响应曲面法优化KOH改性污泥生物炭的制备及其强化去除Pb（Ⅱ）的研究

采用响应曲面法优化了KOH改性污泥生物炭（SB-KOH）的制备条件,研究了各因素之间对生物炭吸附性能的交互影响,并且探讨了KOH强化生物炭吸附能力的机制.同时,研究了吸附时间、吸附温度及pH对SB-KOH吸附Pb（Ⅱ）的影响,探讨其吸附机理.结果表明：KOH浸渍浓度是最显著因素,较高浸渍浓度有利于提高SB-KOH的吸附性能;增加KOH浸渍浓度和升高热解温度可以协同提高SB-KOH的吸附性能;最佳制备条件为2.5 mol·L^-1的KOH浸渍浓度、7 h的浸渍时间、631 ℃的热解温度和44 min的热解时间.KOH改性后的污泥生物炭表面粗糙, 比表面积增大,微孔数量增加,SB-KOH的比表面积为141.22 m²·g^-1,是原污泥生物炭（SB,5.93 m²·g^-1）的24倍,改性后的生物炭碱性提高、K元素含量增加.SB-KOH吸附Pb（Ⅱ）是以化学吸附为主的多分子层混合吸附,膜扩散是主要的速率控制步骤,增加溶液pH、提高温度可促进吸附.吸附机制涉及矿物沉淀（Q_mp）、离子交换（Q_ie）、含氧官能团的络合（Q_oc）和金属π键结合（Q_mπ）,不同吸附机理的贡献顺序为：Q_mp（143.5 mg·g^-1）>Q_ie（39.67 mg·g^-1）>Q_oc（8.56 mg·g^-1）>Q_mπ （1.65 mg·g^-1）,KOH改性强化了生物炭对Pb（Ⅱ）的矿物沉淀和离子交换吸附量.本研究丰富了KOH改性污泥生物炭的制备理论,阐明了SB-KOH吸附Pb（Ⅱ）吸附机理及其影响的主要机制.     

NaHCO3活化荞麦皮生物炭对碘帕醇的吸附

采用NaHCO₃活化荞麦皮生物炭,优化得到生物炭0.25N-BC[m（NaHCO₃）：m（荞麦皮）=0.25：1],通过SEM、BET、XRD、Raman、FTIR和XPS等方法进行表征,分析NaHCO₃对生物炭理化性质的影响,探究其对非离子型碘代X射线造影剂碘帕醇（IPM）的吸附性能和机制.结果表明,与荞麦皮生物炭相比（BC）,NaHCO₃活化生物炭的结构缺陷程度更高（比表面积和孔体积分别由480.40 m²·g^-1和0.29 cm³·g^-1增至572.83 m²·g^-1和0.40 cm³·g^-1,I_D/I_G是BC的1.22倍）,表面含碳和含氧官能团数量发生显著变化,极性增强[（N+O）/C由0.15增至0.24],能够有效吸附IPM,0.25N-BC对IPM最大吸附量达到74.94 mg·g^-1,是BC （7.88 mg·g^-1）的9.51倍.拟二级吸附动力学和Langmuir、Freundlich等温线模型可很好地拟合0.25N-BC对IPM的吸附,吸附过程主要以化学吸附和单层、非均质多层吸附为主;孔隙填充、氢键、π—π和n—π相互作用是0.25N-BC吸附IPM的主要机制.对比不同碱[KOH、Na₂CO₃、NaHCO₃、KHCO₃和Ca （HCO₃）₂]活化荞麦皮生物炭对IPM的吸附,0.25N-BC吸附效率高,达到吸附平衡时间短,能有效去除实际水体（二沉池出水和湖水）中IPM的残留,并具有良好的循环使用性能,吸附-解吸3次后对IPM的去除率仍保持在74.91%.研究表明NaHCO₃活化荞麦皮生物炭是一种绿色有效,可持续去除含碘有机物的优良吸附剂.     

硼掺杂介孔炭吸附四环素的效能与机制

以椰壳和硼酸为原料,通过简单的一步热解法制备出新型硼掺杂椰壳介孔炭材料（B-CSC）用于水中四环素类污染物的高效吸附去除.系统研究了关键制备条件热解温度和硼碳质量比对其吸附性能的影响,使用比表面积及孔径分析仪（BET）、场发射扫描电镜（SEM）、X射线光子能谱仪（XPS）、拉曼光谱仪（Raman）以及Zeta电位仪（Zeta）对其微观结构及物化性质进行了表征分析.系统考察了初始pH值、不同金属阳离子以及不同背景水质条件对其吸附效果的影响.结合材料表征与相关分析等对其强化吸附机制进行了深入讨论与分析.结果表明,一步热解能够将硼掺入椰壳炭的表面及晶格,导致其拥有更大的比表面积和孔体积,引入硼的形态主要是H₃BO₃、B₂O₃、B和B₄C.B-CSC对四环素的吸附量达到297.65 mg·g^-1,是原始椰壳介孔炭（CSC）的8.9倍.同时,B-CSC对于水环境中常见污染物罗丹明B（RhB）、双酚A（BPA）和亚甲基蓝（MB）的吸附量分别高达372.65、255.24和147.82 mg·g^-1.B-CSC对四环素的吸附过程是物理化学作用共同主导的,主要涉及液膜扩散、表面吸附、介孔与微孔内扩散和活性位点吸附,H₃BO₃是其主要吸附位点.吸附强化机制主要是硼掺杂降低了其碳网络的化学惰性,增强了其与四环素分子的π—π相互作用和氢键作用.     

