David R. Cocker

Organic aerosol formation from the oxidation of biogenic hydrocarbons

A series of outdoor chamber experiments has been used to establish and characterize the significant atmospheric aerosol-forming potentials of the most prevalent biogenic hydrocarbons emitted by vegetation. These compounds were also studied to elucidate the effect of structure on aerosol yield for these types of compounds. Because oxidation products partition between the gas and aerosol phases, the aerosol yields of the parent biogenic hydrocarbons depend on the concentration of organic aerosol into which these products can be absorbed. For organic mass concentrations between 5 and 40 µg m^(-3), mass-based yields in photooxidation experiments range from 17 to 67% for sesquiterpenes, from 2 to 23% for cyclic diolefins, from 2 to 15% for bicyclic olefins, and from 2 to 6% for the acyclic triolefin ocimene. In these photooxidation experiments, hydroxyl and nitrate radicals and ozone can contribute to consumption of the parent hydrocarbon. For bicyclic olefins (α-pinene, β-pinene, Δ^3-carene, and sabinene), experiments were also carried out at daytime temperatures in a dark system in the presence of ozone or nitrate radicals alone. For ozonolysis experiments, resulting aerosol yields are less dependent on organic mass concentration, when compared to full, sunlight-driven photooxidation. Nitrate radical experiments exhibit extremely high conversion to aerosol for β-pinene, sabinene, and Δ^3-carene. The relative importance of aerosol formation from each type of reaction for bicyclic olefin photooxidation is elucidated.

Gas-phase Ozone Oxidation of Monoterpenes: Gaseous and Particulate Products

Smog chamber experiments have beenconducted in which cyclic monoterpenes were oxidisedin the gas phase by OH. The evolved secondary organicaerosol (SOA) was analysed by LC-MSn and thegas-phase products were analysed by FT-IR. Theconcentrations of the identified compoundscorresponded to carbon mass balances in the range of40%–90%. The identified compounds in the particularphase corresponded to 0.5%–4.2% of the reactedcarbon. The most abundant compounds in SOA fromterpenes with an endocyclic C=C double bond wereC10-keto-aldehydes, C10-keto-carboxylicacids, C10-hydroxy-keto-carboxylic acids, andC10-hydroxy-keto-aldehydes (pinonaldehyde,pinonic acid, hydroxy-pinonic acid isomers, andhydroxy-pinonaldehyde isomers from α-pinene;3-caronaldehyde, 3-caronic acid, hydroxy-3-caronicacid isomers, and hydroxy-3-caronaldehyde isomers from3-carene). The most abundant compounds in SOA fromterpenes with an exocyclic C=C double bond wereC9-ketones, C9-dicarboxylic acids, andC10-hydroxy-keto-carboxylic acids (nopinone,pinic acid, and hydroxy-pinonic acid isomers fromβ-pinene; sabinaketone, sabinic acid andhydroxy-sabinonic acid isomers from sabinene).Decarboxylated analogues of most of the compounds werepresent in SOA in minor concentrations, such asC9-keto-carboxylic acids (norpinonic acid,nor-3-caronic acid) and C8-dicarboxylic acids(norpinic acid, nor-3-caric acid, norsabinic acid). InSOA from limonene, which contains an endocyclic aswell as an exocyclic C=C double bond, the mostabundant compounds were a C10-keto-aldehyde andits oxo-derivative (limononaldehyde and keto-limononaldehyde) together with hydroxy-derivatives of aC10-keto-carboxylic acid (isomers ofhydroxy-limononic acid). Also aC10-keto-carboxylic acid (limononic acid) waspresent together with minor concentrations of aC9-dicarboxylic acids (limonic acid), itsoxo-derivative (keto-limonic acid), and itsdecarboxylated analogue (norlimonic acid). Mechanisticpathways for the formation of these products, some ofwhich are identified here for the first time, areproposed.Smog chamber experiments have beenconducted in which cyclic monoterpenes were oxidisedin the gas phase by OH. The evolved secondary organicaerosol (SOA) was analysed by LC-MSn and thegas-phase products were analysed by FT-IR. Theconcentrations of the identified compoundscorresponded to carbon mass balances in the range of40%–90%. The identified compounds in the particularphase corresponded to 0.5%–4.2% of the reactedcarbon. The most abundant compounds in SOA fromterpenes with an endocyclic C=C double bond wereC10-keto-aldehydes, C10-keto-carboxylicacids, C10-hydroxy-keto-carboxylic acids, andC10-hydroxy-keto-aldehydes (pinonaldehyde,pinonic acid, hydroxy-pinonic acid isomers, andhydroxy-pinonaldehyde isomers from α-pinene;3-caronaldehyde, 3-caronic acid, hydroxy-3-caronicacid isomers, and hydroxy-3-caronaldehyde isomers from3-carene). The most abundant compounds in SOA fromterpenes with an exocyclic C=C double bond wereC9-ketones, C9-dicarboxylic acids, andC10-hydroxy-keto-carboxylic acids (nopinone,pinic acid, and hydroxy-pinonic acid isomers fromβ-pinene; sabinaketone, sabinic acid andhydroxy-sabinonic acid isomers from sabinene).Decarboxylated analogues of most of the compounds werepresent in SOA in minor concentrations, such asC9-keto-carboxylic acids (norpinonic acid,nor-3-caronic acid) and C8-dicarboxylic acids(norpinic acid, nor-3-caric acid, norsabinic acid). InSOA from limonene, which contains an endocyclic aswell as an exocyclic C=C double bond, the mostabundant compounds were a C10-keto-aldehyde andits oxo-derivative (limononaldehyde and keto-limononaldehyde) together with hydroxy-derivatives of aC10-keto-carboxylic acid (isomers ofhydroxy-limononic acid). Also aC10-keto-carboxylic acid (limononic acid) waspresent together with minor concentrations of aC9-dicarboxylic acids (limonic acid), itsoxo-derivative (keto-limonic acid), and itsdecarboxylated analogue (norlimonic acid). Mechanisticpathways for the formation of these products, some ofwhich are identified here for the first time, areproposed.

