between a pair of wavelengths is a function of both aerosol and cloud optical thickness (AOT and COT). For a prescribed set of aerosol and cloud properties and their vertical profiles, thus, the measured reflectance can be associated with a pair of AOT and COT. Based on these results, a retrieval technique has been developed, which is named as the “color ratio method,” which utilizes the measurements at a shorter (470 nm) and a longer (860 nm) wavelength for the simultaneous derivation of AOT and COT. The retrieval technique has been applied to the MODIS 1-km reflectance measurements for the two distinct above-cloud smoke and dust aerosols events. This study is an extension of the previously developed near-UV method to the VIS spectral region. However, it constitutes the first attempt to use non-UV wavelengths to retrieve above-cloud AOT by a passive nonpolarized sensor. An uncertainty analysis has been presented, which estimates the expected error associated with these retrievals.

title: Extending “Deep Blue” aerosol retrieval coverage to cases of absorbing aerosols above clouds: Sensitivity analysis and first case studies
abstract: Cases of absorbing aerosols above clouds (AACs), such as smoke or mineral dust, are omitted from most routinely processed space-based aerosol optical depth (AOD) data products, including those from the Moderate Resolution Imaging Spectroradiometer (MODIS). This study presents a sensitivity analysis and preliminary algorithm to retrieve above-cloud AOD and liquid cloud optical depth (COD) for AAC cases from MODIS or similar sensors, for incorporation into a future version of the "Deep Blue" AOD data product. Detailed retrieval simulations suggest that these sensors should be able to determine AAC AOD with a typical level of uncertainty approximately 25-50 percent (with lower uncertainties for more strongly absorbing aerosol types) and COD with an uncertainty approximately10-20 percent, if an appropriate aerosol optical model is known beforehand. Errors are larger, particularly if the aerosols are only weakly absorbing, if the aerosol optical properties are not known, and the appropriate model to use must also be retrieved. Actual retrieval errors are also compared to uncertainty envelopes obtained through the optimal estimation (OE) technique; OE-based uncertainties are found to be generally reasonable for COD but larger than actual retrieval errors for AOD, due in part to difficulties in quantifying the degree of spectral correlation of forward model error. The algorithm is also applied to two MODIS scenes (one smoke and one dust) for which near-coincident NASA Ames Airborne Tracking Sun photometer (AATS) data were available to use as a ground truth AOD data source, and found to be in good agreement, demonstrating the validity of the technique with real observations.

title: Identifying Absorbing Aerosols Above Clouds From the Spinning Enhanced Visible and Infrared Imager Coupled With NASA A-Train Multiple Sensors
abstract: Geostationary satellite data from the Spinning Enhanced Visible and Infrared Imager (SEVIRI) in conjunction with A-Train data are used to develop an algorithm for detecting biomass-burning smoke aerosols above closed-cell stratocumulus (Sc) clouds. The detection relies on spectral signatures, textural characteristics, and time-dependent spectral variation of SEVIRI data. A-Train data including the Ozone Monitoring Instrument (OMI) and the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) are used as reference data for the SEVIRI algorithm development. The 15-min repeat cycle of SEVIRI provides the capability for identifying smoke above closed-cell Sc with an OMI aerosol index value exceeding 0.5 and a cloud optical thickness greater than 6 at 0.81 m. The user accuracy of this algorithm is ~49% when using only spectral signature and textural tests. When incorporating the “temporal consistency” tests into the algorithm, the user accuracy increases to ~65%. The producer accuracy is over ~77%, implying that the SEVIRI algorithm generally identifies smoke above clouds when CALIOP also identifies the same feature at the collocated pixel. However, CALIOP has the tendency to underestimate the presence of thin smoke aerosols above liquid clouds during daytime. This algorithm can be used to detect and study the daytime variation of smoke above liquid clouds.

