玉米芯对磺胺甲恶唑和甲氧苄啶的吸附效果及机制

为探究农业废物是否能吸附去除抗生素以及不同抗生素之间是否存在相互作用,通过对玉米芯的理化特征分析、傅里叶红外光谱分析、吸附动力学和吸附等温线分析,研究了玉米芯对磺胺甲恶唑（SMX）和甲氧苄啶（TMP）的吸附效果及机制。结果表明：在只含有单一抗生素（初始浓度为10 mg/L）、温度为25℃、玉米芯浓度为25 g/L的体系中,玉米芯对SMX和TMP吸附量分别为131.18和358.75 mg/kg;在同时含有SMX和TMP的体系中（初始浓度均为10 mg/L）,玉米芯对其的吸附量分别为131.02和358.74 mg/kg,SMX和TMP之间为非交互吸附过程。在2种体系中,SMX和TMP的吸附均较好地符合准二级反应动力学方程,Langmuir和Freundlich等温线较好地拟合了SMX的吸附过程,而Freundlich等温线对TMP的拟合效果较好。SMX吸附主要为静电作用、π-π堆积作用,且以静电作用为主;TMP吸附主要通过疏水分配、π-π堆积作用和氢键作用。     

炔雌醇和壬基酚在土壤中的吸附-解吸特征

通过吸附动力学研究和批量平衡试验,以炔雌醇(EE2)和壬基酚(NP)为代表,考察内分泌干扰物在3种不同性质的天然土壤中的吸附-解吸特征.结果表明,双室一级动力学模型比单室一级动力学模型更适合描述EE2、NP在土壤中的动态吸附过程.快吸附过程在吸附初期占据主导地位,之后慢吸附室的相对贡献逐渐增大,直至达到吸附平衡.土壤对NP的吸附速率是EE2的2.0～4.7倍.Freundlich模型和DA模型均能较好地拟合EE2与NP的吸附等温线,但DA模型拟合效果更佳.饱和吸附容量与土壤有机质含量呈显著正相关,EE2的饱和吸附容量(0.85～7.67μg·g-1)明显低于NP(10.47～110.15μg·g-1).吸附自由能计算表明,土壤对EE2和NP的吸附以物理作用为主.此外,3种受试土壤对EE2和NP的解吸附均存在滞后现象,需要预防其潜在的环境风险,其中有机质含量最高、比表面积最大的土样滞后性最明显.     

磺胺甲恶唑在三种湿地基质中的吸附特性研究

研究了磺胺甲恶唑(SMX)在3种人工湿地基质中的吸附特性。结果表明:吸附动力学过程符合一级动力学和二级动力学模型,但不符合粒子内扩散模型,该过程是包括物理和化学吸附的表面扩散过程;等温吸附过程中,基质的吸附量和溶液剩余量均随着SMX投加量的增加而增加,该过程属于物化单分子层吸附;吸附量随温度的变化过程实质是从物理吸附到化学吸附并最终达到吸附平衡的过程;酸性或碱性条件不利于SMX的吸附,最大吸附量点在溶液p H值为7时,偏离理论等电点;SEM从微观角度表征了3种基质对SMX产生了有效吸附。     

17β-雌二醇和炔雌醇在土壤中的吸附特性研究

通过吸附动力学试验和批平衡试验,研究17β-雌二醇(E2)和炔雌醇(EE2)在土壤中的吸附动力学、等温吸附线特征以及pH值对吸附过程的影响。结果表明:E2和EE2在土壤中的吸附过程可以分为快速吸附和慢速平衡过程。整个吸附阶段一级动力学模型拟合效果最好,吸附速率常数分别为2.32 h-1和1.97 h-1。E2和EE2的等温吸附线能够较好的符合线性、Freundlich和Langmuir模型,其中Langmuir模型拟合效果最好,最大吸附量分别为45.27~49.07μg/g和53.14~56.84μg/g。随着温度的增加,E2和EE2的吸附过程会受到抑制。在pH值为2~8时,土壤对E2和EE2的吸附量变化比较平稳;在pH值为8~12时,呈明显的下降趋势。     

