Black carbon (BC) absorbs solar radiation, leading to a strong but uncertain warming effect on climate. A key challenge in modeling and quantifying BC’s radiative effect on climate is predicting enhancements in light absorption that result from internal mixing between BC and other aerosol components. Modeling and laboratory studies show that BC, when mixed with other aerosol components, absorbs more strongly than pure, uncoated BC; however, some ambient observations suggest more variable and weaker absorption enhancement. We show that the lower-than-expected enhancements in ambient measurements result from a combination of two factors. First, the often used spherical, concentric core-shell approximation generally overestimates the absorption by BC. Second, and more importantly, inadequate consideration of heterogeneity in particle-to-particle composition engenders substantial overestimation in absorption by the total particle population, with greater heterogeneity associated with larger model–measurement differences. We show that accounting for these two effects—variability in per-particle composition and deviations from the core-shell approximation—reconciles absorption enhancement predictions with laboratory and field observations and resolves the apparent discrepancy. Furthermore, our consistent model framework provides a path forward for improving predictions of BC’s radiative effect on climate.

Aerosols directly affect Earth's climate by scattering and absorbing solar radiation. Although they are ubiquitous in Earth's atmosphere, direct, in situ, wavelength-resolved measurements of aerosol optical properties remain challenging. As a result, the so-called aerosol direct effects are one of the largest uncertainties in predictions of Earth's future climate, and new instrumentation is needed to provide measurements of the absorption of sunlight by atmospheric particles. We have developed a portable, four-wavelength, single-cell photoacoustic spectrometer for simultaneous measurement of aerosol absorption at 406, 532, 662, and 785 nm, with an additional extinction measurement at 662 nm via a built-in cavity ringdown spectrometer. The instrument, dubbed MultiPAS-IV, is compact, robust, has low power requirements, and utilizes a multipass optical arrangement to achieve typical detection limits of 0.6-0.7 Mm ¡1 for absorption (2s, 2-min average). Tests with nigrosin aerosols show agreement with Mie theory calculations to within 2%, and comparison with a 7-wavelength aethalometer shows good correlation for ambient (Athens, GA, USA) aerosols. We demonstrate the utility of the broad spectral coverage and sensitivity of the MultiPAS-IV for calculating the absorption A ngstr€ om exponent of black carbon (AAE BC , median value of 0.70) in ambient aerosols and use this value to derive the brown carbon contributions to absorption at 406 nm (43%) and 532 nm (13%) and its wavelength dependence (AAE BrC D 6.3).

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Abstract. Photoacoustic spectroscopy (PAS) has become a popular technique for measuring absorption of light by atmospheric aerosols in both the laboratory and field campaigns. It has low detection limits, measures suspended aerosols, and is insensitive to scattering. But PAS requires rigorous calibration to be applied quantitatively. Often, a PAS instrument is either filled with a gas of known concentration and absorption cross section, such that the absorption in the cell can be calculated from the product of the two, or the absorption is measured independently with a technique such as cavity ring-down spectroscopy. Then, the PAS signal can be regressed upon the known absorption to determine a calibration slope that reflects the sensitivity constant of the cell and microphone. Ozone has been used for calibrating PAS instruments due to its well-known UV–visible absorption spectrum and the ease with which it can be generated. However, it is known to photodissociate up to approximately 1120 nm via the O3 + hν(>1.1eV)→O2(3Σg-) + O(3P) pathway, which is likely to lead to inaccuracies in aerosol measurements. Two recent studies have investigated the use of O3 for PAS calibration but have reached seemingly contradictory conclusions with one finding that it results in a sensitivity that is a factor of 2 low and the other concluding that it is accurate. The present work is meant to add to this discussion by exploring the extent to which O3 photodissociates in the PAS cell and the role that the identity of the bath gas plays in determining the PAS sensitivity. We find a 5 % loss in PAS signal attributable to photodissociation at 532 nm in N2 but no loss in a 5 % mixture of O2 in N2. Furthermore, we discovered a dramatic increase of more than a factor of 2 in the PAS sensitivity as we increased the O2 fraction in the bath gas, which reached an asymptote near 100 % O2 that nearly matched the sensitivity measured with both NO2 and nigrosin particles. We interpret this dependence with a kinetic model that suggests the reason for the observed results is a more efficient transfer of energy from excited O3 to O2 than to N2 by a factor of 22–55 depending on excitation wavelength. Notably, the two prior studies on this topic used different bath gas compositions, and although the results presented here do not fully resolve the differences in their results, they may at least partially explain them.