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.     

Plasmonic silver/silver oxide nanoparticles anchored bismuth vanadate as a novel visible-light ternary photocatalyst for degrading pharmaceutical micropollutants

The degradation of pharmaceutical micropollutants is an intensifying environmental problem and synthesis of efficient photocatalysts for this purpose is one of the foremost challenges worldwide. Therefore, this study was conducted to develop novel plasmonic Ag/Ag₂O/BiVO₄ nanocomposite photocatalysts by simple precipitation and thermal decomposition methods, which could exhibit higher photocatalytic activity for mineralized pharmaceutical micropollutants. Among the different treatments, the best performance was observed for the Ag/Ag₂O/BiVO₄ nanocomposites (5 wt.%; 10 min's visible light irradiation) which exhibited 6.57 times higher photodegradation rate than the pure BiVO₄. Further, the effects of different influencing factors on the photodegradation system of tetracycline hydrochloride (TC-HCl) were investigated and the feasibility for its practical application was explored through the specific light sources, water source and cycle experiments. The mechanistic study demonstrated that the photogenerated holes (h⁺), superoxide radicals (?O₂^?) and hydroxyl radicals (?OH) participated in TC-HCl removal process, which is different from the pure BiVO₄ reaction system. Hence, the present work can provide a new approach for the formation of novel plasmonic photocatalysts with high photoactivity and can act as effective practical application for environmental remediation.     

Algal toxicity induced by effluents from textile-dyeing wastewater treatment plants

This research aimed to evaluate the alga Scenedesmus obliquus toxicity induced by textiledyeing effluents(TDE).The toxicity indicator of TDE in alga at the physiological(algal growyth),biochemical(chlorophyll-a(Chl-a) synthesis and superoxide dismutase(SOD) activity) and structural(cell membrane integrity) level were investigated.Then we further study the relationship among toxicity indicators at physiological and biochemical level,and supplemented by research on algal biomacromolecules.According to the analysis of various endpoints of the alga,the general sensitivity sequence of toxicity endpoints of Scenedesmus obliquus was:SOD activity Chl-a synthesis algal growth.The stimulation rate of SOD activity increased from day 3(57.25%～83.02%) to day 6(57.25%～103.81%),and then decreased on day 15(-4.23%～-32.96%),which indicated that the antioxidant balance system of the algal cells was destroyed.The rate of Chl-a synthesis inhibition increased gradually,reaching19.70%～79.39% on day 15,while the rate of growth inhibition increased from day 3(-12.90%～10.16%) to day 15(-21.27%～72.46%).Moreover,the algal growth inhibition rate was positively correlated with the inhibition rate of SOD activity or Chl-a synthesis,with the correlation coefficients were 0.6713 and 0.5217,respectively.Algal cells would be stimulating to produce excessive reactive oxygen species,which would cause peroxidation in the cells,thereby destroying chloroplasts,inhibiting chlorophyll synthesis and reducing photosynthesis.With increasing exposure time,irreversible damage to algae can lead to death.This study is expected to enhance our understanding of the ecological risks through algal tests caused by TDE.     

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.     

Chemical characteristics of road dust PM2.5 fraction in oasis cities at the margin of Tarim Basin

In order to understand the compositions characteristics of particulate matter with aerodynamic diameter less than 2.5 μm (PM_2.5) fraction in road dust (RD_2.5) of oasis cities on the edge of Tarim Basin, 30 road dust (RD) samples were collected in Kashi, Cele, and Yutian in the spring, 2018, and RD_2.5 was collected using the resuspension approach. Eight water-soluble ions, 39 trace elements and 8 fractions of carbon-containing species in PM_2.5 were analyzed. Ca²⁺ and Ca were the most abundant ions and elements in RD_2.5 (7.1% and 9.5%). Cl^- in RD_2.5 was affected not only by attributed to saline-alkali soils in oasis cities of the Tarim Basin and dust from Taklimakan Desert but also by human activities. Moreover, the organic carbon/elemental carbon (OC/EC) ratio indicated that carbon components in RD_2.5 in Cele town mainly come from fossil fuel combustion, while those in Yutian and Kashi mainly come from biomass combustion. It is noteworthy that high Ca in RD_2.5 was seriously affected by anthropogenic emissions, and high Na and K contents in RD_2.5 could be derived from soil and desert dust. It was estimated that Cd, Tl, Sn and Cr were emitted from anthropogenic emissions using the enrichment factor. The coefficients of divergence (COD) result indicated that the influence of local emission on road dust emission is greater than that of long-distance transmission. This study is the first time to comprehensively analyze the chemical characteristics of road dust in oasis cities, and the results provides the sources of road dust at the margin of Tarim Basin.     

