海南岛北部玄武岩上土壤发生研究Ⅱ.铁氧化物特征

研究了海南岛北部玄武岩上发育的不同风化成土年代土壤系列的铁氧化物特征。研究表明,随风化成土时间增加,土壤发生过程中形成的游离铁（Fed）以及铁游离度（Fed/Fet）增大,铁活化度（Feo/Fed）降低。穆斯堡尔谱分析显示风化成土时间从9×104a、64×104a至 181× 104a,土壤黏粒中形成的赤铁矿含量占铁氧化物的比例从16％、25％增至 48％。风化成土时间越短,土壤中针铁矿结晶程度越差。X-射线衍射结果表明土壤细土和黏粒中赤铁矿含量与风化成土时间呈正比增加。同时,土壤有磁铁矿含量减少、磁赤铁矿增加的趋势。     

由石灰性冲积物发育而来的排水不良和排水良好的土壤中游离氧化物的分布

A study on the distribution of free iron and manganese oxides was conducted in soils developed on calcareous alluvial deposits under subhumid climatic conditions, in Western Greece. Soil samples from two well drained soils and from two poorly drained soils, classified as Alfisols, were collected and used in this study. After certification of soil homogeneity the acid ammonium oxalate and dithionite-citrate-bicaxbonate methods were used to extract free iron and manganese oxides from the samples. Iron oxides extracted by the dithionite-citrate-bicarbonate method (Fed) were significantly higher than the iron oxides extracted by the ammonium oxalate method (Feo), indicating that a considerable fraction is present in crystalline forms, independent of drainage status. A confirmation of free iron oxides and fine clay was detected. The ratios Feo/Fed and (Fed-Feo)/total Fe (Fet) could not be used to distinguish the well drained soils from the poorly drained soils. Manganese movement in a soluble form is independent of the fine clay.     

铁氧化物与土壤表面电荷性质的关系

The relationship between iron oxides and surface charge characteristics in variable charge soils (latosol and red earth) was studied in following three ways.(1)Remove free iron oxides (Fed) and amorphous iron oxides (Feo) from the soils with sodium dithionite and acid ammonium oxalate solution respectively.(2) Add 2% glucose (on the basis of air-dry soil weight) to soils and incubate under submerged condition to activate iron oxides,and then the mixtures are dehydrated and air-dried to age iron oxides.(3) Precipitate various crystalline forms of iron oxides onto kaolinite.The results showed that free iron oxides (Fed) were the chief carrier of variable positive charges.Of which crystalline iron oxides (Fed-Feo) presented mainly as discrete particles in the soils and could only play a role of the carrier of positive charges,and did little influence on negative charges.Whereas the amorphous iron oxides (Feo),which presented mainly fas a coating with a large specific surface area,not only had positive charges,but also blocked the negative charge sites in soils.Submerged incubation activated iron oxides in the soils,and increased the amount of amorphous iron oxides and the degree of activation of iron oxide,which resulted in the increase of positive and negative charges of soils.Dehydration and air-dry aged iron oxides in soils and decreased the amount of amorphous iron oxides and the degree of activation of iron oxide,and also led to the decrease of positive and negative charges.Both the submerged incubation and the dehydration and air-dry had no significant influence on net charges.Precipitation of iron oxides onto kaolinite markedly increased positive charges and decreased negative charges.Amorphous iron oxide having a larger surface area contributed more positive charge sites and blocked more negative charge sites in kaolinite than crystalline goethite.     

Iron hydroxides in soils: A review of publications

Iron hydroxides are subdivided into thermodynamically unstable (ferrihydrite, feroxyhyte, and lepidocrocite) and stable (goethite) minerals. Hydroxides are formed either from Fe³⁺ (as ferrihydrite) or Fe²⁺ (as feroxyhyte and lepidocrocite). The high amount of feroxyhyte in ferromanganic concretions is proved, which points to the leading role of variable redox conditions in the synthesis of hydroxides. The structure of iron hydroxides is stabilized by inorganic elements, i.e., ferrihydrite, by silicon; feroxyhyte, by manganese; lepidocrocite, by phosphorus; and goethite, by aluminum. Ferrihydrite and feroxyhyte are formed with the participation of biota, whereas the abiotic formation of lepidocrocite and goethite is possible. The iron hydroxidogenesis is more pronounced in podzolic soils than in chernozems, and it is more pronounced in iron-manganic nodules than in the fine earth. Upon the dissolution of iron hydroxides, iron isotopes are fractioned with light-weight ⁵⁴Fe atoms being dissolved more readily. Unstable hydroxides are transformed into stable (hydr)oxides, i.e., feroxyhyte is spontaneously converted to goethite, and ferrihydrite, to hematite or goethite.     

