Surface chemical properties and pedogenesis of tropical soils derived from basalts with different ages in Hainan,China

Limited information is available on the changes of surface chemical properties of tropical soils with time during the pedogenesis. Soil samples of three profiles derived from basalts of 10, 1330 and 2290 kilo annum (ka) in age were collected from adjacent locations in a tropical region of Hainan Province, China. The changes in soil surface chemical properties and the mineralogy of the soil clay fraction with time were investigated using ion adsorption, micro-electrophoresis, and X-ray diffraction analysis. The content of 2:1-type clay minerals decreased, while those of kaolinite and gibbsite increased with increasing basalt age and degree of soil development. The content of pedogenic free iron (Fe) oxides and the ratio of free Fe oxides/total Fe oxides increased with soil development stage, while soil poorly crystalline Fe and aluminum (Al) oxides had an opposite trend. The positive surface charge of the soils increased with increasing basalt age and degree of soil development; this was consistent with the change in their contents of free Fe/Al oxides. However, the value of negative surface charge had an opposite behavior. The soil derived from 10-ka-basalt had much more negative charge than soils derived from 1330- and 2290-ka-basalt. Soil net surface charge and zeta potential of the soil clay-fraction decreased with the increase in basalt age. Both net charge–pH curves and zeta potential–pH curves shifted to positive values with increased basalt age and degree of soil development. Increasing age also elevated the point of zero net charge of the soil and the isoelectric point of soil colloids.     

土壤电化学性质的研究——Ⅹ.红壤胶体的表面性状和离子专性吸附对表面电荷性质的影响

根据可变电荷和永久电荷共存的土壤体系的模式,研究了一个砖红壤和一个红壤胶体的表面电荷特性。由于两种土壤胶体的矿物成分和铁铝氧化物的含量不同,砖红壤胶体的pH。值、ZPNC和IEP都高于红壤胶体者。红壤胶体的永久负电荷量多,其pH₀与ZPNC的差值也大。土壤加3%的有机质淹水培育4个月后,胶体的腐殖质含量增加不足0.5%,对胶体的pH₀的影响不明显。砖红壤胶体用磷酸盐或硅酸盐处理后,表面正电荷减少,负电荷增多,pH₀值和IEP都降低。磷酸盐的效应较硅酸盐为甚。不同浓度的KCl溶液中存在少量SO₄^2-时,砖红壤胶体的正电荷减少,负电荷增加,ZPNC和pH₀值降低;如存在少量Ca²⁺,则pH₀值升高。以单一的K₂SO₄、为支持电解质时,pH₀值较KCl者为高。     

Interaction of aluminum and iron oxides and clay minerals and their effect on soil physical properties: A review

Abstract

Amorphous and crystalline aluminum and iron oxide minerals play a major role in stabilizing soil structure as measured by aggregate stability and clay dispersion. Aluminum and iron oxide interactions with clays are pH dependent. At low pH, where the oxides carry sufficient positive charge, they precipitate on clay surfaces. These coatings, once formed, are stable at higher pHs. Precipitation of oxides at high pH occurs as phases separate from the clays. Aluminum and iron oxides stabilize clay minerals by decreasing critical coagulation concentration, clay dispersion, water uptake, and clay swelling and by increasing microaggregation. The presence of aluminum and iron oxide minerals in soils has a favorable effect on soil physical properties, increasing aggregate stability, permeability, friability, porosity, and hydraulic conductivity, and reducing swelling, clay dispersion, bulk density, and modulus of rupture.     

