[Aqueous-phase Oxidation of Dissolved Organic Matter (DOM) from Extracts of Ambient Aerosols].

Recently, a large number of laboratory studies have focused on the aqueous-phase photochemistry of single organic compound in atmospheric condensed phases, yet few studies have been conducted on the aqueous-phase photochemical oxidation of real-world complex dissolved organic matter (DOM). Therefore, in this work, we report experimental results for the photochemical oxidation of DOM extracts from ambient fine aerosol samples upon direct photolysis or against OH oxidation, under both simulated sunlight and ultraviolet irradiation conditions. The products at different stages of photolysis were analyzed via UV-vis and spectroscopy and soot-particle aerosol mass spectrometry (SP-AMS) to investigate their optical and chemical characteristics. The results demonstrate the effective degradation of DOM under UV irradiation, and the f44 values of the corresponding products aremuch lower than under sunlight irradiation. A variety of carboxylic acids were generated during liquid-phase photolysis, and oxalic acid was found to be the most abundant. The light absorbance and concentration of HULIS did not change significantly under sunlight illumination; however, under UV and UV+·OH conditions, the concentration of HULIS increased continuously with reaction time. The HULIS concentration at 23 h was approximately four times the initial value, indicating the formation of brown carbon species with carboxyl, hydroxyl, and aromatic and other functional groups. Our results show that the increase in light absorptivity and formation rate of brown carbon from DOM are limited when aqueous-phase oxidation occurs under sunlight illumination. In comparison, DOM can constantly decompose into HULIS or small molecules under ultraviolet light illumination, and the light absorptivity of the remaining organic matter may be relatively high, resulting in final products with a high unit mass absorption efficiency (MAE). We have investigated the aqueous-phase oxidation of actual filter extracts for the first time, and our results provide valuable insights to the formation of air pollution complexes.

[Analysis of Water Soluble Organic Aerosol in Spring PM2.5 with Soot Particle Aerosol Mass Spectrometry (SP-AMS)].

To investigate the chemical composition and pollution characteristics of spring fine particles (PM2.5) in Changzhou, a total of 84 PM2.5 samples were collected from March 1st to May 30th, 2017. We measured and analyzed conventional components, such as water-soluble ions (WSIIs) and carbonaceous components (OC and EC). The water-soluble organic aerosol (WSOA) was also analyzed by an aerodyne soot particle aerosol mass spectrometer (SP-AMS). During the sampling period, the average daily PM2.5 concentration was 101.97 µg·m-3, with more than 73.8% sampling days exceeding the Target-2 standard of the national ambient air quality standard of China. The air quality during the sampling period was dominated by light, moderate, and heavy pollution, accounting for 39.3%, 21.4%, and 13.1% of the total days, respectively. The total WSIIs accounted for 39.86% of PM2.5 mass, of which secondary ions (SO42-, NH4+, and NO3-) accounted for 81.85% of the total WSIIs. The slope of the linear fitted line of the anion and cation charge balance (AE/CE) was greater than 1 (1.09), which indicated that PM2.5 was weakly acidic. The average OC/EC ratio was 2.53, indicating that PM2.5 was influenced by the secondary conversion. WSOA included CxHy+(32.1%), CxHyO+(30.4%), CxHyO2+(25.4%), and HyO+(4.7%) identified by SP-AMS. The average oxygen-to-carbon (O/C), hydrogen-to-carbon (H/C), nitrogen-to-carbon (N/C), and organic matter-to-organic carbon (OM/OC) ratios of the WSOA were 0.72, 1.53, 0.04, and 2.15, respectively. Higher O/C indicated higher contributions from secondary photochemical reaction conversion in spring. Positive matrix factorization (PMF) analysis for AMS mass spectra of WSOA identified three sources, namely hydrocarbon-like (HOA), semi-volatile oxygenated OA (SVOOA)-biomass burning OA (BBOA), and low-volatility oxygenated OA (LVOOA), which on average accounted for 18.4%, 34.1%, and 47.4% of the total WSOA, respectively.

[Secondary Organic Aerosol Mass Yield and Characteristics from 4-ethylguaiacol Aqueous·OH Oxidation: Effects of Initial Concentration].

