Secondary Organic Aerosol Precursors Research Articles

Smog chamber study of secondary organic aerosol formation from gas- and particle-phase naphthalene ozonolysis

Naphthalene (Nap), one of the most abundant PAHs in the atmosphere, has been shown to be an important secondary organic aerosol (SOA) precursor. In this study, the gas- and particle-phases (Suspended Nap-coated polystyrene latex spheres (PSLs) generated by vaporization condensation) Nap ozonolysis were investigated in a 1000 L volume cubic Teflon smog chamber. Gas-phase products and Nap-SOAs were observed from the gas- and particle-phase Nap ozonolysis via homogeneous and heterogeneous reactions, respectively. The time-dependent size distribution and mass concentration of Nap-SOAs were analyzed using a scanning mobility particle sizer and a laboratory-developed single-particle aerosol mass spectrometry (SPAMS) instrument. The chemical components of the homogeneous and heterogeneous reaction products were analyzed on-line by single photo ionization mass spectrometry (SPIMS), SPAMS, as well as by thermal desorption gas chromatograph-mass spectrometry. The results showed that the chemical components of the gas-and particle-phase Nap ozonolysis were essentially the same, with the dominant products being phthalaldehyde, phthalic anhydride, 2-carboxybenzaldehyde, and benzoic acid; Nap-SOA formation was attributed to the formation of new particles as well as the uptake of homogeneous and heterogeneous Nap oxidation products on the gas-phase or/and the particle surface. Based on the online measurement results, the reaction mechanism of Nap-ozonolysis also exhibits an initial carbon atom or double-bond attacks by O3, and kinetic analysis of Nap-coated PSLs ozonolysis shows a heterogeneous reaction rate constant of 2.55E-4 s−1 with R2 = 0.984. This study provides a systematic approach to characterize the chemical and physical properties of the gas- and particle-phase Nap ozonolysis in real time, which will deepen our understanding of the migration and transformation of PAHs in the atmosphere.

Investigation into the differences and relationships between gasSOA and aqSOA in winter haze pollution on Chongming Island, Shanghai, based on VOCs observation

To investigate the formation of secondary organic aerosol (SOA) under current atmospheric conditions, we conducted a field observation of SOA precursors in the downwind region of the Yangtze River Delta (YRD) in winter 2019 using a variety of offline and online instruments. During the entire observation period, the averaged fine particulate SOA was 7.9 ± 2.3 μg m−3, with precursor concentrations of 31 ± 11 ppbv for the measured volatile organic compounds (VOCs) and 16 ± 12 ppbv for NOx. Compared to those on the clean days, SOA on the haze days increased by a factor of 1.6, while the VOC and NOx increased by a factor of 1.3 and 2.0, respectively. Aerosol liquid water content (ALWC) and oxygenated VOCs (OVOCs, including acetaldehyde, formic acid, acetone, acetic acid, methyl ethyl ketone, and methylglyoxal) relationships suggested that the gasSOA and aqSOA occurred simultaneously on Chongming Island in winter. The gasSOA was primarily formed by the oxidation of aromatics and NOx at low RH (RH < 80%) conditions. In contrast, the aqSOA was formed under higher RH (RH > 80%) conditions via a combination of daytime photochemical aqueous phase processes of water-soluble OVOCs and nocturnal dark aqueous phase processes of primary emissions from biomass. The inversed higher mass ratio of NACs to (benzene + toluene) and nitrogen oxidation ratio (NOR) in the daytime during the gasSOA-dominated haze periods indicated that gasSOA could be transformed to aqSOA at high NOx levels. Our results also suggested the importance of NOx and VOC reduction measures in directly mitigating gasSOA and indirectly mitigating aqSOA during winter haze pollution.

