铁锰复合氧化物吸附去除五价锑性能研究

对比研究了铁锰复合氧化物(FMBO)、羟基氧化铁(FeOOH)和二氧化锰(MnO₂)吸附去除五价锑(Sb(V))的性能.结果表明FMBO对Sb(V)具有很好的吸附性能,在pH=5.0的条件下,最大吸附容量达到1.05 mmol·g^-1,略高于FeOOH (0.82 mmol·g^-1)及远高于MnO₂ (0.43 mmol·g^-1);采用Freundlich模型可以很好地描述Sb(V)在FMBO的吸附行为(R² = 0.98).就吸附动力学而言,假二级动力学可很好地描述Sb(V)在FMBO (R² = 0.93)和MnO₂表面的吸附过程(R² = 0.96),而Sb(V)在FeOOH表面的吸附过程可用Elovich模型拟合 (R² = 0.94).Sb(V)的吸附量随着pH值的升高而降低;磷酸盐显著抑制了Sb(V)的吸附,而硫酸盐和碳酸盐影响不大.提高体系离子强度可促进Sb(V)在FMBO表面的吸附,推断Sb(V)在FMBO表面形成内层络合物后被吸附去除.     

壳-核结构Fe3O4/MnO2磁性吸附剂的制备、表征及铅吸附去除研究

采用共沉淀法制备了具有壳-核结构的磁性吸附剂Fe₃O₄/MnO₂,对其性质进行了系统表征,并对其铅吸附行为进行了初步研究.透射电镜(TEM)结果表明,Fe₃O₄/MnO₂为大小不规则的纳米级细小颗粒.X-射线衍射仪(XRD)表征结果表明,Fe₃O₄/MnO₂具有尖晶石的结构.振动样品磁强计(VSM)测得比饱和磁化强度为54.7 A·m²·kg^-1, 吸附剂磁性较强,易于磁分离;BET比表面积为76.5 m²·g^-1.吸附试验结果表明,Fe₃O₄/MnO₂对铅具有良好的去除效果(特别是在低平衡浓度情况下),最大吸附量为142.0 mg·g^-1(pH=5.0);Langmuir等温线能更好地拟合Fe₃O₄/MnO₂对溶液中铅的吸附(R²=0.852);吸附速率较快,在初始30 min内可达到平衡吸附量的80%,准二级动力学模型(R²=0.959)能较好地描述吸附过程;溶液pH对Fe₃O₄/MnO₂吸附铅的影响较为明显,随pH升高,吸附量增大,但离子强度变化对吸附影响不大.     

温榆河水化学特征演变及其影响因素分析

通过对1980—2006年温榆河主要离子浓度和比例及北京市社会经济发展的综合分析,探讨了温榆河水化学特征的演变及其影响因素.结果表明,温榆河河水呈盐渍化趋势,其中1991—2006年温榆河水的Na⁺、Cl^-、SO₄^2-及TDS浓度显著上升,而HCO₃^-浓度保持稳定,总溶解性固体(TDS)浓度多年平均值为678.0 mg·L^-1,略高于1970年代北运河土门楼站TDS的661.4 mg·L^-1.温榆河水化学类型为重碳酸盐钙、镁、钠型,自然因素中主要受岩石风化和蒸发作用的控制.与岩石风化及蒸发作用等自然因素相比,农田排涝和城市退水等人为因素在温榆河1980—2006年水化学特征演变过程中具有更为显著的影响,并且K⁺、Cl^-、SO₄^2-和Ca²⁺受人类活动影响较大.Pearson相关分析结果表明,北京市社会经济发展对温榆河河水中K⁺、Cl^-、Ca²⁺和SO₄^2-的浓度变化影响显著,其中K⁺与人口密度、人均GDP、钾肥施用量和道路面积之间呈显著性正相关(r>0.7,p<0.01),与耕地面积、粮食播种面积、灌溉面积、农业用水呈极显著性负相关(r <-0.7,p<0.01);Ca²⁺和SO₄^2-与城市化率和煤炭使用率均呈显著性正相关(r>0.49,p<0.05).该研究结果可为今后北京市合理开发利用温榆河水资源和建设温榆河绿色生态走廊提供科学依据.     

