Low-volatility Products Research Articles

Chemical Composition of Secondary Organic Aerosol Formed from the Oxidation of Semivolatile Isoprene Epoxydiol Isomerization Products.

3-Methylenebutane-1,2,4-triol and 3-methyltetrahydrofuran-2,4-diols, previously designated "C5-alkene triols", were recently confirmed as in-particle isomerization products of isoprene-derived β-IEPOX isomers that are formed upon acid-driven uptake and partition back into the gas phase. In chamber experiments, we have systematically explored their gas phase oxidation by hydroxyl radical (•OH) as a potential source of secondary organic aerosol (SOA). •OH-initiated oxidation of both compounds in the presence of ammonium bisulfate aerosol resulted in substantial aerosol volume growth. Compositions of low-volatility products in both the gas and particulate phases were established by high-resolution mass spectrometry measurements. Under conditions mimicking the Southeast USA (50% relative humidity, bulk seed aerosol pH 1.4), we estimate the SOA yield from •OH-initiated oxidation of 3-methylenebutane-1,2,4-triol to be 93.1%, equating to 1.95 ± 0.81 Tg C Yr-1, and from 3-methyltetrahydrofuran-2,4-diol oxidation to be 26.7%, equating to 1.76 ± 1.26 Tg C Yr-1. Previously unreported isoprene-derived oxidation products, 2,3-dihydroxy-2-(hydroxymethyl)propanal, 1,3,4-trihydroxybutan-2-one, and four organosulfates have been confirmed in ambient SOA, and aid in understanding isoprene oxidation pathways in HO2• dominated environments as NOx levels continue to decline in the US. This work underlines the need for inclusion of partitioning of in-particle formed semivolatile products and their atmospheric oxidation pathways in atmospheric models.

Ether and ester formation from peroxy radical recombination: a qualitative reaction channel analysis

Abstract. The least volatile organic compounds participating in atmospheric new-particle formation are very likely accretion products from self- and cross-reactions of peroxy radicals (RO2). It has long been assumed that the only possible accretion product channel in this reaction is that forming a peroxide (RO2+RO2→ROOR+O2), but it has recently been discovered that a rapid alkoxy radical (RO) decomposition may precede the accretion step of the mechanism, forming slightly fragmented but more stable ether (ROR) or ester (RC′(O)OR) accretion products. In this work, the atmospheric implications of this new reaction channel have been explored further by using a modified version of the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) software to generate a large amount of representative RO2 + RO2 reactive pairs formed from the oxidation of typical primary hydrocarbons and by applying structure–activity relationships (SARs) to predict the potential accretion products. These data are analysed in terms of the formation of low-volatility products, and new discoveries are presented on what types of RO2 are especially efficient (and which are surprisingly inefficient) at forming accretion products. These findings are discussed in terms of the atmospheric relevance of these new RO2 + RO2 reaction channels. As the generation of these data rests on several simplifications and assumptions, many open questions worthy of later studies are also raised.

Modeling impacts of indoor environmental variables on secondary organic aerosol formation

There are numerous air pollutants indoors including chemicals emitted from building environments as well as outdoor-origin species due to human activities. Despite the significance of indoor air quality, the atmospheric process indoors is not well studied. In this study, the secondary organic aerosol (SOA) formation from the oxidation of α-pinene blended with toluene was simulated under varying indoor environments (lamps, NO2, ozone, and inorganic seed) using the UNIfied Partitioning Aerosol Reaction (UNIPAR) model. Explicitly predicted lumping species produced during the atmospheric oxidation of precursors are used in the model and they process multiphase partitioning and aerosol phase reactions. The performance of the model was demonstrated using indoor chamber experiments in both dark conditions (ozonolysis) and light conditions with commercialized fluorescent or LED lamps. α-Pinene SOA was dominated by ozonolysis even in the presence of indoor light. Toluene, which is known to be photochemically processed, was oxidized in the dark condition with OH radicals that were derived from ozonolysis products of α-pinene. At given dark simulation conditions (10 ppb α-pinene, 30 ppb ozone, and 50 ppb of toluene), toluene contributed 15 % of SOA mass. α-Pinene SOA was insensitive to hygroscopicity of inorganic seed, but toluene blended with α-pinene increased the sensitivity to seed conditions due to the formation of oligomeric matter via aqueous reactions of reactive toluene products. In the presence of NO2. α-pinene SOA formation significantly increased with increasing NO2 owing to the reaction of α-pinene with nitrate radicals to form low volatile products. This study concludes that ozone and NO2, intruded from outdoors to indoors, effectively oxidize terpenes and furthermore aromatic hydrocarbons with OH radicals originating from ozonolysis of terpenes. The reaction paths with ozone and nitrate radicals are more effective at forming SOA than that with OH radical under the indoor light condition with commercialized lamps.