Distribution of iron and manganese oxides in Haploxeralfs and Rhodoxeralfs and their relation to the degree of soil development and soil colour

The status and the distribution of iron and manganese oxides were studied in six soil profiles from Thrace region (Greece), classified as Rhodoxeralfs and Haploxeralfs. The acid ammonium oxalate and the dithionite-citrate-bicarbonate methods were used to extract the free iron and manganese oxides from the soils. In both great groups the Fed and Mnd values are higher than Feo and Mno values, respectively, indicating that a considerable fraction is present in crystalline form. Both Feo/Fed and Fed-Feo values suggest that, in the study area, Haploxeralfs are less developed soils than Rhodoxeralfs. The manganese oxides present in crystalline forms (Mnd-Mno) were more in Rhodoxeralfs than in Haploxeralfs, suggesting that the crystallinity of manganese oxides increases, with the degree of soil development. Significant correlations were found of Redness Rating to Fed-Feo and to Feo/Fed ratio, positive and negative respectively, leading to the conclusion that soil red colouration increases with the degree of soil development.     

The effect of cadmium on the transformation of ferrihydrite into crystalline products at pH 8

Ferrihydrite, prepared in the presence of 0 to 20 mole % Cd in the solution, was used to study the transformation of ferrihydrite into crystalline products. The result showed that the presence of Cd strongly retards the transformation of ferrihydrite into crystalline products, suppressing the formation of goethite and leading to a product which eventually consists entirely of hematite at pH 8 and at 70 °C. The fraction of hematite in the transformation products increased with increasing level of Cd in the system. When 9 mole % Cd was present, the transformation product consisted entirely of hematite. The chemical analysis and XRD data showed that Cd was incorporated into the lattice of iron oxides, Cd-hematite and Cd-goethite being formed. The mole % Cd which replaced iron in the iron oxides increased with increasing level of Cd in the system below 9 mole % Cd. Above this value, but below 20 mole % the mole % of Cd incorporated in the lattice of iron oxides was constant at about 2.9 mole %. The volume of the unit cell of Cd-goethite increased with increasing level of Cd in the system until the goethite production was entirely suppressed. The volume of the unit cell of Cd-hematite also increased with increasing level of Cd, below 9 mole % of Cd in the system. Above this value, it was constant. Scanning electron microscopic examination showed that the presence of Cd affected the morphology of hematite more than that of goethite. The goethite grew from ferrihydrite as acicular crystals independent of the amount of Cd in the system. The shape of hematite particles varied from irregular platelets with lower Cd level, to ellipsoids, with higher Cd level in the system, and it also suggested that Cd prevented the formation of goethite by hindering the dissolution of ferrihydrite rather than by interfering with nucleation and growth of goethite from solution. The rate of transformation was studied at pH 8, 50 °C and 70 °C. The transformations were first order reactions at both temperatures.     

Transformation of poorly-crystalline oxides during boiling with NaOH to concentrate iron oxides from soils

The effect of boiling 5 M NaOH on the nature of poorly crystalline iron oxides in some iron pans from Scottish soils has been investigated by IR and Mössbauer spectroscopy in conjunction with XRD. In samples that contained goethite and other crystalline oxides there was substantial production of goethite from the less well-defined phases as a result of the alkali treatment. Neither kaolinite nor humic acid, when added to the samples, was effective in preventing this transformation, although some inhibition was observed. There was, however, no goethite production with a pan that had no crystalline iron oxides, although this could be stimulated by the addition of small amounts of either goethite or haematite. The practice of using the boiling alkali method routinely for the concentration of crystalline iron oxides in soils should, therefore, be considered carefully, since any co-existing crystalline and non-crystalline phases are likely to lead to the transformation of the latter to goethite.     