title: Evaluation of dust and trace metal estimates from the Community Multiscale Air Quality (CMAQ) model version 5.0
abstract: The Community Multiscale Air Quality (CMAQ) model is a state-of-the-science air quality model that simulates the emission, transformation, transport, and fate of the many different air pollutant species that comprise particulate matter (PM), including dust (or soil). The CMAQ model version 5.0 (CMAQv5.0) has several enhancements over the previous version of the model for estimating the emission and transport of dust, including the ability to track the specific elemental constituents of dust and have the model-derived concentrations of those elements participate in chemistry. The latest version of the model also includes a parameterization to estimate emissions of dust due to wind action. The CMAQv5.0 modeling system was used to simulate the entire year 2006 for the continental United States, and the model estimates were evaluated against daily surface-based measurements from several air quality networks. The CMAQ modeling system overall did well replicating the observed soil concentrations in the western United States (mean bias generally around ±0.5 μg m−3); however, the model consistently overestimated the observed soil concentrations in the eastern United States (mean bias generally between 0.5–1.5 μg m−3), regardless of season. The performance of the individual trace metals was highly dependent on the network, species, and season, with relatively small biases for Fe, Al, Si, and Ti throughout the year at the Interagency Monitoring of Protected Visual Environments (IMPROVE) sites, while Ca, K, and Mn were overestimated and Mg underestimated. For the urban Chemical Speciation Network (CSN) sites, Fe, Mg, and Mn, while overestimated, had comparatively better performance throughout the year than the other trace metals, which were consistently overestimated, including very large overestimations of Al (380%), Ti (370%) and Si (470%) in the fall. An underestimation of nighttime mixing in the urban areas appears to contribute to the overestimation of trace metals. Removing the anthropogenic fugitive dust (AFD) emissions and the effects of wind-blown dust (WBD) lowered the model soil concentrations. However, even with both AFD emissions and WBD effects removed, soil concentrations were still often overestimated, suggesting that there are other sources of errors in the modeling system that contribute to the overestimation of soil components. Efforts are underway to improve both the nighttime mixing in urban areas and the spatial and temporal distribution of dust-related emission sources in the emissions inventory.

title: Current model capabilities for simulating black carbon and sulfate concentrations in the Arctic atmosphere: a multi-model evaluation using a comprehensive measurement data set
abstract: The concentrations of sulfate, black carbon (BC) and other aerosols in the Arctic are characterized by high values in late winter and spring (so-called Arctic Haze) and low values in summer. Models have long been struggling to capture this seasonality and especially the high concentrations associated with Arctic Haze. In this study, we evaluate sulfate and BC concentrations from eleven different models driven with the same emission inventory against a comprehensive pan-Arctic measurement data set over a time period of 2 years (2008–2009). The set of models consisted of one Lagrangian particle dispersion model, four chemistry transport models (CTMs), one atmospheric chemistry-weather forecast model and five chemistry climate models (CCMs), of which two were nudged to meteorological analyses and three were running freely. The measurement data set consisted of surface measurements of equivalent BC (eBC) from five stations (Alert, Barrow, Pallas, Tiksi and Zeppelin), elemental carbon (EC) from Station Nord and Alert and aircraft measurements of refractory BC (rBC) from six different campaigns. We find that the models generally captured the measured eBC or rBC and sulfate concentrations quite well, compared to previous comparisons. However, the aerosol seasonality at the surface is still too weak in most models. Concentrations of eBC and sulfate averaged over three surface sites are underestimated in winter/spring in all but one model (model means for January–March underestimated by 59 and 37 % for BC and sulfate, respectively), whereas concentrations in summer are overestimated in the model mean (by 88 and 44 % for July–September), but with overestimates as well as underestimates present in individual models. The most pronounced eBC underestimates, not included in the above multi-site average, are found for the station Tiksi in Siberia where the measured annual mean eBC concentration is 3 times higher than the average annual mean for all other stations. This suggests an underestimate of BC sources in Russia in the emission inventory used. Based on the campaign data, biomass burning was identified as another cause of the modeling problems. For sulfate, very large differences were found in the model ensemble, with an apparent anti-correlation between modeled surface concentrations and total atmospheric columns. There is a strong correlation between observed sulfate and eBC concentrations with consistent sulfate/eBC slopes found for all Arctic stations, indicating that the sources contributing to sulfate and BC are similar throughout the Arctic and that the aerosols are internally mixed and undergo similar removal. However, only three models reproduced this finding, whereas sulfate and BC are weakly correlated in the other models. Overall, no class of models (e.g., CTMs, CCMs) performed better than the others and differences are independent of model resolution.