Interaction between marine and terrestrial biogenic volatile organic compounds: Non-linear effect on secondary organic aerosol formation

Biogenic volatile organic compounds (BVOCs) are the largest source of secondary organic aerosols (SOA) globally. However, the complex interactions between marine and terrestrial BVOCs remain unclear, inhibiting our in-depth understanding of the SOA formation in the coastal areas and its environmental impacts. Here, we performed smog chamber experiments with mixed α-pinene (a typical monoterpene) and dimethyl sulfide (DMS, a typical marine emission BVOC) to investigate their possible interactions and subsequent SOA formation. It is found that DMS has a non-linear effect on SOA generation: The mass concentration and yield of SOA show increasing and then decreasing trends with the increase of the initial concentration of DMS. The increasing trend can be attributed to OH regeneration from isomerization of the CH3SCH2OO radical together with acid-catalyzed heterogeneous reactions by the oxidation of DMS, while the decreasing trend is explained by the less contribution of isomerization reaction and the high OH reactivity that inhibits the formation of low volatility products. The results from infrared spectra and mass spectra together reveal the contribution of sulfur-containing molecules in the mixed system. Moreover, the mass spectra results indicate that acidic products generated by DMS photooxidation enhance the O:C ratio, while organosulfates are produced to contribute to the formation of mixed SOA. In addition, the trends in relative abundance of highly oxygenated organic molecules (HOMs) with C8 - C10 multiple functional groups in different mixed systems agree well with the turning point of the SOA yield. The findings of this study have significant implications for understanding binary or more complex systems in the atmosphere in the coastal areas.

Can we achieve atmospheric chemical environments in the laboratory? An integrated model-measurement approach to chamber SOA studies.

Secondary organic aerosol (SOA), atmospheric particulate matter formed from low-volatility products of volatile organic compound (VOC) oxidation, affects both air quality and climate. Current 3D models, however, cannot reproduce the observed variability in atmospheric organic aerosol. Because many SOA model descriptions are derived from environmental chamber experiments, our ability to represent atmospheric conditions in chambers directly affects our ability to assess the air quality and climate impacts of SOA. Here, we develop an approach that leverages global modeling and detailed mechanisms to design chamber experiments that mimic the atmospheric chemistry of organic peroxy radicals (RO2), a key intermediate in VOC oxidation. Drawing on decades of laboratory experiments, we develop a framework for quantitatively describing RO2 chemistry and show that no previous experimental approaches to studying SOA formation have accessed the relevant atmospheric RO2 fate distribution. We show proof-of-concept experiments that demonstrate how SOA experiments can access a range of atmospheric chemical environments and propose several directions for future studies.

