腐殖酸改性针铁矿对铀U（Ⅵ）的吸附性能及机理研究

通过人工合成的方法制得腐殖酸改性针铁矿(HA-α-FeOOH),考察了吸附时间、吸附剂用量、U(Ⅵ)初始浓度和pH值等因素对吸附U(Ⅵ)过程的影响.同时,利用傅里叶红外光谱(FTIR)、扫描电镜(SEM)和X射线能谱(EDS)分析了其对U(Ⅵ)的吸附机理.试验结果表明,在25℃、pH为4的条件下,腐殖酸改性针铁矿作用4 h对5 mg·L-1的含铀废水的去除率几乎达到100%.Freundlich等温吸附模型、准二级动力学模型对吸附过程的拟合效果较好,主要吸附模式为多层吸附;改性针铁矿对U(Ⅵ)的吸附是自发的吸热反应.SEM-EDS和FIIR分析结果表明,改性针铁矿吸附U(Ⅵ)的机理主要表现为内层络合作用及离子交换,与U(Ⅵ)作用的基团主要是羟基、酚羟基和羧基.     

某铀尾矿库区周围稻田土壤不同组分对U(Ⅵ)的吸附性能分析

通过斯笃克定律提取土壤胶体,连续提取法吸附土壤中的有机质,得到土壤矿质胶体,采用比表面积(BET)法和Zeta电位对原土、土壤胶体和矿质胶体进行了表征分析,考察了溶液pH、接触时间、U(Ⅵ)初始浓度以及温度等因素对3种样品吸附溶液中U(Ⅵ)的影响性能。结果表明:原土、土壤胶体和矿质胶体的比表面积和平均孔径分别为11.5,31.1,28.8 m2/g和18.76,35.55,17.5 nm。在pH为5.5,固液比在1.0 g/L,温度为20 ℃,U(Ⅵ)初始浓度为10.0 mg/L,土壤、土壤胶体反应时间为50 min,矿质胶体反应时间为40 min时,原土、土壤胶体、矿质胶体的对U(Ⅵ)吸附率分别达到76.67%、83.03%、48.87%,吸附容量分别达到8.53,9.24,5.43 mg/g。对比研究结果可以看出,土壤中的胶体对溶液中U(Ⅵ)有着明显的吸附能力,该研究结果对进一步研究含U(Ⅵ)废水的处理及U(Ⅵ)在土壤和地下水中的迁移过程有一定的参考意义。     

壳聚糖/氧化石墨烯复合材料吸附U（Ⅵ）的特性与机理

采用溶液共混法制备了壳聚糖/氧化石墨烯(CS/GO)复合材料,探讨了GO含量、pH值、CS/GO投加量、时间以及U(Ⅵ)初始浓度等对CS/GO吸附U(Ⅵ)效果的影响.试验结果表明,GO质量分数为40%,pH值为5时吸附效果最好,吸附在5 h达到平衡.准二级动力学模型和Langmuir等温吸附方程可较好地拟合其吸附过程,30℃时饱和吸附量为227.3 mg·g-1.CS/GO对U(Ⅵ)的吸附是自发的吸热反应.SEM、FTIR和XRD分析结果表明,CS/GO表面凹凸不平,羟基和氨基是U(Ⅵ)的主要结合位点.解吸试验结果表明CS/GO具有良好的重复使用性能.     

天然石英砂的表面络合模型研究

天然泥沙颗粒表面特性复杂,其与营养物质及重金属之间的相互作用,是研究天然水体水环境效应的关键科学问题之一.本文以石英砂为例,在考虑天然泥沙表面形貌引起的电荷非均匀分布的基础上,建立了统计意义上的表面电荷分布-表面电位数学关系,并修正表面络合模型,对表面络合常数采用更合理的静电力校正,模拟营养物质及重金属在天然泥沙颗粒表面的吸附-解吸关系.同时,表面滴定实验及吸附实验数据被用来进行模型验证.结果表明,泥沙颗粒的吸附特性受pH值、水相平衡浓度和背景离子强度等影响,考虑颗粒表面电荷非均匀分布的修正模型,更接近天然泥沙的吸附特性,相比传统表面络合模型,能够更好地模拟吸附结果.     