title: Evaluation of black carbon estimations in global aerosol models
abstract: We evaluate black carbon (BC) model predictions from the AeroCom model intercomparison project by considering the diversity among year 2000 model simulations and comparing model predictions with available measurements. These model-measurement intercomparisons include BC surface and aircraft concentrations, aerosol absorption optical depth (AAOD) retrievals from AERONET and Ozone Monitoring Instrument (OMI) and BC column estimations based on AERONET. In regions other than Asia, most models are biased high compared to surface concentration measurements. However compared with (column) AAOD or BC burden retreivals, the models are generally biased low. The average ratio of model to retrieved AAOD is less than 0.7 in South American and 0.6 in African biomass burning regions; both of these regions lack surface concentration measurements. In Asia the average model to observed ratio is 0.7 for AAOD and 0.5 for BC surface concentrations. Compared with aircraft measurements over the Americas at latitudes between 0 and 50N, the average model is a factor of 8 larger than observed, and most models exceed the measured BC standard deviation in the mid to upper troposphere. At higher latitudes the average model to aircraft BC ratio is 0.4 and models underestimate the observed BC loading in the lower and middle troposphere associated with springtime Arctic haze. Low model bias for AAOD but overestimation of surface and upper atmospheric BC concentrations at lower latitudes suggests that most models are underestimating BC absorption and should improve estimates for refractive index, particle size, and optical effects of BC coating. Retrieval uncertainties and/or differences with model diagnostic treatment may also contribute to the model-measurement disparity. Largest AeroCom model diversity occurred in northern Eurasia and the remote Arctic, regions influenced by anthropogenic sources. Changing emissions, aging, removal, or optical properties within a single model generated a smaller change in model predictions than the range represented by the full set of AeroCom models. Upper tropospheric concentrations of BC mass from the aircraft measurements are suggested to provide a unique new benchmark to test scavenging and vertical dispersion of BC in global models.

title: Observations and modeling of air quality trends over 1990–2010 across the Northern Hemisphere: China, the United States and Europe
abstract: Trends in air quality across the Northern Hemisphere over a 21-year period (1990–2010) were simulated using the Community Multiscale Air Quality (CMAQ) multiscale chemical transport model driven by meteorology from Weather Research and Forecasting (WRF) simulations and internally consistent historical emission inventories obtained from EDGAR. Thorough comparison with several ground observation networks mostly over Europe and North America was conducted to evaluate the model performance as well as the ability of CMAQ to reproduce the observed trends in air quality over the past 2 decades in three regions: eastern China, the continental United States and Europe. The model successfully reproduced the observed decreasing trends in SO2, NO2, 8 h O3 maxima, SO42− and elemental carbon (EC) in the US and Europe. However, the model fails to reproduce the decreasing trends in NO3− in the US, potentially pointing to uncertainties of NH3 emissions. The model failed to capture the 6-year trends of SO2 and NO2 in CN-API (China – Air Pollution Index) from 2005 to 2010, but reproduced the observed pattern of O3 trends shown in three World Data Centre for Greenhouse Gases (WDCGG) sites over eastern Asia. Due to the coarse spatial resolution employed in these calculations, predicted SO2 and NO2 concentrations are underestimated relative to all urban networks, i.e., US-AQS (US – Air Quality System; normalized mean bias (NMB) = −38% and −48%), EU-AIRBASE (European Air quality data Base; NMB = −18 and −54%) and CN-API (NMB = −36 and −68%). Conversely, at the rural network EU-EMEP (European Monitoring and Evaluation Programme), SO2 is overestimated (NMB from 4 to 150%) while NO2 is simulated well (NMB within ±15%) in all seasons. Correlations between simulated and observed O3 wintertime daily 8 h maxima (DM8) are poor compared to other seasons for all networks. Better correlation between simulated and observed SO42− was found compared to that for SO2. Underestimation of summer SO42− in the US may be associated with the uncertainty in precipitation and associated wet scavenging representation in the model. The model exhibits worse performance for NO3− predictions, particularly in summer, due to high uncertainties in the gas/particle partitioning of NO3− as well as seasonal variations of NH3 emissions. There are high correlations (R > 0.5) between observed and simulated EC, although the model underestimates the EC concentration by 65% due to the coarse grid resolution as well as uncertainties in the PM speciation profile associated with EC emissions. The almost linear response seen in the trajectory of modeled O3 changes in eastern China over the past 2 decades suggests that control strategies that focus on combined control of NOx and volatile organic compound (VOC) emissions with a ratio of 0.46 may provide the most effective means for O3 reductions for the region devoid of nonlinear response potentially associated with NOx or VOC limitation resulting from alternate strategies. The response of O3 is more sensitive to changes in NOx emissions in the eastern US because the relative abundance of biogenic VOC emissions tends to reduce the effectiveness of VOC controls. Increasing NH3 levels offset the relative effectiveness of NOx controls in reducing the relative fraction of aerosol NO3− formed from declining NOx emissions in the eastern US, while the control effectiveness was assured by the simultaneous control of NH3 emission in Europe.

