响应曲面法优化油茶饼对活性红15的生物吸附特征及机理

基于“以废治废”的理念,以农林业废弃物——油茶饼为原料制备生物吸附剂,吸附去除废水中的RR15(C.I. Reactive Red 15,活性红15)染料,并采用响应曲面法中的Box-Behnken设计对油茶饼生物吸附剂吸附RR15的条件进行优化. 结果表明:pH对油茶饼生物吸附剂吸附RR15的吸附容量和去除率均有显著影响(P<0.000 1);当pH为1.0、初始ρ(RR15)为300 mg/L、吸附温度为20 ℃时,油茶饼生物吸附剂对RR15的吸附效果最佳. 相比于Langmuir和Freundlich吸附等温线模型,Temkin吸附等温线模型可以更好地描述油茶饼生物吸附剂对RR15的吸附平衡数据. 吸附温度为20 ℃时,由Langmuir吸附等温线模型计算得到的Q0(吸附剂的单层饱和吸附量)为74.63 mg/g. 动力学分析显示,油茶饼生物吸附剂对RR15的吸附过程符合准二级动力学模型(R2>0.999 7),支持了限速步骤是化学吸附的理论;内部扩散和边界层扩散都可能影响吸附速率. 热力学分析表明,该吸附过程是一个自发的放热过程. FTIR(fourier transform infrared spectroscopy,傅里叶变换红外光谱)分析发现,油茶饼生物吸附剂上羟基、胺基等官能团可能是RR15染料的主要结合位点. 研究显示,油茶饼生物吸附剂是一种具有潜力的绿色吸附剂,可以有效去除废水中的RR15染料.      

净水污泥柠檬酸钠改性焙烧制备陶粒吸附剂及其对废水中氨氮吸附性能的研究

以净水污泥为原料,选用盐酸、氢氧化钾、柠檬酸钠为改性剂,通过研磨-改性-造粒-焙烧等工艺制备改性净水污泥陶粒吸附剂(以下简称改性陶粒吸附剂),测定其对水中氨氮的吸附量,筛选出最佳改性陶粒吸附剂和最佳改性陶粒吸附剂浓度,并在相同条件下制备原净水污泥陶粒吸附剂(简称原泥陶粒吸附剂)作为对比;采用XRD、BET、FTIR、SEM/EDX分析手段对改性陶粒吸附剂和原泥陶粒吸附剂两种吸附剂进行了表征,并通过静态吸附对比实验,探讨了两种吸附剂对废水中氨氮吸附效果的影响因素;对试验数据进行了吸附等温线和吸附动力学模型拟合研究,并探讨了饱和改性陶粒吸附剂对氨氮的解吸和重复再生效果。结果表明:(1)净水污泥的最佳改性条件为采用0.5 mol/L的柠檬酸钠搅拌混合并在65℃水浴温度下浸泡5 h;(2)改性陶粒吸附剂对氨氮的去除效果与原泥陶粒吸附剂相比有显著提高,当溶液最佳pH为7、饱和吸附时间为6 h、吸附剂投加量为20 g/L、氨氮初始浓度为50 mg/L时,改性陶粒吸附剂的最大吸附量为1.938 mg/g,为原泥陶粒吸附剂的2.46倍;(3)吸附等温线和吸附动力学的拟合结果表明,改性陶粒吸附剂和原泥陶粒吸附剂对氨氮的吸附过程均符合Langmuir模型和准二级动力学模型;(4)饱和改性陶粒吸附剂的最佳再生液为0.1 mol/L的NaOH溶液,经过5次解吸再生后,对氨氮的解吸率仅下降6.53%。     

