Decomposition of trifluoromethane in a dielectric barrier discharge non-thermal plasma reactor

The decomposition of trifluoromethane (CHF₃) was carried out using non-thermal plasma generated in a dielectric barrier discharge (DBD) reactor. The effects of reactor temperature, electric power, initial concentration and oxygen content were examined. The DBD reactor was able to completely destroy CHF₃ with alumina beads as a packing material. The decomposition efficiency increased with increasing electric power and reactor temperature. The destruction of CHF₃ gradually increased with the addition of O₂ up to 2%, but further increase in the oxygen content led to a decrease in the decomposition efficiency. The degradation pathways were explained with the identified by-products. The main by-products from CHF₃ were found to be COF₂, CF₄, CO₂ and CO although the COF₂ and CF₄ disappeared when the plasma were combined with alumina catalyst.     

Volatile organic compounds concentration profiles and control strategy in container manufacturing industry: Case studies in China

Volatile organic compounds (VOCs), important precursors of ozone (O₃) and fine particulate matter (PM_2.5), are the key to curb the momentum of O₃ growth and further reducing PM_2.5 in China. Container manufacturing industry is one of the major VOC emitters, and more than 96% containers of the world are produced in China, with the annual usage of coatings of over 200,000 tons in recent years. This is the first research on the emission characteristics of VOCs in Chinese container manufacturing industry, including concentration and ozone formation potential (OFP) of each species. The result shows that the largest amounts of VOCs are emitted during the pretreatment process, followed by the paint mixing process and primer painting process, and finally other sprays process. The average VOC concentrations in the workshops, the exhausts before treatment and the exhausts after treatment are ranging from 82.67–797.46 , 170–1,812.65 , 66.20–349.63 mg/m³, respectively. Benzenes, alcohols and ethers are main species, which contribute more than 90% OFP together. Based on the emission characteristics of VOCs and the technical feasibility, it is recommended to set the emission limit in standard of benzene to 1.0 mg/m³, toluene to 10 mg/m³, xylene to 20 mg/m³, benzenes to 40 mg/m³, alcohols and ethers to 50 mg/m³, and VOCs to 100 mg/m³. The study reports the industry emission characteristics and discusses the standard limits, which is a powerful support to promote VOCs emission reduction, and to promote the coordinated control of PM_2.5 and O₃ pollution.     

Peroxymonosulfate decomposition by homogeneous and heterogeneous Co: Kinetics and application for the degradation of acetaminophen

Peroxymonosulfate (PMS) decomposition, hydroxyl radical (^?OH) generation, and acetaminophen (ACT) degradation by the Co/PMS system using homogeneous (dissolved cobalt) and heterogeneous (suspended Co₃O₄) cobalt were assessed. For the homogeneous process, >99% PMS decomposition was observed and 10 mmol/L of ^?OH generation was produced using 5 mmol/L of PMS and different dissolved cobalt concentrations after 30 min. A dissolved cobalt concentration of 0.2 mmol/L was used to achieve >99% ACT degradation using the homogeneous process. For the heterogeneous process, 60% PMS decomposition and negligible ^?OH generation were observed for 5 mmol/L of the initial PMS concentration using 0.1 and 0.2 g/L of Co₃O₄. Degradation of ACT greater than 80% was achieved for all experimental runs using 5 mmol/L of the initial PMS concentration independently of the initial Co₃O₄ load used. For the heterogeneous process, the best experimental conditions for ACT degradation were found to be 3 mmol/L of PMS and 0.2 g/L of Co₃O₄, for which >99% ACT degradation was achieved after 10 min. Because negligible ^?OH was produced by the Co₃O₄/PMS process, a second-order kinetic model was proposed for sulfur-based free radical production to allow fair comparison between homogeneous and heterogeneous processes. Using the kinetic data and the reaction by-products identified, a mechanistic pathway for ACT degradation is suggested.     

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process

Characteristics of toluene decomposition and formation of nitrogen oxide (NO_x) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al₂O₃/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO₂ selectivity. In addition,NO_xwas suppressedwith the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NO_x suppression. The MnOx catalyst exhibited the lowest concentration of O₃ and highest CO₂ selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.     