title: Aerosol decadal trends - Part 1: In-situ optical measurements at GAW and IMPROVE stations
abstract: Currently many ground-based atmospheric sta- tions include in-situ measurements of aerosol physical and optical properties, resulting in more than 20 long-term (> 10 yr) aerosol measurement sites in the Northern Hemi- sphere and Antarctica. Most of these sites are located at re- mote locations and monitor the aerosol particle number con- centration, wavelength-dependent light scattering, backscat- tering, and absorption coefficients. The existence of these multi-year datasets enables the analysis of long-term trends of these aerosol parameters, and of the derived light scatter- ing ˚ Angstr¨ om exponent and backscatter fraction. Since the aerosol variables are not normally distributed, three different methods (the seasonal Mann-Kendall test associated with the Sen's slope, the generalized least squares fit associated with an autoregressive bootstrap algorithm for confidence inter- vals, and the least-mean square fit applied to logarithms of the data) were applied to detect the long-term trends and their magnitudes. To allow a comparison among measurement sites, trends on the most recent 10 and 15 yr periods were cal- culated. No significant trends were found for the three con- tinental European sites. Statistically significant trends were found for the two European marine sites but the signs of the trends varied with aerosol property and location. Statistically significant decreasing trends for both scattering and absorp- tion coefficients (mean slope of 2.0 % yr 1 ) were found for most North American stations, although positive trends were found for a few desert and high-altitude sites. The difference in the timing of emission reduction policy for the Europe and US continents is a likely explanation for the decreasing trends in aerosol optical parameters found for most American

title: A multi-year study of lower tropospheric aerosol variability and systematic relationships from four North American regions
abstract: Hourly averaged aerosol optical properties (AOPs) measured over the years 2010–2013 at four continental North American NOAA Earth System Research Laboratory (NOAA/ESRL) cooperative aerosol network sites – Southern Great Plains near Lamont, OK (SGP), Bondville, IL (BND), Appalachian State University in Boone, NC (APP), and Egbert, Ontario, Canada (EGB) are analyzed. Aerosol optical properties measured over 1996–2009 at BND and 1997–2009 at SGP are also presented. The aerosol sources and types in the four regions differ enough so as to collectively represent rural, anthropogenically perturbed air conditions over much of eastern continental North America. Temporal AOP variability on monthly, weekly, and diurnal timescales is presented for each site. Differences in annually averaged AOPs and those for individual months at the four sites are used to examine regional AOP variability. Temporal and regional variability are placed in the context of reported aerosol chemistry at the sites, meteorological measurements (wind direction, temperature), and reported regional mixing layer heights. Basic trend analysis is conducted for selected AOPs at the long-term sites (BND and SGP). Systematic relationships among AOPs are also presented. Seasonal variability in PM1 (sub-1 μm particulate matter) scattering and absorption coefficients at 550 nm (σsp and σap, respectively) and most of the other PM1 AOPs is much larger than day of week and diurnal variability at all sites. All sites demonstrate summer σsp and σap peaks. Scattering coefficient decreases by a factor of 2–4 in September–October and coincides with minimum single-scattering albedo (ω0) and maximum hemispheric backscatter fraction (b). The co-variation of ω0 and b lead to insignificant annual cycles in top-of-atmosphere direct radiative forcing efficiency (DRFE) at APP and SGP. Much larger annual DRFE cycle amplitudes are observed at EGB (~ 40 %) and BND (~ 25 %), with least negative DRFE in September–October at both sites. Secondary winter peaks in σsp are observed at all sites except APP. Amplitudes of diurnal and weekly cycles in σap at the sites are larger for all seasons than those of σsp, with the largest differences occurring in summer. The weekly and diurnal cycle amplitudes of most intensive AOPs (e.g., those derived from ratios of measured σsp and σap) are minimal in most cases, especially those related to parameterizations of aerosol size distribution. Statistically significant trends in σsp (decreasing), PM1 scattering fraction (decreasing), and b (increasing) are found at BND from 1996 to 2013 and at SGP from 1997 to 2013. A statistically significant decreasing trend in PM10 scattering Angstrom exponent is also observed for SGP but not BND. Most systematic relationships among AOPs are similar for the four sites and are adequately described for individual seasons by annually averaged relationships, although relationships involving absorption Angstrom exponent vary with site and season.

