pH变化条件下针铁矿表面吸附的磷酸盐联合态的转化

X-ray photoelectron spectroscopy(XPS) and automatic titrimeter were used to study the relation bewteen pH and the transformation of the coordinate forms of P on goethite surfaces.The results showed that for a given P concentration,increasing the pH of suspension could cause a fast transformation of monodentate complexes of phosphate ions on goethite surfaces to binuclear ones,When lowering the pH,additional adsorption of P occurred and the binuclear complexes reverted slowly to the monodentate ones,The dissociation and association of protons of the sorbed P caused by pH changes was considered to be a major reason leading to the transformation of the coordinate forms of P on the surfaces.The stability of binuclear surface complex of P was greater than that of monodentate omplex.The possible reactions on the interface of goethite and solutions with pH changes,and the reasons causing the different stabilities of the two coordinate P complexes are discussed in the paper.     

中国亚热带山地红黄壤的形成及其宜林特性

亚热带山地红黄壤大都由古红土发育而来，其底土仍保留古红土的特性，在具黄化的Ｂ层中，赤铁矿受到有机质的影响转化成针铁矿或纤铁矿，而粘重滞水的物理性质依旧如故，营造对土壤透气性敏感的用材林易遭失败。     

Simple modelling of the sorption of iron‐cyanide complexes on ferrihydrite

The sorption of the iron‐cyanide complexes ferricyanide, [Fe(CN)₆]^3—, and ferrocyanide, [Fe(CN)₆]^4—, on ferrihydrite was investigated in batch experiments including the effects of pH (pH 3.5 to 8) and ionic strength (0.001 to 0.1 M). The pH‐dependent sorption data were evaluated with a model approach by Barrow (1999): c = a exp(bS)S/(S_max‐S), where c is the solution concentration; S is the sorbed amount; S_max is maximum sorption; b is a parameter; and a is a parameter at constant pH. Ferricyanide sorption was negatively affected by increasing ionic strength, ferrocyanide sorption not at all. More ferricyanide than ferrocyanide was sorbed in the acidic range. In the neutral range the opposite was true. Fitting the pH‐dependent sorption to the model resulted in a strong correlation for both iron‐cyanide complexes with a common sorption maximum of 1.6 μmol m^—2. Only little negative charge was conveyed to the ferrihydrite surface by sorption of iron‐cyanide complexes. The sorption of iron‐cyanide complexes on ferrihydrite is weaker than that on goethite, as a comparison of the model calculations shows. This may be caused by the lower relative amount of high‐affinity sites present on the ferrihydrite surface.     

Mineralogical composition of iron oxides in red- and yellow-colored soils from Southern Japan and Yunnan,China

Six soil samples from the Bt2 horizon of red- and yellow-colored soils collected in Southern Japan and Yunnan, China, were used in this study. Detailed mineralogical studies by differential X-ray diffraction analysis showed the presence of hematite in association with goethite in the red-colored soils, whereas no hematite was detected in the yellow-colored soils. Among the samples studied, the increase in the hematite contents was as follows: Terra rossa-like/Red-Yellow soil in Kikai Island, Red soil in Toyota City, Lateritic Red soil in Minami-Daito Island and Lateritic Red soil in Yunnan, China. Since Lateritic Red soil and Lateritic Yellow soil are distributed adjacently on the Pleistocene raised coral reef terrace in Minami-Daito Island, having a fairly similar soil temperature regime, soil pH, soil organic matter and iron oxide contents, the difference in the soil color between the two soils may be caused by the difference in the hydrologic conditions.     

Proposition for Organo‐mineral Complex Extraction Methodology

The alkali‐insoluble fraction of soil organic matter is a various set of compounds ranging from freshly synthesized carbohydrates to highly condensed amorphous molecules (humin) intimately bound to the mineral phase. When the soil residue of an exhaustive alkaline extraction is washed with cold deionized water, the latter assumes a strong yellow to brown color. This soil fraction was quantified and characterized in an Oxisol from Brazil, and its composition and spectroscopic features were compared with those of both the alkaline extract and the soil residue of the alkaline and cold water extraction. Three land uses (natural forest, eucalyptus plantation, and pasture) were investigated. The fraction recovered by water consists of organo‐mineral complexes that do not pass through a 0.45‐µm filter and thus have to be considered suspended material. The mineral component prevails and comprises kaolinite and goethite, on which the organic matter is encrusted.     

Effects of Crystal Modification on the Binding of Trace Metals and Arsenate by Goethite (7 pp)