Selected enzyme activities as affected by free iron oxides and clay particle size

Abstract

The effect of soil clay size phyllosilicates, particle size, and iron oxides on the activities of α‐ and β‐glucosidases, phosphomonoesterases, and urease were examined. The two clay fractions (0.2–2 and <0.2 μm) of selected soils had similar mineralogy and were illitic, kaolinitic, and smectitic in composition. In general, enzyme activities were reduced in the presence of clay size phyllosilicates. The montmorillonitic samples were the most effective inhibitors. Activities were generally lower in the presence of the finer clay fractions. The effect of iron oxides on enzyme activities varied. Acid phosphatase activity was significantly influenced by phyllosilicate type, iron oxides, and particle size. The inhibitory effect of phyllosilicates on acid phosphatase activity increased when iron oxides were removed from the clay fraction. Removal of iron oxides, on the other hand, enhanced the activity of alkaline phosphatase. Unlike β‐glucosidase, α‐glucosidase was deactivated in the presence of montmorillonitic and illitic samples regardless of clay particle size. The activity of urease was significantly reduced in the presence of iron oxides.     

土壤电化学性质的研究Ⅲ.红壤胶体的电荷特征

土壤胶体的电荷性质,与土壤的一系列物理化学性质有密切关系。红壤的某些与肥力有关的物理化学性质,与其它类型土壤有所不同。例如,它的阳离子交换量较小,而阴离子吸附量则较大,分散性较弱,胀缩性也较小。红壤在物理化学性质方面的这些特点,大多是由其胶体的电荷特点所引起。     

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.     

Adsorption of cobalt by soil iron oxides at low solution concentration

Abstract

Eleven selected soils from Denmark and Tanzania were treated with ammonium acetate (controls), EDTA, and dithionite‐EDTA (DE) to fractionate iron and (manganese) oxides. The amounts of cobalt adsorbed were determined from a 3 μM equilibrium cobalt solution, corresponding to the cobalt level in natural soil solutions using sodium nitrate (0.2 M) to suppress non‐specific adsorption, by the extracted soils as well as by two synthetic iron oxides.

No significant correlations were found between cobalt adsorption and the contents of organic matter and extractable manganese, presumably due to their low contents in the soils investigated. Close correlations were, however, found between the amounts of cobalt adsorbed, especially fractions thereof, and the contents of iron oxides.

The amounts of cobalt adsorbed by the DE‐ex‐tracted soils, void of iron (and manganese) oxides, were attributed to the clay silicates. The remaining cobalt adsorption, i.e. the difference between cobalt adsorbed by acetate‐extracted and DE‐extracted samples, was attributed to the iron oxides. This portion of adsorbed cobalt was well described by considering soil iron oxides composed of only two fractions, an EDTA‐extractable fraction of high reactivity and a less reactive fraction corresponding to the difference between DE‐extractable iron and EDTA‐extractable iron.

The amounts of cobalt adsorbed by the soil iron oxides were well predicted from the contents and specific surface of the two iron oxide fractions in soil together with the amount of cobalt adsorbed by the synthetic iron oxides.     

平原区水田改林地后土壤黏土矿物及氧化铁的变化

近年来水田改为林地在我国南方地区非常普遍,为了解这种转变对土壤矿物(黏土矿物和氧化铁)演变的影响,在浙江省平原地区构建了4个水田改林地系列土壤,采用野外调查和室内分析相结合的方法,研究水田改林地后土壤剖面中氧化铁形态和黏土矿物类型的演变规律。结果表明,改林地后,土壤剖面中全铁含量变化不明显,耕作层和犁底层土壤游离氧化铁有轻微增加趋势。改林地15～20 a后,4个系列土壤耕作层活性铁和活化度降幅分别在18.0%～38.4%和24.7%～48.9%;耕作层土壤铁氧化物的晶胶比增幅在0.73倍～1.62倍;耕作层土壤亚铁含量明显下降,降幅最高达95.8%,变异系数达到143.9%;耕作层络合铁降幅在21.3%～36.2%,并与有机质呈极显著正相关(P<0.01)。改林地后,犁底层土壤中绿泥石相对含量及其与高岭石的比值都呈降低趋势,其他黏土矿物相对含量变化规律不明显,土壤有机质显著下降,土壤明显酸化。土壤铁氧化物形态和数量的变化对土壤结构以及土壤重金属的迁移转化等产生重要影响。     

