Pollution characteristics, source appointment and environmental effect of oxygenated volatile organic compounds in Guangdong-Hong Kong-Macao Greater Bay Area: Implication for air quality management.

Same as other bay areas, the Guangdong-Hong Kong-Macao Greater Bay Area (GBA) is also suffering atmospheric composite pollution. Even a series of atmospheric environment management policies have been conducted to win the "blue sky defense battle", the atmospheric secondary pollutants (e.g., O3) originated from oxygenated volatile organic compounds (OVOCs) still threaten the air quality in GBA. However, there lacks a systematic summary on the emission, formation, pollution and environmental effects of OVOCs in this region for further air quality management. This review focused on the researches related to OVOCs in GBA, including their pollution characteristics, detection methods, source distributions, secondary formations, and impacts on the atmosphere. Pollution profile of OVOCs in GBA revealed that the concentration percentage among total VOCs from Guangzhou and Dongguan cities exceeded 50 %, while methanol, formaldehyde, acetone, and acetaldehyde were the top four highest concentrated OVOCs. The detection technique on regional atmospheric OVOCs (e.g., oxygenated organic molecules (OOMs)) underwent an evolution of off-line derivatization method, on-line spectroscopic method and on-line mass spectrometry method. The OVOCs in GBA were mainly from primary emissions (up to 80 %), including vehicle emissions and biomass combustion. The anthropogenic alkenes and aromatics in urban area, and natural isoprene in rural area also made a significant contribution to the secondary emission (e.g., photochemical formation) of OVOCs. About 20 % in average of ROx radicals was produced from photolysis of formaldehyde in comparison with O3, nitrous acid and rest OVOCs, while the reaction between OVOCs and free radical accelerated the NOx-O3 cycle, contributing to 15 %-60 % cumulative formation of O3 in GBA. Besides, the heterogeneous reactions of dicarbonyls generated 21 %-53 % of SOA. This review also provided suggestions for future research on OVOCs in terms of regional observation, analytical method and mechanistic study to support the development of a control and management strategy on OVOCs in GBA and China.

Oligomerization Mechanism of Methylglyoxal Regulated by the Methyl Groups in Reduced Nitrogen Species: Implications for Brown Carbon Formation.

Uncertain chemical mechanisms leading to brown carbon (BrC) formation affect the drivers of the radiative effects of aerosols in current climate predictions. Herein, the aqueous-phase reactions of methylglyoxal (MG) and typical reduced nitrogen species (RNSs) are systematically investigated by using combined quantum chemical calculations and laboratory experiments. Imines and diimines are identified from the mixtures of methylamine (MA) and ammonia (AM) with MG, but not from dimethylamine (DA) with the MG mixture under acidic conditions, because deprotonation of DA cationic intermediates is hindered by the amino groups occupied by two methyl groups. It leads to N-heterocycle (NHC) formation in the MG + MA (MGM) and MG + AM (MGA) reaction systems but to N-containing chain oligomer formation in the MG + DA (MGD) reaction system. Distinct product formation is attributed to electrostatic attraction and steric hindrance, which are regulated by the methyl groups of RNSs. The light absorption and adverse effects of NHCs are also strongly related to the methyl groups of RNSs. Our finding reveals that BrC formation is mainly contributed from MG reaction with RNSs with less methyl groups, which have more abundant and broad sources in the urban environments.

Revelation of contributing mechanism of reactive oxygen species in photocatalytic ozonation heterocyclization of gaseous hexane isomers.

The reactive oxygen species (ROS) involved photocatalytic ozonation of gaseous n-hexane to heterocyclic compounds has been recently reported. However, whether such heterocyclization reaction happens on other alkanes and what is the contributing mechanism of ROS to the heterocyclic compound formation are still unclear. In present study, photocatalytic ozonation of three n-hexane's isomers (i.e. 2-methypentane, 3-methylpentane and 2,3-dimethylbutane) on Cu2O-CuO/TiO2-foam ceramic was investigated. Within reaction period, 2-methylpentane and 3-methylpentane not only showed higher average degradation efficiency than 2,3-dimethylbutane, but also separately converted to interfacial heterocyclic compounds of 5,5-dimethyldihydro-2(3H)-furanone and 4,5-dimethyl-4,5-dihydro-2(3H)-furanone. Enough reaction time, optimum experimental atmosphere and shorter light wavelength benefited the formation of heterocyclization products. None of O3, 1O2, electron and hole directly contributed to the heterocyclic compound formation. While •O2- dominated the production of the heterocyclic compound under the dry reaction atmosphere and •OH showed more important role than •O2- in the heterocyclic compound formation under the moist reaction atmosphere. Theoretical calculation confirmed that •OH or •O2- induced heterocyclization reaction of alkane was exothermic, while the former reaction released 0.47 eV higher energy than the later reaction. The findings provide a comprehensive understanding of contributing roles of ROS in heterocyclization reaction of alkanes, and are helpful for effective elimination of industrial alkanes by advanced oxidation methods.