title: Wet removal of black carbon in Asian outflow: Aerosol Radiative Forcing in East Asia (A‐FORCE) aircraft campaign
abstract: The Aerosol Radiative Forcing in East Asia (A-FORCE) aircraft campaign was conducted over East Asia in March–April 2009. During the A-FORCE campaign, 120 vertical profiles of black carbon (BC) and carbon monoxide (CO) were obtained in the planetary boundary layer (PBL) and the free troposphere. This study examines the wet removal of BC in Asian outflow using the A-FORCE data. The concentrations of BC and CO were greatly enhanced in air parcels sampled at 3–6 km in altitude over the Yellow Sea on 30 March 2009, associated with upward transport due to a cyclone with modest amounts of precipitation over northern China. In contrast, high CO concentrations without substantial enhancements of BC concentrations were observed in air parcels sampled at 5–6 km over the East China Sea on 23 April 2009, caused by uplifting due to cumulus convection with large amounts of precipitation over central China. The transport efficiency of BC (TEBC, namely the fraction of BC particles not removed during transport) in air parcels sampled above 2 km during the entire A-FORCE period decreased primarily with the increase in the precipitation amount that air parcels experienced during vertical transport, although their correlation was modest (r2 = 0.43). TEBC also depended on the altitude to which air parcels were transported from the PBL and the latitude where they were uplifted locally over source regions. The median values of TEBC for air parcels originating from northern China (north of 33°N) and sampled at 2–4 km and 4–9 km levels were 86% and 49%, respectively, during the A-FORCE period. These median values were systematically greater than the corresponding median values (69% and 32%, respectively) for air parcels originating from southern China (south of 33°N). Use of the A-FORCE data set will contribute to the reduction of large uncertainties in wet removal process of BC in global- and regional-scale models.

title: Airborne observations of IEPOX-derived isoprene SOA in the Amazon during SAMBBA
abstract: Isoprene is a potentially highly significant but currently poorly quantified source of secondary organic aerosols (SOA). This is especially important in the tropics, where large rainforests act as significant sources of isoprene. Methylfuran, produced through thermal decomposition during analysis, has recently been suggested as a marker for isoprene SOA formation through the isoprene epoxydiol (IEPOX) route, which mostly occurs under low NOx conditions. This is manifested as a peak at m/z=82 in Aerodyne Aerosol Mass Spectrometer (AMS) data. Here we present a study of this marker measured during five flights over the Amazon rainforest on board the UK Facility for Airborne Atmospheric Measurement (FAAM) BAe-146 research aircraft during the South American Biomass Burning Analysis (SAMBBA) campaign. Cases where this marker is and is not present are contrasted and linked to the presence of acidic seed particles, lower NOx concentrations and higher humidities. There are also data to suggest a role of organic nitrogen in the particulate composition. Furthermore, an inspection of the vertical trends of the marker indicates that concentrations are highest at the top of the boundary layer (possibly due to semivolatile repartitioning) and that upwards through the free troposphere, the mass spectral profile evolves towards that of low volatility oxygenated aerosol. These observations offer insights into the behaviour of IEPOX-derived SOA formation above the Amazon rainforest and the suitability of methylfuran as a marker for this process.

title: Will a perfect model agree with perfect observations? The impact of spatial sampling
abstract: The spatial resolution of global climate models with interactive aerosol and the observations used to evaluate them is very different. Current models use grid spacings of  ∼ 200 km, while satellite observations of aerosol use so-called pixels of  ∼ 10 km. Ground site or airborne observations relate to even smaller spatial scales. We study the errors incurred due to different resolutions by aggregating high-resolution simulations (10 km grid spacing) over either the large areas of global model grid boxes ("perfect" model data) or small areas corresponding to the pixels of satellite measurements or the field of view of ground sites ("perfect" observations). Our analysis suggests that instantaneous root-mean-square (RMS) differences of perfect observations from perfect global models can easily amount to 30–160 %, for a range of observables like AOT (aerosol optical thickness), extinction, black carbon mass concentrations, PM2.5, number densities and CCN (cloud condensation nuclei). These differences, due entirely to different spatial sampling of models and observations, are often larger than measurement errors in real observations. Temporal averaging over a month of data reduces these differences more strongly for some observables (e.g. a threefold reduction for AOT), than for others (e.g. a twofold reduction for surface black carbon concentrations), but significant RMS differences remain (10–75 %). Note that this study ignores the issue of temporal sampling of real observations, which is likely to affect our present monthly error estimates. We examine several other strategies (e.g. spatial aggregation of observations, interpolation of model data) for reducing these differences and show their effectiveness. Finally, we examine consequences for the use of flight campaign data in global model evaluation and show that significant biases may be introduced depending on the flight strategy used.