N-doped mesoporous alumina for adsorption of carbon dioxide

N-doped mesoporous alumina has been synthesized using chitosan as the biopolymer template. The adsorbent has been thoroughly investigated for the adsorption of CO₂ from a simulated flue gas stream (15% CO₂ balanced with N₂) and compared with commercially available mesoporous alumina procured from SASOL, Germany. CO₂ adsorption was studied under different conditions of pre-treatment and adsorption temperature, inlet CO₂ concentration and in the presence of oxygen and moisture. The adsorption capacity was determined to be 29.4 mg CO₂/g of adsorbent at 55℃. This value was observed to be 4 times higher in comparison to that of commercial mesoporous alumina at a temperature of 55℃. Basicity of alumina surface coupled with the presence of nitrogen in template in synthesized sample is responsible for this enhanced CO₂ adsorption. Adsorption capacity for CO₂ was retained in the presence of oxygen; however moisture had a deteriorating effect on the adsorption capacity reducing it to nearly half the value.     

Seasonal variation characteristics of hydroxyl radical pollution and its potential formation mechanism during the daytime in Lanzhou

Hydroxyl free radicals (OH radicals) play the main role in atmospheric chemistry and their involving reactions are the dominant rate determining step in the formation of secondary fine particulate matter and in the removal of air pollutants from the atmosphere. In this paper, we studied the seasonal variation characteristics of OH radicals during the daytime in Lanzhou and explored the potential formation mechanism of high concentration OH radicals. We found that the OH radicals in four seasons was 2.7 × 10⁶, 2.6 × 10⁶, 3.1 × 10⁶, and 2.2 × 10⁶ cm^?3, respectively. Since the rainfall was concentrated in summer, the wet deposition had a significant effect on removing OH radicals. Among the four pollutants (including ozone (O₃), volatile organic compounds (VOCs), nitrogen dioxide (NO₂) and fine particulate matter (PM_2.5)), the variation of OH radicals were closely related to ozone concentration especially in spring and summer. In autumn, the correlation between PM_2.5 and OH radicals were the closest among the observing pollutants and its formation mechanism was different conventional regeneration pathway. In Event 1, high concentration of ozone was the main source of OH radicals; under the high humidity condition, except for ozone, the multiple factors including VOCs, NO₂ and PM_2.5 interplayed and leaded to the Event 2.     

Investigations on removal of SO2 from flue gas by aerosol formation in pulsed corona discharge process

The removal of SO₂ from flue gas by pulsed corona discharge in presence of ammonia was experimentally investigated. The results showed that the SO₂ removal mainly depends on thermal reaction of SO₂ with NH₃ and enhancements of 0%—25% by pulsed corona discharge in the range of the specific energy 0—5 Wh/Nm³. The aerosol mass concentration, mainly composed of ammonium sulfate, increased with specific energy dissipated into the reactor. With an initial concentration of 2000—2100 ppmv SO₂ and energy consumption of 3 Wh/Nm³, when a stoichiometric amount of ammonia is injected, the removal efficiency of SO₂ and percentage of ammonium sulfates in reaction products are all ≥80%. The collection efficiency of the reactor for aerosol is about 74% at a flue gas temperature of 60 to 65℃ and a water vapor content of 9% to 11% volume.     

Characteristics of volatile organic compounds, NO2, and effects on ozone formation at a site with high ozone level in Chengdu

Chengdu is a megacity in the southwest of China with high ozone (O₃) mixing ratio. Observation of volatile organic compounds (VOCs), NO₂ and O₃ with high temporal resolution was conducted in Chengdu to investigate the chemical processes and causes of high O₃ levels. The hourly mixing ratios of VOCs, NO₂, and O₃ were monitored by an online system from 28 August to 7 October, 2016. According to meteorological conditions, Chengdu, with relative warm weather and low wind speed, is favorable to O₃ formation. Part of the O₃ in Chengdu may be transported from the downtown area. In O₃ episodes, the average mixing ratios of NO₂ and O₃ were 20.20?ppbv and 47.95?ppbv, respectively. In non-O₃ episodes, the average mixing ratios of NO₂ and O₃ were 16.38?ppbv and 35.15?ppbv, respectively. The average mixing ratio of total VOCs (TVOCs) was 40.29?ppbv in non-O₃ episodes, which was lower than that in O₃ episodes (53.19?ppbv). Alkenes comprised 51.7% of the total O₃ formation potential (OFP) in Chengdu, followed by aromatics which accounted for 24.2%. Ethylene, trans-pentene, propene, and BTEX (benzene, ethylbenzene, toluene, m/p-xylene, o-xylene) were also major contributors to the OFP in Chengdu. In O₃ episodes, intensive secondary formations were observed during the campaign. Oxygenated VOCs (OVOCs), such as acetone, Methylethylketone (MEK), and Methylvinylketone (MVK) were abundant. Isoprene rapidly converted to MVK and Methacrolein (MACR) during O₃ episodes. Acetone was mainly the oxidant of C3-C5 hydrocarbons.     