Chemical composition, thermal profile and functional properties of grasshopper (Sphenarium purpurascens Ch.), cockroach (Nauphoeta cinerea) flours and their mixtures

SummaryThe use of insects as food is a hot topic today and the obtaining and comprehensive characterisation of insect meals is relevant since any scientific information represents progress towards the real use of these ‘new foods’. Therefore, the objective of this study was to evaluate the chemical composition of flours obtained from Sphenarium purpurascens Ch. and Nauphoeta cinerea, identify the main components and know their functional properties and thermal profile in flours and their mixtures to establish their potential applications as ingredients in the food and feed industry. The results revealed that flours and their mixtures can be used to increase the nutritional value of foods, especially thanks to their high protein content (35%–38%); in addition, their potential uses are numerous and range from baking, snacks, drinks and meat substitutes thanks to their techno‐functional and thermal properties. Regarding the thermal profile, this study presents results above 250 °C that have not been reported before for these insects and relate to the decomposition of acetylglucosamine units and the evaporation of low molecular weight volatile products that have not been reported for the flours of these insects. This study represents an advance in terms of the use of insects, pending attention to issues such as innocuity.

Dual roles of the inorganic aqueous phase on secondary organic aerosol growth from benzene and phenol

Abstract. Benzene, emitted from automobile exhaust and biomass burning, is ubiquitous in ambient air. Benzene is a precursor hydrocarbon (HC) that forms secondary organic aerosol (SOA), but its SOA formation mechanism is not well studied. To accurately predict the formation of benzene SOA, it is important to understand the gas mechanisms of phenol, which is one of the major products formed from the atmospheric oxidation of benzene. Laboratory data presented herein highlight the impact of the aqueous phase on SOA generated through benzene and phenol oxidation. The roles of the aqueous phase consist of (1) suppression of the aging of hydrocarbon and (2) conventional acid-catalyzed reactions in the inorganic phase. To explain this unusual effect, it is hypothesized that a persistent phenoxy radical (PPR) effectively forms via a heterogeneous reaction of phenol and phenol-related products in the presence of wet inorganic aerosol. These PPR species are capable of catalytically consuming ozone during an NOx cycle and negatively influencing SOA growth. In this study, explicit gas mechanisms were derived to produce the oxygenated products from the atmospheric oxidation of phenol or benzene. Gas mechanisms include the existing Master Chemical Mechanism (MCM v3.3.1), the reaction path for peroxy radical adducts originating from the addition of an OH radical to phenols forming low-volatility products (e.g., multi-hydroxy aromatics), and the mechanisms to form heterogeneous production of PPR. The simulated gas products were classified into volatility- and reactivity-based lumped species and incorporated into the Unified Partitioning Aerosol Reaction (UNIPAR) model that predicts SOA formation via multiphase reactions of phenol or benzene. The predictability of the UNIPAR model was examined using chamber data, which were generated for the photooxidation of phenol or benzene under controlled experimental conditions (NOx levels, humidity, and inorganic seed types). The SOA formation from both phenol and benzene still increased in the presence of wet inorganic seed because of the oligomerization of reactive organic species in the aqueous phase. However, model simulations show a significant suppression of ozone, the oxidation of phenol or benzene, and SOA growth compared with those without PPR mechanisms. The production of PPR is accelerated in the presence of acidic aerosol and this weakens SOA growth. In benzene oxidation, up to 53 % of the oxidation pathway is connected to phenol formation in the reported gas mechanism. Thus, the contribution of PPR to gas mechanisms is less than that of phenol. Overall, SOA growth in phenol or benzene is negatively related to NOx levels in the high-NOx region (HC ppbC / NOx ppb < 5). However, the simulation indicates that the significance of PPR rises with decreasing NOx levels. Hence, the influence of NOx levels on SOA formation from phenol or benzene is complex under varying temperature and seed type conditions. Adding the comprehensive reaction of phenolic compounds will improve the prediction of SOA formation from aromatic HCs due to the missing mechanisms in the current air quality model.

