Intermediate Volatility Organic Compounds Research Articles

NEIVAv1.0: Next-generation Emissions InVentory expansion of Akagi et al. (2011) version 1.0

Abstract. Accurate representation of fire emissions is critical for modeling the in-plume, near-source, and remote effects of biomass burning (BB) on atmospheric composition, air quality, and climate. In recent years application of advanced instrumentation has significantly improved knowledge of the compounds emitted from fires, which, coupled with a large number of recent laboratory and field campaigns, has facilitated the emergence of new emission factor (EF) compilations. The Next-generation Emissions InVentory expansion of Akagi (NEIVA) version 1.0 is one such compilation in which the EFs for 14 globally relevant fuel and fire types have been updated to include data from recent studies, with a focus on gaseous non-methane organic compounds (NMOC_g). The data are stored in a series of connected tables that facilitate flexible querying from the individual study level to recommended averages of all laboratory and field data by fire type. The querying features are enabled by assignment of unique identifiers to all compounds and constituents, including thousands of NMOC_g. NEIVA also includes chemical and physical property data and model surrogate assignments for three widely used chemical mechanisms for each NMOC_g. NEIVA EF datasets are compared with recent publications and other EF compilations at the individual compound level and in the context of overall volatility distributions and hydroxyl (OH) reactivity (OHR) estimates. The NMOC_g in NEIVA include ∼4–8 times more compounds with improved representation of intermediate volatility organic compounds, resulting in much lower overall volatility (lowest-volatility bin shifted by as much as 3 orders of magnitude) and significantly higher OHR (up to 90 %) than other compilations. These updates can strongly impact model predictions of the effects of BB on atmospheric composition and chemistry.

Secondary Organic Aerosol Formation from the Photooxidation of Aromatic Ketone Intermediate Volatile Organic Compounds.

Oxygenated aromatics are substantial secondary organic aerosol (SOA) precursors, such as benzyl alcohol and phenolic compounds. Aromatic ketone intermediate volatile organic compounds (IVOCs), as a subclass of oxygenated aromatics, were found in anthropogenic source emissions and may contribute to SOA formation. However, the SOA yields and formation pathways of aromatic ketone IVOCs remain unknown. In this study, the photooxidations of aromatic ketone IVOCs in the absence and presence of NOx were studied in an oxidation flow reactor, and the particle- and gas-phase oxidation products were measured. The maximum SOA yields of benzophenone and 1,2-diphenylethanone are 0.24 and 0.33-0.35, respectively, relatively high among oxygenated aromatics. The SOA yields in the presence of NOx are 2-3 times higher than those in the absence of NOx in the late stage of oxidation. As the photooxidation proceeds, H/C of SOA slightly increases with O/C, and a greater amount of more-oxidized ring-retaining products exists in the particle phase in the presence of NOx. Based on gas-phase products and possible reaction pathways, functionalization of benzoic acid via the phenolic pathway is favored in the presence of NOx. Thus, our study highlights the significant SOA formation from aromatic ketone IVOCs, especially in the presence of NOx during long-time photooxidation.

Secondary Organic Aerosol Formation during the Oxidation of Large Aromatic and Other Cyclic Anthropogenic Volatile Organic Compounds.

The secondary organic aerosol (SOA) production from the reactions of anthropogenic large volatile (VOCs) and intermediate volatility organic compounds (IVOCs) with hydroxyl radicals under high NO x conditions was investigated. The organic compounds studied include cyclic alkanes of increasing size (amylcyclohexane, hexylcyclohexane, nonylcyclohexane, and decylcyclohexane) and aromatic compounds (1,3,5-trimethylbenzene, 1,3,5-triethylbenzene and 1,3,5-tritert-butylbenzene). A considerable amount of SOA was formed from all examined compounds. For the studied cyclohexanes (C11-C16) there appears that the SOA yield depends nonlinearly on the length of their substitute chain. The large cyclohexanes had higher yields than the aromatic compounds, but the aromatic precursors produced a more oxidized SOA. This was due to the production of lower volatility and O:C first generation products by the cyclohexanes. Most oxidation products (with C* < 104 μg m-3) in the case of cyclohexanes are SVOCs (∼50%), while of aromatics are IVOCs (∼60%). Structure, molecular size, and length of the substitute chain of the parent hydrocarbon were found to play key roles in SOA formation, oxidation state, and volatility. The SOA volatility distribution, effective vaporization enthalpy, and effective accommodation coefficient were also quantified by combining SOA yields, thermodenuder (TD) and isothermal dilution measurements. Parameterizations for the Volatility Basis Set (VBS) are proposed for future use in chemical transport models.