阳离子强度和阳离子类型对诺氟沙星土壤吸附的影响

以OECD Guideline 106为基础,采用批平衡方法研究不同Ca²⁺离子强度（0.01、0.03、0.05、0.08和0.10 mol/L的CaCl₂溶液）和不同阳离子（0.01 mol/L的NaCl、KCl、NH₄Cl、MgCl₂、CaCl₂、ZnCl₂和AlCl₃溶液）对诺氟沙星在4种土壤（潮土、黄棕壤、水稻土和红壤）中的吸附-解吸影响.结果表明,随着溶液中Ca²⁺离子浓度的增加,诺氟沙星在土壤中的吸附参数K_f值逐渐减小并趋于稳定,两者间存在显著负相关（p≤0.05）.同时,Ca²⁺离子浓度的增加对低浓度诺氟沙星溶液的吸附影响相对高浓度而言不明显. 低pH下,诺氟沙星主要以阳离子形态存在,吸附以阳离子吸附或氢键为主;在兼性离子状态时,则主要以静电吸附和偶极力为主.这是造成4种土壤中诺氟沙星吸附差异的根本原因.在不同离子强度下,土壤溶液中二价Ca²⁺离子存在则对诺氟沙星的活性吸附位点造成竞争性吸附,从而降低诺氟沙星的土壤吸附量.同时,不同阳离子导致诺氟沙星的土壤吸附存在差异.其影响趋势主要为价态的影响,即价态越高,竞争吸附能力越强：M⁺（Na⁺、K⁺、NH^＋₄）2+（Ca²⁺、Mg²⁺、Zn²⁺）3+（Al³⁺）.     

锰氧化物负载施氏矿物去除酸性矿山废水中As(III)的性能及机理

施氏矿物是天然的砷吸附剂,但其存在酸性条件下对As(III)吸附性能较弱且无法对As(III)氧化降毒的缺陷. 采用液相沉淀法成功制备出锰氧化物负载施氏矿物(MnO_x@Sch),研究锰负载量、初始pH值和共存离子对MnO_x@Sch去除As(III)的影响,并采用吸附动力学结合XPS、FTIR及TEM等表征探究该过程的机理. 结果表明:在初始pH=3、投加量为0.5 g·L^-1、As(III)初始浓度为1 mg·L^-1的条件下,As(III)与MnO_x@Sch反应后的剩余浓度仅为2.42~3.38 μg·L^-1.MnO_x@Sch去除As(III)受初始pH影响较小,H₂PO₄^-共存时As(III)去除存在明显的抑制作用. MnO_x@Sch 去除As(III)的过程符合准二级动力学方程和颗粒内扩散方程. 液相化学组分和固相产物表征分析显示MnO_x@Sch对As(III)的去除机理可概括为As(III)氧化、静电吸附和络合配位及配体交换. 研究结果可为施氏矿物及其改性材料应用于酸性矿山废水砷污染治理提供理论依据.     

K+对Fe(Ⅵ)生成的稳定促进作用和机理研究

研究了在生成高铁酸盐反应过程中K⁺对Fe(Ⅵ)的稳定促进作用和机理.结果表明,当反应温度大于50℃时,K⁺比Na⁺更有利于高铁酸盐的生成.K⁺促进高铁酸盐溶液生成的最佳反应温度为65℃.在生成高铁酸盐反应过程中,增加K⁺浓度能提高高铁酸盐的产率,并且随着硝酸铁投加量的增加,K⁺影响显著.在硝酸铁投加量为85 g/L时,采用4.4 mol/L KOH制备的Fe(Ⅵ)浓度为0.05 mol/L;加入2 mol/L K⁺后,Fe(Ⅵ)浓度增加到0.15 mol/L.K⁺对高铁酸盐溶液生成浓度的影响在硝酸铁投加量大于75 g/L,反应温度低于55℃,ClO^-浓度低于1.16 mol/L时较为显著.K⁺在一定程度上可替代部分碱度,降低OH^-用量.在反应过程中K⁺能包裹在FeO^2-₄周围,减少Fe³⁺与FeO^2-₄接触,从而减缓Fe³⁺对FeO^2-₄的催化分解作用;同时K⁺能与FeO^2-₄生成K₂FeO₄晶体沉淀析出,降低溶液中FeO^2-₄浓度,Fe(Ⅵ)分解速率减缓,稳定性增加,Fe(Ⅵ)生成浓度增加.     

