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。     

Fe-Al复合柱撑剂制备及对丁基黄药的吸附行为

由于蒙脱石独特的层状结构和离子交换能力,使其在污水治理领域具有良好的应用前景。本文使用共聚法制备Fe-Al复合柱撑蒙脱石（Fe-Al-MT）,采用XRD、比表面积孔径分析仪和SEM等进行表征分析,并探究了Fe-Al-MT对选矿废水中丁基黄药的吸附效果。试验结果表明,当Fe-Al复合柱撑蒙脱石中n(Fe³⁺)/n(Al³⁺)=1﹕5时,Fe-Al-MT的层间距达到1.913nm,比表面积为226.65m²/g,柱撑效果最佳。在Fe-Al-MT用量为6g/L,温度为40℃,p H=5的条件下,Fe-Al-MT对丁基黄药的去除率最高达到84.16%。根据Fe-Al-MT对丁基黄药的吸附作用研究表明该反应更符合Langmuir等温线模型,表明吸附过程属于单分子吸附。吸附动力学分析表明该吸附过程主要以化学吸附为主,符合二级动力学。     

富含Na+ 、Ca2+、Al3+、Cr3+蒙脱石对垃圾渗滤液中有机物的吸附

由于层间含有高价态金属阳离子的蒙脱石对特定有机物的吸附能力可大大增强,故分别用层间含有Na+、Ca2+、Al3+和Cr3+的蒙脱石对垃圾渗滤液中的有机物进行吸附实验,研究它们吸附苯酚、二甲苯和COD的能力及离子形态对吸附效果的影响.结果表明,含高价金属阳离子的蒙脱石对苯酚和COD的吸附能力较高,吸附能力由小到大的顺序为Na+<Ca2+<Al3+<Cr3+蒙脱石;各种类型蒙脱石对二甲苯的吸附能力相对较低,并且没有一定的规律可循.并对氢键吸附机制进行了探讨.     

Cr~(3+)在蒙脱石中吸附位置研究——基于蒙脱石、CTAB-和NH_4~+-交换层间域的蒙脱石吸附铬研究

蒙脱石具良好的阳离子可交换吸附特性。在提纯蒙脱石的基础上,用氯化铵(NH_4Cl)和十六烷基三甲基溴化铵(CTAB)分别交换蒙脱石层间阳离子制备了改性蒙脱石,并用提纯蒙脱石、改性后的蒙脱石吸附碱式硫酸铬溶液中的铬离子,获得含铬蒙脱石样品。针对上述的含铬蒙脱石进行包括粉末X射线衍射术(XRD)、电子顺磁共振谱术(EPR)和傅里叶变换红外吸收光谱术(FTIR)以及电感耦合与等离子体原子发射光谱(ICP-AES)等测试和分析。吸附残余液的化学分析结果和含铬蒙脱石样品的XRD结果显示CTAB对蒙脱石的层间的封闭是较完全的,层间几乎未发生交换吸附;而NH_4~+—蒙脱石和蒙脱石层间则发生交换吸附。吸附前后样品的红外吸收谱发生了较大变化,表明三个含铬样品的红外吸收谱上出现的硅醇和铝醇向低波数延展的现象是由铬离子吸附在蒙脱石结构片的六方孔中所致。EPR的结果指示甚至在蒙脱石的少量四面体和/(或)八面体位中也有Cr~(3+)占位。     

矿物锌肥结构特征及其增效机理研究

采用阳离子交换法制备矿物锌肥.蒙脱石和蛭石对Zn2+的等温吸附线呈双"S"型,而沸石对Zn2+的等温吸附线则呈"Langmuir"型.3种矿物对Zn2+的吸附容量大小顺序为蒙脱石＞蛭石＞沸石.盆栽试验结果显示,施用锌肥后,两造玉米幼苗的生物产量都高于CK(未施用锌肥),在第一造中蛭石锌的增产量最高,而第二造中蒙脱石锌的增产量最高.运用粉晶X射线衍射、红外光谱、差热及热重分析等技术对矿物及矿物锌肥的结构特征进行了研究,结果表明,蛭石锌可作为速效锌肥,而蒙脱石锌则可作为长效缓释锌肥.     

