蒙脱石对盐酸四环素吸附特性的实验研究

基于当前发生的抗生素污染环境严峻问题,本文开展高活性粘土矿物蒙脱石吸附水中盐酸四环素(TC)的实验研究。采用批处理吸附实验方法,着重考查溶液初始TC浓度、初始pH值、电解质的阳离子类型及其浓度等对蒙脱石吸附性能的影响。结果显示,蒙脱石对TC的吸附行为可用Freundlich吸附等温线进行描述,并表现出显著的非线性特征;Langmuir方程确定其最大吸附量为625 mg/g;在较强酸性介质条件下(pH=2～4)蒙脱石对TC的吸附能力最强,其次为弱酸性-弱碱性环境(pH=5～9);不同阳离子类型也能显著影响蒙脱石对TC的吸附,表现为阳离子价态越高,对TC吸附的影响程度越明显。蒙脱石可被认为是一种TC的高效吸附剂,应用于盐酸四环素污染废水的处理过程。     

有机改性硅藻土对甲基橙、酸性绿两种阴离子的吸附实验研究

阳离子表面活性剂十六烷基三甲基溴化铵可以有效对天然硅藻土进行有机改性,获得有机改性硅藻土。有机改性硅藻土对富含甲基橙、酸性绿溶液的吸附实验研究结果表明,在相同条件下,改性硅藻土对甲基橙的吸附效果比较好,对酸性绿的吸附效果不是很理想,但也远远高于硅藻土原土对这两种阴离子的吸附效果。在室温条件下,当甲基橙溶液的浓度为20mg/L时,改性硅藻土投加量为0.2g、pH值为4、吸附时间为80min,改性硅藻土对其的吸附效果较好;在室温条件下,当染料酸性绿溶液的浓度为20mg/L时,改性硅藻土投加量为0.15g、pH值为4、吸附时间为80min,改性硅藻土对其的吸附效果较好;两种阴离子的吸附过程均符合Freundlich模型。基于n值对比分析,改性硅藻土对甲基橙的吸附属于优惠吸附,而对酸性绿的吸附属于非优惠吸附。     

BiOBr/铁改性蒙脱石对罗丹明B的光催化降解性能研究

在低温条件下通过铁改性蒙脱石与BiOBr复合成功合成了一种新型的光催化材料,称为BiOBr/Fe-Mt。运用X射线粉末衍射(XRD)、透射电镜(TEM)、傅立叶转换红外光谱(FTIR)、紫外可见漫反射光谱(UV-Vis DRS)对BiOBr/Fe-Mt材料进行表征。同时以λ400 nm的可见光为光源,开展该催化剂对罗丹明B(Rh B)的光催化降解实验以评估其光催化活性。结果表明,支撑材料投加量被固定在2.5 g的条件下,采用铁改性蒙脱石制备的BiOBr/Fe-Mt材料对Rh B的光催化降解活性高于采用钠基蒙脱石制备的BiOBr/Na-Mt。光催化活性的显著提高,主要归因于:1 BiOBr/Fe-Mt的禁带宽度降低至2.46 e V,或可能形成了BiOBr/铁氧化物异质结结构;2 BiOBr/Fe-Mt上仅发生较少的十六烷基三甲基溴化铵有机分子残留。这些结构因素均可以有效促进BiOBr/Fe-Mt上Rh B的光催化降解。     

低聚合羟基铁-蒙脱石复合体吸附铬酸根的实验研究

摘要：在模拟的酸性土壤条件下，利用制备的低聚合羟基铁蒙脱石复合体对铬酸根进行吸附实验。重点研究了吸附条件对复合体铬吸附能力的影响，对比了蒙脱石和含水氧化铁。结果表明，实验条件下复合体有较强的铬吸附能力，其铬吸附量低于铁沉积物而明显高于蒙脱石。铬初始质量浓度是影响复合体铬吸附量的最主要因素，离子强度次之。吸附时间(12h以上)、温度、pH值对复合体铬吸附量的影响很小；说明在酸性土壤条件下，复合体有强且稳定的铬吸附能力。     