Underestimated contribution of fugitive emission to VOCs in pharmaceutical industry based on pollution characteristics, odorous activity and health risk assessment.

Fugitive emission has been becoming an important source of volatile organic compounds (VOCs) in pharmaceutical industry, but the exact contribution of fugitive emission remains incompletely understood. In present study, pollution characteristics, odorous activity and health risk of stack and fugitive emissions of VOCs from four functional units (e.g., workshop, sewage treatment station, raw material storage and hazardous waste storage) of three representative pharmaceutical factories were investigated. Workshop was the dominant contributor to VOCs of fugitive emission in comparison with other functional units. Extreme high concentration of VOCs from fugitive emission in unsealed workshop (94.87 mg/m3) was observed relative to sealed one (1.18 mg/m3), accounting for 31% and 5% of total VOCs, respectively. Fugitive emission of VOCs in the unsealed workshop mainly consisted of n-hexane, 1-hexene and dichloromethane. Odorous activity indexes and non-cancer hazard ratios of these VOCs from fugitive emission in the unsealed workshop were as high as that from stack exhaust. Furthermore, cancer risk of dichloromethane from fugitive emission and stack exhaust was up to (1.6-1.8) × 10-5. Odorous activity or health risk index of the VOCs from fugitive emission was up to 13 or 11 times of the corresponding threshold value, posing remarkable health threat on pharmaceutical workers. Our findings highlighted the possibly underestimated contribution of fugitive emission on VOCs in the pharmaceutical industry.

Bridged-ozonolysis of mixed aromatic hydrocarbons and organic amines: Inter-inhibited decay rate, altered product yield and synergistic-effect-enhanced secondary organic aerosol formation.

Ozonolysis of aromatic hydrocarbons (AHs) or organic amines (OAs) occurs via different transformation processes, with varying rate constants and contributions to secondary organic aerosol (SOA) formation. However, to date no data is available on the ozonolysis of mixtures of AHs and OAs. This study investigated the kinetics, products and SOA yield from ozonolysis of mixture of trimethylamine with styrene, toluene or m-xylene. In the mixed system, the decay rates of styrene and trimethylamine were (1.32 ± 0.26) × 10-4 s-1 and (0.80 ± 0.02) × 10-4 s-1, decreasing up to 36.5 % and 54.4 % compared with their respective individual systems. This inter-inhibition of decay rates increased the yield of main products from styrene (i.e. benzaldehyde) by 23.5 % and trimethylamine (i.e. nitromethane) by 346.4 %. Ozonolysis of styrene or trimethylamine produced formaldehyde, which acted as a bridged product connecting the ozonolysis pathways of these two substrates, altering the yields of all products. Ozonolysis of styrene to benzaldehyde determined the increase of SOA particle number concentration (from 9.5 × 105 to 1.9 × 106 particles cm-3), while trimethylamine ozonolysis to N, N-dimethylformamide contributed to synergistic-effect-enhanced SOA yield (from (64.3 ± 3.5)% to (68.1 ± 4.8)%). The findings provide a novel insight into the kinetics and mechanism of ozonolysis, as well as the resulting SOA formation from mixtures of AHs and OAs, helping to comprehensively understand the transformation and fate of organics in real atmospheric environments.

Detection of excited triplet species from photolysis of carbonyls: Direct evidence for single oxygen formation in atmospheric environment.

