新型氨化菌丝体吸附剂的制备及吸附典型内分泌干扰物的研究

以产黄青霉(Penicillium chrysogenum)菌丝体为原料,通过2步化学反应将含有大量氨基的聚乙烯亚胺(PEI)嫁接到菌丝体表面,优化反应条件,得到最佳的氨化菌丝体吸附剂.该氨化吸附剂的等电点为pH 10.2,是一种表面带正电荷的菌丝体吸附剂,能有效吸附水中的阴离子内分泌干扰物五氯酚钠(PCP)、2,4二氯苯氧乙酸(2,4-D)和全氟辛烷磺酸钾(PFOS).3种污染物的吸附等温线符合Langmuir方程,15℃时最大吸附量分别为342.9、234.1、1725.6 mg/g.热力学计算表明,3种污染物的吸附均是自发发生的,2,4-D和PFOS的吸附是吸热反应,而PCP是放热反应.     

Preparation and utilization of wheat straw anionic sorbent for the removal of nitrate from aqueous solution

In order to reduce the impact of eutrophication caused by agricultural residues(i.e.,excess nitrate)in aqueous solution,economic and effective anionic sorbents are required.In this article,we prepared anionic sorbent using wheat straw.Its structural characteristics and adsorption properties for nitrate removal from aqueous solution were investigated.The results indicate that the yield of the prepared anionic sorbent,the total exchange capacity,and the maximum adsorption capacity were 350%,2.57 mEq/g,and 2.08 mmol/g, respectively.The Freundlich isotherm mode is more suitable than the Langmuir mode and the adsorption process accords with the first order reaction kinetic rate equation.When multiple anions(SO_4~(2-),H_2PO_4~-,NO_3~-,and NO_2~-)were present,the isotherm mode of prepared anionic sorbent for nitrate was consistent with Freundlich mode;however,the capacity of nitrate adsorption was reduced by 50%.In alkaline solutions,about 90% of adsorbed nitrate ions could be desorbed from prepared anionic sorbent.The results of this study confirmed that the wheat straw anionic sorbent can be used as an excellent nitrate sorbent that removes nitrate from aqueous solutions.     

Preparation1 and utilization of wheat straw anionic sorbent for the removal of nitrate from aqueous solution

In order to reduce the impact of eutrophication caused by agricultural residues (i.e. excess nitrate) in aqueous solution, economic and effective anionic sorbents are required. In this article, we prepared anionic sorbent using wheat straw. Its structural characteristics and adsorption properties for nitrate removal from aqueous solution were investigated. The results indicate that the yield of the prepared anionic sorbent, the total exchange capacity, and the maximum adsorption capacity were 350%, 2.57 mEq/g, and 2.08 mmol/g, respectively. The Freundlich isotherm mode is more suitable than the Langmuir mode and the adsorption process accords with the first order reaction kinetic rate equation. When multiple anions (SO42-, H2PO4-, NO3-, and NO2-) were present, the isotherm mode of prepared anionic sorbent for nitrate was consistent with Freundlich mode; however, the capacity of nitrate adsorption was reduced by 50%. In alkaline solutions, about 90% of adsorbed nitrate ions could be desorbed from prepared anionic sorbent. The results of this study confirmed that the wheat straw anionic sorbent can be used as an excellent nitrate sorbent that removes nitrate from aqueous solutions.     

Factors affecting the adsorption of 2,4-D and methyl parathion in soils and sediments

The adsorption of methyl parathion and 2,4-dichlorophenoxyacetic acid (2,4-D) by 19 soil and sediment materials differing widely in their physical and chemical properties was investigated using a batch equilibration technique. Organic matter was the most important single factor affecting adsorption of methyl parathion and 2,4-D. Soil pH and cation exchange capacity were also reasonably well associated with 2,4-D adsorption whereas cation exchange capacity contributed significantly for methyl parathion. Data are presented which indicate that in soil and sediment materials where the organic matter content in less than 1 %, oxalate extractable Mn and Ca were associated with the adsorption of these synthetic organics. Additional work should be done in low organic matter soil materials to better quantify the relationship between adsorption and soil geochemical properties.     