低分子有机酸对聚合羟基铁铝-蒙脱石复合体吸附磷的影响

在一定条件下,利用钠基化蒙脱石(Na-Mt)合成聚合羟基铁铝-蒙脱石复合体(HyFeAl-Mt),M3+/Mt比为10mmol/g,Fe3+/Al3+摩尔比分别为0.1、0.2和0.5。研究了酸性和弱酸性条件下低分子有机酸(以柠檬酸、草酸和苹果酸为代表)及其添加顺序对HyFeAl-Mt复合体吸附磷的影响。结果表明,低分子有机酸对HyFeAl-Mt复合体吸附磷有抑制作用,且随着低分子有机酸浓度的增加愈加明显,酸性条件下的抑制作用比弱酸性条件下明显;低分子有机酸羧基个数越多、分子结构越大,对HyFeAl-Mt对吸附磷的影响越大;酸性环境中低分子有机酸与磷共存时,磷吸附曲线较好地符合Freundlich方程,且其对磷在HyFeAl-Mt0.2上的最大吸附量影响较小;磷与低分子有机酸的添加顺序不同也影响HyFeAl-Mt复合体对磷的吸附。     

聚合羟基铁铝蒙脱石复合体对磷的吸附行为及其动力学

在一定条件下利用钠基化蒙脱石合成了聚合羟基铝-蒙脱石复合体(HyA1-Mt)、2个不同铁含量的聚合羟基铁-蒙脱石复合体(HyFe-Mt)和3个不同Fe:Al摩尔比的聚合羟基铁铝-蒙脱石复合体(HyFeAl-Mt),研究了酸性和弱酸性条件下(pH=3.0～6.5)以上蒙脱石复合体对磷的吸附行为和动力学特征。结果表明,HyFeAl-Mt对磷的吸附容量大于HyA1-Mt和HyFe-Mt复合体,且随着Fe:Al摩尔比的增大,对磷的吸附容量依次增加。随pH升高,蒙脱石复合体对磷的吸附量容量变小。但随Fe:Al摩尔比增大,HyFeAl-Mt复合体零电荷点(pHZPC)升高,pH对磷的吸附的影响越来越小,HyFe-Mt对磷的吸附几乎不受pH的影响。随Fe:A1摩尔比的增大,HyFeAl-Mt对磷的吸附能力增强,铁含量是磷吸附量的重要控制因素。磷在各蒙脱石复合体上的吸附实验数据可很好地用Langmuir吸附等温方程拟合。磷在各蒙脱石复合体上的吸附动力学过程可分为快速和慢速两个过程,快速过程中的动力学受铁含量影响明显。动力学数据可同时用准二级动力学方程和Elovich方程拟合。     

钛柱撑蒙脱石光催化降解亚甲基蓝的实验研究

采用TiCl4水解法制备钛柱化剂与钠蒙脱石离子交换后,自然风干、焙烧得到具有稳定层结构、大晶面间距(2.26 nm)和大比表面积(285.7 m2/g)的钛柱撑蒙脱石(Ti-PILM)。用制备的Ti-PILM对亚甲基蓝(MB)进行紫外光作用下的光催化降解实验,并与层结构不规则的Ti-PILM在相同条件下对MB的光催化效果进行对比,研究MB的初始浓度、Ti-PILM投放量、pH对光催化降解效果的影响。结果表明,室温条件下,降解时间120 min,当Ti-PILM投样量等于2 g/L,MB初始浓度为50 mg/L,pH为7时,Ti-PILM对MB降解速度最高。与纳米TiO2不同,Ti-PILM对MB的降解率和降解初速率与MB在其表面的吸附行为密切相关。     

蒙脱石吸附模拟核素Sr、Cs的性能研究

基于蒙脱石具有良好的阳离子交换性能,采用静态吸附法,对阜新钙基蒙脱石吸附模拟核素Sr、Cs的吸附条件和吸附行为进行了研究。结果表明:蒙脱石样品对Sr2+、Cs+的饱和吸附量分别为0.271mmol/g和0.780mmol/g,在较大的pH值范围(4～11)内具有良好的吸附稳定性;蒙脱石对Sr2+、Cs+的吸附类型以阳离子交换吸附为主,符合Langmuir和Freundlich模型,但与Langmuir吻合更好,相关系数分别达到0.99924和0.99995。本实验研究对于处理低浓度的含Sr、Cs放射性废液具有重要的意义。     

