Bias in Filter-Based Aerosol Light Absorption Measurements Due to Organic Aerosol Loading: Evidence from Ambient Measurements

During the 2006 Texas Air Quality Study/Gulf of Mexico Atmospheric Composition and Climate Study (TexAQS/GoMACCS 2006) a filter-based (Particle Soot Absorption Photometer, or PSAP) and a photoacoustic-based aerosol light absorption technique were deployed and here the data are compared. The level of agreement between the two techniques with ambient aerosol depended on the abundance of organic aerosol (OA), with the ratio of OA to light absorbing carbon (LAC) mass (R _OA?LAC ) of particular importance. When OA mass concentration was low the agreement between the methods was within instrumental uncertainties (PSAP measuring 12% higher), however at high (R _OA?LAC ) (～15–20) the difference in agreement was between 50 and 80%. This difference is similar to the bias observed in the laboratory studies of a companion paper using non-absorbing OA and LAC (Cappa et al. 2008a Cappa, C., Lack, D., Burkholder, J. and Ravishankara, A. 2008a. Bias in Filter-Based Aerosol Light Absorption Measurements Due to Organic Aerosol Loading: Evidence from Laboratory Measurements. Aerosol Sci. Technol, 42: 1022–1033. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]). It was found that most of the OA was oxidized and non-absorbing in nature. We postulate that the observed differences results from a bias in the filter-based measurements due to (a) the redistribution of liquid-like organic particulate matter (PM) around the fiber filters thereby modifying the filter surface and subsequent light scattering, and (b) the possible coating and absorption enhancement of pre-existing absorbing PM (i.e., soot) as OA deposition and redistribution occurs. We stop short or recommending a universal correction using these findings due to the magnitude of the bias showing some dependence on air mass type. Any use of this data for a correction must consider the uncertainties in measuring OA mass concentrations, LAC mass concentrations and type of OA present. The observed PSAP bias may have a significant impact on the accuracy of aerosol single scatter albedo (SSA) and LAC mass concentrations derived from filter-based aerosol absorption methods from regions impacted by large amounts of OA. Although this study was performed using the PSAP we caution users of other filter-based instrumentation to the possibility of a similar bias in those instruments.     

Bias in Filter-Based Aerosol Light Absorption Measurements Due to Organic Aerosol Loading: Evidence from Laboratory Measurements

Light absorption by soot or nigrosin dye aerosol particles were measured in the laboratory using a particle soot absorption photometer (PSAP) and a photo-acoustic spectrometer (PAS) to assess the influence of non-absorbing organic aerosol (OA) on the PSAP measurements. For the PSAP, particle light absorption is measured after collection on a filter, whereas for the PAS light absorption is measured while the particles remain suspended in the gas phase. OA was generated from the reaction of α -pinene with ozone. It was observed that the presence of this OA in an external mixture of absorbing aerosol and OA can cause an increase in the light absorption measured by the PSAP, relative to that measured by the PAS, by more than a factor of two. This enhancement in the PSAP absorption was found to increase as the amount of OA increased relative to the absorbing compound. Additionally, experiments where absorbing aerosol was deposited on a PSAP filter prior to addition of OA demonstrated that the non-absorbing OA can actually appear as if it were absorbing, with measured single scattering albedo values as low as 0.92. These results indicate that filter-based measurement techniques may significantly overestimate light absorption by aerosols in the atmosphere under conditions where the organic loading is large, with consequent implications for understanding and calculating the Earth's radiation budget. These laboratory experiments aid in the interpretation of results from a recent field study, discussed in a companion article (Lack et al. 2008 Lack, D. A., Cappa, C. D., Baynard, T., Massoli, P., Covert, D. S., Sierau, B., Bates, T. S., Quinn, P. K., Lovejoy, E. R. and Ravishankara, A. R. 2008. Bias in Filter-Based Aerosol Absorption Measurements Due to Organic Aerosol Loading: Evidence from Ambient Measurements. Aerosol Sci. and Technol., 42: 1033–1041. [Taylor & Francis Online], [Web of Science ®] , [Google Scholar]).     

