Enrichment of short-chain organic acids transferred to submicron sea spray aerosols.

Organic acids, considered to be a substantial component of the marine carbon cycle, can enter the atmosphere through sea spray aerosol (SSA) and further affect the climate. Despite their importance, the distribution and mixing state of organic acids in SSA over the marine boundary layer are poorly understood and therefore need more investigation. Here, we have used ion chromatography (IC) in anion mode to measure short-chain organic acids concentrations in SSA collected throughout a custom-made SSA simulation chamber. The enrichment behavior and morphology of monocarboxylic acids (MAs, C1-8) and dicarboxylic acids (DAs) in submicron SSA were studied in seawater. We found that with MAs addition, the number concentration and mass concentration of SSA particles decreased gradually for C5-8 MAs, whereas they weakly varied with DAs addition due to the fact that carboxyl groups at both ends of DAs increased the surface tension of seawater. Moreover, the target compounds in submicron SSA displayed a surface activity-dependent enrichment behavior, where seawater with stronger surface activity, such as that containing MAs with >5 carbons, was more enriched in SSA in comparison to seawater with weaker surface activity. MAs with chain length <5 carbons were slightly enriched in SSA, whereas the enrichment factor (EF) of C5-8 MAs further increased with increasing chain length. These findings are of utmost importance in further understanding and quantifying the contribution of organic matter to SSA, which is crucial for assessing the atmosphere feedback of the marine carbon cycle. MAIN FINDING OF THE WORK: Surface tension of seawater is the key factor affecting the enrichment of short-chain organic acids in SSA.

Assessing the influence of environmental conditions on secondary organic aerosol formation from a typical biomass burning compound.

The atmospheric chemistry in complex air pollution remains poorly understood. In order to probe how environmental conditions can impact the secondary organic aerosol (SOA) formation from biomass burning emissions, we investigated the photooxidation of 2,5-dimethylfuran (DMF) under different environmental conditions in a smog chamber. It was found that SO2 could promote the formation of SOA and increase the amounts of inorganic salts produced during the photooxidation. The formation rate of SOA and the corresponding SOA mass concentration increased gradually with the increasing DMF/OH ratio. The addition of (NH4)2SO4 seed aerosol accelerated the SOA formation rate and significantly shortened the time for the reaction to reach equilibrium. Additionally, a relatively high illumination intensity promoted the formation of OH radicals and, correspondingly, enhanced the photooxidation of DMF. However, the enhancement of light intensity accelerated the aging of SOA, which led to a gradual decrease of the SOA mass concentration. This work shows that by having varying influence on atmospheric chemical reactions, the same environmental factor can affect SOA formation in different ways. The present study is helpful for us to better understand atmospheric complex pollution.

Heterogeneous reaction of SO2 on CaCO3 particles: Different impacts of NO2 and acetic acid on the sulfite and sulfate formation.

Despite the heterogeneous reaction of sulfur dioxide (SO2) on mineral dust particles significantly affects the atmospheric environment, the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear. In this work, using the in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique, we employed a mineral dust particle model (CaCO3) combined with NO2 and acetic acid to investigate their effects on the heterogeneous reaction of SO2 on CaCO3 particles. It was found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate. The addition of NO2 or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly. There was a synergistic effect between NO2 and SO2 that promoted the oxidation of sulfite to sulfate, and a competitive effect between acetic acid and SO2 that inhibited the formation of sulfite. Moreover, light and water vapor can also affect the heterogeneous reaction of SO2 with the coexistence of multiple gases. These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.

Water-soluble matter in PM2.5 in a coastal city over China: Chemical components, optical properties, and source analysis.