高岭石和蒙脱石吸附胡敏酸的对比研究

高岭石和蒙脱石分别是暖湿和冷干气候带内典型土壤的代表性矿物,对二者吸附胡敏酸特点的对比研究可以为探索不同地带土壤中重金属的环境行为提供重要的依据。笔者通过一系列实验研究了pH值、离子强度和胡敏酸初始浓度对胡敏酸在高岭石和蒙脱石上吸附量的影响,重点剖析了引起高岭石和蒙脱石在吸附胡敏酸方面表现出的共性和差异的原因。研究结果表明:1)在pH=5条件下,胡敏酸在高岭石和蒙脱石上的吸附量均随着胡敏酸初始浓度和离子强度的升高而逐渐增加;2)胡敏酸在高岭石和蒙脱石上的吸附量均随着pH值的升高而降低;3)pH<6时,高岭石吸附的胡敏酸量多于蒙脱石,pH>6时则相反。这是由高岭石和蒙脱石在不同pH条件下吸附胡敏酸的机制不同造成的。在pH<6时,高岭石与胡敏酸之间的静电引力起主导作用,其次是配位交换作用和氢键作用。此时,蒙脱石以氢键作用为主要吸附机制。在pH>6时,高岭石和蒙脱石的主要吸附机制分别是疏水性作用和阳离子键桥。     

高岭石和蒙脱石吸附Li~+的实验研究

为探讨粘土矿物从溶液中吸附锂的基本特征,选取蒙脱石和高岭石与合成的含锂人工海水(ρ(Li)=1.4mg/L)在室温下进行吸附反应,探讨其吸附平衡时间、pH和水岩比对吸附的影响。实验结果表明蒙脱石和高岭石与锂溶液在2 h内均达到吸附平衡。pH从4升高至8时,高岭石对锂吸附的量从33.2μg/g升高到72.4μg/g。而pH>8时,高岭石对锂吸附的量开始减小。水岩比明显的影响到高岭石的吸附能力。水岩比从50mL/g变化到100 mL/g和200 mL/g,其吸附量从25.2μg/g增加到58.8μg/g和142.6μg/g。这说明所用高岭石量足够与实验溶液达到吸附平衡,可以用本实验来研究吸附过程的锂同位素分馏特征。     

天山乌鲁木齐河源1号冰川融水径流水化学特征研究

2006年和2007年的整个消融期内,在天山乌鲁木齐河源1号冰川末端水文控制点逐日定时采集融水径流样品,对样品的主要可溶离子、pH、电导率EC、总溶解固体TDS和悬移质颗粒物SPM进行了分析. 结果表明：天山乌鲁木齐河源1号冰川融水径流离子类型为Ca²⁺-HCO₃^--SO₄^2-,呈弱碱性. 融水径流中TDS变化受日径流量调节显著,表现为消融初期和末期浓度较高,消融强烈时浓度较低;SPM以细颗粒物质为主,各粒度组分含量变化幅度较大,且质量浓度SSC年内变化与TDS呈相反的变化趋势. 融水径流中离子组成主要受岩石风化作用影响,离子摩尔比值和Piper图分析表明,控制冰川径流离子组成的主要过程是碳酸盐、黄铁矿和长石类矿物风化作用.     

