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The chemical and optical properties of particulate organic compounds remain unclear, which leaves large uncertainties in the estimation of global radiative transfer balance. Gas and find particle (PM2.5) phase formic acid concentrations were measured with online instrumentation during separate one-month studies in the summer of 2010 in Los Angeles (LA), CA, and Atlanta, GA, and the gas-particle partitioning behavior was investigated and compared with that of water-soluble organic compounds (WSOC). The diurnal profiles clearly indicated that the photochemistry production serves as a strong source for the formation of organics, while the correlation between the gas and particle phase suggested that another partitioning route, the aqueous reactions, is also very important. Later, the optical properties of light-absorbing organic compounds were examined. Little is known about the optical importance of light absorbing particulate organic compounds (brown carbon), especially its extent and absorption relative to black carbon throughout the tropospheric column. Mie theory was applied to size-resolved spectrophotometric absorption measurements of methanol and water-extracts from cascade impactor substrates collected at three surface sites around Atlanta, GA, including both urban and rural. These results were applied to similar measurements of brown carbon in extracts from aircraft bulk filter samples collected over central USA. At the surface sites predicted light absorption by brown carbon relative to total absorption (brown carbon plus pure black carbon) was about 10% and 30% at 350 nm, versus 1 and 11% at 450 nm, for water and methanol extracts, respectively. The relative contribution of brown carbon was greater in the free troposphere and significantly increased with altitude. Although this approach has limitations, it demonstrates the ubiquity and significant potential contribution of brown carbon.

A particle counting instrument, the Coherent Optical Particle Spectrometer (COPS) has been developed for measuring particles in aerosol systems. It optically counts and sizes single particles one at a time as they pass through an optically defined inspection region so particle size distributions can be directly measured. COPS uses the coherent nature of light available in a laser beam to measure the phase shift in the scattered light, which is fundamentally different from previous intensity based techniques. The Van-Cittert-Zernike theorem shows that scattered light from small particles will be coherent if viewed upon at the focal point of a gathering lens. Optical homodyne detection can then be used to measure the extent of the phase shift due to the particle. Scattering mechanisms can relate the phase shift to particle diameter so particle size can be determined. An optical inspection region is given by the resolution limited blur spot diameter and depth of focus of the gathering lens. Particles scattering outside this zone will not contribute to measured phase signals. Calculations show that COPS can count in concentrations of 10('9) particles per cubic centimeter with 5% coincidence error. Mie scattering calculations, coupled with homodyne theory, predict a minimum detectable particle diameter ranging from 0.03 to 0.3 micrometers, depending on optical configuration. Theory shows that small, strongly absorbing particles impart a much larger phase shift than refractive particles so a lower detection limit is predicted for particles such as soot and silicon. Particles above one micrometer show classic resonance typical of Mie calculations. An experimental COPS system verified the predicted results from the model. Resolution of particle size ranged from 25 to 60 percent of particle diameter. Preliminary experiments showed that COPS has in situ sampling possibilities and will work for liquid systems as well. Coherent detection of scattered light shows promise for in situ measurement of submicrometer aerosols in high particle laden streams with maximum sensitivity for strongly absorbing particles.

MSc., Faculty of Science, University of the Witwatersrand, 2011 / Atmospheric aerosols have direct and indirect impacts on the earth’s radiation budget and the radiative forcing on the climate system. A large uncertainty exists regarding aerosols and the effect they have on the earth’s radiation budget and global change. The distribution, concentration and types of aerosols are therefore of great importance regarding global warming and climate change. The purpose of this study is to present the atmospheric aerosol characteristics found over the South Atlantic, Southern Ocean and Antarctic continent as well as identify their origin. The aerosol optical properties over the South Atlantic and Southern Ocean region is analysed during the South African National Antarctic Expedition 2007/2008 (SANAE 47) take over cruise on board the M/V S.A. Agulhas. Very low aerosol optical thickness (AOT) values were obtained for the Antarctic Coastal region with a mean AOT500nm of 0.03 and a mean Angstrom exponent of 1.78. The South Atlantic region showed a mean AOT500nm of 0.06 and a mean Angstrom exponent of 0.72. AOT values for the South African coastal region had a mean AOT500nm of 0.07 and a mean Angstrom exponent of 0.76. Data comparisons confirm that the data acquired during the study are consistent with previous research from the study region. Comparisons were made between the dataset and the MODIS satellite aerosol product. A discrepancy was shown to exist between the MODIS aerosol product and the acquired dataset using the Microtops II Sunphotometer. Both MODIS TERRA and AQUA overestimate AOT at 550nm.

