Treatability studies of naphthalene in soil,water and air with persulfate activated by iron(Ⅱ)

Chemical oxidation was applied to an artificially contaminated soil with naphthalene (NAP). Evaluation of NAP distribution and mass reduction in soil, water and air phases was carried out through mass balance. Evaluation of NAP distribution and mass reduction in soil, water and air phases was carried out through mass balance. The importance of the air phase analysis was emphasized by demonstrating how NAP behaves in a sealed system over a 4 hr reaction period. Design of Experiments method was applied to the following variables: sodium persulfate concentration [SP], ferrous sulfate concentration [FeSO₄], and pH. The system operated with a prefixed solid to liquid ratio of 1:2. The following conditions resulted in optimum NAP removal [SP] = 18.37 g/L, [FeSO₄] = 4.25 g/L and pH = 3.00. At the end of the 4 hr reaction, 62% of NAP was degraded. In the soil phase, the chemical oxidation reduced the NAP concentration thus achieving levels which comply with Brazilian and USA environmental legislations. Besides the NAP partitioning view, the monitoring of each phase allowed the variabilities assessment over the process, refining the knowledge of mass reduction. Based on NAP distribution in the system, this study demonstrates the importance of evaluating the presence of semi-volatile and volatile organic compounds in the air phase during remediation, so that there is greater control of the system as to the distribution and presence of the contaminant in the environment. The results highlight the importance of treating the contaminant in all its phases at the contaminated site.     

Effects of SO2 and H2O on low-temperature NO conversion over F-V2O5-WO3/TiO2 catalysts

F-V_2 O_5-WO3/Ti02 catalysts were prepared by the impregnation method.As the content of F ions increased from 0.00 to 0.35 wt.%,the NO conversion of F-V_2 O_5-WO_3/TiO_2 catalysts initially increased and then decreased.The 0.2 F-V_2 O_5-WO_3/TiO_2 catalyst(0.2 wt.% F ion)exhibited the best denitration(De-NOx) performance,with more than 95% NO conversion in the temperature range 160-360℃,and 99.0% N2 selectivity between 110 and 280℃.The addition of an appropriate amount of F ions eroded the surface morphology of the catalyst and reduced its grain size,thus enhancing the NO conversion at low temperature as well as the sulfur and water resistance of the V_2 O_5-WO3/Ti02 catalyst.After selective catalytic reduction(SCR) reaction in a gas flow containing SO_2 and H_2 O,the number of NH3 adsorption sites,active component content,specific surface area and pore volume decreased to different degrees.Ammonium sulfate species deposited on the catalyst surface,which blocked part of the active sites and reduced the NO conversion performance of the catalyst.On-line thermal regeneration could not completely recover the catalyst activity,although it prolonged the cumulative life of the catalyst.In addition,a mechanism for the effects of S02 and H_2 O on catalyst NO conversion was proposed.     

Density functional theory (DFT) studies of vanadium-titanium based selective catalytic reduction (SCR) catalysts

Based on density functional theory (DFT) and basic structure models, the chemical reactions on the surface of vanadium-titanium based selective catalytic reduction (SCR) denitrification catalysts were summarized. Reasonable structural models (non-periodic and periodic structural models) are the basis of density functional calculations. A periodic structure model was more appropriate to represent the catalyst surface, and its theoretical calculation results were more comparable with the experimental results than a non-periodic model. It is generally believed that the SCR mechanism where NH₃ and NO react to produce N₂ and H₂O follows an Eley-Rideal type mechanism. NH₂NO was found to be an important intermediate in the SCR reaction, with multiple production routes. Simultaneously, the effects of H₂O, SO₂ and metal on SCR catalysts were also summarized.     

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

Methylglyoxal(CH_3COCHO,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 SO_2.Particle size distribution was measured by using a scanning mobility particle sizer(SMPS) and the results showed that the addition of SO_2 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 SO_2.In addition,the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO_2 and MG/OH/NOx/SO_2 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 SO_2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.     

The study of biological activity of transformation products of diclofenac and its interaction with chlorogenic acid

In the present work we compared the biological activity of DCF, 4′-OHDCF and 5-OHDCF as molecules of most biodegradation pathways of DCF and selected transformation products (2-hydroxyphenylacetic acid; 2,5-dihydroxyphenylacetic acid and 2,6-dichloroaniline) which are produced during AOPs, such as ozonation and UV/H₂O₂. We also examined the interaction of DCF with chlorogenic acid (CGA). CGA is commonly used in human diet and entering the environment along with waste mainly from the processing and brewing of coffee and it can be toxic for microorganisms included in activated sludge. In the present experiment the evaluation of following parameters was performed: E. coli K-12 cells viability, growth inhibition of E. coli K-12 culture, LC₅₀ and mortality of Chironomus aprilinus, genotoxicity, sodA promoter induction and ROS generation. In addition the reactivity of E. coli SM recA:luxCDABE biosensor strain in wastewater matrices was measured. The results showed the influence of DCF, 4′-OHDCF and 5-OHDCF on E. coli K-12 cells viability and bacteria growth, comparable to AOPs by-products. The highest toxicity was observed for selected, tested AOPs by-products, in comparison to the DCF, 4′-OHDCF and 5-OHDCF. Genotoxicity assay indicated that 2,6-dichloroaniline (AOPs by-product) had the highest toxic effect. The oxidative stress assays revealed that the highest level of ROS generation and sodA promoter induction were obtained for DCF, 4′-OHDCF and 5-OHDCF, compared to other tested compounds. We have also found that there is an interaction between chlorogenic acid and DCF, which resulted in increased toxicity of the mixture of the both compounds to E. coli K-12, comparable to parent chemicals. The strongest response of E. coli SM biosensor strain with recA:luxCDABE genetic construct in filtered treated wastewaters, comparable to control sample was noticed. It indicates, that E. coli SM recA:luxCDABE biosensor strains is a good tool for bacteria monitoring in wastewater environment. Due to toxicity and biological activity of tested DCF transformation products, there is a need to use additional wastewater treatment systems for wastewater contaminated with pharmaceutical residues.     