斜发沸石对模拟核素Sr2+的吸附/解吸动力学研究

以Sr（NO3）2为核素源、新疆富蕴县所产斜发沸石为吸附剂,研究斜发沸石对Sr2＋的动力吸附/解吸效果。探讨吸附时间、Sr2＋初始浓度与吸附量的关系以及吸附机理。用pH=6的水溶液对饱和吸附了Sr2＋的斜发沸石进行解吸。结果表明：斜发沸石对Sr2＋的吸附在4 h能达到最大吸附率的99%,Freundlich吸附等温式能对吸附曲线进行很好的描述,单位质量沸石对Sr2＋的最大吸附量为38.34 mg/g,以阳离子交换吸附为主。4.5 h后解吸率为1.78%,解吸速率远小于吸附速率,解吸量与解吸时间的自然对数呈现明显的线性关系,用Elovich方程对解吸曲线进行拟合,R=0.9994,拟合方程为：qt=0.03375＋0.11916lnt。理论上将5%的Sr2＋解吸出来约需5044 d。该斜发沸石固Sr2＋能力很强,对于处理含Sr2＋放射性废液具有重要的意义。     

海藻酸钠造粒酸改凹凸棒石对Sr、Cs吸附效能影响分析

凹凸棒石黏土(凹土)对重金属类污染组分具有较强吸附作用,但受原状凹土固液难以分离的制约,目前尚未应用于实际工程。本文利用海藻酸钠对酸改性凹土进行造粒,通过静态批实验分析了其对Sr和Cs的吸附性能,并利用柱迁移实验分析动态迁移规律。结果表明,Sr和Cs浓度为100 mg/L,投加量为10 g/L时,120 min内达到平衡,造粒后的凹土颗粒对Sr和Cs去除率分别为40.4%和45.9%,造粒作用引起吸附效能低于凹土原土,具有明显负效应;柱实验结果表明,吸附剂用量为10.0 g、流速为10 m L/min时Sr和Cs的去除率达到41.8%和61.5%,随流速增加或降低,去除率均减小。因此,海藻酸钠造粒改性凹土颗粒可作为含Sr和Cs废水处理的备选材料。     

高表面活性矿物对Zn~(2+)的吸附机理及其环境意义

本文利用高表面活性矿物蒙脱石、蛭石、沸石在一定的介质条件下对Zn2 +进行吸附实验研究。蒙脱石和蛭石对Zn2 +的等温吸附线呈双“S”型 ,而沸石对Zn2 +的等温吸附线则呈“Langmuir”型。三种矿物对Zn2 +的吸附容量大小顺序为 :蒙脱石 >蛭石 >沸石。运用粉晶X射线衍射、红外光谱、差热及热重分析等技术对矿物及矿物吸附Zn2 +后的结构特征进行了研究。结果表明 ,蒙脱石吸附锌后其层间域中吸附锌大量水解形成新的物相 ,而蛭石与沸石吸附锌后水解很少。这为利用高表面活性矿物控制和治理环境污染及其可循环利用提供了理论依据。     

齐齐哈尔碾子山麦饭石物化性能及其对Pb2+、Cd2+、Cr3+的吸附行为研究

以齐齐哈尔碾子山麦饭石为研究对象,通过比表面积及孔隙分析、阳离子交换容量(CEC)测试以及p H值缓冲能力测试等,对碾子山区麦饭石的结构和性能进行表征,并进一步研究麦饭石对Pb~(2+)、Cd~(2+)、Cr~(3+)的吸附行为。结果显示:碾子山区麦饭石具有海绵体大孔结构,阳离子交换容量(CEC)13~20 mmol/100 g。碾子山麦饭石对酸碱溶液都具有较好的调节能力,尤其对酸液的调节更高效。重金属吸附性能方面,对Pb~(2+)、Cd~(2+)、Cr~(3+)这3种离子吸附关系为:Pb~(2+)Cr~(3+)Cd~(2+)。     