Identification of volatile organic compound emissions from anthropogenic and biogenic sources based on satellite observation of formaldehyde and glyoxal

Anthropogenic volatile organic compounds (VOCs) are serious pollutants in the atmosphere because of their toxicity and as precursors of secondary organic aerosols and ozone pollution. Although in-situ measurements provide accurate information on VOCs, their spatial coverage is limited and insufficient. In this study, we provide a global perspective for identifying anthropogenic VOC emission sources through the ratio of glyoxal to formaldehyde (RGF) based on satellite observations. We assessed typical cities and polluted areas in the mid latitudes and found that some Asian cities had higher anthropogenic VOC emissions than cities in Europe and America. For heavily polluted areas, such as the Yangtze River Delta (YRD), the areas dominated by anthropogenic VOCs accounted for 23 % of the total study areas. During the COVID-19 pandemic, a significant decline in RGF values was observed in the YRD and western United States, corresponding to a reduction in anthropogenic VOC emissions. Furthermore, developing countries appeared to have higher anthropogenic VOC emissions than developed countries. These observations could contribute to optimising industrial structures and setting stricter pollution standards to reduce anthropogenic VOCs in developing countries.

Emission characteristics and inventory of volatile organic compounds from the Chinese cement industry based on field measurements

Volatile organic compounds (VOCs) are major precursors of ozone (O3) and secondary organic aerosols (SOA), which degrade air quality and pose a serious risk to human health and ecological systems. Previous studies on the emission characteristics of VOCs have predominantly focused on petrochemical and solvent-using sources, while localized studies on the cement industry are scarce in China. Field measurements for four cement plants were carried out in this study to investigate the emission levels, source profiles, and secondary pollutant generation potential of 98 VOCs species emitted from rotary and shaft kilns in China. Furthermore, a species-differentiated VOCs emission inventory was compiled for the Chinese cement industry in 2019. The results demonstrated that the mass concentration of VOCs emitted from shaft kiln was more than 20-fold higher than that emitted from rotary kilns, and the alkanes was the dominant species (56%) in shaft kilns, while oxygenated VOCs (OVOCs) and halocarbons were the main species in rotary kilns. Moreover, alkenes & alkyne were the dominant contributors to ozone formation potential (OFP) in shaft kilns, whereas alkenes & alkyne and OVOCs were comparable and prominent contributors in rotary kilns. In contrast, secondary organic aerosol potential (SOAP) for the two types of kilns was dominated by aromatics. In 2019, approximately 18.18 kt VOCs were emitted from cement production and were found to be largely concentrated in the southeast and central provinces of China. Considering the influence on environmental conditions, high OFP-contributing species in cement kilns are suggested to be a priority in the pollution mitigation of O3. This study provides a new, comprehensive, and reasonable cognition of the current VOCs emissions from both rotary and shaft kilns in China, which will aid in a better understanding of VOCs emission characteristics and guide future policy-making.

Real-world emission characteristics of semivolatile/intermediate-volatility organic compounds originating from nonroad construction machinery in the working process

Detailed emission characterization of semivolatile/intermediate-volatility organic compounds (S/IVOCs) originating from nonroad construction machines (NRCMs) remains lacking in China. Twenty-one NRCMs were evaluated with a portable emission measurement system in the working process. Gas phase S/IVOCs were collected by Tenax TA tubes and analyzed via thermal desorption-gas chromatography–mass spectrometry (TD–GC–MS). Particle phase S/IVOCs were collected by quartz filters and analyzed via GC–MS. The average emission factors (EFs) for fuel-based total (gas + particle phase) IVOCs and SVOCs of the assessed NRCMs were 221.45 ± 194.60 and 11.68 ± 10.67 mg/kg fuel, respectively. Compared to excavators, the average IVOC and SVOC EFs of loaders were 1.32 and 1.55 times higher, respectively. Compared to the working mode, the average IVOC EFs under the moving mode (only moving forward or backward) were 1.28 times higher. The IVOC and SVOC EFs for excavators decreased by 69.06% and 38.37%, respectively, from China II to China III. These results demonstrate the effectiveness of emission control regulations. In regard to individual NRCMs, excavators and loaders were affected differently by emission standards. The volatility distribution demonstrated that IVOCs and SVOCs were dominated by gas- and particle-phase compounds, respectively. The mode of operation also affected S/IVOC gas-particle partitioning. Combined with previous studies, the mechanical type significantly affected the volatility distribution of IVOCs. IVOCs from higher volatile fuels are more distributed in the high-volatility interval. The total secondary organic aerosol (SOA) production potential was 104.36 ± 79.67 mg/kg fuel, which originated from VOCs (19.98%), IVOCs (73.87%), and SVOCs (6.15%). IVOCs were a larger SOA precursor than VOCs and SVOCs. In addition, normal (n-) alkanes were suitably correlated with IVOCs, which may represent a backup solution to quantify IVOC EFs. This work provides experimental data support for the refinement of the emission characteristics and emission inventories of S/IVOCs originating from NRCMs.

