磁性炭微球表面印迹吸附材料的制备及其对氨苄西林识别与选择性吸附

以核桃壳为原料,利用溶剂热法制备了磁性炭微球(MCMs),结合表面印迹技术制备了基于MCMs的磁性炭微球表面分子印迹材料(MMIPs).通过FT-IR、TGA、VSM和TEM等表征手段对其理化性能进行了表征,结果表明MMIPs为球形,印迹聚合层厚度50~80 nm,具有热稳定性和磁稳定性.采用吸附实验研究了MMIPs对AMP的识别与选择性吸附性能.Langmuir等温模型能较好地描述MMIPs对AMP的吸附平衡数据,25℃时MMIPs的单分子层最大吸附容量为40.96 mg·g-1.准二级动力学模型能较好的描述MMIPs对AMP吸附动力学行为.选择性分析结果表明,MMIPs对AMP具有较好地选择识别性,并且MMIPs可以循环使用5次.结合高效液相色谱分析技术,MMIPs已成功应用于牛奶样品中痕量AMP的分离、富集和回收,AMP的回收率为92.78%.     

Fe3O4@SiO2-NH2磁性复合材料对水中单宁酸的吸附性能研究

通过简单方法制备出Fe3O4@SiO2-NH2磁性复合材料,并利用XRD、FT-IR、VSM和SEM等手段对其物理化学性质进行了表征,最后对水中单宁酸进行了吸附性能研究.结果表明,所制备复合材料上的氨基基团(N—H的特征吸收峰出现在1549.53cm-1)能够与单宁酸上的酚羟基反应,使—NH2质子化形成NH+3,并利用良好的磁性(42.5emu.g-1)使单宁酸从水中分离去除;对单宁酸的吸附符合Langmuir吸附模型和拟二级吸附动力学方程;在pH=6时,基于氢键和静电吸附的协同作用,吸附能力达到最强,为85.18mg.g-1(吸附温度为25℃,吸附时间为60min).研究证实,Fe3O4@SiO2-NH2磁性复合材料与Fe3O4@SiO2和SiO2相比,对单宁酸有更好的吸附性能,同时通过外磁场可以达到固液分离的效果.     

多壁碳纳米管表面共价偶联分子印迹聚合物及其对水中双酚A的吸附性能

通过羧化、酰氯化、酰胺化反应在多壁碳纳米管(MWCNTs)表面引入不饱和侧链(－CH＝CH2),然后以双酚A(BPA)为模板分子,4-乙烯吡啶(4-VP)为功能单体,乙二醇二甲基丙烯酸酯(EGDMA)为交联剂,在MWCNTs－CH＝CH2表面制备一种新型的分子印迹聚合物纳米材料.采用扫描电镜、傅里叶变换红外光谱(FT-IR)、热重分析对制备吸附剂(MWCNTs@BPA-MIPs)的结构与形态进行了表征且证实有一层稳定的分子印迹聚合物(MIPs)接枝在MWCNTs的表面通过平衡结合实验与斯卡查德(Scatchard)分析证实了印迹聚合物的吸附性质.结果证实,BPA的吸附容量高达123.8 mg·g-1,而且与模板分子BPA的类似物双酚C(BPC)和邻硝基酚(o-NP)比较,MWCNTs@BPA-MIPs对BPA具有更好的选择性和更快的吸附动力学特性.     

MY@SiO2-PEI磁性复合生物材料对二元Ce3+/Sr2+混合离子的吸附性能研究

采用生物材料酵母作为基质材料,纳米四氧化三铁为磁敏源,3-氯丙基三甲氧基硅烷(CP)作为硅源与偶联剂,聚乙烯亚胺(PEI)为功能单体,利用两步溶液聚合法制备磁性复合生物材料(MY@SiO2-PEI).同时,采用FT-IR、SEM、VSM、等电位点测定及接触角测定等方法对材料的理化性能进行了表征,并考察其对二元体系(Ce3+/Sr2+)混合液的吸附性能及机理.结果表明,MY@SiO2-PEI实现了PEI的成功嫁接,材料的表面变得粗糙,等电位点pHzpc变大,材料的接触角由疏水变成亲水.吸附实验结果表明,MY@SiO2-PEI具有更好的吸附性能,对二元体系中Ce3+和Sr2+的最大吸附量分别为80.24 mg·g-1和63.51 mg·g-1.准二级动力学方程与Freundlich吸附等温模型的线性回归系数(R2)均大于0.99,准二级动力学模拟的理论吸附容量(Qe,cal)更接近于实验值(Qe,exp),Freundlich等温模型中的吸附强度(1/n)均小于1,吸附为多层,有利于化学吸附过程;pH=5.5~6.0为最适吸附pH范围;MY@SiO2-PEI的磁性强度为10.03 emu·g-1,满足分离富集的要求.     

磁性多壁碳纳米管对BPA的吸附特性

针对普通碳材料吸附BPA需要过滤或离心等复杂过程,将Fe3O4晶体沉积到多壁碳纳米管(MWCNTs)表面,合成饱和磁化度为23.3 emu/g的磁性多壁碳纳米管(MMWCNTs)以实现简便的固液分离.MMWCNTs对水相BPA的吸附是一个快速过程,饱和吸附量为14.9 mg/g.MMWCNTs对水相BPA的吸附过程△G为负值,是一个自发过程;△H为负值,是一个放热过程;△S为正值,是一个熵增过程.MMWCNTs对BPA的吸附具有物理吸附特征,MMWCNTs与BPA之间的相互作用力主要为范德华力.     