甘肃金昌红泉镁基膨润土属型分类

膨润土是一种以蒙脱石为主要成分的粘土类矿物。确定膨润土的属型,实质上是依据蒙脱石晶层间吸附阳离子的种类及其丰度。 (一) 蒙脱石吸附阳离子的主要原因 1.蒙脱石是属于一种2:1层状结构,即由二个硅氧四面体片夹一个铝氧八面体片构成的层状体。蒙脱石因四面体中Al~(3+)置换Si~(4+)和八面体中Mg~(2+)置换Al~(3+),使蒙脱石晶层间产生永久性负电荷,为了保持晶格电荷平衡,因而晶层间具有吸附阳离子和交换性阳离子的性能。     

Quantitative assessment of radionuclide retention in the Quaternary sediments/granite interface of the Fennoscandian shield (Sweden)

The Quaternary sediments representing the interface between the granite host rock and the Earth surface are of paramount importance when determining the potential cycling of anthropogenic and natural radionuclides in near-surface systems. This is particularly true in the case of high-level nuclear waste (HLNW) repositories placed in granite. In this work a modelling procedure is presented to quantitatively determine the retention capacity of a Quaternary till in the Forsmark area, which has been recently selected to host the deep geologic storage of HLNW in Sweden. Reactive transport numerical models have been used to simulate the intrusion of a deep groundwater carrying radionuclides potentially released from a repository into a Quaternary till. Four radionuclides (²³⁵U, ¹³⁵Cs, ²²⁶Ra and ⁹⁰Sr) have been selected according to their different geochemical behaviour and potential dose relevance to surface ecosystems. Numerical results indicate that repository-derived: (i) U will have a minor impact in the till, mainly due to the high natural concentration of U and its adsorption on ferrihydrite; (ii) Cs will be efficiently retained by cation exchange on illite; (iii) Ra will be retained via co-precipitation with barite; and although (iv) Sr will be retained via co-precipitation with calcite and cation exchange on illite, the retention capacity of the Quaternary till for Sr is limited.     

Application of Chitin and Zeolite adsorbents for treatment of low level radioactive liquid wastes

Two types of Shrimp Chitin derivatives and two types of Iranian natural Zeolite derivatives (Firuzkooh Clinoptiliolite) were studied for adsorption and treatment of low-level radioactive liquid waste (LLW). Chitin with lowers than 10% and Chtiosan with higher than 90% deacetylation factor were selected as natural organic adsorbents. Natural Cliniptilolite of Firuzkooh area and Na form derivatives of it were selected as natural inorganic adsorbents. The static and dynamic ion exchange experimental results show that the adadsorption efficiency depend on particle size, PH, adsorbent type, deacetylation factor (in Chitin adsorbents) and cation type. The best Cs adsorption occurred in Na form Clinoptilolite. Nevertheless Chitin derivatives, particularly Chitosan, are more efficient than Zeolite adsorbents for removing of radionuclides such as ¹³⁷Cs, ⁵⁴Mn, ⁹⁰Sr and ⁶⁰Co. Adsorption performance was discussed and compared with each other.     

Radioactive removal by adsorption on Yesan clay and zeolite

The adsorption of Cs, Sr, Ni, and Co radioactive substitutes onto Yesan clay and zeolite was studied through batch and column tests using Cs, Sr, Ni, and Co as substitutes for radioactive isotopes. Adsorption values of 0.189–1.865 μg/g onto Yesan clay and 0.595–9.055 μg/g onto zeolite were observed, with the radioactive substitutes being almost 100 % adsorbed from the onset of column testing. Adsorption was achieved through ionic bonding. These materials demonstrated suitability for use as backfill or foundation materials for nuclear power plants, radioactive waste disposal facilities, and other radioactive facilities.     