Estimate of global atmospheric organic aerosol from oxidation of biogenic hydrocarbons

The results from a series of outdoor chamber experiments establishing the atmospheric aerosol-forming potential of fourteen terpenoid hydrocarbons have been used to estimate the annual amount of secondary organic aerosol formed globally from compounds emitted by vegetation. Hydroxyl radical, ozone, and nitrate radical oxidation each contribute to aerosol formation in full-photooxidation experiments; because oxidation by nitrate radical under ambient, remote conditions is likely to be negligible, parameters describing aerosol formation from hydroxyl radical and ozone reaction only are developed. Chamber results, temporally and spatially resolved, compound-specific estimates of biogenic hydrocarbon emissions, and hydroxyl radical and ozone fields are combined to lead to an estimate for atmospheric secondary organic aerosol formed annually from biogenic precursors of 18.5 Tg, a number smaller than the previously published estimate of 30–270 Tg [Andreae and Crutzen, 1997].

New particle formation from photooxidation of diiodomethane (CH2I2)

Photolysis of CH_2I_2 in the presence of O_3 has been proposed as a mechanism leading to intense new particle formation in coastal areas. We report here a comprehensive laboratory chamber study of this system. Rapid homogeneous nucleation was observed over three orders of magnitude in CH_2I_2 mixing ratio, down to a level of 15 ppt (∼4 × 10^8 molec. cm^(−3)) comparable to the directly measured total gas-phase iodine species concentrations in coastal areas. After the nucleation burst, the observed aerosol dynamics in the chamber was dominated by condensation of additional vapors onto existing particles and particle coagulation. Particles formed under dry conditions are fractal agglomerates with mass fractal dimension, D_f ∼ 1.8–2.5. Higher relative humidity (65%) does not change the nucleation or growth behavior from that under dry conditions, but results in more compact and dense particles (D_f ∼ 2.7). On the basis of the known gas-phase chemistry, OIO is the most likely gas-phase species to produce the observed nucleation and aerosol growth; however, the current understanding of this chemistry is very likely incomplete. Chemical analysis of the aerosol using an Aerodyne Aerosol Mass Spectrometer reveals that the particles are composed mainly of iodine oxides but also contain water and/or iodine oxyacids. The system studied here can produce nucleation events as intense as those observed in coastal areas. On the basis of comparison between the particle composition, hygroscopicity, and nucleation and growth rates observed in coastal nucleation and in the experiments reported here, it is likely that photooxidation of CH_2I_2, probably aided by other organic iodine compounds, is the mechanism leading to the observed new particle formation in the west coast of Ireland.