Sorption kinetics of parent and substituted PAHs for low-density polyethylene (LDPE): Determining their partition coefficients between LDPE and water (KLDPE) for passive sampling

Low-density polyethylene (LDPE) has been widely used as a sorbent for passive sampling of hydrophobic organic contaminants (HOCs) in aquatic environments. However, it has seen only limited application in passive sampling for measurement of freely dissolved concentrations of parent and substituted PAHs (SPAHs), which are known to be toxic, mutagenic and carcinogenic. Here, the 16 priority PAHs and some typical PAHs were selected as target compounds and were simultaneously determined by gas chromatography–mass spectrometer (GC–MS). Some batch experiments were conducted in the laboratory to explore the adsorption kinetics of the target compounds in LDPE membranes. The results showed that both PAHs and SPAHs could reach equilibrium status within 19–38?days in sorption kinetic experiments. The coefficients of partitioning between LDPE film (50?μm thickness) and water (K_LDPE) for the 16 priority PAHs were in good agreement with previously reported values, and the values of K_LDPE for the 9 SPAHs are reported in this study for the first time. Significant linear relationships were observed, i.e., log K_LDPE?=?0.705?×?log K_OW?+?1.534 for PAHs (R²?=?0.8361, p?<?0.001) and log K_LDPE?=?0.458?×?log K_OW?+?3.092 for SPAHs (R²?=?0.5609, p?=?0.0077). The selected LDPE film was also proven to meet the condition of “zero sink” for the selected target compounds. These results could provide basic support for the configuration and in situ application of passive samplers.     

一株耐铬细菌的鉴定及其还原铬性能分析

从浙江温州工业区六价铬废水污染的土壤中采样分离得到一株耐铬细菌Y73.16S rRNA基因序列分析表明,该菌株为Staphylococcus(葡萄球菌)属菌,最高可在加有1600 mg·L^-1六价铬(K₂Cr₂O₇)的 LB培养基中生长.该菌为好氧生长,但在3种不同的氧压力下,包括有氧、无氧和兼性无氧(先有氧生长)的条件下都可以还原六价铬,而在兼性无氧(先有氧生长)的条件下达到最高还原效率,可在96 h内将1000 mg·L^-1的六价铬还原83%.另外,该菌株能在较宽的pH值(5~11)和温度(10~50℃)范围内还原六价铬,而最佳反应条件是pH=7 和30℃.随着接种量的增加,六价铬的还原率增加,但接种量超过10%时再增加接种量对六价铬还原的影响不明显.供试的大多数金属离子(50 mg·L^-1)对该菌株还原六价铬的影响也不明显.上述结果说明,菌株Y73有其独特的还原铬性能,以及在处理六价铬污染废水中的应用潜力.     

响应面法优化MAP沉淀去除回收尿液中磷的研究

基于模拟尿液的组成特点,利用Box-Behnken Design实验及响应面法对磷酸铵镁(MAP)沉淀去除回收尿液磷过程中反应pH值、Mg²⁺与PO₄^3-物质的量比(Mg/P比)及Ca²⁺与PO₄^3-物质的量比(Ca/P比)3个重要影响因素(分别表示为X₁、X₂、X₃)及各因素之间的交互式影响进行考察,并利用SEM、FTIR、ICP和XRD表征手段分析结晶沉淀组成和晶形特征.实验结果表明,回归方程中X₁、X₂、X₃、X₁X₃、X₂X₃、X₁²、X²₂、X₃²对磷去除率影响显著;当反应pH值和Mg/P比范围分别在8.5~9.5和1.0~1.2之间时,磷去除率响应值能达到99%.产物表征结果表明,模拟尿液中K⁺和Na⁺对结晶干扰较小;当Ca²⁺的浓度相对较低(Ca/P比小于0.25)时,沉淀中MAP的纯度高于85%,晶体形状大部分为斜方形;当Ca²⁺的浓度相对较高(Ca/P比大于0.25)时,沉淀中的MAP下降明显,晶体形状开始不规则,杂质增多;当模拟尿液中Ca/P比为0.5时,MAP纯度仅有约70%.     

