Nonequilibrium Behavior in Isoprene Secondary Organic Aerosol.

Recent studies have shown that instantaneous gas-particle equilibrium partitioning assumptions fail to predict SOA formation, even at high relative humidity (∼85%), and photochemical aging seems to be one driving factor. In this study, we probe the minimum aging time scale required to observe nonequilibrium partitioning of semivolatile organic compounds (SVOCs) between the gas and aerosol phase at ∼50% RH. Seed isoprene SOA is generated by photo-oxidation in the presence of effloresced ammonium sulfate seeds at <1 ppbv NOx, aged photochemically or in the dark for 0.3-6 h, and subsequently exposed to fresh isoprene SVOCs. Our results show that the equilibrium partitioning assumption is accurate for fresh isoprene SOA but breaks down after isoprene SOA has been aged for as short as 20 min even in the dark. Modeling results show that a semisolid SOA phase state is necessary to reproduce the observed particle size distribution evolution. The observed nonequilibrium partitioning behavior and inferred semisolid phase state are corroborated by offline mass spectrometric analysis on the bulk aerosol particles showing the formation of organosulfates and oligomers. The unexpected short time scale for the phase transition within isoprene SOA has important implications for the growth of atmospheric ultrafine particles to climate-relevant sizes.

Unified theoretical framework for black carbon mixing state allows greater accuracy of climate effect estimation.

Black carbon (BC) plays an important role in the climate system because of its strong warming effect, yet the magnitude of this effect is highly uncertain owing to the complex mixing state of aerosols. Here we build a unified theoretical framework to describe BC's mixing states, linking dynamic processes to BC coating thickness distribution, and show its self-similarity for sites in diverse environments. The size distribution of BC-containing particles is found to follow a universal law and is independent of BC core size. A new mixing state module is established based on this finding and successfully applied in global and regional models, which increases the accuracy of aerosol climate effect estimations. Our theoretical framework links observations with model simulations in both mixing state description and light absorption quantification.

Monoterpene Photooxidation in a Continuous-Flow Chamber: SOA Yields and Impacts of Oxidants, NOx, and VOC Precursors.

Monoterpene photooxidation plays an important role in secondary organic aerosol (SOA) formation in the atmosphere. The low-volatility products can enhance new particle formation and particle growth and thus influence climate feedback. Here, we present the results of α-pinene and Δ-3-carene photooxidation experiments conducted in continuous-flow mode in an environmental chamber under several reaction conditions. The roles of oxidants, addition of NO, and VOC molecular structure in influencing SOA yield are illustrated. SOA yield from α-pinene photooxidation shows a weak dependence on H2O2 concentration, which is a proxy for HO2 concentration. The high O/C ratios observed in the α-pinene photooxidation products suggest the production of highly oxygenated organic molecules (HOM). Addition of ozone to the chamber during low-NOx photooxidation experiments leads to higher SOA yield. With the addition of NO, the production of N-containing HOMs is enhanced and the SOA yield shows a modest, nonlinear dependence on the input NO concentration. Carene photooxidation leads to higher SOA yield than α-pinene under similar reaction conditions, which agrees with the lower volatility retrieved from evaporation kinetics experiments. These results improve the understanding of SOA formation from monoterpene photooxidation and could be applied to refine the representation of biogenic SOA formation in models.

Rapid growth of anthropogenic organic nanoparticles greatly alters cloud life cycle in the Amazon rainforest.

Aerosol-cloud interactions remain uncertain in assessing climate change. While anthropogenic activities produce copious aerosol nanoparticles smaller than 10 nanometers, they are too small to act as efficient cloud condensation nuclei (CCN). The mechanisms responsible for particle growth to CCN-relevant sizes are poorly understood. Here, we present aircraft observations of rapid growth of anthropogenic nanoparticles downwind of an isolated metropolis in the Amazon rainforest. Model analysis reveals that the sustained particle growth to CCN sizes is predominantly caused by particle-phase diffusion-limited partitioning of semivolatile oxidation products of biogenic hydrocarbons. Cloud-resolving numerical simulations show that the enhanced CCN concentrations in the urban plume substantially alter the formation of shallow convective clouds, suppress precipitation, and enhance the transition to deep convective clouds. The proposed nanoparticle growth mechanism, expressly enabled by the abundantly formed semivolatile organics, suggests an appreciable impact of anthropogenic aerosols on cloud life cycle in previously unpolluted forests of the world.