复合磁性纳米凝胶球对典型抗生素的吸附特性

以复合磁性纳米凝胶球(Fe₃O₄@PVA-SA-PAC)为吸附剂,探究其对水中磺胺甲噁唑(SMX)、环丙沙星(CIP)、甲氧苄啶(TMP)抗生素类污染物去除效果,并分析pH、投加量、污染物初始浓度、吸附时间等因素对吸附过程的影响。结果表明:pH=3时最有利于抗生素吸附;吸附量随着初始浓度增大而上升,随着投加量增加而下降;3种抗生素吸附表现为物理吸附和化学吸附共存、均质单分子层吸附与非均质多分子层吸附共同作用的状态。其中SMX与CIP吸附更符合准二级动力学模型,而TMP更符合准一级动力学模型;温度为308 K时,Langmuir与Freundlich方程均达到较高拟合度(0.938≤R2≤0.998),此时SMX、TMP和CIP的最大吸附量分别为47.188,59.649,96.468 mg/g;竞争性吸附试验表明复合凝胶球可同时吸附多种目标抗生素污染物,具备良好吸附应用前景。     

玉米芯生物炭对2,4-D在土壤中吸附性能的研究

研究了玉米芯生物炭剂对土壤中2,4-D的吸附性能,并探讨了影响吸附的因素和吸附机理.结果表明:生物炭可使土壤对2,4-D的吸附容量显著增大.吸附结果用Freundlich和Redlich-Peterson方程都可以较好地拟合(R20.95).60 h后,与对照土壤相比,添加质量分数为0.5%生物炭的土壤对2,4-D的最大吸附量从20.83μg·g-1升高到58.82μg·g-1.吸附动力学研究表明,伪二级动力学速率方程对土壤吸附2,4-D的过程拟合效果较好(R20.99),优于一级动力学速率模型;p H和温度对土壤中2,4-D的吸附影响显著,p H接近3.1和40℃的水浴环境更利于添加生物炭的土壤对2,4-D的吸附.玉米芯生物炭可作为原位修复剂吸附土壤中的2,4-D,从而降低土壤中有机污染物的迁移性和生物有效性.     

碳基吸附剂对典型有机防晒剂二苯甲酮-3的吸附性能及热力学研究

针对环境水体中药物及个人护理用品(PPCPs)的污染问题,选择在环境水体中存在的有机紫外防晒剂二苯甲酮-3(BP-3)作为典型污染物,以颗粒活性炭(GAC)、粉末活性炭(PAC)和碳纳米管(CNT)作为吸附剂,考察吸附剂对BP-3的吸附性能、吸附特性和吸附热力学.结果表明:吸附性碳材料对BP-3具有良好的吸附性能,3种碳材料的最大吸附容量排列为:PACGACCNT,其中,PAC的单层最大吸附容量为450.36mg·g-1.Freundlich、Redlich-Peterson和Temkin吸附等温线方程能够较好地拟合吸附数据,Langmuir吸附等温线方程对PAC的吸附拟合效果较好,而对粒径较大的吸附剂(GAC、CNT)的拟合效果不理想.PAC、GAC的吸附过程可以采用一级动力学或者二级动力学模型拟合,而CNT适合采用一级动力学模型来描述.吸附热力学分析表明,PAC、GAC和CNT对BP-3的吸附过程都是自发进行的,其中,PAC和GAC的吸附过程是吸热的,升高温度有利于吸附反应的进行;而CNT的吸附过程是放热的.     

木质素降解酶在不同堆肥基质中的吸附传输特性研究

为了深入探究木质素降解酶在不同堆肥基质中的吸附传输特性,通过批量实验对比了土壤、菜叶、稻草和米糠对木质素降解酶的吸附性能,并进行了动力学分析和等温吸附模型拟合,同时通过柱淋洗实验考察了木质素降解酶在4种堆肥基质中的迁移传输特性.结果表明,堆肥基质对木质素降解酶的吸附与基质种类有关,土壤、菜叶、稻草和米糠对木素过氧化物酶(LiP)和锰过氧化物酶(MnP)的吸附量分别为1.22、 1.27、 1.13、 1.22 U·g-1和5.09、 4.88、 4.43、 3.95 U·g-1.比较LiP和MnP吸附的动力学模型,准二级动力学方程为表征木质素降解酶吸附的最佳模型,其R2值为0.9732～0.9997, Elovich方程拟合较差,准一级动力学方程拟合最差;Langmuir模型对等温吸附数据进行拟合效果最好,而实验数据不适合用Freundlich方程表征.土壤、菜叶、稻草和米糠对LiP和MnP饱和吸附容量分别为1.23、1.30、1.17、1.14 U·g-1和5.70、 5.19、 4.73、 4.14 U·g-1.LiP和MnP在稻草和米糠基质中传输效果较好,可传输到最深层10 mL处,而在土壤和菜叶基质中则被滞留在浅层.     