水体中主要阴离子及pH值对双氯芬酸液相色谱定量的影响

双氯芬酸(DCF)是一种常用的非甾体消炎药,随着生产量和使用量的不断增大,其在环境中被频繁检出。DCF能在生物体内富集,对生物具有潜在毒性,已经引起了广大学者的关注。DCF的准确定量是开展其相关研究的基础,在应用液相色谱测试DCF的过程中,通常通过前处理消除样品基质干扰,但关于基质如何干扰DCF测量并没有详细研究。为了满足野外及实验室测试需要,本文针对高效液相色谱-紫外检测DCF过程中,水体中常见的阴离子SO_4~(2-)、Cl~-和NO_3~-,液相色谱流动相组成和水样pH对DCF准确定量的影响展开研究。结果表明:(1)SO_4~(2-)和Cl~-对DCF的最大吸收波长(277 nm)没有影响,但是NO_3~-的存在会使DCF的最大吸收峰发生偏移,产生红移现象,并且使吸光度略微增大;(2)同等条件下,在酸性介质(pH5)中DCF的定量结果比在碱性介质中的低。与碱性介质(pH=7.26)中DCF的峰面积相比,样品在pH=2.01的酸性介质中测得的峰面积减少73.14%,因此在碱性条件下DCF定量更为准确。     

Calculation of the visible-UV absorption spectra of hydrogen sulfide,bisulfide, polysulfides,and As and Sb sulfides,in aqueous solution

Recently we showed that visible-UV spectra in aqueous solution can be accurately calculated for arsenic (III) bisulfides, such as As(SH)₃, As(SH)₂S^- and their oligomers. The calculated lowest energy transitions for these species were diagnostic of their protonation and oligomerization state. We here extend these studies to As and Sb oxidation state III and v sulfides and to polysulfides S _n ^2- , n = 2–6, the bisulfide anion, SH^-, hydrogen sulfide, H₂S and the sulfanes, S _n H₂, n = 2–5. Many of these calculations are more difficult than those performed for the As(iii) bisulfides, since the As and Sb(v) species are more acidic and therefore exist as highly charged anions in neutral and basic solutions. In general, small and/or highly charged anions are more difficult to describe computationally than larger, monovalent anions or neutral molecules. We have used both Hartree-Fock based (CI Singles and Time-Dependent HF) and density functional based (TD B3LYP) techniques for the calculations of absorption energy and intensity and have used both explicit water molecules and a polarizable continuum to describe the effects of hydration. We correctly reproduce the general trends observed experimentally, with absorption energies increasing from polysulfides to As, Sb sulfides to SH^- to H₂S. As and Sb(v) species, both monomers and dimers, also absorb at characteristically higher energies than do the analogous As and Sb(III)species. There is also a small reduction in absorption energy from monomeric to dimeric species, for both As and Sb III and v. The polysufides, on the other hand, show no simple systematic changes in UV spectra with chain length, n, or with protonation state. Our results indicate that for the As and Sb sulfides, the oxidation state, degree of protonation and degree of oligomerization can all be determined from the visible-UV absorption spectrum. We have also calculated the aqueous phase energetics for the reaction of S₈ with SH^- to produce the polysulfides, S _n H^-, n = 2–6. Our results are in excellent agreement with available experimental data, and support the existence of a S₆ species.     

Chemical factors controlling the solubility of uraninite and their significance in the genesis of unconformity-related uranium deposits

A quantitative evaluation of the solubility of uraninite (UO₂) in aqueous solutions under hydrothermal conditions was made using previously reported thermodynamic data, so as to inquire into the controlling factors for Canadian unconformity-type ore mineralization as observed in the Athabasca uranium field. The results of solubility calculations suggest that uranyl carbonate complexes, such as UO₂CO ₃ ^o , UO₂(CO₃) ₂ ^2- and UO₂(CO₃) ₃ ^4- , predominate under relatively oxidizing and slightly acidic-alkaline conditions and that the uranyl chloride complex, UO₂Cl⁺ is dominant under acidic conditions. These features are predicted at temperatures up to 200 °C over reasonable ranges of CO₂ pressure (Pco₂) and salinity. Consequently, the physico-chemical parameters, such as oxygen activity (ao₂), and pH are regarded as the most important factors controlling uraninite solubility. Judging from the paragenetic sequences observed in most unconformity-type uranium deposits in the Athabasca district, appreciable decreases in the above variables are postulated to have occurred in the stage of principal uranium deposition. Such changes would be due to fluid-mixing phenomenon accompanied by the diagenetic-hydrothermal activity (Hoeve and Quirt 1987).     