Although marine and terrestrial emissions simultaneously affect the formation of atmospheric fine particles in coastal areas, knowledge on the optical properties and sources of water-soluble matter in these areas is still scarce. In this work, taking Qingdao, China as a typical coastal location, the chemical composition of PM2.5 during winter 2019 was analyzed. Excitation-emission matrix fluorescence spectroscopy was combined with parallel factor analysis model to explain the components of water-soluble atmospheric chromophores of PM2.5. Our analysis indicated that NO3-, NH4+ and SO42- ions accounted for 86.80% of the total ion mass, dominated by NO3-. The ratio of [NO3-]/[SO42-] was up to 2.42 ± 0.84, suggesting that mobile sources play an important role in local pollutants emission. The result of positive correlation between Abs365 with K+ suggests that biomass burning is an important source of water-soluble organic compounds (WSOC). Six types of fluorophores (C1-C6), all humic-like substances, were identified in WSOC. Humification index, biological index and fluorescence index in winter were 1.66 ± 0.34, 0.51 ± 0.44 and 1.09 ± 0.78, respectively, indicating that WSOC in Qingdao were mainly terrestrial organic matters. Overall, although the study area is close to the ocean, the contribution of terrestrial sources to PM2.5, especially vehicle exhaust and coal combustion, is still much higher than that of marine sources. Our study provides a more comprehensive understanding of chemical and optical properties of WSOC based on PM2.5 in coastal areas, and may provide ground for improving local air quality.

Seasonal variation of water-soluble brown carbon in Qingdao, China: Impacts from marine and terrestrial emissions.

Brown carbon (BrC) has been attracting more and more attention owing to its significant effects on climate. However, the limited knowledge on its chemical composition and sources limits the precision of aerosol radiative forcing estimated by climate models. In this study, the chemical components of PM2.5 and optical properties of water-soluble BrC (WS-BrC) were investigated from atmospheric particles collected in summer and winter in Qingdao, China. On the whole, though there were slight diurnal variations, seasonal differences were more obvious. Due to the influence of emission sources and meteorological conditions, the heavier pollution of carbonaceous aerosols occurred in winter. By comparison, the absorption Ångström exponent (AAE) and mass absorption efficiency of WS-BrC at 365 nm (MAE365) showed that WS-BrC in winter had stronger wavelength dependence and light absorption capacity, which might be associated with biomass burning source contributions. This was further confirmed by a strong correlation between the light absorption coefficient at 365 nm (Abs365) and non-sea salt K+, an indicator for biomass burning emissions. Four fluorescent components (C1∼C4) with high unsaturation in water-soluble organic carbon (WSOC) were identified by excitation-emission matrix fluorescence spectroscopy combined with parallel factor analysis method, which showed that WSOC in Qingdao was mainly related to humic-like chromophores. It is worth noting that C1 was similar to the water-soluble chromophore of simulated marine aerosols, which proved that marine emissions do have a certain impact on atmospheric particulate matter in coastal areas. In addition, the results of source analysis showed that WS-BrC originated from different terrestrial sources in different seasons. The current results may help to improve the knowledge of optical properties of WS-BrC in coastal cities, optimize the global climate model and formulate air management policies.

Nitrogen-Containing Compounds Enhance Light Absorption of Aromatic-Derived Brown Carbon.

The formation of secondary brown carbon (BrC) is chemically complex, leading to an unclear relationship between its molecular composition and optical properties. Here, we present an in-depth investigation of molecular-specific optical properties and aging of secondary BrC produced from the photooxidation of ethylbenzene at varied NOx levels for the first time. Due to the pronounced formation of unsaturated products, the mass absorption coefficient (MAC) of ethylbenzene secondary organic aerosols (ESOA) at 365 nm was higher than that of biogenic SOA by a factor of 10. A high NOx level ([ethylbenzene]0/[NOx]0 < 10 ppbC ppb-1) was found to significantly increase the average MAC300-700nm of ESOA by 0.29 m2 g-1. The data from two complementary high-resolution mass spectrometers and quantum chemical calculations suggested that nitrogen-containing compounds were largely responsible for the enhanced light absorption of high-NOx ESOA, and multifunctional nitroaromatic compounds (such as C8H9NO3 and C8H9NO4) were identified as important BrC chromophores. High-NOx ESOA underwent photobleaching upon direct exposure to ultraviolet light. Photolysis did not lead to the significant decomposition of C8H9NO3 and C8H9NO4, indicating that nitroaromatic compounds may serve as relatively stable nitrogen reservoirs and would effectively absorb solar radiation during the daytime.

