Intermediate Volatility Organic Compounds Research Articles

Model bias in simulating major chemical components of PM<sub>2.5</sub> in China

Abstract. High concentrations of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 µm) in China have caused severe visibility degradation. Accurate simulations of PM2.5 and its chemical components are essential for evaluating the effectiveness of pollution control strategies and the health and climate impacts of air pollution. In this study, we compared the GEOS-Chem model simulations with comprehensive datasets for organic aerosol (OA), sulfate, nitrate, and ammonium in China. Model results are evaluated spatially and temporally against observations. The new OA scheme with a simplified secondary organic aerosol (SOA) parameterization significantly improves the OA simulations in polluted urban areas, highlighting the important contributions of anthropogenic SOA from semivolatile and intermediate-volatility organic compounds. The model underestimates sulfate and overestimates nitrate for most of the sites throughout the year. More significant underestimation of sulfate occurs in winter, while the overestimation of nitrate is extremely large in summer. The model is unable to capture some of the main features in the diurnal pattern of the PM2.5 chemical components, suggesting inaccuracies in the presented processes. Potential model adjustments that may lead to a better representation of the boundary layer height, the precursor emissions, hydroxyl radical concentrations, the heterogeneous formation of sulfate and nitrate, and the wet deposition of nitric acid and nitrate have been tested in the sensitivity analysis. The results show that uncertainties in chemistry perhaps dominate the model biases. The proper implementation of heterogeneous sulfate formation and the good estimates of the concentrations of sulfur dioxide, hydroxyl radical, and aerosol liquid water are essential for the improvement of the sulfate simulation. The update of the heterogeneous uptake coefficient of nitrogen dioxide significantly reduces the modeled concentrations of nitrate. However, the large overestimation of nitrate concentrations remains in summer for all tested cases. The possible bias in the chemical production and the wet deposition of nitrate cannot fully explain the model overestimation of nitrate, suggesting issues related to the atmospheric removal of nitric acid and nitrate. A better understanding of the atmospheric nitrogen budget, in particular, the role of the photolysis of particulate nitrate, is needed for future model developments. Moreover, the results suggest that the remaining underestimation of OA in the model is associated with the underrepresented production of SOA.

Volatility Distribution of Organic Compounds in Sewage Incineration Emissions.

Intermediate volatility and semivolatile organic compounds (IVOC/SVOC) are important precursors of secondary organic aerosol (SOA) while SVOC is an important contributor to primary organic aerosol (POA). However, combustion emissions data for volatility classes are limited. This study reports the gas and particle emissions that were sampled with various dilution factors from a sewage sludge incinerator burning fuel oil. Volatility distributions were determined using measurements from online mass spectrometry and offline organic compound analyses. In the low volatility organic compound (LVOC) to IVOC range, volatility bins with organic saturation concentrations of 10-100 μg m-3 were most abundant, which was due to organic acids generated from sludge burning. Organic aerosol (OA) emission factors (EFOA) increased 1.4 times after cooling to ambient temperatures in comparison to those of the samples from the hot stack. Upon further isothermal dilution at 25 °C, the EFOA decreased while organic gas phase EFs increased with increasing dilution. Phase partitioning in volatility bins with saturation concentrations of 10-100 μg m-3 was sensitive to isothermal dilution that influenced the EFs. Therefore, gas- and particle-phase measurements alone cannot constrain EFs for these volatility classes. Low dilution factors may overestimate the particle phase and underestimate the gas phase EFs compared with real-world emission conditions.

Chemical formation pathways of secondary organic aerosols in the Beijing-Tianjin-Hebei region in wintertime