低温地下水净化工艺中氨氮去除性能及机制

在东北某自来水厂,以中试滤柱开展了低温（5~6℃）高铁锰氨[Fe（Ⅱ）11.9~14.8 mg·L^-1、Mn（Ⅱ）1.1~1.5 mg·L^-1和NH₄⁺-N 1.1~3.2 mg·L^-1]净化工艺实验,以探究氨氮去除途径与生物滤柱的除氨性能.结果表明,滤柱在启动初期就对氨氮具有良好的去除效果,通过理论分析与实验验证可知,TN_loss是由铁氧化物对氨氮吸附造成,氨氮转化为硝氮的过程是生物硝化作用.氨氮质量浓度提高过程中,由于吸附位点有限,铁氧化物对氨氮的吸附量稳定在1 mg·L^-1左右,氨氮氧化去除量不断增加,其中在滤柱上部滤层的去除量远大于下部滤层,DO是限制氨氮氧化去除量进一步增加的限制因素.滤速提升过程中,铁氧化物对氨氮吸附时间缩短,吸附量有所减少,空床接触时间（empty bed contact time,EBCT）缩短,使得单位体积滤料中硝化菌硝化去除的氨氮减少,需要增加滤层厚度以提升氨氮去除效果.     

水合氧化铁去除Cu~(2+)的实验研究

研究了实时生成的水合氧化铁(HFO)对Cu2+的去除。研究结果表明:生成的水合氧化铁是棕黄色无定形铁的氧化物,盐滴定方法测得其零电荷点PZC为8.28±0.02;它对Cu2+吸附的动力学特征受控于HFO的生成动力学,其吸附等温线可用Henry公式和类似Langmuir公式的叠加来拟合;随着吸附剂量的增加,它对Cu2的吸附率和吸附量的影响分别呈现出指数形式(Y=aXb)的增加和减少。Cu2+从溶液中去除的可能机理包括表面络合反应、共沉淀、表面沉淀、Cu2+的水解作用、Cu2+的水解产物与水合氧化铁的絮凝作用等。     

Adsorption behavior of condensed phosphate on aluminum hydroxide

Sodium pyrophosphate （pyro-P, Na4P2OT）, sodium tripolyphosphate （tripoly-P, Na3P3O10）, and sodium hexametaphosphate （meta-P, （NaPO3）6） were selected as the model compounds of condensed phosphate to investigate the adsorption behavior of condensed phosphate on aluminum hydroxide. The adsorption was found to be endothermic and divisible into two stages： （1） fast adsorption within 1 h; and （2） slow adsorption between 1 and 24 h. The modified Freundlich model simulated the fast adsorption stage well; the slow adsorption stage was described well by the first-order kinetics. The activation energies of pyro-P, tripoly-P, and meta-P adsorption on aluminum hydroxide were determined to be 20.2, 22.8 and 10.9 kJ/mol P adsorbed, respectively, in the fast adsorption stage and to be 66.3, 53.5 and 72.5 kJ/mol P adsorbed, respectively, in the slow adsorption stage. The adsorption increased the negative charge of the aluminum hydroxide surface. Transmission electron microscopy and energy dispersive X-ray analysis analyses provided evidence that the adsorption was not uniform on the surface and that the small crystals contributed more to the fast adsorption than the normal sites did. The results from X-ray fluorescence spectrometry and X-ray photoelectron spectroscopy tests also revealed the uneven adsorption of condensed phosphate as a function of the penetration depth. More condensed phosphates were adsorbed on the outer surface of aluminum hydroxide than in its inner parts.     

ATR-FTIR and XPS study on the structure of complexes formed upon the adsorption of simple organic acids on aluminum hydroxide