Scientists have been observing a change in the climate since the beginning of the 20th century that cannot be attributed to any of the natural influences of the past. Natural and anthropogenic substances and processes perturb the Earth's energy budget, contributing to climate change. In particular, aerosols (particles suspended in air) have long been recognized to be important in processes throughout the atmosphere that affect climate. They directly influence the radiative balance of the Earth's atmosphere, affect cloud formation and properties, and are also key air pollutants that contribute to a variety of respiratory and cardiovascular diseases. Despite their importance, aerosol particles are less well-characterized than greenhouse gases with respect to their sources, temporal and spatial concentration distribution, and physical and chemical properties. This uncertainty is mainly caused by the variable and insufficiently understood sources, formation and transformation processes, and complex composition of atmospheric particles. Instruments that can precisely and accurately measure and characterize the aerosol physical and chemical properties are in great demand. Atmospheric relative humidity (RH) has a crucial impact on the particles' optical properties; the RH dependence of the particle extinction coefficient is an important parameter for radiative forcing and thus climate change modeling. In this work a Humidity-Controlled Cavity Ring-Down (HC-CRD) aerosol optical instrument is described and its ability to measure RH dependent extinction coefficients and related hygroscopicity parameters is characterized. The HC-CRD is capable of simultaneously measuring the aerosol extinction coefficient at three wavelengths (λ = 355, 532, and 1064 nm) and three different RHs (typically 20%, 50%, and 80%). A range of chemicals and their mixtures were used to produce laboratory generated aerosols. Three mixture systems include one inorganic salts mixture system consisting of (NH4)2SO4, NH4HSO4, Na2SO4, NaHSO4 serve as surrogates of the ionic salts found in the atmosphere. Two organic mixture systems were investigated: mixtures of NaCl, D-glucose, sucrose, and glycine are benchmarks for compounds emitted from biomass burning. Finally, mixtures of (NH4)2SO4 (ammonium sulfate, AS) with a series of dicarboxylic acids including malonic acid, adipic acid, and azelaic acid are used as benchmarks to mimic urban pollutants. The extinction coefficients were obtained as a function of RH from the HC-CRD measurements, from which optical growth factors f(RH) and γ(RH) values can be determined to examine their dependence on chemical composition. A volume mixing rule was used to calculate the effective refractive index of the binary substrate mixtures, since both size and composition change during water uptake. The SDA/FMC algorithm developed by O'Neill, et al. 2005 is used to extract the van de Hulst phase shift parameter (Ρeff) from three-wavelength measurements of extinction. The fine mode fraction of extinction (η) and fine mode effective radius (Reff) of laboratory generated aerosol particles can be then determined. An iterative algorithm was developed to retrieve the change in refractive index of particles as function of RH. The calculated Reff of aerosols at different RHs were used to obtain the physical size growth factor (gf), and κ(RH). The size changes as a function of water uptake describe the dependence of aerosol optical properties on chemical composition. This work demonstrates the capability of conducting aerosol optical measurements using HC-CRD to determine the RH dependence of aerosol optical properties. The HC-CRD measurements combined with the SDA/FMC method to retrieve aerosol size for laboratory generated aerosols establish the connection between the optical properties and the aerosol particles' chemical compositions. It also underlines the importance and need for future investigation on the hygroscopic properties of atmospheric aerosols. This work is successfully developed a method that enables using the aerosols optical measurements to predict the compositions; it will greatly contribute to the atmospheric aerosol measurement and global climate modelling.

