Predicting Thermal Behavior of Secondary Organic Aerosols

Volume concentrations of secondary organic aerosol (SOA) are measured in 139 steady-state, single precursor hydrocarbon oxidation experiments after passing through a temperature controlled inlet. The response to change in temperature is well predicted through a feedforward Artificial Neural Network. The most parsimonious model, as indicated by Akaike’s Information Criterion, Corrected (AIC,C), utilizes 11 input variables, a single hidden layer of 4 tanh activation function nodes, and a single linear output function. This model predicts thermal behavior of single precursor aerosols to less than ±5%, which is within the measurement uncertainty, while limiting the problem of overfitting. Prediction of thermal behavior of SOA can be achieved by a concise number of descriptors of the precursor hydrocarbon including the number of internal and external double bonds, number of methyl- and ethyl- functional groups, molecular weight, and number of ring structures, in addition to the volume of SOA formed, and an indicator of which of four oxidant precursors was used to initiate reactions (NO_<i>x</i> photo-oxidation, photolysis of H₂O₂, ozonolysis, or thermal decomposition of N₂O₅). Additional input variables, such as chamber volumetric residence time, relative humidity, initial concentration of oxides of nitrogen, reacted hydrocarbon concentration, and further descriptors of the precursor hydrocarbon, including carbon number, number of oxygen atoms, and number of aromatic ring structures, lead to over fit models, and are unnecessary for an efficient, accurate predictive model of thermal behavior of SOA. This work indicates that predictive statistical modeling methods may be complementary to descriptive techniques for use in parametrization of air quality models

Trends in the oxidation and relative volatility of chamber-generated secondary organic aerosol

<p>The relationship between the oxidation state and relative volatility of secondary organic aerosol (SOA) from the oxidation of a wide range of hydrocarbons is investigated using a fast-stepping, scanning thermodenuder interfaced with a high-resolution time-of-flight aerosol mass spectrometer (AMS). SOA oxidation state varied widely across the investigated range of parent hydrocarbons but was relatively stable for replicate experiments using a single hydrocarbon precursor. On average, unit mass resolution indicators of SOA oxidation (e.g., AMS <i>f</i>₄₃ and <i>f</i>₄₄) are consistent with previously reported values. Linear regression of H:C vs. O:C obtained from parameterization of <i>f</i>₄₃ and <i>f</i>₄₄ and elemental analysis of high-resolution spectra in Van Krevelen space both yield a slope of ∼−0.5 across different SOA types. A similar slope was obtained for a distinct subset of toluene/NO<i>_x</i> reactions in which the integrated oxidant exposure was varied to alter oxidation. The relative volatility of different SOA types displays similar variability and is strongly correlated with SOA oxidation state (_C). On average, relatively low oxidation and volatility were observed for aliphatic alkene (including terpenes) and <i>n-</i>alkane SOA while the opposite is true for mono- and polycyclic aromatic hydrocarbon SOA. Effective enthalpy for total chamber aerosol obtained from volatility differential mobility analysis is also highly correlated with _C indicating a primary role for oxidation levels in determining the volatility of chamber SOA. Effective enthalpies for chamber SOA are substantially lower than those of neat organic standards but are on the order of those obtained for partially oligomerized glyoxal and methyl glyoxal.</p> <p>© 2018 American Association for Aerosol Research</p

Photochemical Conversion of Surrogate Emissions for Use in Toxicological Studies: Role of Particulate- and Gas-Phase Products

