CINDI-3 glyoxal intercomparison

Secondary organic aerosol formation from straw burning using an oxidation flow reactor

Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

Reutilization of Cr-Y zeolite obtained by biosorption in the catalytic oxidation of volatile organic compounds

Abstract. Secondary pollutants such as ozone, secondary inorganic aerosol, and secondary organic aerosol formed in the plumes of megacities can affect regional air quality. In the framework of the FP7/EU MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) project, an intensive campaign was launched in the greater Paris region in July 2009. The major objective was to quantify different sources of organic aerosol (OA) within a megacity and in its plume. In this study, we use airborne measurements aboard the French ATR-42 aircraft to evaluate the regional chemistry-transport model CHIMERE within and downwind of the Paris region. Two mechanisms of secondary OA (SOA) formation are used, both including SOA formation from oxidation and chemical aging of primary semivolatile and intermediate volatility organic compounds (SI-SOA) in the volatility basis set (VBS) framework. As for SOA formed from traditional VOC (volatile organic compound) precursors (traditional SOA), one applies chemical aging in the VBS framework adopting different SOA yields for high- and low-NOx environments, while another applies a single-step oxidation scheme without chemical aging. Two emission inventories are used for discussion of emission uncertainties. The slopes of the airborne OA levels versus Ox (i.e., O3 + NO2) show SOA formation normalized with respect to photochemical activity and are used for specific evaluation of the OA scheme in the model. The simulated slopes were overestimated slightly by factors of 1.1, 1.7 and 1.3 with respect to those observed for the three airborne measurements, when the most realistic "high-NOx" yields for traditional SOA formation in the VBS scheme are used in the model. In addition, these slopes are relatively stable from one day to another, which suggests that they are characteristic for the given megacity plume environment. The configuration with increased primary organic aerosol (POA) emissions and with a single-step oxidation scheme of traditional SOA also agrees with the OA / Ox slopes (about ± 50 % with respect to the observed ones); however, it underestimates the background. Both configurations are coherent with observed OA plume buildup, but they show very different SI-SOA and traditional anthropogenic SOA (ASOA) contributions. It is hence concluded that available theoretical knowledge and available data in this study are not sufficient to discern the relative contributions of different types of anthropogenic SOA in the Paris pollution plume, while its sum is correctly simulated. Based on these simulations, for specific plumes, the anthropogenic OA buildup can reach between 8 and 10μg m−3. For the average of the month of July 2009, maximum OA increases due to emissions from the Paris agglomeration are noticed close to the agglomeration at various length scales: several tens (for primary OA) to hundreds (for SI-SOA and ASOA) of kilometers from the Paris agglomeration. In addition, BSOA (SOA formed from biogenic VOC precursors) is an important contributor to regional OA levels (inside and outside the Paris plume).