An Inter-Comparison of Two Black Carbon Aerosol Instruments and a Semi-Continuous Elemental Carbon Instrument in the Urban Environment

Aerosol absorption coefficients were obtained using two versions of the Magee Scientific Aethalometer and a Particle Soot Absorption Photometer (PSAP) in Riverside, California during July and August of 2005. These measurements were subsequently compared to each other and to hourly elemental carbon (EC) mass concentrations as determined by a Sunset Labs semi-continuous OCEC analyzer. Measurements from all four instruments were shown to be highly correlated (R ² = 0.83 to 0.92). Differences between absorption values measured by the PSAP and the Aethalometer were found to be dominated by differences in the filter media used by the respective instruments. Comparison of optical and thermal measurements revealed that the specific attenuation cross section (σ _ATN ) of light absorbing carbon (LAC) varied as a function of the time of the day, most notably during weekdays. Minimum σ _ATN values were observed during morning rush hour when EC concentrations were at their greatest and maxima were seen in the late afternoon. These variations correlated with changes in the OC/EC ratio and the Angstrom exponent for absorption, which is consistent with changes in the mixing state of elemental carbon associated with secondary aerosol condensation on primary EC particles.     

Secondary Organic Aerosol Coating Formation and Evaporation: Chamber Studies Using Black Carbon Seed Aerosol and the Single-Particle Soot Photometer

We report a protocol for using black carbon (BC) aerosol as the seed for secondary organic aerosol (SOA) formation in an environmental chamber. We employ a single-particle soot photometer (SP2) to probe single-particle SOA coating growth dynamics and find that SOA growth on nonspherical BC aerosol is diffusion-limited. Aerosol composition measurements with an Aerodyne high resolution time-of-flight aerosol mass spectrometer (AMS) confirm that the presence of BC seed does not alter the composition of SOA as compared to self-nucleated SOA or condensed SOA on ammonium sulfate seed. We employ a 3-wavelength photoacoustic soot spectrometer (PASS-3) to measure optical properties of the systems studied, including fullerene soot as the surrogate BC seed, nucleated naphthalene SOA from high-NO_x photooxidation, and nucleated α-pinene SOA from low-NO_x photooxidation. A core-and-shell Mie scattering model of the light absorption enhancement is in good agreement with measured enhancements for both the low- and high-NO_x α-pinene photooxidation systems, reinforcing the assumption of a core-shell morphology for coated BC particles. A discrepancy between measured and modeled absorption enhancement factors in the naphthalene photooxidation system is attributed to the wavelength-dependence of refractive index of the naphthalene SOA. The coating of high-NO_x α-pinene SOA decreases after reaching a peak thickness during irradiation, reflecting a volatility change in the aerosol, as confirmed by the relative magnitudes of f₄₃ and f₄₄ in the AMS spectra. The protocol described here provides a framework by which future studies of SOA optical properties and single-particle growth dynamics may be explored in environmental chambers.

Copyright 2013 American Association for Aerosol Research     

二次有机气溶胶的特征和形成机制

二次有机气溶胶(SOA)的形成是当今大气化学过程的研究热点之一. 城市大气中二次有机碳占颗粒物总有机碳的17%~65%. 单萜烯和芳香族化合物分别是SOA最重要的天然和人为源前体物,在大气中与×OH, NO3-和O3等氧化剂发生多途径反应形成有机酸、多官能团羰基化合物、硝基化合物等半挥发性有机物,通过吸附、吸收等过程进入颗粒相,改变了气溶胶的特性及其环境效应. 有机化合物表现出较强的源特征性,可以作为示踪分子解析颗粒物来源,二元羧酸是SOA的潜在示踪物. 论述了SOA研究的最新进展并指出了未来的研究方向.     

种子气溶胶对甲苯光氧化生成二次有机气溶胶的生长影响

在烟雾腔内进行了羟基自由基启动的甲苯光氧化生成二次有机气溶胶的实验.通过向烟雾腔内添加硫酸铵、硝酸铵、硅酸钠和氯化钙4种不同的种子气溶胶,考察它们对二次有机气溶胶形成的影响.结果表明:种子气溶胶的浓度越低,越有利于二次有机气溶胶的生成;在反应开始阶段,种子气溶胶对二次有机气溶胶的形成起促进作用,随着反应时间的增长,反而起阻止作用:在相同的种子气溶胶浓度下,硅酸钠和硝酸铵对二次有机气溶胶的形成的影响几乎相同;4种种子气溶胶对甲苯氧化生成的二次有机气溶胶的生长影响顺序为:氯化钙》硝酸铵、硅酸钠》硫酸铵.     