Adsorption capacity of iron oxide-coated gravel for landfill leachate: simultaneous study

Landfill leachate is a high-strength wastewater. If it is not managed properly, it can pollute surrounding environment. The aim of this study is to determine the simultaneous adsorption capacity of iron oxide-coated gravel for metals such as Cd(II), Cu(II), Fe(II), Ni(II) and Zn(II) in high-strength leachate sample. Different operating conditions such as pH, time, and dosages were investigated to determine the kinetics and mechanism of adsorption process. Coating with iron oxide changed the external surface of gravel. The adsorption capacities increased with increased pH, and the optimum pH was found to be 7. High removal rates were observed in a short period of time. The Freundlich model fitted reasonably well to the experimental data, indicating multilayer adsorption process and the heterogeneity of the surface (R ² ranging 0.57–0.94). The Temkin model fitted well to the experimental data as well (R ² ranging 0.67–0.98), indicating that the adsorption is an exothermic process. The adsorption of ions was found to obey second-order kinetics, indicating one-step, surface-only adsorption process. The degree of metal adsorption on iron oxide-coated gravel at pH 7 was in the order Cu(II) > Cd(II) > Fe(II) > Zn(II) > Ni(II).     

Kinetics and equilibrium study of chromium adsorption on zeoliteNaX

This study aims to report Batch adsorption study of hexavalent chromium, Cr (VI) on zeoliteNaX. Kinetics of Cr (VI) adsorption and adsorption isotherms were determined by varying operating parameters such as pH, initial concentration, temperature and contact time. ZeoliteNaX was found to remove Cr (VI) in acidic solutions down to ppm level at pH of about 4. Removal rate of Cr (VI) was found to decrease as pH rises above 4.0. Langmuir, Freundlich, Temkin and Redlich-Peterson models were applied to adsorption equilibrium data to find the best amongst these models. Langmuir model with R² = 0.9711 best fits the adsorption data. The kinetics of adsorption was found to follow the first order reversible reaction. The separation parameter, R_L values of less than 1.0 i.e., 0.7369, 0.5834 and 0.4828 corresponding to initial concentrations of 10, 20 and 30 mg/L, respectively indicated that adsorption of Cr (VI) on zeoliteNaX is favoured. The estimated values of thermodynamic parameters such as heat of adsorption and standard gibbs free energy confirmed the exothermic nature of adsorption of Cr (VI) on zeoliteNaX.     

Comparative study of the absorptive potential of raw and activated carbon <Emphasis Type="Italic">Acacia nilotica</Emphasis> for Reactive Black 5 dye

Acacia nilotica was used for the adsorption of Reactive Black 5 (RB5) dye from an aqueous solution. Both the raw and activated (with H₃PO₄) carbon forms of Acacia nilotica (RAN and ANAC, respectively) were used for comparison. Various parameters (including dye concentration, contact time, temperature, and pH) were optimized to obtain the maximum adsorption capacity. RAN and ANAC were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The maximum experimental adsorption capacities for RAN and ANAC were 34.79 and 41.01 mg g^?1, respectively, which agreed with the maximum adsorption capacities predicted by the Langmuir, Freundlich, and Dubinin–Radushkevich equilibrium isotherm models. The adsorption data of ANAC showed a good fit to the isotherm models based on the coefficient of determination (R ²): Langmuir type II (R ² = 0.99) > Freundlich (R ² = 0.9853) > Dubinin–Radushkevich (R ² = 0.9659). This result suggested monolayer adsorption of RB5 dye. The adsorption of RB5 dye followed pseudo-second-order kinetics. The RAN adsorbent reflected an exothermic reaction (enthalpy change, ΔH = ?0.006 kJ mol^?1) and increased randomness (standard entropy change, ΔS = 0.038 kJ mol^?1) at the solid–solution interface. In contrast, ANAC reflected both exothermic [?0.011 kJ mol^?1 (303–313 K)] and endothermic [0.003 kJ mol^?1 (313–323 K)] reactions. However, the ΔS value of ANAC was lower when the RB5 adsorption increased from 313 to 323 K. The negative values for the Gibbs free energy change at all temperatures indicated that the adsorption of RB5 dye onto RAN and ANAC was spontaneous in the forward direction.     