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N₂, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N₂ selectivity was impacted by the Brønsted acidity and the isolated Cu²⁺ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.     

郑州市VOCs组分排放清单及其臭氧生成潜势

基于人为源挥发性有机物（VOCs）活动水平统计和源成分谱梳理,采用排放因子法,建立了郑州市2016年VOCs组分排放清单,评估了各类源臭氧生成潜势（OFP）.结果表明,2016年郑州市人为源VOCs排放总量为96215.3 t,排放量最高的是道路移动源（29.7%）,其次是有机溶剂使用源（28.1%）;排放量最高的组分是烷烃（29.8%）,其次是芳香烃（29.0%）.郑州市人为源VOCs的OFP为341291.0 t,贡献最高的排放源是道路移动源（30.5%）,其次是溶剂使用源（28.8%）,其中轻型汽油车、内墙涂料使用、机动车表面涂层、加油站装卸油和非金属矿物制造是OFP的主要次级排放源,也是郑州市降低臭氧污染时需重点管控的VOCs排放源.对于VOCs种类而言,贡献较高的是芳香烃（42.8%）,其次是烯烃（38.9%）,未来应加强对间/对-二甲苯、丙烯和乙烯等物种排放来源的控制.     

德州市夏季臭氧敏感性特征及减排方案

近年来德州市臭氧污染频发,2018年夏季（6~8月）,德州市发生了严重臭氧污染事件,臭氧日最大8 h浓度值超标天数达60 d,超标率65%,3个月平均值为176 μg ·m^-3,最高达262 μg ·m^-3.本研究利用WRF-CAMx耦合的HDDM模块,分析期间德州臭氧敏感性特征及减排方案.结果表明,在空间上,德州市中心城区为VOCs控制区,而郊区为NO_x与VOCs协同控制区.在时间上,VOCs敏感值每日为正值,但dO₃_V₅₀在6月（城区18.7 μg ·m^-3,郊区19.7 μg ·m^-3）和8月（城区15.3 μg ·m^-3,郊区16.4 μg ·m^-3）高于7月（城区13.0 μg ·m^-3,郊区11.8 μg ·m^-3）,NO_x敏感值城区呈正负交错,郊区大部分为正值,并与VOCs敏感值接近.对于城区减排方案应考虑以仅VOCs削减为优先,而郊区由于NO_x和VOCs对臭氧减排效果相当,建议以NO_x：VOCs=1：1为优.     

利用HYSPLIT模型研究珠三角地区VOCs时空分布特征

于2016年在中国广东大气超级监测站,开展4个季节的VOCs长时间观测,共获得2142组有效数据,并利用HYSPLIT模型分析珠三角地区VOCs时空分布特征.结果表明,各类VOCs混合比和化学反应活性具有明显的季节变化特点.观测期间,VOCs平均浓度为（18.523±20.978）×10^-9,其中,低碳烯烃和苯系物二者混合比之和仅占46%,但贡献了85%的·OH消耗速率（L_OH）、82%的臭氧生成潜势（OFP）和97%的二次气溶胶生成潜势（SOAFP）.观测站点主要受来自北部内陆地区气团（1#）、西部内陆地区气团（2#）、台湾海峡南端气团（3#）以及南部海洋地区气团（4#）的影响.1#气团中炔烃和苯系物的混合比占比最高,分别达到10%、37%,而3#气团中低碳烷烃的浓度水平最高,达到（8.437±5.561）×10^-9.通过估算气团中VOCs的化学反应活性,可以发现,1#气团的VOCs化学反应活性最强,其对O₃和SOA的生成贡献最高.1#、2#、3#和4#气团中VOCs的化学反应活性主要由苯系物和低碳烯烃贡献.     

CeO2形貌结构对催化湿式空气氧化苯酚性能的影响

采用水热法、沉淀法和溶胶凝胶法制备了3种不同形貌的CeO₂催化材料,并将其用于湿式空气氧化苯酚水溶液过程中,探讨了CeO₂形貌结构对催化湿式氧化苯酚水溶液性能的影响.采用扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线衍射（XRD）、程序升温还原（TPR）等手段对CeO₂催化材料进行了表征.结果表明,水热法制备的CeO₂催化材料表现出较好催化性能,主要原因是水热法合成的CeO₂呈现交错的纳米棒状结构,主要暴露（220）晶面,且沿着（220）晶向生长.在反应温度为200℃、空气压力为2MPa、苯酚初始浓度500mg/L的条件下,最终（240min）COD的去除率为95.5%.