Observation-constrained kinetic modeling of isoprene SOA formation in the atmosphere

Abstract. Isoprene has the largest global non-methane hydrocarbon emission, and the oxidation of isoprene plays a crucial role in the formation of secondary organic aerosol (SOA). Two primary processes are known to contribute to SOA formation from isoprene oxidation: (1) the reactive uptake of isoprene-derived epoxides on acidic or aqueous particle surfaces and (2) the absorptive gas–particle partitioning of low-volatility oxidation products. In this study, we developed a new multiphase condensed isoprene oxidation mechanism that includes these processes with key molecular intermediates and products. The new mechanism was applied to simulate isoprene gas-phase oxidation products and SOA formation from previously published chamber experiments under a variety of conditions and atmospheric observations during the Southern Oxidant and Aerosol Studies (SOAS) field campaign. Our results show that SOA formation from most of the chamber experiments is reasonably reproduced using our mechanism, except when the concentration ratios of initial nitric oxide to isoprene exceed ∼ 2, the formed SOA is significantly underpredicted. The SOAS simulations also reasonably agree with the measurements regarding the diurnal pattern and concentrations of different product categories, while the total isoprene SOA remains underestimated. The molecular compositions of the modeled SOA indicate that multifunctional low-volatility products contribute to isoprene SOA more significantly than previously thought, with a median mass contribution of ∼ 57 % to the total modeled isoprene SOA. However, this contribution is intricately intertwined with IEPOX-derived SOA (IEPOX: isoprene-derived epoxydiols), posing challenges for their differentiation using bulk aerosol composition analysis (e.g., the aerosol mass spectrometer with positive matrix factorization). Furthermore, the SOA from these pathways may vary greatly, mainly dependent on the volatility estimation and treatment of particle-phase processes (i.e., photolysis and hydrolysis). Our findings emphasize that the various pathways to produce these low-volatility species should be considered in models to more accurately predict isoprene SOA formation. The new condensed isoprene chemical mechanism can be further incorporated into regional-scale air quality models, such as the Community Multiscale Air Quality Modelling System (CMAQ), to assess isoprene SOA formation on a larger scale.

Modeling the influence of carbon branching structure on secondary organic aerosol formation via multiphase reactions of alkanes

Abstract. Branched alkanes represent a significant proportion of hydrocarbons emitted in urban environments. To accurately predict the secondary organic aerosol (SOA) budgets in urban environments, these branched alkanes should be considered as SOA precursors. However, the potential to form SOA from diverse branched alkanes under varying environmental conditions is currently not well understood. In this study, the Unified Partitioning Aerosol Phase Reaction (UNIPAR) model is extended to predict SOA formation via the multiphase reactions of various branched alkanes. Simulations with the UNIPAR model, which processes multiphase partitioning and aerosol-phase reactions to form SOA, require a product distribution predicted from an explicit gas kinetic mechanism, whose oxygenated products are applied to create a volatility- and reactivity-based αi species array. Due to a lack of practically applicable explicit gas mechanisms, the prediction of the product distributions of various branched alkanes was approached with an innovative method that considers carbon lengths and branching structures. The αi array of each branched alkane was primarily constructed using an existing αi array of the linear alkane with the nearest vapor pressure. Generally, the vapor pressures of branched alkanes and their oxidation products are lower than those of linear alkanes with the same carbon number. In addition, increasing the number of alkyl branches can also decrease the ability of alkanes to undergo autoxidation reactions that tend to form low-volatility products and significantly contribute to alkane SOA formation. To account for this, an autoxidation reduction factor, as a function of the degree and position of branching, was applied to the lumped groups that contain autoxidation products. The resulting product distributions were then applied to the UNIPAR model for predicting branched-alkane SOA formation. The simulated SOA mass was compared to SOA data generated under varying experimental conditions (i.e., NOx levels, seed conditions, and humidity) in an outdoor photochemical smog chamber. Branched-alkane SOA yields were significantly impacted by NOx levels but insignificantly impacted by seed conditions or humidity. The SOA formation from branched and linear alkanes in diesel fuel was simulated to understand the relative importance of branched and linear alkanes with a wide range of carbon numbers. Overall, branched alkanes accounted for a higher proportion of SOA mass than linear alkanes due to their higher contribution to diesel fuel.

Fostering a Holistic Understanding of the Full Volatility Spectrum of Organic Compounds from Benzene Series Precursors through Mechanistic Modeling.