Heavy metal sorption on soil minerals affected by the siderophore desferrioxamine B: the role of Fe(III) (hydr)oxides and dissolved Fe(III)

Phytoextraction of heavy metals from polluted soils has often been found to be limited by the bioavailability of the pollutants. Inorganic or organic ligands are occasionally used as complexing agents to enhance the mobility of the heavy metals. However, the opposite effect is also possible. We studied the influence of the hydroxamate siderophore desferrioxamine B (DFOB) on the sorption of Cu, Zn and Cd to clay minerals, with the emphasis on the role of dissolved Fe(III) and Fe(III) minerals. Depending on the surface charge of the minerals and on pH, sorption of heavy metals can be either enhanced or diminished. We show here that this effect of DFOB disappears if dissolved Fe(III) is added to suspensions of clay minerals in excess to DFOB. We found that the solid Fe(III) phases ferrihydrite and goethite did not impede the effect of DFOB on the sorption of heavy metal, however. Between pH 4 and 10, DFOB completely prevented Cu sorption on ferrihydrite. A strong mobilizing effect was also observed for Zn, but not for Cd. In presence of goethite, concentrations of dissolved Cu, Zn and Cd were enhanced only above approximately pH 5, 7 and 8, respectively. Below these pH values the binding of these metals to goethite was even stronger with than without DFOB. In the absence of heavy metals, DFOB‐promoted dissolution of ferrihydrite was much faster than that of goethite due to the larger surface area of ferrihydrite. In the alkaline pH range, where sorption of DFOB on the surfaces of the iron oxides was greater, dissolution of both minerals was reduced.     

水稻土中铁氧化物的厌氧还原及其对微生物过程的影响

采用厌氧泥浆恒温培养实验 ,测定了添加 6种外源氧化铁后土壤中Fe(Ⅱ )和Fe(Ⅲ )浓度的变化 ,探讨了不同氧化铁的还原能力及其对土壤产H2 、产CO2 、产乙酸和产CH4 过程的影响。结果表明 :无定形氧化铁和纤铁矿易于被还原 ,两者的最终还原程度大体相同 ,但无定形氧化铁存在还原滞后现象 ;针铁矿、赤铁矿、Al取代针铁矿和Al取代赤铁矿难以被还原 ,表现出与对照相同的还原特征 ;铁还原能导致土壤中H2 和乙酸稳态浓度的降低 ,有效抑制了甲烷产生 ;添加Fe(OH) 3和纤铁矿后 ,Fe(Ⅲ )还原占总电子传递的贡献率由对照的 1 8.3 0 %增至 63 .3 2 %和 46.90 % ,而形成甲烷的电子传递贡献率由对照的 80 .92 %降至 3 5 .85 %和 5 2 .3 2 % ,Fe(Ⅲ )还原对电子的竞争消耗 ,使土壤产甲烷过程被强烈抑制     

台湾红壤及森林土壤中之氧化铁

本文综合汇整近年来在台湾，应用高梯度磁场分离技术，配合一般化学分析，Ｘ－射线衍射法，磁测分析，电子显微镜观察与电子衍射鉴定，以及铁－５７穆期堡尔谱学分析等方法，研究红壤与森林土壤中，氧化铁的分布及其结构性质之成果回顾；关于氧化铁之分布情形，其研究结果显示：台湾红壤中普遍存在有赤铁矿与针铁矿等氧化铁矿物，而在化育自大屯山更新世纪安山岩母质与澎湖列岛更新世纪玄武岩母质的红壤中，以及兰屿绿岛海边之银白色     

Types of Crystalline Iron Oxides and Phosphate Adsorption in Variable Charge Soils