大肠杆菌对铬(Ⅵ)的吸附研究

以常见重金属铬(Ⅵ)为目标污染物,通过大肠杆菌与含铬废水在不同环境条件下接触反应,研究大肠杆菌对铬(Ⅵ)的吸附规律,并探讨大肠杆菌吸附铬的影响因素、吸附动力学、吸附等温线和吸附热力学。结果表明大肠杆菌吸附铬的过程同时受初始铬(Ⅵ)浓度、温度、p H和菌浓度的影响。动力学模拟的吸附过程符合准二级动力学模型;等温线模拟的吸附过程符合Langmuir吸附模型,属于单层吸附,同时包含了物理吸附和化学吸附;大肠杆菌吸附铬的活化能Ea=13.93 k J/mol,热力学研究表明吸附过程较容易发生,为吸热过程。     

诱变绳状青霉吸附铀的行为研究

先后采用盐酸羟胺和紫外光辐射,对绳状青霉(Penicillium funiculosum)进行诱变,并用红外光谱分析了诱变绳状青霉细胞表面官能团的变化,采用静态吸附试验研究了铀溶液的pH、温度、初始铀浓度、吸附时间、菌体投加量等因素对其吸附铀的影响.通过对动力学模型、等温吸附模型和热力学方程进行拟合,研究了诱变绳状青霉吸附铀的行为.采用扫描电镜、能谱仪和红外光谱仪分析了吸附前后诱变绳状青霉细胞表面的形貌、化学组成和官能团结构的变化,进而探讨了吸附过程可能涉及的反应机理.结果表明,诱变绳状青霉在pH=6时吸附铀的效果最好,8h即达到吸附平衡,最大吸附量为200mg·g-1,对铀的吸附为细胞表面的缔合—OH、—CHO、不饱和键、—NH2、—PO43-等与铀的配位络合反应.     

污泥基生物炭负载纳米零价铁除U(Ⅵ)性能及机理

为了考察污泥基生物炭负载纳米零价铁（n ZVI/SB）对铀(U(Ⅵ))的去除性能与机理,该文研究了环境条件对nZVI/SB除铀的影响,发现在初始pH为5、投加量0.2 g/L、温度313 K、吸附时间4 h条件下,n ZVI/SB对U(Ⅵ)的吸附量最大（231.80 mg/g）。nZVI/SB对U(Ⅵ)的吸附过程与行为符合准二级动力学与Langmuir吸附等温线模型。通过扫描电镜、能谱分析、X衍射分析仪和X射线光电子能谱等手段对nZVI/SB去除U(Ⅵ)的机理进行分析,发现铀去除方式包括吸附和还原共同作用。经过5次循环实验后,nZVI/SB对U(Ⅵ)去除率保持在90%以上,表明nZVI/SB复合材料用于含U(Ⅵ)废水处理具有良好的重复使用性能。     

高岭土的改性及其对Cr(Ⅵ)的吸附特性

采用煅烧、酸浸的方法对高岭土进行改性,通过对SEM、XRD、FT-IR、EDS、孔结构表征及高岭土对Cr(Ⅵ)的去除能力研究,确定高岭土的改性条件,考察改性高岭土对Cr(Ⅵ)的吸附特性. 结果表明:①高岭土的改性适宜条件为煅烧温度800℃、煅烧时间3h、c(HCl)为4mol/L;煅烧使高岭土的结构发生变化,活性增强;酸改使高岭土孔隙通畅,吸附性能增强. ②改性高岭土吸附Cr(Ⅵ)的优化条件为粒度0.15mm、用量10g/L、吸附温度30℃、吸附时间15min,该条件下ρ〔Cr(Ⅵ)〕为100mg/L时废水中Cr(Ⅵ)的去除率可达91.4%. ③高岭土对Cr(Ⅵ)的吸附过程符合准二级吸附动力学模型,相比于Freundlich方程,其吸附等温式更符合Langmuir方程.      

三种微生物对铀的吸附行为研究

开展了酵母菌(真菌)、枯草芽孢杆菌(细菌)、小球藻(藻类)对水体中铀(Ⅵ)的吸附性能及机理研究.结果表明:3种微生物对铀都具有较好的吸附效果.酵母菌,小球藻,枯草芽孢杆菌对铀的最佳吸附率分别为97.19%、97.13%、98.03%;且最大吸附量分别达到341.2、356.5、512.5mgU/g(DW).3种微生物对铀的吸附过程和机理有所不同,酵母菌和小球藻符合Langmuir模型,枯草芽孢杆菌更适合Freundlich模型,吸附至12h,酵母菌表面逐渐出现铀和磷的片状结晶及含铀沉积物堆积,小球藻和枯草芽孢杆菌与铀(50mgU/L)作用后细胞出现明显变形,菌体表面未出现铀的结晶物.     