水/载O_3有机溶剂两相臭氧氧化法降解水体中2,4-二氯苯氧乙酸

以水/载O3有机溶剂(全氟萘烷)为新型两相臭氧氧化体系,研究了臭氧在全氟萘烷中的溶解度和稳定性,并以水体中2,4-二氯苯氧乙酸(2,4-D)为研究对象,考察了初始pH值、臭氧投加量、自由基抑制剂对两相臭氧氧化体系降解2,4-D效果的影响.结果表明:臭氧在全氟萘烷中有很高的溶解度和很好的稳定性;碱性pH环境有利于2,4-D的降解,随着水相初始pH的增加,2,4-D在水/载饱和O3全氟萘烷两相体系中的去除率明显增加;随着初始全氟萘烷载O3量与2,4-D物质的量比的增加,2,4-D总去除率明显增加;叔丁醇(20mg·mL-1)对两相体系中2,4-D降解影响不显著.     

2,4-D完全抗原的合成及其免疫性能评价

以2,4-D为半抗原,BSA为载体蛋白,通过EDC的偶联反应条件优化试验,合成了多种结合比的完全抗原,制备了小分子环境污染物的多克隆抗体.结果表明,偶联反应优化步骤是2,4-D、BSA和EDC同时反应,4°C条件下反应18h.偶联反应可以在2,4-D的浓度为10.0～12.0 mg/mL的0.05mol/L的磷酸盐缓冲溶液中进行,反应缓冲体系pH控制在5.4～6.1之间.EDC的加入量低于12 mg时,采用2,4-D和多聚赖氨酸的偶联物为包被抗原.通过balb/c小鼠免疫试验评价结合比分别为6、12、18和25的完全抗原的免疫性能,结果表明结合比为12和18的完全抗原具有很好的免疫原性.其中以结合比为18的完全抗原免疫小鼠获得的抗血清对包被抗原载体的非特异性吸附低于阴性血清,2,4-D特异性血清含量高,适于作为完全抗原免疫小鼠进一步制备单克隆抗体.     

Removal of phosphate by Fe-coordinated amino-functionalized 3D mesoporous silicates hybrid materials

Phosphate removal from aqueous waste streams is an important approach to control the eutrophication downstream bodies of water. A Fe(III) coordinated amino-functionalized silicate adsorbent for phosphate adsorption was synthesized by a post-grafting and metal cation incorporation process. The surface structure of the adsorbent was characterized by X-ray di raction, N2 adsoropion/desoprotion technique, and Fourier transform infrared spectroscopy. The experimental results showed that the adsorption equilibrium data were well fitted to the Langmuir equation. The maximum adsorption capacity of the modified silicate material was 51.8 mg/g. The kinetic data from the adsorption of phosphate were fitted to pseudo second-order model. The phosphate adsorption was highly pH dependent and the relatively high removal of phosphate fell within the pH range 3.0–6.0. The coexistence of other anions in solutions has an adverse e ect on phosphate adsorption; a decrease in adsorption capacity followed the order of exogenous anions: F?? > SO2?? 4 > NO??3 > Cl??. In addition, the adsorbed phosphate could be desorbed by NaOH solutions. This silicate adsorbent with a large adsorption capacity and relatively high selectivity could be utilized for the removal of phosphate from aqueous waste streams or in aquatic environment.     

碳气凝胶的制备及其对极性农药的吸附性能

以机械球磨联合TEMPO氧化对木浆纤维进行预处理,并通过高温热解制备碳气凝胶,对其形貌、元素组成、比表面积、孔径结构以及表面官能团进行表征分析,并以阳离子型吡虫啉（IMI）和阴离子型2,4-D为目标物评价其吸附性能.结果表明：经机械球磨联合TEMPO氧化改性显著增加碳气凝胶的孔和表面C=O官能团含量、比表面积及极性,降低其片层厚度和芳香性,其表面积可达2631m²/g.碳气凝胶对IMI和2,4-D的吸附均符合Freundlich模型.IMI在碳气凝胶上的主要吸附机制为阳离子/p/π-π电子供体-受体相互作用、氢键、孔填充作用、静电吸引作用等,而静电排斥作用是抑制2,4-D吸附的主要因素,且IMI和2,4-D最高吸附量分别可达437和286mg/g.因此,通过机械球磨联合TEMPO氧化改性制备碳气凝胶在吸附去除水体有机污染物领域具有潜在应用价值.     