A comprehensive understanding of the full volatility spectrum of organic oxidation products from the benzene series precursors is important to quantify the air quality and climate effects of secondary organic aerosol (SOA) and new particle formation (NPF). However, current models fail to capture the full volatility spectrum due to the absence of important reaction pathways. Here, we develop a novel unified model framework, the integrated two-dimensional volatility basis set (I2D-VBS), to simulate the full volatility spectrum of products from benzene series precursors by simultaneously representing first-generational oxidation, multigenerational aging, autoxidation, dimerization, nitrate formation, etc. The model successfully reproduces the volatility and O/C distributions of oxygenated organic molecules (OOMs) as well as the concentrations and the O/C of SOA over wide-ranging experimental conditions. In typical urban environments, autoxidation and multigenerational oxidation are the two main pathways for the formation of OOMs and SOA with similar contributions, but autoxidation contributes more to low-volatility products. NOx can reduce about two-thirds of OOMs and SOA, and most of the extremely low-volatility products compared to clean conditions, by suppressing dimerization and autoxidation. The I2D-VBS facilitates a holistic understanding of full volatility product formation, which helps fill the large gap in the predictions of organic NPF, particle growth, and SOA formation.

Unpacking the diversity of monoterpene oxidation pathways via nitrooxy–alkyl radical ring-opening reactions and nitrooxy–alkoxyl radical bond scissions

Terrestrial vegetation emits vast quantities of monoterpenes to the atmosphere. These compounds, once oxidized, can contribute to the formation and growth of secondary organic aerosol (SOA) particles. However, studies report widely different SOA yields from atmospheric oxidation of different monoterpenes, despite their structural similarities. The NO3-radical-initiated oxidation of α-pinene for instance, leads to minimal SOA yields, whereas with Δ-carene a high SOA yield is observed. A previous study indicated that their oxidation mechanisms diverge after formation of a nitrooxy–alkoxyl radical intermediate, whose C–C bond scission reactions can either lead to early termination of the oxidative chain, thus limiting the yield of condensable vapors, or further propagate it, leading to low-volatility products. In this study, we employ computational methods to investigate these reactions in the NO3-radical oxidation of five other monoterpenes: limonene, sabinene, β-pinene, α-thujene and camphene. Additionally, we explore the possibility of rearrangement via ring-opening of the nitrooxy-alkyl radical adducts produced immediately after NO3 radical attack. Our calculations predict that alkyl radical rearrangement is dominant over O2-addition for sabinene, minor but competitive for α-thujene and β-pinene, and negligible for camphene. These rearrangements can induce further propagation of the oxidative chain, and thus higher SOA yields. Concerning alkoxyl radical C–C bond scissions, our results indicate that endocyclic nitrate species (derived from limonene and α-thujene) react preferentially via the channel leading to oxidative chain termination, whereas exocyclic nitrate species (sabinene, β-pinene, and camphene) react preferentially via channels leading to further propagation.

Unexpected high yield of acrolein underlies the importance of the hydrogen-abstraction mechanism in photooxidation of allyl methyl sulfide (AMS).

This work explores theoretically the gas phase oxidation of allyl methyl sulfide (AMS, H2CCHCH2SCH3) initiated by •OH radicals, focusing on the H-abstraction pathway at the M06-2X-D3/aug-cc-pVTZ and MN15/aug-cc-pVTZ levels of theory (m06Tz and mn15Tz). The formation of a prereactive complex (PRC) is involved in H-abstraction processes with two potential directions of approach for the OH radical, denoted as “α” and “β”. The PRCs, demonstrate increased reactivity, primarily due to the interaction between the sulfur atoms and the hydroxyl hydrogen. A scheme for the H-abstraction mechanism that supports the experimentally identified products and predicts the formation of some S-containing low volatility products is proposed. The comparison of the potential energy surface (PES) between the double bond addition and H-abstraction paths in the AMS molecule shows that at the m06Tz level of theory, the H-abstraction on C3 and the addition to C1 have nearly the same profile of energy, while at the mn15Tz level, the minimum energy channel is the addition to C1. The theoretical rate coefficient for each reaction channel was calculated, considering the formation of a PRC prior to reaching the transition state of each channel and assuming thermal equilibrium between reactants and the PRC. The rate constants were calculated in a multi-TS/multi-conformer way at the SVECV-f12/m06Tz and SVECV-f12/mn15Tz levels of theory. The SVECV-f12 method is consistent in its predictions in both systems and exhibits only minor deviations from the experimental rate constants. Despite some specific differences due to the DFT method supporting the SVECV-f12 calculations, both methodologies predict a significant H-abstraction contribution in the AMS + OH gas phase reaction, which explains the high formation yield for acrolein determined experimentally.

Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols.

Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (•OH), singlet molecular oxygen (1O2*), and triplet excited states of organic compounds (3C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase •OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with •OH, 1O2*, and 3C* in cloud droplets and aerosol liquid water. We investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.

CAMx–UNIPAR simulation of secondary organic aerosol mass formed from multiphase reactions of hydrocarbons under the Central Valley urban atmospheres of California

Abstract. The UNIfied Partitioning-Aerosol phase Reaction (UNIPAR) model was integrated into the Comprehensive Air quality Model with extensions (CAMx) to process secondary organic aerosol (SOA) formation by capturing multiphase reactions of hydrocarbons (HCs) in regional scales. SOA growth was simulated using a wide range of anthropogenic HCs, including 10 aromatics and linear alkanes with different carbon lengths. The atmospheric processes of biogenic HCs (isoprene, terpenes, and sesquiterpene) were simulated for major oxidation paths (ozone, OH radicals, and nitrate radicals) to predict day and night SOA formation. The UNIPAR model streamlined the multiphase partitioning of the lumping species originating from semi-explicitly predicted gas products and their heterogeneous chemistry to form non-volatile oligomeric species in both organic aerosol and inorganic aqueous phase. The CAMx–UNIPAR model predicted SOA formation at four ground urban sites (San Jose, Sacramento, Fresno, and Bakersfield) in California, United States, during wintertime 2018. Overall, the simulated mass concentrations of the total organic matter, consisting of primary organic aerosol and SOA, showed a good agreement with the observations. The simulated SOA mass in the urban areas of California was predominated by alkane and terpene oxidation products. During the daytime, low-volatility products originating from the autoxidation of long-chain alkanes considerably contributed to the SOA mass. In contrast, a significant amount of nighttime SOA was produced by the reaction of terpene with ozone or nitrate radicals. The spatial distributions of anthropogenic SOA associated with aromatic and alkane HCs were noticeably affected by the southward wind direction, owing to the relatively long lifetime of their atmospheric oxidation, whereas those of biogenic SOA were nearly insensitive to wind direction. During wintertime 2018, the impact of inorganic aerosol hygroscopicity on the total SOA budget was not evident because of the small contribution of aromatic and isoprene products, which are hydrophilic and reactive in the inorganic aqueous phase. However, an increased isoprene SOA mass was predicted during the wet periods, although its contribution to the total SOA was little.

Volatile oxidation products and secondary organosiloxane aerosol from D5 + OH at varying OH exposures