Atmospheric chemical processes of microcystin-LR at the interface of sea spray aerosol.

Microcystins are the most toxic toxins released by cyanobacteria and they have adverse effects on aquatic ecosystems and even human health. Although the removal and detoxification of microcystins in various water bodies have been extensively studied, the interaction mechanism and reaction process of microcystins once they enter the atmosphere are largely unknown, especially at the organic-enriched sea spray aerosol (SSA) interface. Herein, using the surface technique of Langmuir trough coupled in-situ infrared reflection-absorption spectra, we studied the interfacial behavior of microcystin-LR (MC-LR) in artificial seawater containing humic acid and typical surfactants in the presence or absence of UV-irradiation. Zwitterionic 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) and anionic stearic acid (SA) were chosen as typical film-forming species, results obtained from the surface pressure-area isotherms showed that MC-LR caused greater expansion of the DSPC monolayer. The comparable results of MC-LR in DSPC/SA-containing systems indicated that the interaction ability was closely related to the monolayer molecular structure and was regulated by electrostatic interaction. Furthermore, the presence of humic acid (HA) could enhance the interaction between microcystin and monolayer molecules. UV-irradiation experiments showed that the photosensitized reaction greatly promoted the removal of microcystin embedded in the SSA surface compared with the direct photolysis effect in the absence of HA. These findings highlight that the toxic effects of microcystins after entering the atmosphere may be weakened by photochemical reactions.

Molecular size of surfactants affects their degree of enrichment in the sea spray aerosol formation.

Sea spray aerosol (SSA), the largest source of natural primary aerosol, plays an important role in atmospheric chemical processes and the earth radiation balance. Its formation process is controlled by many factors. In this study, ethylene glycol (EG) and polyethylene glycol (PEG) with three different molecular weights (200, 400, 600) were used to investigate the influence of molecular size on the properties of submicron SSA produced by plunging jet from an adjustable home-built SSA generator. Different parameters were tested to obtain the optimum experimental conditions. The addition of EG and PEG inhibited the production of SSA and increased the geometric mean diameter (GMD) between 10 and 35 nm. However, PEG with a molecular weight of 600 could promote the production of SSA at higher concentrations, which means that the molecular weight and concentration of the polymer would affect the production efficiency of SSA. Combining with the measurement of surface tension, we found no clear relationship between surface tension and the yield of SSA, due to the properties of the substances themselves. Transmission electron microscopy images show that the addition of EG and PEG could significantly change the structure of salt nuclei in SSA. PEG was significantly enriched in SSA (with enrichment factors within the range 92.9-133.4), and the enrichment was independent of the sampling time, while increasing with the increase of molecular weight. Our results highlight the influence of polymer molecular weight on the properties of SSA, and their importance to improve the accuracy of aerosol emission model parameters.

Relative Humidity Changes the Role of SO2 in Biogenic Secondary Organic Aerosol Formation.

SO2 influences secondary organic aerosol (SOA) and organosulfates (OSs) formation but mechanisms remain elusive. This study focuses on this topic by investigating biogenic γ-terpinene ozonolysis under various SO2 and relative humidity (RH) conditions. With a constant SO2 concentration (∼110 ppb), the increase in RH transformed SO2 sinks from stabilized Criegee intermediates (sCIs) to peroxides in aerosol particles. The associated changes in particle acidity and liquid water content may collectively first lead to decreased and then increased SOA yield with increasing RH, with the turning point appearing at ∼30% RH. The abundance of most OSs formed under 45% RH was more than 5 times higher than that of OSs formed under 10% RH, possibly due to interactions of dissolved SO2 with hydroperoxides (ROOH) in SOA. ROOHs formed from the autoxidation processes of alkylperoxy radicals were proposed to be precursors for highly oxidized OSs (HOOSs) that decreased SOA volatility and showed a certain abundance in ambient aerosols. This study highlights that high RH potentially enhances the contribution of SO2 to OSs formation, and particularly, HOOSs formation during monoterpene ozonolysis in the atmosphere.