纳米四氧化三铁对2,4-D的降解研究

采用纳米Fe3O4降解溶液中的2,4-D,考察了2,4-D初始浓度、纳米Fe3O4的投加量、溶液pH对2,4-D降解效率的影响,并探讨了2,4-D的降解机理。实验结果表明,Fe3O4对2,4-D有明显的降解作用,纳米Fe3O4的降解效果优于微米级Fe3O4,降解过程中溶液中的氯离子浓度随着2,4-D的降解而升高,Fe3O4对2,4-D的降解机理是还原脱氯。当2,4-D初始浓度在0～10mg/L、纳米Fe3O4投加量0～300mg/L的范围内,2,4-D降解率随初始浓度和纳米Fe3O4投加量的增加而增大。在2,4-D初始浓度为10mg/L、pH3.0、纳米Fe3O4投加量300mg/L时降解效率最高,48h内2,4-D的降解率可达40%。     

One-step preparation of polyimide-inlaid amine-rich porous organic block copolymer for efficient removal of chlorophenols from aqueous solution

A novel polyimide-inlaid amine-rich porous organic block copolymer (PI-b-ARPOP) was prepared via one-step polymerization by using different molar ratios of melamine (MA)/terephthalaldehyde (TA)/pyromellitic dianhydride (PMDA), at molar ratios of 4/3/1, 4/2/2 and 4/1/3. The copolymer contained both aminal groups belonging to ARPOP and imide groups belonging to PI, and the bonding styles of the monomers and growth orientations of the polymeric chains were diversiform, forming an excellent porous structure. Notably, MA/TA/PMDA (4/2/2) had a surface area and pore volume of 487.27?m²/g and 1.169?cm³/g, respectively. The adsorption performance of the materials towards 2,4-dichlorophenol (2,4-DCP) in ultra-pure water was systematically studied. The pH value of 7 was optimal in aqueous solution. Na⁺ and Cl^? ions did not negatively affect the adsorption process, while humic acid (HA) slightly decreased the capacity. The equilibrium time was 40 sec, and the maximum adsorption capacity reached 282.49?mg/g at 298?K. The removal process was endothermic and spontaneous, and the copolymer could maintain its porous structure and consistent performance after regeneration by treatment with alkali. Moreover, to further assess the practical applicability of the material, the adsorption performance towards 2,4-DCP in river water was also investigated. This paper demonstrated that the PI-b-ARPOP can be an efficient and practical adsorbent to remove chlorophenols from aqueous solution.     

Biosorption of phenol by chicken feathers

This work aimed at exploring the potential use of chicken feathers as a biosorbent for the removal of phenol from aqueous solutions. Batch kinetics and isotherm studies were performed to evaluate the effects of process parameters such as pH, temperature, initial phenol concentration, and sorbent concentration. Complete adsorption of phenol was noticed under certain process conditions. The adsorption of phenol increased with increasing initial phenol concentration, solution pH, temperature, and sorbent concentration. The adsorption equilibrium was well represented by the Freundlich and Langmuir adsorption isotherm models. The thermodynamic parameters obtained by means of the Langmuir model showed that the adsorption process was endothermic.     

A novel use of TiO2 fiber for photocatalytic ozonation of 2,4-dichlorophenoxyacetic acid in aqueous solution

More efficient oxidation methods are needed to degrade especially newly emerging recalcitrant organic contaminants at low concentrations in the water environment. Reduced photonic efficiency of immobilized TiO2 is a major challenge in TiO2-assisted advanced oxidation processes (AOP). Mineralization of 2,4-dichllorophenoxyacetic acid (2,4-D) in low aqueous solution by O3/UV/TiO2 using the world's first high-strength TiO2 fiber was investigated and compared with O3, UV/TiO2, and O3/TiO2 in laboratory batch ex...     

检测2,4-D的一次性安培型免疫传感器

2,4-D是广泛使用的除草剂,以2,4-D为检测目标,研究了安培型免疫传感器.首先采用1-乙基-3-(3-二甲基氨丙基)碳二亚胺盐酸盐(EDC)作为交联剂制备2,4-D与BSA以及PLL的偶联物.用结合比1∶16的2,4-D与偶联物制备兔抗血清.免疫传感器的制备包括2个步骤,使用丝网印刷工艺制备一次性碳电极,然后通过戊二醛交联在电极表面固定2,4-D与多聚赖氨酸(PLL)的偶联物.待测水样与2,4-D抗血清和HRP酶标二抗进行间接免疫竞争反应.在HRP酶在邻苯二胺和H₂O₂的共同作用下发生酶促反应,检测还原电流以反映2,4-D的浓度.试验了不同浓度抗血清和酶标二抗对检测信号的影响,结果表明,2,4-D的检测下限达到1.69ng/mL,线性区间1.69～30 000ng/mL,适合饮用水中2,4-D的检测要求.     

