不同环境因子对黑土胶体在饱和多孔介质中运移特性的影响

为评价不同环境条件下黑土胶体在地下水多孔介质中的运移,采用离心法对采自于黑龙江海伦黑土样品中的胶体颗粒进行提取. 通过胶体在石英砂填充柱中的淋溶试验研究了pH、离子强度和溶解性有机质等环境因子对胶体在多孔介质中运移特性的影响. 结果表明:当pH在4～9的范围内变化时,MR(回收率)和k(沉积速率系数)没有发生显著变化,即其对胶体运移能力影响不显著. 随着离子强度从0.001 mmol/L升至1 mmol/L,黑土胶体穿透曲线MR降低,k值升高,说明高无机离子强度使胶体易于沉积在石英砂表面,运移能力降低. 当溶液中含有溶解性有机质HA(胡敏酸)和FA(富里酸)时,MR降低,k值增加,表明胶体运移能力受到抑制,并且FA对胶体颗粒运移的抑制作用比HA强. 溶液离子强度、HA和FA含量对黑土胶体在饱和多孔介质中的运移过程影响较大,是影响地下水中胶体运移过程的关键环境因子.      

水体组分对聚苯乙烯纳米颗粒聚沉行为的影响

微/纳米塑料在环境水体中的团聚和沉降行为是影响其迁移和分布的重要因素.以聚苯乙烯纳米颗粒（PS-NPs）为对象,研究了Na⁺和天然有机质（NOM）两种典型水体组分对其团聚粒径和沉降性能的影响规律,分析了海水、湖水和生活污水等6种水体中团聚、沉降效果及潜在影响因子.结果表明,c（Na⁺） < 80 mmol·L^-1时有利于PS-NPs沉降;反之,则促进其团聚和悬浮.NOM可借助Na⁺在颗粒表面形成多层吸附结构,改变颗粒表面电势和相对密度,进而影响PS-NPs团聚和沉降性能.ρ（NOM） > 10 mg·L^-1时可增强PS-NPs分散和悬浮性能,可能归因于大量附着在颗粒表面的NOM降低了PS-NPs相对密度.环境水体较实验室合成水体更能促进颗粒团聚,这可能与环境水体富含氨基酸和蛋白质等大分子有关.     

常规金属离子对Fe3O4磁性纳米颗粒悬浮和沉降的影响

水体中的有机质、无机盐及酸碱度是影响纳米材料迁移转化的主要因素.考察了Na~+、Mg~(2+)、Ca~(2+)、Sr~(2+)和Ba~(2+)对Fe_3O_4磁性纳米材料(Magnetic Nanoparticles,MNPs)的沉降作用.结果表明,Fe_3O_4MNPs的沉降作用是水体pH、金属离子化合价、离子强度共同影响的结果.整体上,碱土金属离子较Na~+更能加速Fe_3O_4MNPs的沉降.当pH为5.0时,浓度低于1.0 mmol·L~(-1)的Na~+、Mg~(2+)和Ca~(2+)有助于Fe_3O_4MNPs的悬浮;当浓度大于1.0 mmol·L~(-1)时,较强的离子强度促使Fe_3O_4MNPs团聚,发生沉降.当pH为9.0时,碱土金属离子较Na~+更能促使Fe_3O_4MNPs聚沉.因此,纳米颗粒在水体中的扩散和聚沉需要综合考虑金属离子种类和浓度.     