The effect of water on gas–particle partitioning of secondary organic aerosol. Part I: α-pinene/ozone system

The effect of relative humidity (RH) on aerosol formation by the semi-volatile oxidation products of the α-pinene/O_3 system has been comprehensively studied. Experiments were performed in the presence of ammonium sulfate (aqueous, dry), ammonium bisulfate seed (aqueous, dry), and aqueous calcium chloride seed aerosols to ascertain their effect on the partitioning of the oxidation products. The yield of organic aerosol varies little with RH, and is not affected by the presence of dry inorganic salt aerosols. Aqueous salt aerosols reduce the yield of organic aerosol compared to that under seed-free or dry seed conditions. The degree of reduction is electrolyte dependent, with aqueous ammonium sulfate leading to the largest reduction and aqueous calcium chloride the smallest. Hygroscopic growth of the organic aerosol from <2% to 85% RH was also monitored, and could be satisfactorily represented as the sum of the individual contributions of the organic and inorganic fractions. The implications of the growth factor measurements for concentration/activity relationships of the condensed phase organic material (assuming a liquid solution) was explored. The formation of the organic aerosol was investigated using a simple two component model, and also one including the 12 product compounds identified in a previous study. The experimental results for <2% and 50% RH (without salt seed aerosols) could be satisfactorily predicted. However, the aqueous salt seed aerosols are predicted to increase the overall yield due to the dissolution of the organic compounds into the water associated with the seed aerosol—the opposite effect to that observed. The implications of two distinct phases existing the aerosol phase were investigated.

Observation of gaseous and particulate products of monoterpene oxidation in forest atmospheres

Atmospheric oxidation of biogenic hydrocarbons, such as monoterpenes, is estimated to be a significant source of global aerosol. Whereas laboratory studies have established that photochemical oxidation of monoterpenes leads to aerosol formation, there are limited field studies detecting such oxidation products in ambient aerosols. Drawing on prior results of monoterpene product analysis under controlled smog chamber conditions, we have identified organic aerosol components attributable to monoterpene oxidation in two forest atmospheres, Kejimkujik National Park, Nova Scotia, Canada, and Big Bear, San Bernardino National Forest, California, U.S.A. The major identified aerosol products derived from α-pinene and β-pinene oxidation include pinic acid, pinonic acid, norpinonic acid and its isomers, hydroxy pinonaldehydes, and pinonaldehyde, concentrations of which in the aerosol phase are in the sub ng m^(−3) range. Identification of oxidation products in atmospheric aerosol samples serves as direct evidence for aerosol formation from monoterpenes under ambient conditions.

The effect of water on gas-particle partitioning of secondary organic aerosol: II. m-xylene and 1,3,5-trimethylbenzene photooxidation systems

An investigation of the effect of relative humidity on aerosol formation from m-xylene and 1,3,5-trimethylbenzene photooxidation is reported. Experiments were performed in the presence and absence of ammonium sulfate seed particles (both aqueous and dry) to ascertain the effect of partitioning of oxidation products into a strong electrolytic solution or onto dry crystalline seed particles. In marked contrast to the α-pinene/ozone system, the final measured secondary organic aerosol yield was unaffected by the presence of gas-phase or liquid-phase water at relative humidities (RH) up to 50%. The hygroscopic nature of the aerosol generated upon photooxidation of m-xylene and 1,3,5-trimethylbenzene was examined; the hygroscopicity of the aerosol at 85% RH for both parent organics increased with the extent of the reaction, indicating that the first-generation oxidation products undergo further oxidation. Limited identification of the gas- and aerosol-phase products of m-xylene and 1,3,5-trimethylbenzene photooxidation is reported. It is evident that a more complete molecular identification of aromatic photooxidation aerosol awaits analytical techniques not yet brought to bear on this problem.