Enhanced photocatalytic performance of PdO-loaded heterostructured nanobelts to degrade phenol.

Heterostructured catalysts play a significant role in the photodegradation of pollutants in wastewater. Combining the large surface of nanobelts with the high photocatalytic property of titanium dioxide (TiO2) nanoparticles is a promising method for preparing photocatalysts, which have an advanced photocatalytic activity and are easy to precipitate. In this work, titanium dioxide nanobelts (NB) and acid corroded titanium dioxide nanobelts (C-NB) were synthesized via a hydrothermal process under alkaline conditions. Their surfaces were then loaded with palladium oxide (PdO) nanoparticles to prepare heterostructured photocatalysts (PdO-NB and PdO-C-NB) by a well-designed chemical precipitation method. The photodegradation efficiencies of the four catalysts for phenol, as well as for methyl orange, were tested and the order of degradation efficiency was found to be PdO-C-NB > PdO-NB > C-NB > NB. A degradation efficiency of 61% for phenol was achieved within 90 min using PdO-C-NB, which was nearly twice as much as using NB. The enhanced photocatalytic property of PdO-C-NB was due to the large specific surface area, abundant photocatalytic active sites and the low recombination rate of electron-hole pairs. Therefore, the degradation of phenol and methyl orange was speeded up considerably. Considering the high catalytic activity of PdO-C-NB, the heterostructure catalyst is of great significance to the degradation of organic wastewater, and has an important impact on our ecological environment and human health.

Anthropogenic-Biogenic Interactions at Night: Enhanced Formation of Secondary Aerosols and Particulate Nitrogen- and Sulfur-Containing Organics from ß-Pinene Oxidation.

Mixing of anthropogenic gaseous pollutants and biogenic volatile organic compounds impacts the formation of secondary aerosols, but still in an unclear manner. The present study explores secondary aerosol formation via the interactions between ß-pinene, O3, NO2, SO2, and NH3 under dark conditions. Results showed that aerosol yield can be largely enhanced by more than 330% by NO2 or SO2 but slightly enhanced by NH3 by 39% when the ratio of inorganic gases to ß-pinene ranged from 0 to 1.3. Joint effects of NO2 and SO2 and SO2 and NH3 existed as aerosol yields increased with NO2 but decreased with NH3 when SO2 was kept constant. Infrared spectra showed nitrogen-containing aerosol components derived from NO2 and NH3 and sulfur-containing species derived from SO2. Several particulate organic nitrates (MW 215, 229, 231, 245), organosulfates (MW 250, 264, 280, 282, 284), and nitrooxy organosulfates (MW 295, 311, 325, 327, and 343) were identified using high-resolution orbitrap mass spectrometry in NO2 and SO2 experiments, and their formation mechanism is discussed. Most of these nitrogen- and sulfur-containing species have been reported in ambient particles. Our results suggest that the complex interactions among ß-pinene, O3, NO2, SO2, and NH3 during the night might serve as a potential pathway for the formation of particulate nitrogen- and sulfur-containing organics, especially in polluted regions with both anthropogenic and biogenic influences.

Unraveling interfacial properties of organic-coated marine aerosol with lipase incorporation.

Marine aerosols are believed to have an organic surface coating on which fatty acids act as an important component due to their high surface activity. In addition, various kinds of enzyme species are abundantly found in seawater, some of which have been identified to exist in marine aerosols. Herein, from the perspective of marine aerosol interface simulation, we investigate the effect of Burkholderia cepacia lipase on the surface properties of stearic acid (SA) monolayer at the air-water interface by using surface-sensitive techniques of Langmuir trough and Infrared reflection-absorption spectroscopy (IRRAS). Our findings indicate that the stearic acid film undergoes a significant expansion, especially when the lipase concentration is 500 nM, because of the incorporation of lipase as observed from the surface pressure-area (π-A) isotherms. IRRAS spectra also show reduced intensities and ordering in the methylene stretching vibration region of stearic acid as a result of low surface density and disordered packing as the enzyme concentration increases. In particular, when the concentration of lipase is 500 nM, the lowest Ias/Is values are shown on both pure water subphase and artificial seawater subphase, indicating more gauche conformations for SA. Furthermore, SA films with lipase incorporation were also studied at three different pH of subphase environment, considering the decrease of pH caused by the reaction with acidic gases during the aerosol aging process. The results reflect a more pronounced expansion of SA monolayer in acidic environment at pH 2.5, suggesting that hydrophobic interaction plays an important role in the disorder of the SA monolayer. In view of the coexistence of fatty acids and enzymes in the marine environment, this study provides a further understanding of the surface organization and behavior of organic-coated marine aerosols and deepen the knowledge of lipid-enzyme interfacial interactions occurring in the atmosphere.