Diurnal evolution of organic aerosol over boreal and tropical forests The first research question of this thesis is: how do local surface forcings and large-scale meteorological forcings shape the evolution of organic aerosol over the boreal and tropical forest? This question is dealt with in Chapters 3 and 4 in case studies for the boreal and tropical forest, respectively. To answer this question a modeling tool (MXLCH-SOA) is developed, which represents land surface conditions and dynamical and chemical processes that influence the evolution of organic aerosol (OA) in a balanced way. The novelty of our approach is that it combines the dynamics of a convective boundary layer (BL) with a reduced gas-phase chemistry mechanism and a module for gas/particle-partitioning of semi-volatile organic species. The principles and governing equations of this modeling tool are described in Chapter 2 and in the subsequent chapters the simplified chemical reaction schemes are presented to calculate secondary organic aerosol (SOA) formation from terpenes (Chapter 3 and 4) and from isoprene (Chapter 4). Despite its simplicity, MXLCH-SOA is able to satisfactorily reproduce the main observed characteristics of dynamics, gas-phase chemistry and gas/particle partitioning for the two studied forest ecosystems and it enables us to explain the temporal variability of the concentrations of organic aerosol and its precursors as a function of the various processes. In short, the results show that the diurnal evolution of organic aerosol in a boreal and a tropical forest is the net result of land surface conditions, boundary layer dynamics, chemical transformations and gas/particle partitioning. In the case study for the boreal forest, the entrainment term of the background OA dominates the OA tendency, while in the tropical forest case it is the interplay of several local and large scale processes that shape the diurnal evolution of OA. A sensitivity analysis for the boreal forest case further shows that the OA concentration is sensitive to both volatile organic compound (VOC) emissions and the partitioning of the surface energy budget into a latent and a sensible heat flux. We have identified two regimes, based on which of the two studied land surface drivers dominates: one in which OA is mainly driven by SOA formation from the emitted VOCs and another in which dilution due to entrainment, as driven by the surface energy fluxes, determines the OA concentration. A background OA to fresh SOA ratio is introduced to facilitate the interpretation of this analysis and is used to quantify the contributions of both fresh and background components to the total OA concentration. One main difference between the two case studies is that in the boreal forest entrainment appears to dominate the diurnal cycle, which leads to a decreasing OA concentration during the day, while in the tropical forest the formation of SOA from both isoprene and terpenes leads to increasing OA concentrations during day time. The MXLCH-SOA framework therefore shows the need to represent all these biochemical and physical processes simultaneously in order to understand the diurnal evolution of OA. As the boundary layer dynamics-chemistry system is not a closed system, it is necessary to further study the influence of external forcings on the diurnal evolution of OA, besides the surface forcings. Two types of large-scale meteorological forcings and their effects on OA evolution through their impact on BL dynamics have been studied: subsidence due to the presence of a high pressure system and advection of relatively cool air. In Chapter 3 a theoretical sensitivity analysis is given of OA evolution to subsidence, which is applied to the tropical forest case study in Chapter 4. Subsidence has a rather counter-intuitive effect on OA concentrations: even though it suppresses the growth of the BL and consequently decreases the mixing volume for chemical species, it leads to decreased OA concentrations. The reason for this is that entrainment is strongly enhanced in case of subsidence due to thermodynamic effects, which results in a stronger dilution of OA. This knowledge is applied in the case study for the tropical forest in Chapter 4, since results from a large-scale model show subsiding air motions over the measurement site and surroundings at Borneo. In addition to subsidence, the advection of cool air is needed to reproduce the observed boundary layer dynamics at Borneo: only if subsidence and advection of relatively cool air are accounted for, the observed low BL height can be reconciled with the large observed surface sensible and latent heat flux. This cool air suppresses BL growth and entrainment. Consequently, the aerosol is trapped in a shallower layer, which leads to an increased concentration compared to the case without advection of cooler air. In conclusion, the large-scale meteorological forcings subsidence and advection of cool air have opposing effects on the diurnal evolution of OA, even though both suppress BL growth. These findings show the utility of our method in identifying effects that should be accounted for in large-scale chemistry transport models. The second research question is whether recently discovered pathways of isoprene chemistry are the key to closing the gap between measured and modeled organic aerosol concentrations in tropical forests and other high isoprene environments. To address this issue, several mechanisms which may affect SOA formation from isoprene are implemented in MXLCH-SOA and discussed in Chapter 4. The hydroxyl radical (OH), the main oxidant of isoprene, is thought to be regenerated in the oxidation of isoprene. We find that for the tropical forest case study, we cannot reconcile the modeled concentrations of VOCs, OH and OA with their observed concentrations and fluxes both for cases with and without OH recycling. Therefore, we conclude that the issue of recycling of the OH radical in the oxidation of isoprene has to be solved before its effect on SOA formation can be determined. The formation of SOA from isoprene involves multiple generations of oxidation and due to this complex chemistry there is no single mechanism which can explain SOA formation from isoprene under all conditions. To gain understanding in this issue, we have implemented different pathways through which isoprene SOA is known to form, although we do not explicitly account for the detailed isoprene oxidation chain. A central aspect of this branching approach is whether the isoprene peroxy radical chemistry follows the low- or the high-NOx pathway. We find that the latter channel dominates in our case study. For SOA formed through the high-NOx channel, we further account for the effect of the NO2/NO ratio on SOA yields. In the presented case study this has little effect as this ratio is low, it but could be more important in regions with slower photochemistry or higher emissions of anthropogenic pollution. In the low-NOx regime, isoprene epoxides (IEPOX) are important intermediate gas-phase species in the formation of isoprene SOA. Even though the low-NOx pathway is only a minor one here, the amount of IEPOX SOA formed is likely substantial, although a better understanding of the exact mechanisms for its formation is needed to confirm this. However, as in previous studies we systematically underestimate the organic aerosol concentration in a tropical forest even though we incorporate the state-of-the-art knowledge on isoprene SOA formation in MXLCH-SOA. Nevertheless, we advocate accounting for NOx regime specific chemical pathways when modeling isoprene SOA formation. As this field is rapidly evolving in terms of the development of new measurement techniques and the discovery of chemical mechanisms, we strongly recommend the intensive use of our modeling system to gain further understanding of the diurnal variability of OA and for testing new hypotheses under atmospheric conditions. Satellite observations of cloud droplet concentration over the boreal forest The final objective of this thesis is to understand how aerosols and meteorological factors influence cloud droplet concentration over the boreal forest. This is a first step in translating the process understanding such as addressed in the previous chapters to larger spatio-temporal scales. Since this objective considers different temporal and spatial scales, a different method is applied in Chapter 5 than in the foregoing chapters. Observations of cloud properties by the MODIS instrument onboard the Terra satellite are combined with a model that contains the microphysics and thermodynamics of a single-layered water cloud to obtain a seasonal cycle of cloud droplet number concentrations, averaged over 9 years of data. This seasonal cycle in cloud droplet concentration is compared with aerosol concentrations at the surface and meteorological fields from ECMWF reanalysis. We find that the cloud droplet number concentration is related to the potential temperature gradient in the boundary layer, a measure for the strength of convection, while it shows no clear relationship with the cloud active aerosol concentration at the surface. From this we conclude that the convective transport of the aerosols from the surface to cloud base is the limiting factor for their activation as cloud droplets. However, convection will also influence the formation of clouds from a thermodynamic perspective. Therefore, it is likely that convection, as driven by land surface conditions, regulates both transport of aerosols to cloud base and the height of the cloud base, defined as the height at which water vapor reaches its saturation pressure. To ultimately understand the effect of the boreal forest on cloud properties, the effects of aerosols and thermodynamics should be studied simultaneously.