title: The Global Aerosol Synthesis and Science Project (GASSP): Measurements and Modeling to Reduce Uncertainty
abstract: The largest uncertainty in the historical radiative forcing of climate is caused by changes in aerosol particles due to anthropogenic activity. Sophisticated aerosol microphysics processes have been included in many climate models in an effort to reduce the uncertainty. However, the models are very challenging to evaluate and constrain because they require extensive in-situ measurements of the particle size distribution, number concentration and chemical composition that are not available from global satellite observations. The Global Aerosol Synthesis and Science Project (GASSP) aims to improve the robustness of global aerosol models by combining new methodologies for quantifying model uncertainty, an extensive global dataset of aerosol in-situ microphysical and chemical measurements, and new ways to assess the uncertainty associated with comparing sparse point measurements with low resolution models. GASSP has assembled over 45,000 hours of measurements from ships and aircraft as well as data from over 350 ground stations. The measurements have been harmonized into a standardized format that is easily used by modellers and non-specialist users. Available measurements are extensive, but they biased to polluted regions of the northern hemisphere, leaving large pristine regions and many continental areas poorly sampled. The aerosol radiative forcing uncertainty can be reduced using a rigorous model-data synthesis approach. Nevertheless, our research highlights significant remaining challenges because of the difficulty of constraining many interwoven model uncertainties simultaneously. Although the physical realism of global aerosol models still needs to be improved, the uncertainty in aerosol radiative forcing will be reduced most effectively by systematically and rigorously constraining the models using extensive syntheses of measurements.

title: Influences on the fraction of hydrophobic and hydrophilic black carbon in the atmosphere
abstract: Black carbon (BC) is a short term climate forcer that directly warms the atmosphere, slows convection, and hinders quantification of the effect of greenhouse gases on climate change. The atmospheric lifetime of BC particles with respect to nucleation scavenging in clouds is controlled by their ability to serve as cloud condensation nuclei (CCN). To serve as CCN under typical conditions, hydrophobic BC particles must acquire hygroscopic coatings. However, the quantitative relationship between coatings and hygroscopic properties for ambient BC particles is not known nor is the time scale for hydrophobic-to-hydrophilic conversion. Here we introduce a method for measuring the hygroscopicity of externally and internally mixed BC particles by coupling a single particle soot photometer with a humidified tandem differential mobility analyzer. We test this technique using uncoated and coated laboratory generated model BC compounds and apply it to characterize the hygroscopicity distribution of ambient BC particles. From these data we derive that the observed number fraction of BC that is CCN active at 0.2 % supersaturation is generally low in an urban area near sources and that it varies with the trajectory of the airmass. We anticipate that our method can be combined with measures of air parcel physical and photochemical age to provide the first quantitative estimates for characterizing hydrophobic-to-hydrophilic conversion rates in the atmosphere.

title: Technique and theoretical approach for quantifying the hygroscopicity of black-carbon-containing aerosol using a single particle soot photometer
abstract: A single particle soot photometer (SP2), an instrument that measures the optical size and refractory black carbon (BC) mass content of individual aerosol particles, was modified to include a compact humidification system, described here. This permits quantification of water uptake by BC-containing particles, an important process that can affect their optical properties and lifetime. A Mie and κ -Kohler theory framework was developed to relate measured humidity-dependent changes in BC aerosol optical size to the hygroscopicity parameter ( κ ) of the non-BC content in the particles (which is responsible for water uptake by these particles). Laboratory testing of this experimental and theoretical system with both homogeneous non-light-absorbing particles and BC-containing particles was carried out. Agreement between the theoretical predictions and laboratory measurements for the homogenous aerosols validates the experimental methodology. For BC with a 70-nm thick coating of ammonium sulfate, reasonable agreement (equivalent to ~20% in κ ) between measurements and theoretical predictions were observed over a span of RH from 70% to 90%. Two SP2s were configured to sample in parallel, one dry and one humidified, permitting continuous monitoring of water uptake by BC-containing aerosol. Operational refinements in SP2 setup to optimize the optical size measurement of BC-containing aerosol, and the consistency between the two SP2s are presented. This system was flown on the NASA DC8 research aircraft during the 2012 DC3 and 2013 SEAC4RS campaigns, providing engineering data included here that demonstrate the system׳s performance under challenging sampling conditions. Finally, SP2-scattering lookup tables used in the theoretical portions of this work are provided for reference.