Clay mineral weathering and contaminant dynamics in a caustic aqueous system: I. Wet chemistry and aging effects

Caustic high level radioactive waste induces mineral weathering reactions that can influence the fate of radionuclides released in the vicinity of leaking storage tanks. The uptake and release of Cs^I and Sr^II were studied in batch reactors of 2:1 layer-type silicates—illite (Il), vermiculite (Vm) and montmorillonite (Mt)—under geochemical conditions characteristic of leaking tank waste at the Hanford Site in WA (0.05 m Al_T, 2 m Na⁺, 1 m NO₃⁻, pH ∼14, Cs and Sr present as co-contaminants). Time series (0 to 369 d) experiments were conducted at 298 K, with initial [Cs]₀ and [Sr]₀ concentrations from 10⁻⁵ to 10⁻³ mol kg⁻¹. Clay mineral type affected the rates of (i) hydroxide promoted dissolution of Si, Al and Fe, (ii) precipitation of secondary solids and (iii) uptake of Cs and Sr. Initial Si release to solution followed the order Mt > Vm > Il. An abrupt decrease in soluble Si and/or Al after 33 d for Mt and Vm systems, and after 190 d for Il suspensions was concurrent with accumulation of secondary aluminosilicate precipitates. Strontium uptake exceeded that of Cs in both rate and extent, although sorbed Cs was generally more recalcitrant to subsequent desorption and dissolution. After 369 d reaction time, reacted Il, Vm and Mt solids retained up to 17, 47 and 14 mmol kg⁻¹ (0.18, 0.24 and 0.02 μmol m⁻²) of Cs, and 0, 27 and 22 mmol kg⁻¹ (0, 0.14 and 0.03 μmol m⁻²) Sr, respectively, which were not removed in subsequent Mg exchange or oxalic acid dissolution reactions. Solubility of Al and Si decreased with initial Cs and Sr concentration in Mt and Il, but not in Vm. High co-contaminant sorption to the Vm clay, therefore, appears to diminish the influence of those ions on mineral transformation rates.     

Assessment of 137Cs and 90Sr fluxes in the Barents Sea

The annual balance of radionuclides inflow/outflow was assessed for ¹³⁷Cs and ⁹⁰Sr isotopes in the Barents Sea, taking into account the atmospheric precipitation, inflow from the Norwegian and the White seas, as well as riverine discharge, liquid radioactive waste disposal (LRWD), and outflow to the adjacent seas. The original and published data for the period of 1950–2009 were analyzed. According to the multiyear dynamics (1960–2009), the inflow of ¹³⁷Cs and ⁹⁰Sr into the Barents Sea was significantly preconditioned by the Norwegian Sea currents; and precipitation played a major role in the 1950s, 1960s, and in 1986. Currently, the trans-border redeposition of ⁹⁰Sr prevails over ¹³⁷Cs redeposition in the Barents Sea, and constitutes about 99% of inflow of each element.     

Results of Marine Radioecological Study of Fjords of Western Spitsbergen

The patterns of the distribution of technogenic radionuclides ¹³⁷Cs and ⁹⁰Sr in the water mass and bottom deposits of three fjords of Western Spitsbergen (Isfjorden and its arms Grønfjorden and Billefjorden) were studied. The hydrological processes affecting migration of radionuclides in these water bodies were described. It was shown that the ice sheet of the archipelago that accumulates atmospheric precipitation is a source of radioactive contamination of the marine environment of the coast. Technogenic isotopes were accumulated during nuclear weapon testing in the second half of the twentieth century. The current climatic changes strengthen the role of glaciers in the contamination of arctic seas. It was noted that extrema of the ¹³⁷Cs and ⁹⁰Sr specific activity is mainly concentrated in the areas of glacier runoff discharge.

