Hydrothermal-treated Pt/Al2O3 as an excellent catalyst for toluene total oxidation

The preparation of highly active supported noble metal catalysts with a low noble metal loading has always been the ultimate goal of researchers working on catalysis. Hydrothermally treated Pt/Al₂O₃ (Pt/Al₂O₃-H) exhibits better catalytic activity than that (Pt/Al₂O₃-C) treated via the conventional calcination approach. At the high space velocity of 100,000 mL/(g∙hr), the temperature that correspond to 50% toluene conversion (T₅₀) of Pt/Al₂O₃-H is 115°C lower than that of Pt/Al₂O₃-C, and the turnover frequency (TOF) value can reach 0.0756 sec⁻¹. The mechanism by which the hydrothermal approach enhances Pt/Al₂O₃ activity has been investigated. The structure associated with the high catalytic activity of Pt nanoparticles (NPs) can be retained via hydrothermal treatment. Furthermore, the support is transformed to AlO(OH) with numerous surface hydroxyl groups, which in turn can facilitate the adsorption of toluene. And the synergistic effects of Pt NPs and AlO(OH) increases the contents of Pt in oxidation state and active oxygen, which are beneficial for toluene oxidation.     

Low-temperature (NO + O2) adsorption performance of alkaline earth metal-doped C-FDU-15

To improve the removal capacity of NO + O₂ effectively, the alkaline earth metal-doped order mesoporous carbon (A-C-FDU-15(0.001) (A = Mg, Ca, Sr and Ba)) and Mg-C-FDU-15(x) (x = 0.001?0.003) samples were prepared, and their physicochemical and NO + O₂ adsorption properties were determined by means of various techniques. The results show that the sequence in (NO + O₂) adsorption performance was as follows: Mg-C-FDU-15(0.001) (93.2 mg/g) > Ca-C-FDU-15(0.001) (82.2 mg/g) > Sr-C-FDU-15(0.001) (76.1 mg/g) > Ba-C-FDU-15(0.001) (72.9 mg/g) > C-FDU-15 (67.1 mg/g). Among all of the A-C-FDU-15(0.001) samples, Mg-C-FDU-15(0.001) possessed the highest (NO + O₂) adsorption capacity (106.2 mg/g). The species of alkaline earth metals and basic sites were important factors determining the adsorption of NO + O₂ on the A-C-FDU-15(x) samples, and (NO + O₂) adsorption on the samples was mainly chemical adsorption. Combined with the results of (NO + O₂)-temperature-programmed desorption ((NO + O₂)-TPD) and in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS) characterization, we deduced that there were two main pathways of (NO + O₂) adsorption: one was first the conversion of NO and O₂ to NO₂ and then part of NO₂ was converted to NO₂^? and NO₃^?; and the other was the direct oxidation of NO to NO₂^? and NO₃^?.     

Effect of alkaline earth metal promoter on catalytic activity of MnO2 for the complete oxidation of toluene

Herein, Na⁺ and Ca²⁺ are introduced to MnO₂ through cation-exchange method. The presence of Na⁺ and Ca²⁺ significantly enhance the catalytic activity of MnO₂ in toluene oxidation. Among them, the Ca-MnO₂ catalyst exhibits the best catalytic activity (T₅₀ = 194°C, T₉₀ = 215°C, E_a = 57.2 kJ/mol, reaction rate 8.40 × 10^?10 mol/(sec?m²) at 210°C. T₅₀ and T₉₀: the temperature of 50% and 90% toluene conversion; E_a: apparent activation energy) and possess high tolerance against 2.0 vol.% water vapor. Results reveal that the increased acidic sites of the MnO₂ sample can enhance the adsorption of gaseous toluene, and the mobility of oxygen species and the content of reactive oxygen species in the catalyst are significantly improved due to the formed oxygen vacancy. Thus these two factors result in excellent catalytic performance for toluene oxidation combining with the weak CO₂ adsorption ability.     