改性污泥基生物炭的性质与重金属吸附效果

为提高污泥基生物炭在高钙溶液体系中对重金属阳离子的吸附能力,将Fe₂O₃、MnO₂、ZnO与市政污泥以质量比1 ∶10（以过渡金属元素质量计）混合共热解,制备改性生物炭;表征改性生物炭的组成、官能团分布和表面性质,考察其对典型重金属阳离子Cd²⁺的吸附效果.过渡金属氧化物可促进污泥的热解,改性生物炭的H/C原子比均低于0.31,碳链裂解脱氢更彻底.改性生物炭中Fe、Mn保留较好,分别主要以单质和氧化物形态存在;而Zn流失较多.改性生物炭中的孔隙以介孔为主,平均孔径约3.8 nm,比表面积在50 m²·g^-1以上.初始浓度约200 mg·L^-1的Cd²⁺溶液中,Ca²⁺初始浓度从0 mg·L^-1升高到约200 mg·L^-1,Fe改性生物炭对Cd²⁺的吸附容量从43.17 mg·g^-1降至27.88 mg·g^-1,但仍较未改性生物炭高10 mg·g^-1以上,在含钙溶液体系中表现出了对Cd²⁺更强的吸附性能.Fe₂O₃较MnO₂和ZnO对市政污泥基生物炭吸附重金属的强化效果更好.     

木屑生物炭在雨水径流中的氮磷淋出和吸附特性

现阶段生物滞留系统的填料存在氮磷营养素淋出及吸附净化效果不稳定的问题.为评估木屑生物炭作为生物滞留系统过滤层填料的可行性,选用传统填料（椰糠、堆肥、陶粒和火山石）作为对比材料,通过理化性质测试、批量淋洗实验、等温吸附和解吸实验,研究木屑生物炭的基本性质、淋出特性和吸附特性,探究木屑生物炭对生物滞留系统的优化效果与改良机制.结果表明,经高温热解生成的木屑生物炭具有疏松和多孔的特性,饱和含水率为195.65%,持水效果好;热解后木屑生物炭表面的氮磷元素转换为稳定的化合物,在批量淋洗实验中其氮素淋出量低、淋出速度快,磷素淋出滞缓但在人造雨水径流的淋洗中保持线型负值增长,吸附效果稳定;在典型雨水径流浓度（2mg·L^-1的NH₄⁺及2mg·L^-1的PO₄^3-）下,木屑生物炭可吸附34.6mg·kg^-1的NH₄⁺和59.5mg·kg^-1的PO₄^3-,具有突出的综合吸附能力;NH₄⁺及PO₄^3-吸附平衡后的木屑生物炭在去离子水中的平均解吸率为21.23%和17.43%,吸附效果稳定.综上所述,木屑生物炭的施用可解决填料营养盐过剩淋出的问题,且具有较好的氮磷吸附效果,可用作生物滞留系统的填料解决雨水径流污染问题.     

剑麻纤维基多孔炭材料的制备及其吸附氯苯的研究

以剑麻纤维为原料,通过简易的一步炭化活化法制备了一系列多孔炭材料,分别探究了3种温和的金属盐活化剂、活化剂与剑麻纤维的质量比和活化温度对炭材料的氯苯吸附量的影响,并通过BET、SEM、XRD、Raman、FT-IR、元素分析等手段表征其物理化学性质.结果表明,当采用CuCl₂为活化剂、CuCl₂与剑麻纤维的质量比为10∶1及活化温度为800 ℃时,制备得到的剑麻纤维基多孔炭（PCC）吸附性能最佳,其在氯苯浓度为1560 mg·m^-3时,吸附量达到856 mg·g^-1,而未经CuCl₂活化的炭材料（PC）的氯苯吸附量仅为15 mg·g^-1.氯苯吸附性能的提升主要归因于比表面积、孔容、无序性和表面含氧官能团的增加.此外,采用巨正则系综蒙特卡洛（GCMC）方法模拟氯苯分子在制备的多孔炭材料中的吸附行为,结果表明,该材料中孔径为0.5 nm的孔对氯苯分子的吸附能力最强,且对氯苯吸附起主导作用的为苯环中心和Cl原子与炭材料上连接含氧官能团的H原子之间的静电作用力.     