Low-Temperature Catalytic Ozonation of Multitype VOCs over Zeolite-Supported Catalysts.

Volatile organic compounds (VOCs) are an important source of air pollution, harmful to human health and the environment, and important precursors of secondary organic aerosols, O3 and photochemical smog. This study focused on the low-temperature catalytic oxidation and degradation of benzene, dichloroethane, methanethiol, methanol and methylamine by ozone. Benzene was used as a model compound, and a molecular sieve was selected as a catalyst carrier to prepare a series of supported active metal catalysts by impregnation. The effects of ozone on the catalytic oxidation of VOCs and catalysts' activity were studied. Taking benzene as a model compound, low-temperature ozone catalytic oxidation was conducted to explore the influence of the catalyst carrier, the active metal and the precious metal Pt on the catalytic degradation of benzene. The optimal catalyst appeared to be 0.75%Pt-10%Fe/HZSM(200). The catalytic activity and formation of the by-products methylamine, methanethiol, methanol, dichloroethane and benzene over 0.75%Pt-10%Fe/HZSM(200) were investigated. The structure, oxygen vacancy, surface properties and surface acidity of the catalysts were investigated. XRD, TEM, XPS, H2-TPR, EPR, CO2-TPD, BET, C6H6-TPD and Py-IR were combined to establish the correlation between the surface properties of the catalysts and the degradation activity.

A lumped species approach for the simulation of secondary organic aerosol production from intermediate-volatility organic compounds (IVOCs): application to road transport in PMCAMx-iv (v1.0)

Abstract. Secondary organic aerosol (SOA) is formed in the atmosphere through the oxidation and condensation of organic compounds. Intermediate-volatility compounds (IVOCs), compounds with effective saturation concentration (C∗) at 298 K between 103 and 106 µg m−3, have high SOA yields and can be important SOA precursors. The first efforts to simulate IVOCs in chemical transport models (CTMs) used the volatility basis set (VBS), a highly parametrized scheme that oversimplifies their chemistry. In this work we propose a more detailed approach for simulating IVOCs in CTMs, treating them as lumped species that retain their chemical characteristics. Specifically, we introduce four new lumped species representing large alkanes, two lumped species representing polyaromatic hydrocarbons (PAHs) and one species representing large aromatics, all in the IVOC range. We estimate IVOC emissions from road transport using existing estimates of volatile organic compound (VOC) emissions and emission factors of individual IVOCs from experimental studies. Over the European domain, for the simulated period of May 2008, estimated IVOC emissions from road transport were about 21 Mmol d−1, a factor of 8 higher than emissions used in previous VBS applications. The IVOC emissions from diesel vehicles were significantly higher than those from gasoline ones. SOA yields under low-NOx and high-NOx conditions for the lumped IVOC species were estimated based on recent smog chamber studies. Large cyclic alkane compounds have both high yields and high emissions, making them an important, yet understudied, class of IVOCs.