A regional air quality model system (RAQMS) was developed by incorporating an aqueous reaction mechanism for secondary organic aerosol (SOA) formation and primary semi-volatile (SVOC) and intermediate volatile organic compounds (IVOC) precursors to investigate various chemical pathways for SOA formation in the Beijing-Tianjin-Hebei (BTH) region in wintertime. Model comparison against observations demonstrates that the model is able to well reproduce meteorological variables and major aerosol chemical components, and the model improves SOA simulation significantly by including primary S/IVOCs (SVOC + IVOC) and aqueous reactions into the model. SVOC and IVOC emissions were relatively higher over the regions from southern Hebei province to Beijing and Tianjin, with the emission rates up to 0.15 mg m−2 hr−1 and 0.3 mg m−2 hr−1, respectively. The glyoxal (GLY) and methylglyoxal (MGLY) emissions were similar in distribution to those of S/IVOC emissions, with the maximum of 0.08 mg m −2 hr−1. The simulated SOA concentrations exhibited a southwest-northeast belt extending from southern Hebei to Beijing, with the maximum of 35 μg m−3 in southern Hebei province. The average contributions from various precursors or chemical pathways to SOA formation during the study period were estimated, in which AVOCs (anthropogenic VOCs), SVOCs, IVOCs, BVOCs (biogenic VOCs), GLY and MGLY contributed 38.4%, 24.9%, 28.4%, 0.2% and 8.1% of SOA mass concentration, respectively, in the BTH region. The maximum average contribution of GLY and MGLY to SOA reached 16% in southern Hebei province during a severe haze episode. From the clean to haze periods, concentrations of all SOA components apparently increased along with increasing atmospheric stability and weakening dispersion, but the increasing rates of SOA concentration produced by AVOCs and aqueous reactions were larger than those by primary S/IVOCs due to different chemical processes, and the AVOC-produced SOA dominated over the other SOA components during the haze periods.

Emission Inventory of Intermediate Volatility Organic Compounds(IVOCs) from Biomass Burning in the Yangtze River Delta During 2010-2018

Intermediate volatility organic compounds (IVOCs) are important precursors of secondary organic aerosols (SOA) but are currently not included in the conventional emissions inventories. Biomass burning represents an important source of IVOCs that could contribute to SOA formation. This study estimated the IVOC emissions from biomass burning in the Yangtze River Delta (YRD) region from 2010 to 2018 based on the fire inventory from NCAR (FINN) and the IVOCs/primary organic aerosol (POA) ratio reported in literature. During this period, the total number of fire events over the YRD region presented a declining trend, with an average of 104 fire events detected per year. During 2016-2018, the average number of fire events was approximately 6000 per year, which was 60% less than that prior to 2016. In terms of the monthly variation, the period from May to August was the period with the most fires observed, which was followed by a small peak in October. The results calculated based on the IVOCs/POA ratio method showed that the IVOC emissions from biomass burning exhibited large differences with different combinations of POA/OC and IVOCs/POA ratios, ranging from a maximum of 305.7×104 t to as small as 10.5×104 t. Monte Carlo simulation revealed that the uncertainties associated with the IVOCs/POA ratio method range from -99% to 68%.

Modeling organic aerosol over Europe in summer conditions with the VBS-GECKO parameterization: sensitivity to secondary organic compound properties and IVOC (intermediate-volatility organic compound) emissions

Abstract. The VBS-GECKO (volatility basis set – Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere) parameterization for secondary organic aerosol (SOA) formation was integrated into the chemistry-transport model CHIMERE. Concentrations of organic aerosol (OA) and SOA were simulated over Europe for the July–August 2013 period. Simulated concentrations with VBS-GECKO were compared to results obtained with the former H2O parameterization implemented in CHIMERE and to observations from EMEP, ACTRIS and other observations available in the EBAS database. The model configuration using the VBS-GECKO parameterization slightly improves the performances compared to the model configuration using the former H2O parameterization. The VBS-GECKO model configuration performs well for stations showing a large SOA concentration from biogenic sources, especially in northern Europe, but underestimates OA concentrations over stations close to urban areas. Simulated OA was found to be mainly secondary (∼85 %) and from terpene oxidation. Simulations show negligible contribution of the oxidation of mono-aromatic compounds to SOA production. Tests performed to examine the sensitivity of simulated OA concentrations to hydro-solubility, volatility, aging rates and NOx regime have shown that the VBS-GECKO parameterization provides consistent results, with a weak sensitivity to changes in the parameters provided by the gas-phase mechanism included in CHIMERE (e.g., HOx or NOx concentrations). Different scenarios considering intermediate-volatility organic compound (IVOC) emissions were tested to examine the contribution of IVOC oxidation to SOA production. At the continental scale, these simulations show a weak sensitivity of OA concentrations to IVOC emission variations. At the local scale, accounting for IVOC emissions was found to lead to a substantial increase in OA concentrations in the plume from urban areas. This additional OA source remains too small to explain the gap between simulated and measured values at stations where anthropogenic sources are dominant.

Simulation of organic aerosol formation during the CalNex study: updated mobile emissions and secondary organic aerosol parameterization for intermediate-volatility organic compounds.

