Al13改性羟基磷灰石的除氟性能研究

为了提高羟基磷灰石（HAP）的除氟效果,采用化学沉淀法合成3种不同Al/Ca值的Al₁₃改性后的HAP吸附材料,并对其进行XRD、FTIR、SEM、BET等表征,考察吸附过程中pH的影响,同时通过吸附热力学、吸附动力学等探讨了其除氟性能.结果表明,Al₁₃-HAP材料比HAP更加疏松多孔,当Al/Ca=0.7时,比表面积增大到了137.2 m²·g^-1,孔容增大到0.8217 cm³·g^-1.FTIR结果表明,Al₁₃的掺入给吸附材料中带入了大量—OH.根据Al₁₃-HAP吸附F^-前后的表征,F^-主要通过配体交换取代Al₁₃-HAP中的—OH从环境中被去除.当Al/Ca=0.4时,Al₁₃-HAP最大除氟效果达到5.03 mg·L^-1;零电荷点pH_PZC为8.46,大于HAP的pH_PZC,具体表现为对天然水体pH值适用性较广.吸附过程与Langmuir吸附模型以及拟二级动力学模型契合度高,这也证实了化学吸附为主要作用,吸附热力学结果表明Al₁₃-HAP吸附氟是自发的吸热过程.     

改性活性炭除亚砷酸盐的性能研究

制备了2种负载铁锰氧化物的改性活性炭（FM-GAC-1、FM-GAC-2）并研究其对水中的亚砷酸盐的去除性能.考察了2种改性活性炭除三价砷的吸附等温线、反应动力学及pH、温度、水中共存离子对其去除三价砷的影响,发现FM-GAC-1和FM-GAC-2对三价砷均有较好的去除效果,吸附容量分别为32.37、 26.67 mg·g^-1.吸附速率符合拟二级反应动力学,化学反应控制过程是改性活性炭除砷的限速步骤.pH值偏酸性有利于吸附的进行,温度升高,吸附容量有所下降,该吸附过程是自发的放热过程.同时,水体中的共存阴离子在其浓度值为三价砷的200倍时,SiO^2-₃、 PO^2-₃、NO^-₃对FM-GAC-1吸附三价砷有明显影响; SiO^2-₃、CO^2-₃对FM-GAC-2吸附三价砷有显著影响.总体上讲,FM-GAC-1较FM-GAC-2有更为优异的去除三价砷性能.     

CaO2@FA复合材料富集磷效能及其回收物对土壤改良作用

为实现污水中磷和工业废弃物粉煤灰的资源化利用,通过表面沉淀法将纳米CaO₂负载于粉煤灰（FA）表面以及孔隙中,制备出一种高效除磷的复合材料（CaO₂@FA）.结果表明,粉煤灰表面负载CaO₂后,其具有更大的比表面积和孔隙率,比表面积增加至4.641 m² ·g^-1,总孔容增大至0.025 cm³ ·g^-1;CaO₂@FA对磷的吸附过程符合Langmuir等温吸附模型,其最大吸附容量为185.776 mg ·g^-1（20℃）,吸附机制为化学沉淀,主要是形成羟基磷酸钙.CaO₂@FA复合材料对磷的富集效率显著高于粉煤灰,并随着投加量增加,对磷的富集效率增加.共存离子中HCO^3-和CO₃^2-对复合材料吸附磷有一定的负面作用.当CaO₂@FA复合材料投加量为2.0 g ·L^-1时,对生活污水中磷的富集率可达93%,回收沉淀物中的有效磷含量达到1.658 mg ·g^-1.土壤改良实验表明,加入回收的沉淀物可使土壤中有效磷含量增加102.9%,该复合材料回收100 mg磷酸盐的运行成本则低至0.76元.     

