蒙脱石-氧化铁二元复合胶体吸附钨的研究

本研究选取代表性层状硅酸盐蒙脱石，两种代表性氧化铁(水铁矿、针铁矿)，合成蒙脱石-水铁矿、蒙脱石-针铁矿二元复合体，通过宏观吸附以及光谱学技术探究钨(WO₄^2-)在蒙脱石-氧化铁复合体上的吸附行为和潜在机制。结果表明：氧化铁紧密覆盖在蒙脱石表面，使表面颗粒更加细小；钨的吸附量随pH升高而降低，3种吸附剂对钨吸附量大小顺序为：蒙脱石-水铁矿>蒙脱石-针铁矿>蒙脱石；原位红外光谱实验表明，钨在蒙脱石表面主要以外圈络合物形式存在，而在蒙脱石-氧化铁复合体上形成内圈络合物(Fe-O-W)，且在低pH时，形成聚合态钨；X-射线光电子能谱进一步表明，针铁矿和水铁矿表面铁羟基参与了钨的络合反应。本研究证实，氧化铁覆盖不仅增大蒙脱石对钨的吸附量，而且使钨由外圈络合物形态转变为内圈络合态，进一步生成聚合态钨。研究结果对预测钨在土壤中的迁移转化、生物有效性和归宿有重要指导意义。     

三种铁氧化物对As(Ⅲ)和As(Ⅴ)的吸附研究

采用批量吸附试验,研究实验室制备的水铁矿、磁铁矿和纤铁矿对As(Ⅲ)和As(Ⅴ)的吸附性能。结果表明,在p H中性条件下,结晶差的水铁矿吸附砷的能力明显优于结晶较好的磁铁矿和纤铁矿,准二级动力学方程拟合效果较好,说明存在多种吸附过程,并可能涉及专性吸附作用;在酸性条件下,三种铁氧化物对As(Ⅲ)和As(Ⅴ)的吸附能力大小顺序均为水铁矿磁铁矿纤铁矿,铁氧化物吸附As(Ⅴ)的能力优于As(Ⅲ),Langmiur方程和Freundlich方程拟合效果均较好,说明铁氧化物对砷的吸附为均匀介质表面的单层吸附或非均匀介质表面的多层吸附;在弱酸至弱碱范围内,三种铁氧化物对As(Ⅲ)的吸附效果均较好且吸附量变化不大,强酸和强碱条件都会引起铁氧化物吸附As(Ⅲ)量的降低,三种铁氧化物对As(Ⅴ)的吸附均随着p H升高而逐渐减少;由于竞争吸附作用,磷酸盐浓度的增加使三种铁氧化物对As(Ⅲ)和As(Ⅴ)的吸附显著减少;随着腐殖酸浓度的增加,三种铁氧化物对As(Ⅲ)的吸附能力逐渐减小,低浓度的腐殖酸微弱地促进铁氧化物对As(Ⅴ)的吸附,高浓度的腐殖酸抑制As(Ⅴ)的吸附。     

针铁矿和针铁矿—胡敏酸复合体对Se(Ⅳ)吸附机制

研究了针铁矿和针铁矿—胡敏酸复合体对Se(Ⅳ)的吸附机制。结果表明:针铁矿和复合体对Se(Ⅳ)的最大吸附容量分别为0.202 mmol g-1和0.159 mmol g-1。针铁矿的等温吸附数据适合用Langmuir模型拟合,而Freundlich模型更适合描述复合体的等温吸附过程。针铁矿的等电点(IEP)在7.0附近,复合体的IEP3.0;当p H=4.0时,它们的表面电位分别为46.6 m V和-40.5 m V。X—射线光电子能谱(XPS)分析显示,针铁矿和复合体表面Fe2p3/2的电子结合能(B.E.)分别为711.4e V和711.5 e V,复合体表面C1s的B.E.值为284.8 e V。初始p H=4.0时,样品与Se(Ⅳ)相互作用后的主要变化体现在:(1)针铁矿和复合体的悬浮液p H分别升高至4.4和4.2,表面电位分别降低了39.08 m V和升高了1.8 m V;(2)针铁矿表面Fe(Ⅲ)的B.E.值降低了0.4 e V,但吸附态Se(Ⅳ)的B.E.值无明显变化;(3)复合体表面Fe(Ⅲ)的B.E.值降低了0.3 e V,表面C-O中C的B.E.值由285.7 e V升高至286.5e V,吸附态Se(Ⅳ)的B.E.值升高了0.6 e V。针铁矿和复合体吸附Se(Ⅳ)的主要机制包括表面配合反应(复合体表面铁羟基与HSe O3-之间存在双齿配位)、静电引力、氢键等作用。此外,复合体表面吸附态Se(Ⅳ)同时与针铁矿和胡敏酸发生了作用,形成了针铁矿—Se(Ⅳ)—胡敏酸三元体。     