Excited triplet species play an important role in the photolytic formation of 1O2 from carbonyls, but the related mechanism is still uncertain, due to lack of direct evidence. In this study, steady-state and transient photolysis of eleven carbonyls to produce 1O2 was investigated. Dicarbonyl displayed greater 1O2 production ability than monocarbonyl, while dicarbonyl containing both ketone and carboxyl groups connected by CC bond (i.e., pyruvic acid (PA)) showed the highest 1O2 steady-state concentration ([1O2]SS). For the first time, the production of 3PA* from PA with narrow energy gap was confirmed by laser flash photolysis technique and the second-order decay rate constant of 3PA* was 2.78 × 107 M-1 s-1. Quenching results verified the dominant contribution of 3PA* to 1O2 production from PA. Addition of inorganic salt or increase in solution pH showed negligible effect on 3PA*, but significantly decreased the [1O2]SS of PA by up to two orders of magnitude, due to reduction of hydrate content. Photolysis of methylglyoxal and dimethylamine mixture led to higher content of excited triplet species at pH ≈ 11 and remarkably enhanced [1O2]SS, which was 2.3 times of that from PA and dimethylamine mixture. These findings provide direct evidence for the contribution of transient species from carbonyls or their product to 1O2 formation in atmospheric environment.

Competing pathways of cresol formation in toluene photooxidation: OH-toluene adducts react with NO2 or with O2?

Methyl-hydroxy-cyclohexadienyl radicals (OTAs) are the key products of the photooxidation of toluene, with implications for the fate of toluene. Hence, we investigated the photooxidation mechanisms and kinetics of three main OTAs (o-OTA, m-OTA, and p-OTA) with NO2 using quantum chemical calculations as well as the fate of OTAs under the different concentration ratios of NO2 and O2. The mechanism results show that the pathway of H-abstraction by NO2 to anti-HONO (anti-H-abstraction) is more favorable than the syn-H-abstraction pathway, because the strong interaction between OTAs and NO2 is formed in the transition states of the anti-H-abstraction pathways. The branching ratios of the anti-H-abstraction pathways are more than 99% in the temperature range of 216-298 K. The total rate constant of the OTA-NO2 reaction is 9.9 × 10-12 cm3/(molecule∙sec) at 298 K, which is contributed about 90% by o-OTA + NO2, and the main products are o-cresol and anti-HONO. The half-lives of the OTA-NO2 reaction in some polluted areas of China are 35 times longer than those of the OTA-O2 reaction. In the atmosphere, the NO2- and O2- initiated reactions of OTAs have the same ability to form cresols as [NO2] is up to 142.1 ppmV, which is impossible to achieve. It implies that under the experimental condition, the [NO2]/[O2] should be controlled to be less than 7.8 × 10-5 to simulate real atmospheric oxidation of toluene. Our results reveal that for the photooxidation of toluene, the yield of cresol is not affected by the concentration of NO2 under the atmospheric environment.

The underappreciated role of monocarbonyl-dicarbonyl interconversion in secondary organic aerosol formation during photochemical oxidation of m-xylene.

Photochemical oxidation (including photolysis and OH-initiated reactions) of aromatic hydrocarbon produces carbonyls, which are involved in the formation of secondary organic aerosols (SOA). However, the mechanism of this process remains incompletely understood. Herein, the monocarbonyl-dicarbonyl interconversion and its role in SOA production were investigated via a series of photochemical oxidation experiments for m-xylene and representative carbonyls. The results showed that SOA mass concentration peaked at 113.5 ± 3.5 µg m-3 after m-xylene oxidation for 60 min and then decreased. Change in the main oxidation products from dicarbonyl (e.g., glyoxal, methylglyoxal) to monocarbonyl (e.g., formaldehyde) was responsible for this decrease. The photolysis of methylglyoxal or glyoxal produced formaldehyde, favoring SOA formation, while photopolymerization of formaldehyde to glyoxal decreased SOA production. The presence of ·OH altered the balance of photolysis interconversion, resulting in greater production of formaldehyde and SOA from glyoxal than methylglyoxal. Both photolysis and OH-initiated transformations of glyoxal to formaldehyde were suppressed by methylglyoxal, while glyoxal accelerated the reaction of ·OH with methylglyoxal to generate products which reversibly converted to glyoxal and methylglyoxal. These interconversion reactions reduced SOA production. The present study provides a new research perspective for the contribution mechanism of carbonyls in SOA formation and the findings are also helpful to efficiently evaluate the atmospheric fate of aromatic hydrocarbons.

Atomic-level insight into effect of substrate concentration and relative humidity on photocatalytic degradation mechanism of gaseous styrene.