Vehicular evaporative emissions make an increasing contribution to anthropogenic sources of volatile organic compounds (VOCs), thus contributing to secondary organic aerosol (SOA) formation. However, few studies have been conducted on SOA formation from vehicle evaporative VOCs under complex pollution conditions with the coexistence of NOx, SO2, and NH3. In this study, the synergistic effects of SO2 and NH3 on SOA formation from gasoline evaporative VOCs with NOx were examined using a 30 m3 smog chamber with the aid of a series of mass spectrometers. Compared with the systems involving SO2 or NH3 alone, SO2 and NH3 coexistence had a greater promotion effect on SOA formation, which was larger than the cumulative effect of the two promotions alone. Meanwhile, contrasting effects of SO2 on the oxidation state (OSc) of SOA in the presence or absence of NH3 were observed, and SO2 could further increase the OSc with the coexistence of NH3. The latter was attributed to the synergistic effects of SO2 and NH3 coexistence on SOA formation, wherein N-S-O adducts can be formed from the reaction of SO2 with N-heterocycles generated in the presence of NH3. Our study contributes to the understanding of SOA formation from vehicle evaporative VOCs under highly complex pollution conditions and its atmospheric implications.

Abstract. Biogenic secondary organic aerosol (SOA) makes up a substantial fraction of atmospheric fine particulate mass, with important implications for climate and human health. However, its chemical formation processes remain poorly understood and are often oversimplified in 3D atmospheric models. Recent studies have found that the peroxy radical (RO2) isomerization and the RO2 accretion reactions (RO2 + RO2) can lead to SOA formation. We expand the RO2 chemical mechanism in the Community Earth System Model version 2 to include these two additional pathways for biogenic SOA formed through the OH oxidation of volatile organic compounds (VOCs). Using this mechanism, we quantify the contribution of each RO2 pathway to biogenic SOA formation and examine how these contributions evolve from the pre-industrial (PI) to present-day (PD) and future (F). We find that in PD conditions, RO2 isomerization accounts for 44–46 % of monoterpene SOA, while the contribution from RO2 + RO2 pathways is minor. From PI to F, the RO2 fate varies in response to atmospheric NOx levels and climate, but the contribution from RO2 isomerization is consistently high for monoterpenes, underscoring the importance of representing this pathway in SOA parameterizations. In addition, total biogenic SOA formed through OH oxidation decreases by 41 % from PI to PD and increases by 113 % from PD to F, driven primarily by changes in biogenic VOC emissions. Our results highlight the need to better constrain RO2 pathways for SOA formation through laboratory studies and represent this RO2 chemistry in SOA modeling.

