金属改性对SAPO-34低温还原NO性能的影响

采用浸渍法制备金属改性SAPO-34分子筛催化剂,分析比较了不同单金属（Cu或Co）及不同比例双金属（Cu：Co=1：1、3：1、5：1,质量比）改性催化剂对NO的催化还原性能,评价了不同催化剂的N₂选择性,并采用扫描电子显微镜（SEM）、比表面积测试、X射线衍射分析（XRD）、NH₃-程序升温脱附（NH₃-TPD）等表征手段对催化剂的物化性能进行了分析.结果表明,单金属Cu改性催化剂具有较宽的温度区间,在250~450℃范围内NO的转化率始终保持在100%;双金属改性使NO转化率保持为100%的最低温度下降了25~50℃,显著拓宽了低温段窗口,其中,Cu₃Co₁/SAPO-34催化剂的低温催化还原性能最好,200℃即可实现100%的NO转化率,175℃下的转化率也高达80%以上.Cu-Co双金属改性SAPO-34分子筛催化剂具有优异的低温催化还原NO性能,具有在机动车尾气、工业废气的低温脱硝治理领域应用的潜力.     

核壳结构KNbO3@Co(OH)2的制备及其活化过一硫酸盐降解帕珠沙星的研究

制备了以KNbO₃为载体材料的Co（OH）₂复合材料并对其进行了详细的表征,分析了材料的组成成分、组成形态进而确定了其为核壳结构形貌的KNbO₃@Co（OH）₂.利用合成的样品作为催化剂活化过一硫酸盐（peroxymonosulfate,PMS）来降解帕珠沙星（pazufloxacin,PZF）,结果表明制备的催化剂对PZF的去除效率显著增加.讨论了不同初始PMS剂量对降解效率的影响,发现随着PMS增加可活化生成更多的硫酸根自由基（sulfate radicals,SO₄^·-）和羟基自由基（hydroxyl radicals,HO^·）来降解PZF,但继续增大PMS用量降解效率未见明显提升.酸性和中性pH值条件下利于反应活化PMS降解PZF,而碱性体系减缓反应,甚至强碱体系更易形成Co（OH）₂沉淀不利于反应体系中活性组分CoOH⁺的形成,大大抑制了催化性能.此外,在体系中加入淬灭剂叔丁醇（tert-Butanol,TBA）或者乙醇（ethanol,ETOH）进行自由基的淬灭实验,结果表明SO₄^·-自由基为体系降解PZF过程中主要贡献的自由基,而HO^·自由基的贡献较少.催化剂具有较好的稳定性5次循环之后仍能在10 min之内完全去除PZF.本研究提出了新的思路为制备其他载体的Co（OH）₂核壳结构提供参考依据,同时将该催化剂结合高级氧化技术应用到水体新兴有机污染物净化领域具有很好的应用前景.     

船舶排放及不确定性对中国空气质量的影响

船舶排放是我国沿海地区重要的人为排放源,但现有的船舶排放评估研究大多只关注区域尺度的影响分析,而且忽视了排放清单的不确定性,这在一定程度上削弱了评估结果的可靠性.为此,本文利用WRF-SMOKE-CAMQ空气质量模型,定量评估了船舶排放及其不确定性对我国七大沿海港口城市夏季空气质量的影响,结果表明：船舶排放对我国主要沿海港口城市的SO₂、NO_x和PM_2.5浓度贡献范围分别为16.5%~62.5%、21.9%~72.9%和5.9%~26.0%,尤其对宁波、青岛和深圳等港口城市空气质量的影响显著,主要是由于港口较高的船舶排放以及气象传输两方面原因造成的;如果考虑船舶排放清单的总量不确定性,船舶排放对沿海港口城市夏季SO₂、NO_x和PM_2.5的影响分别呈现1.0~3.1,2.1~5.5,0.3~0.9μg/m³的波动;考虑船舶排放清单的时空分配不确定性,船舶排放对沿海港口城市夏季SO₂、NO_x和PM_2.5的影响分别呈现1.9~15.7,5.1~29.3,0.6~2.5μg/m³的波动.可见,船舶排放清单的不确定性对沿海城市船舶排放贡献影响量化有明显的影响.所以在评估船舶排放对港口城市空气质量的影响时,要考虑船舶排放清单的不确定性,尤其是时空分配的不确定性.而合理的时空分配能够提高船舶排放清单的质量和对沿海空气质量模拟的准确性.     