The production of photochemical atmospheres under controlled conditions in an irradiation chamber permits the manipulation of parameters that influence the resulting air-pollutant chemistry and potential biological effects. To date, no studies have examined how contrasting atmospheres with a similar Air Quality Health Index (AQHI), but with differing ratios of criteria air pollutants, might differentially affect health end points. Here, we produced two atmospheres with similar AQHIs based on the final concentrations of ozone, nitrogen dioxide, and particulate matter (PM_2.5). One simulated atmosphere (SA-PM) generated from irradiation of ∼23 ppmC gasoline, 5 ppmC α-pinene, 529 ppb NO, and 3 μg m^–3 (NH₄)₂SO₄ as a seed resulted in an average of 976 μg m^–3 PM_2.5, 326 ppb NO₂, and 141 ppb O₃ (AQHI 97.7). The other atmosphere (SA-O₃) generated from 8 ppmC gasoline, 5 ppmC isoprene, 874 ppb NO, and 2 μg m^–3 (NH₄)₂SO₄ resulted in an average of 55 μg m^–3 PM_2.5, 643 ppb NO₂, and 430 ppb O₃ (AQHI of 99.8). Chemical speciation by gas chromatography showed that photo-oxidation degraded the organic precursors and promoted the de novo formation of secondary reaction products such as formaldehyde and acrolein. Further work in accompanying papers describe toxicological outcomes from the two distinct photochemical atmospheres

2‑Hydroxyterpenylic Acid: An Oxygenated Marker Compound for α‑Pinene Secondary Organic Aerosol in Ambient Fine Aerosol

An oxygenated MW 188 compound is commonly observed in substantial abundance in atmospheric aerosol samples and was proposed in previous studies as an α-pinene-related marker compound that is associated with aging processes. Owing to difficulties in producing this compound in sufficient amounts in laboratory studies and the occurrence of isobaric isomers, a complete assignment for individual MW 188 compounds could not be achieved in these studies. Results from a comprehensive mass spectrometric analysis are presented here to corroborate the proposed structure of the most abundant MW 188 compound as a 2-hydroxyterpenylic acid diastereoisomer with 2<i>R</i>,3<i>R</i> configuration. The application of collision-induced dissociation with liquid chromatography/electrospray ionization-ion trap mass spectrometry in both negative and positive ion modes, as well as chemical derivatization to methyl ester derivatives and analysis by the latter technique and gas chromatography/electron ionization mass spectrometry, enabled a comprehensive characterization of MW 188 isomers, including a detailed study of the fragmentation behavior using both mass spectrometric techniques. Furthermore, a MW 188 positional isomer, 4-hydroxyterpenylic acid, was tentatively identified, which also is of atmospheric relevance as it could be detected in ambient fine aerosol. Quantum chemical calculations were performed to support the diastereoisomeric assignment of the 2-hydroxyterpenylic acid isomers. Results from a time-resolved α-pinene photooxidation experiment show that the 2-hydroxyterpenylic acid 2<i>R</i>,3<i>R</i> diastereoisomer has a time profile distinctly different from that of 3-methyl-1,2,3-butanetricarboxylic acid, a marker for oxygenated (aged) secondary organic aerosol. This study presents a comprehensive chemical data set for a more complete structural characterization of hydroxyterpenylic acids in ambient fine aerosol, which sets the foundation to better understand the atmospheric fate of α-pinene in future studies

Epoxide Pathways Improve Model Predictions of Isoprene Markers and Reveal Key Role of Acidity in Aerosol Formation

Isoprene significantly contributes to organic aerosol in the southeastern United States where biogenic hydrocarbons mix with anthropogenic emissions. In this work, the Community Multiscale Air Quality model is updated to predict isoprene aerosol from epoxides produced under both high- and low-NO_<i>x</i> conditions. The new aqueous aerosol pathways allow for explicit predictions of two key isoprene-derived species, 2-methyltetrols and 2-methylglyceric acid, that are more consistent with observations than estimates based on semivolatile partitioning. The new mechanism represents a significant source of organic carbon in the lower 2 km of the atmosphere and captures the abundance of 2-methyltetrols relative to organosulfates during the simulation period. For the parametrization considered here, a 25% reduction in SO_<i>x</i> emissions effectively reduces isoprene aerosol, while a similar reduction in NO_<i>x</i> leads to small increases in isoprene aerosol