Phase State and Deliquescence Hysteresis of Ammonium-Sulfate-Seeded Secondary Organic Aerosol

The phase state of secondary organic aerosol (SOA) has an impact on its lifetime, composition, and its interaction with water. To better understand the effect of phase state of SOA on climate interactions, we studied the SOA phase state and the effect of its history and report here the phase state and the humidity-induced phase hysteresis of multicomponent-seeded SOA particles produced in a large, continuously stirred tank reactor. We determined the phase state of the particles by their bounced fraction impacting on a smooth substrate in a low-pressure impactor. The particles were composed of ammonium sulfate ([NH₄]₂SO₄) seed and a secondary organic matter (SOM) shell formed from oxidized α-pinene or isoprene. The ammonium sulfate (AS) seed dominated the deliquescence of the α-pinene SOM multicomponent particles, whereas their efflorescence was strongly attenuated by the SOM coating. Particles coated with isoprene SOM showed continuous phase transitions with a lesser effect by the AS seed. The results agree with and independently corroborate contemporary research.

Copyright 2015 American Association for Aerosol Research     

甲苯与氯原子光氧化产生二次有机气溶胶粒子实时探测研究

在烟雾腔内,用紫外光照射甲苯、氯气、一氧化氮和空气的混合物,启动甲苯和氯原子的光氧化反应和一系列的后续反应,产生非挥发性和半挥发性有机化合物.半挥发性有机化合物可以在气态和粒子态之间进行分配,产生二次有机气溶胶粒子.用实验室自制的气溶胶飞行时间质谱仪实时测量这些粒子产物的分子成分和粒径分布,并初步探讨了这些组分的可能反应机理.     

Interpretation of Secondary Organic Aerosol Formation from Diesel Exhaust Photooxidation in an Environmental Chamber

Secondary organic aerosol (SOA) formation from diesel exhaust was investigated using an environmental chamber. Particle volume measurement based solely on mobility diameter underestimated the SOA formation from diesel exhaust due to the external void space of agglomerate particles. Therefore, particle mass concentration and fractal-like dimension was determined from the particle effective density as a function of particle mass using an aerosol particle mass analyzer and scanning mobility particle sizer (APM–SMPS). Continuous aging of aerosol measured by an increase of atomic ratio (O/C) underscored the importance of multigenerational oxidation of low-volatile organic vapors emitted from diesel engine as a possible significant source of ambient oxygenated SOA. Higher particle effective densities were observed when raw exhaust was injected into a full bag as opposed to filling a bag with diluted exhaust using an ejector diluter. This suggests that the dilution method, in addition to dilution ratio, may impact the evaporation of semivolatile species. This study demonstrates the critical need to evaluate particle mass when evaluating SOA formation onto fractal particles such as diesel exhaust.     

Diurnal and Nocturnal Measurements of Aerosol Optical Depth at a Desert Site in Namibia

The Namibian desert is a candidate site for astrophysical observations with ground-based instrumentation, such as the High Energy Stereoscopic System experiment. For this kind of application, the characterization of the atmospheric transmittance is mandatory. In this context, a first campaign of both solar and lunar direct irradiance measurements has been performed from 7 July 1998 to 10 July 1998 on a desert plateau in Namibia. The aerosol optical depth in the visible range (330-700 nm) has been measured; we found daily values (at 483 nm) ranging from 0.10 to 0.26, while the nightly ones range from 2.5 2 10 m 3 up to 0.86. By means of a least square fitting procedure, the Ångström turbidity parameters have been estimated. ( f daily values 0.92 1 3.64, f nightly values 0.008 1 4.2; g daily values 0.06 1 0.56, g nightly values 0.001 1 0.68). Furthermore, a relationship between Ångström parameters and meteorological variables such as relative humidity and wind speed has been investigated. The results do not highlight any correlation, except for two diurnal data sets that show a negative correlation between the optical thickness and the wind speed. Although preliminary, our measurements allow us to have a first insight into characterizing the aerosol optical properties of the Namibian background aerosol. On the other hand, an extended campaign of measurements is needed for a full characterization of the site.     