Substrate concentration and relative humidity (RH) impact the photocatalytic efficiency of industrial aromatic hydrocarbons, but how they influence intermediate formation and degradation pathway remains unclear. With the help of oxygen isotope tracing method, the effects of these two environmental parameters on degradation mechanism of styrene were revealed at atomic level. Increasing styrene concentration favored product formation, which was however inhibited by RH elevation. Gaseous products were not directly formed in gaseous phase, but originated from desorption of interfacial intermediates. The volatile aldehydes and furans further exchanged their 16O with 18O in H218O. Increase of RH showed higher enhancement on 18O distribution in all products and pathways than that of substrate concentration. Low RH preferred high generation of 16O2•- and (16)1O2, dominating reaction to form 1-phenyl-1,2-ethandiol, 2-hydroxy-1-phenyl-ethanon and phenylglyoxal monohydrate in sequence. Successive production of benzyl alcohol, benzaldehyde and benzoic acid through the reaction of styrene with promoted •18OH by increasing RH became predominant. Hydration was firstly observed and confirmed as an important gaseous transformation step of aldehyde and furan products. Our findings provide a deep insight into photocatalytic degradation mechanism of aromatic hydrocarbons regulated by environmental parameters to further improve their industrial purification efficiency, and are helpful predicting environmental geochemistry fate of organics and preventing their negative impact on natural environment.

Oxygen Isotope Tracing Study to Directly Reveal the Role of O2 and H2O in the Photocatalytic Oxidation Mechanism of Gaseous Monoaromatics.

O2 and H2O influence the photocatalytic oxidation mechanism of gaseous monoaromatics, but still in an unclear manner, due to the lack of direct evidence. Tracing an oxygen atom from 16O2 and H218O to intermediates can clarify their roles. The low H218O content suppressed the formation of benzenedicarboxaldehydes during the oxidation of xylenes and 16O2 greatly affected the yield of total intermediates, while neither of them altered the percentage order of the products. Methylbenzaldehydes, methylbenzyl alcohols, and benzenedicarboxaldehydes possessed greater 16O percentage (≥69.49%), while higher 18O distribution was observed in methylbenzoic acids and phthalide (≥59.51%). Together with the interconversion results of the products revealed, 16O2 determined the transformation of xylenes initially to methylbenzaldehydes and then to methylbenzyl alcohols or benzenedicarboxaldehydes, while H218O mainly contributed to conversion of methylbenzaldehydes to methylbenzoic acids or phthalide. Further interaction sites of xylene and its products with H2O and O2 were confirmed by molecular dynamics calculations. The same roles of 16O2 and H218O in the degradation of toluene, ethylbenzene, 1,2,4-trimethylbenzene, and 1,3,5-trimethylbenzene were also verified. This is the first report that provides direct evidence for the roles of O2 and H2O in the photocatalytic oxidation mechanism of gaseous monoaromatics. These findings are helpful to achieve controllable product formation from the oxidation of monoaromatics and predict their migration process in the atmospheric environment.

Assessing the role of mineral particles in the atmospheric photooxidation of typical carbonyl compound.

Mineral particles are ubiquitous in the atmosphere and exhibit an important effect on the photooxidation of volatile organic compounds (VOCs). However, the role of mineral particles in the photochemical oxidation mechanism of VOCs remains unclear. Hence, the photooxidation reactions of acrolein (ARL) with OH radical (OH) in the presence and absence of SiO2 were investigated by theoretical approach. The gas-phase reaction without SiO2 has two distinct pathways (H-abstraction and OH-addition pathways), and carbonyl-H-abstraction is the dominant pathway. In the presence of SiO2, the reaction mechanism is changed, i.e., the dominant pathway from carbonyl-H-abstraction to OH-addition to carbonyl C-atom. The energy barrier of OH-addition to carbonyl C-atom deceases 21.33 kcal/mol when SiO2 is added. Carbonyl H-atom of ARL is occupied by SiO2 via hydrogen bond, and carbonyl C-atom is activated by SiO2. Hence, the main product changes from H-abstraction product to OH-adduct in the presence of SiO2. The OH-adduct exhibits a thermodynamic feasibility to yield HO2 radical and carboxylic acid via the subsequent reactions with O2, with implications for O3 formation and surface acidity of mineral particles.

Superoxide radical enhanced photocatalytic performance of styrene alters its degradation mechanism and intermediate health risk on TiO2/graphene surface.