不同环境条件下水铁矿和针铁矿纳米颗粒稳定性

纳米颗粒的团聚和分散是控制许多重要环境过程的关键因素.本研究通过测定水铁矿纳米颗粒(FHNPs)和针铁矿纳米颗粒(GTNPs)的粒径和Zeta电位,计算DLVO相互作用能,探究了不同pH、离子和有机质条件下两种纳米颗粒的稳定性.结果表明Na~+和Ca~(2+)通过离子强度的作用促进FHNPs和GTNPs团聚;低浓度PO_4~(3-)(2mmol·L~(-1))、HA和FA(2 mg·L~(-1)和10 mg·L~(-1))吸附在铁矿物纳米颗粒上,改变其表面电荷,提高FHNPs和GTNPs在中高pH条件下的稳定性.高浓度的PO_4~(3-)(10mmol·L~(-1))虽然也可改变铁矿物纳米颗粒的电性,但由于离子强度的作用,对GTNPs的稳定性贡献不大.FHNPs或GTNPs的Zeta电位接近于0时,其相互作用的一级势垒和次级势阱常常同时不存在,两种纳米颗粒主要以不可逆的方式在一级势阱中团聚;当一级势垒和次级势阱同时存在时,次级势阱造成的可逆FHNPs和GTNPs团聚比例会增大.本研究结果为进一步考察FHNPs和GTNPs的环境行为和它们在负载污染物迁移中的作用提供数据支撑.     

离子强度和胡敏酸影响下不同土壤胶体稳定性研究

土壤胶体的稳定性对其携带污染物的能力产生重要影响,但离子强度和胡敏酸（HA）对不同土壤胶体稳定性的影响程度尚不明确.本实验通过土壤胶体沉降实验以及DLVO理论研究离子强度、HA对黑钙土、潮土和黄壤3种土壤胶体稳定性的影响.结果表明：即使在高离子强度背景下,黑钙土胶体和黄壤胶体因有机质和黏土矿物（黑钙土胶体：伊/蒙混合层;黄壤胶体：伊利石）较高,表面负电荷多、静电斥力大,故稳定性好;而潮土胶体的稳定性受离子强度影响明显,在低离子强度下,静电斥力占主导,稳定性达到最高.HA通过增加土壤胶体表面的负电荷,提高土壤胶体间静电斥力而增强其稳定性,且HA浓度越高土壤胶体的稳定性越强.不同粒径HA对土壤胶体稳定性的影响受pH值控制,相对于大粒径HA,酸性条件下,小粒径HA （F-HA）自身稳定性更强,同时也会自凝聚形成较大的团聚体来提高土壤胶体的稳定性;中、碱性条件下,F-HA产生的链状凸起结构较小,导致空间弹性斥力和渗透性斥力减弱,进而降低土壤胶体的稳定性.结果为明晰离子强度和HA对不同土壤胶体稳定性产生差异性影响提供数据支撑.     

固液界面NOM吸附中疏水效应的影响研究

文章以腐殖酸和纳米Fe2O3为对象,着重研究了腐殖酸分子在纳米Fe2O3表面的吸附过程中的疏水效应,借助红外光谱和热重等分析方法研究了腐殖酸吸附前后的疏水性随溶液环境变化的规律。结果表明,当离子强度为0、0.005、0.01和0.05 mol/kg,pH值从7变到12时,纳米Fe2O3吸附溶解性腐殖酸分子后形成的复合体的热失重量随着pH值的升高先减小后增大。当pH值从7升高到10时,亲水性降低,疏水性增强;当pH值从10升高到12时,亲水性增强,疏水性降低。当离子强度为0.001 mol/kg,pH值从7变到12时,复合体的热失重量随着pH值的升高而减小,亲水性降低,疏水性增强。当pH值为定值,离子强度变化时,纳米Fe2O3吸附溶解性腐殖酸分子后形成的复合体的热失重量随着离子强度的增加不断变化,曲线呈现出波动趋势,亲、疏水性在交替变化。红外光谱分析结果说明,对纳米Fe2O3吸附溶解性腐殖酸分子后形成的复合体的亲疏水性起主要影响的官能团可能是亲水性的羟基-OH、羰基C=O和疏水性的CH2烷烃。     