Adsorption of methylene blue and crystal violet on low-cost adsorbent: waste fruits of <Emphasis Type="Italic">Rapanea ferruginea</Emphasis> (ethanol-treated and H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-treated)

This study assesses the ability of two low-cost adsorbents made from waste of Rapanea ferruginea treated with ethanol (WRf) and its H₂SO₄-treated analog (WRf/H₂SO₄) for the removal of two cationic dyes methylene blue (MB) and crystal violet (CV) from aqueous solutions. The adsorbent was characterized by scanning electron microscopy, Fourier transform infrared spectrometry, thermogravimetric analysis, point of zero charge (pH_pzc), specific surface, and functional groups. The adsorption of dye onto the adsorbents was studied as a function of pH solution (2–12), contact time (up to 120 min) and initial concentration (20–120 mg/L), and temperature (25, 35, and 55 °C). The influence of these parameters on adsorption capacity was studied using the batch process. The response surface methodology (RSM) was used in the experimental design, modeling of the process, and optimizing of the variables and was optimized by the response involving Box–Behnken factorial design (15 runs). The results show that the data correlated well with the Sips isotherm. The maximum adsorption capacities of MB and CV onto WRf were found to be 69 and 106 mg/g, and onto WRf/H₂SO₄, the adsorption capacities were 33 and 125 mg/g, respectively. The kinetic data revealed that adsorption of cationic dyes onto the adsorbents closely follows the pseudo-second-order kinetic model. Regression analysis showed good fit of the experimental data to the second-order polynomial model, with coefficient of determination (R²) values for MB (R²?=?0.9685) and MB (R²?=?0.9832) for WRf and CV (R²?=?0.9685) and CV (R²?=?0.9832) for WRf/H₂SO₄ indicated that regression analysis is able to give a good prediction of response for the adsorption process in the range studied. The results revealed that waste from R. ferruginea is potentially an efficient and low-cost adsorbent for adsorption of MB and CV.     

Geochemical and Sr-isotopic characteristics of stream and spring waters from small-forested catchments at Seto,central Japan

Hydrogeochemical processes controlling surface water chemistry were examined in five small (<1.5 km ²) forested catchments that have contrasting bedrock lithologies of granite, and conglomerate, and are distributed in the southeast of Seto district, central Japan. Watersheds developed on these two bedrocks differ in their ability to neutralize atmospheric acid (pH ~4.5) deposition. The study was conducted to (1) characterize the hydrogeochemical processes controlling surface water chemistry, and (2) to elucidate acidification of spring and stream waters using data from three sampling campaigns conducted from August to October 2000. Stream and spring water solutes fall into two general groups according to concentration: alkaline, relatively high pH (5.2–7.7) and high cation concentrations (HCO ₃ ^-, Cl ^-, base cations), and dilute, low pH (4.2–5.5) waters. Concentrations of trace metals (Al, Ba, Sr) showed a strong negative correlation with pH, suggesting the mobility of these metals in the dissolved load of catchments underlain by Tokai conglomerate. The strontium isotope ratio ( ⁸⁷Sr/ ⁸⁶Sr) of rock and soil, plant, precipitation, and surface water samples was used to identify different reservoirs within the ecosystem. Low Si concentrations in stream and spring waters from the conglomerate area, with a relatively high pool of SiO ₂, >90 (wt%), suggest slow chemical weathering. The dissolved solute concentrations are generally of similar magnitude in stream waters within the catchments of similar bedrock lithology. The high inverse correlation ( r ²=0.72) between pH and SO ₄ ^– concentrations and the high positive correlation ( r ² =0.90) between Ba and SO ₄ ^– concentrations in waters draining Tokai conglomerate suggest that barite (BaSO ₄) is being dissolved in an acidic environment. The three catchments were identified as being sensitive to acidic deposition because the bedrock conglomerate provided little capacity to buffer acidic inputs. The soils from the granite area have a high cation-exchange capacity (CEC an average of 868 µmol/kg), and are nearly ten times greater than the soils from the conglomerate area. Because ion exchange, besides weathering, is the main source that counteracts soil acidification, the sensitivity to further acidification may increase.