Photocatalytic degradation of 4-tert-octylphenol in a spiral photoreactor system

A spiral photoreactor system (SPS) was developed for the degradation of 4-tert-octylphenol (4-t-OP) in aqueous phase. 4-t-OP was previously considered as a endocrine disrupting compound frequently present in water. The direct photodegradation reaction caused by the SPS was found to accord with the characteristic of apparent first-order reaction with reaction rate constantk= 4.8 × 10^-2 min^-1. However, the direct photodegradation reaction could not make the 4-t-OP mineralized. The photodegradation efficiency increased from 88% to 91.2% in 45 min irradiation period after the internal surface of SPS was sintered with TiO₂ thin film as catalyst. Catalyst concentration, number of catalyst coating layers and initial concentration of 4-t-OP were proven to be the factors affecting the photocatalytic degradation performance of the SPS on aqueous 4-t-OP. The degradation mechanism was investigated and the byproducts were analyzed using total organic carbon analyzer (TOC) and LC-MS. The possible chemical structures of the products were suggested. SPS with single layer of TiO₂ prepared by sintering 13.6% of TiO₂ precursor was proven to be more efficient than most of previous systems for removal of 4-t-OP from aqueous phase. 28.3% of the 4-t-OP was mineralized in 45 min according to the decreased amount of TOC value.     

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.     

Concurrent catalytic removal of typical volatile organic compound mixtures over Au-Pd/α-MnO2 nanotubes

α-MnO_2 nanotubes and their supported Au-Pd alloy nanocatalysts were prepared using hydrothermal and polyvinyl alcohol-protected reduction methods, respectively. Their catalytic activity for the oxidation of toluene/m-xylene, acetone/ethyl acetate, acetone/m-xylene and ethyl acetate/m-xylene mixtures was evaluated. It was found that the interaction between Au-Pd alloy nanoparticles and α-MnO_2 nanotubes significantly improved the reactivity of lattice oxygen, and the 0.91 wt.% Au0.48 Pd/α-MnO_2 nanotube catalyst outperformed the α-MnO_2 nanotube catalyst in the oxidation of toluene, m-xylene, ethyl acetate and acetone. Over the0.91 wt.% Au0.48 Pd/α-MnO_2 nanotube catalyst,(i) toluene oxidation was greatly inhibited in the toluene/m-xylene mixture, while m-xylene oxidation was not influenced;(ii) acetone and ethyl acetate oxidation suffered a minor impact in the acetone/ethyl acetate mixture; and(iii) m-xylene oxidation was enhanced whereas the oxidation of the oxygenated VOCs(volatile organic compounds) was suppressed in the acetone/m-xylene or ethyl acetate/m-xylene mixtures. The competitive adsorption of these typical VOCs on the catalyst surface induced an inhibitive effect on their oxidation, and increasing the temperature favored the oxidation of the VOCs. The mixed VOCs could be completely oxidized into CO_2 and H_2 O below 320°C at a space velocity of 40,000 m L/(g·hr). The 0.91 wt.% Au0.48 Pd/α-MnO_2 nanotube catalyst exhibited high catalytic stability as well as good tolerance to water vapor and CO_2 in the oxidation of the VOC mixtures. Thus, the α-MnO_2 nanotube-supported noble metal alloy catalysts hold promise for the efficient elimination of VOC mixtures.     

An assessment of how distance and diesel oxidation catalyst will impact thermal decomposition behaviors of particles

Decomposition mass loss and pyrolysis products analyses of particles sampled at various locations along the tailpipe of a Euro-IV diesel engine were performed using a thermogravimetry in conjunction with Fourier transformation infrared spectrometry-mass spectrum. Diesel particles were collected at the same location with and without diesel oxidation catalyst (DOC) mounted on the test engine separately. The three poles in thermal gravity-differential thermal gravity images suggested that the decomposition process of diesel particles could be divided into three stages which correspond to the decompositions of lower boiling substances, higher boiling substances and soot respectively. It is noticed that no matter whether DOC was mounted or not, the further the particles were sampled away from the engine block, the lower the peak temperatures and the heavier the mass losses within the first two stages, which indicated that the soluble organic fraction in the particle samples increased and therefore lowering the activation energy of thermal decomposition. Hydroxyl, ammonia, C_xH_y fragments, benzene, toluene, and phenol were found to be the primary products of particle decomposition, which didn't change with the location of particle sample point. The employment of DOC increased the activation energy for particle oxidation and resulted in a higher peak temperature and lower mass loss within the first-stage. Moreover, the CO stretching bands of aldehyde and ketone at 1771 cm^?1 was only detected without a DOC, while the NO₂ peak at 1634 cm^?1 was solely noticed with the presence of DOC. Compared to the first-stage pyrolysis products, more polycyclic aromatic hydrocarbons and less C_xH_y fragments were seen in the second-stage.     