铝改性粉煤灰漂珠材料吸附水中氟的性能研究

采用湿法+干法制备铝改性漂珠材料,借助静态吸附实验研究吸附剂用量、pH值、共存离子、反应时间和反应温度对去除水溶液中氟离子性能的影响,并对实验数据进行吸附等温线和动力学拟合。结果表明:铝改性漂珠材料吸附水中氟离子的最佳pH值为3;最佳吸附剂用量2.5 g/L;共存离子影响由强到弱的顺序为H2PO4-,SO42-和NO3-的混合物﹥H2PO4-﹥SO42-﹥NO3-;在温度298 K、吸附剂用量2.5 g/L、pH值为3和反应时间24 h的条件下,最大吸附容量约10.2 mg/g;吸附等温线符合Langmuir单层吸附模型;动力学过程符合准二级动力学模型。     

改性磁性纳米颗粒固定内生菌Bacillus nealsonii吸附废水中Cd2+的特性研究

从重金属超累积植物龙葵体内提取内生菌Bacillus nealsonii,采用二氧化硅改性纳米Fe_3O_4颗粒与海藻酸钠将其包埋交联进行固定化,制得一种新型球状生物吸附剂,并应用于废水中Cd~(2+)的吸附处理.同时,通过正交实验研究了该球状生物吸附剂的最佳制备条件和吸附处理条件,并采用扫描电镜等表征手段与构建吸附动力学考察了其吸附特征.结果表明,球状生物吸附剂的最佳制备条件为:改性纳米Fe3O4颗粒质量分数为0.1%,海藻酸钠质量分数为8.0%,菌液接种量为0.4%,交联时间为2 h;其最佳吸附处理条件为p H=6、吸附时间12 h、吸附剂用量(干重)2.5 g·L-1,在Cd~(2+)初始浓度为50 mg·L-1时的吸附率可达96%以上.研究发现,球状生物吸附剂的内外部结构孔隙率较大,有利于促进Cd~(2+)的吸附.该吸附过程遵循准二级反应动力学,以化学吸附为主,符合Freundlich等温吸附模型,最大单分子吸附量可达13.02 mg·g-1.解吸实验结果表明,该吸附剂具有较好的可重复利用性.     

牛粪生物炭对水中氨氮的吸附特性

以牛粪生物炭为吸附剂,研究了p H、粒径、投加量、温度和共存阳离子等因素对牛粪生物炭吸附氨氮的影响及吸附特性.结果表明,共存阳离子Na+、Ca2+的存在对牛粪生物炭吸附氨氮有抑制作用,在Na+、Ca2+浓度相同条件下对氨氮吸附影响大小顺序为Na+Ca2+;牛粪生物炭吸附氨氮的最佳初始p H值应在5~8范围;通过对动力学数据进行分析,发现准二级动力学方程(R2=0.967 3)比准一级动力学方程(R2=0.765 9)和Elovich方程(R2=0.724 9)能更好地拟合动力学数据,颗粒内扩散方程拟合结果发现牛粪生物炭对氨氮的吸附包括表面吸附和颗粒内扩散两个过程.吸附等温线拟合发现Freundlich方程(R2=0.976 2)能很好地描述氨氮在牛粪生物炭上的吸附行为.吉布斯自由能变化(ΔGθ)、焓变(ΔHθ)和熵变(ΔSθ)的计算结果表明,牛粪生物炭对氨氮的吸附是自发的吸热过程.     

柠檬酸改性木薯秸秆阳离子吸附剂的制备及其对Cu~(2+)的吸附

以柠檬酸为改性剂对木薯秸秆进行改性制备阳离子吸附剂。以铜离子去除率作为评价吸附剂吸附性能指标,对制备最佳条件进行了优化,利用FT-IR、SEM、Zeta电位和X衍射技术对制备的吸附剂进行了结构表征,考察了对铜离子吸附过程动力学和等温吸附规律。实验结果表明:最佳的改性反应物(木薯秸秆∶柠檬酸)剂量比为1 g∶7.2×10~(-3)mol,反应温度为120℃,反应时间30 min;表征结果证明了改性吸附剂中羧基的存在;柠檬酸改性木薯秸秆吸附剂能够快速吸附重金属铜离子,吸附过程符合准二级动力学模型;吸附等温线符合Langmuir模式,饱和吸附量达到2.19 mmol/g。证明柠檬酸改性木薯秸秆吸附剂是一种潜在的重金属废水处理剂。     