基于野外原位抽注试验和同位素技术的含水层反硝化速率研究

反硝化作用是地下水硝酸盐污染去除最重要的过程.由于水文地质条件和水文地球化学环境的复杂性和不确定性,精准测定含水层反硝化速率是反硝化过程的研究难点.选取潮白河冲洪积扇中部中国环境科学研究院地下水创新野外基地作为研究区,基于野外原位试验和15N同位素示踪法提出一种含水层反硝化速率的测定方法.该方法综合体现了研究区实际水文地质条件和水文地球化学环境对反硝化作用的影响,并充分考虑了硝酸盐在含水层中稀释弥散作用对计算结果的影响.结果表明:①潮白河冲洪积扇中部某地地下26~28 m处于还原环境,含水介质以粉细砂为主,ρ（NO₃-N）平均值为2.77 mg/L.②地下26~28 m反硝化速率在349.52~562.99 μg/（kg·d）（以N计,下同）之间,平均值为450.31 μg/（kg·d）.通过与研究区含水介质、采样深度和硝酸盐背景值相似的国内外案例对比研究,初步评估结果处于合理区间.③测试结果具有一定不确定性,主要来自忽略中间产物NO₂-和NO的计算方法、扰动采样方法、N₂O的操作规范程度及采样频率等方面.研究方法为测定含水层硝酸盐速率研究提供了新的思路,研究结果可为地下水中硝酸盐转化过程机理研究、地下水硝酸盐污染修复及风险管控提供关键的理论支撑数据.      

厦门市冬季PM2.5污染情境识别及其与气象条件的关系

为研究厦门市冬季不同PM_2.5污染情境与气象条件和气团轨迹路径特征的关系,结合PM_2.5观测数据,使用AGAGE（Advanced Global Atmospheric Gases Experiment）统计方法识别2014—2018年冬季厦门市PM_2.5观测值、基线值和污染值情境,通过气象数据统计和气团后向轨迹聚类对不同PM_2.5污染情境下气象条件和气团轨迹路径特征进行探究.结果表明:①厦门市冬季不同PM_2.5污染情境下,ρ（PM_2.5）及PM_2.5污染值情境时长占比均呈波动中下降的趋势,具体表现为冬季PM_2.5观测值、污染值和基线值情境下,ρ（PM_2.5）平均值分别从2014年的42.2、90.7、16.4 μg/m3降至2018年的26.3、56.9、8.8 μg/m3,冬季PM_2.5污染值情境时长占比从2014年的10.2%降至2018年的3.0%.②冬季PM_2.5污染值情境下气象要素呈低风速、低气压、高温度、高相对湿度的特征.③冬季到达厦门市的气团轨迹路径中,局地路径由于大气条件稳定易累积形成PM_2.5污染;偏北路径和西北路径易从临近省份携带污染物输入导致PM_2.5污染,属于重要的外源污染输入路径;沿海路径和偏西路径均属于清洁路径,但沿海路径易在福建省北部与偏北路径重合形成污染输入,加强了偏北路径的污染物输送能力.研究显示,近年来厦门市冬季PM_2.5污染有明显减弱趋势,但不利的气象条件和外来污染输入仍会造成PM_2.5污染的发生.      

嘉兴地区农村生活污水时空分布及处理设施现状分析

研究选取嘉兴市下辖农村的160座生活污水处理设施进出水为研究对象,分析了区域农村生活污水污染物时空分布特征及其处理设施现状,以期提高处理设施效率。结果表明:嘉兴市农村生活污水中氮、磷污染较有机污染更严重,ρ（COD）、ρ（TP）、ρ（TN）、ρ（NH₄+-N）年均值分别为142.23,4.02,44.19,27.74 mg/L,各污水处理设施处理效果有很大优化空间,COD、TP、TN、NH₄+-N年均去除率分别为50.5%、29.7%、36.8%、51.7%。农村生活污水空间上呈自西向东、由北至南逐渐减小的分布特征,时间上表现为冬季 > 春季 > 秋季 > 夏季。相关性分析表明,COD、TP、TN、NH₄+-N之间呈极显著正相关（P<0.01）,相关系数为0.688±0.946。设施进水C/N、NH₄+-N/TN年均值分别为3.21、68.9%,传统的单一A2/O处理工艺对低碳源污水处理效果不理想,可通过组合工艺设计、规范运营管理、加强后期监测等有效措施来进一步加强污水处理设施处理效果。     

特殊区域地表水环境背景值表征技术方法研究与应用

选取黑龙江省源头水保护区作为研究对象,根据DEM数据对保护区内随机布设的水质监测点控制单元进行划分并提取单元内的相关指标建立监测点背景特性量化模型,基于量化结果提出地表水环境背景值监测方案,建立背景值数据库.选取研究区自然属性指标与空间属性指标,以空间叠置技术与聚类分析方法对研究区地表水进行背景值分区,最终将黑龙江省分为六大地表水水质背景值地理分区,并计算了各分区地表水环境背景值表征范围.表征范围显示：依据现行标准进行水质评价,保护区内水质背景值已超出Ⅱ类水质标准限值.因此,基于水质背景值研究成果提出了考虑背景值影响下的水环境质量评价方法,并将方法应用于研究区,结果表明方法切实可行且优于单因子评价法.研究成果可为区域制定背景值影响下的水环境评价方法提供科学的数据支撑与理论依据.