Effects of Relative Humidity on Ozone and Secondary Organic Aerosol Formation from the Photooxidation of Benzene and Ethylbenzene

The formation of ozone and secondary organic aerosol (SOA) from benzene–NO _x and ethylbenzene–NO_x irradiations was investigated under different levels of relative humidity (RH) in a smog chamber. In benzene and ethylbenzene irradiations, the intensity of the bands of O?H, C?O, C?O, and C?OH from SOA samples all greatly increased with increasing RH. The major substances in SOA were determined to be carboxylic acids and glyoxal hydrates. It was also found that SOA contained aromatic products, and NO₂- and ONO₂-containing products. The results show that the increase in RH can greatly reduce the maximum O₃ by the transfer of NO₂- and ONO₂-containing products into the particle phase. During the process of evaporation, the lost substances from the collected SOA have similar structures for both benzene and ethylbenzene. This demonstrates that ethyl-containing substances are very stable and difficult to evaporate. For benzene, some of glyoxal hydrates were left to form C?O?C- and C?O-containing species like hemiacetal and acetal after evaporation, whereas for ethylbenzene, glyoxal favored cross reactions with ethylglyoxal during evaporation. Only a few species in SOA were released into the gas phase during evaporation while a large part of SOA remained, which is mainly composed of carboxylic acid. It is concluded that the aqueous radical reactions and the hydration from glyoxal can be enhanced under high RH conditions, which can irreversibly enhance the formation of SOA from both benzene and ethylbenzene.

Copyright 2014 American Association for Aerosol Research     

Real-Time Measurements of Black Carbon Indoors and Outdoors: A Comparison of the Photoelectric Aerosol Sensor and the Aethalometer

A real-time instrument employing photoelectric emission has been suggested as a semiquantitative tracer of black carbon (BC). The instrument is known as the Photoelectric Aerosol Sensor (PAS) and has been manufactured in Europe since the 1980s. As a test of this relationship, real-time measurements were made using two models of this instrument side by side with two Aethalometers for one year (1998) and for an additional six months (December 1999–May 2000) inside and outside an occupied house in Reston, VA. Four sources, two outdoors and two indoors, were investigated. The outdoor sources included automobile traffic and woodburning; the indoor sources included cooking and candle burning. Correlations between the Aethalometer and both models of PAS instruments for three of the four sources ranged from R² = 72% to 85%. For cooking, the earlier PAS Model 1001i using mercury vapor as a UV source was correlated with the Aethalometer for broiled foods, but the later PAS Model 2000 using a krypton chloride excimer lamp showed almost no response. When all sources were combined, both the outdoor PAS 2000 and the indoor PAS 1001i correlated with the corresponding Aethalometers (R² = 63%, N = 36,558, p < 0.0001; and R² = 68%, N = 34,954, p < 0.0001, respectively). Although the precision of the Aethalometer and PAS 2000 was high (4.5% and 5.4%, respectively), and correlations between them fairly good for some sources, the accuracy of both instruments is essentially unknown, due in part to the lack of a standard capable of providing calibrations in the field. There is also an unexplained difference of about a factor of 10 between the PAS 1001i and PAS 2000 models used in this study. The PAS/Aethalometer ratio varies widely across studies, suggesting that both instruments have site-specific and/or source-specific responses. Nonetheless, for certain uses, such as identifying sources, determining indoor-outdoor relationships, mapping diurnal variation, identifying peaks, and measuring personal exposures, the PAS has important advantages.     