Humidity Dependence of the Condensational Growth of α-Pinene Secondary Organic Aerosol Particles.

The influence of relative humidity (RH) on the condensational growth of organic aerosol particles remains incompletely understood. Herein, the RH dependence was investigated via a series of experiments for α-pinene ozonolysis in a continuously mixed flow chamber in which recurring cycles of particle growth occurred every 7 to 8 h at a given RH. In 5 h, the mean increase in the particle mode diameter was 15 nm at 0% RH and 110 nm at 75% RH. The corresponding particle growth coefficients, representing a combination of the thermodynamic driving force and the kinetic resistance to mass transfer, increased from 0.35 to 2.3 nm2 s-1. The chemical composition, characterized by O:C and H:C atomic ratios of 0.52 and 1.48, respectively, and determined by mass spectrometry, did not depend on RH. The Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) was applied to reproduce the observed size- and RH-dependent particle growth by optimizing the diffusivities Db within the particles of the condensing molecules. The Db values increased from 5 α-1 × 10-16 at 0% RH to 2 α-1 × 10-12 cm-2 s-1 at 75% RH for mass accommodation coefficients α of 0.1 to 1.0, highlighting the importance of particle-phase properties in modeling the growth of atmospheric aerosol particles.

Development and Evaluation of Chemistry-Aerosol-Climate Model CAM5-Chem-MAM7-MOSAIC: Global Atmospheric Distribution and Radiative Effects of Nitrate Aerosol.

An advanced aerosol treatment, with a focus on semivolatile nitrate formation, is introduced into the Community Atmosphere Model version 5 with interactive chemistry (CAM5-chem) by coupling the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) with the 7-mode Modal Aerosol Module (MAM7). An important feature of MOSAIC is dynamic partitioning of all condensable gases to the different fine and coarse mode aerosols, as governed by mode-resolved thermodynamics and heterogeneous chemical reactions. Applied in the free-running mode from 1995 to 2005 with prescribed historical climatological conditions, the model simulates global distributions of sulfate, nitrate, and ammonium in good agreement with observations and previous studies. Inclusion of nitrate resulted in ∼10% higher global average accumulation mode number concentrations, indicating enhanced growth of Aitken mode aerosols from nitrate formation. While the simulated accumulation mode nitrate burdens are high over the anthropogenic source regions, the sea-salt and dust modes respectively constitute about 74% and 17% of the annual global average nitrate burden. Regional clear-sky shortwave radiative cooling of up to -5 W m-2 due to nitrate is seen, with a much smaller global average cooling of -0.05 W m-2. Significant enhancements in regional cloud condensation nuclei (at 0.1% supersaturation) and cloud droplet number concentrations are also attributed to nitrate, causing an additional global average shortwave cooling of -0.8 W m-2. Taking into consideration of changes in both longwave and shortwave radiation under all-sky conditions, the net change in the top of the atmosphere radiative fluxes induced by including nitrate aerosol is -0.7 W m-2.

Impact of Urban Pollution on Organic-Mediated New-Particle Formation and Particle Number Concentration in the Amazon Rainforest.

A major challenge in assessing the impact of aerosols on climate change is to understand how human activities change aerosol loading and properties relative to the pristine/preindustrial baseline. Here, we combine chemical transport simulations and field measurements to investigate the effect of anthropogenic pollution from an isolated metropolis on the particle number concentration over the preindustrial-like Amazon rainforest through various new-particle formation (NPF) mechanisms and primary particle emissions. To represent organic-mediated NPF, we employ a state-of-the-art model that systematically simulates the formation chemistry and thermodynamics of extremely low volatility organic compounds, as well as their roles in NPF processes, and further update the model to improve organic NPF simulations under human-influenced conditions. Results show that urban pollution from the metropolis increases the particle number concentration by a factor of 5-25 over the downwind region (within 200 km from the city center) compared to background conditions. Our model indicates that NPF contributes over 70% of the total particle number in the downwind region except immediately adjacent to the sources. Among different NPF mechanisms, the ternary NPF involving organics and sulfuric acid overwhelmingly dominates. The improved understanding of particle formation mechanisms will help better quantify anthropogenic aerosol forcing from preindustrial times to the present day.

Particle Size Distribution Dynamics Can Help Constrain the Phase State of Secondary Organic Aerosol.