间苯二胺改性磁性壳聚糖对六价铬的还原-吸附协同作用机制研究

通过改进后的方法制备出具有良好颗粒形态的磁性壳聚糖颗粒,并使用间苯二胺(mPD)对其进行改性,在颗粒表面形成了一层含有大量含氮官能团的有机壳层,有效改善了颗粒的比表面积和活性官能团数量.通过序批实验法探究mPD改性磁性壳聚糖颗粒对六价铬Cr(Ⅵ)的吸附行为,实验结果显示初始pH为酸性有利于其对Cr(Ⅵ)的去除;吸附行为复合拟二级动力学模型,以化学吸附为主;在25℃、pH3条件下,由Langmuir等温线计算得吸附量可以达到212.21 mg·g~(-1),优于此前报道过的很多非纳米级新型磁性吸附剂;通过Redlich-Peterson模型的拟合和吸附反应前后的X射线光电子能谱分析,可知mPD改性磁性壳聚糖颗粒对六价铬Cr(Ⅵ)的去除是通过氧化还原反应和吸附作用协同进行的;经过6次吸附-解吸再生过程,mPD改性磁性壳聚糖颗粒仍具有100 mg·g~(-1)以上的吸附能力.综上,mPD改性磁性壳聚糖颗粒体现出其对Cr(Ⅵ)突出的去除性能,同时具有便于分离和再生能力强等特点,对于应用于含铬废水的处理具有良好的前景.     

双酚A和邻苯二甲酸二正丁酯在纸类上的吸附特性研究

采用序批式实验,考察了报纸对双酚A(BPA)和邻苯二甲酸二正丁酯(DnBP)的吸附能力,用Freundlich、Langmuir、Dubinin-Radushkevich(D-R)、Flory-Huggins(F-H)、BET、Temkin 6种吸附等温线模型对实验数据进行了拟合.并选择了回归系数(R2)、均方根差(RMSE)和卡方检验(X2检验)3种非线性回归方法评价了模型拟合度.结果表明,Freundlich和Temkin吸附等温线模型能很好地描述BPA和DnBP在纸类表面的吸附,BPA和DnBP的R2均大于0.95(P<0.01),RMSE和X2分别小于0.05和0.02;吸附能力与吸附质的疏水性呈正相关.由D-R和F-H吸附等温线模型拟合结果可知,BPA和DnBP的吸附平均自由能分别为1.484和1.609 kJ/mol;Gibbs自由能分别为-6.559和-7.021 kJ/mol.说明BPA和DnBP在纸类上的吸附为自发的物理吸附.BPA和DnBP在纸类上的Freundlich吸附常数k分别为0.147和0.502 mg(1-n)·L"·g-1,均高于文献报道的底泥等的吸附常数,说明生活垃圾填埋场中纸类会阻碍BPA和DnBP的迁移和生物可利用性.     

3种吸附剂对污水磷污染去除性能与机制比较

为探索高效利用膨润土、红壤和炉渣去除农业污水磷污染的可行性,对比分析了3种吸附剂对人工合成含磷污水的吸附去除特性,结合SEM、XDS和BET等测试结果以及等温吸附、吸附动力学及Ca2+释放量探讨了3种材料对磷的吸附机制。结果表明,炉渣对磷的吸附能力高于膨润土和红壤,吸附过程均适合Langmuir等温吸附方程(R20.96),对磷的理论饱和吸附量为炉渣(16.87mg·g-1)红壤(1.21mg·g-1)膨润土(0.92mg·g-1)。炉渣对磷的吸附动力学特征符合Elovich方程(R2=0.966),而膨润土和红壤对磷的吸附特征则更适合准二级动力学方程(R2为0.982和0.959)。炉渣的Ca2+释放量(10.46mg·g-1)显著大于膨润土(0.31mg·g-1)和红壤(0.03mg·g-1)(P0.05)。红壤对磷的吸附量随着pH的升高而降低;膨润土在初始pH为7.0时,吸附量最低;但初始pH值对炉渣去除磷的影响不大。相比红壤和炉渣,膨润土解吸较快,易于进行重复利用。综上所述,吸附材料的磷吸附能力主要与其结构、化学组成、Ca2+释放能力及溶液初始pH值等有关,炉渣较膨润土和红壤对磷酸盐有着更强的去除能力,适合处理农村污水磷污染。     

磁性壳聚糖衍生物对阴离子染料的吸附行为

以自制的阳离子磁性壳聚糖季铵盐(CS/EPTAC/Fe3O4)为吸附剂,采用静态法研究了其对酸性红1、二甲酚橙的吸附行为.结果表明,在25℃,p H=3.0的条件下,两种酸性染料的吸附等温线由Langmiur方程拟合的吸附量分别为781.55 mg·g-1和537.40 mg·g-1;由Frendlich方程得到的n值分别为1.71和1.92,说明染料吸附为优惠吸附;Temkin方程说明吸附剂的非均匀表面为主要吸附位.两种染料的吸附动力学符合拟二级动力学模型,说明吸附过程以化学吸附为主.与粉末活性炭相比,CS/EPTAC/Fe3O4体现出吸附性能优良,快速分离和容易再生的优点.     

Fe/Si/Al分子印迹材料的制备及其对酸性橙II(AOII)的选择吸附性能

以Fe/Si凝胶作为基底,酸性橙II(AOII)为模板分子,引入Al3+形成Lewis酸识别位点,制备全无机型Fe/Si/Al分子印迹型材料(MIPs),通过SEM、XRD、BET、FT-IR等对其进行表征,并研究了其对AOII的选择吸附性能.研究结果表明,与同具有苯环结构的干扰物双酚A(BPA)相比,MIPs对AOII的吸附能力明显高于BPA,说明其对模板分子具有吸附选择性.此外,MIPs对AOII的吸附行为符合Langmuir吸附等温线和拟二级吸附动力学方程,且主要为化学吸附.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.