Pd/silicalite-1: An highly active catalyst for the oxidative removal of toluene

Catalytic combustion is thought as an efficient and economic pathway to remove volatile organic compounds, and its critical issue is the development of high-performance catalytic materials. In this work, we used the in situ synthesis method to prepare the silicalite-1 (S-1)-supported Pd nanoparticles (NPs). It is found that the as-prepared catalysts displayed a hexagonal prism morphology and a surface area of 390−440 m²/g. The sample (0.28Pd/S-1-H) derived after reduction at 500°C in 10 vol% H₂ showed the best catalytic activity for toluene combustion (T_50% = 180°C and T_90% = 189°C at a space velocity of 40,000 mL/(g·hr), turnover frequency (TOF_Pd) at 160°C = 3.46 × 10⁻³ sec⁻¹, and specific reaction rate at 160°C = 63.8 µmol/(g_Pd·sec)), with the apparent activation energy (41 kJ/mol) obtained over the best-performing 0.28Pd/S-1-H sample being much lower than those (51−70 kJ/mol) obtained over the other samples (0.28Pd/S-1-A derived from calcination at 500°C in air, 0.26Pd/S-1-im derived from the impregnation route, and 0.27Pd/ZSM-5-H prepared after reduction at 500°C in 10 vol% H₂). Furthermore, the 0.28Pd/S-1-H sample possessed good thermal stability and its partial deactivation due to CO₂ or H₂O introduction was reversible, but SO₂ addition resulted in an irreversible deactivation. The possible pathways of toluene oxidation over 0.28Pd/S-1-H was toluene → p-methylbenzoquinone → maleic anhydride, benzoic acid, benzaldehyde → carbon dioxide and water. We conclude that the good dispersion of Pd NPs, high adsorption oxygen species concentration, large toluene adsorption capacity, strong acidity, and more Pd⁰ species were responsible for the good catalytic performance of 0.28Pd/S-1-H.     

Nocturnal atmospheric chemistry of NO3 and N2O5 over Changzhou in the Yangtze River Delta in China

Comprehensive observations of the nocturnal atmospheric oxidation of NO₃ and N₂O₅ were conducted at a suburban site in Changzhou in the YRD using cavity ring-down spectroscopy (CRDS) from 27 May to 24 June, 2019. High concentrations of NO₃ precursors were observed, and the nocturnal production rate of NO₃ was determined to be 1.7 ± 1.2 ppbv/hr. However, the nighttime NO₃ and N₂O₅ concentrations were relatively low, with maximum values of 17.7 and 304.7 pptv, respectively, illustrating the rapid loss of NO₃ and N₂O₅. It was found that NO₃ dominated the nighttime atmospheric oxidation, accounting for 50.7%, while O₃ and OH only contributed 34.1% and 15.2%, respectively. For the reactions of NO₃ with volatile organic compounds (VOCs), styrene was found to account for 60.3%, highlighting its dominant role in the NO₃ reactivity. In general, the contributions of the reactions between NO₃ and VOCs and the N₂O₅ uptake to NO₃ loss were found to be about 39.5% and 60.5%, respectively, indicating that N₂O₅ uptake also played an important role in the loss of NO₃ and N₂O₅, especially under the high humidity conditions in China. The formation of nitrate at night mainly originated from N₂O₅ uptake, and the maximum production rate of NO₃⁻ reached 6.5 ppbv/hr. The average NO_x consumption rate via NO₃ and N₂O₅ chemistry was found to be 0.4 ppbv/h, accounting for 47.9% of the total NO_x removal. The predominant roles of NO₃ and N₂O₅ in nitrate formation and NOx removal in the YRD region was highlighted in this study.     