We describe simulations using an updated version of the Community Multiscale Air Quality model version 5.3 (CMAQ v5.3) to investigate the contribution of intermediate-volatility organic compounds (IVOCs) to secondary organic aerosol (SOA) formation in southern California during the CalNex study. We first derive a model-ready parameterization for SOA formation from IVOC emissions from mobile sources. To account for SOA formation from both diesel and gasoline sources, the parameterization has six lumped precursor species that resolve both volatility and molecular structure (aromatic versus aliphatic). We also implement new mobile-source emission profiles that quantify all IVOCs based on direct measurements. The profiles have been released in SPECIATE 5.0. By incorporating both comprehensive mobile-source emission profiles for semivolatile organic compounds (SVOCs) and IVOCs and experimentally constrained SOA yields, this CMAQ configuration best represents the contribution of mobile sources to urban and regional ambient organic aerosol (OA). In the Los Angeles region, gasoline sources emit 4 times more non-methane organic gases (NMOGs) than diesel sources, but diesel emits roughly 3 times more IVOCs on an absolute basis. The revised model predicts all mobile sources (including on- and off-road gasoline, aircraft, and on- and off-road diesel) contribute ~ 1 μgm-3 to the daily peak SOA concentration in Pasadena. This represents a ~ 70% increase in predicted daily peak SOA formation compared to the base version of CMAQ. Therefore, IVOCs in mobile-source emissions contribute almost as much SOA as traditional precursors such as single-ring aromatics. However, accounting for these emissions in CMAQ does not reproduce measurements of either ambient SOA or IVOCs. To investigate the potential contribution of other IVOC sources, we performed two exploratory simulations with varying amounts of IVOC emissions from nonmobile sources. To close the mass balance of primary hydrocarbon IVOCs, IVOCs would need to account for 12% of NMOG emissions from nonmobile sources (or equivalently 30.7 t d-1 in the Los Angeles-Pasadena region), a value that is well within the reported range of IVOC content from volatile chemical products. To close the SOA mass balance and also explain the mildly oxygenated IVOCs in Pasadena, an additional 14.8% of nonmobile-source NMOG emissions would need to be IVOCs (assuming SOA yields from the mobile IVOCs apply to nonmobile IVOCs). However, an IVOC-to-NMOG ratio of 26.8% (or equivalently 68.5 t d-1 in the Los Angeles-Pasadena region) for nonmobile sources is likely unrealistically high. Our results highlight the important contribution of IVOCs to SOA production in the Los Angeles region but underscore that other uncertainties must be addressed (multigenerational aging, aqueous chemistry and vapor wall losses) to close the SOA mass balance. This research also highlights the effectiveness of regulations to reduce mobile-source emissions, which have in turn increased the relative importance of other sources, such as volatile chemical products.

Triple Isotopes (δ13C, δ2H, and Δ14C) Compositions and Source Apportionment of Atmospheric Naphthalene: A Key Surrogate of Intermediate-Volatility Organic Compounds (IVOCs).

Naphthalene (NAP), as a surrogate of intermediate-volatility organic compounds (IVOCs), has been proposed to be an important precursor of secondary organic aerosol (SOA). However, the relative contribution of its emission sources is still not explicit. This study firstly conducted the source apportionment of atmospheric NAP using a triple-isotope (δ13C, δ2H, and Δ14C) technique combined with a Bayesian model in the Beijing-Tianjin-Hebei (BTH) region of China. At the urban sites, stable carbon (-27.7 ± 0.7‰, δ13C) and radiocarbon (-944.0 ± 20.4‰, Δ14C) isotope compositions of NAP did not exhibit significant seasonal variation, but the deuterium system showed a relatively more 2H depleted signature in winter (-86.7 ± 8.9‰, δ2H) in comparison to that in summer (-56.4 ± 3.9‰, δ2H). Radiocarbon signatures indicated that 95.1 ± 1.8% of NAP was emitted from fossil sources in these cities. The Bayesian model results indicated that the emission source compositions in the BTH urban sites had a similar pattern. The contribution of liquid fossil combustion was highest (46.7 ± 2.6%), followed by coal high-temperature combustion (26.8 ± 7.1%), coal low-temperature combustion (18.9 ± 6.4%), and biomass burning (7.6 ± 3.1%). At the suburban site, the contribution of coal low-temperature combustion could reach 70.1 ± 6.4%. The triple-isotope based approach provides a top-down constraint on the sources of atmospheric NAP and could be further applied to other IVOCs in the ambient atmosphere.