Gas-Wall Partitioning of Organic Compounds in a Teflon Film Chamber and Potential Effects on Reaction Product and Aerosol Yield Measurements

Gas-wall partitioning of organic compounds (OC) that included C ₈ –C ₁₆ n-alkanes and 1-alkenes and C ₈ –C ₁₃ 2-alcohols and 2-ketones was investigated in two Teflon FEP chambers whose walls were either untreated, oxidized in sunlight, or previously exposed to secondary organic aerosol (SOA). Partitioning was nearly independent of chamber treatment, reversible, and obeyed Henry's law. The fraction of an OC that partitioned to the walls at equilibrium ranged from 0 to ～ 65%. Values increased with increasing carbon number within an OC class and for OC with similar vapor pressures increased in the order n-alkanes <1-alkenes <2-alcohols <2-ketones. Estimated time constants for achieving partitioning equilibrium ranged from ～ 60 min for n -alkanes to ? 8 min for 2-ketones. The observations are consistent with a sorption mechanism in which OC dissolve into the film but are restricted to the near-surface region by a sharp permeability gradient that develops in response to OC-induced stresses in polymer chains. When the results were analyzed using a model analogous to one commonly employed for gas-particle partitioning, it was estimated that the sorption properties of the chamber walls were equivalent to organic aerosol mass concentrations of 2, 4, 10, and 24 mg m^{– 3} with respect to the partitioning of n -alkanes, 1-alkenes, 2-alcohols, and 2-ketones. These values are up to ～ 4 orders of magnitude larger than concentrations used in most laboratory studies of SOA, which are typically 1–10 ³ μ g m^{– 3} , meaning that if full partitioning equilibrium is established in the chamber then semi-volatile OC will reside overwhelmingly in the chamber walls. Model simulations of gas-particle-wall partitioning were also carried out using the experimental data, and demonstrate quantitatively the large potential effects of Teflon walls on measured yields of gas-phase OC products and SOA.     

Aerosol Growth in a Steady-State,Continuous Flow Chamber: Application to Studies of Secondary Aerosol Formation

An analytical solution for the steady-state aerosol size distribution achieved in a steady-state, continuous flow chamber is derived, where particle growth is occurring by gas-to-particle conversion and particle loss is occurring by deposition to the walls of the chamber. The solution is presented in the case of two condensing species. By fitting the predicted steady-state aerosol size distribution to that measured, one may infer information about the nature of the condensing species from the calculated values of the species's molecular weights. The analytical solution is applied to three sets of experiments on secondary organic aerosol formation carried out in the U.S. Environmental Protection Agency irradiated continuous flow reactor, with parent hydrocarbons: toluene, f -pinene, and a mixture of toluene and f -pinene. Fits to the observed size distributions are illustrated by assuming two condensing products for each parent hydrocarbon; this is a highly simplified picture of secondary organic aerosol formation, which is known to involve considerably more than two condensing products. While not based on a molecular-level model of the gas-to-particle conversion process, the model does allow one to evaluate the extent to which the observed size distribution agrees with that based on a simple, two-component picture of condensation, and to study the sensitivity of those size distributions to variation of the essential properties of the condensing compounds, such as molecular weight. An inherent limitation of the steady-state experiment is that it is not possible to calculate the vapor pressures of the condensing species.     

Aerosol and Carbon Monoxide Emissions from Low-Temperature Combustion in a Sawdust Packed-Bed Stove

Low-temperature combustion in biomass-burning stoves used for cooking results in poor thermal efficiency and high emissions. A sawdust packed-bed stove has been shown to give more stable combustion at higher temperatures than woodstoves. The study examines pollutant emissions from this stove and their dependence on stove dimensions, specifically the vertical port radius and the stove-pot spacing. Emission rates of particulate matter (PM)—along with size resolution—and of carbon monoxide (CO) were measured during steady-state combustion. The stove power increased with increased spacing and vertical port radius. However, the air-flow rate, combustion temperature, and air-fuel ratio showed complex variations with stove dimensions from the described coupling among the pyrolysis, combustion, induced air flow, and mixing. Emission rates of PM (0.21–0.36 gh^?1 and CO (3–8 gh^?1 and were a factor of ten lower than those previously measured from woodstoves. Emission rates of CO decreased, while PM increased, with increasing combustion temperature. Aerosol size distributions were unimodal with mass median aerodynamic diameters (MMAD) of 0.24–0.40 𝛍 a factor of two smaller than from woodstoves. Cool combustion at 534–625°C gave lower PM emission rates but particles of larger MMAD, while hot combustion at 625–741°C gave higher PM emission rates with smaller particle MMAD. The OC/EC ratio obtained for cool combustion was higher (1.20) than that for hot combustion (0.96). Greater elemental carbon formation was seen at the higher temperatures. PM and CO emission rates followed opposite trends with combustion temperature and stove configuration, resulting in no single configuration at which both CO and PM emissions were minimized. However, its superior thermal efficiency and significantly lower emissions than wood stoves should motivate further study of this device to optimize thermal and emissions performance.     