颗粒尺寸对纳米氧化物环境行为的影响

随着纳米技术迅猛发展,纳米颗粒的环境行为和生态效应越来越受到关注.纳米氧化物作为环境中的重要组成,广泛存在于水体、大气、土壤以及沉积物中,其大比表面积和高表面活性,控制和影响着环境中一些污染物和营养元素的形态、迁移、转化和生物有效性.纳米尺寸是纳米颗粒特有属性,颗粒尺寸大小调控和决定纳米氧化物的结构及物理化学特性,从而在较大程度上影响其与相关元素的界面反应性和环境地球化学行为.综述了纳米氧化物的尺寸对吸附、(还原)溶解、(催化)氧化、聚集和迁移等环境行为的影响,讨论了尺寸效应的作用机制,最后展望了环境中纳米金属氧化物尺寸效应有关的研究热点和方向.     

nTiO2在水中的分散沉降行为研究

nTiO2进入水环境后,其存在形态及环境行为主要受水环境因素影响.以P25 nTiO2为研究对象,通过改变nTiO2悬浊液的pH值、电解质和表面活性剂种类,分析了nTiO2的分散、团聚及沉降行为.结果表明,pH通过改变nTiO2颗粒的Zeta电位影响nTiO2在水中的稳定性,等电点附近nTiO2发生显著聚沉.nTiO2颗粒选择性吸附AlCl3、CaCl2、NaCl及Na2SO4电离产生的荷电离子,阳离子的吸附中和了TiO2颗粒表面的负电荷,导致颗粒急速聚沉;阴离子的吸附使颗粒间静电斥力增强,颗粒稳定存在于水中.不同类型的表面活性剂通过改变nTiO2颗粒表面性质,增强nTiO2颗粒在水中的稳定性.运用DLVO理论建立了nTiO2的势能方程,势能曲线拟合结果表明,水环境条件通过影响颗粒间势能大小影响nTiO2在水中的分散沉降行为.     

纳米金属颗粒在土壤-植物系统中的迁移转化及生物效应研究进展

纳米金属颗粒的安全性是我国纳米产业发展亟需解决的重要课题,认识纳米金属颗粒在土壤-植物系统中的迁移转化和生物效应是其安全性研究的重要内容. 本文系统阐述了纳米金属颗粒在土壤中的迁移转化、在植物中的运输过程和机制以及在植物中的生物转化及其对植物的生物学效应,并在此基础上提出未来研究展望. 结果表明:①复杂的土壤环境(pH、离子强度、离子价态、温度、溶解性有机质)能够影响纳米金属颗粒在土壤中的迁移及其形态转化(吸附/解吸、分散/沉降、解离和氧化/还原);②纳米金属颗粒首先吸附在植物的根部,再通过质外体或共质体途经向植物内部转移,由木质部和韧皮部组成的维管系统进行转运;③根际分泌物以及植物体内的蛋白质与有机酸等对纳米金属颗粒在植物中的生物转化起到重要作用;④纳米金属颗粒可以通过引起氧化应激或抑制营养元素吸收对植物产生毒性效应. 为此,提出未来研究展望:建议重点关注纳米金属颗粒在土壤中形态转变过程的耦合效应,以及各赋存形态在植物体内的运输途径、生物转化过程机制及其对植物生物效应的贡献等.      

腐殖酸与镉离子在水合二氧化锰表面的分配系数研究

水体中腐殖酸(HA)和金属离子广泛存在,二者的相互作用对其在水中天然矿物颗粒表面的吸附、降解等环境行为具有重要影响.本文采用离子交换平衡法测定了HA和镉离子(Cd(Ⅱ))的配位数(co-ordination number,x)和络合稳定常数(complex stability constant,K),系统考察了pH值和离子强度对x和K的影响,并研究了HA和Cd(Ⅱ)在水合二氧化锰(HMO)表面的分配关系.结果表明:pH值对HA和Cd(Ⅱ)的配位数影响较小(x=1.651~1.752),而对络合稳定常数影响显著(log K=1.652~3.548);在不同pH值条件下,离子强度对HA和Cd(Ⅱ)的络合稳定常数影响均较小,而其配位数均随溶液离子强度的增加而提高;不同温度条件下,HA-Cd(Ⅱ)络合物在HMO表面的分配系数(Kd)均低于HA和Cd(Ⅱ)在HMO表面的分配系数,表明HA-Cd(Ⅱ)络合体系的存在抑制了HMO对Cd(Ⅱ)和HA的去除作用.     