An alternative semi-quantitative GC/MS method to estimate levels of airborne intermediate volatile organic compounds (IVOCs) in ambient air

Abstract Intermediate volatile organic compounds (IVOCs) have attracted much attention due to their contributions to the formation of secondary organic aerosol (SOA) in ambient air. Determination of total IVOCs in ambient air is therefore important for assessing their roles in air pollution. Currently, concentrations of IVOCs are estimated using a previously published semi-quantitative method. In this paper we propose an alternative method for the determination of IVOCs concentrations, in which speciated IVOCs of n-alkanes, polycyclic aromatic hydrocarbons (PAHs) and phthalates are treated as speciated IVOCs and quantified using their respective standards. The ion signal attributed to the speciated IVOCs is then subtracted from the total ion chromatogram (TIC) and the remaining peak area is used to semi-quantitatively estimate the remaining mass regarded as unspeciated complex mixture (UCM) IVOCs. The TIC peak area of speciated IVOCs in ambient air samples is reconstructed based on the peak area ratio of extracted ion chromatogram (EIC) of the quantifying ion and the TIC from their respective standards. The total IVOCs is then calculated as the sum of the speciated IVOCs and the UCM IVOCs. Twenty-one ambient air samples, collected from November 7 to December 12, 2018 in the urban area of Shanghai, were used to compare our method with the previously published method. Although the overall differences in UCM IVOCs and total IVOCs values were small between the two methods, different values of UCM IVOCs and total IVOCs in several sections of the chromatogram that contain phthalates were observed. Analysis of the ambient air samples also revealed that levels of IVOCs were significantly correlated with atmospheric PM2.5. Our method has the advantage that more accurate results in the determination of total IVOCs can be achieved when more compounds are identified and added to the list of speciated IVOCs.

Behaviour of traffic emitted semi-volatile and intermediate volatility organic compounds within the urban atmosphere

Particulate matter originated from traffic has attracted major interest over the last few years. The semi-volatile organic component of the particles may evaporate with dispersion away from the emission source, creating vapour which may oxidise to form secondary organic aerosol. Air samples were collected from a street canyon, the adjacent park and an urban background site during the winter-spring period in central London, UK. Emissions of semi-volatile organic compounds (SVOCs) and intermediate volatility organic compounds (IVOCs) ranging from C10 to C36 in both the gas phase and particle phase were measured by using thermal desorption coupled to comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (TD-GC × GC-ToF-MS). Main compound groups identified and quantified were grouped alkanes (n-alkanes and branched alkanes), monocyclic alkanes, bicyclic alkanes and monocyclic aromatics. The carbon preference index (CPI) of n-alkanes was estimated to distinguish the emission sources. Pearson correlations between I/SVOCs and traffic tracers (black carbon, NOx and benzene) in different locations were compared to analyse the influence of this emission source. The results indicate that while the major emission source at the roadside site is traffic, the lower correlations at background sites are indicative of other source contributions and/or differential reactivity of compounds. Gas-particle phase partitioning of n-alkanes is evaluated and compared between sites. The potential influence of gas phase I/SVOCs upon OH reactivity and secondary organic aerosol (SOA) formation is estimated and found to be relatively small.

Water-soluble iron emitted from vehicle exhaust is linked to primary speciated organic compounds

Abstract. Iron is the most abundant transition element in airborne particulate matter (PM), primarily existing as Fe(II) or Fe(III). Generally, the fraction of water-soluble iron is greater in urban areas compared to areas dominated by crustal emissions. To better understand the origin of water-soluble iron in urban areas, tailpipe emission samples were collected from 32 vehicles with emission certifications of Tier 0 low emission vehicles (LEV I), Tier 2 low emission vehicles (LEV II), ultralow emission vehicles (ULEVs), super-ultralow emission vehicles (SULEVs), and partial-zero emission vehicles (PZEVs). The components quantified included gases, inorganic ions, elemental carbon (EC), organic carbon (OC), total metals, and water-soluble metals. Naphthalene and intermediate-volatility organic compounds (IVOCs) were quantified for a subset of vehicles. The IVOCs quantified contained 12 to 18 carbons and were divided into three subgroups: aliphatic, single-ring aromatic (SRA), and polar (material not classified as either aliphatic or SRA). Iron solubility in the tested vehicles ranged from 0 % to 82 % (average 30 %). X-ray absorption near-edge structure (XANES) spectroscopy showed that Fe(III) was the primary oxidation state in 14 of the 16 tested vehicles, confirming that the presence of Fe(II) was not the main driver of water-soluble Fe. The correlation of water-soluble iron with sulfate was insignificant, as was correlation with every chemical component except naphthalene and some C12–C18 IVOCs with R2 values as high as 0.56. A controlled benchtop study confirmed that naphthalene alone increases iron solubility from soils by a factor of 5.5 and that oxidized naphthalene species are created in the extract solution. These results suggest that the large driver in water-soluble iron from primary vehicle tailpipe emissions is related to the organic composition of the PM. We hypothesize that, during the extraction process, specific components of the organic fraction of the PM are oxidized and chelate the iron into water.