title: Seasonal differences in the vertical profiles of aerosol optical properties over rural Oklahoma
abstract: A small airplane made 597 aerosol optical property (light absorption and light scattering) vertical profile measurements over a rural Oklahoma site between March 2000 and December 2007. The aerosol profiles obtained during these 8 yr of measurements suggest significant seasonal differences in aerosol loading (scattering and absorption). The highest amounts of scattering and absorbing aerosol are observed during the summer and the lowest loading occurs during the winter. The relative contribution of aerosol absorption is highest in the winter (i.e., single scattering albedo is lowest in winter), particularly aloft. Aerosol absorption generally decreased with altitude below ~1.5 km and then was relatively constant or decreased more gradually above that. Aerosol scattering decreased sharply with altitude below ~1.5 km but, unlike absorption, also decreased at higher altitudes, albeit less sharply. Scattering Angstrom exponents suggest that the aerosol was dominated by sub-micron aerosol during the summer at all altitudes, but that larger particles were present, especially in the spring and winter above 1 km. The seasonal variability observed for aerosol loading is consistent with AERONET aerosol optical depth (AOD) although the AOD values calculated from in situ adjusted to ambient conditions and matching wavelengths are up to a factor of two lower than AERONET AOD values depending on season. The column averaged single scattering albedo derived from in situ airplane measurements are similar in value to the AERONET single scattering albedo inversion product but the seasonal patterns are different – possibly a consequence of the strict constraints on obtaining single scattering albedo from AERONET data. A comparison of extinction Angstrom exponent and asymmetry parameter from the airplane and AERONET platforms suggests similar seasonal variability with smaller particles observed in the summer and fall and larger particles observed in spring and winter. The observed seasonal cycle of aerosol loading corresponds with changes in air mass back trajectories: the aerosol scattering was higher when transport was from polluted areas (e.g., the Gulf Coast) and lower when the air came from cleaner regions and/or the upper atmosphere.

