David S. Covert

Performance Characteristics of a High-Sensitivity, Three-Wavelength, Total Scatter/Backscatter Nephelometer

Abstract As designed in the 1940s by Beuttell and Brewer, the integrating nephelometer offers a direct method of measuring light scattering by airborne particles without assumptions about particle composition, shape, or physical state. A large number of such instruments have been deployed; however, only a limited number of validation experiments have been attempted. This paper reports a set of closure experiments in which a gas-calibrated nephelometer is used to measure the scattering coefficient of laboratory-generated particles of known size and refractive index. Specifically, it evaluates the performance of a high-sensitivity, three-wavelength, total scatter/backscatter integrating nephelometer (TSI, Inc., model 3563). Sources of uncertainty associated with the gas-calibration procedure, with photon-counting statistics, and with nonidealities in wavelength and angular sensitivity are investigated. Tests with particle-free gases indicate that noise levels are well predicted by photon-counting statistics...

Size distributions and mixtures of dust and black carbon aerosol in Asian outflow: Physiochemistry and optical properties

[1] During Transport and Chemical Evolution over the Pacific (TRACE-P) and Asian Aerosol Characterization Experiment (ACE-Asia) we measured the dry size distribution of Asian aerosols, their state of mixing, and the optical properties of dust, black carbon (BC) and other aerosol constituents in combustion and/or dust plumes. Optical particle sizing in association with thermal heating extracted volatile components and resolved sizes for dust and refractory soot that usually dominated light absorption. BC was internally mixed with volatile aerosol in � 85% of accumulation mode particles and constituted � 5–15% of their mass. These optically effective sizes constrained the soot and dust size distributions and the imaginary part of the dust refractive index, k, to 0.0006 ± 0.0001. This implies a single-scatter albedo, v (550 nm), for dust ranging from 0.99+ for Dp <1 m mt o� 0.90 at Dp =1 0mm and a size-integrated campaign average near 0.97 ± 0.01. The typical mass scattering efficiency for the dust was � 0.3 m 2 g � 1 , and the mass absorption efficiency (MAE) was 0.009 m 2 g � 1 . Less dust south of 25� N and stronger biomass burning signatures resulted in lower values for v of � 0.82 in plumes aloft. Chemically inferred elemental carbon was moderately correlated with BC light absorption (R 2 = 0.40), while refractory soot volume between 0.1 and 0.5 mm was highly correlated (R 2 = 0.79) with absorption. However, both approaches yield an MAE for BC mixtures of � 7±2m 2 g � 1 and higher than calculated MAE values for BC of 5 m 2 g � 1 . The increase in the mass fraction of soot and BC in pollution aerosol in the presence of elevated dust appears to be due to uptake of the volatile components onto the coarse dust. This predictably lowered v for the accumulation mode from 0.84 in typical pollution to � 0.74 in high-dust events. A chemical transport model revealed good agreement between model and observed BC absorption for most of SE Asia and in biomass plumes but underestimated BC for combustion sources north of 25� N by a factor of � 3. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0350 Atmospheric Composition and Structure: Pressure, density, and temperature; 0360 Atmospheric Composition and Structure: Transmission and scattering of radiation; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0368 Atmospheric Composition and Structure: Troposphere— constituent transport and chemistry; KEYWORDS: dust, black carbon, absorption, single scatter albedo

Optical characteristics of atmospheric aerosols

Techniques have been developed to make point measurements of particle size, chemical nature, scattering and absorption extinction coefficients. These measurements have been shown to be sufficient to describe the optical or visual effects of trace materials in urban or rural air. These techniques and methods of analysis are described in this document. Conclusions include: scattering extinction and fine particle mass, absorption extinction and graphitic carbon are highly correlated. SO2−4 is usually the dominant scattering species and it occurs both in acid and neutral salt (with NH+4) forms. The role of organic carbon, especially in rural atmospheres appears small.

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.

