Secondary organic aerosol formation from phenolic compounds in the absence of NO_x

SOA formation from benzene, toluene, <i>m</i>-xylene, and their corresponding phenolic compounds were investigated using the UCR/CE-CERT Environmental Chamber to evaluate the importance of phenolic compounds as intermediate species in aromatic SOA formation. SOA formation yield measurements coupled to gas-phase yield measurements indicate that approximately 20% of the SOA of benzene, toluene, and <i>m</i>-xylene could be ascribed to the phenolic route under low NO_x conditions. The SOA densities tend to be initially as high as approximately 1.8 g cm^&minus;3 and eventually reach the range of 1.3–1.4 g cm^&minus;3. The final SOA density was found to be independent of elemental ratio (O/C) indicating that applying constant density (e.g., 1.4 g cm^&minus;3) to SOA formed from different aromatic compounds tested in this study is a reasonable approximation. Results from a novel on-line PILS-TOFMS (Particle-into-Liquid Sampler coupled with Agilent Time-of-Flight Mass Spectrometer) are reported. Major signals observed by the on-line/off-line Agilent TOFMS indicated that products had the same number of carbon atoms as their parent aromatics, suggesting importance of ring-retaining products or ring-opening products following ring-cleavage

Cloud condensation nuclei (CCN) activity of aliphatic amine secondary aerosol

Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g., hydroxyl radical and nitrate radical). The particle can contain both secondary organic aerosol (SOA) and inorganic salts. The ratio of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, κ, ≤ 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N_2O_5 (source of nitrate radical, NO_3) contains less volatile compounds than the primary aliphatic amine (BA) aerosol. As relative humidity (RH) increases, inorganic amine salts are formed as a result of acid–base reactions. The CCN activity of the humid TMA–N_2O_5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. The humid BA + N_2O_5 aerosol products were found to be very sensitive to the temperature at which the measurements were made within the streamwise continuous-flow thermal gradient CCN counter; κ ranges from 0.4 to 0.7 dependent on the instrument supersaturation (ss) settings. The variance of the measured aerosol κ values indicates that simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems' κ ranges within 0.2 < κ < 0.7. This work indicates that aerosols formed via nighttime reactions with amines are likely to produce hygroscopic and volatile aerosol, whereas photochemical reactions with OH produce secondary organic aerosol of lower CCN activity. The contributions of semivolatile secondary organic and inorganic material from aliphatic amines must be considered for accurate hygroscopicity and CCN predictions from aliphatic amine systems

New particle formation from photooxidation of diiodomethane (CH_2I_2)

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

Are sesquiterpenes a good source of secondary organic cloud condensation nuclei (CCN)? Revisiting β-caryophyllene CCN

Secondary organic aerosol (SOA) was formed in an environmental reaction chamber from the ozonolysis of β-caryophyllene (β-C) at low concentrations (5 ppb or 20 ppb). Experimental parameters were varied to characterize the effects of hydroxyl radicals, light and the presence of lower molecular weight terpene precursor (isoprene) for β-C SOA formation and cloud condensation nuclei (CCN) characteristics. Changes in β-C SOA chemicophysical properties (e.g., density, volatility, oxidation state) were explored with online techniques to improve our predictive understanding of β-C CCN activity. In the absence of OH scavenger, light intensity had negligible impacts on SOA oxidation state and CCN activity. In contrast, when OH reaction was effectively suppressed (&gt; 11 ppm scavenger), SOA showed a much lower CCN activity and slightly less oxygenated state consistent with previously reported values. Though there is significant oxidized material present (O / C &gt; 0.25), no linear correlation existed between the mass ratio ion fragment 44 in the bulk organic mass (&lt;i&gt;f&lt;/i&gt;&lt;sub&gt;44&lt;/sub&gt;) and O / C for the β-C-O&lt;sub&gt;3&lt;/sub&gt; system. No direct correlations were observed with other aerosol bulk ion fragment fraction (&lt;i&gt;f&lt;/i&gt;&lt;sub&gt;&lt;i&gt;x&lt;/i&gt;&lt;/sub&gt;) and κ as well. A mixture of β-C and lower molecular weight terpenes (isoprene) consumed more ozone and formed SOA with distinct characteristics dependent on isoprene amounts. The addition of isoprene also improved the CCN predictive capabilities with bulk aerosol chemical information. The β-C SOA CCN activity reported here is much higher than previous studies (&amp;kappa; &lt; 0.1) that use higher precursor concentration in smaller environmental chambers; similar results were only achieved with significant use of OH scavenger. Results show that aerosol formed from a mixture of low and high molecular weight terpene ozonolysis can be hygroscopic and can contribute to the global biogenic SOA CCN budget