Influences of anion concentration and valence on dispersion and aggregation of titanium dioxide nanoparticles in aqueous solutions

Dispersion and aggregation of nanoparticles in aqueous solutions are important factors for safe application of nanoparticles. In this study, dispersion and aggregation of nano-TiO₂ in aqueous solutions containing various anions were investigated. The influences of anion concentration and valence on the aggregation size, zeta potential and aggregation kinetics were individually investigated. Results showed that the zeta potential decreased from 19.8 to − 41.4 mV when PO₄^3 − concentration was increased from 0 to 50 mg/L, while the corresponding average size of nano-TiO₂ particles decreased from 613.2 to 540.3 nm. Both SO₄^2 − and NO₃⁻ enhanced aggregation of nano-TiO₂ in solution. As SO₄^2 − concentration was increased from 0 to 500 mg/L, the zeta potential decreased from 19.8 to 1.4 mV, and aggregate sizes increased from 613.2 to 961.3 nm. The trend for NO₃⁻ fluctuation was similar to that for SO₄^2 − although the range of variation for NO₃⁻ was relatively narrow. SO₄^2 − and NO₃⁻ accelerated the aggregation rapidly, while PO₄^3 − did so slowly. These findings facilitate the understanding of aggregation and dispersion mechanisms of nano-TiO₂ in aqueous solutions in the presence of anions of interest.     

Sorption of uranyl ions on TiO2: Effects of pH, contact time, ionic strength, temperature and HA

Sorption of U(VI) onto TiO₂ as functions of pH, ionic strength, contact time, soil humic acid (SHA), solid-to-liquid ratio and temperature was studied under ambient conditions using batch and spectroscopic approaches. The sorption of U(VI) on TiO₂ was significantly dependent on pH and ionic strength. The presence of SHA slightly enhanced the sorption of U(VI) on TiO₂ below pH 4.0, while it inhibited U(VI) sorption in the higher pH range. U(VI) sorption on TiO₂ was favored at high temperatures, and the sorption process was estimated to be endothermic and spontaneous. Reduction of U(VI) to lower valent species was confirmed by X-ray photo-electron spectroscopy analysis. It is very interesting to find that U(VI) sorption on TiO₂ was promoted in solutions with higher back-ground electrolyte concentrations. In the presence of U(VI), higher back-ground electrolyte made more TiO₂ particles aggregate through (001) facets, leading more (101) facets to be exposed. Therefore, the reduction of U(VI) was enhanced by the exposed (101) facets and more U(VI) removal was observed.     

纳米TiO2对土壤重金属释放及形态变化的影响

通过室外模拟淹水实验研究纳米Ti O_2对土壤重金属迁移转化的影响,分析了两种纳米Ti O_2对三峡水库典型消落区土壤中Cr、Zn、Pb、Cu和Cd释放和形态变化的影响.结果表明,淹水两个月后,添加4 g·kg~(-1)金红石和锐钛矿颗粒处理均导致约30%的Cr释放到水中,主要促进可氧化态和残渣态Cr的溶出,从而促进土壤Cr的活化,大大提高其生态风险;另外,添加4 g·kg~(-1)金红石颗粒处理导致酸可交换态和可氧化态Pb含量分别下降25.92%和33.09%,增强其迁移性;但添加锐钛矿颗粒处理促进土壤中可氧化态Zn的生成,含量提高约30%,有利于Zn的固定;此外,两种纳米Ti O_2颗粒对Cu和Cd的形态均没有明显的影响.因此,纳米Ti O_2对土壤中Cr释放和形态变化影响最大,其次是Pb和Zn,在进行重金属污染土壤的修复及其风险评估时需要特别注意.     