Information on the binding of organic ligands to metal （hydr）oxide surfaces is useful for understanding the adsorption behaviour of natural organic matter on metal （hydr）oxide. In this study, benzoate and salicylate were employed as the model organic ligands and aluminum hydroxide as the metal hydroxide. The attenuated total reflectance Fourier transform infrared （ATR-FTIR） spectra revealed that the ligands benzoate and salicylate do coordinate directly with the surface of hydrous aluminum hydroxide, thereby forming innersphere surface complexes. It is concluded that when the initial pH is acidic or neutral, monodentate and bridging complexes are to be formed between benzoate and aluminum hydroxide while bridging complexes predominate when the initial pH is alkalic. Monodentate and bridging complexes can be formed at pH 5 while precipitate and bridging complexes are formed at pH 7 when salicylate anions are adsorbed on aluminum hydroxide. The X-ray photoelectron （XP） spectra demonstrated the variation of C 1 s binding energy in the salicyate and phenolic groups before and after adsorption. It implied that the benzoate ligands are adsorbed through the complexation between carboxylate moieties and the aluminum hydroxide surface, while both carboxylate group and phenolic group are involved in the complexation reaction when salicylate is adsorbed onto aluminum hydroxide. The information offered by the XPS confirmed the findings obtained with ATR-FTIR.     

Enhanced phosphate removal using zirconium hydroxide encapsulated in quaternized cellulose

Zirconium-based materials are efficient adsorbent for aqueous phosphate removal. However, current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity. Here, we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose (QC–Zr) for the selective phosphate removal. Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional (3D) cross-linked cellulose chains. The maximum P adsorption capacity of QC–Zr was 83.6 mg P/g. Furthermore, the QC–Zr shows high P adsorption performance in a wide pH range, generally due to the electrostatic effects of quaternized cellulose. The enhanced adsorption of P was also achieved in the presence of competing anions (including Cl^?, NO₃^?, ${\text{SO}}_4^{2?}$, ${\text{SO}}_4^{\mathrm{4}?}$) and humic acid (HA) even at a molar ratio up to 20 levels. The column adsorption capacity of QC–Zr reached 4000 bed volumes (BV) at EBCT = 0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L. Mechanism study revealed that both –N⁺(CH₃)₃ groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between –N⁺(CH₃)₃ and phosphate, and the formation of zirconium hydrogen phosphate (Zr(HPO₄)x). The ³¹P nuclear magnetic resonance (NMR) study implied that P surface–precipitated and inner–sphere complexed with zirconium hydroxide at a ratio of 3:1.     

水溶性有机物的电子穿梭功能研究

以源于污泥的DOM(dissolved organic matter)为供试材料,以中国希瓦氏菌(Shewanella cinica)D14T为电子转移驱动力,研究了DOM的氧化还原性能与电子穿梭功能.结果表明,污泥DOM可作为末端电子受体接受醌还原菌D14T呼吸链上的电子,从而转变为还原态DOM,而还原态DOM可将电子再次转移给Fe(Ⅲ).经D14T还原后,DOM电子供给量(e-/C)由初始2.2~14μmol.g-1增加到253~347μmol.g-1.循环伏安法与多次还原-氧化循环实验表明,DOM呈现2对明显的氧化还原峰,经3次还原-氧化循环后电子供给量可稳定维持在150~250μmol.g-1之间,说明DOM具有重复利用、反复转移电子的特性.在菌株D14T还原水铁矿的体系中,加入DOM可提高水铁矿的还原溶解速率,其原因是DOM在D14T与水铁矿之间充当了电子穿梭体的角色.这些结果反映了DOM在电子转移反应中的重要性,为DOM的环境属性提出了一个新见解.     

Removal efficiency of fluoride by novel Mg-Cr-Cl layered double hydroxide by batch process from water

The fluoride ion removal from aqueous solution using synthesized Mg-Cr-Cl layered double hydroxide has been reported.Mg-Cr-Cl was characterized by X-ray powder diffraction,Fourier-transform infrared,thermo-gravimetric analysis,differential thermal analysis,and scanning electron microscope.Adsorption experiments were carried out in batch mode as a function of adsorption dosages,contact time,pH,and initial fluoride concentration to get optimum adsorption capacity.The adsorption kinetic study showed that the adsorption process followed first order kinetics.The fluoride removal was 88.5% and 77.4% at pH 7 with an adsorbent dose of 0.6 g/100 mL solution and initial fluoride concentration of 10 mg/L and 100 mg/L,respectively.The equilibrium was established at 40 min.Adsorption experiment data were fitted well with Langmuir isotherm with R 2 = 0.9924.Thermodynamic constants were also measured and concluded that the adsorption process was spontaneous and endothermic in nature.The removal percentage decreased slowly with increasing pH.This process is suitable for industrial effluents.The regeneration of the material is not possible.     