Aqueous-Phase Production of Secondary Organic Aerosols from Oxidation of Dibenzothiophene (DBT)

Intermediate-volatility organic compounds (IVOCs) have been recognized as an important contributor to the secondary organic aerosol (SOA) formation via gas-phase reactions. However, it is unclear whether or not IVOCs-SOA can be produced in the aqueous phase. This work investigated aqueous oxidation of one model compound of IVOCs, dibenzothiophene (DBT). Results show that DBT can be degraded by both hydroxyl radical and the triplet excited states of organic light chromophores (3C*). Aqueous dark oxidation of DBT was also possible. SOA yields of 32% and 15% were found for hydroxyl radical (OH)-mediated photo-oxidation and dark oxidation, respectively. A continuous and significant increase of oxidation degree of SOA was observed during OH photo-oxidation, but not during the dark oxidation. Factor analyses revealed that there was a persistent production of highly oxygenated compounds from the less oxygenated species. OH-initiated photochemical reactions can also produce species with a relatively large light-absorbing ability, while such photo-enhancement due to direct light irradiation and 3C*-initiated oxidation could occur, but is much less important. In the future, studies on the second-order rate constants, molecular characterization of the oxidation products from this and other IVOCs precursors are needed to better understand the role of this reaction pathway in SOA budget, air quality and climate change.

Emissions of intermediate volatility organic compound from waste cooking oil biodiesel and marine gas oil on a ship auxiliary engine

Ship auxiliary engines contribute large amounts of air pollutants when at berth. Biodiesel, including that from waste cooking oil (WCO), can favor a reduction in the emission of primary pollutant when used with internal combustion engines. This study investigated the emissions of gaseous intermediate-volatile organic compounds (IVOCs) between WCO biodiesel and marine gas oil (MGO) to further understand the differences in secondary organic aerosol (SOA) production of exhausts. Results revealed that WCO exhaust exhibited similar IVOC composition and volatility distribution to MGO exhaust, despite the differences between fuel contents. While WCO biodiesel could reduce IVOC emissions by 50% as compared to MGO, and thus reduced the SOA production from IVOCs. The compositions and volatility distributions of exhaust IVOCs varied to those of their fuels, implying that fuel-component-based SOA predicting model should be used with more cautions when assessing SOA production of WCO and MGO exhausts. WCO biodiesel is a cleaner fuel comparing to conventional MGO on ship auxiliary engines with regard to the reductions in gaseous IVOC emissions and corresponding SOA productions. Although the tests were conducted on test bench, the results could be considered as representative due to the widely applications of the test engine and MGO fuel on real-world ships.

Emission Inventory of Intermediate Volatility Organic Compounds from Vehicles in the Yangtze River Delta in 2017 and the Impact on the Formation Potential of Secondary Organic Aerosols

Intermediate volatility organic compounds (IVOCs) have a significant contribution to the formation of secondary organic aerosols (SOA) in the atmosphere, but are not included in the current emission inventory. In this study, IVOC emissions from vehicles are estimated for the Yangtze River Delta region (YRD) for 2017 based on two methods:the emission factor method and the IVOCs/POA scaling factor method. Uncertainties in the estimated IVOCs emissions and the impact on their potential formation are discussed. The results based on the emission factor method showed that the total vehicular IVOCs emission in the YRD in 2017 was 35800 tons, and that the formation potential of SOA was an estimated 695 tons. IVOCs emissions from trucks accounted for>70% of total IVOCs emissions in most cities in the YRD region. In terms of fuel type, IVOCs emissions from diesel vehicles were much higher than of those from gasoline vehicles. Results based on the IVOCs/POA scaling factor method showed that the emissions calculated by different combinations of IVOCs/POA ratios and POA/PM2.5 ratios that could vary significantly, with a maximum of 64.2×104 tons and a minimum of just 5.2×104 tons. The resultant SOA formation potential was 1.55×104 tons and 1032 tons for the maximum and minimum, respectively. This study shows that the results of IVOCs emissions based on different estimation methods are associated with large uncertainties, which could directly affect the simulation results of SOA in subsequent air quality models. Therefore, it is necessary to use different inventory results in air quality models and perform model evaluation of SOA in order to obtain more accurate IVOCs emission inventories of vehicles in the YRD region.