Particle phase state is a property of atmospheric aerosols that has important implications for the formation, evolution, and gas/particle partitioning of secondary organic aerosol (SOA). In this work, we use a size-resolved chemistry and microphysics model (Statistical Oxidation Model coupled to the TwO Moment Aerosol Sectional (SOM-TOMAS)), updated to include an explicit treatment of particle phase state, to constrain the bulk diffusion coefficient (Db) of SOA produced from α-pinene ozonolysis. By leveraging data from laboratory experiments performed in the absence of a seed and under dry conditions, we find that the Db for SOA can be constrained ((1-7) × 10-15 cm2 s-1 in these experiments) by simultaneously reproducing the time-varying SOA mass concentrations and the evolution of the particle size distribution. Another version of our model that used the predicted SOA composition to calculate the glass-transition temperature, viscosity, and, ultimately, Db (∼10-15 cm2 s-1) of the SOA was able to reproduce the mass and size distribution measurements when we included oligomer formation (oligomers accounted for about a fifth of the SOA mass). Our work highlights the potential of a size-resolved SOA model to constrain the particle phase state of SOA using historical measurements of the evolution of the particle size distribution.

High concentration of ultrafine particles in the Amazon free troposphere produced by organic new particle formation.

The large concentrations of ultrafine particles consistently observed at high altitudes over the tropics represent one of the world's largest aerosol reservoirs, which may be providing a globally important source of cloud condensation nuclei. However, the sources and chemical processes contributing to the formation of these particles remain unclear. Here we investigate new particle formation (NPF) mechanisms in the Amazon free troposphere by integrating insights from laboratory measurements, chemical transport modeling, and field measurements. To account for organic NPF, we develop a comprehensive model representation of the temperature-dependent formation chemistry and thermodynamics of extremely low volatility organic compounds as well as their roles in NPF processes. We find that pure-organic NPF driven by natural biogenic emissions dominates in the uppermost troposphere above 13 km and accounts for 65 to 83% of the column total NPF rate under relatively pristine conditions, while ternary NPF involving organics and sulfuric acid dominates between 8 and 13 km. The large organic NPF rates at high altitudes mainly result from decreased volatility of organics and increased NPF efficiency at low temperatures, somewhat counterbalanced by a reduced chemical formation rate of extremely low volatility organic compounds. These findings imply a key role of naturally occurring organic NPF in high-altitude preindustrial environments and will help better quantify anthropogenic aerosol forcing from preindustrial times to the present day.

Photolysis Controls Atmospheric Budgets of Biogenic Secondary Organic Aerosol.

Secondary organic aerosol (SOA) accounts for a large fraction of the tropospheric particulate matter. Although SOA production rates and mechanisms have been extensively investigated, loss pathways remain uncertain. Most large-scale chemistry and transport models account for mechanical deposition of SOA but not chemical losses such as photolysis. There is also a paucity of laboratory measurements of SOA photolysis, which limits how well photolytic losses can be modeled. Here, we show, through a combined experimental and modeling approach, that photolytic loss of SOA mass significantly alters SOA budget predictions. Using environmental chamber experiments at variable relative humidity between 0 and 60%, we find that SOA produced from several biogenic volatile organic compounds undergoes photolysis-induced mass loss at rates between 0 and 2.2 ± 0.4% of nitrogen dioxide (NO2) photolysis, equivalent to average atmospheric lifetimes as short as 10 h. We incorporate our photolysis rates into a regional chemical transport model to test the sensitivity of predicted SOA mass concentrations to photolytic losses. The addition of photolysis causes a ∼50% reduction in biogenic SOA loadings over the Amazon, indicating that photolysis exerts a substantial control over the atmospheric SOA lifetime, with a likely dependence upon the SOA molecular composition and thus production mechanisms.

Particle-Phase Diffusion Modulates Partitioning of Semivolatile Organic Compounds to Aged Secondary Organic Aerosol.

The diffusivity of semivolatile organic compounds (SVOCs) in the bulk particle phase of a viscous atmospheric secondary organic aerosol (SOA) can have a profound impact on aerosol growth and size distribution dynamics. Here, we investigate the bulk diffusivity of SVOCs formed from photo-oxidation of isoprene as they partition to a bimodal aerosol consisting of an Aitken (potassium sulfate) and accumulation mode (aged α-pinene SOA) particles as a function of relative humidity (RH). The model analysis of the observed size distribution evolution shows that liquid-like diffusion coefficient values of Db > 10-10 cm2 s-1 fail to explain the growth of the Aitken mode. Instead, much lower values of Db between 2.5 × 10-15 cm2 s-1 at 32% RH and 8 × 10-15 cm2 s-1 at 82% RH were needed to successfully reproduce the growth of both modes. The diffusivity within the aged α-pinene SOA remains appreciably slow even at 80% RH, resulting in hindered partitioning of SVOCs to large viscous particles and allowing smaller and relatively less viscous particles to effectively absorb the available SVOCs and grow much faster than would be possible otherwise. These results have important implications for modeling SOA formation and growth in the ambient atmosphere.