Emission inventory of IVOCs from diesel engine emissions in China based on real-world measured data

Intermediate volatility organic compounds (IVOCs), recognized as significant precursors of secondary organic aerosols, play a pivotal role in environmental pollution. This study utilized measured real-world emission factors to construct an inventory of IVOC emissions from diesel engines and to analyze their spatial distribution across China in 2022. Furthermore, the emission inventory derived from this approach was compared with that obtained through the IVOC/primary organic aerosol (POA) ratio method. The following findings were observed: (1) In 2022, the total IVOC emissions from diesel engines in China amounted to approximately 430 Gg, surpassing those emitted by gasoline engines and residential solid fuel combustion. Specifically, the IVOC emissions attributed to on-road diesel vehicles, inland vessels, agricultural machinery, and non-road construction machinery were recorded at 377, 39.3, 10.4 and 3 Gg, respectively. (2) In terms of geographical distribution in 2022, IVOC emissions from diesel engines were predominantly concentrated in Eastern, Southern and Northern China; on-road diesel vehicle emissions were primarily located within logistics hubs or regions characterized by extensive national and arterial road networks; while non-road construction and agricultural machinery emissions were largely confined to Eastern and Central China. Emissions from inland vessels exhibited a more distinct regional pattern concentrated mainly within the Yangtze River Delta, Pearl River Delta, and Bohai Rim areas. (3) A comparative analysis between the inventory established using real-world measured emission factors and that derived via IVOC/POA ratios indicated that the latter methodology may have overestimated emissions associated with inland vessels and non-road construction machinery. Moving forward, reducing IVOC emissions from diesel engines is crucial for enhancing air quality and safeguarding human health-particularly concerning heavy-duty vehicles, light-duty vehicles, and inland vessels.

Characterizing Wall Loss Effects of Intermediate-Volatility Hydrocarbons in a Smog Chamber with a Teflon Reactor

Intermediate-volatility organic compounds (IVOCs) serve as pivotal precursors to secondary organic aerosol (SOA). They are highly susceptible to substantial wall losses both in indoor environments and within smog chambers even with Teflon walls. Accurately characterizing the wall loss effects of IVOCs is thus essential for simulation studies aiming to replicate their atmospheric behaviors in smog chambers to ensure precise modeling of their physical and chemical processes, including SOA formation, yet a comprehensive understanding of the wall loss behavior of IVOCs remains elusive. In this study, we conducted a thorough characterization of wall losses for typical intermediate-volatility hydrocarbon compounds, including eight normal alkanes (n-alkanes) and eight polycyclic aromatic hydrocarbons (PAHs), using the smog chamber with a 30 m3 Teflon reactor. Changes in the concentrations of gaseous IVOCs with the chamber were observed under dark conditions, and the experimental data were fitted to the reversible gas–wall mass transfer theory to determine the key parameters such as the wall accommodation coefficient (αw) and the equivalent organic aerosol concentration (Cw) for different species. Our results reveal that Cw values for these hydrocarbon IVOCs range from 0.02 to 5.41 mg/m3, which increase with volatility for the PAHs but are relative stable for alkanes with an average of 3.82 ± 0.92 mg/m3. αw span from 1.24 × 10−7 to 1.01 × 10−6, with the values for n-alkanes initially showing an increase followed by a decrease as carbon numbers rise and volatility decreases. The average αw for n-alkanes and PAHs are 3.34 × 10−7 and 6.53 × 10−7, respectively. Our study shows that IVOCs exhibit different loss rates onto clean chamber walls under dry and dark conditions, with increasing rate as the volatility decreases. This study demonstrates how parameters can be acquired to address wall losses when conducting smog chamber simulation on atmospheric processes of IVOCs.