A Closure Study of Secondary Organic Aerosol Estimation at an Urban Site of Yangtze River Delta, China

Secondary organic aerosols (SOA) are crucial components of ambient particulate matters. However, their composition and formation mechanisms remain uncertain. To investigate the SOA formation and evaluate various SOA estimation approaches, a comprehensive measurement was conducted at an urban site, Changzhou, in Yangtze River Delta (YRD) region. 98 kinds of volatile organic compounds (VOCs) were measured by an online gas chromatography-mass spectrometer/flame ionization detector (GC-MS/FID). Non-refractory submicron particulate matters (NR-PM1) were measured by an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Both bottom-up approaches, i.e., VOCs oxidation yield method, and top-down approaches, i.e., elemental carbon (EC) tracer method and ACSM, combined with positive matrix factorization (PMF) method, were utilized to estimate SOA. ACSM-PMF method estimated the highest SOA concentration, followed by EC tracer method. SOA from VOCs oxidation yield method accounted for 43.2 ± 41.9% of that from EC tracer method, suggesting the existence of missing SOA precursors, e.g., semivolatile organic compounds. The influencing factors of SOA formation were investigated and a good correlation of SOA with odd oxygen rather than aerosol liquid water content was found, suggesting the importance of photochemical formation of SOA.

Mobile Sources Are Still an Important Source of Secondary Organic Aerosol and Fine Particulate Matter in the Los Angeles Region.

Secondary organic aerosol (SOA) is a significant component of atmospheric fine particulate matter. Mobile sources have historically been a major source of SOA precursors in urban environments, but decades of regulations have reduced their emissions. Less regulated sources, such as volatile chemical products (VCPs), are of growing importance. We analyzed ambient and emissions data to assess the contribution of mobile sources to SOA formation in Los Angeles during the period of 2009-2019. During this period, air quality in the Los Angeles region has improved, but organic aerosol (OA) concentrations did not decrease as much as primary pollutants. This appears to be largely due to SOA, whose mass fraction in OA increased over this period. In 2010, about half of the freshly formed SOA measured in Pasadena, CA appears to be formed from hydrocarbon (non-oxygenated) precursors. Chemical mass balance analysis indicates that these hydrocarbon SOA precursors (including intermediate volatility organic compounds) can largely be explained by emissions from mobile sources in 2010. Our analysis indicates that continued reduction in emissions from mobile sources should lead to additional significant decreases in atmospheric SOA and PM2.5 mass in the Los Angeles region.

Source Diversity of Intermediate Volatility n-Alkanes Revealed by Compound-Specific δ13C-δD Isotopes.

Intermediate volatility organic compounds (IVOCs) are important precursors of secondary organic aerosols, and their sources remain poorly defined. N-alkanes represent a considerable portion of IVOCs in atmosphere, which can be well identified and quantified out of the complex IVOC pool. To investigate the potential source diversity of intermediate volatility n-alkanes (IVnAs, nC12-nC20), we apportioned the sources of IVnAs in the atmosphere of four North China cities, based on their compound-specific δ13C-δD isotope compositions and Bayesian model analysis. The concentration level of IVnAs reached 1195 ± 594 ng/m3. The δ13C values of IVnAs ranged -32.3 to -27.6‰ and δD values -161 to -90‰. The δD values showed a general increasing trend toward higher carbon number alkanes, albeit a zigzag odd-even prevalence. Bayesian MixSIAR model using δ13C and δD compositions revealed that the source patterns of individual IVnAs were inconsistent; the relative contributions of liquid fossil combustion were higher for lighter IVnAs (e.g., nC12-nC13), while those of coal combustion were higher for heavier IVnAs (e.g., nC17-nC20). This result agrees with principal component analysis of the dual isotope data. Overall, coal combustion, liquid fossil fuel combustion, and biomass burning contributed about 47.8 ± 0.1, 35.7 ± 4.0, and 16.3 ± 4.2% to the total IVnAs, respectively, highlighting the importance of coal combustion as an IVnA source in North China. Our study demonstrates that the dual-isotope approach is a powerful tool for source apportionment of atmospheric IVOCs.

Acylperoxy Radicals as Key Intermediates in the Formation of Dimeric Compounds in α-Pinene Secondary Organic Aerosol.