The Acidity of Atmospheric Particles and Clouds.

Acidity, defined as pH, is a central component of aqueous chemistry. In the atmosphere, the acidity of condensed phases (aerosol particles, cloud water, and fog droplets) governs the phase partitioning of semi-volatile gases such as HNO3, NH3, HCl, and organic acids and bases as well as chemical reaction rates. It has implications for the atmospheric lifetime of pollutants, deposition, and human health. Despite its fundamental role in atmospheric processes, only recently has this field seen a growth in the number of studies on particle acidity. Even with this growth, many fine particle pH estimates must be based on thermodynamic model calculations since no operational techniques exist for direct measurements. Current information indicates acidic fine particles are ubiquitous, but observationally-constrained pH estimates are limited in spatial and temporal coverage. Clouds and fogs are also generally acidic, but to a lesser degree than particles, and have a range of pH that is quite sensitive to anthropogenic emissions of sulfur and nitrogen oxides, as well as ambient ammonia. Historical measurements indicate that cloud and fog droplet pH has changed in recent decades in response to controls on anthropogenic emissions, while the limited trend data for aerosol particles indicates acidity may be relatively constant due to the semi-volatile nature of the key acids and bases and buffering in particles. This paper reviews and synthesizes the current state of knowledge on the acidity of atmospheric condensed phases, specifically particles and cloud droplets. It includes recommendations for estimating acidity and pH, standard nomenclature, a synthesis of current pH estimates based on observations, and new model calculations on the local and global scale.

Extensive Soot Compaction by Cloud Processing from Laboratory and Field Observations.

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models.

Urban pollution greatly enhances formation of natural aerosols over the Amazon rainforest.

One of the least understood aspects in atmospheric chemistry is how urban emissions influence the formation of natural organic aerosols, which affect Earth's energy budget. The Amazon rainforest, during its wet season, is one of the few remaining places on Earth where atmospheric chemistry transitions between preindustrial and urban-influenced conditions. Here, we integrate insights from several laboratory measurements and simulate the formation of secondary organic aerosols (SOA) in the Amazon using a high-resolution chemical transport model. Simulations show that emissions of nitrogen-oxides from Manaus, a city of ~2 million people, greatly enhance production of biogenic SOA by 60-200% on average with peak enhancements of 400%, through the increased oxidation of gas-phase organic carbon emitted by the forests. Simulated enhancements agree with aircraft measurements, and are much larger than those reported over other locations. The implication is that increasing anthropogenic emissions in the future might substantially enhance biogenic SOA in pristine locations like the Amazon.

Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol.

Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. Here, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversibly reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.

Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol.

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry-climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

Semivolatile POA and parameterized total combustion SOA in CMAQv5.2: impacts on source strength and partitioning.

