Geoffrey D. Smith

Ozonolysis of oleic acid particles: evidence for a surface reaction and secondary reactions involving Criegee intermediates

The heterogeneous reactions of ozone with monodisperse oleic acid and methyl oleate particles were studied by monitoring the loss of the condensed-phase species using an aerosol chemical ionization mass spectrometer (Aerosol CIMS). The reaction of ozone with oleic acid was determined to occur at the surface of the particles despite previous assumptions that it reacts in the bulk. The ozonolysis of methyl oleate particles, on the other hand, was found to be limited by the diffusion of ozone and does react in the bulk. The difference in reaction mechanisms is attributed to the larger degree of order in oleic acid known to result from the formation of hydrogen-bonded dimers. The reactive uptake coefficients, gamma, calculated from the rate of loss of the particle species are gamma = (1.38 +/- 0.06) x 10(-3) for oleic acid and gamma = (1.23 +/- 0.10) x 10(-3) for methyl oleate. However, it is found that secondary reactions between Criegee intermediates and the carboxylic acid moiety in oleic acid are responsible for 36% (+/-4%) of its observed loss. Hence, the rate of loss of ozone cannot be equated to the rate of loss of oleic acid. Accounting for this additional reaction the uptake coefficient for ozone on oleic acid particles is calculated to be gamma = (8.8 +/- 0.5) x 10(-4). The magnitude of these secondary reactions quantitatively reconciles discrepancies between previous coated flow tube and particle-based studies, and it illustrates the need to include additional loss mechanisms when calculating uptake coefficients from the rates of loss of particle species. Implications of reactions with Criegee intermediates in atmospheric particles are discussed.

A mixed-phase relative rates technique for measuring aerosol reaction kinetics

A mixed-phase relative rates approach for measuring rates of reaction in aerosols is presented. Using this method the rate of reaction of methyl oleate (MO) particles, normalized to the gas-particle collision rate, was measured to be γ Mo = 1.12 (±0.36) x 10-3 with 2-methyl-2-butene as the gas-phase reference. This value compares favorably with our previously published value of 1.23 x 10 -3 measured using an absolute technique. Reaction of bis(2-ethylhexyl) sebacate (BES) particles with Cl and OH radicals was also studied using acetone and hexanal, respectively, as the gas-phase references. The rates of reaction of BES, normalized to the gas-particle collision rate, were measured to be γ BES = 1-8 ( +0.8 -0.3 and γ BES = 2.0 ( +0.6 -0.1 with Cl and OH, respectively. These fast rates of reaction (γ BES > 1) imply that secondary reactions, perhaps involving radical chain mechanisms, could impact the rate at which organic particles are oxidized in the atmosphere.

Measuring rates of reaction in supercooled organic particles with implications for atmospheric aerosol.

The kinetics of heterogeneous reactions involving supercooled organic droplets is reported for the first time. Reactions between ozone and internally-mixed sub-micrometre particles containing an unsaturated alkenoic acid, oleic acid, and an n-alkanoic acid, myristic acid, were studied as a simple model for the oxidation of meat-cooking aerosol. The reactions were followed by monitoring the rate of oleic acid loss using an Aerosol CIMS (chemical ionization mass spectrometry) instrument for real-time particle analysis. Evidence of as much as 32 degrees C supercooling at room temperature was observed depending on particle composition. FTIR spectra of the aerosol also demonstrate features indicative of supercooling. Particles in which crystallization was induced by cooling below room temperature demonstrated decreased reactivity by a factor of 12 compared to supercooled particles of the same composition. This drastic difference in reactivity could have significant implications for the lifetimes of reactive species in ambient aerosol as well as for the accurate source apportionment of particulate matter.

Kinetics and products from reaction of Cl radicals with dioctyl sebacate (DOS) particles in O2: a model for radical-initiated oxidation of organic aerosols

The reaction of Cl radicals with bis (2-ethylhexyl) sebacate (also known as dioctyl sebacate, DOS) particles in the presence of O(2) is studied as a model of radical-initiated oxidation of organic aerosols. The uptake coefficient as measured from the rate of loss of DOS is gamma(DOS) = 1.7 (+/-0.3) indicating that a radical chain is operative. It is observed that nearly all of the detected products, accounting for 86% (+/-12%) of the reacted DOS, remain in the particles indicating that they are not efficiently volatilized. Correspondingly, the particles do not decrease in volume even after 60% of the DOS has reacted; upon further reaction the volume does decrease by up to 20%. Additionally, the mass of a DOS film increases with reaction indicating that the density increases. The two primary products identified are the ketone (38 +/- 10% yield) and alcohol (14 +/- 4% yield) resulting from reactions of alkylperoxy radicals originating from DOS oxidation. The fact that the ketone/alcohol ratio is >1 implies that the Russell mechanism, the typical fate of alkylperoxy radicals in liquids whereby both a ketone and an alcohol are generated, is not the only source of ketones. In fact, the ketone yield demonstrates a Langmuir-Hinshelwood type dependence on the O(2) concentration indicating that 44% (+/-8%) of the ketone is created from the reaction of alkoxy radicals with O(2) at the surface of the particles (at 20% O(2)). While this is a common reaction in the gas phase, it is generally not considered to occur in organic solvents. Furthermore, the appearance of gas-phase H(2)O(2) suggests that peroxy radicals react to form two ketones and H(2)O(2)via the Bennett and Summers mechanism. The absence of aldehyde products, both in the gas phase and in the particles, indicates that beta-scission of the alkoxy radicals is not significant. The results of this study suggest that organic aerosols in the troposphere are efficiently oxidized by gas-phase radicals but that their chemical transformation does not lead to their removal through volatilization.

