Aki Virkkula

A simple procedure for correcting loading effects of aethalometer data

A simple method for correcting for the loading effects of aethalometer data is presented. The formula BC(CORRECTED) = (1 + k x ATN) x BC(NONCORRECTED), where ATN is the attenuation and BC is black carbon, was used for correcting aethalometer data obtained from measurements at three different sites: a subway station in Helsinki, an urban background measurement station in Helsinki, and a rural station in Hyytiälä in central Finland. The BC data were compared with simultaneously measured aerosol volume concentrations (V). After the correction algorithm, the BC-to-V ratio remained relatively stable between consequent filter spots, which can be regarded as indirect evidence that the correction algorithm works. The k value calculated from the outdoor sites had a clear seasonal cycle that could be explained by darker aerosol in winter than in summer. When the contribution of BC to the total aerosol volume was high, the k factor was high and vice versa. In winter, the k values at all wavelengths were very close to that obtained from the subway station data. In summer, the k value was wavelength dependent and often negative. When the k value is negative, the noncorrected BC concentrations overestimated the true concentrations.

Modification, Calibration and a Field Test of an Instrument for Measuring Light Absorption by Particles

A filter-based single-wavelength photometer (Particle Soot Absorption Photometer, PSAP) for measuring light absorption by aerosols was modified to measure at three wavelengths, 467 nm, 530 nm, and 660 nm. The modified and an unmodified photometer were calibrated during the Reno Aerosol Optics Study (RAOS) 2002 against two absorption standards: a photoacoustic instrument and the difference between the extinction and scattering coefficient. This filter-based absorption method has to be corrected for scattering aerosol and transmission changes. A simple function for this was derived from the calibration experiment as a function of transmission and single-scattering albedo. For an unmodified PSAP at typical atmospheric absorption coefficients the algorithm yields about 5–7% lower absorption coefficients than does the usually used method. The three-wavelength PSAP was used for atmospheric measurements both during RAOS and during the New England Air Quality Study (NEAQS).

The Reno Aerosol Optics Study: An Evaluation of Aerosol Absorption Measurement Methods

The Reno Aerosol Optics Study (RAOS) was designed and conducted to compare the performance of many existing and new instruments for the in situ measurement of aerosol optical properties with a focus on the determination of aerosol light absorption. For this study, simple test aerosols of black and white particles were generated and combined in external mixtures under low relative humidity conditions and delivered to each measurement system. The aerosol mixing and delivery system was constantly monitored using particle counters and nephelometers to ensure that the same aerosol number concentration and amount reached the different instruments. The aerosol light-scattering measurements of four different nephelometers were compared, while the measurements of seven light-absorption instruments (5 filter based, 2 photoacoustic) were evaluated. Four methods for determining the aerosol light-extinction coefficient (3 cavity ring-down instruments and 1 folded-path optical extinction cell) were also included in the comparisons. An emphasis was placed on determining the representativeness of the filter-based light absorption methods, since these are used widely and because major corrections to the raw attenuation measurements are known to be required. The extinction measurement from the optical extinction cell was compared with the scattering measurement from a high-sensitivity integrating nephelometer on fine, nonabsorbing ammonium sulfate aerosols, and the two were found to agree closely (within 1% for blue and green wavelengths and 2% for red). The wavelength dependence of light absorption for small kerosene and diesel soot particles was found to be very near λ− 1, the theoretical small-particle limit. Larger, irregularly shaped graphite particles showed widely variable wavelength dependencies over several graphite runs. The light-absorption efficiency at a wavelength of 530 nm for pure kerosene soot with a number size distribution peak near 0.3 μ m diameter was found to be 7.5 ± 1.2 m2 g− 1. The two most fundamental independent absorption methods used in this study were photoacoustic absorption and the difference between suspended-state light extinction and scattering, and these showed excellent agreement (typically within a few percent) on mixed black/white aerosols, with the photoacoustic measurement generally slightly lower. Excellent agreement was also observed between some filter-based light-absorption measurements and the RAOS reference absorption method. For atmospherically relevant levels of the aerosol light-absorption coefficient (< 25 Mm− 1), the particle soot absorption photometer (PSAP) absorption measurement at mid-visible wavelengths agreed with the reference absorption measurement to within ∼ 11% for experiment tests on externally mixed kerosene soot and ammonium sulfate. At higher absorption levels (characterized by lower single-scattering albedo aerosol tests), this agreement worsened considerably, most likely due to an inadequate filter loading correction used for the PSAP. The PSAP manufacturers filter loading correction appears to do an adequate job of correcting the PSAP absorption measurement at aerosol single-scattering albedos above 0.80–0.85, which represents most atmospheric aerosols, but it does a progressively worse job at lower single-scattering albedos. A new filter-based light-absorption photometer was also evaluated in RAOS, the multiangle absorption photometer (MAAP), which uses a two-stream radiative transfer model to determine the filter and aerosol scattering effects for a better calculation of the absorption coefficient. The MAAP absorption measurements agreed with the reference absorption measurements closely (linear regression slope of ∼ 0.99) for all experimental tests on externally mixed kerosene soot and ammonium sulfate.