Measurement of Formation Rates of Secondary Aerosol in the Ambient Urban Atmosphere Using a Dual Smog Chamber System.

A dual smog chamber system was used to quantify the formation rates of secondary organic and inorganic aerosol in an urban environment (Pittsburgh, US). Ambient air was introduced in both chambers, and HONO photolysis was used to produce hydroxyl radicals (OH) in the perturbed chamber. The second chamber was used as a reference. The production rate of secondary organic aerosol (SOA) under typical noon-time OH concentrations ranged from 0.2 to 0.8 μg m-3 h-1. The production rate of sulfate was approximately five times less than that of the SOA. Nucleation and growth of new particles were observed in the perturbation chamber. The produced SOA had a similar composition with the preexisting oxygenated ambient OA. The reacted amounts of the measured VOCs were able to explain 5-50% of the formed SOA in the perturbed chamber. Intermediate volatility organic compounds could be responsible for the rest. The oxygen to carbon ratio (O:C) in the perturbed chamber remained approximately the same during SOA production, while an increase was observed in the control chamber. A possible explanation could be the loss of less oxidized species to the chamber walls. After 2 h, the OA increased by 70% on average and the sulfate by 40%.

Intermediate-Volatility Organic Compound Emissions from Nonroad Construction Machinery under Different Operation Modes.

Intermediate-volatility organic compounds (IVOCs) have been found as important sources for secondary organic aerosol (SOA) formation. IVOC emissions from nonroad construction machineries (NRCMs), including two road rollers and three motor graders, were characterized under three operation modes using an improved portable emission measurement system. The fuel-based IVOC emission factors (EFs) of NRCMs varied from 245.85 to 1802.19 mg/kg·fuel, which were comparable at magnitudes to the reported results of an ocean-going ship and on-road diesel vehicles without filters. The discrepancy of IVOC EFs is significant within different operation modes. IVOC EFs under the idling mode were 1.24-3.28 times higher than those under moving/working modes. Unspeciated b-alkanes and cyclic compounds, which were the unresolved components in IVOCs at the molecular level, accounted for approximately 91% of total IVOCs from NRCMs. The SOA production potential analysis shows that IVOCs dominated SOA formation of NRCMs. Our results demonstrate that IVOC emissions from NRCMs are non-negligible. Thus, an accurate estimation of their IVOC emissions would benefit the understanding of SOA formation in the urban atmosphere.

Source apportionment of secondary organic aerosols in the Pearl River Delta region: Contribution from the oxidation of semi-volatile and intermediate volatility primary organic aerosols

Secondary organic aerosols (SOAs) are some of the most important components of aerosol over south China, especially, in the Pearl River Delta (PRD). However, traditional SOA simulations usually result in severe underestimates because of the limited understanding of SOA formation. Furthermore, the source contribution features of SOAs in the PRD region remain poorly understood. In this study, a 1-D Volatility Basis-Set (VBS) scheme, and a 1.5-D VBS scheme are implemented in the Comprehensive Air Quality Model with Extensions (CAMx) to improve the poor model performance with the traditional SOA scheme, and a 1-year simulation of SOAs over the PRD region are conducted for each scheme. A comparison of the simulated results with the observational data reveals that the 1-D VBS scheme shows better model performance for SOA simulation in both absolute concentrations and time series agreement, which suggests that the VBS scheme effectively reduces the underestimation in SOA simulations. The missing processes [oxidation of intermediate-volatility organic compound (IVOC)/semi-volatility organic compound (SVOC)] contribute to SOA concentration of 4–7 μg/m3, (relatively as high as about 400–500%) at the center of the PRD region and of 1–2 μg/m3 (relatively about 100–300%) in the rural areas of the PRD region.By implementing the SOA source apportionment technology (SSAT) with 1-D VBS scheme in CAMx, the source contributions from geographic source regions and source types are discussed. The results at a rural supersite (HKUST) with SOA observation data show that the super-regional transport accounts for 56.5%–76.9% of SOA concentration, PRD region contribution accounts for 13.1%–32.7% of SOA concentration. Of the SOAs from the PRD region, mobile emission takes the largest contribution among the emissions categories, which suggests that the anthropogenic emission significantly contribute to the SOAs over the PRD region. Our results also indicate that the applications of VBS models and SSAT algorithm provide new insights into policy implications for improving local and regional air quality.