The types,contents and morphologies of crystalline Fe oxides and their relations to phosphate adsorption on the clay fractions in soils with varable charge in southern China were investigated by means of XRD,TEM,EMA and chemical analysis methods.Results indicated that the types and contents of crystalline Fe oxides varied with the soils examined.The dominant crystaline Fe oxide was hematite in the latosols and goethites in the red soils.In yellow-brown soils,the only crystalline Fe oxide was goethite.The difference between Ald and Alo came mainly from the Al Substituting for Fe in the Fe oxides.The crystal morphology of goethite appeared mainly as subrounded flat or iso-dimensional rather than acicular particles,Hematities occurred in plates of various thickness,Their MCDa/MCDc ratios in the latosols and red soils were generally above 1.5 and below 1.5,respectively.The MCD values of goethites and hematites were 15-25nm and 20-35nm,and their specific surface areas were 80-120m^2/g and 35-75m^2/g,respectively.The goethite crystals were generally smaller,Variations of the total amounts of crystalline Fe oxides in clay fractions were not related to plhophats adsorption.The types,contents and morphologies of crystalline Fe oxides in the soils remarkably affected phosphate adsorption characteristics of the soils.The phosphate adsorption of goethite was much greater than that of hematite,The higher th MCDa/MCDc ratio of hematite,the lower the phosphate adsorption.     

Factors Affecting the Formation,Nature, and Properties of Iron Precipitation Products at the Soil–Root Interface

Abstract

A number of iron oxides (hematite, goethite, lepidocrocite, maghemite, and magnetite) or short‐range ordered precipitates (ferrihydrite) may be found in soil environments, but in the rhizosphere the presence of organic ligands released by plants (exudates) or microorganisms promote the formation of ferrihydrite. Iron ions are liberated into soil solution by acidic weathering of minerals and then precipitated either locally or after translocation in soil environments. Humic and fulvic acids as well as organic substances produced by plants and microorganisms are involved in the weathering of primary minerals. Organic compounds play a very important role in the hydrolytic reactions of iron and on the formation, nature, surface properties, reactivity, and transformation of Fe oxides. Organic substances present in the rhizosphere interact with Fe promoting the formation of ferrihydrite and organo‐mineral complexes. The solubility of Fe precipitation products is usually low. However, the formation of soluble complexes of Fe(II) or Fe(III) with organic ligands, usually present in the rhizosphere increases the solubility of Fe‐oxides. Mobilization of Fe from Fe oxides by siderophores is of great importance in natural systems. They can form stable Fe(III) complexes (pK up to 32) and thus mobilize Fe from Fe(III) compounds. These higher Fe concentrations are important for the supply of Fe to plant roots which excrete organic acids at the soil–root interface. Iron oxides adsorb a wide variety of organic and inorganic anions and cations, which include natural organics, nutrients, and xenobiotics. There is competition between anions and cations for the surfaces of Fe‐oxides. Root exudates suppress phosphate or sulfate adsorption on Fe‐oxides. This is a mechanism by which plant roots mobilize adsorbed phosphate and improve their phosphate supply. Anions adsorption on iron oxides modify their dispersion/flocculation behavior and thus their mobility in the soil system. That can increase or decrease the possibility of contact between Fe‐oxides and organics or organisms able to dissolve them.     

植物多酚与低分子量有机酸联合作用对紫色土铁形态分布的影响

植物多酚(PP)和低分子量有机酸(LMWOA)对土壤铁形态转化有重要影响。以酸性、中性和石灰性紫色土为研究对象,采用不完全随机区组试验,用2种PP(即表没食子儿茶素没食子酸酯(EGCG)和芦丁)和2种LMWOA(即柠檬酸和草酸)溶液浸提供试土壤,测定其可溶铁(Fes)、游离铁(Fed)、活性铁(Feo)、络合铁(Fep)含量,探讨了PP与LMWOA对紫色土铁形态分布的影响。结果表明:PP与LMWOA各自单独作用均能使酸性紫色土Fes增加、中性紫色土Fes减少;对于石灰性紫色土,PP会促进其Fes增加,而LMWOA作用相反。EGCG与LMWOA联合作用,在酸性和石灰性紫色土上均表现为LMWOA通过促使本应转化为Fes的转化为Fep而掩蔽EGCG对铁的溶解作用;芦丁与LMWOA联合作用,在酸性紫色土铁的溶解上表现为协同效应,在石灰性紫色土上则表现为LMWOA会抑制芦丁对铁的溶解作用;对于中性紫色土,PP与LMWOA联合作用可促进Fed向Fes转化而削弱PP对铁溶解的抑制作用。     

Mineralogy and Arsenic Mobility in Arsenic-rich Brazilian Soils and Sediments (11 pp)