蒙脱石-氧化铁复合体的表征及其对不同形态磷的吸附特性

制备了蒙脱石-针铁矿复合体(Mt-Goe)和蒙脱石-非/弱晶质氧化铁复合体(Mt-HFO),研究了它们的结构、表面性质及其对无机磷酸盐(Pi)和植酸(IHP)的吸附特性。结果显示,Mt-Goe中少量羟基铁离子进入了蒙脱石晶层间导致其层间距增大,针铁矿颗粒较好地包被在蒙脱石外表面;Mt-HFO中蒙脱石层间则发生了Fe~(3+)水解,生成了(羟基)铁氧化物,并在蒙脱石表面形成非晶质氧化铁颗粒。蒙脱石、Mt-Goe和Mt-HFO的比表面积分别为258.7、185.4和226.4 m~2·g~(–1),其表面分形度、等电点和表面羟基含量均依次升高,pH5.5时的表面Zeta电位分别为–46.1、–13.6和–19.4 mV。3种样品对Pi和IHP的吸附模式以匀质性表面单层吸附为主,Langmuir饱和吸附量(qmax)和吸附亲和力均表现为由大到小依次为Mt-HFO、Mt-Goe、蒙脱石。3种样品对Pi和IHP的动力学吸附过程适合用准二级动力学模型描述,其速率常数由小到大依次为Mt-HFO、Mt-Goe、蒙脱石。与吸附Pi相比,3种样品吸附IHP的动力学速率常数明显减小,吸附量明显增大;Mt-HFO对IHP的吸附速率尤其缓慢,而吸附量远大于对Pi的吸附量。     

可变电荷土壤对As(Ⅲ)和As(Ⅴ)的吸附及二者的竞争作用

三种可变电荷土壤对砷的吸附实验结果表明,在pH3~7范围内,As(Ⅲ)的吸附量随pH的升高而增加,三种土壤对As(Ⅲ)吸附能力的大小顺序为砖红壤>黄壤>红壤。红壤和砖红壤对As(Ⅴ)的吸附量随pH的升高而降低,黄壤中呈相反的变化趋势,三种土壤对As(Ⅴ)吸附能力的大小顺序是黄壤>砖红壤>红壤。三种可变电荷土壤对As(Ⅴ)的吸附能力较对As(Ⅲ)大得多,砷的吸附量既与土壤游离氧化铁的含量有关,又与氧化铁的结晶形态密切联系,由于黄壤中水化氧化铁在游离铁中所占比例较高,其对As(Ⅴ)吸附能力较砖红壤和红壤大。As(Ⅲ)与As(Ⅴ)共存体系的研究结果表明,两种形态的砷可以竞争可变电荷土壤表面的吸附位,但在酸性条件下As(Ⅴ)较As(Ⅲ)有更强的竞争能力,因为As(Ⅴ)使土壤对As(Ⅲ)的吸附量显著减小,而As(Ⅲ)对红壤和砖红壤吸附As(Ⅴ)有一定的影响,对黄壤中As(Ⅴ)的吸附几乎没有影响。     

Sb(V)在三种矿物表面的吸附行为

用研究了蒙脱土、高岭土和针铁矿在不同的pH与离子强度的介质条件下对Sb(V)的吸附及解吸行为。3种矿物对Sb(V)的吸附能力差别较大,蒙脱土的吸附量远大于针铁矿和高岭土,针铁矿与高岭土的吸附能力相近。pH对Sb(V)在3种矿物表面的吸附行为影响显著。随pH的升高,Sb(V)的吸附均减弱。吸附在高岭土表面的Sb(V)易解吸,而针铁矿和蒙脱土表面的Sb(V)不易解吸。随离子强度升高,高岭土对Sb(V)的吸附减弱;离子强度对Sb(V)在针铁矿和蒙脱土表面吸附的影响较小。     

土壤腐殖质-矿物质交互作用的机制及研究进展

腐殖质、氧化物、层状硅酸盐矿物间的相互作用主要通过阴离子交换、配体表面交换、疏水作用、熵效应、氢键作用及阳离子桥键、静电作用等多种结合键能进行.影响有机-矿质复合体相互作用的主要因素是腐殖质、粘土矿物的性质及溶液pH值和离子强度等.矿物的比表面积、表面酸碱反应位、表面电荷以及腐殖酸的羧基、酚羟基、醇羟基、羰基、氨基等官能团含量和酸度、芳香性、干湿状况、分子大小等基本性质都会影响腐殖酸被矿物吸附的状况.矿物对腐殖酸的吸附量随着pH值的升高而降低,随着离子强度的增加而升高.本文针对土壤腐殖质、铁/铝氧化物、层状硅酸盐矿物相互作用的机制及其影响因素进行了综述.     