Role of Organic Vapor Precursors in Secondary Organic Aerosol Formation: Concurrent Observations of IVOCs and VOCs in Guangzhou

AbstractSecondary organic aerosol (SOA) formed through the atmospheric transformation of organic vapors constitutes a significant portion of fine particulate matter or PM2.5. While recent laboratory studies underscore the importance of intermediate‐volatility organic compounds (IVOCs) as key precursors to SOA, field observations that recognize the role of both volatile organic compounds (VOCs) and IVOCs in SOA formation remain scarce. In this study, we conducted concurrent measurements of VOCs and IVOCs in ambient air at urban and suburban sites in Guangzhou during a PM2.5 pollution event in winter 2021. The results reveal that between 12:00–15:00 local time, the photochemically adjusted initial concentrations of VOCs at both sites were approximately 7 times higher than that of IVOCs. However, the SOA formation potential (SOAFP) of primary hydrocarbon IVOCs exceeded that of VOCs by over 3–4 times. Receptor modeling results further indicated that while ship emissions contributed to less than 10% of the C2–C22 primary hydrocarbons concentration (VOCs + primary carbonaceous IVOCs), they accounted for the most significant source (approximately 40%) of SOA formation. This study highlights the substantial role of IVOCs in SOA formation and emphasizes the importance of future PM2.5 pollution control measures targeting major IVOCs contributors, such as ship emissions in harbor cities.

PM10 Organic Aerosol Fingerprints by Using Liquid Chromatography Orbitrap Mass Spectrometry: Urban vs. Suburban in an Eastern Mediterranean Medium-Sized Coastal City

This study compares the PM10 (particulate matter of diameter smaller than 10 μm) organic aerosol composition between urban and suburban stations in Heraklion, Crete, during winter 2024 in order to highlight the impact of local anthropogenic activities on urban atmospheric particulate matter pollution. Using an HPLC-ESI-MS Orbitrap analyzer (High Performance Liquid Chromatography-Electrospray Ionization-Mass Spectrometry) in full MS scan mode at a resolution of 140,000, 48 daily aerosol filter extracts were analyzed in both positive and negative modes, resulting in the detection of 2809 and 3823 features, respectively. Features with at least five times higher intensity in the urban environment compared to the suburban, and p &lt; 0.05, were deemed significant. A correlation with black carbon (r &gt; 0.6) was observed for 71% of significant urban features in positive mode. These features showed a predominance of low O:C ratios (&lt;0.2) and the majority were classified as intermediate volatility organic compounds (IVOCs), indicating fresh primary emissions. A clear urban–suburban distinction was shown by PCA of positive mode features, unlike the negative mode features. Regarding the total intensity of the features, urban samples were on average 55% higher than suburban samples in positive mode and 39% higher in negative mode. This study reveals the molecular profile of locally emitted combustion related organics observed in positive mode in an urban environment.

Failure of the three-way catalyst (TWC) introduces “super emitters”

Vehicle exhaust is one of the major organic sources in urban areas. Old taxis equipped with failed three-way catalysts (TWCs) have been regarded as “super emitters”. Compressed natural gas (CNG) is a regular substitution fuel for gasoline in taxis. The relative effect of fuel substitution and TWC failure has not been thoroughly investigated. In this work, vehicle exhausts from gasoline and CNG taxis with optimally functioning and malfunctioning TWCs are sampled by Tenax TA tubes and then analyzed by a comprehensive two-dimensional gas chromatography-mass spectrometer (GC×GC–MS). A total of 216 organics are quantified, including 80 volatile organic compounds (VOCs) and 132 intermediate volatility organic compounds (IVOCs). Failure of TWC introduces super emitters with 30 – 70 times emission factors (EFs), 60 – 112 times ozone formation potentials (OFPs), and 34 – 92 times secondary organic aerosols (SOAs) more than normal vehicles. Specifically, for the taxi with failed TWC, the total organic EF of CNG is 16 times that of gasoline, indicating that the failure of TWC exceeds the emission reduction achieved by CNG-gasoline substitution. A significant but unbalanced reduction of ozone and SOA is observed after TWC, whereas a notable “enrichment” in IVOCs was observed. Naphthalene is a typical IVOC component strongly associated with CNG-gasoline substitution and TWC failure, which is lacking in current VOC measurement. We especially emphasize that there is an urgent need to scrap vehicles with failed TWCs in order to significantly reduce air pollution.