High molecular weight dimeric compounds constitute a significant fraction of secondary organic aerosol (SOA) and have profound impacts on the properties and lifecycle of particles in the atmosphere. Although different formation mechanisms involving reactive intermediates and/or closed-shell monomeric species have been proposed for the particle-phase dimers, their relative importance remains in debate. Here, we report unambiguous experimental evidence of the important role of acyl organic peroxy radicals (RO2) and a small but non-negligible contribution from stabilized Criegee intermediates (SCIs) in the formation of particle-phase dimers during ozonolysis of α-pinene, one of the most important precursors for biogenic SOA. Specifically, we find that acyl RO2-involved reactions explain 50-80% of total oxygenated dimer signals (C15-C20, O/C ≥ 0.4) and 20-30% of the total less oxygenated (O/C < 0.4) dimer signals. In particular, they contribute to 70% of C15-C19 dimer ester formation, likely mainly via the decarboxylation of diacyl peroxides arising from acyl RO2 cross-reactions. In comparison, SCIs play a minor role in the formation of C15-C19 dimer esters but react noticeably with the most abundant C9 and C10 carboxylic acids and/or carbonyl products to form C19 and C20 dimeric peroxides, which are prone to particle-phase transformation to form more stable dimers without the peroxide functionality. This work provides a clearer view of the formation pathways of particle-phase dimers from α-pinene oxidation and would help reduce the uncertainties in future atmospheric modeling of the budget, properties, and health and climate impacts of SOA.

Emission characteristics and formation pathways of carbonyl compounds from the combustion of biomass and their cellulose, hemicellulose, and lignin at different temperatures and oxygen concentrations

Carbonyl compounds are important precursors of free radicals, ozone (O3), and secondary organic aerosols (SOA) in the atmosphere. Biomass burning is an important source of carbonyl compounds. To explore the formation pathway of carbonyl compounds from biomass burning and the effects of fuel composition and burning conditions, this study performed tube-furnace combustion experiments using three biomass types (rice straw, pine, and poplar) and their three component extracts (cellulose, hemicellulose, and lignin) at seven ignition temperatures (300–900 °C, 100 °C gradient) and two oxygen concentrations (21% and 10.5%). The results showed that the average emission factors of carbonyl compounds (EFCC) from rice straw, pine, and poplar were 2.28 ± 1.72, 3.09 ± 2.98, and 2.90 ± 2.78 g/kg, respectively. EFCC were significantly higher (5.37 ± 0.25 g/kg) in lower temperature (300–500 °C) stage than in higher temperature (0.55 ± 0.03 g/kg). Furthermore, oxygen reduction promoted the emission of carbonyl compounds, increasing the EFCC by 21.6% on average. The average EFCC for the three components of biomass decreased in the order of cellulose (3.78 ± 3.90 g/kg), hemicellulose (2.90 ± 2.60 g/kg) and lignin (1.98 ± 1.72 g/kg), and their CCs profiles were also different. Cellulose and hemicellulose produced more formaldehyde and acetaldehyde than lignin, contributing 71.1 ± 12.6%, 69.0 ± 4.4% and 62.4 ± 15.5% in CCs, respectively. Acetone was mainly produced by the combustion of hemicellulose and lignin. Aromatic aldehydes were mainly produced by lignin burning, and also were significantly affected by temperature, the proportion under higher temperature is 2.7 times that under lower temperature. The EFCC values by weighted average calculation from the three components were good matched with those of parent fuels (r = 0.98), while the fitting results for those species such as aromatic aldehydes were relatively weak (r = 0.66), showing that there are different formation pathways and sensitivity to fuel composition and burning condition among different CCs.

Improvement of the Theoretical Model for Evaluating Evaporative Emissions in Parking and Refueling Events of Gasoline Fleets Based on Thermodynamics.