Design and Calibration of a Counterflow Virtual Impactor for Sampling of Atmospheric Fog and Cloud Droplets

An instrument is described that samples cloud droplets by removing them from the surrounding air and small unactivated particles through inertial impaction. The sampled droplets are then evaporated, leaving behind the material dissolved or suspended in the droplets as residue particles or gases. The instrument is capable of sampling droplets as a function of their size; it has an adjustable cut size in the range between about 9 and 30 μm in diameter, rejects droplets and particles smaller than the cut size, and captures droplets larger than the cut size. Details of the instrumental design and construction are discussed, as well as a relative calibration of the collection efficiency. Results from the calibration experiments indicate that the counterflow virtual impactor probe behaves in accordance with theoretical predictions using Stokes number calculations. A complete description of the calibration methodology is presented.

Comparison of methods for deriving aerosol asymmetry parameter

Received 21 December 2004; revised 19 March 2005; accepted 7 June 2005; published 21 January 2006. [1] Values for Mie-equivalent aerosol asymmetry parameter (g) were derived using a variety of methods from the large suite of measurements (in situ and remote from surface and aircraft) made in Oklahoma during the 2003 aerosol Intensive Operations Period (IOP). Median values derived for dry asymmetry parameter at 550 nm ranged between 0.55 and 0.63 over all instruments and for all derivation methods, with the exception of one instrument which did not measure over the full size range of optically important aerosol. Median values for the ‘‘wet’’ asymmetry parameter (i.e., asymmetry parameter at humidity conditions closer to ambient) were between 0.59 and 0.72. Values for g derived for surface and airborne in situ measurements were highly correlated, but in situ and remote sensing measurements both at the surface and aloft did not agree as well because of vertical inhomogeneity of the aerosol. Radiative forcing calculations suggest that a 10% decrease in g would result in a 19% reduction in top of atmosphere radiative forcing for the conditions observed during the IOP. Comparison of the different methods for deriving g suggests that in computing the asymmetry parameter, aerosol size is the most important parameter to measure; composition is less important except for how it influences the hygroscopic growth (i.e., size) of particles.

Processes controlling the distribution of aerosol particles in the lower marine boundary layer during the First Aerosol Characterization Experiment (ACE 1)

The goals of the International Global Atmospheric Chemistry (IGAC) Programs First Aerosol Characterization Experiment (ACE 1) are to determine and understand the properties and controlling factors of the aerosol in the remote marine atmosphere that are relevant to radiative forcing and climate. A key question in terms of this goal and the overall biogeochemical sulfur cycle is what factors control the formation, growth, and evolution of particles in the marine boundary layer (MBL). To address this question, simultaneous measurements of dimethylsulfide (DMS), sulfur dioxide (SO2), the aerosol chemical mass size distribution, and the aerosol number size distribution from 5 to 10,000 nm diameter were made on the National Oceanic and Atmospheric Administration (NOAA) ship Discoverer. From these data we conclude that the background MBL aerosol during ACE 1 often was composed of four distinct modes: an ultrafine (UF) mode (Dp = 5–20 nm), an Aitken mode (Dp = 20–80 nm), an accumulation mode (Dp = 80–300 nm), and a coarse mode (Dp > 300 nm). The presence of UF mode particles in the MBL could be explained by convective mixing between the free troposphere (FT) and the MBL associated with cloud pumping and subsidence following cold frontal passages. There was no evidence of major new particle production in the MBL. Oceanic emissions of DMS appeared to contribute to the growth of Aitken and accumulation mode particles. Coarse mode particles were comprised primarily of sea salt. Although these particles result from turbulence at the air-sea interface, the instantaneous wind speed accounted for only one third of the variance in the coarse mode number concentration in this region.

Measurements of chloride depletion and sulfur enrichment in individual sea-salt particles collected from the remote marine boundary layer

