Aerosols generated from aqueous samples of readily obtainable humic material standards are often used as proxies for organic particulates found in the atmosphere in various investigations, such as consideration of radiative forcing effects. Here, we present results for the retrieved complex index of refraction, m = n + ik, at a wavelength of 403 nm for aerosols prepared from six humic material standards using a calibrated cavity ring-down spectrometer: a humic acid sodium salt, Pahokee peat humic and fulvic acids, Elliott soil humic and fulvic acids, and Suwannee river fulvic acid. In addition, we have conducted UV-vis spectrometric studies to measure the mass absorption coefficients, molar absorptivities, and absorption Angstrom exponents of bulk aqueous solutions of the humic materials. We find clear differences between the humic acid (HA) and fulvic acid (FA) samples with the HA having larger values for the imaginary part of the refractive index, k. The mean value for the HA samples is k = 0.170 while the mean is k = 0.037 for the FA materials. We have examined correlations between the retrieved refractive index and humic material characteristics obtained from spectroscopic and elemental analysis, including aromatic content and the oxygen-to-carbon atomic ratio, where the molar absorption coefficient yields the strongest correlation. Finally, we compare the humic material optical properties to those of authentic and laboratory generated organic carbon samples in order to assess the usefulness of these humic standards as proxies for light absorbing aerosol.
The impact of water droplets on soils has recently been found to drive emissions of airborne soil organic particles (ASOP). The chemical composition of ASOP include macromolecules such as polysaccharides, tannins, and lignin (derived from degradation of plants and biological organisms), which determine light absorbing (brown carbon) particle properties. Optical properties of ASOP were inferred from the quantitative analysis of the electron energy-loss spectra acquired over individual particles using transmission electron microscopy. The optical constants of ASOP are compared with those measured for laboratory generated particles composed of Suwanee River Fulvic Acid (SRFA) reference material, which is used as a laboratory surrogate of ASOP. The chemical composition of the particles was analyzed using energy dispersive X-ray spectroscopy, electron energy-loss spectroscopy, and synchrotron-based scanning transmission X-ray microscopy with near edge X-ray absorption fine structure spectroscopy. ASOP and SRFA exhibit similar carbon composition, with minor differences in other elements present. When ASOP are heated to 350 degrees C their absorption increases as a result of pyrolysis and partial volatilization of semivolatile organic constituents. The retrieved refractive index (RI) at 532 nm of SRFA particles, ASOP, and heated ASOP were 1.22-0.07i, 1.29-0.07i, and 1.90-0.38i, respectively. Retrieved imaginary part of the refractive index of SRFA particles derived from EELS measurements was higher and the real part was lower compared to data from more common optical methods. Therefore, corrections to the EELS data are needed for incorporation into models. These measurements of ASOP optical constants confirm that they have properties characteristic of atmospheric brown carbon and therefore their potential effects on the radiative forcing of climate need to be assessed in atmospheric models.