Nitrogen-containing heterocyclic volatile organic compounds (VOCs) are important components of wildfire emissions that are readily reactive toward nitrate radicals (NO3) during nighttime, but the oxidation mechanism and the potential formation of secondary organic aerosol (SOA) and brown carbon (BrC) are unclear. Here, NO3 oxidation of three nitrogen-containing heterocyclic VOCs, pyrrole, 1-methylyrrole (1-MP), and 2-methylpyrrole (2-MP), was investigated in chamber experiments to determine the effect of precursor structures on SOA and BrC formation. The SOA chemical compositions and the optical properties were analyzed using a suite of online and offline instrumentation. Dinitro- and trinitro-products were found to be the dominant SOA constituents from pyrrole and 2-MP, but not observed from 1-MP. Furthermore, the SOA from 2-MP and pyrrole showed strong light absorption, while that from 1-MP were mostly scattering. From these results, we propose that NO3-initiated hydrogen abstraction from the 1-position in pyrrole and 2-MP followed by radical shift and NO2 addition leads to light-absorbing nitroaromatic products. In the absence of a 1-position hydrogen, NO3 addition likely dominates the 1-MP chemistry. We also estimate that the total SOA mass and light absorption from pyrrole and 2-MP are comparable to those from phenolic VOCs and toluene in biomass burning, underscoring the importance of considering nighttime oxidation of pyrrole and methylpyrroles in air quality and climate models.

There have been growing interests in modeling studies to understand oxidation of volatile organic compounds in the gas phase and their mass transfer to the aqueous phase for their potential roles in cloud chemistry, formation of secondary organic aerosols, and fate of atmospheric organics. Temperature-dependent Henry's law constants, key parameters in the atmospheric models to account for mass transfer, are often unavailable. In the present work, we investigated gas-liquid equilibriums of isoprene, limonene, α-pinene, and linalool using a bubble column technique. These compounds, originating from biogenic sources, were selected for their implications in atmospheric cloud chemistry and secondary organic aerosol formation. We reported Henry's law constants (K(H)), first order loss rates (k), and gas phase diffusion coefficients over a range of temperatures relevant to the lower atmosphere (278-298 K) for the first time. The measurement results of K(H) values for isoprene, limonene, α-pinene, and linalool at 298 K were 0.036 ± 0.003; 0.048 ± 0.004; 0.029 ± 0.004; and 21.20 ± 0.30 mol L(-1) atm(-1), respectively. The fraction for these compounds in stratocumulus and cumulonimbus clouds at 278 K were also estimated in this work (isoprene, 1.0 × 10(-6), 6.8 × 10(-6); limonene, 1.5 × 10(-6), 1.0 × 10(-5); α-pinene, 4.5 × 10(-7), 3.1 × 10(-6); and linalool, 6.2 × 10(-4), 4.2 × 10(-3)). Our measurements in combination with literature results indicated that noncyclic alkenes could have smaller K(H) values than those of cyclic terpenes and that K(H) values may increase with an increasing number of double bonds. It was also shown that estimated Henry's law constants and their temperature dependence based on model prediction can differ from experimental results considerably and that direct measurements of temperature-dependent Henry's law constants of atmospheric organics are necessary for future work.

Source profiles and emission factors of VOCs from solvent-based architectural coatings and their contributions to ozone and secondary organic aerosol formation in China

Plants produce a variety of volatile organic compounds (VOCs). Under abiotic and biotic stresses, the number and amount of produced compounds can increase. Due to their long life span and large size, trees can produce biogenic VOCs (BVOCs) in much higher amounts than many other plants. It has been suggested that at cellular and tree physiological levels, induced production of VOCs is aimed at improving plant resistance to damage by reactive oxygen species generated by multiple abiotic stresses. In the few reported cases when biosynthesis of plant volatiles is inhibited or enhanced, the observed response to stress can be attributed to plant volatiles. Reported increase, e.g., in photosynthesis has mostly ranged between 5 and 50%. A comprehensive model to explain similar induction of VOCs under multiple biotic stresses is not yet available. As a result of pathogen or herbivore attack on forest trees, the induced production of VOCs is localized to the damage site but systemic induction of emissions has also been detected. These volatiles can affect fungal pathogens and the arrival rate of herbivorous insects on damaged trees, but also act as signalling compounds to maintain the trophic cascades that may improve tree fitness by improved efficiency of herbivore natural enemies. On the forest scale, biotic induction of VOC synthesis and release leads to an amplified flow of BVOCs in atmospheric reactions, which in atmospheres rich in oxides of nitrogen (NOx) results in ozone formation, and in low NOx atmospheres results in oxidation of VOCs, removal in ozone from the troposphere and the resulting formation of biogenic secondary organic aerosol (SOA) particles. I will summarize recent advances in the understanding of stress-induced VOC emissions from trees, with special focus on Populus spp. Particular importance is given to the ecological and atmospheric feedback systems based on BVOCs and biogenic SOA formation.