Enhancement of reactive oxygen species (ROS) on semiconductor coupled by carbon material promotes photocatalytic performance toward aromatic hydrocarbons, while the contribution to their degradation mechanism and health risk is not well understood. Herein, photocatalytic degradation of styrene on TiO2 and TiO2/reduced graphene oxide (TiO2/rGO) surface is compared under dry air condition to investigate the role of ·O2- in styrene degradation. TiO2/rGO shows 4.8 times higher degradation efficiency than that of TiO2, resulting in 16% reduced production of intermediates with identical composition. The improved formation of ·O2- on TiO2/rGO is confirmed responsible for these variations. Theoretical calculation further reveals the enhancement of ·O2- thermodynamically favoring conversion of styrene to acetophenone, turning the most dominant intermediate from benzoic acid on TiO2 to acetophenone on TiO2/rGO. The accumulated formation of acetophenone on TiO2/rGO poses increased acute threat to human beings. Our findings proclaim that ROS promoted photocatalytic performance of semiconductor after carbon material composition ultimately changes the priority order of degradation pathways to form by-product with higher threat toward human beings. And more attentions are advised focusing on the relevance with degradation efficiency, intermediate and toxicity of aromatic hydrocarbons on carbon material based photocatalyst.

Reactor characterization and primary application of a state of art dual-reactor chamber in the investigation of atmospheric photochemical processes.

Increasing attention has been paid to the air pollution more recently. Smog chamber has been proved as a necessary and effective tool to study atmospheric processes, including photochemical smog and haze formation. A novel smog chamber was designed to study the atmospheric photochemical reaction mechanism of typical volatile organic compounds (VOCs) as well as the aging of aerosols. The smog chamber system includes an enclosure equipped with black lights as the light source, two parallel reactors (2 m3 of each) with separate control of light source and temperature, with a series of coupled instruments for online monitoring of gas phase and particle phase reactants and products. Chamber characterization, including air source stability, effective light intensity, temperature stability, as well as gas phase and particle phase wall losses, were carried out before further research. The results showed that our smog chamber systems developed by other domestic and international groups. It was also observed that the wall loss of aromatic VOCs varied with different functional groups as well as the isomerism. The results of preliminary simulation experiment from styrene-NOx demonstrated that the chamber can be well utilized to simulate gas-particle conversion progresses in the atmosphere.

Carbenium ion-mediated oligomerization of methylglyoxal for secondary organic aerosol formation.

Secondary organic aerosol (SOA) represents a major constituent of tropospheric fine particulate matter, with profound implications for human health and climate. However, the chemical mechanisms leading to SOA formation remain uncertain, and atmospheric models consistently underpredict the global SOA budget. Small α-dicarbonyls, such as methylglyoxal, are ubiquitous in the atmosphere because of their significant production from photooxidation of aromatic hydrocarbons from traffic and industrial sources as well as from biogenic isoprene. Current experimental and theoretical results on the roles of methylglyoxal in SOA formation are conflicting. Using quantum chemical calculations, we show cationic oligomerization of methylglyoxal in aqueous media. Initial protonation and hydration of methylglyoxal lead to formation of diols/tetrol, and subsequent protonation and dehydration of diols/tetrol yield carbenium ions, which represent the key intermediates for formation and propagation of oligomerization. On the other hand, our results reveal that the previously proposed oligomerization via hydration for methylglyoxal is kinetically and thermodynamically implausible. The carbenium ion-mediated mechanism occurs barrierlessly on weakly acidic aerosols and cloud/fog droplets and likely provides a key pathway for SOA formation from biogenic and anthropogenic emissions.

Mechanism of atmospheric organic amines reacted with ozone and implications for the formation of secondary organic aerosols.

Organic amines are one of the most important nitrogen-containing compounds in the atmosphere, and their reactions with tropospheric ozone contribute significantly to the formation of secondary organic aerosols (SOA). However, the chemical pathways of their reaction with atmospheric ozone are poorly understood. This study investigates the atmospheric ozonolysis mechanism of two typical organic amines-diethylamine and triethylamine using experimental and theoretical methods. Intermediate results from GC-MS and PTR-TOF-MS analysis confirm the formation of eight and eleven nitrogen- and oxygen-containing products during the ozonolysis of diethylamine and triethylamine, respectively. N-ethylethanimine (56.5% in average) or acetaldehyde (64.9% in average) is formed as the dominant product from the ozonolysis of each organic amine. Ozonolysis pathway results indicate that the conversion to N-ethylethanimine is the dominant pathway for diethylamine ozonolysis. At the same time, triethylamine prefers the initial transformation to diethylamine with the discharge of acetaldehyde and then converts to N-ethylethanimine. Higher SOA mass concentration is obtained from the ozonolysis of triethylamine than diethylamine, probably because the former releases a larger amount of intermediate products, especially acetaldehyde. Our results provide a deep insight into the atmospheric processing of organic amines via ozonolysis and the implications of this mechanism for SOA formation.