Aqueous-phase chemical processing, as an essential formation pathway of secondary organic aerosol (SOA), has attracted widespread attention from within atmospheric chemistry fields. Due to the complicated reaction nature, reaction mechanisms, and product characteristics of aqueous-phase chemical processing, its contribution to the SOA budget is still not fully understood. In this work, we investigate how the initial concentration (0.03-3 mmol·L-1) of 4-ethylguaiacol affects SOA formation of aqueous·OH photochemical oxidation. We use soot-particle aerosol mass spectrometry (SP-AMS) to monitor SOA mass yield and oxidation character, and gas chromatography-mass spectrometry (GC-MS) and ion chromatography (IC) to measure products and organic acids. Additionally, we use ultraviolet visible spectroscopy (UV-vis) and high-performance liquid spectrometry (HPLS) to track the formation of light-absorbing products such as humic-like substances (HULIS). Our research indicated that the range of the O/C ratio of EG-aqSOA measured by the SP-AMS exhibited increasing trends with increased reaction time 0.42-0.61 (0.03 mmol·L-1), 0.49-0.84 (0.3 mmol·L-1), and 0.49-0.63 (3 mmol·L-1). Dimers (C16H18 O2+, m/z 302) via SP-AMS were obviously higher under a higher initial concentration, thereby demonstrating that the oligomerization reaction proceeded more easily. The absorption at 250 nm recorded by UV-vis was distinctly enhanced, which might be attributed to new light-absorbing products with absorbance at 250 nm. Furthermore, the HULIS concentration increased with reaction time, in accordance with enhancement of absorbance in the 300-400 nm region, thus suggesting that aqueous-phase processing formed brown carbon. Small organic acids, including formic acid, malic acid, and oxalic acid, were detected by IC in all reaction solutions, with the highest concentration being for formic acid. GC/MS detected ketone, an OH monomer, and dimers in the aqSOA, which further indicates that functionalization and oligomerization took place.

[Day-night Characteristics of Humic-like Substances in PM2.5 During Winter in Changzhou].

To investigate the characteristics of diurnal variation of humic-like substances (HULIS) in atmospheric aerosols during winter in Changzhou, a total of 64 fine particle (PM2.5) samples were collected from January 1 to February 28, 2017. In this study, the concentration as well as light absorption parameters of humic-like substances of carbon (HULIS-C) were examined. The results showed that the average day PM2.5 and HULIS-C concentrations were 122.60 µg·m-3 and 4.18 µg·m-3, respectively, slightly higher than those (111.72 µg·m-3 and 3.74 µg·m-3) at night. Via UV-vis analysis, we found that the ratios of absorbance at 250 nm (A250) of HULIS and WSOA (day:~77%, night:~75%) were significantly higher than the concentration ratios of HULIS-C and WSOC (day:~51%, night:~50%), indicating that more UV-absorbing substances and poly-conjugated aromatic structures exist in HULIS. The daytime E250/E365 and SUVA280 in HULIS were close to the nighttime ones, indicating that there was no obvious difference between day and night in HULIS with reference to aromaticity and molecular weight. There were no significant differences in MAE365 and AAE300-400 of HULIS between day and night. In addition, to obtain the main influencing factors of HULIS in winter in Changzhou, the correlation analysis of HULIS-C and other chemical components were conducted. The results show that biomass burning, fossil fuel combustion, factory emissions, and especially secondary formation, were the main influencing factors. Moreover, daytime HULIS were mainly influenced by secondary reaction of anthropogenic precursor contaminants, while nighttime HULIS were affected not only by secondary formation by but by also primary combustion emissions.

[Characteristics and Sources of Water-soluble Organic Carbon/Nitrogen in PM2.5 During Spring in Changzhou].

To understand the characteristics and sources of water-soluble organic carbon (WSOC) and organic nitrogen (WSON) in atmospheric aerosols during spring in Changzhou, 84 fine particle (PM2.5) samples were collected from March 1 to May 30, 2017, in Changzhou. The water-soluble components, including water-soluble organic carbon, water-soluble total nitrogen (WSTN), water-soluble ions, and carbonaceous components (OC and EC), were analyzed. The levels of WSOC and WSON and their source characteristics were discussed. The results show that the average concentrations of PM2.5, WSOC, and WSON are 101.97, 7.63, and 1.50 µg·m-3, respectively, during the sampling period. The WSON accounts for 12.9% of the WSTN and the water-soluble inorganic nitrogen mainly exists in two forms, that is, NH4+ and NO3-, accounting for 86.15% of the WSTN. The WSOC is weakly correlated with WSON (r=0.58), indicating that WSOC and WSON do not have the same sources. The WSOC is related to SOC, K+, and secondary ions (SO42-, NH4+, and NO3-), indicating that it is mainly derived from biomass burning and secondary conversion; WSON is strongly correlated to secondary ions, indicating that it is mainly derived from secondary conversion. The wind speed is the main factor affecting the WSOC and WSON concentration levels. Furthermore, the WSON is positively correlated with the air pressure and negatively correlated with the temperature. The results of the principal component analysis show that PM2.5 mainly originates from four sources:secondary formation, dust, coal combustion, biomass burning, and the ocean. The backward trajectory analysis indicates that the total concentrations of PM2.5, WSOC, and WSON in air masses from long-distance transformation are higher than that from short-distance transmission, whereas there is no significant difference in the WSON/WSTN ratio from different transmission paths.