新型改性壳聚糖微球的制备及其对氯酚的吸附研究

采用反相悬浮法制备交联壳聚糖微球,再与庚醛反应生成Schiff's碱,最后与NaBH4还原制得N-烷基化改性壳聚糖微球,用红外光谱和光学显微镜进行表征,并用于吸附2,4-二氯酚的研究.试验考察了微球的溶解性能,以及吸附时间、溶液pH值、氯化钠含量和2,4-二氯酚浓度等因素对吸附的影响.结果表明,庚醛改性交联壳聚糖微球不溶于水、酸和碱,对2,4-二氯酚有良好的吸附性能;在pH为6的条件下,3h吸附量达492.2 mg·g-1,吸附数据符合Freundlich等温方程.     

经丁二酮肟修饰的改性皂土对废水中镍的吸附

采用十六烷基三甲基溴化铵(CTMAB)对皂土改性,用丁二酮肟(DMG)对其表面修饰,并制备了新型固态吸附剂.研究了该吸附剂对水中Ni2+的吸附行为.结果表明,该固态吸附剂对水中Ni2+具有较强的吸附能力.吸附量受介质pH值、温度和吸附时间的影响.其吸附行为符合Langmuir吸附等温模型和HO准二级动力学方程,吸附焓变(△H)为58.759kJ/mol,各温度下,吸附自由能变(△G)均＜0,熵变(△S)均＞0,该吸附反应为吸热的自发过程.吸附了Ni2+的丁二酮肟修饰改性皂土,可用0.1mol/L的HNO3溶液洗脱再生.     

NC-PC锚定微量Fe活化PMS降解水中2,4-二氯苯氧乙酸

采用分步热分解法制备了NC-PC（三维多孔碳材料）锚定的微量Fe基催化剂,用于活化过一硫酸盐（PMS）氧化降解水中2,4-二氯苯氧乙酸（2,4-D）.采用透射电子显微镜（TEM）、高精度比表面积仪（BET）、X射线光电子能谱分析（XPS）和电感耦合等离子体发射光谱分析（ICP）对催化剂进行表征.考察了不同金属、制备方法、催化剂投加量、PMS投加量、初始pH值以及水中不同阴离子（Cl^-、NO₃^-、HCO₃^-）对2,4-D降解的影响.结果表明,通过热分解法合成的Fe-NC-PC对2,4-D具有更好的降解效果,当2,4-D初始浓度为0.1mmol/L,初始pH=3.4,催化剂投加量0.15g/L,PMS浓度0.7mmol/L时,反应20min内2,4-D的去除率可达91%.随着催化剂投加量、PMS投加量的提高,2,4-D的降解效果提高;随着初始pH值的提高,2,4-D的降解效率逐渐降低;水中不同阴离子（Cl^-、NO₃^-、HCO₃^-）和腐殖酸（HA）对2,4-D的降解有轻微的抑制作用.通过自由基淬灭实验、EPR测试以及XPS分析了反应的主要活性物种和反应机理,发现材料制备过程中形成的Fe-N_x是主要的反应活性位,能够有效的活化PMS降解水中2,4-D,¹O₂在2,4-D的降解过程中起到主要作用.     