Changes in the elemental ratios of Cl/Na and S/Na in sea-salt particles are expected from the atmospheric reactions of sulfuric and nitric acids with these particles. Chloride depletion is expected to occur upon the liberation of HCl to the gas phase, with the particles remaining enriched in sulfate or nitrate. The elemental ratios of Ca/Na, Mg/Na and K/Na should remain constant during this process. Analysis of chloride depletion and sulfur enrichment was obtained for individual sodium-containing particles from the remote marine Pacific atmosphere in both the accumulation mode (0.06 ≤ Dp ≤ 1.0 μm, where Dp is the particle diameter) and the coarse mode (Dp > 1.0 μm) size range. Sodium-containing particles comprised close to 100% of the coarse mode and 11 to 31% of the accumulation mode by number. Aerosols were collected with a low-perssure impactor and examined with a transmission electron microscope (TEM) coupled with an energy-dispersive X ray (EDX) detector. The elemental ratios obtained from the atmospheric particles were determined by comparison with values obtained from laboratory-generated sea-salt, sodium chloride, and sodium sulfate particles of known size and chemical composition, which served as a calibration set. The elemental ratios of Ca/Na, Mg/Na, and K/Na were found to remain fairly constant between individual sea-salt particles of various sizes for more than 85% of the particles examined. Deviations in the ratio of Cl/Na and S/Na from that of reference seawater values were observed most commonly for the submicrometer sea-salt aerosol. The Cl/Na ratio was significantly (Students t test, 99.9%) lower than that of reference seawater for 89% of the particles examined, while the S/Na ratios were higher for 100% of the particles. The Cl/Na ratio measured in 48% of the coarse sea-salt particles (1.0 < Dp ≤ 2.5 μm) reflected the ratio in bulk seawater, while the remaining particles had statistically lower ratios and qualitatively different morphologies. All but 3% of these coarse particles had enhanced S/Na ratios over that of bulk seawater. Estimates of non-sea-salt (nss) sulfate mass ranged from 216 to 1422 fg for particles of 0.50 μm in diameter to 861 and 5235 fg for particles of 0.80 μm in diameter, corresponding to 74 to 96% of the sea-salt particle mass. These values are compared with the recent measurements of Mouri and Okada [1993] as well as predictions from the atmospheric chemistry models of in-cloud sulfate production of Hegg et al., [1992] and estimations of S(IV) oxidation in sea-salt aerosol water by Chameides and Stelson [1992].

Hygroscopic properties of aerosol particles in the north-eastern Atlantic during ACE-2

Measurements of the hygroscopic properties of sub-micrometer atmospheric aerosol particles were performed with hygroscopic tandem differential mobility analysers (H-TDMA) at 5 sites in the subtropical north-eastern Atlantic during the second Aerosol Characterization Experiment (ACE-2) from 16 June to 25 July 1997. Four of the sites were in the marine boundary layer and one was, at least occasionally, in the lower free troposphere. The hygroscopic diameter growth factors of individual aerosol particles in the dry particle diameter range 10−440 nm were generally measured for changes in relative humidity (RH) from <10% to 90%. In the marine boundary layer, growth factors at 90% RH were dependent on location, air mass type and particle size. The data was dominated by a unimodal growth distribution of more-hygroscopic particles, although a bimodal growth distribution including less-hygroscopic particles was observed at times, most often in the more polluted air masses. In clean marine air masses the more-hygroscopic growth factors ranged from about 1.6 to 1.8 with a consistent increase in growth factor with increasing particle size. There was also a tendency toward higher growth factors as sodium to sulphate molar ratio increased with increasing sea-salt contribution at higher wind speeds. During outbreaks of European pollution in the ACE-2 region, the growth factors of the largest particles were reduced, but only slightly. Growth factors at all sizes in both clean and polluted air masses were markedly lower at the Sagres, Portugal site due to more proximate continental influences. The frequency of occurrence of less-hygroscopic particles with a growth factor of ca. 1.15 was greatest during polluted conditions at Sagres. The free tropospheric 50 nm particles were predominately less-hygroscopic, with an intermediate growth factor of 1.4, but more-hygroscopic particles with growth factors of about 1.6 were also frequent. While these particles probably originate from within the marine boundary layer, the less-hygroscopic particles are probably more characteristic of lower free tropospheric air masses. For those occasions when measurements were made at 90% and an intermediate 60% or 70% RH, the growth factor G(RH) of the more-hygroscopic particles could be modelled empirically by a power law expression. For the ubiquitous more-hygroscopic particles, the expressions G(RH)=(1-RH/100)-0.210 for 50 nm Aitken mode particles and G(RH)=(1-RH/100)-0.233 for 166 nm accumulation mode particles are recommended for clean marine air masses in the north-eastern Atlantic within the range 0