[Day-Night Differences and Source Apportionment of Inorganic Components of PM2.5 During Summer-Winter in Changzhou City].

To investigate the day-night variation characteristics of inorganic components in atmospheric aerosol, PM2.5 samples were continuously collected for one month in Changzhou during summer and winter. Eleven water-soluble ions (WSⅡs) and 13 metal elements were compared in terms of their day-night character and sources. The results indicated that the day time average PM2.5 mass concentration was higher than the night time, while the percentage of the total WSⅡs in PM2.5 during the night was higher. The total WSⅡs fractions in PM2.5 were higher in winter (44%-45%) compared to summer (31%-36%), with an opposite seasonal character for metal elements (winter day 3.03%, winter night 2.29%, summer day 4.40%, summer night 4.51%). SO42-, NO3-, and NH4+, were the three main secondary ions, comprising 77%-85% of the total WSⅡs, suggesting that air pollution in Changzhou exhibits complex pollution characteristics dominated by secondary processes. The day time SO42-/WSⅡs ratio (49.0%) was slightly higher than that of the night (41.1%) due to the photochemical reaction under stronger solar radiation, while the lower NO3-(1.98 µg·m-3) in the day compared to the night (5.10 µg·m-3) was attributed to the decomposition of NH4NO3 during summer days. A good linear correlation among NH4+, SO42- and NO3-, accompanied by a ratio of predicted NH4+ to measured NH4+ near 1, illustrated that NH4+ ions mainly existed in the form of (NH4)2SO4, NH4NO3, and NH4Cl. It was concluded from the ion balance that PM2.5 was weakly alkaline in summer but neutral in winter. Fe, Al, and Zn were the largest contributors to the total metal elements, with higher concentrations of Fe and Al and lower levels of Zn in the day time. A correlation coefficient analysis and principle component analysis revealed that inorganic components come from sources that include secondary aerosol formation, suspended dust, and vehicle emissions, but there is some seasonal variation and day-night differences.

[Secondary Organic Aerosols from Aqueous Reaction of Aerosol Water].

Liquid water (cloud/fog droplets and aerosols) is ubiquitous in the atmosphere and can provide an important reaction media for aqueous-phase chemical reactions. Gaseous precursors (mainly VOCs) or their gas-phase initial or first-generation oxidation products (including intermediate-volatility and semi-volatile organic compounds; I/SVOCs) can undergo chemical reactions in the atmospheric condensed phase (aqueous phase) to form low-volatility, highly oxidized organic matter[e.g., some key tracer species such as organosulfates (OSs) and organonitrogens (ONs)]. These products largely remain in the particle phase upon water evaporation and are referred to as aqueous secondary organic aerosols (aqSOAs). aqSOAs have been emerging as a research hot topic in atmospheric chemistry, as they can contribute significantly to OAs and thus have important impacts on the environment, climate, and human health. Despite considerable progress, so far, aqSOAs remain poorly understood owing to their complex formation mechanisms. In this review, we focus mainly on the relevant research results on the SOAs formed in aerosol water-aqueous aerosol SOAs (aaSOAs)-including gas-phase precursors, formation mechanisms, laboratory simulations, and field observations, as well as SOA yield and contribution to OAs. Meanwhile, we propose future directions regarding studies of sources and formation mechanisms of aaSOAs, including identification of unknown aaSOA precursors and tracer products, photosensitizer-triggered radical chemistry, formation pathways of OS and ON compounds, field observations and model simulations of aaSOAs.

Template-Assisted Hydrothermal Growth of One-Dimensional Zinc Oxide Nanowires for Photocatalytic Application.

One-dimensional (1D) semiconductor ZnO nanowires have been successfully synthesized by a novel soft-chemical hydrothermal method with allylpolyethoxy amino carboxylate (AA-APEA) at low temperature. Their structure and properties have been characterized by a series of techniques, including X-ray diffraction (XRD), energy dispersive X-ray analysis (EDX) and transmission electron microscopy (TEM). It was found that ZnO nanowires with diameters around 50 nm and lengths up to about several micrometers are well-distributed. The photocatalytic activity toward degradation of methylene blue (MB) aqueous solution under ultraviolet (UV) was investigated and the results showed that the ZnO nanowires exhibit a markedly higher photoactivity compared to the ZnO nanoparticles which were obtained without AA-APEA polymer assistant, and it can be ascribed to the special 1D morphology of the ZnO nanowires. In particular, the rate of degradation of the ZnO nanowires was 11 times faster than that of ZnO nanoparticles. In addition, the ZnO nanowires could be easily recycled in UV photocatalytic activity. These observations could promote new applications of photocatalyst for wastewater treatment utilizing oxide semiconductor nanostructures.