The Indian Ocean Experiment (INDOEX) had as a primary objective determining the radiative forcing due to anthropogenic aerosols over climatologically significant space and time scales: the Indian Ocean during the winter monsoon, January-March. During the winter monsoon, polluted, low-level air from the Asian subcontinent blows over the Arabian Sea and Indian Ocean. As part of INDOEX, aerosol optical depths were derived from Advanced Very High Resolution Radiometer (AVHRR) data for the cloud-free ocean regions. The AVHRR radiances were first calibrated using the interior zone of the Antarctic and Greenland ice sheets, which proved to be radiometrically stable calibration targets. Optical depths were derived by matching the observed radiances to radiances calculated for a wide range of optical depths and viewing geometry. Optical depths derived with the AVHRR were compared with those derived with NASA's Aerosol Robotic Network (AERONET) CIMEL instrument at the Center for Clouds, Chemistry, and Climate's Kaashidhoo Observatory, as well as with other surface and shipboard observations taken in the INDOEX region. The retrieved and surface-based optical depths agreed best for a new 2-channel, 2- aerosol model scheme in which the AVHRR observations at O·64 and O·84 microns were used to determine relative amounts of marine and polluted continental aerosol and then the resulting aerosol mixture was used to derive the optical depths. Broadband radiative transfer calculations for the mixture of marine and polluted continental aerosols were combined with the 0·64 and 0·84-micron AVHRR radiances to determine the radiative forcing due to aerosols in the INDOEX region. Monthly composites of aerosol optical depth and top of the atmosphere, surface, and atmospheric radiative forcing were derived from calibrated AVHRR radiances for January-March 1996-2000. An inter-annual variability in the magnitude and spatial extent of high value regions is noted for derived optical depths and radiative forcing, with highest values reached in 1999, particularly in the Bay of Bengal which during the IFP was covered by plumes from Indochina. Frequency distributions of the optical depth for 1⁰ x 1⁰ latitude-longitude regions are well represented by gamma distribution functions. The day-to-day and year-to-year variability of the optical depth for such regions is correlated with the long term average optical depth. Interannual variability of the monthly mean optical depths for such regions is found to be as large as the day to day. / Graduation date: 2001

Black carbon (BC) is the light-absorbing component of soot, a combustion-generated aerosol that warms the climate by absorbing solar radiation. Its impacts on climate depend on its microphysical properties, which are modified by atmospheric processes including condensation, coagulation and wet removal. State of the art climate models consider soot in a concentric core/shell configuration, with a BC core coated by nonrefractory material such as organics or sulphate. Within this model, thicker coatings enhance visible light absorption, but also wet removal efficiency, and these have opposing effects on the total amount of light absorbed over BC’s lifetime. How well the core/shell model can calculate Mass Absorption Coefficient (MAC, the ratio of absorption to BC mass) is uncertain, as real soot forms more complex (often fractal) shapes, and detailed optical models using these morphologies predict the core/shell model may under- or over-estimate MAC depending on the precise properties of the particles. Few reliable measurements of variations in ambient MAC are available, as most older measurement techniques suffer from systematic uncertainties. In this work, a Single Particle Soot Photometer (SP2) and PhotoAcoustic Soot Spectrometer (PASS) were used to measure BC mass concentration and absorption, and these instruments do not suffer from such uncertainties. The SP2 was also used to report core size and coating thickness distributions that are required to test state of the art climate models. Firstly, a method was developed to minimise bias in the measured coating thicknesses related to the limited detection range of the SP2. The sensitivity of this technique to the assumed density and refractive index of the BC core was also explored, and the most appropriate parameters to use with ambient measurements were determined. Core and shell distributions were measured in Pasadena, California under a range of different photochemical ages. These were then used to calculate MAC, which was compared to that measured using the SP2 and PASS. The measured and modelled MAC agreed within 10% at 532 nm, though this was dependent on the assumed refractive index of the BC core. Overall MAC increased by 15 –25% in around one third of a day of photochemical ageing. This is quite modest compared to some climate models, but not compared to the previous best estimate, which predicted MAC may increase by a factor of ~1.5 over BC’s lifetime. Core and coating distributions were also measured in Canadian boreal biomass burning plumes. A case study was presented comparing the properties of BC in three plumes, one of which had passed through a precipitating cloud. It was demonstrated that larger and more coated BC-containing particles were removed more efficiently, in agreement with previous thermodynamic theory. By calculating MAC using the measured core/shell distributions and comparing to measured scattering, it was demonstrated that the MAC and single-scattering albedo in the plumes were likely not significantly affected by the wet removal, as greater differences were observed between the two plumes not affected by precipitation.