镁铝层状双金属氢氧化物及其煅烧产物对水体W(Ⅵ)的吸附特征与机制

采用微波陈化法制备了物质的量比为2:1的硝酸型镁铝层状双金属氢氧化物(LDH),系统地研究了LDH及其煅烧产物(CLDH)对W(Ⅵ)的吸附特征,并通过对吸附W(Ⅵ)前后LDH和CLDH的结构进行表征阐明相关吸附机制.LDH和CLDH对W(Ⅵ)的吸附动力学更符合拟二级动力学模型,表明化学吸附是决定吸附速率的关键.LDH和CLDH对W(Ⅵ)具有较高的亲和性,最大吸附量分别达176.0,124.5mg/g,远高于同类LDH.LDH吸附W(Ⅵ)的最佳pH值范围为4.0～10.0,酸性条件有利于CLDH吸附W(Ⅵ).综合对比,LDH具有更高的吸附容量、更快的吸附速率以及更弱的水质影响(Mg、Al溶出低,pH变化小),更适宜用于W(Ⅵ)吸附.LDH吸附W(Ⅵ)的主要机制包括离子交换、外层络合和内层络合,而CLDH对W(Ⅵ)的吸附机制还包括重构层状结构时仲钨酸盐(W₇O₂₄^6-)的插层作用.以上结果表明,采用微波法合成LDH和CLDH均可高效地吸附污染水体的W(Ⅵ),是一类性能优越的W(Ⅵ)吸附材料.     

地浸井场外围含水层砂岩对铀的吸附行为

天然含水层介质对铀的吸附是地下水铀天然衰减的决定因素.然而,人们对天然含水层砂岩吸附铀行为的认识相当有限.因此,本文采用静态实验及数值模拟相结合的方法研究了地浸井场外围砂岩对铀的吸附行为,探究了天然砂岩对溶液中铀的吸附动力学和等温吸附特征,研究了铀初始浓度、pH、其他离子种类与浓度对铀吸附的影响.结果表明,准二级动力学方程与Freundlich等温吸附模型可以更好地表征砂岩对铀的吸附行为;随着溶液中铀初始浓度的增大,砂岩对水溶液中铀的吸附量增大,吸附率减小;在初始pH=3时,铀的吸附率达到最大,为77%;砂岩对溶液中铀的吸附率会随反应体系中Ca²⁺、Mg²⁺、SO₄^2-、HCO₃^-等离子浓度的升高而下降,4种共存离子对该吸附过程抑制能力的顺序为：SO₄^2- < Mg²⁺ < Ca²⁺ < HCO₃^-.这些研究结果可为地浸铀矿山地下水的修复提供理论支持.     

Ethyl thiosemicarbazide intercalated organophilic calcined hydrotalcite as a potential sorbent for the removal of uranium(VI) and thorium(IV) ions from aqueous solutions

This work was conducted to determine the practicability of using a new adsorbent 4-ethyl thiosemicarbazide intercalated,organophilic calcined hydrotalcite(ETSC-OHTC) for the removal of uranium(U(VI)),and thorium(Th(IV)) from water and wastewater.The FTIR analysis helped in realizing the involvement of nitrogen and sulphur atoms of ETSC in binding the metal ions through complex formation.Parameters like adsorbent dosage,solution pH,initial metal ions concentration,contact time and ionic strength,that influence adsorption phenomenon,were studied.The optimum pH for maximum adsorption of U(VI) and Th(IV) was found to be in the range 4.0-6.0.The contact time required for reaching equilibrium was 4 hr.The pseudo second-order kinetic model was the best fit to represent the kinetic data.Analysis of the equilibrium adsorption data using Langmuir,Freundlich and Sips models showed that the Freundlich model was well suited to describe the metal ions adsorption.The K F values were 25.43 and 29.11mg/g for U(VI) and Th(IV),respectively,at 30°C.The adsorbent can be regenerated effectively from U(VI) and Th(IV) loaded ones using 0.01mol/L HCl.The new adsorbent was quite stable for many cycles,without much reduction in its adsorption capacity towards the metals.     