Kinetics studies of the gas-phase reactions of NO3 radicals with series of 1-alkenes, dienes, cycloalkenes, alkenols, and alkenals.

The gas-phase reactions of NO(3) radicals with series of 1-alkenes, dienes, cycloalkenes, alkenols, and alkenals were studied in pure N(2) or 20% O(2)/80% N(2) bath gas at room temperature and atmospheric pressure using a relative rates technique. Rate coefficients were derived from rates of loss of the organic compounds observed using a chemical ionization mass spectrometer. No difference in the measured kinetic data was observed in the presence or absence of O(2). The rate coefficients obtained (k (10(-13) cm(3) molecule(-1) s(-1)), with uncertainties representing 95% confidence intervals) are as follows: 1-hexene, 0.233 ± 0.021; 1-heptene, 0.245 ± 0.029; 1-octene, 0.292 ± 0.044; 1,3-butadiene, 1.24 ± 0.09; isoprene, 6.24 ± 0.11; 2,3-dimethyl-1,3-butadiene, 14.1 ± 0.5; 1,3-cyclohexadiene, 112 ± 8; cyclopentene, 4.82 ± 0.13; cyclohexene, 5.38 ± 0.20; cycloheptene, 5.28 ± 0.23; 2-buten-1-ol (crotyl alcohol), 3.23 ± 0.12; cis-2-penten-1-ol, 3.11 ± 0.11; cis-2-hexen-1-ol, 3.81 ± 0.38; trans-2-pentenal, 0.193 ± 0.040; trans-2-hexenal, 0.136 ± 0.029; trans-2-heptenal, 0.231 ± 0.036; cis-4-heptenal, 4.03 ± 0.24. The measured rate coefficients are compared to values from previous studies and three structure-activity relationships (SARs), and good agreement is found, in general. In particular, the recently developed SAR of Kerdouci et al. (Kerdouci, J.; Picquet-Varrault, B.; Doussin, J. ChemPhysChem2010, 11, 3909-3920.) is found to estimate the rate coefficients within 35% for all of the measured reactions except for NO(3) + 1,3-butadiene. The SAR prediction for that reaction is nearly 50% lower than the measured value, suggesting that it underestimates the effect of conjugation on the reaction of NO(3) with this small diene. The measured rate coefficients for reactions with a series of alkenols are used to modify the SAR substituent factor for the -CH(2)OH group, and those for reactions with a series of trans-2-alkenals are used to derive a substituent factor for the -C(O)H group, which was not included in the original SAR because of insufficient experimental data.

A UV–Vis Photoacoustic Spectrophotometer

A novel photoacoustic spectrophotometer (PAS) for the measurement of gas-phase and aerosol absorption over the UV-visible region of the spectrum is described. Light from a broadband Hg arc lamp is filtered in eight separate bands from 300 to 700 nm using bandpass interference filters (centered at 301 nm, 314 nm, 364 nm, 405 nm, 436 nm, 546 nm, 578 and 687 nm) and modulated with an optical chopper before entering the photoacoustic cell. All wavelength bands feature a 20-s detection limit of better than 3.0 Mm(-1) with the exception of the lower-intensity 687 nm band for which it is 10.2 Mm(-1). Validation measurements of gas-phase acetone and nigrosin aerosol absorption cross sections at several wavelengths demonstrate agreement to within 10% with those measured previously (for acetone) and those predicted by Mie theory (for nigrosin). The PAS instrument is used to measure the UV-visible absorption spectrum of ambient aerosol demonstrating a dramatic increase in the UV region with absorption increasing by 300% from 405 to 301 nm. This type of measurement throughout the UV-visible region and free from artifacts associated with filter-based methods has not been possible previously, and we demonstrate its promise for classifying and quantifying different types of light-absorbing ambient particles.