Evaporative emissions from gasoline vehicles are known as an emission source of volatile organic compounds that are the precursors of tropospheric ozone and secondary organic aerosols. We formulated new estimation models based on thermodynamics for two main evaporation processes, namely diurnal breathing loss (DBL) and refueling loss (RFL) from gasoline vehicles. The models enable us to evaluate real-world evaporative emissions using the fuel composition and environmental temperature as input parameters. The proposed models well replicated the experimental results of the canister breakthrough emission from DBL (DBLb) and RFL obtained in previous experimental studies. The evaporative DBLb and RFL emissions in Japan in 2015 were then estimated using the new models. The evaporative emission from DBLb was approximately 8800 t/y, and that from RFL was 73,300 t/y. In addition, we estimated the variation in fuel evaporative emissions due to the market penetration of zero-emission vehicles. Even if the sale of gasoline vehicles is banned from 2035, the evaporative emissions of DBLb and RFL from gasoline vehicles will only be halved after 2040. The two models proposed for estimating the DBLb and RFL in this study are expected to be applied in the evaluation of the emission inventories of volatile organic compounds in future work.

Atmospheric gaseous aromatic hydrocarbons in eastern China based on mobile measurements: Spatial distribution, secondary formation potential and source apportionment

Monocyclic aromatic hydrocarbons (MAHs) and polycyclic aromatic hydrocarbons (PAHs) are both well known as hazardous air pollutants and also important anthropogenic precursors of tropospheric ozone (O3) and secondary organic aerosols (SOA). In recent years, there have been intensive studies covering MAHs emission from various sources and their behavior under stimulated photochemical conditions. Yet in-situ measurements of PAHs presence and variations in ambient air are sparse. Herein we conducted large geometrical scale mobile measurements for 16 aromatic hydrocarbons (AHs, including 7 MAHs and 9 PAHs) in eastern China between October 27 and November 8, 2019. This unique dataset has allowed for some insights in terms of AHs concentration variations, accompanying chemical composition, source contributions and spatial distributions in eastern China. In general, AHs showed a clear concentration variability between the south and the north of the Yangtze River Delta (YRD). The concentrations of PAHs were approximately 9% of AHs, but contributed 23% of SOA formation potential. Source apportionment via positive matrix factorization (PMF) model revealed that industrial processes as the largest source (44%) of observed AHs, followed by solvent usage (21%), vehicle exhaust (19%), coal combustion (11%) and coking processes (6%). In the perspective of PAHs sources, coal combustion emissions were identified as the dominating factor of a share of 41%–52% in eastern China. Our findings complemented the simultaneously monitoring information of PAHs and MAHs in eastern China, revealed the importance of PAHs to SOA formation and highlighted the necessity of formulating strategies to reduce emissions from anthropogenic sources and reduce risks to human health.

Watching Paint Dry: Organic Vapor Emissions from Architectural Coatings and their Impact on Secondary Organic Aerosol Formation.

Emissions from volatile chemical products (VCPs) are emerging as a major source of anthropogenic secondary organic aerosol (SOA) precursors. Paints and coatings are an important class of VCPs that emit both volatile and intermediate volatility organic compounds (VOCs and IVOCs). In this study, we directly measured I/VOC emissions from representative water- (latex) and oil-based paints used in the U.S. Paint I/VOC emissions vary by several orders of magnitude by both the solvent and gloss level. Oil-based paints had the highest emissions (>105 μg/g-paint), whereas low-gloss interior paints (Flat, Satin, and Semigloss) all emitted ∼102 μg/g-paint. Emissions from interior paints are dominated by VOCs, whereas exterior-use paints emitted a larger fraction of IVOCs. Extended emission tests showed that most I/VOC emissions occur within 12-24 h after paint application, though some paints continue to emit IVOCs for 48 h or more. We used our data to estimate paint I/VOC emissions and the subsequent SOA production in the U.S. Total annual paint I/VOC emissions are 48-155 Gg (0.15-0.48 kg/person). These emissions contribute to the formation of 2.2-7.5 Gg of SOA annually. Oil-based paints contribute 70-98% of I/VOC emissions and 61-99% of SOA formation, even though they only account for a minority of paint usage.

Formation potential and source contribution of secondary organic aerosol from volatile organic compounds.