The formation and evolution of secondary organic aerosol during haze events in Beijing in wintertime

A regional air quality model system (RAQMS) with a volatility basis set approach for secondary organic aerosol (SOA) formation and an emission inventory of semi-volatile (SVOC) and intermediate volatile organic compounds (IVOC) are applied to investigate the distribution and evolution of organic aerosols over the Beijing-Tianjin-Hebei (BTH) region in winter 2014, with focus on Beijing. Model validation demonstrates the model is capable of reproducing meteorological variables and major aerosol components, and the model significantly improves SOA and organic aerosol (OA) simulations by taking S/IVOCs (SVOC + IVOC) and relevant aging processes into account. SVOC and IVOC emissions in the BTH region are estimated to be 0.47 Tg and in a range of 0.09–0.36 Tg, respectively, which are about 18% and 4–14% of the emission amounts of volatile organic compounds (VOCs). The distribution of mean organic aerosols is characterized by a high concentration belt oriented southwest-northeast from southern Hebei to Beijing, with the maximum concentration up to 50 μg m−3 in Beijing and Shijiazhuang. The simulated SOA concentration is comparable in magnitude to primary organic aerosol (POA) concentration, and the SOA/OA ratio is around 50% in most areas of the BTH region. In terms of domain average, the percentage contributions to SOA mass concentration from anthropogenic volatile organic compounds (AVOCs), SVOCs, IVOCs and biogenic VOCs are estimated to be 46.1%, 40.1%, 9.4% and 4.4%, respectively, in the BTH region during the study period, which indicates an important role of S/IVOCs in SOA formation. From clean to haze periods, both POA and SOA concentrations apparently increase, with an increasing (decreasing) trend of the SOA/OA (POA/OA) ratio. SOA dominates over POA in fine organic aerosols during the haze periods. The increase of POA in hazy days is mainly due to the weakened vertical diffusion and accumulation near the surface, whereas the increase of SOA is likely attributed to both the reduced diffusivity and a series of competing chemical processes, in which the decreased photolysis rate by aerosol attenuation tends to decrease SOA concentration by about 6% during the most severe haze day, whereas the lower surface air temperature and higher POA and S/IVOC concentrations in haze days both enhance gas to particle partition, and consequently lead to higher SOA concentration.

Emission Characteristics of IVOCs from the Combustion of Residential Solid Fuels and the Impact of Burning Temperature

Intermediate-volatility organic compounds (IVOCs) are important precursors of secondary organic aerosols that have received much recent attention; however, there is a lack of emission data for IVOCs from combustion sources, especially for residential solid fuel combustion. In this study, two bituminous coals with different geological maturity (XZ and LW) and two biomass types (rice stalk and pinewood) were tested at seven temperature points (300-900℃ with an interval of 100℃) using a quartz tube furnace together with a dilution sampling system. The results showed that the averaged emission factor for IVOCs from biomass combustion[(483±182) mg·kg-1] was 2.5 times higher than that of bituminous coal combustion (190±108) mg·kg-1. The remaining unresolved complex mixture (UCM) dominated the IVOC content for both biomass and coal combustions (81%±11% and 68%±6%, respectively). The fraction of normal and branched alkanes for biomass combustions was lower than for coal combustion, while the fraction of aromatics was higher. The effect of temperature on the emission of IVOCs and their composition was significantly different between the two types of fuel. The emission factor for IVOCs from coal (using LW as an example) at 500℃[(340±113) mg·kg-1] was 5.4 times higher than at 900℃[(63±15) mg·kg-1], while two comparable peaks are observed at 400-500℃ and 800-900℃. As the combustion temperature increased, the proportion of aromatic hydrocarbons in pinewood IVOCs increased from 1% to 29%, while the remaining UCM decreased from 92% to 61%. However, there was little variation for coal combustion. The effects of fuel type and temperature on the emission of IVOCs were further explained with respect to the modified combustion efficiency (MCE).