The role of naphthalene and its derivatives in the formation of secondary organic aerosol in the Yangtze River Delta region, China

Abstract. Naphthalene (Nap) and its derivatives, including 1-methylnaphthalene (1-MN) and 2-methylnaphthalene (2-MN), serve as prominent intermediate volatile organic compounds (IVOCs) and contribute to the formation of secondary organic aerosol (SOA). In this study, the Community Multiscale Air Quality (CMAQ) model coupled with detailed emissions and reactions of these compounds was utilized to examine their roles in the formation of SOA and other secondary pollutants in the Yangtze River Delta (YRD) region during summer. Significant underestimations of Nap and MN concentrations (by 79 % and 85 %) were observed at the Taizhou site based on the model results using the default emissions. Constrained by the observations, anthropogenic emissions of Nap and MN in the entire region were multiplied by 5 and 7, respectively, to better capture the evolution of pollutants. The average concentration of Nap reached 25 ppt (parts per trillion) in the YRD, with Nap contributing 4.1 % and 8.1 % (up to 12.6 %) of total aromatic emissions and aromatic-derived secondary organic carbon (SOC), respectively. The concentrations of 1-MN and 2-MN were relatively low, averaging 2 and 5 ppt, respectively. Together, they accounted for only 2.4 % of the aromatic-derived SOC. The impacts of Nap and MN oxidation on ozone and radicals were insignificant at regional scales but were not negligible when considering daily fluctuations in locations with high emissions of Nap and MN. This study highlights the significant roles of Nap and MN in the formation of SOA, which may pose environmental risks and result in adverse health effects.

Emission of Intermediate Volatile Organic Compounds from Animal Dung and Coal Combustion and Its Contribution to Secondary Organic Aerosol Formation in Qinghai-Tibet Plateau, China.

Intermediate volatility organic compounds (IVOCs) are important precursors to secondary organic aerosols (SOAs), but they are often neglected in studies concerning SOA formation. This study addresses the significant issue of IVOCs emissions in the Qinghai-Tibetan plateau (QTP), where solid fuels are extensively used under incomplete combustion conditions for residential heating and cooking. Our field measurement data revealed an emission factor of the total IVOCs (EFIVOCs) ranging from 1.56 ± 0.03 to 9.97 ± 3.22 g/kg from various combustion scenarios in QTP. The markedly higher EFIVOCs in QTP than in plain regions can be attributed to oxygen-deficient conditions. IVOCs were dominated by gaseous phase emissions, and the primary contributors of gaseous and particulate phase IVOCs are the unresolved complex mixture and alkanes, respectively. Total IVOCs emissions during the heating and nonheating seasons in QTP were estimated to be 31.7 ± 13.8 and 6.87 ± 0.45 Gg, respectively. The estimated SOA production resulting from combined emissions of IVOCs and VOCs is nearly five times higher than that derived from VOCs alone. Results from this study emphasized the pivotal role of IVOCs emissions in air pollution and provided a foundation for compiling emission inventories related to solid fuel combustion and developing pollution prevention strategies.

Obscured Contribution of Oxygenated Intermediate-Volatility Organic Compounds to Secondary Organic Aerosol Formation from Gasoline Vehicle Emissions.