In situ growth of well-aligned Ni-MOF nanosheets on nickel foam for enhanced photocatalytic degradation of typical volatile organic compounds.

Exploitation of highly efficient catalysts for photocatalytic degradation of volatile organic compounds (VOCs) under visible light irradiation is highly desirable yet challenging. Herein, well-aligned 2D Ni-MOF nanosheet arrays vertically grown on porous nickel foam (Ni-MOF/NF) without lateral stacking were successfully prepared via a facile in situ solvothermal strategy. In this process, Ni foam could serve as both a skeleton to vertically support the Ni-MOF nanosheets and a self-sacrificial template to afford Ni ions for MOF growth. The Ni-MOF/NF nanosheet arrays with highly exposed active sites and light harvesting centres as well as fast mass and e- transport channels exhibited excellent photocatalytic oxidation activity and mineralization efficiency to typical VOCs emitted from the paint spray industry, which was almost impossible for their three-dimensional (3D) bulk Ni-MOF counterparts. A mineralization efficiency of 86.6% could be achieved at 98.1% of ethyl acetate removal. The related degradation mechanism and possible reaction pathways were also attempted based on the electron paramagnetic resonance (EPR) and online Time-of-Flight Mass Spectrometer (PTR-ToF-MS) results.

Enhanced H-abstraction contribution for oxidation of xylenes via mineral particles: Implications for particulate matter formation and human health.

Xylenes are important aromatic hydrocarbons having broad industrial emissions and profound implication to air quality and human health. Generally, homogeneous atmospheric oxidation of xylenes is initiated by hydroxyl radical (OH) resulting in minor H-abstraction and major OH-addition pathways. However, the effect of mineral particles on the homogeneous atmospheric oxidation mechanism of xylenes is still not well understood. In the present study, the heterogeneous atmospheric oxidation of xylenes on mineral particles (TiO2) is examined in detail. Both the experimental data and theoretical calculations are combined to achieve the feast. The experimental results detected a major H-abstraction (≥87.18%) and minor OH-addition (≤12.82%) pathways for the OH-initiated heterogeneous oxidation of three xylenes on TiO2 under ultraviolet (UV) irradiation. Theoretical calculations demonstrated favorable H-abstraction on methyl group of xylenes by surface OH with large exothermic energies, because of the reason that their methyl group rather than the phenyl ring is more occupied by TiO2 via hydrogen bonding. Furthermore, the particle monitor and acute risk assessment results indicated that the H-abstraction products significantly enhance the formation of particulate matter and health risk to human beings. Taken together, these results indicate that the atmospheric oxidation mechanism of xylenes is altered in the presence of mineral particles, highlighting the necessity to re-evaluate its implication in the environment and human health.

Mechanism of the atmospheric chemical transformation of acetylacetone and its implications in night-time second organic aerosol formation.

Recently, a high concentration of acetylacetone (AcAc) has been measured in China, and its day-time chemistry with OH reaction has been evaluated. The phenomenon has profound implications in air pollution, human health and climate change. To systematically understand the atmospheric chemistry of AcAc and its role in the atmosphere, the night-time chemistry of AcAc with O3 and NO3 radical were investigated in this work in detail using density functional theory. The results show that for O3- and NO3-initiated atmospheric oxidation reactions of AcAc, the barrier energies of O3/NO3-addition are found to be much lower than those of H-abstraction, suggesting that O3/NO3-addition to AcAc is a major contributing pathway in the atmospheric chemical transformation reactions. The total degradation rate constants were calculated to be 2.36 × 10-17 and 1.92 × 10-17 cm3 molecule-1 s-1 for the O3- and NO3-initiated oxidation of AcAc at 298 K, respectively. The half-life of AcAc+O3 in some polluted areas (such as, Pearl River Delta and Yangtze River Delta) is close to 3 h under typical tropospheric conditions. Due to its short half-life, the ozonolysis of AcAc plays a more significant role in the night-time hours, leading to fast transformations to form primary ozonides (POZs). A prompt, thermal decomposition of POZs occurred to yield methylglyoxal, acetic acid and Criegee intermediates, which mainly contributed to the formation of secondary organic aerosol (SOA). Subsequently, using the high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS), a non-negligible concentration of AcAc was measured in the field observation during the night-time in Nanjing, China. The obtained results reveal that the atmospheric oxidation of AcAc can successively contribute to the formation of SOA under polluted environments regardless of the time (day-time or night-time). This is due to its high reactivity to tropospheric oxidant species (such as, O3 and NO3 radicals at night-time).