The potential leaching and mobilization of trace elements from FGD-gypsum of a coal-fired power plant under water re-circulation conditions

Experimental and geochemical modelling studies were carried out to identify mineral and solid phases containing major, minor, and trace elements and the mechanism of the retention of these elements in Flue Gas Desulphurisation (FGD)-gypsum samples from a coal-fired power plant under filtered water recirculation to the scrubber and forced oxidation conditions. The role of the pH and related environmental factors on the mobility of Li, Ni, Zn, As, Se, Mo, and U from FGD-gypsums for a comprehensive assessment of element leaching behaviour were also carried out. Results show that the extraction rate of the studied elements generally increases with decreasing the pH value of the FGD-gypsum leachates. The increase of the mobility of elements such as U, Se, and As in the FGD-gypsum entails the modification of their aqueous speciation in the leachates; UO₂SO₄, H₂Se, and HAsO₂ are the aqueous complexes with the highest activities under acidic conditions. The speciation of Zn, Li, and Ni is not affected in spite of pH changes; these elements occur as free cations and associated to SO₄ ² in the FGD-gypsum leachates. The mobility of Cu and Mo decreases by decreasing the pH of the FGD-gypsum leachates, which might be associated to the precipitation of CuSe₂ and MoSe₂, respectively. Time-of-Flight mass spectrometry of the solid phase combined with geochemical modelling of the aqueous phase has proved useful in understanding the mobility and geochemical behaviour of elements and their partitioning into FGD-gypsum samples.     

The potential leaching and mobilization of trace elements from FGD-gypsum of a coal-fired power plant under water re-circulation conditions

Experimental and geochemical modelling studies were carried out to identify mineral and solid phases containing major, minor, and trace elements and the mechanism of the retention of these elements in Flue Gas Desulphurisation (FGD)-gypsum samples from a coal-fired power plant under filtered water recirculation to the scrubber and forced oxidation conditions. The role of the pH and related environmental factors on the mobility of Li, Ni, Zn, As, Se, Mo, and U from FGD-gypsums for a comprehensive assessment of element leaching behaviour were also carried out. Results show that the extraction rate of the studied elements generally increases with decreasing the pH value of the FGD-gypsum leachates. The increase of the mobility of elements such as U, Se, and As in the FGD-gypsum entails the modification of their aqueous speciation in the leachates; UO₂SO₄, H₂Se, and HAsO₂ are the aqueous complexes with the highest activities under acidic conditions. The speciation of Zn, Li, and Ni is not affected in spite of pH changes; these elements occur as free cations and associated to SO₄² in the FGD-gypsum leachates. The mobility of Cu and Mo decreases by decreasing the pH of the FGD-gypsum leachates, which might be associated to the precipitation of CuSe₂ and MoSe₂, respectively. Time-of-Flight mass spectrometry of the solid phase combined with geochemical modelling of the aqueous phase has proved useful in understanding the mobility and geochemical behaviour of elements and their partitioning into FGD-gypsum samples.     

Biosorption of copper ions from dilute aqueous solutions on base treated rubber (Hevea brasiliensis) leaves powder: kinetics, isotherm, and biosorption mechanisms

The effciency of sodium hydroxide treated rubber (Hevea brasiliensis) leaves powder (NHBL) for removing copper ions from aqueous solutions has been investigated. The e?ects of physicochemical parameters on biosorption capacities such as stirring speed, pH, biosorbent dose, initial concentrations of copper, and ionic strength were studied. The biosorption capacities of NHBL increased with increase in pH, stirring speed and copper concentration but decreased with increase in biosorbent dose and ionic strength...     

Effects of surfactants on the combined toxicity of TiO2 nanoparticles and cadmium to Escherichia coli