Secondary organic aerosol (SOA) formation from gasoline vehicles spanning a wide range of emission types was investigated using an oxidation flow reactor (OFR) by conducting chassis dynamometer tests. Aided by advanced mass spectrometric techniques, SOA precursors, including volatile organic compounds (VOCs) and intermediate/semivolatile organic compounds (I/SVOCs), were comprehensively characterized. The reconstructed SOA produced from the speciated VOCs and I/SVOCs can explain 69% of the SOA measured downstream of an OFR upon 0.5-3 days' OH exposure. While VOCs can only explain 10% of total SOA production, the contribution from I/SVOCs is 59%, with oxygenated I/SVOCs (O-I/SVOCs) taking up 20% of that contribution. O-I/SVOCs (e.g., benzylic or aliphatic aldehydes and ketones), as an obscured source, account for 16% of total nonmethane organic gas (NMOG) emission. More importantly, with the improvement in emission standards, the NMOG is effectively mitigated by 35% from China 4 to China 6, which is predominantly attributed to the decrease of VOCs. Real-time measurements of different NMOG components as well as SOA production further reveal that the current emission control measures, such as advances in engine and three-way catalytic converter (TWC) techniques, are effective in reducing the "light" SOA precursors (i.e., single-ring aromatics) but not for the I/SVOC emissions. Our results also highlight greater effects of O-I/SVOCs to SOA formation than previously observed and the urgent need for further investigation into their origins, i.e., incomplete combustion, lubricating oil, etc., which requires improvements in real-time molecular-level characterization of I/SVOC molecules and in turn will benefit the future design of control measures.

Molecular Characterization of Gaseous Organic Acids and Nitrogen‐Containing Compounds From Crop Straw and Wood Burning

AbstractBiomass burning serves as important sources of volatile organic compounds (VOCs), yet our understanding of the molecular characteristics of oxygenated volatile organic compounds (OVOCs) from fresh emissions remains limited. In this study, gaseous organic compounds in fresh smokes from burning typical Chinese crop straws and woods are measured using an iodide time‐of‐flight chemical ionization mass spectrometer. Approximately 750 molecular formulas are identified, with CHO compounds containing carbon, hydrogen and oxygen atoms accounting for 77%–95% of the total. C1–C3 organic acids and dicarboxylic acids dominate the total CHO signal intensities by 27%–48%, while well‐known molecular markers of biomass burning, such as monosaccharide, guaiacol and syringol derivatives, contribute 7%–17%. Notably, crop straw and wood burning emit a higher abundance of guaiacol than syringol derivatives by a factor of 5. Additionally, a variety of nitrogen‐containing compounds (mainly in the CHON group) is identified, including isocyanate, amide, amino acids, and pyridine. The mass spectral profiles of organic compounds are largely similar between crop straw and wood burning fuels, although wood burning produces higher contributions of compounds with carbon atoms numbers &gt;10. The saturation concentrations of organic compounds are estimated using molecular formula‐based volatility parameterization, revealing that semi‐volatile and intermediate VOCs (S/intermediate volatility organic compounds (IVOCs)) predominate smoke releases by 35%–60% and 20%–43%, respectively, with only a small fraction of low‐volatility compounds. Given the widespread nature of biomass burning in winter China, our results may have significant implications for interpreting secondary organic aerosol formation through gas‐particle partitioning or aqueous‐phase reactions.

Cloud response to co-condensation of water and organic vapors over the boreal forest