2018年春节期间京津冀地区污染过程分析

为了解2018年春节期间京津冀地区空气污染情况,利用近地面污染物浓度数据、激光雷达组网观测数据,结合WRF气象要素、颗粒物输送通量和HYSPLIT气团轨迹综合分析污染过程.结果表明,春节期间出现3次污染过程.春节前一次污染过程,各站点PM_2.5浓度均未超过200μg/m³;除夕夜,廊坊站点PM_2.5峰值浓度达到504μg/m³,是清洁天气的26倍;年初二~初五,各站点PM_2.5始终高于120μg/m³,且污染主要聚集在500m高度以下,北京地区存在高空传输,800m处最大输送通量达939μg/（m³·s）,此次重污染过程为一次典型的区域累积和传输过程.京津冀地区处于严格管控状态时,燃放烟花爆竹期间PM_2.5峰值浓度可达无燃放时PM_2.5峰值的3.2倍.为防止春节期间重污染现象的发生,需对静稳天气下燃放烟花炮竹采取预防对策.     

二乙烯三胺五甲叉膦酸酸解磷尾矿的实验探究

为减少磷尾矿堆积带来的环境污染问题,实现磷尾矿的钙、镁、磷元素的分离,以高镁磷尾矿为原料,采用二乙烯三胺五甲叉膦酸(DTPMP)进行酸解,探究磷尾矿中主要物相在DTPMP中的分解机制,并通过单因素实验探究pH、反应时间、反应温度及投料比对磷尾矿中MgO、CaO和P_2O_5分解率的影响。实验结果表明:pH对P_2O_5的分解率影响较大,高温更有利于尾矿中镁的溶出,在pH为2. 5,反应时间为60 min,反应温度为80℃,投料比为1. 56时,MgO、CaO和P_2O_5的分解率分别达到61. 05%、38. 23%和9. 67%。     

Adsorption of 17β-estradiol from aqueous solution by raw and direct/pre/post-KOH treated lotus seedpod biochar

Five biochars derived from lotus seedpod(LSP) were applied to examine and compare the adsorption capacity of 17β-estradiol(E2) from aqueous solution.The effect of KOH activation and the order of activation steps on material properties were discussed.The effect of contact time,initial concentration,p H,ionic strength and humic acid on E2 adsorption were investigated in a batch adsorption process.Experimental results demonstrated that the pseudo second-order model fitted the experimental data best and that adsorption equilibrium was reached within 20 hr.The efficiency of E2 removal increased with increasing E2 concentration and decreased with the increase of ionic strength.E2 adsorption on LSP-derived biochar(BCs) was influenced little by humic acid,and slightly affected by the solution p H when its value ranged from 4.0 to 9.0,but considerably affected at p H 10.0.Low environmental temperature is favorable for E2 adsorption.Chemisorption,π–π interactions,monolayer adsorption and electrostatic interaction are the possible adsorption mechanisms.Comparative studies indicated that KOH activation and the order of activation steps had significant impacts on the material.Post-treated biochar exhibited better adsorption capacity for E2 than direct treated,pretreated,and raw LSP biochar.Pyrolyzed biochar at higher temperature improved E2 removal.The excellent performance of BCs in removing E2 suggested that BCs have potential in E2 treatment and that the biochar directly treated by KOH would be a good choice for the treatment of E2 in aqueous solution,with its advantages of good efficiency and simple technology.     