Secondary organic aerosol formation from the photooxidation of isoprene, 1,3-butadiene, and 2,3-dimethyl-1,3-butadiene under high NO&lt;sub&gt;x&lt;/sub&gt; conditions

Secondary organic aerosol (SOA) formation from atmospheric oxidation of isoprene has been the subject of multiple studies in recent years; however, reactions of other conjugated dienes emitted from anthropogenic sources remain poorly understood. SOA formation from the photooxidation of isoprene, isoprene-1-13C, 1,3-butadiene, and 2,3-dimethyl-1,3-butadiene is investigated for high NOx conditions. The SOA yield measured in the 1,3-butadiene/NOx/H2O2 irradiation system (0.089–0.178) was close to or slightly higher than that measured with isoprene under similar NOx conditions (0.077–0.103), suggesting that the photooxidation of 1,3-butadiene is a possible source of SOA in urban air. In contrast, a very small amount of SOA particles was produced in experiments with 2,3-dimethyl-1,3-butadiene. Off-line liquid chromatography – mass spectrometry analysis revealed that the signals of oligoesters comprise a major fraction (0.10–0.33) of the signals of the SOA products observed from all dienes investigated. The oligoesters originate from the unsaturated aldehyde gas phase diene reaction products; namely, semi-volatile compounds produced by the oxidation of the unsaturated aldehyde undergo particle-phase oligoester formation. Oligoesters produced by the dehydration reaction between nitrooxypolyol and 2-methylglyceric acid monomer or its oligomer were also characterized in these experiments with isoprene as the starting diene. These oligomers are possible sources of the 2-methyltetrols found in ambient aerosol samples collected under high NOx conditions. Furthermore, in low-temperature experiments also conducted in this study, the SOA yield measured with isoprene at 278 K was 2–3 times as high as that measured at 300 K under similar concentration conditions. Although oligomerization plays an important role in SOA formation from isoprene photooxidation, the observed temperature dependence of SOA yield is largely explained by gas/particle partitioning of semi-volatile compounds

Chamber studies of SOA formation from aromatic hydrocarbons: observation of limited glyoxal uptake

Abstract. This study evaluates the significance of glyoxal acting as an intermediate species leading to secondary organic aerosol (SOA) formation from aromatic hydrocarbon photooxidation under humid conditions. Rapid SOA formation from glyoxal uptake onto aqueous (NH4)2SO4 seed particles is observed in agreement with previous studies; however, glyoxal did not partition significantly to SOA (with or without aqueous seed) during aromatic hydrocarbon photooxidation within an environmental chamber (RH less than 80%). Rather, glyoxal influences SOA formation by raising hydroxyl (OH) radical concentrations. Four experimental approaches supporting this conclusion are presented in this paper: (1) increased SOA formation and decreased SOA volatility in the toluene + NOx photooxidation system with additional glyoxal was reproduced by matching OH radical concentrations through H2O2 addition; (2) glyoxal addition to SOA seed formed from toluene + NOx photooxidation did not increase SOA volume under dark; (3) SOA formation from toluene + NOx photooxidation with and without deliquesced (NH4)2SO4 seed resulted in similar SOA growth, consistent with a minor contribution from glyoxal uptake onto deliquesced seed and organic coatings; and (4) the fraction of a C4H9+ fragment (observed by Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer, HR-ToF-AMS) in SOA from 2-tert-butylphenol (BP) oxidation was unchanged in the presence of additional glyoxal despite enhanced SOA formation. This study suggests that glyoxal uptake onto aerosol during the oxidation of aromatic hydrocarbons is more limited than previously thought.</jats:p

Laboratory Characterization of PM Emissions from Combustion of Wildland Biomass Fuels