Reply to the 'comment on "impact of water on the BrO + HO2 gas-phase reaction: mechanism, kinetics and products"' by R. Chow, D. K. W. Mok, E. P. F. Lee and J. M. Dyke, Phys. Chem. Chem. Phys., 2021, 23, DOI.

We reply to the comment on our recent paper entitled "Impact of water on the BrO + HO2 gas-phase reaction: mechanism, kinetics and products" by Chow et al. In their comment, the authors raised the differences between our results and their results in an earlier paper (R. Chow, D. K. W. Mok, E. P. F. Lee and J. M. Dyke, Phys. Chem. Chem. Phys., 2016, 18, 30554-30569), in terms of kinetics and potential energy surface, and they attributed these differences to the use of a small integration grid size and closed-shell wavefunctions for geometry optimizations in our study. Indeed, in our original manuscript, we did not ensure the proper use of UHF wavefunctions for singlet states, which led the singlet states to be treated with restricted M06-2X wavefunctions during optimizations. Furthermore, the default integration grid was used. New geometry optimizations have been performed where reactant complexes on the singlet surface were treated in their open-shell singlet states (ensured by using unrestricted-spin wave-functions) and using very tight convergence criteria, and new reaction rate constants have been calculated based on new energy barriers. No barrierless hydrogen abstraction reactions were observed as reported in our previous results and, consequently, the outer rate coefficient in the two-transition state approach (given by eqn (5) in Tsona et al., 2019) was determined by the collision theory. Overall rate constants exhibit a negative temperature dependency in the 200-400 K range. Despite the changes on the reaction energies and kinetics due to wrong UHF wavefunctions, our main conclusion that water has no net effect on the BrO + HO2 → BrOH + O2 reaction is still valid.

Influence of Water on the Gas-Phase Reaction of Dimethyl Sulfide with BrO in the Marine Boundary Layer.

The effect of a single water molecule on the reaction of dimethyl sulfide (DMS) with BrO reaction has been investigated using quantum chemical calculations at the CCSD(T)/6-311++G**//BH&HLYP/aug-cc-pVTZ level of theory. Two reaction mechanisms have been considered both in the absence and the presence of water, namely, oxygen atom transfer and hydrogen abstraction, among which the oxygen atom transfer was predominant. Five reaction channels were found in the absence of water, in which the channels starting from the cis-configuration of the pre-reaction complexes were more favorable because of the low energy barrier. The inclusion of water slightly decreased the energy barrier height of most oxygen atom transfer channels, while making the hydrogen abstraction channels more complex. While the effective rate coefficients for the oxygen atom transfer paths are found to have decreased by 3-7 orders of magnitude in the presence of water relative to the water-free reactions, the negligible fraction of reactants that are effectively clustered with water does not significantly change the overall rate of the formation of dimethyl sulfoxide and Br. The present results show that the overall mechanism and rate of the DMS + BrO reaction may not be affected by humidity under atmospheric conditions.

Aqueous-phase oxidation of syringic acid emitted from biomass burning: Formation of light-absorbing compounds.