Cr(VI)和As(V)在东北地区不同类型土壤中的迁移特征研究

利用土柱淋溶实验研究Cr(VI)和As(V)在不同类型土壤中的垂向迁移特征。结果表明,Cr(VI)和As(V)在含砂砾和砾石的河流冲积物中迁移速度最大,而在粘粒含量较高的黄土中迁移速度最小。土壤砂粒含量和pH值越高,Cr(VI)和As(V)的迁移速度越大。粉粒、粘粒、铁氧化物和锰氧化物含量越高,越不利于Cr(VI)和As(V)的迁移,说明以上因素对于Cr(VI)和As(V)在土壤中的吸附具有很大的贡献。总有机碳(Total Organic Carban,TOC)的含量升高不利于Cr(VI)和As(V)的迁移,但是影响不大。     

长期定位施肥对非石灰性潮土粘土矿物组成及主要理化性质的影响

土壤粘土矿物中层状硅酸盐与氧化物共存及晶质和非品质共存。土壤中含钾的粘土矿物主要有水云母、蛭石和绿泥石等。这些粘土矿物影响土壤钾素的固定和释放，进而影响土壤钾的生物有效性。有研究表明，土壤中的层状硅酸盐矿物彼此之间存在着一种相互演变的关系。例如在云母风化初期，通常会出现水化云母，在钾比较丰富的条件下，就会出现伊利石；水化云母进一步风化并释放出更多的钾以后，则形成蛭石和蒙脱石。相反，蛭石和蒙脱石在吸收了钾离子并脱水后，也可以向伊利石及云母类矿物转变。     

三种铁氧化物的磷吸附解吸特性以及与磷吸附饱和度的关系

采用三种人工合成铁氧化物(针铁矿、赤铁矿和水铁矿)比较了结晶态和无定形铁氧化物对磷的吸附—解吸特性以及与磷吸附饱和度的关系。结果表明,三种铁氧化物的磷吸附特性均可用Langumir方程来描述,相关系数均大于0.9,达到极显著水平。从磷最大吸附量(Qm)、吸附反应常数(K)和最大缓冲容量(MBC)三项吸附参数综合考虑,水铁矿(无定形)对磷的吸附无论在容量还是强度方面均比结晶态铁氧化物针铁矿和赤铁矿大得多。水铁矿吸附的磷比针铁矿和赤铁矿所吸附的磷更难解吸;水铁矿的大量活性表面并没有表现出增加磷释放的作用。磷吸附饱和度有望作为评价土壤或铁氧化物磷吸附—解吸的强度和容量因子的一个综合指标。     

离子强度和磷酸盐对铁铝矿物及土壤吸附As（V）的影响

选用针铁矿、赤铁矿、水铁矿、水铝矿4种铁铝矿物以及性质差异较大的黑土、紫色土和红壤3种土壤,研究离子强度和磷酸盐对其吸附As（V）的影响。结果表明,在0．01、0．1、1mol·L^-13种离子强度下,矿物和土壤对As（V）的吸附量无明显差异或随离子强度增大而增大,其对砷的吸附以专性吸附为主。磷酸盐对矿物和土壤吸附砷的影响与其添加顺序及摩尔浓度比有关。水铝矿和水铁矿在这3种添加顺序下的砷吸附量无明显差异,仅在P／As摩尔比较大时表现出下降趋势;而在针铁矿和赤铁矿两种矿物上,先添加砷时的砷吸附量高于先添加磷时或两者同时添加时,且砷吸附量随WAs摩尔比的增加而逐渐下降。在黑土、紫色土和红壤上,先添加砷比先添加磷或两者同时添加时的砷吸附量均要高,尤其是在紫色土上。随P／As摩尔比升高,土壤对砷的吸附量表现出下降趋势。     

Adsorption of Cr(VI) ion on synthetic hydrated oxides of iron

Abstract

The adsorption of Cr(VI) ion on synthetic hydrated oxides of iron (goethite (α-FeOOH) and lepidocrocite (γ-FeOOH)) with different crystallinities was studied in order to remove the Cr(VI) ion from polluted water. At pH 4.5, the amounts of the adsorbed Cr(V1) ion on goethite and lepidocrocite were 51.9 and 62.2 mmol g^?, respectively. Probably, this is due to the fact that the structure of lepidocrocite is more open than that of goethite. Lepidocrocite, therefore, is more effective for the removal of Cr( V1) ion from Cr(Vl)-contaminated and acidic groundwater and sewage.     