Multi-function adsorbent-photocatalyst MXene-TiO2 composites for removal of enrofloxacin antibiotic from water

MXenes, a new family of two-dimensional transition metal carbides or nitrides, have attracted tremendous attention for various applications due to their unique properties such as good electrical conductivity, hydrophilicity, and ion intercalability. In this work, Ti₃C₂ MXene, or MX, is converted to MX-TiO₂ composites using a simple and rapid microwave hydrothermal treatment in HCl/NaCl mixture solution that induces formation of fine TiO₂ particles on the MX parent structure and imparts photocatalytic activity to the resulting MX-TiO₂ composites. The composites were used for enrofloxacin (ENR), a frequently found contaminating antibiotic, removal from water. The relative amount of the MX and TiO₂ can be controlled by controlling the hydrothermal temperature resulting in composites with tunable adsorption/photocatalytic properties. NaCl addition was found to play important role as composites synthesized without NaCl could not adsorb enrofloxacin well. Adding NaCl into the hydrothermal treatment causes sodium ions to be simultaneously intercalated into the composite structure, improving ENR adsorption greatly from 1 to 6 mg ENR/g composite. It also slows down the MX to TiO₂ conversion leading to a smaller and more uniform distribution of TiO₂ particles on the structure. MX-TiO₂/NaCl composites, which have sodium intercalated in their structures, showed both higher ENR adsorption and photocatalytic activity than composites without NaCl despite the latter having higher TiO₂ content. Adsorbed ENR on the composites can be efficiently degraded by free radicals generated from the photoexcited TiO₂ particles, leading to high photocatalytic degradation efficiency. This demonstrates the synergetic effect between adsorption and photocatalytic degradation of the synthesized compounds.     

几种水合金属氧化物的磷酸根吸附性能

利用简单的碱沉淀法制备不同的水合金属氧化物,并对所得七种水合金属氧化物的磷酸根吸附等温线进行了系统的探讨比较.研究表明,25℃条件下,Al、Fe、Ni、Cu和Ce的水合金属氧化物对磷酸根的吸附最符合Langmuir线性吸附方程,而水合氧化锌和水合氧化钴吸附剂最符合线性等温线模型.所有这七种水合金属氧化物对磷酸根的吸附都...     

热活化和酸活化给水处理厂废弃铁铝泥的吸磷效果

探讨了酸活化和热活化方式对给水厂废弃铁铝泥(ferric and alum water treatment residuals,FARs)吸附磷能力的影响.结果表明,酸活化和热活化均能提高FARs的磷吸附能力,其中经2mol·L-1HCl酸活化的FARs(AH2.0-FARs)和300℃热活化的FARs(H300-FARs)取得最好的磷吸附效果.结合SEM和XRD表征技术对活化机制分析得知,两种活化方式均会使FARs变得疏松、多孔,从而提高FARs对磷的吸附能力.Langmuir和Freundlich两种模型均可很好地反映活化前后FARs的等温吸附过程,FARs对磷的理论饱和吸附量由活化前的20.48mg·g-1分别增加到22.86mg·g-1(AH2.0-FARs)和29.66mg·g-1(H300-FARs).低pH值有利于FARs对磷的吸附.此外,解吸附实验结果表明活化后的FARs能够更好地固定磷.因此,活化后的FARs是一种相对更好的磷的吸附材料.     

改性大豆荚吸附剂对甲基蓝废水吸附性能研究

将天然大豆荚分别用氢氧化钠,硫酸,乙醇,过氧化氢进行改性,制备一系列改性大豆荚吸附剂,研究了改性大豆荚吸附阴离子染料甲基蓝废水的适宜条件及吸附机理.经筛选,采用氢氧化钠作为大豆荚的改性剂.结果表明:当甲基蓝溶液初始浓度300 mg·L-1,pH=10.0,吸附剂投加量为5 g·L-1,吸附时间为40 min时,改性大豆荚对甲基蓝废水的去除率达到96.30%,最大吸附量为57.53 mg·g-1.此吸附过程符合准二级动力学方程,以化学吸附为主;Langmuir方程能较好的拟合等温吸附过程.