Rural vehicle emission as an important driver for the variations of summertime tropospheric ozone in the Beijing-Tianjin-Hebei region during 2014–2019

Tropospheric ozone (O₃) pollution is increasing in the Beijing-Tianjin-Hebei (BTH) region despite a significant decline in atmospheric fine aerosol particles (PM_2.5) in recent years. However, the intrinsic reason for the elevation of the regional O₃ is still unclear. In this study, we analyzed the spatio-temporal variations of tropospheric O₃ and relevant pollutants (PM_2.5, NO₂, and CO) in the BTH region based on monitoring data from the China Ministry of Ecology and Environment during the period of 2014–2019. The results showed that summertime O₃ concentrations were constant in Beijing (BJ, 0.06 µg/(m³•year)) but increased significantly in Tianjin (TJ, 9.09 µg/(m³•year)) and Hebei (HB, 6.06 µg/(m³•year)). Distinct O₃ trends between Beijing and other cities in BTH could not be attributed to the significant decrease in PM_2.5 (from -5.08 to -6.32 µg/(m³•year)) and CO (from -0.053 to -0.090 mg/(m³•year)) because their decreasing rates were approximately the same in all the cities. The relatively stable O₃ concentrations during the investigating period in BJ may be attributed to a faster decreasing rate of NO₂ (BJ: -2.55 µg/(m³•year); TJ: -1.16 µg/(m³•year); HB: -1.34 µg/(m³•year)), indicating that the continued reduction of NO_x will be an effective mitigation strategy for reducing regional O₃ pollution. Significant positive correlations were found between daily maximum 8 hr average (MDA8) O₃ concentrations and vehicle population and highway freight transportation in HB. Therefore, we speculate that the increase in rural NO_x emissions due to the increase in vehicle emissions in the vast rural areas around HB greatly accelerates regional O₃ formation, accounting for the significant increasing trends of O₃ in HB.     

Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T_90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOF_Co) being 245°C, 1.23 × 10⁻³ mol_toluene/(g_cat·sec), and 11.58 × 10⁻³ sec⁻¹ for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO₂, SO₂ or NH₃, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O₂ and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H₂O and CO₂.     

Activation of sulfite by metal-organic framework-derived cobalt nanoparticles for organic pollutants removal

Sulfite (SO₃²⁻) activation is one of the most potential sulfate-radical-based advanced oxidation processes, and the catalysts with high efficiency and low-cost are greatly desired. In this study, the cobalt nanoparticles embedded in nitrogen-doped graphite layers (Co@NC), were used to activate SO₃²⁻ for removal of Methyl Orange in aqueous solution. The Co@NC catalysts were synthesized via pyrolysis of Co²⁺-based metal-organic framework (Co-MOF), where CoO was firstly formed at 400℃ and then partially reduced to Co nanoparticles embedded in carbon layers at 800℃. The Co@NC catalysts were more active than other cobalt-based catalysts such as Co²⁺, Co₃O₄ and CoFe₂O₄, due to the synergistic effect of metallic Co and Co_xO_y. A series of chain reaction between Co species and dissolved oxygen was established, with the production and transformation of SO₃^•−, SO₅²⁻, and subsequent active radicals SO₄^•− and HO•. In addition, HCO₃⁻ was found to play a key role in the reaction by complexing with Co species on the surface of the catalysts. The results provide a new promising strategy by using the Co@NC catalyst for SO₃²⁻ oxidation to promote organic pollutants degradation.     

Effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria: Soot-ceria contact and interfacial oxygen evolution

Ceria is widely used as a catalyst for soot combustion, but effects of Zr substitution on the reaction mechanism is ambiguous. The present work elucidates effects of Zr substitution on soot combustion over cubic fluorite-structured nanoceria. The nanostructured CeO₂, Ce_0.92Zr_0.08O₂, and Ce_0.84Zr_0.16O₂ composed of 5–6 nm crystallites display T_m-CO2 (the temperature at maximum CO₂ yield) at 383, 355, and 375°C under 10 vol.% O₂/N₂, respectively. The size of agglomerate decreases from 165.5 to 51.9–57.3 nm, which is beneficial for the soot-ceria contact. Moreover, Zr increases the amount of surface oxygen vacancies, generating more active oxygen (O₂^? and O^?) for soot oxidation. Thus, the activities of Ce_0.92Zr_0.08O₂ and Ce_0.84Zr_0.16O₂ in soot combustion are better than that of CeO₂. Although oxygen vacancies promote the migration of lattice O^2?, the enriched surface Zr also inhibits the mobility of lattice O^2?. Therefore, the T_m-CO2 of Ce_0.84Zr_0.16O₂ is higher than that of Ce_0.92Zr_0.08O₂. Based on reaction kinetic study, soot in direct contact with ceria preferentially decomposes with low activation energy, while the oxidation of isolated soot occurs through diffusion with high activation energy. The obtained findings provide new understanding on the soot combustion over nanoceria.     