Study on the photoreaction of 1-(2-chlorohenzoyl)-3-(4-chlorophenyl 1 urea in methanol

A photoreaction of 1-(2-chlorobenzoyl)-3-(4-chlorophenyl)urea(CCU)m methanol was studied．Rate constants of its reactions，which are found both of the first order，in methanol solution saturated with N₂ or O₂ upon irradiation with xenon lamp,are determined to be O,118 and O.129 h^-1，respectively．Its half life changes from 5.37 to 4.42 h when the light intensity is changed from O.50 to O.62 cal/cm²．min．The main photoproducts identified arc 2-chloro-benzamide．N-phenyl methylearbamate，N-(4-chlorophenyl) methylcarbamate，4-chlorophenyl urea and others．Meanwhile．the mechanism of the photochemical reaction of this compound in methanol was discussed．     

Mechanisms of photochemical release of dissolved organic matter and iron from resuspended sediments

Photochemical reactions can alter the transformation of sedimentary organic matter into dissolved organic matter (DOM) and affect its ultimate fate in water ecosystems. In the present study, the photorelease of DOM and Fe from resuspended lake sediments was investigated under different O₂ and NO₃^? concentration conditions to study the mechanisms of DOM and Fe photorelease. The amount of photoreleased Fe, which ranged from 0.22 to 0.70 μmol/L, was significantly linearly correlated with the amount of photoreleased DOM. O₂ and NO₃^? could promote the photochemical release of DOM and Fe, especially during the initial 4 h irradiation. In general, the order of the photorelease rates of DOM and Fe under different conditions was as follows: NO₃^?/aerobic > aerobic ≈ NO₃^?/anaerobic > anaerobic. The photorelease rates of DOM and Fe were higher for the initial 4 hr irradiation than these for the subsequent 8 hr irradiation. The photorelease of DOM and Fe is thought to proceed via direct photodissolution and indirect processes. The relative contributions of indirect processes (>60%) was much greater than that of direct photodissolution (<40%). The photoproduced H₂O₂ under aerobic and anaerobic conditions indicated that hydroxyl radicals (?OH) are involved in the photorelease of DOM. Using ?OH scavengers, it was found that 38.7%, 53.7%, and 77.6% of photoreleased DOM was attributed to ?OH under anaerobic, aerobic, and NO₃^?/aerobic conditions, respectively. Our findings provide insights for understanding the mechanisms and the important role of ?OH in the DOM and Fe photorelease from resuspended sediments.     

Decomposition of CF3CI by corona discharge

In this paper pulsed corona discharge is shown to be effective for the decomposition of CF₃Cl(Freon-13).The pressure of CF₃Cl was 2.67×10³Pa,after discharged for 2 min,39.5% of CF₃Cl was decomposed.The products were mainly CF₄,Cl₂ and CF₂Cl₂.The yield increased by adding O₂ or air.Under the same conditions,more than 94% decomposition yield was obtained if 5.32×10³Pa O₂ or air was added.The composition of products became CF₂O,Cl₂ and CF₄.While the partial pressure of O₂ or air reached 1 arm,the decomposition yield decreased to 54.5% and 48. 5% respectively.     

Comparative study of degradation of toluene and methyl isobutyl ketone (MIBK) in aqueous solution by pulsed corona discharge plasma

Effectiveness of pulsed power plasma for the degradation of two toxic volatile organic compounds (VOCs), toluene and methyl isobutyl ketone (MIBK), in aqueous solution was evaluated. The plasma degradation of MIBK has been studied for the first time. The influence of initial concentration of target compound, solution pH and scavengers on percentage degradation was evaluated. 100% removal of 200 mg/L of toluene and MIBK was achieved both in liquid and gaseous phases after 12 and 16 min of plasma treatment, respectively. The first order rate constant of toluene and MIBK degradation (for 200 mg/L each) was 0.421 and 0.319 min^?1 respectively when they were treated individually, and these values decreased slightly during degradation of their mixture. MIBK degradation was slower than toluene and it might be due to semi volatile and hydrophilic nature of MIBK. The effect of initial concentration of toluene and MIBK showed different degradation patterns. Highest degradation of both the compounds was obtained in neutral pH and in absence of scavengers. ?OH radical was the major reactive species involved in their degradation. Their degradation in real environmental matrices showed that removal reduced significantly in secondary effluent due to scavenging of reactive species by various ions and organic matter. The total number of degradation intermediates identified in case of toluene and MIBK was 11 and 14 respectively and formate was the one recalcitrant byproduct generated. The degradation pathway of toluene and MIBK involving reactions of reactive oxygen and nitrogen species and reductive species is proposed.     