Evaluation of Multiangle Absorption Photometry for Measuring Aerosol Light Absorption

A new multiangle absorption photometer for the measurement of aerosol light absorption was recently introduced that builds on the simultaneous measurement of radiation transmitted through and scattered back from a particle-loaded fiber filter at multiple detection angles. The absorption coefficient of the filter-deposited aerosol is calculated from the optical properties of the entire filter system, which are determined by a two-stream-approximation radiative transfer scheme. In the course of the Reno Aerosol Optics Study (RAOS), the response characteristics of multiangle absorption photometry (MAAP) for white aerosol, pure black carbon aerosol from different sources, external mixtures of black and white aerosol, and ambient aerosol was investigated. The MAAP response characteristics were compared to basic filter transmittance and filter reflectance measurements. MAAP showed close agreement with a reference absorption measurement by extinction minus scattering. The slopes of regression lines vary between 0.99 ± 0.01 and 1.07 ± 0.02 for pure black carbon particles and external mixtures with ammonium sulphate to 1.03 ± 0.05 for ambient aerosol. No effect of the filter aerosol loading or the single-scattering albedo ω0 of the sampled aerosol on the MAAP response characteristics was observed. In contrast, transmittance and reflectance methods showed a clear impact of ω0 and the filter loading on the response characteristics, which requires the application of a correction function for the reliable determination of the aerosol absorption coefficient. In the case of nonabsorbing aerosol, the MAAP approach reduced the magnitude of the apparently measured absorption coefficient by one order of magnitude compared to a basic transmittance measurement.

Chemical mass closure and assessment of the origin of the submicron aerosol in the marine boundary layer and the free troposphere at Tenerife during ACE-2

The organic, inorganic, mineral content and mass concentration of the submicron aerosol were measured in June−July 1997 on Tenerife in the marine boundary layer (MBL) and the free troposphere (FT). Aerosol size distributions were measured simultaneously at the same sites. The submicron aerosol mass concentrations derived from the chemical composition and calculated from the number size distributions agreed within the experimental uncertainties both in the MBL (±47%) and the FT (±75%). However, the analytical uncertainties in the concentration of organic compounds (OC) for the average sample collected in the MBL (-97, +77%) and the FT (±74%) were high. The average contribution of aerosol various components to the submicron aerosol mass were calculated for different air masses. The absolute uncertainties in these contributions were calculated by adding random uncertainties quadratically and possibly systematic errors in a conservative way. In the unperturbed MBL, the aerosol average composition (± the absolute uncertainty in the contribution) was 37 (-3, +9)% for non-sea-salt SO42-+ NH4+, 21 (-2, +10)% for sea-salt, and 20 (-7, +11)% OC (N=19). In the unperturbed FT, OC and SO42- accounted for 43 (±20)% and 32 (-5, +3)% of the submicron aerosol mass, respectively (N=15). Considering these aerosol compositions, we suggest that the source for the FT aerosol could be the transport of continental aerosol through precipitating convective clouds. A simple budget calculation shows, that in background conditions, the MBL and FT aerosol compositions are consistent with the hypothesis that the MBL aerosol is formed by the dilution of continental aerosol by FT air, modified by deposition and condensation of species of oceanic origin. Dramatic continental aerosol outbreaks were observed in both the MBL and the FT. The aerosol outbreaks in the MBL were due to transport of polluted air masses from Europe. They were characterized mainly by increases in SO42-+ NH4+, making up 75 (-5, +19)% of the submicron aerosol mass. The aerosol outbreaks in the FT were due to advection of desert dust, probably mixed with pollution aerosol.