有机质对p,p′-DDE在土壤中的吸附影响

为研究有机质对p, p′-DDE在土壤中的吸附影响因素,采用批量试验方法,分析p, p′-DDE在包气带土壤及含水层土壤上吸附量的变化及有机质对p, p′-DDE在土壤中的吸附影响.结果表明,p, p′-DDE在土壤中的吸附均符合先快后慢、最后达到吸附平衡的规律;其吸附动力学曲线用一级和二级反应动力学方程均能较好拟合,说明p, p′-DDE在这两种物质中的吸附以简单吸附为主,同时包含表面吸附、颗粒内部扩散等过程.包气带土壤和含水层土壤等温吸附线的拟合相关系数(R2)均大于0.95,符合Freundlich模型和线性模型,而含水层样品与Freundlich模型拟合得更好,表明p, p′-DDE在包气带土壤中的吸附以单分子层吸附为主,而在含水层土壤中的吸附还伴随着多分子层吸附的复杂过程;去除内源DOM(溶解性有机质)后,样品对p, p′-DDE的吸附量呈增加趋势,按吸附增加量由小到大的排序为1-1(0~10 cm) < 1-2(120~150 cm) < 2-4(100~120 cm),说明内源DOM的存在总体上抑制了p, p′-DDE的吸附,并且w(DOM)越高,其抑制作用越强;外源DOM的加入抑制了土壤对p, p′-DDE的吸附;去除有机质后样品对p, p′-DDE的吸附量与w(黏土矿物)具有正相关性.研究显示,有机质对土壤中有机污染物的吸附迁移研究对土壤修复有重要意义,需要对有机质影响土壤的吸附机制进行更深层次的研究.      

锑矿冶炼区周边土壤吸附Sb(Ⅴ)的行为研究

本文通过吸附平衡和动力学实验方法对Sb(V)在锑矿冶炼区周边土壤表面开展吸附行为研究,用常用的等温吸附模型和动力学吸附模型分别对等温吸附曲线和动力学吸附曲线进行拟合。结果表明:Langmuir与Freundlich模型对荒地土和林地土吸附Sb(Ⅴ)的等温吸附曲线均有较好的拟合效果,拟合系数R~2≥0. 988。荒地土对Sb(Ⅴ)的吸附能力大于林地土,其吸附量是林地土的2. 9±0. 2倍,这与Langmuir模型预测的该两种土壤的吸附倍数相当,荒地土表现出强烈吸附Sb(Ⅴ)的能力,尤其在锑浓度较高的体系中更为明显。结合土壤基本理化性质及矿物学特征,认为土壤秥粒、铁矿物和碳酸钙是影响土壤吸附Sb(V)的主要因素。有机质对土壤吸附Sb(Ⅴ)有一定促进作用,但这种影响只表现在Sb(Ⅴ)初始浓度低的条件下;而在Sb(Ⅴ)初始浓度高的条件下,有机质对土壤吸附Sb(Ⅴ)的影响不明显。土壤吸附Sb(Ⅴ)的过程分为快速吸附和慢速吸附两个阶段,快速反应发生在70 min以内。初始浓度低(0. 01 mmol/L)的条件下,Elovich方程能够很好地拟合荒地土和林地土吸附Sb(V)的动态曲线;初始浓度高(2 mmol/L)的条件下,双常数方程对荒地土吸附Sb(V)的拟合效果较好,拟一级动力学方程和拟二级动力学方程则适用于拟合林地土吸附Sb(V)的过程。     

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.     

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.     

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.     

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.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.