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.

Aerosol are solid or liquid particles suspended in the atmosphere ranging in size from 10 3 to 102 m. Aerosol influence both the regional and global climate of the earth by its direct and indirect effect. Role of atmospheric aerosols on the radiative forcing of atmosphere is a matter of serious research for past few decades and still it remains highly uncertain as acknowledged by Intergovernmental Panel on Climate Change. Heterogeneous nature of aerosol both spatially and temporally makes it more complex in estimating radiative forcing compared to that of greenhouse gases. Compounding to the existing difficulty in determining the climate effects, changing aerosol concentration and nature of the aerosol further increases the complexity in determining its effects in both regional and global climate. Increasing aerosol loading is emerging to be an issue of major concern over several regions. The first step towards achieving this goal is by determining the trends in the physical and optical properties of aerosol over the globe. Main objective of the thesis is the determination of the recent trends in aerosol loading over the globe and then to focus specifically on the properties of aerosol over an urban site in southern India. Specific objectives are (a) to determine the trend in aerosol physical and optical properties over the globe using AERONET surface observations (b) to characterize the chemical properties of water soluble inorganic aerosol over an urban site in Southern India, Bangalore (c) to have a better estimation of aerosol radiative forcing over Bangalore with measured aerosol chemical concentration, black carbon concentration and aerosol optical depth (AOD). To quantify the recent trends in aerosol loading over the globe, we have used the surface observations from AERONET and the study provided the first step in giving a global picture of the recent trends in the fundamental optical and physical property of aerosol. Trend analysis showed a significant spatial inhomogenity, and Asian continent clearly showed an increasing trend in AOD compared to other continents. Solar village (24.9oN, 46.4oE) of Saudi Arabia showed a maximum with a value of 0.04/yr and Bac -Giang (21oN, 106oE) of Vietnam showed the minimum value of -0.04/yr. North American study region included 18 sites in which eastern US (E.US) exhibited a decreasing trend while the scenario in western US (W.US) is different with more of sites with increasing AOD trend. Single scattering albedo (SSA) trend in W. US showed a decreasing trend irrespective of the AOD trend. Study sites in South America include Cordoba -CETT (31.5oNS, 64.5 oN W) Alta Floresta (9.8oS, 56.1 o W), Riobranco (9.9oNS, 67.8o W) and Soa Poulo (23.5oS, 46.7o W).Except Riobranco which has a positive trend in AOD, all other sites exhibited a statistically signi cant negative trend. Over Australia, there is an inclination towards increasing AOD in sites and all the three sites in Australia exhibit a statistically significant increasing trend in SSA. According to the recent trends in AOD over African region, there exists a significant decrease in AOD compared to that reported for few years earlier, showing the high temporal in homogeneity and need for continuous observation of aerosol over the regions. European study region included 15 stations, among them only 3 sites showed an increasing trend in AOD, remaining 12 sites showed a significant decreasing trend in aerosol loading over the period of study. SSA was also observed to be decreasing over most of the European sites, even with a decreasing AOD over most of the sites. A Comparison study carried out to determine the relation of population growth rate and aerosol loading, and it revealed that the increasing AOD trend not always coincided with the sites having high population growth rate. Having determined the trends in AOD and other aerosol parameters over the globe and seeing an alarmingly increasing trend over most of the Asian sites, especially over Indian region, we have then focused over work on the aerosol properties of one of the rapidly growing urban location in southern India, Bangalore. While physical properties of aerosol have been extensively studied over Bangalore, chemical characteristics are still an unexplored area. Extensive information on aerosol chemical composition is not available over Indian region except for a few locations based on campaign mode. Even available data is of very coarse temporal resolution, since hours or full day sampling is needed to gather enough samples for chemical analysis. High temporal resolution data of aerosol chemical characteristics, especially for all season is completely lacking over Indian subcontinent. Among aerosol, water soluble aerosol form an important component in particulate matter, since it can change its size, composition, can easily mix with other aerosols and can act as cloud condensation nuclei, based