Abstract. Accounting for the condensation of organic vapors along with water vapor (co-condensation) has been shown in adiabatic cloud parcel model (CPM) simulations to enhance the number of aerosol particles that activate to form cloud droplets. The boreal forest is an important source of biogenic organic vapors, but the role of these vapors in co-condensation has not been systematically investigated. In this work, the environmental conditions under which strong co-condensation-driven cloud droplet number enhancements would be expected over the boreal biome are identified. Recent measurement technology, specifically the Filter Inlet for Gases and AEROsols (FIGAERO) coupled to an iodide-adduct chemical ionization mass spectrometer (I-CIMS), is utilized to construct volatility distributions of the boreal atmospheric organics. Then, a suite of CPM simulations initialized with a comprehensive set of concurrent aerosol observations collected in the boreal forest of Finland during spring 2014 is performed. The degree to which co-condensation impacts droplet formation in the model is shown to be dependent on the initialization of temperature, relative humidity, updraft velocity, aerosol size distribution, organic vapor concentration, and the volatility distribution. The predicted median enhancements in cloud droplet number concentration (CDNC) due to accounting for the co-condensation of water and organics fall on average between 16 % and 22 %. This corresponds to activating particles 10–16 nm smaller in dry diameter that would otherwise remain as interstitial aerosol. The highest CDNC enhancements (ΔCDNC) are predicted in the presence of a nascent ultrafine aerosol mode with a geometric mean diameter of ∼ 40 nm and no clear Hoppel minimum, indicative of pristine environments with a source of ultrafine particles (e.g., via new particle formation processes). Such aerosol size distributions are observed 30 %–40 % of the time in the studied boreal forest environment in spring and fall when new particle formation frequency is the highest. To evaluate the frequencies with which such distributions are experienced by an Earth system model over the whole boreal biome, 5 years of UK Earth System Model (UKESM1) simulations are further used. The frequencies are substantially lower than those observed at the boreal forest measurement site (&lt; 6 % of the time), and the positive values, peaking in spring, are modeled only over Fennoscandia and the western parts of Siberia. Overall, the similarities in the size distributions between observed and modeled (UKESM1) are limited, which would limit the ability of this model, or any model with a similar aerosol representation, to project the climate relevance of co-condensation over the boreal forest. For the critical aerosol size distribution regime, ΔCDNC is shown to be sensitive to the concentrations of semi-volatile and some intermediate-volatility organic compounds (SVOCs and IVOCs), especially when the overall particle surface area is low. The magnitudes of ΔCDNC remain less affected by the more volatile vapors such as formic acid and extremely low- and low-volatility organic compounds (ELVOCs and LVOCs). The reasons for this are that most volatile organic vapors condense inefficiently due to their high volatility below the cloud base, and the concentrations of LVOCs and ELVOCs are too low to gain significant concentrations of soluble mass to reduce the critical supersaturations enough for droplet activation to occur. A reduction in the critical supersaturation caused by organic condensation emerges as the main driver of the modeled ΔCDNC. The results highlight the potential significance of co-condensation in pristine boreal environments close to sources of fresh ultrafine particles. For accurate predictions of co-condensation effects on CDNC, also in larger-scale models, an accurate representation of the aerosol size distribution is critical. Further studies targeted at finding observational evidence and constraints for co-condensation in the field are encouraged.

Molecular-Level Insights into the Relationship between Volatility of Organic Aerosol Constituents and PM2.5 Air Pollution Levels: A Study with Ultrahigh-Resolution Mass Spectrometry.

Volatility of organic aerosols (OAs) significantly influences new particle formation and the occurrence of particulate air pollution. However, the relationship between the volatility of OA and the level of particulate air pollution (i.e., particulate matter concentration) is not well understood. In this study, we compared the chemical composition (identified by an ultrahigh-resolution Orbitrap mass spectrometer) and volatility (estimated based on a predeveloped parametrization method) of OAs in urban PM2.5 (particulate matter with aerodynamic diameter ≤ 2.5 μm) samples from seven German and Chinese cities, where the PM2.5 concentration ranged from a light (14 μg m-3) to heavy (319 μg m-3) pollution level. A large fraction (71-98%) of compounds in PM2.5 samples were attributable to intermediate-volatility organic compounds (IVOCs) and semivolatile organic compounds (SVOCs). The fraction of low-volatility organic compounds (LVOCs) and extremely low-volatility organic compounds (ELVOCs) decreased from clean (28%) to heavily polluted urban regions (2%), while that of IVOCs increased from 34 to 62%. We found that the average peak area-weighted volatility of organic compounds in different cities showed a logarithmic correlation with the average PM2.5 concentration, indicating that the volatility of urban OAs increases with the increase of air pollution level. Our results provide new insights into the relationship between OA volatility and PM pollution levels and deepen the understanding of urban air pollutant evolution.