Hygroscopic properties of aerosol formed by oxidation of limonene, α-pinene, and β-pinene

The hygroscopic properties of aerosol formed by oxidation of three monoterpenes, limonene, α-pinene, and β-pinene, were measured using a tandem differential mobility analyzer (TDMA). The experiments were performed in the European Photoreactor (EUPHORE) in Valencia, Spain. The experiments included ozonolysis and photooxidation with and without ammonium sulfate seed aerosol. Pure organic particles, formed by oxidation of the terpenes in the absence of the seed aerosol, proved to be slightly hygroscopic. The hygroscopic growth factor (G) was close to 1.10 at relative humidity 84% ± 1%, which is often observed as the G of the less hygroscopic mode of atmospheric aerosol in field measurements. In the experiments with ammonium sulfate seed aerosol G decreased from approximately 1.5 before the start of terpene oxidation to approximately 1.1 as the oxidation products condensed on the particles. G was not proportional to the organic layer thickness but decreased with increasing organic volume fraction. Our analysis shows that in the internally mixed particles, ammonium sulfate and the organic products take up water independently of one another.

Aerosols in polar regions: A historical overview based on optical depth and in situ observations

Large sets of filtered actinometer, filtered pyrheliometer and Sun photometer measurements have been carried out over the past 30 years by various groups at different Arctic and Antarctic sites and ...

Saharan dust absorption and refractive index from aircraft-based observations during SAMUM 2006

During the Saharan Mineral Dust Experiment (SAMUM) conducted in summer 2006 in southeast Morocco, the complex refractive index of desert dust was determined from airborne measurements of particle size distributions and aerosol absorption coefficients at three different wavelengths in the blue (467 nm), green (530 nm) and red (660 nm) spectral regions. The vertical structure of the dust layers was analysed by an airborne high spectral resolution lidar (HSRL). The origin of the investigated dust layers was estimated from trajectory analyses, combined with Meteosat 2nd Generation (MSG) scenes and wind field data analyses. The real part n of the dust refractive index was found almost constant with values between 1.55 and 1.56, independent of the wavelength. The values of the imaginary part k varied between the blue and red spectral regions by a factor of three to ten depending on the dust source region. Absolute values of k ranged from 3.1 × 10−3 to 5.2 × 10−3 at 450 nm and from 0.3 × 10−3 to 2.5 × 10−3 at 700 nm. Groupings of k values could be attributed to different source regions.

Secondary organics and atmospheric cloud condensation nuclei production

The influence of secondary organics on atmospheric cloud condensation nuclei (CCN) production was investigated using a zero-dimensional box model that simulates the production of secondary organics in the gas phase, the transportation of these organics from gas to the particulate phase, and the resulting growth of the particles. Model simulations demonstrated that the growth of nanometer-size nuclei to a CCN size requires the presence of organics of extremely low volatility. These “nonvolatile” organics need to have saturation vapors pressures of the order of 0.01–0.1 parts per trillion or lower and, in order to induce sufficient nuclei growth, must have gas phase production rates of the order of 0.3–1 μg m−3 d−1 under conditions typical for continental background areas. As the nuclei grow in size, they start to uptake volatile organics more efficiently. As a result, organic matter in both the nuclei grown into a CCN size and in the preexisting accumulation mode particles is expected to be dominated by “low-volatile” organics rather than organics that actually are responsible for the nuclei growth. The modeling results suggest that the monoterpene oxidation products identified so far in field or laboratory experiments, although important contributors to secondary particulate matter, are unlikely to be the ones that grow nuclei to a CCN size. In field experiments, positive identification of organics producing new CCN would require information on the chemical composition of particles smaller than about 0.1 μm in diameter, which is the size range where nonvolatile organics are likely to be enriched compared with other secondary or primary organics. Since the gas phase production rate of nonvolatile organics needs not to be very large in order to induce significant nuclei growth, more attention should also be paid to reaction products that have minor yields in smog chamber experiments.

Correction of the Calibration of the 3-wavelength Particle Soot Absorption Photometer (3λ PSAP)

During the Reno Aerosol Optics Study (RAOS) in June 2002, the prototype of the 3-wavelength Particle Soot Absorption Photometer (3λ PSAP) was calibrated and a correction scheme was subsequently published (Virkkula, A., Ahlquist, N. C., Covert, D. S., Arnott, W. P., Sheridan, P. J., Quinn, P. K., and Coffman, D. J. (2005). Modification, Calibration and a Field Test of an Instrument for Measuring Light Absorption by Particles. Aerosol. Sci. Technol., 39:68–83). Unfortunately, the 3 λ PSAP flow rate had not been corrected during that analysis. The factors in the transmittance correction change after reanalysis with flow-corrected data. Reanalysis of the data also resolves an apparent discrepancy between the 1 λ PSAP and the 3 λ PSAP, and the two instruments now agree well.