Spatial and temporal distribution characteristics and ozone formation potentials of volatile organic compounds from three typical functional areas in China.

BACKGROUND: Ozone is currently one of the most important air pollutants. Volatile organic compounds (VOCs) can easily react with atmospheric radicals to form ozone. In-field measurement of VOCs may help in estimating the local VOC photochemical pollution level. METHOD: This study examined the spatial and temporal distribution characteristics of VOCs during winter at three typical sites of varying classification in China; industrial (Guangzhou Economic and Technological Development District (GETDD)), urban (Guangzhou higher education mega center (HEMC)), and rural (Pingyuan county (PYC)), using Proton-Transfer-Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS). RESULTS: The concentrations of total VOCs (TVOCs) at the GETDD, HEMC and PYC sites were 352.5, 129.2 and 75.1 ppb, respectively. The dominant category of VOCs is nitrogen-containing VOCs (NVOCs, accounting for 43.3% of TVOCs) at GETDD, of which C4H11N (m/z+ = 74.10, butyl amine) was the predominant chemical species (80.5%). In contrast, oxygenated VOCs (OVOCs) were the most abundant at HEMC and PYC, accounting for 60.2% and 64.1% of the total VOCs, respectively; here, CH4O (m/z+ = 33.026, methanol) was the major compound, accounting for 40.5% of the VOCs at HEMC and 50.9% at PYC. The ratios of toluene to benzene (T/B) were calculated for different measured sites, as the ratios of T/B can reveal source resolution of aromatic VOCs. The average contributions to total ozone formation potentials (OFP) of the total measured VOCs in each area were 604.9, 315.9 and 111.7 µg/m3 at GETDD, HEMC and PYC, respectively; the highest OFP contributors of the identified VOCs were aliphatic hydrocarbons (AlHs) at GETDD, aromatic hydrocarbons (AHs) at HEMC, and OVOCs at PYC. CONCLUSIONS: OFP assessment indicated that the photochemical pollution caused by VOCs at GETDD was serious, and was also significant in the HEMC region. The dominant VOC OFP groups (AlHs and AHs) should be prioritized for control, in order to help reduce these effects.

Solar light induced transformation mechanism of allyl alcohol to monocarbonyl and dicarbonyl compounds on different TiO2: A combined experimental and theoretical investigation.

Enols are an important group of photochemical precursors of atmospheric carbonyl compounds. However, the transformation mechanism is not fully understood. In this study, the photo-induced transformation of a typical enol, allyl alcohol, to carbonyl compounds on TiO2 (P25) and aluminum reduced TiO2 (P25, rutile and anatase TiO2) were investigated. Intermediate results confirmed that a total of seven carbonyl compounds, including four monocarbonyl compounds (acetone, glycolaldehyde, 1,3-dihydroxyacetone and acrolein) and three dicarbonyl compounds (glyoxal, methylglyoxal and dimethylglyoxal), were formed on studied TiO2. This is the first time to report the transformation of allyl alcohol to dicarbonyl compounds on TiO2. The same byproducts formation indicated negligible effects of reduction treatment and crystal phase to the composition of carbonyl intermediates. However, the relative content ratio of dicarbonyl compounds to monocarbonyl ones on reduced P25 is ca. 4.1 times higher than that on P25, suggesting reduction treatment significantly accelerated the transformation of allyl alcohol or monocarbonyl compounds to dicarbonyl ones. Furthermore, both rutile and anatase crystal phases were found beneficial for the dicarbonyl compounds generation within enough reaction time, especially for anatase. The enhanced •OH was responsible for all accelerations. Furthermore, the intermediate results together with quantum chemical calculations confirmed that •OH addition and O2 oxidation preferred converting allyl alcohol to dicarbonyl compounds rather than monocarbonyl ones. The present work could provide a deep insight into the transformation of allyl alcohol to carbonyl compounds, and efficiently replenish atmospheric transformation fate of enols.