Light absorbing organic carbon, often called brown carbon, has the potential to significantly contribute to the visible light-absorption budget, particularly at shorter wavelengths. Currently, the relative contributions of particulate brown carbon to light absorption, as well as the sources of brown carbon, are poorly understood. With this in mind size-resolved direct measurements of brown carbon were made at both urban (Atlanta), and rural (Yorkville) sites in Georgia. Measurements in Atlanta were made at both a representative urban site and a road-side site adjacent to a main highway. Fine particle absorption was measured with a multi-angle absorption photometer (MAAP) and seven-wavelength Aethalometer, and brown carbon absorption was estimated based on Mie calculations using direct size-resolved measurements of chromophores in solvents. Size-resolved samples were collected using a cascade impactor and analyzed for water-soluble organic carbon (WSOC), organic and elemental carbon (OC and EC), and solution light-absorption spectra of water and methanol extracts. Methanol extracts were more light-absorbing than water extracts for all size ranges and wavelengths. Absorption refractive indices of the organic extracts were calculated from solution measurements for a range of wavelengths and used with Mie theory to predict the light absorption by fine particles comprised of these components, under the assumption that brown carbon and other aerosol components were externally mixed. For all three sites, chromophores were predominately in the accumulation mode with an aerodynamic mean diameter of 0.5 μm, an optically effective size range resulting in predicted particle light absorption being a factor of 2 higher than bulk solution absorption. Mie-predicted brown carbon absorption at 350 nm contributed a significant fraction (20 to 40%) relative to total light absorption, with the highest contributions at the rural site where organic to elemental carbon ratios were highest. Brown carbon absorption, however, was highest by the roadside site due to vehicle emissions. The direct size-resolved measurement of brown carbon in solution definitively shows that it is present and optically important in the near-UV range in both a rural and urban environment during the summer when biomass burning emissions are low. These results allow estimates of brown carbon aerosol absorption from direct measurements of chromophores in aerosol extracts.

PH is a fundamental aerosol property that affects ambient particle concentration and composition, linking pH to all aerosol environmental impacts. Here, PM₁ and PM_2. 5 pH are calculated based on data from measurements during the California Research at the Nexus of Air Quality and Climate Change (CalNex) study from 15 May to 15 June 2010 in Pasadena, CA. Particle pH and water were predicted with the ISORROPIA-II thermodynamic model and validated by comparing predicted to measured gas–particle partitioning of inorganic nitrate, ammonium, and chloride. The study mean ± standard deviation PM₁ pH was 1.9 ± 0.5 for the SO₄²⁻–NO₃⁻–NH₄⁺–HNO₃–NH₃ system. For PM_2. 5, internal mixing of sea salt components (SO₄²⁻–NO₃⁻–NH₄⁺–Na⁺–Cl⁻–K⁺–HNO₃–NH₃–HCl system) raised the bulk pH to 2.7 ± 0.3 and improved predicted nitric acid partitioning with PM_2. 5 components. The results show little effect of sea salt on PM₁ pH, but significant effects on PM_2. 5 pH. A mean PM₁ pH of 1.9 at Pasadena was approximately one unit higher than what we have reported in the southeastern US, despite similar temperature, relative humidity, and sulfate ranges, and is due to higher total nitrate concentrations (nitric acid plus nitrate) relative to sulfate, a situation where particle water is affected by semi-volatile nitrate concentrations. Under these conditions nitric acid partitioning can further promote nitrate formation by increasing aerosol water, which raises pH by dilution, further increasing nitric acid partitioning and resulting in a significant increase in fine particle nitrate and pH. This study provides insights into the complex interactions between particle pH and nitrate in a summertime coastal environment and a contrast to recently reported pH in the eastern US in summer and winter and the eastern Mediterranean. All studies have consistently found highly acidic PM₁ with pH generally below 3.

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.

The light-absorbing organic aerosol (OA) commonly referred to as “brown carbon” (BrC) has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various volatile organic carbon (VOC) precursors, NO_x concentrations, photolysis time, and relative humidity (RH) on the light absorption of selected secondary organic aerosols (SOA). Light absorption of chamber-generated SOA samples, especially aromatic SOA, was found to increase with NO_x concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficient (MAC) value is observed from toluene SOA products formed under high-NO_x conditions at moderate RH, in which nitro-aromatics were previously identified as the major light-absorbing compounds. BrC light absorption is observed to decrease with photolysis time, correlated with a decline of the organic nitrate fraction of SOA. SOA formed from mixtures of aromatics and isoprene absorb less visible (Vis) and ultraviolet (UV) light than SOA formed from aromatic precursors alone on a mass basis. However, the mixed SOA absorption was underestimated when optical properties were predicted using a two-product SOA formation model, as done in many current climate models. Further investigation, including analysis on detailed mechanisms, are required to explain the discrepancy.

Chemical components of organic aerosol (OA) selectively absorb light at short wavelengths. In this study, the prevalence, sources, and optical importance of this so-called brown carbon (BrC) aerosol component are investigated throughout the North American continental tropospheric column during a summer of extensive biomass burning. Spectrophotometric absorption measurements on extracts of bulk aerosol samples collected from an aircraft over the central USA were analyzed to directly quantify BrC abundance. BrC was found to be prevalent throughout the 1 to 12 km altitude measurement range, with dramatic enhancements in biomass-burning plumes. BrC to black carbon (BC) ratios, under background tropospheric conditions, increased with altitude, consistent with a corresponding increase in the absorption Ångström exponent (AAE) determined from a three-wavelength particle soot absorption photometer (PSAP). The sum of inferred BC absorption and measured BrC absorption at 365 nm was within 3 % of the measured PSAP absorption for background conditions and 22 % for biomass burning. A radiative transfer model showed that BrC absorption reduced top-of-atmosphere (TOA) aerosol forcing by ~ 20 % in the background troposphere. Extensive radiative model simulations applying this study background tropospheric conditions provided a look-up chart for determining radiative forcing efficiencies of BrC as a function of a surface-measured BrC : BC ratio and single scattering albedo (SSA). The chart is a first attempt to provide a tool for better assessment of brown carbon's forcing effect when one is limited to only surface data. These results indicate that BrC is an important contributor to direct aerosol radiative forcing.

We present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO₂ and low-NO conditions, highly oxygenated (O : C ≥ 1) C₅ compounds were major components (∼ 50 %) of SOA. The SOA composition and effective volatility evolved both as a function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, > 30 % of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.