on its hygroscopic nature. Present study provided the rst time results from a high temporal resolution water soluble inorganic aerosol chemical data over Indian region, which is first step towards estimating aerosol climate impacts more accurately. Water soluble inorganic aerosol ions over Bangalore namely, sulphate, nitrate, chloride, potassium, calcium, magnesium, sodium and ammonium are measured using Particle Into Liquid Sampler Ion Chromatograph (PILS-IC). PILS is an online sampling technique for quantitatively measuring the chemical concentration of ion in water soluble aerosol particles. PILS IC used in the present study is developed in Georgia Institute of Technology. Instrument samples ambient air at a flow rate of 16.7Lmin 1. Particles below PM 2.5 micron are collected for the analysis using cyclone impactor. Two annular glass denuders are used to remove inorganic gases which else will interfere with the aerosol ion concentration. Ambient air which is deprived of the inorganic gases is then mixed with steam vapours at 150oC, eventually high supersaturated atmosphere is produced with rapid adiabatic mixing of steam and ambient air. High supersaturated air allows droplets to grow enough to be collected by inertial impaction onto a quartz impactor plate. Entire PILS condensation unit is kept at a slight tilt of 15o, to remove all condensate through drain tube connected to the end of the PILS condensate body. Condensed liquid sample is collected from the impaction chamber and known concentration LiF is allowed to mix with the collected sample at a constant rate. LiF known as carrier liquid is added to know the dilution occurring to the collected sample. Sample with carrier liquid is then collected to a debubbler and is supplied to the IC through peristaltic tubings for determining the ion chemical concentration. Seasonal variation of mass concentration of water soluble aerosol species and the influence of long range transport is carried out using HYSPILT back trajectory analysis. Marine air mass from Arabian Sea dominated the air parcel reaching the site for both SW monsoon and summer. Continental air mass dominated the site during both NE monsoon and winter with slight contribution from marine atmosphere. Source characteristics of sulphate, potassium, calcium and magnesium ions are carried out based on sea salt (ss) and non sea salt (nss) origin and it is observed that the nss contribution is dominant over the site for all these ions except magnesium where ss component comparatively dominates the source. SO24 and NO3 form the dominant anions while NH+4 makes the dominant cation species. Monthly variation of the ratio of ammonium to nss -sulphate is carried out to determine the possible cation -anion relation existing between these two major ions. During later winter and summer months ammonium bi sulphate is found to be the existing chemical form and ammonium sulphate during other seasons. High temporal resolution data enabled us to study the diurnal variation of aerosol ions and it is influenced by various mechanisms from boundary layer to local emissions. Optical properties of aerosols depend upon the size and the relative abun-dance of each components. It is usual practice to assume default aerosol chemical composition in radiative transfer models due to unavailability of data, which can lead to errors in forcing estimates. Incorporating realistic aerosol chemical composition in models is essential to reduce the uncertainty in aerosol radiative forcing. Hence we have included measured aerosol chemical compositions, black carbon and AOD to improve the determination of radiative forcing of aerosol. OPAC and SBDART models were used for estimating the aerosol radiative forcing over Bangalore. We have used mainly four components namely, soot, water soluble, sea salt and dust. Except dust all are other components are measured over the site and formed a constrain for the calculation. Dust concentration was altered so that the OPAC AOD matched the measured AOD within 5%. Mineral dust shows the highest contribution in AOD among the four components, however water soluble and soot even being less is mass concentration compared to mineral dust, has significant impact on the AOD. This clearly indicate the influence of both water soluble and soot aerosol over the regional climate of the site. Sea Salt exhibited low AOD compared to other three constituents. The results presented in the thesis highlights the importance of varying trends in the aerosol properties and its effects on a global picture and speci - cally over an urban site in Indian region , we explored the temporal variations of water soluble inorganic aerosol ions and its effects on regional climate. Hence the thesis addressed some of the unexplored areas in aerosol science. This study also suggests the need of continuous observation of aerosol over both spatial and temporal scale, which is essential to estimate their effects on earth's climate.