title: Vertical profiles of aerosol optical properties over central Illinois and comparison with surface and satellite measurements
abstract: Between June 2006 and September 2009, an instrumented light aircraft measured over 400 vertical profiles of aerosol and trace gas properties over eastern and central Illinois. The primary objectives of this program were to (1) measure the in situ aerosol properties and determine their vertical and temporal variability and (2) relate these aircraft measurements to concurrent surface and satellite measurements. The primary profile location was within 15 km of the NOAA/ESRL surface aerosol monitoring station near Bondville, Illinois. Identical instruments at the surface and on the aircraft ensured that the data from both platforms would be directly comparable and permitted a determination of how representative surface aerosol properties were of the lower column. Aircraft profiles were also conducted occasionally at two other nearby locations to increase the frequency of A-Train satellite underflights for the purpose of comparing in situ and satellite-retrieved aerosol data. Measurements of aerosol properties conducted at low relative humidity over the Bondville site compare well with the analogous surface aerosol data and do not indicate any major sampling issues or that the aerosol is radically different at the surface compared with the lowest flyby altitude of ~ 240 m above ground level. Statistical analyses of the in situ vertical profile data indicate that aerosol light scattering and absorption (related to aerosol amount) decreases substantially with increasing altitude. Parameters related to the nature of the aerosol (e.g., single-scattering albedo, Angstrom exponent, etc.), however, are relatively constant throughout the mixed layer, and do not vary as much as the aerosol amount throughout the profile. While individual profiles often showed more variability, the median in situ single-scattering albedo was 0.93–0.95 for all sampled altitudes. Several parameters (e.g., submicrometer scattering fraction, hemispheric backscattering fraction, and scattering Angstrom exponent) suggest that the fraction of smaller particles in the aerosol is larger near the surface than at high altitudes. The observed dependence of scattering on size, wavelength, angular integration range, and relative humidity, together with the spectral dependence of absorption, show that the aerosol at higher altitudes is larger, less hygroscopic, and more strongly absorbing at shorter wavelengths, suggesting an increased contribution from dust or organic aerosols. The aerosol profiles show significant differences among seasons. The largest amounts of aerosol (as determined by median light extinction profile measurements) throughout most of the sampled column were observed during summer, with the lowest amounts in the winter and intermediate values in the spring and fall. The highest three profile levels (3.1, 3.7, 4.6 km), however, showed larger median extinction values in the spring, which could reflect long-range transport of dust or smoke aerosols. The aerosols in the mixed layer were darkest (i.e., lowest single-scattering albedo) in the fall, in agreement with surface measurements at Bondville and other continental sites in the US. In situ profiles of aerosol radiative forcing efficiency showed little seasonal or vertical variability. Underflights of the CALIPSO satellite show reasonable agreement in a majority of retrieved profiles between aircraft-measured extinction at 532 nm (adjusted to ambient relative humidity) and CALIPSO-retrieved extinction, and suggest that routine aircraft profiling programs can be used to better understand and validate satellite retrieval algorithms. CALIPSO tended to overestimate the aerosol extinction at this location in some boundary layer flight segments when scattered or broken clouds were present, which could be related to problems with CALIPSO cloud screening methods. The in situ aircraft-collected aerosol data suggest extinction thresholds for the likelihood of aerosol layers being detected by the CALIOP lidar. In this study, aerosol layers with light extinction (532 nm) values > 50 Mm −1 were detected by CALIPSO ~ 95% of the time, while aerosol layers with extinction values lower than 10 Mm −1 had a detection efficiency of −1 . These statistical data offer guidance as to the likelihood of CALIPSO's ability to retrieve aerosol extinction at various locations around the globe.

title: SAM-CAAM: A Concept for Acquiring Systematic Aircraft Measurements to Characterize Aerosol Air Masses.
abstract: A modest operational program of systematic aircraft measurements can resolve key satellite-aerosol-data-record limitations. Satellite observations provide frequent, global aerosol-amount maps, but offer only loose aerosol property constraints needed for climate and air quality applications. We define and illustrate the feasibility of flying an aircraft payload to measure key aerosol optical, microphysical, and chemical properties in situ. The flight program could characterize major aerosol air-mass types statistically, at a level-of-detail unobtainable from space. It would: (1) enhance satellite aerosol retrieval products with better climatology assumptions, and (2) improve translation between satellite-retrieved optical properties and species-specific aerosol mass and size simulated in climate models to assess aerosol forcing, its anthropogenic components, and other environmental impacts. As such, Systematic Aircraft Measurements to Characterize Aerosol Air Masses (SAM-CAAM) could add value to data records representing several decades of aerosol observations from space, improve aerosol constraints on climate modeling, help interrelate remote-sensing, in situ, and modeling aerosol-type definitions, and contribute to future satellite aerosol missions. Fifteen Required Variables are identified, and four Payload Options of increasing ambition are defined, to constrain these quantities. "Option C" could meet all the SAM-CAAM objectives with about 20 instruments, most of which have flown before, but never routinely several times per week, and never as a group. Aircraft integration, and approaches to data handling, payload support, and logistical considerations for a long-term, operational mission are discussed. SAM-CAAM is feasible because, for most aerosol sources and specified seasons, particle properties tend to be repeatable, even if aerosol loading varies.

title: Wildfire smoke injection heights: Two perspectives from space
abstract: The elevation at which wildfire smoke is injected into the atmosphere has a strong influence on how the smoke is dispersed, and is a key input to aerosol transport models. Aerosol layer height is derived with great precision from space-borne lidar, but horizontal sampling is very poor on a global basis. Aerosol height derived from space-borne stereo imaging is limited to source plumes having discernable features. But coverage is vastly greater, and captures the cores of major fires, where buoyancy can be sufficient to lift smoke above the near-surface boundary layer. Initial assessment of smoke injection from the Alaska-Yukon region during summer 2004 finds at least about 10% of wildfire smoke plumes reached the free troposphere. Modeling of smoke environmental impacts can benefit from the combined strengths of the stereo and lidar observations.