Reactions of nucleic acid bases with inorganic soil constituents

The adsorption at pH's 4, 6 and 8 of adenine, guanine, cytosine, thymine and uracil on clays (montmorillonite, illite and kaolinite), Fe- and Al-oxides (goethite, hematite and gibbsite), a soil, and on a laboratory-prepared fulvic acid-montmorillonite complex was investigated. Portions of the clays and soil were saturated with H⁺, Fe³⁺ and Ca²⁺.Quantitatively, the extent of adsorption of nucleic acid bases by the clays was proportional to their exchange capacities, but the nature of the dominant cation had only minor effects. By contrast, the adsorption was strongly affected by pH, tending to decrease with increase in pH. Adsorption on goethite and gibbsite was lower than that on clays, while adsorption of nucleic acid bases on soils was slightly lower than that on oxides. The fulvic acid-montmorillonite complex adsorbed substantial, although smaller amounts of purines and pyrimidines, than did montmorillonite alone. The main adsorption mechanism at pH 4 appeared to be cation exchange whereas at pH 8 complex formation between the nucleic acid bases and cations on inorganic surfaces seemed to occur.The results of this and earlier work show that both inorganic and organic soil constituents adsorb nucleic acid bases. Which adsorption reaction predominates will depend on the clay and organic matter content and on the pH.     

温度对硼在三种矿物上吸附-解吸特性的影响

在实验室对天然Ca 蒙脱进行了纯化 ,并在一定条件下人工合成了针铁矿、水锰矿 ,以此作为实验材料 ,用吸附—解吸平衡法和反应动力学方法研究了温度对硼在Ca 蒙脱 ,针铁矿 ,水锰矿上的吸附、解吸特性的影响。结果表明 :随温度升高 ,Ca 蒙脱对硼的吸附量升高 ,其对硼的解吸滞后性下降 ,水锰矿和针铁矿对硼的吸附量下降 ,其对硼的解吸滞后性加强。计算表明 ,在常温下 ,硼在Ca 蒙脱上的吸附热为 63.0 8kJmol- 1 ,在针铁矿和水锰矿上分别为 - 1 2 2 .45和 - 93 .91kJmol- 1 ,硼在Ca 蒙脱、针铁矿和水锰矿上的解吸热分别为- 31 .0 2 ,53 .95和 46 .30kJmol- 1 。上述结果说明 ,硼在Ca 蒙脱上的吸附为吸热过程 ,解吸为放热过程 ;硼在针铁矿、水锰矿上的吸附为放热过程 ,解吸为吸热过程。随着温度的升高 ,硼与矿物的初始反应速率明显加快 ,而整体反应速率略有下降。     

不同氧化物硼负载体吸附锰离子的特性研究

以人工合成针铁矿（Goethite，简写为G），水锰矿（Manganite，简写为M），经硼砂处理的吸附态针铁矿（简写为Ad—B-G），吸附态水锰矿（简写为Ad—B-M），经硼酸处理的包被态针铁矿（简写为Oc—B—G），包被态水锰矿（简写为Oc-B—M）等6种氧化物为研究对象，在等温条件下，用吸附平衡法研究了6种硼负载体对Mn^2＋的吸附解吸行为。结果表明，吸附Mn^2＋能力：Oc—B—G〉Ad—B—G〉G；Ad—B—M和Oc—B—M吸附Mn^2＋量最大，M吸附能力最弱。6种硼负载体Mn^2＋吸附量随pH升高而增加,但铁氧化物和锰氧化物之间有差别。不同形态锰氧化物吸附Mn^2＋前后溶液pH变化不同，吸附等量Mn^2＋离子时，Ad—B—M向溶液中释放H^＋量最多，Oc—B—M最少。上述结果说明，硼的参与不仅可改变氧化物吸附Mn^2＋离子的行为，而且对反应体系的影响也不尽相同。     