     

Environmental evaluation of elemental cesium and strontium contents and their isotopic activity concentrations in different soils of La Mancha (Central Spain)

Cesium and Strontium concentrations were analyzed in eight pedogenetic soil profiles developed on different rocks from a semiarid mediterranean region: La Mancha (Central Spain). Concentration activities of ¹³⁷Cs and ⁹⁰Sr, as for some soil properties, were also measured. The results are presented in this document: Cs concentrations range between 0.4 and 18.3 mg kg⁻¹ and Sr varies widely between 11.0 and 3,384 mg kg⁻¹. Therefore, it is clear that there is a broad range of concentrations and there are also values significantly higher than the average values stated by several authors. Concentrations of long-life artificial radionuclides (¹³⁷Cs, ⁹⁰Sr) were determined in some of the same soils. The activity concentration mean values (Bq kg⁻¹) were ranging between 0.82 and 21.76 for ¹³⁷Cs and ⁹⁰Sr variations range between 6.73 and 0.35. There were no significant correlations between radionuclides and stable trace elements. The data indicate that the soils do not show significant radioactivity of these elements and therefore they do not pose a danger. By the same token, no risk of contamination by this activity was detected. Finally, spatial patterns seem to be affected by the soil type and some soil properties.     

A model of radionuclide transfer by groundwater on the territory of the Russian Research Centre Kurchatov Institute

The convective transfer of ¹³⁷Cs and ⁹⁰Sr by groundwater on the territory of the Russian Research Centre Kurchatov Institute (RRCKI) was modeled. Geological data on the RRCKI site and possible sources of radionuclides show that the uppermost aquifer, composed of Quaternary sediments, is the most probable region of spreading of radioactive contamination. Since the lateral migration of radionuclides is predominant, a 2D horizontal model was used for the forecasting of spreading of radioactive contaminants in the subsurface medium. Transient or long-term repositories of radioactive materials at the RRCKI site (concentrated sources) and aquifer rocks contaminated in the course of removal of radionuclides from these repositories (distributed source) are responsible for groundwater pollution. The initial ¹³⁷Cs and ⁹⁰Sr distributions used in the forecasting of radionuclide migration were determined from their contents in core samples taken from wells drilled in contaminated areas of the RRCKI site. The zone of radionuclide migration is limited by poorly permeable moraine loam from below and by the water table from above. To determine the upper and lower boundaries, these surfaces were mapped in plan view. The data of meteorological observations over a long period were used to map the intensity of precipitation in the studied territory. The density of rocks in the uppermost aquifer and partition coefficients of radionuclides between rocks and groundwater were estimated from the data of laboratory examination of the core samples. The available data on the permeability of rock samples and the results of test pumping out of some wells were involved in the consideration. The results obtained and the data on the water table allowed us to define a gauge problem for determining the distribution of the filtration coefficient in the uppermost aquifer. This problem was solved taking the intensity of precipitation into account. The properties of the uppermost aquifer and the initial radionuclide distribution therein were used as initial data for modeling ¹³⁷Cs and ⁹⁰Sr migration on the territory of the RRCKI over 50 years.     

含蛭石晶层间层矿物的可交换性阳离子及交换容量研究

对采自新疆尉犁蛭石矿、河南灵宝-陕西潼关蛭石矿的工业蛭石矿物样品进行了可交换性阳离子与交换容量研究，发现新疆尉犁蛭石矿金云母-蛭石中可交换性阳离子主要为Na^ 和Ca^2 ，其次为Mg^2 、K^ 、Ba^2 和Sr^2 ；而河南灵宝-陕西潼关蛭石矿工业蛭石样品的可交换性阳离子主要为Ca^2 和Mg^2 ，其次为Na^ 、K^ 等。金云母-蛭石和绿泥石-蛭石间层矿物的阳离子交换容量随间层结构中蛭石晶层的含量增加而增大，一般在56．92～98．95mmol／100g之间，仅为蛭石最大阳离子交换容量的一半。金云母-蛭石样品阳离子交换容量大小与K2O含量呈负相关关系，与(Na2O CaO)含量呈正相关关系。