碳纳米管对水中4-氯酚和2,4-二氯酚的吸附性能研究

碳纳米管是一种具有独特结构和优异性能的新型纳米材料。文章利用碳纳米管对水溶液中的4-氯酚和2,4-二氯酚进行了吸附研究,考察了吸附时间、pH值、温度等对吸附效果的影响,并采用Langmuir和Freundlich方程进行拟合,探讨了其可能的吸附机理。研究结果表明,碳纳米管对4-氯酚和2,4-二氯酚的最佳吸附酸度在pH=2～6。碳纳米管对2,4-二氯酚吸附量大于对4-氯酚的吸附量,二者动力学特征均符合准二级动力学方程。研究了4-氯酚和2,4-二氯酚在碳纳米管上的吸附等温线。研究结果表明:4-氯酚和2,4-二氯酚在碳纳米管上的吸附量随着温度的升高而下降。吸附过程是一个放热的过程,Langmuir和Freundlich等温吸附方程均能较好地拟合吸附等温线。碳纳米管能较好地用于除去水溶液中的4-氯酚和2,4-二氯酚。     

溶解性有机质对铁铝土吸附2,4-D的影响

以动力学吸附和等温吸附实验研究了2,4-D在铁铝土中的吸附特征,并比较了不同亲/疏水性溶解性有机质（DOM）对此的影响.结果表明：2,4-D在铁铝土中的动力学吸附符合伪一级动力学方程,等温吸附符合Henry,Freundlich方程,是一个物理作用主导的,自发的,放热的非均质吸附过程.吸附系数K_d为0.61~2.02L/kg,是一种难吸附有机污染物,对地下水存在环境风险.吸附量受土壤pH值影响显著,与土壤中矿物含量,粘粒组成等也密切相关.DOM共存条件下,高疏水性DOM,中疏水性DOM抑制了2,4-D在铁铝土的吸附,使K_d值下降10.7%~58.8%.低疏水性DOM对铁铝土吸附2,4-D作用不明显.DOM对铁铝土吸附2,4-D的作用效应与土壤理化性质和DOM性质密切相关.土壤矿物组分越多,粘粒含量越高,堵孔效应越大.DOM疏水性越大,对2,4-D吸附作用的增溶作用,堵孔作用也越大,其中HOA,HON是关键组分.     

纳米四氧化三铁对2,4-D的脱氯降解

采用纳米四氧化三铁(Fe3O4)降解水溶液中的2,4-二氯苯氧乙酸(2,4-D),考察了2,4-D初始浓度、纳米Fe3O4投加量、溶液pH和温度等因素对2,4-D降解率的影响.结果表明,纳米Fe3O4对2,4-D有显著的降解效果,初始浓度为10 mg/L的2,4-D, 48 h内降解率可达48%.纳米Fe3O4对2,4-D的降解是一个还原脱氯过程,反应体系中氯离子浓度随2,4-D浓度降低而升高.LC/MS分析表明,2,4-D降解的主要产物是苯酚,其他中间产物是2,4-二氯苯酚(2,4-DCP)、4-氯苯酚(4-CP)和2-氯苯酚(2-CP).溶液中2,4-D的降解符合准一级反应动力学,产物4-CP、2,4-DCP和苯酚的反应速率常数K分别为0.0043、0.0026和0.0032 h -1.环境条件对降解效率有显著影响,2,4-D初始浓度在0～10 mg/L、纳米Fe3O4投加量0～300 mg/L的范围内,2,4-D降解率随初始浓度和纳米Fe3O4投加量的增加而增大;pH对2,4-D的脱氯降解有显著影响,在pH为3.0时,纳米Fe3O4对2,4-D的还原脱氯效果最好;温度升高,可以提高脱氯反应速率.     

质粒基因强化活性污泥系统对2,4–D的降解

以携带质粒pJP4[含编码2,4-二氯苯氧基乙酸(2,4-D)降解功能的基因片段]的基因工程菌Pseudomonas putida SM1443::gfp2x (pJP4::dsRed)为供体菌,通过半连续流实验研究了质粒基因强化对活性污泥系统的2,4-D的降解效应及菌群结构的影响.结果表明,以初始浓度约为320mg/L的2,4-D为唯一碳源,向活性污泥系统投加携带pJP4质粒的基因工程菌P. putida,运行初期,降解促进作用不明显;随着半连续流反应的进行,促进作用显著增强.与对照系统相比,降解速率之差最高为6.67mg/(L·h).从基因强化系统中筛选到1株占有优势的接合子,经鉴定为Alcaligenes sp.::pJP4. Alcaligenes sp.本身不具备降解2,4-D的能力,获得质粒pJP4后,对2,4-D降解能力大幅度提高,与野生型2,4-D高效降解菌Bacillus sp.相当. PCR-DGGE分析表明,在受到2,4-D冲击条件下基因强化的活性污泥系统较对照系统保持了相对更加稳定的菌群结构.