Effect of intermittent aeration mode on nitrogen concentration in the water column and sediment pore water of aquaculture ponds

Nitrogen in pond sediments is a major water quality concern and can impact the productivity of aquaculture. Dissolved oxygen is an important factor for improving water quality and boosting fish growth in aquaculture ponds, and plays an important role in the conversion of ammonium-nitrogen (NH₄⁺-N) to nitrite-nitrogen (NO₂^?-N) and eventually nitrate-nitrogen (NO₃^?-N). A central goal of the study was to identify the best aeration method and strategy for improving water quality in aquaculture ponds. We conducted an experiment with six tanks, each with a different aeration mode to simulate the behavior of aquaculture ponds. The results show that a 36 hr aeration interval (T_c = 36 hr: 36 hr) and no aeration resulted in high concentrations of NH₄⁺-N in the water column. Using a 12 hr interval time (T_c = 12 hr: 12 hr) resulted in higher NO₂^?-N and NO₃^?-N concentrations than any other aeration mode. Results from an 8 hr interval time (T_c = 8 hr: 8 hr) and 24 hr interval time (T_c = 24 hr: 24 hr) were comparable with those of continuous aeration, and had the benefit of being in use for only half of the time, consequently reducing energy consumption.     

Mechanochemical synthesis of MAPbBr3/carbon sphere composites for boosting carrier-involved superoxide species

Lead halide perovskites MAPbX₃ (MA = CH₃NH₃ or Cs; X = I, Br, Cl) are well considered to be potential candidates for photocatalytic reaction due to its excellent photoelectrical properties, but they still suffer from the low charge separation efficiency and slow catalytic reaction dynamics. To tackle the drawbacks, herein, MAPbBr₃/carbon sphere (CS) composite photocatalysts using glucose as the carbon source were elaborately designed and fabricated via a dry mechanochemical grinding process. The interfacial interaction Pb-O-C chemical bonds were constructed between MAPbBr₃ and the carbon sphere surface containing organic functional groups. By optimizing the content of CSs, the enhanced photocatalytic degradation kinetic rate of Malachite Green (MG) pollutants (92% within 20 min) for MAPbBr₃/CS_x (x = 17 wt.%) is about 3.6-fold of that for pristine MAPbBr₃, which is attributed to the corporative adsorption and enhanced carrier transportation and separation of MAPbBr₃/CS_x. Furthermore, the possible degradation mechanism was proposed on basis of the electrochemical, mass spectrometry and optical characterization results. Owing to the robust interfacial interaction, effective electron extraction rate (k_et = 4.6 × 10⁷ sec^?1) from MAPbBr₃ to CS can be established, which driven oxygen activation where superoxide radicals (?O₂^?) played an important role in MG degradation. It is expected that mechanochemistry strategy may provide a new route to design efficient lead halide perovskite-carbon or metal oxide or sulfide composite photocatalysts.     