A Calibration Technique for Improving Refractive Index Retrieval from Aerosol Cavity Ring-Down Spectroscopy

Cavity ring-down spectroscopy (CRDS) is a technique that is commonly used to measure the extinction of light by aerosol particles in situ. This extinction, when normalized to particle concentration, yields the extinction cross section, a measure of a single particles ability to scatter and absorb light. The complex index of refraction can then be retrieved by comparison of the extinction cross sections at several particle diameters with those predicted by Mie theory. This approach requires accurate determination of particle diameter and concentration as well as the length of the extinction region in the cavity, but it is often difficult to quantify the systematic errors in the measurements of these quantities. Here, we introduce a calibration technique using particles of a reference compound to account for these systematic errors. The two calibration parameters are: Cf , which scales the measured extinction cross sections, and Δd, which shifts the particle diameters. It is found that Cf correlates strongly with the condensation particle counter (CPC) used to measure particle concentration and that Δd is associated with the differential mobility analyzer (DMA) used to select particle diameters. Calibration is shown to reduce errors of subsequently-measured extinction cross sections of a test aerosol from 11% to with a concomitant improvement in the accuracy of the retrieved complex index of refraction and corresponding atmospheric radiative forcing estimates. Copyright 2013 American Association for Aerosol Research

BULLET: a computer simulation of shotgun DNA sequencing.

BULLET is a computer program that simulates shotgun sequencing of DNA. The program has been used to simulate the sequencing of DNA fragments from 2 to 30 kb. To obtain 80% single or double-stranded sequence, a doubling of the DNA fragment size necessitates twice the number of sequencing reactions. However, a similar linear relationship does not apply to the determination of 100% single or double-stranded sequence. Data from BULLET were used to derive simple linear formulae that estimate the number of sequencing reactions necessary to partially sequence a fragment of DNA irrespective of size. When 80% of the double-stranded sequence has been determined, approximately 98% of single-stranded sequence will be known. This is a reasonable point to change to a more directed strategy of DNA sequencing.

Spectroscopic comparison of water- and methanol-soluble brown carbon particulate matter

ABSTRACT It is now recognized that some organic components of ambient aerosols absorb light with a spectrum distinct from that of other absorbers such as black carbon and mineral components. The most common method for isolating this light-absorbing organic fraction, or “brown carbon,” is to collect particulate matter on filters and extract in a solvent, usually water or methanol. Here, we compare the absorption spectra of water-soluble (WS) and methanol-soluble (MS) extracts from ambient samples collected in Athens, Georgia. We find that despite syringe filtering the MS extracts, extinction by suspended particles is evident in the spectra leading to an overestimation of absorption by a factor of two on average. No such particle extinction is evident in the WS extracts. We demonstrate that it is possible to subtract the extinction contribution in the MS extracts by fitting the spectrum to the sum of two power-law functions, one describing the absorption spectrum and the other describing the extinction spectrum. With extinction thus removed, we find that integrated absorption (300–800 nm) by the MS brown carbon extract is highly correlated with the WS extract and is on average 1.55× larger. The wavelength dependence of the WS and MS spectra are also correlated and very similar with average absorption Ångström exponents of 6.1 (±0.7) and 6.7 (±1.1), respectively. This study demonstrates that for the samples collected: (1) brown carbon absorption can be overestimated if scattering in MS spectra is not accounted for, (2) there is no spectral evidence that the WS and MS chromophores are different, and (3) it may be possible to use WS spectra to represent total brown carbon absorption using a simple scaling factor. These findings may differ for other types of aerosol samples and analytical methods.

A portable, four-wavelength, single-cell photoacoustic spectrometer for ambient aerosol absorption

ABSTRACT Aerosols directly affect Earths climate by scattering and absorbing solar radiation. Although they are ubiquitous in Earths atmosphere, direct, in situ, wavelength-resolved measurements of aerosol optical properties remain challenging. As a result, the so-called aerosol direct effects are one of the largest uncertainties in predictions of Earths future climate, and new instrumentation is needed to provide measurements of the absorption of sunlight by atmospheric particles. We have developed a portable, four-wavelength, single-cell photoacoustic spectrometer for simultaneous measurement of aerosol absorption at 406, 532, 662, and 785 nm, with an additional extinction measurement at 662 nm via a built-in cavity ringdown spectrometer. The instrument, dubbed MultiPAS-IV, is compact, robust, has low power requirements, and utilizes a multipass optical arrangement to achieve typical detection limits of 0.6–0.7 Mm−1 for absorption (2σ, 2-min average). Tests with nigrosin aerosols show agreement with Mie theory calculations to within 2%, and comparison with a 7-wavelength aethalometer shows good correlation for ambient (Athens, GA, USA) aerosols. We demonstrate the utility of the broad spectral coverage and sensitivity of the MultiPAS-IV for calculating the absorption Ångström exponent of black carbon (AAEBC, median value of 0.70) in ambient aerosols and use this value to derive the brown carbon contributions to absorption at 406 nm (43%) and 532 nm (13%) and its wavelength dependence (AAEBrC = 6.3). Copyright