Background   Soils and sediments in certain mining regions of Brazil contain an unusually large amount of arsenic (As), which raises concerns that mining could promote increased As mobility, and thereby increase the risks of contaminating water supplies. Objectives   The purpose of this study was to identify the most important factors governing As mobility in sediments and soils near three gold-mining sites in the State of Minas Gerais, Brazil. Methods   Surface and sub-surface soil samples were collected at those sites and characterized by chemical and mineralogical analyses. Oxalate (Feo) and citrate-bicarbonate-dithionite (Fed) iron contents were determined by atomic absorption spectroscopy (AAS). Arsenic mobilization was measured after incubating the samples in a 2.5 mM CaCl2 solution under anaerobic conditions for 1, 28, 56, 84, or 112 days. The solution concentrations of As, Fe, and Mn were then measured by inductively coupled plasma-mass spectrometry (ICP-MS) and AAS, respectively. Results and Discussion   Results indicated that As mobilization is largely independent of both the total As and the Feo/Fed ratio of the solid phase. Soluble As is roughly controlled by the Fe (hydr)oxide content of the soil, but a closer examination of the data revealed the importance of other highly weathered clay minerals and organic matter. Large amounts of organic matter and a low iron oxide content should favor As leaching from soils and sediments. Under reducing conditions, As is mobilized by the reductive dissolution of Fe and/or Mn oxides. However, released As may be readsorbed depending on the sorptive properties of the soil. Gibbsite is particularly effective in adsorbing or readsorbing As, as is the remaining unreduced fraction of the iron (hydr)oxides. Conclusion and Outlook   In general, low soluble As is related to the presence of gibbsite, a large amount of iron oxides, and a lack of organic matter in the solid phase. This has environmental significance because gibbsite is thermodynamically more stable than Fe oxides under anaerobic conditions, such as those found in waterlogged soils and lake sediments.     

Standard potentials (Eo) of iron(III) oxides under reducing conditions

Partial reduction of iron(III) oxides with hydrogen in the presence of a platinum catalyst leads to an equilibrium state after 4–20 h. From the measured Eh, pH, and Fe²⁺ concentration conditional standard potentials can be calculated using the formula E_o (volt) = Eh + 0.059 lg(Fe²⁺) + 0.18 pH which indicate the stability of Fe oxides against reduction. The reduceability decreases following the order ferrihydrite > lepidocrocite > hematite > goethite. The difference between hematite and goethite was more pronounced than that predicted from thermodynamic data.     

Iron oxide‐humic acid coprecipitates as iron source for cucumber plants

In soil, iron (Fe) solubility depends on complex interactions between Fe minerals and organic matter, but very little is known about plant availability of Fe present in Fe oxides associated with humic substances. For this purpose, this study investigates the effect of Fe mineral crystallinity in the presence of humic acids (HA) on Fe availability to plants. Four Fe–HA mineral coprecipitates were prepared, either in the presence or absence of oxygen, i.e., two goethite (G)‐HA samples containing large amounts of Fe as nanocrystalline goethite and ferrihydrite mixed phases, and two magnetite (M)‐HA samples containing crystalline magnetite. Bioavailability studies were conducted in hydroponic systems on cucumber plants (Cucumis sativus L.) grown under Fe deficient conditions and supplied with the Fe–HA coprecipitates containing goethite or magnetite. Results showed that plants grown in the presence of Fe–HA coprecipitates exhibited a complete recovery from Fe deficiency, albeit less efficiently than plants resupplied with Fe‐chelate fertilizer used as control (Fe‐diethylene triamine penta acetic acid, Fe‐DTPA). However, the supply with either G‐ or M–HA coprecipitates produced different effects on plants: G–HA‐treated plants showed a higher Fe content in leaves, while M–HA‐treated plants displayed a higher leaf biomass and SPAD (Soil–Plant Analysis Development) index recovery, as compared to Fe‐DTPA. The distribution of macronutrients in the leaves, as imaged by micro X‐ray fluorescence (µXRF) spectroscopy, was different in G–HA and M–HA‐treated plants. In particular, plants supplied with the poorly crystalline G–HA coprecipitate with a lower Fe/HA ratio showed features more similar to those of fully recovered plants (supplied with Fe‐DTPA). These results highlight the importance of mineral crystallinity of Fe–HA coprecipitates on Fe bioavailability and Fe uptake in hydroponic experiments. In addition, the present data demonstrate that cucumber plants can efficiently mobilize Fe, even from goethite and ferrihydrite mixed phases and magnetite, which are usually considered unavailable for plant nutrition.     