Measurement of heterogeneous uptake of NO2 on inorganic particles, sea water and urban grime

Heterogeneous reactions of NO₂ on different surfaces play an important role in atmospheric NO_x removal and HONO formation, having profound impacts on photochemistry in polluted urban areas. Previous studies have suggested that the NO₂ uptake on the ground or aerosol surfaces could be a dominant source for elevated HONO during the daytime. However, the uptake behavior of NO₂ varies with different surfaces, and different uptake coefficients were used or derived in different studies. To obtain a more holistic picture of heterogeneous NO₂ uptake on different surfaces, a series of laboratory experiments using different flow tube reactors was conducted, and the NO₂ uptake coefficients (γ) were determined on inorganic particles, sea water and urban grime. The results showed that heterogeneous reactions on those surfaces were generally weak in dark conditions, with the measured γ varied from <10^?8 to 3.2 × 10^?7 under different humidity. A photo-enhanced uptake of NO₂ on urban grime was observed, with the obvious formation of HONO and NO from the heterogeneous reaction. The photo-enhanced γ was measured to be 1.9 × 10^?6 at 5% relative humidity (RH) and 5.8 × 10^?6 at 70% RH on urban grime, showing a positive RH dependence for both NO₂ uptake and HONO formation. The results demonstrate an important role of urban grime in the daytime NO₂-to-HONO conversion, and could be helpful to explain the unknown daytime HONO source in the polluted urban area.     

Study on the reaction of 3-methyl-2-butenal and 3-methylbutanal with Cl atoms: kinetics and reaction mechanism

The reaction of Cl atoms with two C₅ aldehydes (3-methyl-2-butenal and 3-methylbutanal) were investigated by proton-transfer-reaction mass spectrum (PTR-MS) using smog chamber at 298 ± 1 K and 760 Torr. A relative rate method was used to determine the rate constants of the title reactions with m-xylene and trans-2-butene as reference compounds: (3.04 ± 0.18)  ×  10⁻¹⁰ and (2.07 ± 0.14)  ×  10⁻¹⁰ cm³/(molecule⋅sec) for 3-methyl-2-butenal and 3-methylbutanal, respectively. Additionally, the gas-phase products were also identified by PTR-MS, and the possible reaction mechanisms were proposed basing on the identified products. The detected gas-phase products are similar for two C₅ aldehydes reactions, mainly including small molecules of aldehydes, ketones and chlorinated aldehyde compounds. The atmospheric lifetimes (τ) calculated for 3-methyl-2-butenal (τ = 7.0 hr, marine boundary layer (MBL)) and 3-methylbutanal (τ = 10.3 hr, MBL) according to the obtained rate constants. The results indicate that Cl atoms at MBL are competitive with OH radicals for the degradation contribution of C₅ aldehyde compounds.     

Formation mechanisms of nitrous acid (HONO) during the haze and non-haze periods in Beijing, China

As an important precursor of hydroxyl radical (OH), nitrous acid (HONO) plays a significant role in atmospheric chemistry. Here, an observation of HONO and relevant air pollutants in an urban site of Beijing from 14 to 28 April, 2017 was performed. Two distinct peaks of HONO concentrations occurred during the observation. In contrast, the concentration of particulate matter in the first period (period Ⅰ) was significantly higher than that in the second period (period Ⅱ). Comparing to HONO sources in the two periods, we found that the direct vehicle emission was an essential source of the ambient HONO during both periods at night, especially in period Ⅱ. The heterogeneous reaction of NO₂ was the dominant source in period Ⅰ, while the homogeneous reaction of NO with OH was more critical source at night in period Ⅱ. In the daytime, the heterogeneous reaction of NO₂ was a significant source and was confirmed by the good correlation coefficients (R²) between the unknown sources (P_unknown) with NO₂, PM_2.5, NO₂ × PM_2.5 in period Ⅰ. Moreover, when solar radiation and OH radicals were considered to explore unknown sources in the daytime, the enhanced correlation of P_unknown with photolysis rate of NO₂ and OH ($J_{{\mathrm{NO}}_2}$ × OH) were 0.93 in period Ⅰ, 0.95 in period Ⅱ. These excellent correlation coefficients suggested that the unknown sources released HONO highly related to the solar radiation and the variation of OH radicals.     