Determination of Arbitrary Moments of Aerosol Size Distributions from Measurements with a Differential Mobility Analyzer

A method to determine arbitrary moments of aerosol size distributions from differential mobility analyzer measurements has been proposed. The proposed method is based on a modification of the algorithm developed by Knutson and Whitby to calculate the moments of electrical mobility distributions. For this modification, the electrical mobility and the charge distribution have been approximately expressed by power functions of the particle diameter. To evaluate the validity of the approximation, we have carried out numerical simulations for typical size distributions. We have found that for typical narrowly distributed aerosols such as polystyrene latex particles and particles that arise in the tandem differential mobility analyzer configuration, the distribution parameters can be accurately determined by this method. For a log-normally distributed aerosol, the accuracy of the distribution parameters determined by this method has been evaluated as a function of the geometric standard deviation. We have also compared the accuracy of the proposed method with other existing methods in the case of the asymmetric Gaussian distribution.     

Investigation of Aerosol Surface Area Estimation from Number and Mass Concentration Measurements: Particle Density Effect

For nanoparticles with nonspherical morphologies, e.g., open agglomerates or fibrous particles, it is expected that the actual density of agglomerates may be significantly different from the bulk material density. It is further expected that using the material density may upset the relationship between surface area and mass when a method for estimating aerosol surface area from number and mass concentrations (referred to as “Maynard's estimation method”) is used. Therefore, it is necessary to quantitatively investigate how much the Maynard's estimation method depends on particle morphology and density. In this study, aerosol surface area estimated from number and mass concentration measurements was evaluated and compared with values from two reference methods: a method proposed by Lall and Friedlander for agglomerates and a mobility based method for compact nonspherical particles using well-defined polydisperse aerosols with known particle densities. Polydisperse silver aerosol particles were generated by an aerosol generation facility. Generated aerosols had a range of morphologies, count median diameters (CMD) between 25 and 50 nm, and geometric standard deviations (GSD) between 1.5 and 1.8. The surface area estimates from number and mass concentration measurements correlated well with the two reference values when gravimetric mass was used. The aerosol surface area estimates from the Maynard's estimation method were comparable to the reference method for all particle morphologies within the surface area ratios of 3.31 and 0.19 for assumed GSDs 1.5 and 1.8, respectively, when the bulk material density of silver was used. The difference between the Maynard's estimation method and surface area measured by the reference method for fractal-like agglomerates decreased from 79% to 23% when the measured effective particle density was used, while the difference for nearly spherical particles decreased from 30% to 24%. The results indicate that the use of particle density of agglomerates improves the accuracy of the Maynard's estimation method and that an effective density should be taken into account, when known, when estimating aerosol surface area of nonspherical aerosol such as open agglomerates and fibrous particles.     

Exhaust Aerosol of a Plasma Enhanced CVD System: I. Size Distribution Measurements