Composition of iron-manganese concretions from some New Zealand soils

A selection of iron-manganese concretions from five reference soil profiles and a buried loess deposit in New Zealand have been studied. Concretions appear to have developed by the precipitation of amorphous iron and manganese oxides among soil particles. X-ray fluorescence analysis shows that the concentrations of Fe, Mn, Co and Ba in the concretions are generally higher, and those of K, Ca, Si, and Al are generally lower, than in the soil materials surrounding the concretions, whereas Ti, Zn, S, and P show little variation. Other approximate analyses indicate that Cu, Ni, Mo, V, and Pb tend to be concentrated in concretions but for Ga, Zr, Sr, Li, and Rb there was no discernible trend. Electron probe microanalyses of some concretions show that Co and Ba are concentrated in Mn-rich phases rather than Fe-rich phases.Comparison with published results for concretions (Mn nodules) from the ocean floor and the floor of Lake Ontario indicates that, on average, marine concretions have higher Mn, and lower Si and Al concentrations than soil concretions, and that marine concretions have lower Fe concentrations than either Ontario or soil concretions.     

石灰石成土过程中Zn在土壤中的演化和重新分布

The long-term redistribution of Zn in a naturally Zn-enriched soil during pedogenesis was quantified based on mass balance calculations. According to their fate, parent limestones comprised three Zn pools: bound to calcite and pyritesphalerite grains, bound to phyllosilicates and bound to goethite in the inherited phosphate nodules. Four pedological processes, i.e., carbonate dissolution, two stages of redox processes and eluviation, redistributed Zn during pedogenesis. The carbonate dissolution of limestones released Zn bound to calcite into soil solution. Due to residual enrichment, Zn concentrations in the soil are higher than those in parent limestones. Birnessite, ferrihydrite and goethite dispersed in soil horizon trapped high quantities of Zn during their formation. Afterwards, primary redox conditions induced the release of Zn and Fe into soil solution, and the subsequent individualization of Fe and Mn into Zn-rich concretions. Both processes and subsequent aging of the concretions formed induced significant exportation of Zn through the bottom water table. Secondary redox conditions promoted the weathering of Fe and Mn oxides in cements and concretions. This process caused other losses of Zn through lateral exportation in an upper water table. Concomitantly, eluviation occurred at the top of the solum. The lateral exportation of eluviated minerals through the upper water table limited illuviation. Eluviation was also responsible for Zn loss, but this Zn bound to phyllosilicates was not bioavailable.     

Precipitation of iron in a poorly drained alluvial soil

Abstract

Ferruginous deposits from the outfall and backfill of a newly‐installed drainage scheme in a poorly drained alluvial soil have been characterised using selective chemical dissolution, X‐ray diffraction, and chemical analysis and compared with the iron (Fe) deposits found in various micro‐environments within the soil profile. In the drainage ditch and on the permeable backfill around the drainage pipes, the mineralogy of the ferruginous deposits is dominated by the poorly ordered mineral, ferrihydrite, whereas within the soil environment the hydrous iron oxides display a wider range of structural order. It is probable that the initial precipitation product is poorly‐ordered material but that within the soil transformation to a more well ordered mineral, goethite, can occur.     

高梯度磁场分离后土壤矿物组成的变化

The changes of clay mineral association after high-gradient magnetic separation(HGMS) treatment,and the effects of chemical and physical technologies on concentrating Fe oxides for mian soils in central and southern China were investigated by means of X-ray diffraction (XRD) and chemical analysis methods.Results indicated that the concentrating times of Fe oxides by HGMS treatment were the largest for 0.2-2μm size fraction in the examined soils .For the soils in which 2:1 phyllosilicates were dominant,concentrating times of iron oxides by HGMS treatment were larger than by 5 mol L^-1 NaOH treatment .Phyllosili-cates were decreased after HGMS treatment ;however,the decrease was less than that of kaolinite,The goethite/(goethite hematite) values in Fe oxides of the soils kept virtually constant after HGMS treatment.