Measurement of tropospheric HO2 radical using fluorescence assay by gas expansion with low interferences

An instrument to detect atmospheric HO₂ radicals using fluorescence assay by gas expansion (FAGE) technique has been developed. HO₂ is measured by reaction with NO to form OH and subsequent detection of OH by laser-induced fluorescence at low pressure. The system performance has been improved by optimizing the expansion distance and pressure, the influence factors of HO₂ conversion efficiency are also studied. The interferences of RO₂ radicals were investigated by determining the conversion efficiency of RO₂ to OH during the measurement of HO₂. The dependence of the conversion of HO₂ on NO concentration was investigated, and low HO₂ conversion efficiency was selected to realize the ambient HO₂ measurement, where the conversion efficiency of RO₂ derived by propane, ethene, isoprene and methanol to OH has been reduced to less than 6% in the atmosphere. Furthermore, no significant interferences from PM_2.5 and NO were found in the ambient HO₂ measurement. The detection limits for HO₂ (S/N = 2) are estimated to 4.8 × 10⁵ cm^?3 and 1.1 × 10⁶ cm^?3 (${\rho }_{\mathrm{H}{\mathrm{O}}_2}$= 20%) under night and noon conditions, with 60 sec signal integration time. The instrument was successfully deployed during STORM-2018 field campaign at Shenzhen graduate school of Peking University. The concentration of atmospheric HOx radical and the good correlation of OH with j(O¹D) was obtained here. The diurnal variation of HOx concentration shows that the OH maximum concentration of those days is about 5.3 × 10⁶ cm^?3 appearing around 12:00, while the HO₂ maximum concentration is about 4.2 × 10⁸ cm^?3 appearing around 13:30.     

Humidity and PM2.5 composition determine atmospheric light extinction in the arid region of northwest China

Atmospheric visibility can directly reflect the air quality. In this study, we measured water-soluble ions (WSIs), organic and element carbon (OC and EC) in PM_2.5 from September 2017 to August 2018 in Urumqi, NW China. The results show that SO₄^2?, NO₃^? and NH₄⁺ were the major WSIs, together accounting for 7.32%–84.12% of PM_2.5 mass. Total carbon (TC=OC+EC) accounted for 12.12% of PM_2.5 mass on average. And OC/EC > 2 indicated the formation of secondary organic carbon (SOC). The levels of SO₄^2?, NO₃^? and NH₄⁺ in low visibility days were much higher than those in high visibility days. Relative humidity (RH) played a key role in affecting visibility. The extinction coefficient (b_ext) that estimated via Koschmieder formula with visibility was the highest in winter (1441.05 ± 739.95 Mm^?1), and the lowest in summer (128.58 ± 58.00 Mm^?1). The b_ext that estimated via IMPROVE formula with PM_2.5 chemical component was mainly contributed by (NH₄)₂SO₄ and NH₄NO₃. The b_ext values calculated by both approaches presented a good correlation with each other (R² = 0.87). Multiple linear regression (MLR) method was further employed to reconstruct the empirical regression model of visibility as a function of PM_2.5 chemical components, NO₂ and RH. The results of source apportionment by Positive Matrix Factorization (PMF) model showed that residential coal combustion and vehicle emissions were the major sources of b_ext.     

Wall losses of oxygenated volatile organic compounds from oxidation of toluene: Effects of chamber volume and relative humidity

Vapor wall losses can affect the yields of secondary organic aerosol. The effects of surface-to-volume (S/V) ratio and relative humidity (RH) on the vapor-wall interactions were investigated in this study. The oxygenated volatile organic compounds (OVOCs) were generated from toluene-H₂O₂ irradiations. The average gas to wall loss rate constant (k_gw) of OVOCs in a 400 L reactor (S/V = 7.5 m⁻¹) is 2.47 (2.41 under humid conditions) times higher than that in a 5000 L reactor (S/V = 3.6 m⁻¹) under dry conditions. In contrast, the average desorption rate constant (k_wg) of OVOCs in 400 L reactor is only 1.37 (1.20 under humid conditions) times higher than that in 5000 L reactor under dry conditions. It shows that increasing the S/V ratio can promote the wall losses of OVOCs. By contrast, the RH effect on k_gw is not prominent. The average k_gw value under humid conditions is almost the same as under dry conditions in the 400 L (5000 L) reactor. However, increasing RH can decrease the desorption rates. The average k_wg value under dry conditions is 1.45 (1.27) times higher than that under humid conditions in the 400 L (5000 L) reactor. The high RH can increase the partitioning equilibrium timescales and enhance the wall losses of OVOCs.     