磁性含磷油茶壳生物炭对水中磺胺甲唑的吸附特性

以废弃油茶壳为原料,采用磷酸活化和铁盐共沉积进行改性制备得到磁性含磷生物炭（MPBC）.通过扫描电镜（SEM）、X射线衍射（XRD）、比表面积和孔径分析（BET）、傅立叶红外光谱（FT-IR）和X射线光电子能谱（XPS）等技术对材料进行表征分析,MPBC孔隙多、比表面积高（1 139.28 m²·g^-1）、表面官能团丰富,且能够在外加磁场的作用下快速实现固液分离.探究了其对水体中磺胺甲唑（SMX）的吸附行为和影响因素,该吸附剂在酸性和中性环境中对SMX表现出优异的吸附性能,而碱性条件和CO₃^2-的存在对吸附具有明显的抑制作用.其吸附过程符合准二级动力学和Langmuir模型,其吸附速率快,最大吸附容量可达356.49 mg·g^-1.吸附机制主要是SMX分子和 MPBC的焦磷酸盐表面官能团（C—O—P键）发生的化学吸附作用,此外还包括氢键作用、π—π电子供体-受体（π—π EDA）作用和孔隙填充效应.MPBC吸附剂的开发为废弃油茶壳的资源化利用和磺胺甲唑废水处理提供一条有效途径.     

对比研究生物炭和秸秆对麦玉轮作系统N2O排放的影响

基于华北集约化农田麦玉轮作系统,对比研究了添加生物炭和秸秆还田对整个轮作周期土壤N₂O排放的影响,为农田土壤N₂O减排和秸秆的资源化利用提供理论依据.试验共设4个处理：①对照（CK）;②生物炭9.0 t·（hm²·a）^-1（C）;③秸秆全量还田（SR）;④在全量秸秆还田的基础上添加生物炭9.0 t·（hm²·a）^-1（C+SR）.结果表明,小麦季,C处理土壤N₂O排放略有降低但差异不显著,SR和C+SR处理促进了土壤N₂O的排放（47.4%和71.8%）;玉米季,C处理降低了土壤N₂O的排放（29.8%）,SR和C+SR处理促进了土壤N₂O的排放（13.4%和35.8%）;小麦季,土壤含水量、NH₄⁺-N和MBN含量是影响土壤N₂O排放的主要环境因子;玉米季,NO₃^--N、NH₄⁺-N和MBC含量是影响土壤N₂O排放的主要环境因子.因此,生物炭对农田N₂O具有巨大的减排潜力,而秸秆直接还田不利于减少N₂O排放,并且在秸秆还田基础上添加生物炭并不能改善这种影响,今后应加强对秸秆腐熟还田技术的研究.     

3种人工湿地基质材料对氨氮的吸附特性

对陶粒、石英砂和砾石这3种人工湿地基质材料进行了氨氮（NH₄⁺-N）吸附特性研究.通过扫描电镜和BET比表面积分析仪对材料进行表征分析,发现陶粒表面相比石英砂和砾石更为粗糙,内部孔隙也较发达,陶粒（18.97 m²·g^-1）比表面积高于石英砂和砾石.在纯氨氮溶液和模拟污水厂出水一级B标准的混合溶液中,3种基质对NH₄⁺-N的吸附能力均表现为：陶粒>砾石>石英砂.陶粒对NH₄⁺-N的饱和吸附容量在混合溶液中最大（63.55 mg·g^-1）.陶粒对NH₄⁺-N的吸附过程符合伪二级动力学模型（在纯氨氮溶液中R²为0.99、在混合溶液中R²为0.98）.在纯氨氮溶液中运用Freundlich和Langmuir模型对等温吸附试验结果进行拟合,发现Freundlich模型（R²=0.93）描述陶粒的吸附特性比Langmuir模型更为精确（R²为0.93）,表明陶粒对NH₄⁺-N的吸附为多层吸附.综上所述,陶粒的吸附容量较强,在混合溶液中吸附容量较纯氨氮溶液增大了31%,适用于作为人工湿地基质填料.     

PEI改性生物炭的制备及对CO2吸附性能的评价

采用超声辅助-水热法将聚乙烯亚胺（PEI）成功接枝到玉米芯生物炭表面,制备了PEI改性生物炭材料（PBC）,并通过X射线衍射（XRD）、扫描电子显微镜（SEM）、比表面积分析仪和傅里叶红外光谱仪（FTIR）等方法对其表征.结果表明,虽然PEI通过CN、C-N和离子键与生物炭表面的活性基团链接,但制备的PBC材料仍保持原生炭的无定型结构和形貌,且比表面积高达928.1 m²·g^-1.同时,还研究了PBC的吸附性能和热力学行为,结果表明,吸附过程符合Langmuir等温吸附机制,属于微孔单层吸附过程,而且随温度的降低,吸附量增大,在10、20和30℃时,饱和吸附量（Q_m）分别为6.47、4.75和2.64 mmol·g^-1.此外,PBC重复利用性能良好,容易实现热再生,即使循环利用10次,吸附性能也无显著变化（p>0.05）,且穿透吸附量（Q_B）保持在2.6~2.7 mmol·g^-1.     

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.     

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.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.