Elucidating the unexpected importance of intermediate-volatility organic compounds (IVOCs) from refueling procedure

Evaporative emissions release organic compounds comparable to gasoline exhaust in China. However, the measurement of intermediate volatility organic compounds (IVOCs) is lacking in studies focusing on gasoline evaporation. This study sampled organics from a real-world refueling procedure and analyzed the organic compounds using comprehensive two-dimensional gas chromatography coupled with a mass spectrometer (GC×GC-MS). The non-target analysis detected and quantified 279 organics containing 93 volatile organic compounds (VOCs, 64.9 ± 7.4 % in mass concentration), 182 IVOCs (34.9 ± 7.4 %), and 4 semivolatile organic compounds (SVOCs, 0.2 %). The refueling emission profile was distinct from that of gasoline exhaust. The b-alkanes in the B12 volatility bin are the most abundant IVOC species (1.9 ± 1.4 μg m−3) in refueling. A non-negligible contribution of 17.5 % to the ozone formation potential (OFP) from IVOCs was found. Although IVOCs are less in concentration, secondary organic aerosol potential (SOAP) from IVOCs (58.1 %) even exceeds SOAP from VOCs (41.6 %), mainly from b-alkane in the IVOC range. At the molecular level, the proportion of cyclic compounds in SOAP (12.1 %) indeed goes above its mass concentration (3.1 %), mainly contributed by cyclohexanes and cycloheptanes. As a result, the concentrations and SOAP of cyclic compounds (>50 %) could be overestimated in previous studies. Our study found an unexpected contribution of IVOCs from refueling procedures to both ozone and SOA formation, providing new insights into secondary pollution control policy.

VOC and IVOC emission features and inventory of motorcycles in China

How did the motorcycle emissions evolve during the economic development in China? To address data gaps, this study firstly measured the volatile organic compound (VOC) and intermediate-volatility organic compound (IVOC) emissions from motorcycles. The results confirmed that the emission control of motorcycles, especially small-displacement motorcycles, significantly lagged behind other gasoline-powered vehicles. For the China IV motorcycles, the average VOC and IVOC emission factors (EFs) were 2.74 and 7.78 times higher than the China V–VI light-duty gasoline vehicles, respectively. The notable high IVOC emissions were attributed to a dual influence from gasoline and lubricating oil. Furthermore, based on the complete EF dataset and economy-related activity data, a county-level emission inventory was developed in China. Motorcycle VOC and IVOC emissions changed from 2536.48 Gg and 197.19 Gg in 2006 to 594.21 Gg and 12.66 Gg in 2020, respectively. The absence of motorcycle IVOC emissions in the existed vehicular inventories led to an underestimation of up to 20%. Across the 15 years, the motorcycle VOC and IVOC emission hotspots were concentrated in the undeveloped regions, with the rural emissions reaching 5.81–10.14 times those of the urban emissions. This study provides the first-hand and close-to-realistic data to support motorcycle emission management and accurate air quality simulations.

An updated modeling framework to simulate Los Angeles air quality - Part 1: Model development, evaluation, and source apportionment.

This study describes a modeling framework, model evaluation, and source apportionment to understand the causes of Los Angeles (LA) air pollution. A few major updates are applied to the Community Multiscale Air Quality (CMAQ) model with a high spatial resolution (1 km × 1 km). The updates include dynamic traffic emissions based on real-time, on-road information and recent emission factors and secondary organic aerosol (SOA) schemes to represent volatile chemical products (VCPs). Meteorology is well predicted compared to ground-based observations, and the emission rates from multiple sources (i.e., on-road, volatile chemical products, area, point, biogenic, and sea spray) are quantified. Evaluation of the CMAQ model shows that ozone is well predicted despite inaccuracies in nitrogen oxide (NO x ) predictions. Particle matter (PM) is underpredicted compared to concurrent measurements made with an aerosol mass spectrometer (AMS) in Pasadena. Inorganic aerosol is well predicted, while SOA is underpredicted. Modeled SOA consists of mostly organic nitrates and products from oxidation of alkane-like intermediate volatility organic compounds (IVOCs) and has missing components that behave like less-oxidized oxygenated organic aerosol (LO-OOA). Source apportionment demonstrates that the urban areas of the LA Basin and vicinity are NO x -saturated (VOC-sensitive), with the largest sensitivity of O3 to changes in VOCs in the urban core. Differing oxidative capacities in different regions impact the nonlinear chemistry leading to PM and SOA formation, which is quantified in this study.