[1] Particle emissions from open burning of southwestern (SW) and southeastern (SE) U.S. fuel types during 77 controlled laboratory burns are presented. The fuels include SW vegetation types: ceanothus, chamise/scrub oak, coastal sage scrub, California sagebrush, manzanita, maritime chaparral, masticated mesquite, oak savanna, and oak woodland, as well as SE vegetation types: 1 year, 2 year rough, pocosin, chipped understory, understory hardwood, and pine litter. The SW fuels burned at higher modified combustion efficiency (MCE) than the SE fuels resulting in lower particulate matter mass emission factor. Particle mass distributions for six fuels and particle number emission for all fuels are reported. Excellent mass closure (slope = 1.00, r2 = 0.94) between ions, metals, and carbon with total weight was obtained. Organic carbon emission factors inversely correlated (R2 = 0.72) with average MCE, while elemental carbon (EC) had little correlation with average MCE (R2 = 0.10). The EC/total carbon ratio sharply increased with MCE for MCEs exceeding 0.94. The average levoglucosan and total polycyclic aromatic hydrocarbon (PAH) emissions factors ranged from 25 to 1272 mg/kg fuel and 1.8 to 11.3 mg/kg fuel, respectively. No correlation between average MCE and emissions of PAHs/levoglucosan was found. Additionally, PAH diagnostic ratios were observed to be poor indicators of biomass burning. Large fuel type and regional dependency were observed in the emission rates of ammonium, nitrate, chloride, sodium, and potassium

Cloud condensation nuclei (CCN) activity of aliphatic amine secondary aerosol

Aliphatic amines can form secondary aerosol via oxidation with atmospheric radicals (e.g., hydroxyl radical and nitrate radical). The particle can contain both secondary organic aerosol (SOA) and inorganic salts. The ratio of organic to inorganic materials in the particulate phase influences aerosol hygroscopicity and cloud condensation nuclei (CCN) activity. SOA formed from trimethylamine (TMA) and butylamine (BA) reactions with hydroxyl radical (OH) is composed of organic material of low hygroscopicity (single hygroscopicity parameter, κ, ≤ 0.25). Secondary aerosol formed from the tertiary aliphatic amine (TMA) with N_2O_5 (source of nitrate radical, NO_3) contains less volatile compounds than the primary aliphatic amine (BA) aerosol. As relative humidity (RH) increases, inorganic amine salts are formed as a result of acid–base reactions. The CCN activity of the humid TMA–N_2O_5 aerosol obeys Zdanovskii, Stokes, and Robinson (ZSR) ideal mixing rules. The humid BA + N_2O_5 aerosol products were found to be very sensitive to the temperature at which the measurements were made within the streamwise continuous-flow thermal gradient CCN counter; κ ranges from 0.4 to 0.7 dependent on the instrument supersaturation (ss) settings. The variance of the measured aerosol κ values indicates that simple ZSR rules cannot be applied to the CCN results from the primary aliphatic amine system. Overall, aliphatic amine aerosol systems' κ ranges within 0.2 < κ < 0.7. This work indicates that aerosols formed via nighttime reactions with amines are likely to produce hygroscopic and volatile aerosol, whereas photochemical reactions with OH produce secondary organic aerosol of lower CCN activity. The contributions of semivolatile secondary organic and inorganic material from aliphatic amines must be considered for accurate hygroscopicity and CCN predictions from aliphatic amine systems

Coupling Field and Laboratory Measurements to Estimate the Emission Factors of Identified and Unidentified Trace Gases for Prescribed Fires