Syringic acid is a methoxyphenol model compound derived from biomass burning, and its photooxidation processes have important effects on atmospheric chemistry. However, its aqueous-phase photochemistry remains unclear. In this study, we systematically report the photooxidation of syringic acid induced by OH radicals in the aqueous phase. Employing the relative rate technique, the bimolecular rate constant for syringic acid reaction with OH radicals was acquired to be (1.1 ± 0.3) × 1010 M-1 s-1. Notably, colored products were formed as the reaction progressed. Furthermore, the UV-vis and fluorescence spectra confirmed the formation of light-absorbing organic species, and the results agreed well with previous results on atmospheric and natural humic-like substances (HULIS). The photooxidation products were detected by high performance liquid chromatography mass spectrometry (HPLC/MS), and a possible reaction mechanism was proposed. The aqueous-phase reaction of syringic acid would undergo functionalization process forming a hydroxylation product that enhances the degree of oxidation of aqueous secondary organic aerosol (aqSOA), and goes through dimerization process by C-C or C-O coupling of phenoxy radicals which may conduce to the formation of HULIS. These findings suggest that the photooxidation of syringic acid is an important pathway for highly oxygenated phenolic aqSOA formation, providing a secondary source for HULIS in a liquid phase or in deliquescent particles surrounded by a layer of water.

Effects of NOx and SO2 on the secondary organic aerosol formation from the photooxidation of 1,3,5-trimethylbenzene: A new source of organosulfates.

1,3,5-Trimethylbeneze (TMB) is an important constituent of anthropogenic volatile organic compounds that contributes to the formation of secondary organic aerosol (SOA). A series of chamber experiments were performed to probe the effects of NOx and SO2 on SOA formation from TMB photooxidation. The molecular composition of TMB SOA was investigated by ultra-high performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS). We found that the SOA yield increases notably with elevated NOx concentrations under low-NOx condition ([TMB]0/[NOx]0 > 10 ppbC ppb-1), while an opposite trend is observed in high-NOx experiments ([TMB]0/[NOx]0 < 10 ppbC ppb-1). The increase in SOA yield in low-NOx regime is attributed to the increase of NOx-induced OH concentrations. The formation of low-volatility species might be suppressed, thereby leading to a lower SOA yield in high-NOx conditions. Moreover, SOA formation was promoted in experiment with SO2 addition. Multifunctional products containing carbonyl, acid, alcohol, and nitrate functional groups were characterized in TMB/NOx photooxidation, whereas several organosulfates (OSs) and nitrooxy organosulfates were identified in TMB/NOx/SO2 photooxidation based on HR-Q-TOFMS analysis. The formation mechanism relevant to the detected compounds in SOA were proposed. Based on our measurements, the photooxidation of TMB in the presence of SO2 may be a new source of OSs in the atmosphere. The results presented here also deepen the understanding of SOA formation under relatively complex polluted environments.

Effect of NOx and SO2 on the photooxidation of methylglyoxal: Implications in secondary aerosol formation.

Methylglyoxal (CH3COCHO, MG), which is one of the most abundant α-dicarbonyl compounds in the atmosphere, has been reported as a major source of secondary organic aerosol (SOA). In this work, the reaction of MG with hydroxyl radicals was studied in a 500 L smog chamber at (293 ± 3) K, atmospheric pressure, (18 ± 2)% relative humidity, and under different NOx and SO2. Particle size distribution was measured by using a scanning mobility particle sizer (SMPS) and the results showed that the addition of SO2 can promote SOA formation, while different NOx concentrations have different influences on SOA production. High NOx suppressed the SOA formation, whereas the particle mass concentration, particle number concentration and particle geometric mean diameter increased with the increasing NOx concentration at low NOx concentration in the presence of SO2. In addition, the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO2 and MG/OH/NOx/SO2 reaction systems were detected by gas chromatography mass spectrometry (GC-MS) and attenuated total reflection fourier transformed infrared spectroscopy (ATR-FTIR) analysis. Two products, glyoxylic acid and oxalic acid, were detected by GC-MS. The mechanism of the reaction of MG and OH radicals that follows two main pathways, H atom abstraction and hydration, is proposed. Evidence is provided for the formation of organic nitrates and organic sulfate in particle phase from IR spectra. Incorporation of NOx and SO2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.

Sea spray aerosol formation: Results on the role of different parameters and organic concentrations from bubble bursting experiments.