Fe2O3/PC功能化复合多孔炭材料的制备及除磷机理

采用热活化法辅以加压超声浸渍技术将硅酸盐水泥颗粒（PC）和Fe₂O₃负载于稻壳生物炭（RHC）的表面,得到了具有优异除磷效能和高选择性吸附性能的Fe₂O₃/PC功能化复合多孔炭材料（Fe-PC/RHC）.基于磷吸附容量和磷去除率,对PC和Fe³⁺负载进行量的优化;选取优化炭进行比表面积、孔径分布、物相结构、表面结构、微观形貌和零电位点表征测定.结果表明：复合炭材料表面均匀分散着硅酸钙盐、硅酸铁盐和Fe₂O₃等矿物活性颗粒,对其比表面积、孔结构和吸附性能具有增强作用;当RHC：PC=0.8：1（质量比）,Fe³⁺：RHC=2：1（2 mmol·g^-1）时制备的炭材料Fe₂-PC/RHC,投加0.2 g,处理100 mg·L^-1的磷酸盐溶液,在pH=6~8的条件下表现出了优异的吸附性能;铁盐的掺杂能有效调控介质pH值从11.09降低至7.71,zeta电位从2.82提高到7.57;准二级动力学模型和Langmiur模型更适用于描述Fe₂-PC/RHC吸附磷酸盐的过程,吸附4 h后逐渐趋于平衡,饱和吸附量为69.92 mg·g^-1;在几种常见阴离子和阳离子共存的情况下,Fe₂-PC/RHC对磷酸盐仍然表现出了优异的选择性吸附;结合吸附前后材料的表征结果,化学吸附是主要的除磷机理,此外还可能存在配体交换和静电吸引.     

磁性CeO2-Fe3O4复合材料光催化/吸附去除水中As(III)

原水砷污染问题严重威胁饮用水水质安全,随着生活饮用水标准的提高,致使多地饮用水中砷超标问题突显.本研究利用CeO₂半导体的光催化活性及CeO₂和Fe₃O₄对As（V）的强亲和力,合成了双组份磁性CeO₂-Fe₃O₄复合材料,并采用SEM、XRD、BET和VSM等手段进行表征,考察复合材料的光催化/吸附除砷效果;研究了初始pH值、共存离子等因素对吸附除砷效果的影响;采用等温吸附模型、吸附动力学模型等手段进行吸附特性研究.实验结果表明,在光催化过程中,·OH和·O₂^-为主要的活性氧化物种.在紫外照射下,As（Ⅲ）能完全被氧化为毒性较低的As（V）,同时将As（V）高效吸附于CeO₂-Fe₃O₄粒子表面.在中性条件下,CeO₂-Fe₃O₄粒子对砷的饱和吸附量为122.19 mg·g^-1.共存离子Cl^-和SO₄^2-对As（V）的吸附没有显著影响,而CO₃^2-、SiO₃^2-和PO₄^3-与As（V）存在明显的竞争吸附,使As（V）的吸附去除效果明显降低.吸附动力学和吸附等温线模拟分别符合准二级动力学方程和Freundlich吸附等温线,表明As（V）的吸附以化学吸附为主导.CeO₂-Fe₃O₄复合吸附剂可快速实现固液分离,容易再生且重复利用性较好,具有广泛的应用前景.     

新型饮用水除氟材料Bio-F的除氟特性和比较研究

对3种传统除氟剂活性氧化铝、骨炭和改性沸石与自制的新型生物除氟剂Bio-F的除氟性能及影响因素（材料粒径、pH值、吸附时间、水样含氟浓度、其它离子、再生能力等）进行了比较,并模拟动态实验评估了这4种除氟材料对实际高氟地下水处理的效果.结果表明,Bio-F生物除氟剂对F^-的吸附过程符合Lagergren一级吸附动力学特征（R²=0.958 0）,吸附速率较快,且该过程属于吸热反应; Bio-F吸附F^-符合Langmuir吸附等温模型（R²=0.999 2）,吸附容量高,静态吸附容量可达4.088 3 mg·g^-1,分别约是活性氧化铝和改性沸石的1.8和 5.8倍.4种除氟材料吸附容量与氟浓度正相关,与吸附剂粒径负相关.高浓度的CO^2-₃、HCO^-₃明显抑制Bio-F的除氟（p<0.05）,但高浓度的Ca²⁺、NO^-₃、HPO^2-₄有利于Bio-F的除氟（p<0.001）.Bio-F除氟最佳停留时间3～4 min,远远低于沸石20 min和活性氧化铝11 min.在pH 4.0～9.0范围内Bio-F可保持90％以上吸附F^-的能力.再生性能稳定,10次再生后吸附容量变化不超过15%.Bio-F综合性能优于其它3种传统除氟剂,在我国广大农村地区推广有显著优越性.     