An extensive program of experiments focused on biomass burning emissions began with a laboratory phase in which vegetative fuels commonly consumed in prescribed fires were collected in the southeastern and southwestern US and burned in a series of 71 fires at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The particulate matter (PM2.5) emissions were measured by gravimetric filter sampling with subsequent analysis for elemental carbon (EC), organic carbon (OC), and 38 elements. The trace gas emissions were measured by an open-path Fourier transform infrared (OP-FTIR) spectrometer, proton-transfer-reaction mass spectrometry (PTRMS), proton-transfer ion-trap mass spectrometry (PIT-MS), negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), and gas chromatography with MS detection (GC-MS). 204 trace gas species (mostly non-methane organic compounds (NMOC)) were identified and quantified with the above instruments. Many of the 182 species quantified by the GC-MS have rarely, if ever, been measured in smoke before. An additional 153 significant peaks in the unit mass resolution mass spectra were quantified, but either could not be identified or most of the signal at that molecular mass was unaccounted for by identifiable species. In a second, field phase of this program, airborne and ground-based measurements were made of the emissions from prescribed fires that were mostly located in the same land management units where the fuels for the lab fires were collected. A broad variety, but smaller number of species (21 trace gas species and PM2.5) was measured on 14 fires in chaparral and oak savanna in the southwestern US, as well as pine forest understory in the southeastern US and Sierra Nevada mountains of California. The field measurements of emission factors (EF) are useful both for modeling and to examine the representativeness of our lab fire EF. The lab EF/field EF ratio for the pine understory fuels was not statistically different from one, on average. However, our lab EF for smoldering compounds emitted from the semiarid shrubland fuels should likely be increased by a factor of similar to 2.7 to better represent field fires. Based on the lab/field comparison, we present emission factors for 357 pyrogenic species (including unidentified species) for 4 broad fuel types: pine understory, semiarid shrublands, coniferous canopy, and organic soil. To our knowledge this is the most comprehensive measurement of biomass burning emissions to date and it should enable improved representation of smoke composition in atmospheric models. The results support a recent estimate of global NMOC emissions from biomass burning that is much higher than widely used estimates and they provide important insights into the nature of smoke. 31-72% of the mass of gas-phase NMOC species was attributed to species that we could not identify. These unidentified species are not represented in most models, but some provision should be made for the fact that they will react in the atmosphere. In addition, the total mass of gas-phase NMOC divided by the mass of co-emitted PM2.5 averaged about three (range similar to 2.0-8.7). About 35-64% of the NMOC were likely semivolatile or of intermediate volatility. Thus, the gas-phase NMOC represent a large reservoir of potential precursors for secondary formation of ozone and organic aerosol. For the single lab fire in organic soil about 28% of the emitted carbon was present as gas-phase NMOC and similar to 72% of the mass of these NMOC was unidentified, highlighting the need to learn more about the emissions from smoldering organic soils. The mass ratio of total NMOC to NOx as NO ranged from 11 to 267, indicating that NOx-limited O-3 production would be common in evolving biomass burning plumes. The fuel consumption per unit area was 7.0 +/- 2.3 Mg ha(-1) and 7.7 +/- 3.7 Mg ha(-1) for pine-understory and semiarid shrubland prescribed fires, respectively

Are sesquiterpenes a good source of secondary organic cloud condensation nuclei (CCN)? Revisiting &amp;lt;i&amp;gt;β&amp;lt;/i&amp;gt;-caryophyllene CCN

Abstract. Secondary organic aerosol (SOA) was formed in an environmental reaction chamber from the ozonolysis of β-caryophyllene (β-C) at very low concentrations (5 ppb or 20 ppb) near ambient conditions. Experimental parameters were varied to characterize the effects of hydroxyl radicals, light and the presence of lower molecular weight terpene precursor (isoprene) for β-C SOA formation and Cloud Condensation Nuclei (CCN) characteristics. Changes in β-C SOA chemicophysical properties (e.g. density, volatility, oxidation state) were explored with online techniques to improve our predictive understanding of β-C CCN activity. In the absence of OH scavenger, light intensity had negligible impacts on SOA oxidation state and CCN activity. In contrast, when OH reaction was effectively suppressed (&gt;11ppm scavenger), SOA showed a much lower CCN activity and slightly less oxygenated state consistent with previously reported values. Though there is significant oxidized material present (O/C&gt;0.25), no linear correlation existed between the mass ratio ion fragment 44 in the bulk organic mass (f44) and O/C for the β-C-O3 system. No direct correlations were observed with other aerosol bulk ion fragment fraction (fx) and κ as well. A mixture of β-C and lower molecular weight terpenes (isoprene) consumed more ozone and formed SOA with distinct characteristics dependent on isoprene amounts. The addition of isoprene also improved the CCN predictive capabilities with bulk aerosol chemical information. The β-C SOA CCN activity reported here is much higher than previous studies (κ&gt;0.1) that use higher precursor concentration in smaller environmental chambers; similar results were only achieved with significant use of OH scavenger. Results show that aerosol formed from a mixture of low and high molecular weight terpene ozonolysis can be hygroscopic and can contribute to the global biogenic SOA CCN budget. </jats:p