Submicron sea spray aerosol (SSA) particles play an essential role in atmospheric chemical processes and the Earth's radiative balance. In this study, different combinations of NaCl, MgSO4, malonic acid (MA), d-fructose and sodium malonate were used to explore the effect of MA on submicron SSA generation. SSA particles were produced at room temperature by bubble bursting from an adjustable home-built SSA generator with sintered glass filters. We found that MA could promote the generation of SSA particles and make the geometric mean diameter (GMD) to decrease for MA concentrations ranging between 8 and 32 mM and then, to increase for MA concentrations in the range of 64-160 mM. d-fructose could improve the generation of SSA with increasing GMD. Interestingly, sodium malonate could significantly enhance the production of SSA, with the change of morphology. Besides, different parameters including flow rate, underwater depth, pore size and size span of sintered glass filter and salinity of water were tested to obtain the characterization of our self-made adjustable SSA generator. Three modes could be found among different SSA generation methods, and they exhibited an obvious accumulation mode around 100 nm. The SSA generation under different conditions was compared with oceanic measurements from the literature, which showed that the sintered glass filter has advantages in generating submicron SSA from film drops.

Effects of NO2 and SO2 on the heterogeneous reaction of acetic acid on α-Al2O3 in the presence and absence of simulated irradiation.

The effects of NO2 and SO2 on the atmospheric heterogeneous reaction of acetic acid on α-Al2O3 in the presence and absence of simulated irradiation were investigated at ambient conditions by using the diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique. The experiment was divided into two parts: the heterogeneous reaction experiment and the pre-adsorption reaction experiment under light and dark conditions. In the heterogeneous reaction experiment, solar radiation stimulates the formation of more acetate and nitrate. At the same time, it can promote the partial conversion of sulfites to sulfates in the heterogeneous reaction of SO2 on α-Al2O3 particles. It can be seen that solar radiation plays a significant role in the heterogeneous reactions of inorganic and organic gases on mineral particles. In the pre-adsorption reaction experiment, the pre-adsorbed nitrate, sulfite or sulfate have conspicuous inhibition influence on the formation of acetate in the presence and absence of simulated irradiation. This indicates that the role of pre-adsorbed species should be given more attention for the heterogeneous reaction of acetic acid on the surface of α-Al2O3 particles. When α-Al2O3 particles were pre-adsorbed by different species, simulated irradiation could facilitate the growth of different amounts of acetate. It was found that the extent to which solar radiation contributes to heterogeneous reactions of different kinds of gases on different mineral particles is different. This further emphasizes the complexities of the heterogeneous conversion processes of atmospheric trace gases on the surface of mineral aerosols, promoting a better understanding of the effects of solar radiation and pre-adsorption on the heterogeneous reaction in the atmosphere.

Competitive reactions of SO2 and acetic acid on α-Al2O3 and CaCO3 particles.

Heterogeneous reactions between gaseous pollutants and mineral particles have gradually become a research hotspot in the field of atmospheric chemistry. In this paper, competitive reactions between SO2 and acetic acid on the surface of α-Al2O3 and CaCO3 particles were studied by the diffuse reflectance infrared Fourier transform spectroscopic (DRIFTS) technique in dark and dry conditions. At the same time, the temporary evolution of the integrated absorbance of acetate and sulfite was investigated to further understand the interaction of SO2 and acetic acid on the mineral particles. On the surface of α-Al2O3 particles, acetate and sulfite can compete for surface-active sites, resulting in a decrease in the total amount of acetates. In dark and dry conditions, the effect of acetic acid on SO2 cannot be obtained by the DRIFTS method. On the surface of CaCO3 particles, SO2 can have a competitive impact on acetic acid by grabbing active sites, leading to a slight decrease of the amount of acetates. The heterogeneous reaction of SO2 can be impeded by coexisting acetic acid, resulting in a drastic reduction of the number of sulfites. It can be seen that the formation mechanisms of acetate and sulfite on the surface of different mineral particles in the atmosphere are different, which provides a variety of ideas and possibilities for the formation of related inorganic and organic salts in the atmosphere.