离子强度和三氧化物对土壤吸附Bt毒素的影响

Chemical reactions and fate of the toxins of Bacillus thuringiensis(Bt) in the soil environment are causing increasing concerns due to the large-scale cultivation of transgenic Bt plants.In this study,the effect of ionic strength(0-1 000 mmol kg 1) adjusted by NaCl or CaCl 2 on adsorption of Bt toxin by a lateritic red soil,a paddy soil and these soils after chemical removal of organic-bound or free Fe and Al oxides,as well as by pure minerals(goethite,hematite and gibbsite) which are widespread in these soils,were studied.The results indicated that when the supporting electrolyte was NaCl,the adsorption of Bt toxin by the lateritic red soil and paddy soil increased rapidly until the ionic strength reached 250 mmol kg 1 and then gradually slowed down with the increase of ionic strength;while in case the supporting electrolyte was CaCl 2,the adsorption of Bt toxin enhanced significantly at low ionic strength(< 10 mmol kg 1) and then decreased as the ionic strength increased.The adsorption of Bt toxin by the tested minerals and soils after the removal of organic-bound or free Fe and Al oxides also increased with increasing ionic strength controlled by NaCl.Removing organic-bound Fe and Al oxides obviously increased the adsorption of Bt toxin in the tested soils.Differently,removing free Fe and Al oxides increased the Bt adsorption by the paddy soil,but decreased the adsorption by the lateritic red soil.The study indicated that the varieties of ionic strength and the presence of Fe and Al oxides affected the adsorption of Bt toxin by the soils,which would contribute to the further understanding of the fate of Bt toxin in the soil environment and provide references for the ecological risk assessment of transgenic Bt plants.     

中国土壤胶体研究 Ⅵ.西藏高原几种主要土壤的粘土矿物组成和演变

西藏高原突起于我国西南,绝大部分地面的海拔高度在4000米以上,为世界上最高的大高原。它大致在第三纪开始形成,后来曾受第四纪冰川的深刻作用,高山顶部至今仍是冰川的活动场所^[1,2]。高原为昆仑山、唐古拉山、喜马拉雅山和横断山等大山脉所盘踞。     

铬与对氯苯胺的交互作用对其在土壤胶体上的反应的影响

Adsorption of Cr(VI) and p-chloroaniline on three typical soil colloids and pH influence were studied using batch equilibrium method.Both of Cr(VI) and p-chloroaniline adsorption on the colloids could be well described by general adsorption simulation equations,The adsorption processes changed with media pH.When Cr(VI) and p-chloroaniline coexisted on soil colloids,their interactions could be observed in a certain pH range to be accompanied with Cr(VI) reduction,which clearly suggested that a surface catalytic reaction occurred in this system.Soil colloid acted as an effcient catalyst for the interaction of Cr(VI)and p-chloroaniline.The pH values at which no interaction was observed were 4.0,4.5and 5.0 for the colloids of indigotic black soil,yellow-brown soil and latosol,respectively,Capillary electrophoresis used to analyze p-chloroaniline provided a high separation efficiency and short separation time,and needed no more extensive pretreatment of samples.     

Presence of bacteria reduced phosphate adsorption on goethite

Despite extensive studies, the information obtained from pure iron and aluminum (hydr)oxides cannot fully explain phosphate fixation in natural soils because of the ubiquitous interactions between (hydr)oxides and bacteria in soil. The effect of bacteria (Bacillus subtilis subsp. and Pseudomonas fluorescens) on phosphate adsorption on goethite (α‐FeOOH) was systematically examined under varying reaction times, phosphate concentrations, pH, ionic strength and bacteria dosage. Batch experiments in all cases showed significantly less adsorption on bacteria–goethite complexes than on pure goethite, demonstrating an inhibitory effect of bacteria. The inhibition of phosphate adsorption increased with bacterial loading, and showed a significant, non‐linear correlation with the decrease in the goethite positive charge induced by the bacteria. Moreover, in both the desorption experiment and in situ, the attenuated total reflectance Fourier‐transform infrared (ATR‐FTIR) spectra suggested a competition of bacteria surface groups (phosphate and carboxyl) with solution phosphate for hydroxyl on goethite. Therefore, the negative influences of bacteria on phosphate adsorption on goethite were probably caused by the surface charge modification and the competitive adsorption induced by the bacteria. Under most conditions, the effects of B. subtilis subsp. were conspicuous, while only slight influences were found for P. fluorescens. This difference between the two bacteria species was explained by differences in their surface charge, group content and chemical interaction with goethite. These findings uncover an important role of bacteria in phosphate phyto‐availability and mobility in natural environments.