包埋固定化海洋硅藻吸附材料的制备及其对水中铅离子的吸附特性研究

采用海藻酸钠(SA)凝胶包埋法对海洋硅藻藻粉进行固定化,考察了藻粉用量、海藻酸钠浓度、Ca Cl2质量分数、交联时间及小球粒径对固定化小球吸附铅离子性能的影响,并研究了这种吸附材料对Pb~(2+)的吸附特性.结果表明,固定化海洋硅藻生物吸附剂的最佳制备条件为:藻粉用量5.0 g/100 m L SA、海藻酸钠浓度20 g·L~(-1)、Ca Cl2质量分数0.5%、交联时间1 h、小球粒径2.8 mm左右.Langmuir等温吸附模型能够较好地描述固定化小球吸附对Pb~(2+)的等温吸附特征,R2为0.9983,最大理论吸附量为833.33 mg·g~(-1).准二级动力学模型能够较好地拟合固定化小球吸附Pb~(2+)的动力学过程,理论平衡吸附量为714.29 mg·g~(-1),与实验所得平衡吸附量706.55 mg·g~(-1)较为接近.固定化小球吸附Pb~(2+)的适宜初始p H值为4~5.Na Cl、Ca(NO3)2、Mg(NO3)2对固定化小球的吸附性能有一定的促进作用.本研究所制固定化海洋硅藻球形吸附材料对Pb~(2+)的吸附容量明显优于大部分研究所报道的固定化生物吸附剂,是一种很有潜力的生物吸附材料.     

铝改性粉煤灰漂珠吸附水溶液中砷的性能研究

采用湿法与干法相结合的方法合成铝改性粉煤灰漂珠环境材料,借助静态吸附实验研究吸附剂量、pH值、离子强度、共存离子、反应时间和温度对其吸附水溶液中砷性能的影响,并进行吸附等温线和动力学拟合.结果表明:铝改性粉煤灰漂珠吸附水中As(V)的最佳pH值范围为中性偏酸;混合离子和H2PO4-对As(V)的吸附影响较大,CO32-次之;离子强度对As(V)吸附的影响不明显;在温度298K、吸附剂量2.5g/L和反应时间24h的条件下,最大吸附容量约5000μg/g;吸附等温线符合Langmuir单层吸附模型;动力学过程符合准二级动力学模型.     

纳米Fe3O4负载的浮游球衣菌去除重金属离子的工艺研究

以纳米Fe3O4负载浮游球衣菌(Sphaerotilus natans)制备复合生物吸附剂,对此吸附剂进行表征并考察了其吸附水中重金属离子的性能.红外光谱分析表明,此复合生物吸附剂表面的主要活性基团为酰胺基(-CONH-)和羟基(-OH).吸附性能研究表明,菌含量和流量是影响复合生物吸附剂吸附重金属离子的主要因素,在Cu2 初始浓度c0＜20 mg/L,菌含量1.5 g/L(菌/Fe3O4=3:2),流量0.96 L/h时吸附剂对Cu2 的吸附效果最好;用稀盐酸对复合生物吸附剂进行再生,吸附剂可重复使用10次以上,再生液可重复使用3次;吸附选择性为:Pb2 ＞Cu2 ＞Zn2 ＞Cd2 .     

虾蟹壳对水中刚果红吸附性能的研究

以虾蟹壳为原料,采用酸化一步法制备出具有强吸附能力的虾蟹壳生物吸附剂,通过模拟试验研究了该吸附剂对废水中刚果红的去除特性,分析了吸附剂用量、吸附时间、pH值、吸附温度、刚果红初始浓度对吸附效果的影响。结果表明,最佳的吸附条件为吸附剂用量0.1 g、pH=7、吸附温度65℃、吸附时间2 h,最佳条件下的刚果红去除率达到92.96%。吸附剂对刚果红的吸附过程与拟二级动力学模型相符,吸附反应涵盖了外部液膜扩散、表面吸附和颗粒内扩散,其吸附速率与驱动力的平方成正比。     

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.