磁性核壳CoFe2O4@SiO2@PIL-AO复合材料的制备及其吸附U (VI)性能研究

通过化学合成法制备了磁性核壳CoFe₂O₄@SiO₂@PIL-AO复合材料,采用傅立叶变换红外光谱（FTIR）、扫描电镜（SEM）和X射线光电子能谱（XPS）对其进行了表征,研究了溶液pH、吸附时间、U （VI）初始浓度和温度等参数对U （VI）吸附性能的影响.实验结果表明：在c₀=0.2 mg·L^-1、pH=6.00±0.05、T=298.15 K、m=0.02 g和t=8 h的条件下,CoFe₂O₄@SiO₂@PIL-AO对U （VI）的吸附作用最强,吸附率达到了97.54%;CoFe₂O₄@SiO₂@PIL-AO吸附U （VI）是一个自发进行的吸热反应,U （VI）吸附动力学符合准二级动力学模型,吸附等温线符合Freundlich模型;CoFe₂O₄@SiO₂@PIL-AO复合材料具有良好的可循环使用性,循环使用5次后它对U （VI）的吸附容量没有明显下降,可重复使用.     

Visualizing different uranium oxidation states during the surface alteration of uraninite and uranium tetrachloride

Low-temperature alteration reactions on uranium phases may lead to the mobilization of uranium and thereby poses a potential threat to humans living close to uranium-contaminated sites. In this study, the surface alteration of uraninite (UO₂) and uranium tetrachloride (UCl₄) in air atmosphere was studied by confocal laser scanning microscopy (CLSM) and laser-induced fluorescence spectroscopy using an excitation wavelength of 408 nm. It was found that within minutes the oxidation state on the surface of the uraninite and the uranium tetrachloride changed. During the surface alteration process U(IV) atoms on the uraninite and uranium tetrachloride surface became stepwise oxidized by a one-electron step at first to U(V) and then further to U(VI). These observed changes in the oxidation states of the uraninite surface were microscopically visualized and spectroscopically identified on the basis of their fluorescence emission signal. A fluorescence signal in the wavelength range of 415–475 nm was indicative for metastable uranium(V), and a fluorescence signal in the range of 480–560 nm was identified as uranium(VI). In addition, the oxidation process of tetravalent uranium in aqueous solution at pH 0.3 was visualized by CLSM and U(V) was fluorescence spectroscopically identified. The combination of microscopy and fluorescence spectroscopy provided a very convincing visualization of the brief presence of U(V) as a metastable reaction intermediate and of the simultaneous coexistence of the three states U(IV), U(V), and U(VI). These results have a significant importance for fundamental uranium redox chemistry and should contribute to a better understanding of the geochemical behavior of uranium in nature. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

改性羧甲基纤维素对铀吸附机理的试验研究

对羧甲基纤维素(CMC)进行改性,并将其用于吸附废水中的铀.研究结果表明:在温度为70℃~80℃、单体质量浓度为30%~35%、羧甲基纤维素:丙烯酸(质量比)为10:2.5、反应时间为3.5~4h条件下,CMC改性效果最好;在改性CMC质量浓度为0.10g/L,温度为25℃, pH值为5.0,反应时间60min的条件下,对废水中铀去除率达到了97.1%;改性CMC对溶液中U(VI)的吸附过程符合Freundlich方程,其吸附动力学数据符合准一级方程(R2=0.9618),表明改性CMC的吸附主要是表面吸附;热力学研究表明,改性CMC对铀的吸附吉布斯自由能(ΔG0)0,吸附过程是自发的吸热反应、以物理吸附为主的过程.     

满江红对不同形态铀的吸附行为

首先采用Visual MINTEQ 3.1软件模拟了不同pH及不同浓度的碳酸盐或磷酸盐溶液中不同形态铀所占的比例;随后根据模拟结果,配制了5种分别含有UO_2~(2+)、(UO_2)_3(OH)_5~+、UO_2(OH)_3~-、UO_2(CO_3)_3~(4-)和UO_2PO_4~-的铀溶液;最后通过水培实验研究了满江红对这5种不同形态铀的吸附行为.结果表明,这5种不同形态铀对满江红的生长抑制率有显著差异,UO_2~(2+)、(UO_2)_3(OH)_5~+、UO_2(OH)_3~-及UO_2(CO_3)_3~(4-)均能抑制满江红的生长,其中,UO_2~(2+)对满江红的生长抑制率最高,而UO_2PO_4~-则可以促进满江红的生长,但满江红对UO_2~(2+)和(UO_2)_3(OH)_5~+的吸附效率相对较高.当溶液中铀的浓度为2 mg·L~(-1)时,UO_2~(2+)对满江红的富集量和富集系数分别达到了3831 mg·kg~(-1)和1916,(UO_2)_3(OH)_5~+对满江红的富集量和富集系数分别达到了3057 mg·kg~(-1)和1529.可见,要提高满江红对水中铀的去除率和富集量,应将溶液中铀的形态调控为以UO_2~(2+)或(UO_2)_3(OH)_5~+为主,同时要降低溶液中碳酸盐和磷酸盐的含量.     

