First Advisor

Dean B. Atkinson

Date of Publication

1-1-2012

Document Type

Dissertation

Degree Name

Doctor of Philosophy (Ph.D.) in Environmental Sciences and Resources: Chemistry

Department

Environmental Sciences and Resources

Language

English

Subjects

Relative humidity, NephCam, CCD, Atmospheric aerosols -- Optical properties, Atmospheric aerosols -- Measurement, Greenhouse gases -- Measurement, Climatic changes -- Detection

DOI

10.15760/etd.907

Physical Description

1 online resource (xiii, 181 pages)

Abstract

A Nephelometry camera (NephCam) and Humidity Controlled Cavity Ring-Down Transmissometer (HC-CRDT) were developed for the determination of aerosol optical properties. The NephCams use a reciprocal geometry relative to an integrating nephelometer; a diode laser illuminates a scattering volume orthogonal to a charge coupled device (CCD). The use of a CCD allows for measurement of aerosol scattering in 2 dimensions; scattering coefficients and size information can be extracted. The NephCam's optics were characterized during a set of imaging experiments to optimize the images collected by the camera. An aperture setting of 1.6 was chosen because it allowed for the most light intensity to reach the CCD - albeit with significant vignetting - and also had a constant modular transfer function (MTF) across the image; approximately 0.3. While this MTF value is approaching the minimum usable MTF of 0.2, other aperture settings did not exhibit constant MTF. While the effects of vignetting can be corrected in image post processing, the effects of non-constant MTF cannot. An optical response model was constructed to simulate images collected by the NephCams as a function of particle type and size. Good agreement between modeled and measured images was observed after the effects of contrast on image shape were considered. The image shapes generated by the model also pointed towards the use of polynomial calibration for particle sizes less than 400 nm as a result of multiple charge-to-size effects present from the sizing mechanism of the differential mobility analyzer. Initial calibration of the NephCams using size-selected dry Ammonium sulfate (AS) showed that calibration slopes are a function of particle size which is also in agreement with the model. Calibration slopes decreased as particle size increased to 400 nm; after 400 nm calibration slope oscillated around a common value. This effect is directly related to the forward shift of scattered intensity as particles grow in size and the collection efficiency of the NephCam as particle size increases. The single scattering albedo (SSA) of Nigrosin was calculated using the NephCam; extinction was measured by the HC-CRDT. Good agreement between the SSA and size was noticed for larger particle sizes; particles smaller than 200 nm in diameter over-measured the SSA of Nigrosin because of the multiple charge-to-size effect. In this size regime, light scattering by particles increases much more quickly than absorption; the presence of larger particles causes scattering to be artificially high. The HC-CRDT is a 4 channel, 3 wavelength instrument capable of measuring the extinction coefficients of aerosols at high (> 80%), low (< 10%) and ambient relative humidity. Extinction coefficients as a function of RH were determined for AS, NaNO3, NaCl, and Nigrosin; these particles represent surrogates of the strongly scattering ionic salts and black carbon, respectively. A model was developed to calculate the changes in refractive index and extinction coefficients of these water soluble particles as a function of RH; these particle types were chosen because core-shell morphologies could be avoided. Volume mixing, Maxwell-Garnett and partial molar refraction mixing rules were used to calculate effective refractive indices as a function of water uptake. Particle growth was calculated based upon the Kelvin equation. Measured and modeled results of f(RH) - relative change in extinction between high or ambient RH and dry RH - agree well for all particle types except Nigrosin. This disagreement is thought to stem directly from an incomplete parameter set for Nigrosin; growth parameters were assumed to be identical to NaNO3, density assumed to be 1 g/mL and molecular weight 202 g/mole, which may not be true in reality (different suppliers of Nigrosin quote different molecular weights). The NephCam was not used during these experiments, so the addition of a scattering measurement to better characterize the growth by Nigrosin is necessary. The f(RH) data for NaNO3 showed excellent agreement between measured and modeled data; however particle size information collected by an SMPS does not agree with the theory. This stems from the fact that NaNO3 does not show prompt deliquescence upon drying; instead an amorphous solid forms which exhibits a kinetically limited loss of water.

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Comments

Portland State University. Dept. of Environmental Science and Management

Persistent Identifier

http://archives.pdx.edu/ds/psu/7987

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