Contribution of intermediate-volatility organic compounds from on-road transport to secondary organic aerosol levels in Europe

Abstract. Atmospheric organic compounds with an effective saturation concentration (C∗) at 298 K between 103 and 106 µg m−3 are called intermediate-volatility organic compounds (IVOCs), and they have been identified as important secondary organic aerosol (SOA) precursors. In this work, we simulate IVOCs emitted from on-road diesel and gasoline vehicles over Europe with a chemical transport model (CTM), utilizing a new approach in which IVOCs are treated as lumped species that preserve their chemical characteristics. This approach allows us to assess both the overall contribution of IVOCs to SOA formation and the role of specific compounds. For the simulated early-summer period, the highest concentrations of SOA formed from the oxidation of on-road IVOCs (SOA-iv) are predicted for major European cities, like Paris, Athens, and Madrid. In these urban environments, on-road SOA-iv can account for up to a quarter of the predicted total SOA. Over Europe, unspeciated cyclic alkanes in the IVOC range are estimated to account for up to 72 % of the total on-road SOA-iv mass, with compounds with 15 to 20 carbons being the most prominent precursors. The sensitivity of the predicted SOA-iv concentrations to the selected parameters of the new lumping scheme is also investigated. Active multigenerational aging of the secondary aerosol products has the most significant effect as it increases the predicted SOA-iv concentrations by 67 %.

The newest emission inventory of anthropogenic full-volatility organic in Central China

Organic aerosol (OA) is the largest and most complicated component of aerosols that has significant impacts on human health and global climate. However, current models cannot accurately predict the concentrations and sources of primary and secondary OA due to the oversimplification of traditional organic emission inventories. Traditional emission inventories do not consider important precursors of secondary organic aerosols (SOA), such as semi-volatile and intermediate-volatility organic compounds (SVOCs and IVOCs). To improve the accuracy of OA prediction and source identification, it is essential to refine precursor emissions. In this study, a full-volatility organic compounds emission inventory was established for the Central China, with Henan Province as a representative in 2020. The anthropogenic emissions of ultralow volatility organic compounds (xLVOCs), SVOCs, IVOCs, and VOCs were 53.9 kt, 55.3 kt, 182.1 kt, and 586.3 kt, respectively, effectively filling the gap of 181.3 kt in traditional organic compound emission inventory. Residential biomass burning was identified as the primary contribution source for xLVOCs and SVOCs, accounting for 70.1% and 42.2%, respectively. Industrial process was the main contributor for IVOCs and VOCs, accounting for 31.7% and 44.0% of their emissions, respectively. Meanwhile, the emission of volatile organic compound from different sources showed an increasing trend as volatility increased. The gas-phase emission was 212.1 kt, primarily from industrial process (33.9% contribution), while the particle-phase emission was 79.2 kt, mainly from domestic biomass combustion (65.0% contribution). xLVOCs and SVOCs emissions were mainly concentrated in cities with agricultural activities, such as Zhoukou, while IVOCs and VOCs were concentrated in highly industrialized and urbanized areas, such as Zhengzhou. It is hoped that the incompleteness of emission factors (EFs) for full-volatility organic compounds, which mainly contributes to the uncertainty of this study's results, can be further improved to better understand source contributions.

Uncovering the dominant contribution of intermediate volatility compounds in secondary organic aerosol formation from biomass-burning emissions.

Organic vapors from biomass burning are a major source of secondary organic aerosols (SOAs). Previous smog chamber studies found that the SOA contributors in biomass-burning emissions are mainly volatile organic compounds (VOCs). While intermediate volatility organic compounds (IVOCs) are efficient SOA precursors and contribute a considerable fraction of biomass-burning emissions, their contribution to SOA formation has not been directly observed. Here, by deploying a newly-developed oxidation flow reactor to study SOA formation from wood burning, we find that IVOCs can contribute ∼70% of the formed SOA, i.e. >2 times more than VOCs. This previously missing SOA fraction is interpreted to be due to the high wall losses of semi-volatile oxidation products of IVOCs in smog chambers. The finding in this study reveals that SOA production from biomass burning is much higher than previously thought, and highlights the urgent need for more research on the IVOCs from biomass burning and potentially other emission sources.