Influence of environmental factors on arsenic accumulation and biotransformation using the aquatic plant species Hydrilla verticillata

Hydrilla verticillata(waterthyme) has been successfully used for phytoremediation in arsenic(As) contaminated water.To evaluate the effects of environmental factors on phytoremediation,this study conducted a series of orthogonal design experiments to determine optimal conditions,including phosphorus(P),nitrogen(N),and arsenate(As(Ⅴ))concentrations and initial pH levels,for As accumulation and biotransformation using this aquatic plant species,while also analyzing As species transformation in culture media after 96-hr exposure.Analysis of variance and the signal-to-noise ratio were used to identify both the effects of these environmental factors and their optimal conditions for this purpose.Results indicated that both N and P significantly impacted accumulation,and N was essential in As species transformation.High N and intermediate P levels were critical to As accumulation and biotransformation by H.verticillata,while high N and low P levels were beneficial to As species transformation in culture media.The highest total arsenic accumulation was(197.2±17.4) μg/g dry weight when As(V) was at level 3(375μg/L),N at level 2(4 mg/L),P at level 1(0.02 mg/L),and pH at level 2(7).Although H.verticillata is highly efficient in removing As(Ⅴ) from aquatic environments,its use could be potentially harmful to both humans and the natural environment due to its release of highly toxic arsenite.For cost-effective and ecofriendly phytoremediation of As-contaminated water,both N and P are helpful in regulating As accumulation and transformation in plants.     

Effect of graphene oxide exposure on intestinal Wnt signaling in nematode Caenorhabditis elegans

Exposure to engineered nanomaterials(ENMs), such as graphene oxide(GO), can potentially induce the response of various molecular signaling pathways, which can mediate the protective function or the toxicity induction.Wnt signaling pathway is conserved evolutionarily in organisms.Using Caenorhabditis elegans as an in vivo assay model, we investigated the effect of GO exposure on intestinal Wnt signaling.In the intestine, GO exposure dysregulated Frizzled receptor MOM-5, Disheveled protein DSH-2, GSK-3(a component of APC complex), and two β-catenin proteins(BAR-1 and HMP-2), which mediated the induction of GO toxicity.In GO exposed nematodes, a Hox protein EGL-5 acted as a downstream target of BAR-1, and fatty acid transport ACS-22 acted as a downstream target of HMP-2.Functional analysis on HMP-2 and ACS-22 suggested that the dysregulation of these two proteins provides an important basis for the observed deficit in functional state of intestinal barrier.Our results imply the association of dysregulation in physiological and functional states of intestinal barrier with toxicity induction of GO in organisms.     

Cytotoxicity of the soluble and insoluble fractions of atmospheric fine particulate matter

Inhaled atmospheric fine particulate matter(PM_(2.5)) includes soluble and insoluble fractions,and each fraction can interact with cells and cause adverse effects.PM_(2.5) samples were collected in Jinan,China,and the soluble and insoluble fractions were separated.According to physiochemical characterization,the soluble fraction mainly contains watersoluble ions and organic acids,and the insoluble fraction mainly contains kaolinite,calcium carbonate and some organic carbon.The interaction between PM_(2.5) and model cell membranes was examined with a quartz crystal microbalance with dissipation(QCM-D) to quantify PM_(2.5) attachment on membranes and membrane disruption.The cytotoxicity of the total PM_(2.5) and the soluble and insoluble fractions,was investigated.Negatively charged PM_(2.5) can adhere to the positively charged membranes and disrupt them.PM_(2.5)also adheres to negatively charged membranes but does not cause membrane rupture.Therefore,electrostatic repulsion does not prevent PM_(2.5) attachment,but electrostatic attraction induces remarkable membrane rupture.The human lung epithelial cell line A549 was used for cytotoxicity assessment.The detected membrane leakage,cellular swelling and blebbing indicated a cell necrosis process.Moreover,the insoluble PM_(2.5) fraction caused a higher cell mortality and more serious cell membrane damage than the soluble fraction.The levels of reactive oxygen species(ROS) enhanced by the two fractions were not significantly different.The findings provide more information to better understand the mechanism of PM_(2.5) cytotoxicity and the effect of PM_(2.5) solubility on cytotoxicity.     

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.