Secondary organic aerosol (SOA), a key constituent of fine particulate matter, can be formed through the oxidation of volatile organic compounds (VOCs). However, information on its relevant emission sources remains limited in many cities, especially concerning different types of land use. In this study, VOC concentration in Bangkok Metropolitan Region (BMR), Thailand, was continuously collected for 24 h by 6-L evacuated canister and analyzed by gas chromatography/mass spectrophotometry following USEPA TO15, and the formation of SOA was evaluated through the comprehensive direct measurements and speciation of ambient VOCs. Finally, source contribution of VOCs to SOA formation was characterized using the Positive Matrix Factorization (PMF) model. The results revealed the abundant group of VOCs species in the overall BMR was oxygenated VOCs, accounting for 49.97-57.37%. The SOA formation potential (SOAP) ranged from 1,134.33 to 3,143.74μg m-3 . The VOC species contributing to the highest SOAP was toluene. Results from the PMF model revealed the dominant emission source of VOCs that greatly contributed to SOA was vehicle exhaust emission. Industrial combustion was the main source of VOC emission contributing to SOA in industrial areas. Sources of fuel evaporation, biomass burning, and cooking were also found in the study areas but in small quantities. The results of this study elucidated that different emission sources of VOCs contribute to SOA with respect to different types of land use. Findings of this study highlight the necessity to identify the contribution of potential emission sources of SOA precursors to effectively manage urban air pollution.

Characteristics, Sources, and SOAP of VOCs During Winter in Jiyuan

Haze pollution events often occur in the heavy industry city of Jiyuan. Volatile organic compounds (VOCs) are the precursors of secondary organic aerosol (SOA), which accounts for 15%-20% of particulate matter (PM2.5). Here, PM2.5, O3, VOCs, and trace gases were monitored by using online instruments in Jiyuan from December 1st to 31st. The characteristics, sources, and secondary organic aerosol potential (SOAP) of VOCs were analyzed. The mean concentrations of TVOC were (54.3±27.5)×10-9. Alkanes, halocarbons, and alkynes were the predominant VOCs. The positive matrix factorization model was used to identify and apportion VOCs sources. Eight major sources of VOCs were identified, which included liquefied petroleum gas (LPG) or natural gas (NG), the polyvinyl chloride (PVC) industry, vehicular exhaust, the coking industry, solvent usage, industry, technological process, and fuel evaporation. The SOAP of aromatics was the largest. Among them, BTEXs were the dominant contributors to SOAP.

An online method for monitoring atmospheric intermediate volatile organic compounds with a thermal desorption-gas chromatography/mass spectrometry

As one of important precursors of secondary organic aerosol (SOA), intermediate volatile organic compounds (IVOCs) have attracted much attention in recent years. Most of the previous studies however largely focused on characteristics of IVOCs from different emission sources, while data from field observations to study their temporal variations was limited for lacking the sufficient time resolution monitoring data. In this study, an online thermal desorption-gas chromatography/mass spectrometry (TD-GC/MS) method was developed to generate monitor data with a three-hour time resolution for gaseous atmospheric IVOCs. The method used two multi-sorbent traps that alternated for conducting sample collection and sample analysis. Compounds of C12C22 n-alkanes and 2–4 ring PAHs were chosen as surrogates to evaluate the performance of this method. Regression coefficients of external calibration curves were greater than 0.93 and 0.96 for all individual n-alkanes and PAHs, respectively. Average relative standard deviation (RSD) values among replicate samples spiked at 3 ng for each individual standard were 9% ± 5%. The detection limits of this method for individual n-alkanes and PAHs were 3.1–16.2 ng/m3 and 1.0–2.7 ng/m3, respectively. Atmospheric IVOCs were continuously monitored from September 28 to 30 and October 22 to November 9 in 2018, in an urban area of Shanghai. Besides targeted n-alkanes and PAHs, unspeciated complex mixtures (UCM) of IVOCs as well as total-IVOCs concentrations in the atmosphere were also determined. Measured concentrations and compositions of gaseous IVOCs in the atmosphere in this study were comparable to other similar studies.