Understanding the origin and fate of plasma-enhanced chemical vapor deposition (CVD) contaminant particles is a critical issue in semiconductor manufacturing in order to improve thin film deposition on wafer surfaces. Several competing external forces will affect a particle's motion in the plasma field prior to either landing on the wafer or entering the exhaust line. Electrical forces dominate during plasma radio frequency (RF) activation creating regions of potential wells. If trapped, the nucleated particles can continue to grow and gain electron charges until gas or ion drag forces can overcome the potential barrier. Mutual electrostatic repulsion between particles can also cause the traps to "leak" out contaminants into the exhaust line. In this way, contaminants formed solely in the plasma volume are hypothesized to possess a distinctive size and charge distribution independent of condensation particles originating from gas compression by the oil-based rotary pump. For these reasons, a novel experimental aerosol sampling system was designed to continuously monitor submicron particles carried during a thin film deposition cycle without disturbing the internal operation of the plasma. Sampling from the plasma enhanced chemical vapor deposition (PECVD) process exhaust gases using an oil-free mechanical piston pump parallel to the main vacuum line is considered to be an effective alternative to in situ probe measurement. Concentration and size distribution data were continuously measured using a condensation nucleus counter and an optical spectrometer. Results show that the particles in the reactor exhaust line are bimodal or made up of fine and coarse sizes divided near 100 nm. Experimental results show the fine fraction increases in the exhaust line after a certain time interval. This delay is hypothesized to be the initial period the nucleated particles were trapped inside the plasma's potential wells. Once trapped, reactor particles can continue to grow in agreement with free molecular coagulation models. A larger particle will experience greater gas drag to eventually overcome the electrical forces. The delay, or critical transport time, depends upon the reactor pressure and plasma power, which also affect the size of the trapping field. The second paper in the series "Exhaust Aerosol of a Plasma Enhanced CVD System" compares a computational charging model of the plasma sheath with experimental charge distribution measurements of contaminant particles carried through the CVD exhaust.     

Chemistry of Secondary Organic Aerosol Formation from OH Radical-Initiated Reactions of Linear,Branched, and Cyclic Alkanes in the Presence of NO x

The effects of molecular structure on the products and mechanisms of SOA formation from OH radical-initiated reactions of linear, branched, and cyclic alkanes in the presence of NO _x were investigated in a series of environmental chamber experiments. SOA mass spectra were obtained in real time and off line using a thermal desorption particle beam mass spectrometer and used to identify reaction products. Real-time mass spectra were used to classify products according to their temporal behavior, and off-line temperature-programmed thermal desorption analysis of collected SOA was used to separate products by volatility prior to mass spectral analysis and to gain information on compound vapor pressures. A reaction mechanism that includes gas- and particle-phase reactions was developed that explains the formation of SOA products and is consistent with the various lines of mass spectral information. Results indicate that the SOA products formed from the reactions of linear, branched, and cyclic alkanes are similar, but differ in a few important ways. Proposed first-generation SOA products include alkyl nitrates, 1,4-hydroxynitrates, 1,4-hydroxycarbonyls, and dihydroxycarbonyls. The 1,4-hydroxycarbonyls and dihydroxycarbonyls rapidly isomerize in the particle phase to cyclic hemiacetals that then dehydrate to volatile dihydrofurans. This conversion process is catalyzed by HNO ₃ formed in the chamber and is slowed by the presence of NH ₃ . Volatile products can react further with OH radicals, forming multi-generation products containing various combinations of the same functional groups present in first-generation products. For linear and branched alkanes, the products are acyclic or monocyclic, whereas for cyclic alkanes they are acyclic, monocyclic, or bicyclic. Some of the products, especially those formed from ring-opening reactions of cyclic alkanes appear to be low volatility oligomers. The implications of the results for the formation of atmospheric SOA are discussed.     

Development and Characterization of a Fast-Stepping/Scanning Thermodenuder for Chemically-Resolved Aerosol Volatility Measurements

Numerous sources of liquid aerosols are to be found in industrial environments. Such aerosols may, for instance, be cutting fluids, pesticides, etc., that are harmful or even toxic to humans. To control and reduce worker exposure to potentially toxic aerosols, these latter are usually filtered through fibrous filters. When non-saturated air traverses a clogged filter, however, the drops deposited on the fibers may evaporate. Consequently, workers are exposed to greater amounts of more concentrated vapors than the initial state of the filtered aerosol. Furthermore, exposure readings are distorted by an artifact that may be significant. This study offers an experimental approach to long-term monitoring of the evaporation of a semi-volatile n-hexadecane liquid aerosol deposited on filters of varying efficiency. Results were modeled using two semi-empirical models for identifying the basic parameters of liquid aerosol evaporation on fibers. For the first time ever it has been demonstrated that the Fick's first law, as previously suggested by models proposed in the literature, does not control evaporation kinetic.