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 .     

凤眼莲对二价铁锰离子的吸附及机理研究

利用凤眼莲根、茎、叶粉末吸附水溶液中的Fe2+、Mn2+,并通过一系列的条件优化,确定了最佳的吸附条件.同时,采用等温吸附模型与动力学模型拟合研究了吸附特性.结果表明,凤眼莲根、茎、叶对Fe2+的吸附能力依次为根＞叶＞茎,对Mn2的吸附能力依次为茎＞叶＞根;在Fe2+、Mn2+起始浓度分别为45 mg·L-1和75 mg·L-1,pH分别为4.0和5.0,吸附剂添加量为0.4g,摇床转速为180 r·min-1,温度为50℃的条件下,根对Fe2+的最大吸附量为(21.73±0.38) mg·g-1,茎对Mn2+的最大吸附量为(15.55±0.58) mg·g-1,去除率分别达到96.58％和82.93％.Langmuir模型和准二级动力学模型能够较好地拟合Fe2+、Mn2+的吸附过程,吸附活化能与傅立叶红外光谱等表明该过程为物理化学吸附.与现有的Fe2+、Mn2+吸附生物质相比,凤眼莲粉末吸附水溶液中Fe2+、Mn2+的能力较突出,是一种极具潜力的吸附材料.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

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.     

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.     

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.     

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.     

Chlorobenzenes in waterweeds from the Xijiang River （Guangdong section） of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes (CBs) in both water and waterweeds collected from 4 stations in the Xijiang River (Gangdong section) of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs (∑CBs) in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ∑ CBs in waterweeds ranged from 13.53×102 μg/g to 38.27×102μg/g dry weight (dw). There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs(DCBs), whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip (bioconcentration factor) of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was: Fengkai County ＜ Yunan County ＜Yun'an County ＜ Gaoyao County according to the ∑CBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River.     

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process

Degradation of 2,4-dichlorophenol(2,4-DCP)was studied in a novel three-electrode photoelectrocatalytic(PEC)integrative oxidation process,and the factors influencing the degradation rate,such as applied current,flow speed of O_2,pH,adscititious voltage and initial 2,4-DCP concentration were investigated and optimized.H_2O_2 was produced nearby cathode and Fe~(2 )continuously generated from Fe anode in solution when current and O_2 were applied,so,main reactions,H_2O_2-assisted TiO_2 PEC oxidation and E-Fenton reaction,occurred during degradation of 2,4-DCP in this integrative system.The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process,while it was only 31% in E-Fenton process and 46% in H_2O_2-assisted TiO_2 PEC process.So,it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect.By the investigation of pH,it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

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.