[Pollution Characteristics and Source Identification of PAHs in Atmospheric PM2.5 in Changzhou City].

A total of 55 ambient fine particle (PM2.5) samples were collected in Changzhou City from January to August 2016. The concentrations of 17 PM2.5-bound PAHs in the samples were analyzed by GC-MS. Results showed that seasonal average mass concentrations of PAHs in winter, spring, and summer were 140.24, 41.42, and 2.96 ng·m-3, respectively, which indicating that the pollution of PAHs in winter appeared more serious than in the other two seasons, and 4-6-ring high molecular weight PAHs were predominant in all three seasons. The average daily level of BaP was 3.64 ng·m-3 and the days it exceeded the permitted standard accounted for 41% of total days. PAH concentration had significant negative correlations with temperature (correlation coefficient: -0.643) and visibility (correlation coefficient: -0.466), whereas it had good positive correlations with atmospheric pressure (correlation coefficient: 0.544) and poor correlations with wind speed and relative humidity. PAH concentrations were higher at nighttime than at daytime, because of the influences of temperature difference, atmospheric stratification, as well as pollution sources. The results from the air backward trajectory model indicated that PM2.5-bound PAHs in Changzhou were mainly affected by local emission sources and short-distance transportation, whereas the contribution of long-distance transmission was small (only 11%). Based on analysis of characteristic ratios, PAHs were mainly sourced from coal burning, vehicle emissions, and biomass burning. An incremental lifetime cancer risk (ILCR) model was used to evaluate the health impact of PAHs via breathing exposure pathways. Results revealed that the ILCR of adults was higher than that of children. The ILCRs of the group for winter and spring were slightly higher than the risk threshold, but a difference was not obvious for summer.

[Characteristics and Source Identification of Carbonaceous Aerosols in PM2.5 Measurements During Summer and Fall in Changzhou].

To better understand the characterization and sources of carbonaceous components, a total of 60 fine particle (PM2.5) samples were collected in Changzhou during summer (July to August) and fall (October to November) of 2016. The average mass concentrations of PM2.5, organic carbon (OC), and elemental carbon (EC) during this study period were observed to be 73.0, 14.3 and 3.3 µg·m-3 in summer and 84.2, 13.2, and 3.5 µg·m-3 in fall, respectively. The average mass fraction of carbonaceous aerosols (OC+EC) in the PM2.5 measurement was estimated to be 24.3% in summer and 20.7% in fall. Eight carbonaceous fractions, resolved by following the IMPROVE-A thermal/optical reflectance protocol, showed strong correlation (r>0.92) between OC2, OC3, OC4 and EC1 and close correlations between EC2 and EC3 (r>0.65), indicating probable similar contributors. OC and EC were moderately correlated, suggesting complex contributions to carbonaceous aerosol. The water soluble organic carbon (WSOC) to OC ratio (WSOC/OC) in the fall (60.9%) was slightly higher than that in the summer (57.4%), while secondary organic carbon (SOC) to OC ratio (SOC/OC) was lower in the fall (49.0%) compared with the summer (52.5%). The SOC/OC ratio was lower than the WSOC/OC for both seasons, suggesting that part of WSOC component originates from primary emissions. The significant correlation of WSOC and SOC confirms that most SOC is water soluble. Relationships between each carbonaceous species and the principal component analysis indicate that vehicle emissions and coal combustion are the two main emission sources of carbonaceous aerosols from the observation period. Back trajectory analysis was used to indicate that carbonaceous components at sampling site are mainly affected by local emission sources and short distance transport, whereas the contribution of long-distance transmission is small.

[Photonic Efficiency of Ethyl Acetate Photolysis in Gas Phase: Dependence on Wavelength and Catalyst].