Distribution of pollutants in Le An River

pH change，distribution of anions，metals and complexing capacity in riverwater along Le An River were studied during June，1987 to November，1989．A high so²₄concentration was found in whole river．particularly at Gukou．High metal concentrations were found in upstream of the river，Cu．Fe，Ni and Co mainly from Dexing Copper M ine；Cd and Pb from Jishui River．Heavy water quality pollution occurred in the river section from Gukou to Daicun in Dexing Mine A rea．Complexing capacity of Le An River was low as concentration organic ligands and a high metal concentration．     

Chemical characterization and source identification of PM2.5 in Luoyang after the clean air actions

Luoyang is a typical heavy industrial city in China, with a coal-dominated energy structure and serious air pollution. Following the implementation of the clean air actions, the physicochemical characteristics and sources of PM_2.5 have changed. A comprehensive study of PM_2.5 was conducted from October 16, 2019 to January 23, 2020 to evaluate the effectiveness of previous control measures and further to provide theory basis for more effective policies in the future. Results showed that the aerosol pollution in Luoyang in autumn and winter is still serious with the average concentration of 91.1 μg/m³, although a large reduction (46.9%) since 2014. With the contribution of nitrate increased from 12.5% to 25.1% and sulfate decreased from 16.7% to 11.2%, aerosol pollution has changed from sulfate-dominate to nitrate-dominate. High NO₃⁻/SO₄²⁻ ratio and the increasing of NO₃⁻/SO₄²⁻ ratio with the aggravation of pollution indicating vehicle exhaust playing an increasingly important role in PM_2.5 pollution in Luoyang, especially in the haze processes. Secondary inorganic ions contributed significantly to the enhancement of PM_2.5 during the pollution period. The high value of Cl⁻/Na⁺ and EC concentration indicate coal combustion in Luoyang is still serious. The top three contributor sources were secondary inorganic aerosols (33.3%), coal combustion (13.6%), and industrial emissions (13.4%). Close-range transport from the western and northeastern directions were more important factors in air pollution in Luoyang during the sampling period. It is necessary to strengthen the control of coal combustion and reduce vehicle emissions in future policies.     

Methane emission via sediment and water interface in the Bohai Sea, China

Sediment is recognized as the largest reservoir and source of methane (CH₄) in the ocean, especially in the shallow coastal areas. To date, few data of CH₄ concentration in sediment have been reported in the China shelf seas. In this study, we measured CH₄ concentration in sediment and overlying seawater columns, and conducted an incubation experiment in the Bohai Sea in May 2017. CH₄ concentration was found to be ranged from 3.075 to 1.795 μmol/L in sediment, which was 2 to 3 orders of magnitude higher than that in overlying seawater columns. The surface sediment was an important source of CH₄, while bottom seawater acted as its sink. Furthermore, the net emission rate via sediment water interface (SWI) was calculated as 2.45 μmol/(m²∙day) based on the incubation experiment at station 73, and the earthquake may enhance CH₄ release from sediment to seawater column in the eastern Bohai Sea.     

Sequential use of ultraviolet light and chlorine for reclaimed water disinfection

Several disinfection processes of ultraviolet (UV), chlorine or UV followed by chlorine were investigated in municipal wastewater according to the inactivation of Escherichia coli, Shigella dysenteriae and toxicity formation. The UV inactivation of the tested pathogenic bacteria was not affected by the quality of water. It was found that the inactivated bacteria were obviously reactivated after one day in dark. Fluorescent light irradiation increased the bacteria repair. The increase of UV dosage could cause more damage to bacteria to inhibit bacteria self-repair. No photoreactivation was detected when the UV dose was up to 80 mJ/cm² for E. coli DH5αup, and 23 mJ/cm² for S. dysenteriae. Nevertheless, sequential use of 8 mJ/cm² of UV and low concentration of chlorine (1.5 mg/L) could effectively inhibit the photoreactivation and inactivate E. coli below the detection limits within seven days. Compared to chlorination alone, the sequential disinfection decreased the genotoxicity of treated wastewater, especially for the sample with high NH₃-N concentration.