Abstract. Siloxanes are composed of silicon, oxygen, and alkyl groups and are emitted from consumer chemicals. Despite being entirely anthropogenic, siloxanes are being detected in remote regions and are ubiquitous in indoor and urban environments. Decamethylcyclopentasiloxane (D5) is one of the most common cyclic congeners, and smog chamber and oxidation flow reactor (OFR) experiments have found D5 + OH to form secondary organosiloxane aerosol (SOSiA). However, there is uncertainty about the reaction products and the reported SOSiA mass yields (YSOSiA) appear inconsistent. To quantify small volatile oxidation products (VOPs) and to consolidate the YSOSiA in the literature, we performed experiments using a potential aerosol mass OFR while varying D5 concentration, humidity, and OH exposure (OHexp). We use a proton transfer reaction time-of-flight mass spectrometer to quantify D5, HCHO, and HCOOH and to detect other VOPs, which we tentatively identify as siloxanols and siloxanyl formates. We determine molar yields of HCHO and HCOOH between 52 %–211 % and 45 %–127 %, respectively. With particle size distributions measured with a scanning mobility particle sizer, we find YSOSiA to be < 10 % at OHexp < 1.3 × 1011 s cm−3 and ∼ 20 % at OHexp, corresponding to that of the lifetime of D5 at atmospheric OH concentrations. We also find that YSOSiA is dependent on both organic aerosol mass loading and OHexp. We use a kinetic box model of SOSiA formation and oxidative aging to explain the YSOSiA values found in this study and the literature. The model uses a volatility basis set (VBS) of the primary oxidation products as well as an aging rate coefficient in the gas phase, kage,gas, of 2.2×10-12 cm3 s−1 and an effective aging rate coefficient in the particle phase, kage,particle, of 2.0 × 10−12 cm3 s−1. The combination of a primary VBS and OH-dependent oxidative aging predicts SOSiA formation much better than a standard-VBS parameterization that does not consider aging (root mean square error = 42.6 vs. 96.5). In the model, multi-generational aging of SOSiA products occurred predominantly in the particle phase. The need for an aging-dependent parameterization to accurately model SOSiA formation shows that concepts developed for secondary organic aerosol precursors, which can form low-volatile products at low OHexp, do not necessarily apply to D5 + OH. The resulting yields of HCHO and HCOOH and the parameterization of YSOSiA may be used in larger-scale models to assess the implications of siloxanes for air quality.

Nontrivial Impact of Relative Humidity on Organic New Particle Formation from Ozonolysis of cis-3-Hexenyl Acetate

The impact of relative humidity (RH) on organic new particle formation (NPF) from the ozonolysis of biogenic volatile organic compounds (BVOCs) remains an area of active debate. Previous reports provide contradictory results, indicating both the depression and enhancement of NPF under conditions of high RH. Herein, we report on the impact of RH on NPF from the dark ozonolysis of cis-3-hexenyl acetate (CHA), a green-leaf volatile (GLV) emitted by vegetation. We show that RH inhibits NPF by this BVOC, essentially shutting it down at RH levels > 1%. While the mechanism for the inhibition of NPF remains unclear, we demonstrate that it is likely not due to increased losses of CHA to the humid chamber walls. New oxidation products dominant under humid conditions are proposed that, based on estimated vapor pressures (VPs), should enhance NPF; however, it is possible that the vapor phase concentration of these low-volatility products is not sufficient to initiate NPF. Furthermore, the reaction of C3-excited state Criegee intermediates (CIs) with water may lead to the formation of small carboxylic acids that do not contribute to NPF. This hypothesis is supported by experiments with quaternary O3 + CHA + α-pinene + RH systems, which showed decreases in total α-pinene-derived NPF at ~0% RH and subsequent recovery at elevated RH.

Molecular rearrangement of bicyclic peroxy radicals is a key route to aerosol from aromatics

The oxidation of aromatics contributes significantly to the formation of atmospheric aerosol. Using toluene as an example, we demonstrate the existence of a molecular rearrangement channel in the oxidation mechanism. Based on both flow reactor experiments and quantum chemical calculations, we show that the bicyclic peroxy radicals (BPRs) formed in OH-initiated aromatic oxidation are much less stable than previously thought, and in the case of the toluene derived ipso-BPRs, lead to aerosol-forming low-volatility products with up to 9 oxygen atoms on sub-second timescales. Similar results are predicted for ipso-BPRs formed from many other aromatic compounds. This reaction class is likely a key route for atmospheric aerosol formation, and including the molecular rearrangement of BPRs may be vital for accurate chemical modeling of the atmosphere.