Comparison of UV and UV-LED activated sodium percarbonate for the degradation of O-desmethylvenlafaxine

As an active metabolite of venlafaxine and emerging antidepressant, O-desmethylvenlafaxine (ODVEN) was widely detected in different water bodies, which caused potential harm to human health and environmental safety. In this study, the comparative work on the ODVEN degradation by UV (254 nm) and UV-LED (275 nm) activated sodium percarbonate (SPC) systems was systematically performed. The higher removal rate of ODVEN can be achieved under UV-LED direct photolysis (14.99%) than UV direct photolysis (4.57%) due to the higher values of photolysis coefficient at the wavelength 275 nm. Significant synergistic effects were observed in the UV/SPC (80.38%) and UV-LED/SPC (53.57%) systems and the former exhibited better performance for the elimination of ODVEN. The degradation of ODVEN all followed the pseudo-first-order kinetics well in these processes, and the pseudo-first-order rate constant (k_obs) increased with increasing SPC concentration. Radicals quenching experiments demonstrated that both ·OH and CO₃·⁻ were involved in the degradation of ODVEN and the second-order rate constant of ODVEN with CO₃·⁻ (1.58 × 10⁸ (mol/L)⁻¹ sec⁻¹) was reported for the first time based on competitive kinetic method. The introduction of HA, Cl⁻, NO₃⁻ and HCO₃⁻ inhibited the ODVEN degradation to varying degrees in the both processes. According to quantum chemical calculation, radical addition at the ortho-position of the phenolic hydroxyl group was confirmed to be the main reaction pathways for the oxidation of ODVEN by ·OH. In addition, the oxidation of ODVEN may involve the demethylation, H-abstraction, OH-addition and C-N bond cleavage. Eventually, the UV-LED/SPC process was considered to be more cost-effective compared to the UV/SPC process, although the UV/SPC process possessed a higher removal rate of ODVEN.     

MAX-DOAS observation in the midlatitude marine boundary layer: Influences of typhoon forced air mass

As a passive remote sensing technique, MAX-DOAS method was widely used to investigate the vertical profiles of aerosol and trace gases in the lower troposphere. However, the measurements for midlatitude marine boundary layer are rarely reported, especially during the storm weather system. In this study, the MAX-DOAS was used to retrieve the aerosol, HCHO and NO₂ vertical distribution at Huaniao Island of East China Sea in summer 2018, during which a strong tropical cyclone developed and passed through the measurement site. The observed aerosol optical depth (AOD), HCHO- and NO_2-VCDs (Vertical Column Density) were in the range of 0.19-0.97, (2.57-12.27) × 10¹⁵ molec/cm², (1.24-4.71) × 10¹⁵ molec/cm², which is much higher than remote ocean area due to the short distance to continent. The vertically resolved aerosol extinction coefficient (AEC), HCHO and NO₂ presented the decline trend with the increase of height. After the typhoon passing through, the distribution of high levels of aerosol and HCHO stretched to about 1 km and the abundances of the bottom layer were found as double higher than before, reaching 0.51 km⁻¹ and 2.44 ppbv, while NO₂ was still constrained within about 300 m with 2.59 ppbv in the bottom layer. The impacts of typhoon process forced air mass were also observed at the suburban site in Shanghai in view of both the aerosol extinction and chemical components. The different changes on air quality associated with typhoon and its mechanism in two different environments: coastal island and coastal city are worthy of further investigation as it frequent occurred in East Asia during summer and fall.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.