The combined ecological toxicity of TiO₂ nanoparticles (nano-TiO₂) and heavy metals has been paid more attention. As the common pollutants in water environment, surfactants could affect the properties of nanoparticles and heavy metals, and thus further influence the combined toxicity of nano-TiO₂ and heavy metals. In this study, the effects of sodium dodecyl benzene sulfonate (SDBS) and Tween 80 on the single and combined toxicities of Cd^2 + and nano-TiO₂ to Escherichia coli (E. coli) were examined, and the underlying influence mechanism was further discussed. The results showed both SDBS and Tween 80 enhanced the toxicity of Cd^2 + to E. coli in varying degrees. The reaction of SDBS and Cd^2 + could increase the outer membrane permeability and the bioavailability of Cd, while Tween 80 itself could enhance the outer membrane permeability. The combined toxicity of nano-TiO₂ and Cd^2 + to E. coli in absence of surfactant was antagonistic because of the adsorption of Cd^2 + to nano-TiO₂ particles. However, in the presence of SDBS, both SDBS and nano-TiO₂ influenced the toxicity of Cd^2 +, and also SDBS could adsorb to nano-TiO₂ by binding to Cd^2 +. The combined toxicity was reduced at Cd^2 + lower than 4 mg/L and enhanced at Cd^2 + higher than 4 mg/L under multiple interactions. Tween 80 enhanced the combined toxicity of nano-TiO₂ and Cd^2 + by increasing the outer membrane permeability. Our study firstly elucidated the effects of surfactants on the combined toxicity of nano-TiO₂ and Cd^2 + to bacteria, and the underlying influencing mechanism was proposed.     

纳米TiO2光催化降解对甲基苯磺酸的研究

采用TiO2/UV光催化降解法处理对甲基苯磺酸的水溶液,探讨了二氧化钛的投加量、溶液的初始浓度、溶液的pH、紫外光照射时间和强度、常见无机离子等因素对对甲基苯磺酸的降解效率的影响.结果表明,在浓度为0.030 g·L-1对甲基苯磺酸溶液中,光催化剂TiO2最佳投加量为0.10 g·L-1,控制空气分压为5.2kPa,紫外光照射2h,溶液为中性时,对甲基苯磺酸废水降解率达到67.4%.二氧化钛的用量、溶液的pH是影响纳米TiO2光催化降解对甲基苯磺酸的主要因素.在此基础上还考察了无机阳离子和无机阴离子对反应的影响,并取得了满意的效果.     

EDTA-nSiO2纳米颗粒对Cd2+的吸附

nSiO_2纳米颗粒是一种广泛应用的工程纳米材料,为增加其对水溶液中Cd~(2+)的吸附性能,采用接枝改性的方法制备出乙二胺四乙酸(EDTA)改性nSiO_2纳米颗粒(EDTA-nSiO_2),并用透射电镜、氮气吸附-解吸、红外光谱和差热分析等手段对其进行了结构表征,同时以其为吸附剂,通过批处理实验法探讨了体系pH、吸附时间、温度、离子强度等因素对Cd~(2+)吸附的影响,并结合X射线能谱(XPS)分析对其吸附机制进行了分析.结果表明,以EDTA为改性剂,可以成功制备出稳定性良好的EDTA-nSiO_2纳米颗粒,其对Cd~(2+)的吸附受体系p H控制;nSiO_2对Cd~(2+)的吸附量较小,EDTA改性可增加nSiO_2对Cd~(2+)的吸附作用,随着p H的升高,Cd~(2+)的吸附效果逐渐增强,在p H大于4.0后逐渐趋于稳定.EDTA-nSiO_2对Cd~(2+)的吸附速率较快,可在1 h内达到吸附平衡.EDTA-nSiO_2对Cd~(2+)的吸附为吸热的自发过程,吸附等温线可用Langmuir模型描述.NaCl浓度增加会导致Cd~(2+)的吸附量下降,当体系Na Cl浓度从0增加到100 mmol·L~(-1),Cd~(2+)的最大吸附量从0.433 mmol·g-1降低至0.294mmol·g-1.0.1 mol·L~(-1)HCl是较为合适的吸附剂再生液,Cd~(2+)洗脱率约94.36%.结合pH、温度、离子强度、再生和XPS分析结果,可以推测出EDTA-nSiO_2对Cd~(2+)的吸附是包含有简单的物理吸附和离子交换过程,并以化学络合为主的吸附过程.EDTA-nSiO_2是一种对水体Cd~(2+)具有较好吸附能力的工程纳米材料吸附剂.