Secondary organic aerosols (SOA), formed through the gas-phase oxidation of volatile organic compounds (VOCs), can reside in the atmosphere for many days. The formation of SOA takes place rapidly within hours after VOC emissions, but SOA can undergo much slower physical and chemical processes throughout their lifetime in the atmosphere. The acidity of atmospheric aerosols spans a wide range, with the most acidic particles having negative pH values, which can promote acid-catalyzed reactions. The goal of this work is to elucidate poorly understood mechanisms and rates of acid-catalyzed aging of mixtures of representative SOA compounds. SOA were generated by the ozonolysis of α-pinene in a continuous flow reactor and then collected using a foil substrate. SOA samples were extracted and aged by exposure to varying concentrations of aqueous H2SO4 for 1-2 days. Chemical analysis of fresh and aged samples was conducted using ultra-performance liquid chromatography coupled with photodiode array spectrophotomety and high-resolution mass spectrometry. In addition, UV-vis spectrophotometry and fluorescence spectrophotometry were used to examine the changes in optical properties before and after aging. We observed that SOA that aged in moderately acidic conditions (pH from 0 to 4) experienced small changes in composition, while SOA that aged in a highly acidic environment (pH from -1 to 0) experienced more dramatic changes in composition, including the formation of compounds containing sulfur. Additionally, at highly acidic conditions, light-absorbing and fluorescent compounds appeared, but their identities could not be ascertained due to their small relative abundance. This study shows that acidity is a major driver of SOA aging, resulting in a large change in the chemical composition and optical properties of aerosols in regions where high concentrations of H2SO4 persist, such as upper troposphere and lower stratosphere.

Volatile Organic Compounds (VOCs) could contribute to the formation of secondary organic aerosols and ozone, both of which are detrimental to human health and the environment. There has been growing interest in developing more precise methods for analyzing VOC sources, and Positive Matrix Factorization (PMF) is widely used. However, overlapping chemical compositions of the retrieved factor profiles often pose challenges in accurately distinguishing sources, even with high-resolution VOC data. While the role of organic compounds (OC) in enhancing PMF-based source apportionment of PM2.5 has been well-documented, studies integrating VOCs with organic molecular tracers remain limited. This study aims to integrate VOCs and organic molecular tracers into PMF analysis to improve the accuracy of source identification and quantification.Hourly VOC monitoring and 12-hour integrated filter sampling were conducted during a 21-day period in summer at an industrial complex in southern Taiwan. A two-stage PMF modeling approach was applied, with the first stage focusing on VOC analysis and the second stage incorporating both VOC and OC markers. In Stage 1, seven factors were identified, with the three highest contributors attributed to Vehicle Gasoline Combustion (18%), Industrial Emissions (17%), and Synthetic Resin and Paints (16%). In Stage 2, after incorporating OC data, additional sources were identified, including biogenic emissions, cooking sources and  biomass burning, offering a more comprehensive source apportionment. These findings demonstrate that incorporating organic species can bridge gaps in VOC source apportionment, enhancing the resolution and accuracy of pollution source identification.

A new secondary organic aerosol (SOA) parameterization based on the volatility basis set is implemented in a regional air quality model WRF‐CHEM. Full meteorological and chemistry simulations are carried out for the United States for August–September 2006. Predicted organic aerosol (OA) concentrations are compared against surface measurements made by several networks and aircraft data from the TexAQS‐2006 field campaign. Elemental carbon simulations are also evaluated in order to evaluate the model's ability to capture their emissions, transport, and removal. Certain measurement limitations, such as daily averaged OA concentrations, impose some difficulties on the model evaluation, and hourly averaged OA measurements provide more informative constraints compared to daily concentrations. The updated model demonstrates a significant improvement in simulating the OA concentrations compared to the standard WRF‐CHEM, which predicts very little SOA. The improvement in organic carbon (OC) predictions is noticeable in correlations and model bias. The correlations of OC exceed that of the persistence forecasts for hourly concentrations in the southeast United States during daytime. The updated traditional SOA yields still lead to an underestimation of observed OA, while addition of the multigenerational volatile organic compound (VOC) oxidation drastically improves model performance. However, several key uncertainties remain in SOA formation and loss mechanisms, which are characterized through several perturbation simulations. Dry deposition of VOC oxidation products is an important factor in the atmospheric SOA budget. The combination of the biogenic VOC emissions, updated SOA yields, and aging mechanism result in biogenic SOA being the dominant OA component for much of the nonurban United States.

Emission characteristics of volatile organic compounds and their secondary organic aerosol formation potentials from a petroleum refinery in Pearl River Delta, China.