A potential source of tropospheric secondary organic aerosol precursors: The hydrolysis of N2O5 in water dimer and small clusters of sulfuric acid

The hydrolysis of dinitrogen pentoxide (N2O5) is not only a dominant sink for N2O5 under atmospheric conditions but also a critical route in the formation of acid rains and aerosol clusters. Herein, the hydrolysis of N2O5 assisted by (H2O)2, H2SO4, H2SO4⋯ H2O, and (H2SO4)2 has been investigated theoretically. The calculations show that, as compared with catalysts of H2O and NH3, the addition of (H2O)2, H2SO4, H2SO4⋯ H2O, and (H2SO4)2 in the hydrolysis of N2O5 not only reduces another energy barrier of 8.7–18.2 kcal mol−1, but also plays a more crucial catalytic role in increasing the reaction rate by at least 2 orders of magnitude within the 213–300 K. Pseudo-first-order rate coefficient (kt′) show that (H2SO4)2-assisted reaction is the favorable hydrolysis of N2O5 assisted by small clusters of sulfuric acid (H2SO4 in 108 molecules ⋅ cm−3 and H2O in 100% RH) with its kt′ respectively larger by 2–6 and 1–5 orders of magnitude. Moreover, (H2O)2–assisted N2O5 + H2O reaction dominates over the reaction without and with (H2SO4)2, H2O (100% RH) and NH3 (2900 ppbv) within the 280–300 K and 0 km altitude, whereas (H2SO4)2–assisted reaction can make an important contribution to the hydrolysis of N2O5 under atmospheric conditions of 213–259 K and 5–15 km. This work helps one understand the process of HNO3 formation from the hydrolysis of N2O5 promoted by water clusters and small clusters of sulfuric acid.

Formation and emission characteristics of intermediate volatile organic compounds (IVOCs) from the combustion of biomass and their cellulose, hemicellulose, and lignin

Biomass combustion is an important source of intermediate volatile organic compounds (IVOCs), which are important precursors of secondary organic aerosols. To understand how fuel types and combustion conditions affect the formation and emission characteristics of IVOCs, three biomass materials (rice straw, pine, and poplar) and their three extracted components (cellulose, hemicellulose, and lignin) were burned separately in a quartz tube furnace at different temperatures between 300 and 900 °C and with oxygen supplies (20% and 10%). The results show that 1) the emission factors of IVOCs (EFIVOC) from biomass combustion exhibit a bimodal distribution with an increase in temperature, and are more abundant during low-temperature combustion (300–500 °C). The unresolved complex mixture (UCM) accounts for more than 50% of the total IVOCs for all the biomass material. Among the identifiable compounds, methoxyphenols were the most abundant species and account for 20–30% of the total IVOCs during low-temperature combustion. The proportion of polycyclic aromatic hydrocarbons (PAHs) gradually increased to 30–50% with an increase in temperature from 700 to 900 °C, which indicates that methoxyphenols and PAHs have different formation pathways. 2) The average EFIVOC from cellulose, hemicellulose, and lignin combustion were in the order lignin > hemicellulose > cellulose. Methoxyphenols are primarily derived from lignin at low combustion temperatures. The highest proportions of methoxyphenols in lignin from rice straw and pine were more than 2 and 5 times that of cellulose and hemicellulose, respectively. PAHs are mainly derived from the combustion of cellulose and lignin at high temperatures. 3) A large amount of indene (96.4 mg/kg) is detected in lignin combustion, and indene is believed to be one of the most important precursors of PAHs in resonantly stabilized radical pathways. Indene was hardly observed in cellulose combustion, indicating that PAHs were more inclined to form via H-abstraction acetylene addition pathways. 4) The oxygen supply is also an important factor for EFIVOC during biomass burning. At 10% oxygen supply, most of the EFIVOC were higher than that for the 20% oxygen supply conditions for biomass material and the three components.