Size-resolved physico-chemical characterization of diesel exhaust particles and efficiency of exhaust aftertreatment

Knowledge of physico-chemical characteristics of particle emissions from combustion engines is essential for various modelling purposes and environmental analysis. It is of particular interest to obtain emission factors of intermediate-volatility organic compounds (IVOC) and semi-volatile organic compounds (SVOC) which have not been comprehensively reported in the literature due to the limitations of characterisation methods. In the current study, a multi-stage Nano impactor and the two-dimensional gas chromatography (GC × GC) mass spectrometry (MS) technique were used to comprehensively characterise size fractionated particle phase emissions from a light-duty diesel engine based on the particle size, compound groups and carbon number. The number size distributions of particles between 1.2–1000 nm were also investigated. Exhaust gas samples were taken before a diesel oxidation catalyst (DOC), after the DOC and after the DOC combined with a catalysed diesel particulate filter (DPF). In samples taken before the DOC (engine-out), the total particulate IVOC+SVOC (I+SVOC) emission factor was approximately 105 milligrams per kilogram of fuel consumed (which was ~49% of the total particle mass) and the peak concentration of different classes of I+SVOC was found in the particle size bins close to 100 nm where most of the total particle mass was found. Alkanes, with maximum abundance at C24, were the most dominant class of I+SVOC in samples taken before and after the aftertreatment devices. Total particulate I+SVOC emissions were removed with ~75% efficiency using the DOC and by ~92% using the DOC+DPF. Alkanes, cycloalkanes, bicyclics and monoaromatics were all removed by >90% using the DOC+DPF; however, oxygenates were removed by only ~76% presumably due to the oxidation of different species within the aftertreatment system and reappearance as oxygenates. A high concentration of particles was measured in the sub-2.5 nm range. These particles were efficiently removed by the DOC+DPF due to both the loss of I+SVOC and physical filtration.

Emission inventory of semi-volatile and intermediate-volatility organic compounds and their effects on secondary organic aerosol over the Pearl River Delta region

Abstract. Semi-volatile and intermediate-volatility organic compounds (S–IVOCs) are considered critical precursors of secondary organic aerosol (SOA), which is an important component of fine particulate matter (PM2.5). However, knowledge of the contributions of S–IVOCs to SOA is still lacking in the Pearl River Delta (PRD) region, southern China. Therefore, in this study, an emission inventory of S–IVOCs in the PRD region was developed for the first time for the year 2010. The S–IVOC emissions were calculated based on a parameterization method involving the emission factors of POA (primary organic aerosol), emission ratios of S–IVOCs to POA, and domestic activity data. The total emissions of S–IVOCs were estimated to be 323.4 Gg, with major emissions from central cities in the PRD, i.e., Guangzhou, Foshan, and Shenzhen. On-road mobile sources and industries were the two major contributors of S–IVOC emissions, with contributions of ∼42 % and ∼35 %, respectively. Furthermore, uncertainties of the emission inventory were evaluated through Monte Carlo simulation. The uncertainties ranged from −79 % to 229 %, which could be mainly attributed to mass fractions of OC (organic carbon) to PM2.5 from on-road mobile emissions and emission ratios of IVOCs ∕ POA. The developed S–IVOC emission inventory was further incorporated into the Weather Research and Forecasting with Chemistry (WRF-Chem) model with a volatility basis-set (VBS) approach to improve the performance of SOA simulation and to evaluate the influence of S–IVOCs on SOA formation at a receptor site (Wan Qing Sha (WQS) site) in the PRD. The following results could be obtained. (1) The model could resolve about 34 % on average of observed SOA concentrations at WQS after considering the emissions of S–IVOCs, and 18 %–77 % with the uncertainties of the S–IVOC emission inventory considered. (2) The simulated SOA over the PRD region was increased by 161 % with the input of S–IVOC emissions, and it could be decreased to 126 % after the reaction coefficient of S–IVOCs with OH radical was improved. (3) Among all anthropogenic sources of S–IVOCs, industrial emission was the most significant contributor of S–IVOCs for SOA formation, followed by on-road mobile, dust, biomass burning, residential, and off-road mobile emissions. Overall, this study firstly quantified emissions of S–IVOCs and evaluated their roles in SOA formation over the PRD, which contributes towards significantly improving SOA simulation and better understanding of SOA formation mechanisms in the PRD and other regions in China.