双酚S在两种典型地带性土壤中的吸附/解吸行为研究

采用批平衡实验方法研究了双酚S（BPS）在两种典型地带性土壤中的吸附/解吸行为.结果表明,吸附动力学曲线符合拟二级动力学方程.吸附等温线呈非线性,且同时符合Freundlich和Langmuir方程.相比而言,BPS更易吸附在高有机质含量的黑土中,298 K反应温度下BPS在黑土和红壤上的最大吸附容量分别为497.8和156.6 mg·kg^-1.吸附到两种土壤中的BPS存在解吸滞后现象,这可能是由于BPS以化学吸附和微孔扩散的形式存在于土壤中的缘故.溶液pH与BPS在土壤中的吸附容量呈负相关关系,即中性形态的BPS比阴离子形态的BPS具有更高的吸附容量.与结构类似物双酚A（BPA）的吸附相比,BPS在土壤中的吸附量更低,因此具有更高的迁移能力,可能会引起更高的环境健康风险.本研究结果为了解BPS在土壤中的迁移规律提供了数据支持.     

模拟土壤淋洗废液中重金属的选择性去除与淋洗液的回收研究

土壤淋洗废液中污染物的选择性去除是实现淋洗液回收的关键.本文以硫化钠（Na₂S）、乙基黄原酸钾（PEX）、二甲基二硫代氨基甲酸钠（DTC）作为重金属沉淀剂处理电子垃圾污染土壤模拟淋洗废液,在筛选出Na₂S作为理想重金属沉淀剂的基础上,研究初始pH值、反应温度、沉淀剂浓度等因素对Na₂S分离络合态重金属的影响,并通过软件模拟和产物表征等方式推测反应机理.结果表明：Na₂S对柠檬酸络合态重金属的分离顺序依次为Cu、Pb、Cd,符合硫化物溶度积原则;反应温度、初始pH值对Na₂S处理络合态重金属无显著影响,重金属去除率均保持在90%以上,柠檬酸的回收率约为95%;Visual MINTEQ模拟结果显示,S^2-投加前液相中重金属主要以H₂CA^-、HCA^2-和CA^3-结合形式存在,S^2-投加后液相中重金属则以HS^-和S^2-结合形式存在;扫描电镜及能谱（SEM-EDS）表明,S^2-与金属阳离子按物质的量比1：1生成硫化物沉淀物,沉淀主要呈团聚、成簇和圆片状存在;X射线衍射（XRD）分析结果表明,沉淀产物中存在CuS、CdS、PbS和CuPbS₂.本研究结果可为化学沉淀法处理重金属污染土壤淋洗废液提供技术参考.     

内质网应激在氟暴露致小鼠睾丸损伤中的作用

探讨了内质网应激在亚慢性氟暴露致小鼠睾丸损伤中的作用及分子机制.选用健康初断乳ICR雄性小鼠30只,随机分为对照组（C）、低氟组（LF）和高氟组（HF）,分别饮用自来水、5、30 mg·L^-1氟化钠水溶液90 d.亚慢性氟暴露结束后,以睾丸脏器系数、睾丸组织氧化/抗氧化酶和形态结构、精子质量、睾丸细胞凋亡、葡萄糖调节蛋白78（GRP78）、CCAAT/增强子结合蛋白同源蛋白（CHOP）、半胱氨酸天冬氨酸蛋白酶12（CASPASE-12）、半胱氨酸天冬氨酸蛋白酶3（CASPASE-3）为观测点.结果表明,与对照组比,LF组和HF组LDH、SOD、T-AOC活性下降,MDA含量上升,HF组GSH-PX活性下降,差异有统计学意义（p<0.05或p<0.01）;LF组可见细胞层次减少、间隙变大,成熟精子数量减少,HF组细胞溶解、层次紊乱,空泡化严重,少见成熟精子;LF组和HF组小鼠的精子活力降低,HF组小鼠精子数量下降,畸形率上升,差异有统计学意义（p<0.05或p<0.01）;LF组和HF组睾丸细胞凋亡指数上升,差异有统计学意义（p<0.01）;LF组和HF组Grp78、Caspase-12、Caspase-3基因表达水平上升,差异有统计学意义（p<0.05或p<0.01）.结果提示,除氧化应激以外,Caspase-12和Caspase-3基因表达异常可能是氟暴露致小鼠睾丸细胞凋亡异常的分子机制之一.     

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.     

Preparation of hydrophobic hierarchical pore carbon–silica composite and its adsorption performance toward volatile organic compounds

Carbon–silica materials with hierarchical pores consisting of micropores and mesopores were prepared by introducing nanocarbon microspheres derived from biomass sugar into silica gel channels in a hydrothermal environment.The physicochemical properties of the materials were characterized by nitrogen physical adsorption(BET),scanning electron microscopy(SEM),and thermogravimetric(TG),and the adsorption properties of various organic waste gases were investigated.The results showed that microporous carbon materials were introduced successfully into the silica gel channels,thus showing the high adsorption capacity of activated carbon in high humidity organic waste gas,and the high stability and mechanical strength of the silica gel.The dynamic adsorption behavior confirmed that the carbon–silica material had excellent adsorption capacity for different volatile organic compounds(VOCs).Furthermore,the carbon–silica material exhibited excellent desorption characteristics:adsorbed toluene was completely desorbed at 150℃,thereby showing superior regeneration characteristics.Both features were attributed to the formation of hierarchical pores.     

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.     

Identification of potential electrotrophic microbial community in paddy soils by enrichment of microbial electrolysis cell biocathodes

Electrotrophs are microbes that can receive electrons directly from cathode in a microbial electrolysis cell (MEC). They not only participate in organic biosynthesis, but also be crucial in cathode-based bioremediation. However, little is known about the electrotrophic community in paddy soils. Here, the putative electrotrophs were enriched by cathodes of MECs constructed from five paddy soils with various properties using bicarbonate as an electron acceptor, and identified by 16S rRNA-gene based Illumina sequencing. The electrons were gradually consumed on the cathodes, and 25%–45% of which were recovered to reduce bicarbonate to acetic acid during MEC operation. Firmicutes was the dominant bacterial phylum on the cathodes, and Bacillus genus within this phylum was greatly enriched and was the most abundant population among the detected putative electrotrophs for almost all soils. Furthermore, several other members of Firmicutes and Proteobacteria may also participate in electrotrophic process in different soils. Soil pH, amorphous iron and electrical conductivity significantly influenced the putative electrotrophic bacterial community, which explained about 33.5% of the community structural variation. This study provides a basis for understanding the microbial diversity of putative electrotrophs in paddy soils, and highlights the importance of soil properties in shaping the community of putative electrotrophs.     

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.     

Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst

Direct synthesis of dimethyl ether(DME) by CO_2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods:co-precipitation,sol-gel,and solid grinding to produce mixed Cu,ZnO,ZrO_2 catalysts that were physically mixed with a commercial ferrierite(FER) zeolite.The catalysts were characterized by N_2 physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),temperature programmed desorption of CO_2(CO_2-TPD),temperature programmed desorption of NH_3(NH_3-TPD),and temperature programmed H2 reduction(H_2-TPR).The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases,higher surface area,and lower reduction temperature are all favorable for catalytic activity.The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Methanol appears to be formed via the bidentate-formate(b-HCOO) species undergoing stepwise hydrogenation,while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.