Polyphenylene sulfide based anion exchange fiber: Synthesis, characterization and adsorption of Cr(VI)

A fibrous strong base anion exchanger (QAPPS) was prepared for the first time via chloromethylation and quaternary amination reaction of polyphenylene sulfide fiber (PPS), and its physical-chemical structure and adsorption behavior for Cr(VI) were characterized by FT-IR, Energy Dispersive Spectrometry, TG-DTG, elemental analysis and batch adsorptive technique, respectively. The novel fibrous adsorbent could effectively adsorb Cr(VI) over the pH range 1-12, the maximum adsorption capacity was 166.39 mg/g at pH 3.5, and the adsorption behavior could be described well by Langmuir isotherm equation model. The adsorption kinetics was studied using pseudo first-order and pseudo second-order models, and the t_1/2 and equilibrium adsorption time were 5 and 20 min respectively when initial Cr(VI) concentration was 100 mg/L. The saturated fibers could be regenerated rapidly by a mixed solution of 0.5 mol/L NaOH and 0.5 mol/L NaCl, and the adsorption capacity was well maintained after six adsorption-desorption cycles.     

我国18种不同理化性质的土壤对硒酸盐的吸附解吸作用研究

硒在土壤中的环境化学行为及其生物有效性在很大程度受到吸附解吸作用的影响,土壤对硒的吸附解吸因为土壤理化性质的不同差异很大.本文采用批量吸附实验,选择土壤性质差异较大的我国18种农田土壤,探讨了土壤p H、无定形铁铝氧化物、有机质和机械组成等对SeO_4~(2-)吸附的影响.结果表明,18种土壤对SeO_4~(2-)的吸附均是一个先快后慢的过程,在24 h达到吸附平衡;二级动力学方程为描述SeO_4~(2-)吸附的最佳模型(R20.976),18种土壤对SeO_4~(2-)吸附大多符合Freundlich模型(R20.842);土壤对SeO_4~(2-)吸附量与p H值(P0.01)、碳酸盐含量(P0.05)呈显著负相关,而与无定型铁、铝含量(P0.01)及有机质含量(P0.05)呈正相关;18种土壤对SeO_4~(2-)吸附的固液分配系数(Kd值)均很低(0.99~18.18 L·kg~(-1));土壤SeO_4~(2-)解吸率均大于80%,表明吸附是可逆的;土壤吸附SeO_4~(2-)的低Kd值和高解吸率反映了硒酸盐易迁移淋溶的特性,这应当在区域环境硒的评价和调控中受到关注.     

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: Kinetics, isotherms and thermodynamics

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qm /SSA) and SSA-normalized adsorption coefficient (Kd /SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (△ G0 ) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (△ H0 ), G0 and free energy of adsorption (Ea ), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and K d /SSA or q m /SSA.     

Microbial reduction of uranium (VI) by Bacillus sp. dwc-2: A macroscopic and spectroscopic study

The microbial reduction of U(VI) by Bacillus sp. dwc-2, isolated from soil in Southwest China, was explored using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). Our studies indicated that approximately 16.0% of U(VI) at an initial concentration of 100 mg/L uranium nitrate could be reduced by Bacillus sp. dwc-2 at pH 8.2 under anaerobic conditions at room temperature. Additionally, natural organic matter (NOM) played an important role in enhancing the bioreduction of U(VI) by Bacillus sp. dwc-2. XPS results demonstrated that the uranium presented mixed valence states (U(VI) and U(IV)) after bioreduction, which was subsequently confirmed by XANES. Furthermore, the TEM and high resolution transmission electron microscopy (HRTEM) analysis suggested that the reduced uranium was bioaccumulated mainly within the cell and as a crystalline structure on the cell wall. These observations implied that the reduction of uranium may have a significant effect on its fate in the soil environment in which these bacterial strains occur.