Mounting evidence from field and laboratory observations coupled with atmospheric model analyses shows that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality model version 5.2 (CMAQv5.2) accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the secondary organic aerosol (SOA) from anthropogenic combustion sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: (1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, (2) multigenerational aging of organic vapor products from known SOA precursors (e.g., toluene, alkanes), (3) underestimation of SOA yields due to vapor wall losses in smog chamber experiments, and (4) reversible organic compounds-water interactions and/or aqueous-phase processing of known organic vapor emissions. CMAQ predicts the spatially averaged contribution of pcSOA to OA surface concentrations in the continental United States to be 38.6 and 23.6 % in the 2011 winter and summer, respectively. Whereas many past modeling studies focused on a particular measurement campaign, season, location, or model configuration, we endeavor to evaluate the model and important uncertain parameters with a comprehensive set of United States-based model runs using multiple horizontal scales (4 and 12 km), gas-phase chemical mechanisms, and seasons and years. The model with representation of semivolatile POA improves predictions of hourly OA observations over the traditional nonvolatile model at sites during field campaigns in southern California (CalNex, May-June 2010), northern California (CARES, June 2010), the southeast US (SOAS, June 2013; SEARCH, January and July, 2011). Model improvements manifest better correlations (e.g., the correlation coefficient at Pasadena at night increases from 0.38 to 0.62) and reductions in underprediction during the photochemically active afternoon period (e.g., bias at Pasadena from -5.62 to -2.42 µg m-3). Daily averaged predictions of observations at routine-monitoring networks from simulations over the continental US (CONUS) in 2011 show modest improvement during winter, with mean biases reducing from 1.14 to 0.73µg m-3, but less change in the summer when the decreases from POA evaporation were similar to the magnitude of added SOA mass. Because the model-performance improvement realized by including the relatively simple pcSOA approach is similar to that of more-complicated parameterizations of OA formation and aging, we recommend caution when applying these more-complicated approaches as they currently rely on numerous uncertain parameters. The pcSOA parameters optimized for performance at the southern and northern California sites lead to higher OA formation than is observed in the CONUS evaluation. This may be due to any of the following: variations in real pcSOA in different regions or time periods, too-high concentrations of other OA sources in the model that are important over the larger domain, or other model issues such as loss processes. This discrepancy is likely regionally and temporally dependent and driven by interferences from factors like varying emissions and chemical regimes.

Lability of secondary organic particulate matter.

The energy flows in Earth's natural and modified climate systems are strongly influenced by the concentrations of atmospheric particulate matter (PM). For predictions of concentration, equilibrium partitioning of semivolatile organic compounds (SVOCs) between organic PM and the surrounding vapor has widely been assumed, yet recent observations show that organic PM can be semisolid or solid for some atmospheric conditions, possibly suggesting that SVOC uptake and release can be slow enough that equilibrium does not prevail on timescales relevant to atmospheric processes. Herein, in a series of laboratory experiments, the mass labilities of films of secondary organic material representative of similar atmospheric organic PM were directly determined by quartz crystal microbalance measurements of evaporation rates and vapor mass concentrations. There were strong differences between films representative of anthropogenic compared with biogenic sources. For films representing anthropogenic PM, evaporation rates and vapor mass concentrations increased above a threshold relative humidity (RH) between 20% and 30%, indicating rapid partitioning above a transition RH but not below. Below the threshold, the characteristic time for equilibration is estimated as up to 1 wk for a typically sized particle. In contrast, for films representing biogenic PM, no RH threshold was observed, suggesting equilibrium partitioning is rapidly obtained for all RHs. The effective diffusion rate Dorg for the biogenic case is at least 103 times greater than that of the anthropogenic case. These differences should be accounted for in the interpretation of laboratory data as well as in modeling of organic PM in Earth's atmosphere.

Efficient Isoprene Secondary Organic Aerosol Formation from a Non-IEPOX Pathway.

With a large global emission rate and high reactivity, isoprene has a profound effect upon atmospheric chemistry and composition. The atmospheric pathways by which isoprene converts to secondary organic aerosol (SOA) and how anthropogenic pollutants such as nitrogen oxides and sulfur affect this process are subjects of intense research because particles affect Earth's climate and local air quality. In the absence of both nitrogen oxides and reactive aqueous seed particles, we measure SOA mass yields from isoprene photochemical oxidation of up to 15%, which are factors of 2 or more higher than those typically used in coupled chemistry climate models. SOA yield is initially constant with the addition of increasing amounts of nitric oxide (NO) but then sharply decreases for input concentrations above 50 ppbv. Online measurements of aerosol molecular composition show that the fate of second-generation RO2 radicals is key to understanding the efficient SOA formation and the NOx-dependent yields described here and in the literature. These insights allow for improved quantitative estimates of SOA formation in the preindustrial atmosphere and in biogenic-rich regions with limited anthropogenic impacts and suggest that a more-complex representation of NOx-dependent SOA yields may be important in models.

Response to comment on "Radiative absorption enhancements due to the mixing state of atmospheric black carbon".

Jacobson argues that our statement that "many climate models may overestimate warming by BC" has not been demonstrated. Jacobson challenges our results on the basis that we have misinterpreted some model results, omitted optical focusing under high relative humidity conditions and by involatile components, and because our measurements consist of only two locations over short atmospheric time periods. We address each of these arguments, acknowledging important issues and clarifying some misconceptions, and stand by our observations. We acknowledge that Jacobson identified one detail in our experimental technique that places an additional constraint on the interpretation of our observations and reduces somewhat the potential consequences of the stated implications.