Varying chiral ratio of pinic acid enantiomers above the Amazon rainforest

Abstract. Chiral chemodiversity plays a crucial role in biochemical processes such as insect and plant communication. However, the vast majority of organic aerosol studies do not distinguish between enantiomeric compounds in the particle phase. Here we report chirally specified measurements of secondary organic aerosol (SOA) at the Amazon Tall Tower Observatory (ATTO) at different altitudes during three measurement campaigns at different seasons. Analysis of filter samples by liquid chromatography coupled to mass spectrometry (LC-MS) has shown that the chiral ratio of pinic acid (C9H14O4) varies with increasing height above the canopy. A similar trend was recently observed for the gas-phase precursor α-pinene but more pronounced. Nevertheless, the measurements indicate that neither the oxidation of (+/−)-α-pinene nor the incorporation of the products into the particulate phase proceeds with stereo preference and that the chiral information of the precursor molecule is merely transferred to the low-volatility product. The observation of the weaker height gradient of the present enantiomers in the particle phase at the observation site can be explained by the significant differences in the atmospheric lifetimes of reactant and product. Therefore, it is suggested that the chiral ratio of pinic acid is mainly determined by large-scale emission processes of the two precursors, while meteorological, chemical, or physicochemical processes do not play a particular role. Characteristic emissions of the chiral aerosol precursors from different forest ecosystems, in some cases even with contributions from forest-related fauna, could thus provide large-scale information on the different contributions to biogenic secondary aerosols via the analytics of the chiral particle-bound degradation products.

Relative Humidity Impact on Organic New Particle Formation from Ozonolysis of α- and β-Pinene at Atmospherically Relevant Mixing Ratios

The impact of relative humidity (RH) on organic new particle formation (NPF) from ozonolysis of monoterpenes remains an area of active debate. Previous reports provide contradictory results indicating both depression and enhancement of NPF under conditions of moderate RH, while others do not indicate a potential impact. Only several reports have suggested that the effect may depend on absolute mixing ratio of the precursor volatile organic compound (VOC, ppbv). Herein we report on the impact of RH on NPF from dark ozonolysis of α- and β-pinene at mixing ratios ranging from 0.2 to 80 ppbv. We show that RH enhances NPF (by a factor of eight) at the lowest α-pinene mixing ratio, with a very strong dependence on α-pinene mixing ratio from 4 to 22 ppbv. At higher mixing ratios, the effect of RH plateaus, with resulting modest decreases in NPF. In the case of α- and β-pinene, NPF is enhanced at low mixing ratios due to a combination of chemistry, accelerated kinetics, and reduced partitioning of semi-volatile oxidation products to the particulate phase. Reduced partitioning would limit particle growth, permitting increased gas-phase concentrations of semi- and low-volatility products, which could favor NPF.

Methane production by anaerobic co‐digestion of dairy manure and cassava wastes for energy recovery

AbstractBACKGROUNDIn this study, the anaerobic co‐digestion of cassava wastewater (CW), cassava bagasse (CB), and dairy manure (DM) was investigated to produce biogas with energy recovery. Mixture experimental design was performed to establish the proportion of each substrate, on the basis of total weight (%wt). The digestion was carried out under mesophilic conditions (35 °C) using a batch test.RESULTSThe best methane yields were 150.33 NmLCH4 gVS−1 (114.46 NmLCH4 gCOD−1) for the condition with 100% CW (C/N ratio = 14.04) and 130.43 normal mililiters of methane per gram of volatile solid (NmLCH4 gVS−1) and 93.84 normal mililiters of methane per gram of chemical oxygen demand (NmLCH4 gCOD−1) obtained with 66.7% DM, 16.7% CB and 16.7% CW (C/N ratio = 34.84). Experimental conditions containing high proportions of CB (above 33%) yielded high C/N ratios (above 52), resulting in low pH and high volatile fatty acid production, mainly acetic and butyric acids. Kinetics of methane production under optimal conditions were best described by Groot's multi‐stage model.CONCLUSIONAn energy balance for the best conditions were performed, leading to 452.86 MJ tonsubstrate−1 for a high DM content mixture experiment (DM = 66.7%, CB = 16.7%, CW = 16.7%); thereby showing that anaerobic co‐digestion can replace 22.5% of the energy demanded by cassava processing industry. © 2022 Society of Chemical Industry (SCI).