Four kinds of excilamps with different wavelengths (XeCl*, KrCl*, XeBr* and KrBr*) were used for removing ethyl acetate in gas phase. The removal efficiencies of ethyl acetate by three loaded catalysts (TiO2 loaded on organic film, graphene loaded on organic film, and TiO2 loaded on mesh) were compared, and the effects of lamp sources, irradiation power and initial concentration on the removal efficiency were also investigated. Moreover, irradiation spectra and power of light sources were determined, and photonic efficiencies under different reaction conditions were calculated. The experimental results showed that the removal efficiency of ethyl acetate decreased in the order of KrBr* > KrCl* > XeCl* > XeBr*, while the photonic efficiency seemed to be relatively high with both XeCl* and KrBr* excilamps. In the presence of the catalyst of TiO2 loaded on organic film, both the removal efficiency and the photonic efficiency were higher than those without catalyst, but the increment was not significant. The photonic efficiency increased with increasing initial concentration and gas flow rate. With KrBr* excilamp, a photonic efficiency of 5.63% was obtained when the experimental conditions were set as: irradiation power of 0.76 W, initial concentration of 946 mg x m(-3), and gas flow rate of 600 mL x min(-1).

[Kinetics of alkylphenols degradation in aqueous phase with excilamp irradiation].

The 206 nm irradiation from excilamp was able to directly photo-degrade 4-nonylphenol (4-NP) and 4-octylphenol (4-OP), but it could not oxidize them completely into CO2. Under the same irradiation condition, the removal efficiency of 4-OP was higher than that of 4-NP. Pseudo-first order kinetic model and modified kinetic model were used to fit the kinetics of photo-degradation process, and the direct photolysis rate constants under 206 nm UV irradiation were obtained. The experimental results demonstrated that the photolysis rate constant was higher at lower initial concentration of alkylphenols. Two kinetic models were appropriate for the direct photolysis of alkylphenols at low concentration, but the modified model did not fit for high concentrations. Degradation rate can be obviously enhanced when adding H2O2 into the reaction, but the TOC removal was distinct only when the dosage of H2O2 was high. At last, we concluded that the direct photolysis rate constant k(d) was 0.032 8 min(-1) and the reaction rate constant k(pH) between 4-OP and H2O2 was 17.4520 L x (mol x min)(-1).

[Direct photolysis of methylamine gas by KrBr* excilamp].

A study on methylamine (MA) photo-dissociation in gas phase has been carried out using UV radiation from a 207 nm KrBr* excilamp driven by a sinusoidal electronic control gear. The influence factors including gas flow rate, initial concentration and input power of removal efficiency were investigated. The radiant power and spectrum of the lamp were measured. Several parameters were investigated including removal efficiency, energy yield, carbon balance and CO2 selectivity in order to comprehensively evaluate the photo-dissociation process. It was shown that the removal efficiency increased with enhanced input power, decreased gas flow rate and increased MA initial concentration. Energy yield had positive pertinence with MA initial concentration, and it would obtain optimal value at 65.1 W. Carbon balance and CO2 selectivity showed slighter enhancement when lamp power increased and gas flow rate declined. The removal efficiency of 56.8% was achieved at a lamp power of 79.8 W, a gas flow rate of 9.0 m3 x h(-1) and an MA initial concentration of 2 897 mg x m(-3). Under the above mentioned experimental conditions, energy yield reached 185.6 g (kW x h)(-1), and carbon balance and CO2 selectivity were 16.8% and 10.3%, respectively. At last, secondary products formed were analyzed by gas chromatography-mass spectrometry and the photo-degradation mechanism of MA was suggested on the basis of UV-vis absorption spectrum.

[New-type electrodeless excilamp for advanced treatment on nitrogen-heterocyclic compounds (NHCs) in aqueous solution].

A novel 206 nm excilamp generated by microwave-driven Kr/I2 mixtures was employed for nitrogen-heterocyclic compounds (NHCs) degradation in aqueous solution. The photodissociation efficiencies of indole and quinoline with 206 nm excilamp were estimated on the basis of removal efficiency of targeted compounds and the loss of total organic carbon (TOC). The results indicated that removal efficiency of 20 mg x L(-1) indole was as high as 62.0% after 80 min and TOC loss efficiency of 50.7% for 150 min. The irradiation time, initial concentration and pH value had some influences on quinoline degradation. Indole removal efficiency and TOC loss was markedly higher than that of quinoline under the same condition. The intermediates were identified qualitatively by gas chromatography/mass spectrum (GC/MS) with headspace sampling after they were extracted by rotary evaporator. GC/MS analysis indicated that indole and quinoline underwent ring-open dissociation under 206 nm irradiation, as a result, benzene, xylene, acetate, aldehyde, as well as ester compounds were formed, while indole aggregation reaction occurred during indole photodegradation. At last, degradation mechanisms of quinoline and indole in aqueous media with 206 nm excilamp were proposed on the basis of intermediates.