Real-Time Aerosol Density Determination Utilizing a Modified Scanning Mobility Particle Sizer—Aerosol Particle Mass Analyzer System

Real time secondary organic aerosol (SOA) density evolution for m-xylene photo-oxidation and α-pinene ozonolysis was obtained using an Aerosol Particle Mass Analyzer (APM)/Scanning Mobility Particle Spectrometer (SMPS) setup, which has been modified to achieve higher transmission of particles and improved sampling frequency. The aerosol density of SOA generated from α-pinene ozonolysis was found to be 1.24 ± 0.03 g/cm3 while the aerosol generated from m-xylene photo-oxidation was determined to be 1.35 ± 0.03 g/cm3. These results confirm the measurement approach from a combined SMPS and Aerodyne Aerosol Mass Spectrometer (AMS) system and are found to be within good agreement with the effective density measurements.

The Scanning DMA Transfer Function

The scanning differential mobility analyzer (DMA) has been widely employed for measurement of rapidly evolving aerosol size distributions. Interpretation of data from scanning DMAs is greatly facilitated when an exponential voltage ramp is prescribed, since the shape of the instrumental transfer function remains constant throughout a scan. However, that transfer function may differ significantly from that expected for fixed voltage operation. Because no simple analytical description of the scanning DMA transfer function exists, it has been evaluated numerically by simulating particle trajectories within a TSI 3081 cylindrical DMA. These computations yield transfer functions for the DMA up scan that are roughly triangular but with widths significantly greater than those for fixed voltage operation, and transfer functions for the down scan that are highly asymmetric. The impact of these distortions is most obvious when the size distribution of the measured aerosol is narrow, but errors in recovered size and concentration can be significant even when the aerosol size distribution is much broader than the transfer function. The magnitude of these errors is dependent upon the ratio of the mean gas residence time to the exponential voltage time constant, the sheath-to-aerosol-flow ratio, and the technique used to determine the instrument plumbing time. Experimental results for scans across broad and narrow size distributions compare favorably with predictions based on the simulated transfer functions. Simplified corrections are provided that can be used to adjust the concentration and mobility of size distributions recovered using a fixed voltage transfer function.

Evaluation of the European PMP Methodologies during On-Road and Chassis Dynamometer Testing for DPF Equipped Heavy-Duty Diesel Vehicles

This study evaluated the UN-ECE Particle Measurement Programme (PMP) protocol for the measurement of solid particle number emissions under laboratory and on-road conditions for two passive diesel particle filters (DPF)–equipped medium and heavy-heavy duty diesel vehicles. The PMP number emissions were lower than the European light-duty certification value (9.6 × 1011 #/mi) for all standardized cycles, but exceeded this value during some higher load on-road driving conditions. Particle number measurements were generally less variable than those of the PM mass for the on-road testing, but had comparable or greater variability than PM mass for the laboratory measurements due to outliers. These outliers appear to be real events that are not apparent with integrated filter methods. The particle number measurements for the low cut point CPCs (3–7 nm) below the PMP system were approximately an order of magnitude higher than those for the PMP-compliant CPC (23 nm), indicating the presence of a large fraction of solid sub-23 nm particles. Although such particles are defined as solid by the PMP method, their actual state is unknown. Nucleation particles with a large sulfate contribution formed under a variety of conditions when the exhaust temperature near the DPF exceeded a “critical” temperature, typically >300°C.