纳米磁性磷酸二氢钙对Cd的吸附、回收与再生

以Ca（H₂PO₄）₂、铁盐与亚铁盐为原料,采用共沉淀法制备成纳米磁性材料Ca（H₂PO₄）₂@Fe₃O₄（NMCDP）,研究其对Cd²⁺的吸附、回收与再生效果.透射电镜（TEM）、红外光谱（FTIR）、X射线衍射（XRD）显示,NMCDP粒径约60 nm,稳定性良好,饱和磁化强度为30.9 emu·g^-1.吸附动力学表明,NMCDP对Cd²⁺的吸附1 h之内即可达到平衡,符合准二级动力学模型.吸附热力学表明,NMCDP对Cd²⁺的吸附符合Langmuir与Freundlich等温吸附模型,最大吸附量为142.50 mg·g^-1.在pH值由2增加到3时,吸附量随溶液初始pH值的升高而增加,当pH值大于3后,逐渐保持稳定;溶液中共存离子Na⁺、Mg²⁺、Cu²⁺对材料吸附Cd²⁺均有一定的影响,影响程度Cu²⁺ > Mg²⁺ > Na⁺.采用0.01 mol·L^-1 HCl与EDTA-Na₂均可解吸出部分吸附的Cd²⁺,以EDTA-Na₂解吸率较高,达到68%,从而实现NMCDP的再生.     

镧铁羟基氧化物修饰还原氧化石墨烯复合电极材料电吸附除磷效能及机理研究

污水处理厂尾水中低浓度PO₄^3-的排放是水体中总磷的主要来源,是导致水体富营养化的重要原因之一,对其开展深度去除的应用基础性研究具有重要的理论意义和实践价值.复合金属氧化物材料表现出较好PO₄^3-吸附能力,但仍然存在吸附速率较慢的问题.本研究采用溶剂热、复合薄膜压片法制备了镧铁羟基氧化物（LaFeO_xH_y）修饰还原氧化石墨烯（rGO）复合电极材料（LaFe-rGO）,LaFe-rGO复合电极材料显著提高了对PO₄^3-的吸附速率,5 min可达到吸附平衡,在1.2 V电压下对PO₄^3-的最大吸附量为108.69 mg·g^-1.提出了基于晶格氧提供活性位点及LaFe-rGO双电层电容电促吸附除磷机理,LaFe-rGO复合电极材料中晶格氧La-O与Fe-O同时对PO₄^3-吸附提供吸附位点,PO₄^3-与材料中的La/Fe键合以形成内球表面复合物La/Fe-PO₄,掺杂在rGO表面上的LaFeO_xH_y增加了电极材料电容并提高了其电化学活性,促进了LaFe-rGO复合电极材料对PO₄^3-的吸附.     

CuFeO2改性生物炭对四环素的吸附特性

利用共沉淀和水热法于生物炭（BC250、BC350、BC450、BC550和BC650）负载CuFeO₂,得到的复合材料对水中四环素（TC）具有较好的去除效果.CuFeO₂与BC450质量比为2 ：1的CuFeO₂改性生物炭（CuFeO₂/BC450=2 ：1）对TC的吸附性能最强.TC于CuFeO₂/BC450=2 ：1的吸附符合颗粒内扩散模型,表明吸附是界面和孔隙扩散控制的过程.在中性pH、298 K下,CuFeO₂/BC450=2 ：1对TC的Langmuir最大吸附量为82.8 mg ·g^-1,远大于BC450的13.7 mg ·g^-1和CuFeO₂的14.8 mg ·g^-1.热力学结果表明,CuFeO₂/BC450=2 ：1对TC的吸附是自发和吸热过程.随pH增加,CuFeO₂/BC450=2 ：1对TC的吸附去除呈先增加后降低的趋势,中性条件时效果最佳.CuFeO₂/BC450=2 ：1对TC的强吸附得益于CuFeO₂负载对材料孔隙结构的改善、比表面积的增大和表面官能团、电荷属性的改变.研究结果为净化抗生素污染提供了一种高效的磁性吸附剂.     

热处理对天然富钙粘土矿物除磷能力的影响

以天然富钙粘土矿物（海泡石和凹凸棒）为研究对象,采用热处理的方法对其进行活化,并利用X-射线衍射（XRD）分析了矿物结构的变化,同时研究了热处理粘土矿物的除磷能力和机制.结果表明,热处理能够显著改变海泡石和凹凸棒的矿物组成,大幅提高其对磷的吸附能力,并分别在900 ℃和800 ℃的活化条件下对磷的吸附能力达到最佳,吸附量分别可达37.7 mg·g^-1和30.9 mg·g^-1.Freundlich方程和准二级方程能较好地拟合热处理粘土对磷的吸附热力学和动力学过程.同时还发现,pH值（3~10）对热处理粘土除磷能力基本无影响.热处理富钙粘土的除磷机制主要是与溶液中的磷生成钙磷沉淀.     

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.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.