-  Dedicated to Prof. Dr. Ulrich Förstner on his 65th birthdayGoal, Scope and Background   Goethite (α-FeOOH) as the most frequently occurring iron oxide in the environment plays a significant role in the binding of inorganic pollutants. Accordingly, synthetic goethite is used for the purification of contaminated water. Goethite crystals can be prepared in different shape as porous and non-porous forms. The mineral can also be modified by partial substitution of structural Fe+3 for different foreign elements. The biggest possible substituent known so far is Cd+2 which causes a strong expansion of the unit-cell parameters. An incorporation of Pb+4 generates a permanent positive charge. Goethites with these morphological and structural modifications were selected for sorption experiments with Co2+, Ni2+, Zn2+, Cd2+, Pb2+, and arsenate. It was intended to demonstrate the potential of mineral modification for improving sorption properties.Methods   Batch sorption studies were carried out combining each mineral with a single element at different pH and reaction times. Cations were investigated at a single initial concentration only while arsenate was tested over a range of concentrations in order to establish sorption isotherms. The sorption step was followed by an extraction step to characterize time dependent immobilization reactions.Results and Discussion   A time dependent increase of trace metal and arsenate sorption is attributed to a migration of ions into pores of star-shaped goethite and to a binding by specific sorption sites at the surface. The migration into pores is related to the size of adsorbing cations. The almost identical sorption behaviour of Ni2+ and Co2+ on pure goethite is contrasted by a strong preference of Co over Ni on Cd-goethite. Expansion of the unit-cell dimensions in Cd+2 substituted goethite generates highly specific binding sites at the surface. These are accessible to Co and Zn only. A permanent positive charge in Pb+4 substituted goethite reduces the binding of cations and doubles the sorption capacity for arsenate. Pb-goethite also contains a limited portion of highly specific sites which can only be accessed by Zn2+. Immobilization takes place even after a short contact time of 16 hours. This process results in a growing fraction of non-extractable metals and arsenate with reaction time.Conclusions   Pores and foreign elements in the goethite structure greatly affect the reactivity of the mineral and the ability to immobilize inorganic pollutants. A possible mechanisms for the preferred sorption of Co and Zn by Cd-goethite is seen in the ability of these metal ions to adopt a smaller size: Co by oxidation of Co2+ to Co3+ and Zn by tetrahedral coordination of Zn2+. This kind of binding can be viewed as structural incorporation. The binding properties of modified goethites can well be characterized by sorption tests including an array of elements with different ionic size and charge.Recommendation and Outlook   There is considerable potential for designing goethite modifications with improved surface reactivity for specific purposes such as water purification and possibly catalysis of reactions.     

镉在针铁矿、针铁矿-腐植酸复合胶体中吸附解吸行为比较研究

采用批平衡试验法,比较研究了重金属镉在针铁矿和针铁矿-腐植酸复合胶体中的吸附热力学和动力学行为.结果表明,在试验浓度范围内,两种吸附剂对Cd2+的等温吸附特征均可用Langmuir、Freundlich和Linear方程加以描述.其中以Langmuir方程的拟合效果最佳,线性相关系数为:0.991、0.999,由此推导出的最大吸附量分别为41.667和45.455 mg·g-1,表明腐植酸与针铁矿复合胶体较单一针铁矿的吸附力有所提高,且所吸附的镉均难以解吸,平均解吸率分别为5.871%和1.068%.胶体对Cd2+的吸附是一个快速反应过程,4 h达到吸附平衡.Elovich方程是拟合吸附动力学过程的最优方程(相关系数分别为0.987和0.997).通过计算镉在针铁矿和针铁矿-腐植酸复合胶体中的吸附自由能变化量(△G的绝对值均＜40 kJ·mol-1),推测镉在两种胶体中的吸附为物理吸附过程,其吸附机理可能有氢键、偶极作用力和范德华力等作用,而不存在化学键合作用.     

氧化铁/水界面Cd吸附研究:CD-MUSIC模型模拟

以针铁矿和赤铁矿为研究对象,研究p H、Cd浓度等对不同类型氧化铁Cd吸附行为的影响,构建氧化铁Cd吸附的CD-MUSIC模型,并分析氧化铁表面Cd的形态分布特征。结果表明:氧化铁表面Cd吸附量和吸附密度均随p H升高、Cd浓度增大而增大。针铁矿对Cd的吸附量和吸附密度显著高于赤铁矿。CD-MUSIC模型能准确模拟Cd在氧化铁/水界面的吸附特征,拟合结果表明Cd主要以(Fe OH)2Cd+1、(Fe OH)2Cd OH0两种形态吸附在氧化铁表面,其在针铁矿和赤铁矿表面亲和常数(lg KCd)分别是7.3、12.8和6.1、11.0。Cd的形态分布受p H的影响显著,但几乎不受Cd浓度的影响。p H 5.0和7.0时,针铁矿的Cd形态分布与赤铁矿相似,(Fe OH)2Cd+1是主要吸附形态。p H 9.0时,针铁矿上超过80%的Cd以(Fe OH)2Cd OH0形态存在。赤铁矿上,Cd浓度较低时,(Fe OH)2Cd+1是主要吸附形态;随Cd浓度增大,(Fe OH)2Cd+1和(Fe OH)2Cd OH0所占比例均逐渐接近50%。     

铝代换针铁矿及其加热形成的赤铁矿的矿物学特性

通过Ｘ－射线衍射、电子显微镜、差热重量分析、表面积测定等方法，研究了合成和铝代换针铁矿加热脱水及形成赤铁矿过程中－系列矿物学性质的变化。结果表明，针铁矿的脱水温度随铝代换量增加而升高，在２７０℃加热１ｈ完全转化成赤铁矿后，仍有约５％的过量羟基保留在赤铁矿晶格中。铝代换使针铁矿晶胞变小，而过量羟基的存在使针铁矿晶胞增大，针铁矿晶胞的ａ－轴及与之相应的赤铁矿晶胞的ｃ－轴对过量羟基／水分子的影响最为敏感