Use of a three-plane model to describe charge properties of some iron oxides and soil clays

The pH-dependence of surface charge density of three iron oxides and the clay fraction of five horizons of a variable-charge soil has been studied by adsorption of potential-determining ions (p.d.i.) and by adsorption of electrolyte ions. The general trend of results for iron oxides can be satisfactorily explained by a model which considers a three-plane distribution of electric potential. When the model is applied to soil clays the outcome is less satisfactory and, although their charge properties seem to be largely determined by their high content of minerals with variable charge surfaces, the presence of minerals with a permanent charge (clay minerals) should be considered when explaining the particular data, even for those horizons where clay minerals are present in low proportions.     

Origin of the effect of ph on the saturated hydraulic conductivity of non‐sodic soils

Abstract

The effect of pH on the saturated hydraulic conductivity (K) of repacked columns of two non‐sodic soils (Healaugh and Fagaga soils) was examined. The K value was greater for the Fagaga soil than for the Healaugh soil which is attributed to the difference in the amount of free iron oxides between the soils. The K values reached a maximum when the pH was close to the point of zero net charge (PZNC) (3.7 and 4.8 for the Healaugh and the Fagaga soil, respectively) and decreased on either side of these pH values. The effect of pH on K was related to its effect on surface charge. As the pH of variable‐charge soils approaches the PZNC, the net surface charge decreases resulting in flocculation and maintenance of a high K. Conversely, as the pH deviates from the PZNC, the net surface charge increases, resulting in dispersion and a decrease in K. There was a negative relationship between the amount of dispersed clay and the K values, suggesting that clay dispersion and the resulting clogging of pores decreases K in these soils.     

Mineralogy and chemistry of some variable charge subsoils

Abstract

Colloidal mineralogy is one of the main characteristics of the steady state reached in developed soils. Surface charge and other chemical and physical properties of the soil depend on colloidal mineralogy. It is, therefore, very important to further investigate the clay mineralogy of acidic variable charge subsoils in order to understand better their unusual chemical behavior. The objective of this investigation was to characterize the inorganic colloid mineralogy, chemical (subsoil solution pH and electrical conductivity), and charge properties (PZNC and PZSE) in some variable charge subsoils. Subsoil materials were collected from the southeastern United States and other tropical and subtropical areas around the world. The clay fraction mineralogy in the majority of the subsoils was dominated by the quartet kaolinite, gibbsite, goethite, and hematite. They manifested, however, a significant diversity in their charge and other chemical characteristics because the proportions and contents of mineralogical constituents, particle size distributions, and specific surface areas were very different. The pH_KCl values ranged from 3.69 to 5.91. Under such conditions, pure kaolinite and aluminum/iron (Al/Fe) oxides have opposite net surface charges, and acidic subsoils are mixed charge colloidal systems. They have extremely low EC values, varying from 9.9 to 132 μS cm^‐1, with corresponding ionic strengths between 0.14 and 1.86 mmol L^‐1. They develop towards a “no or little charge state”; and the native pH is near the PZNC or PZSE. The overall charge characteristics and adsorption properties in these heterogenous colloidal systems are clearly a direct function of the relative contents, interactions, and surface reactivity of mineralogical soil constituents in the subsoils.     

鄂湘两省山地土壤粘粒矿物的研究──Ⅲ．神农架自然保护区北坡土壤的粘粒矿物与表面化学特性

本文研究结果表明：（１）神农架垂直带土壤矿物的风化脱硅作用较弱，粘土矿物以２：１型矿物为主，１：１型高岭含量很少。（２）随海拔升高，矿物的淋溶脱钾和层间羟基铝化作用增强，低海拔土壤的２：１型矿物以水云母为主，高海拔土壤以１．４ｎｍ矿物为主，其中１．４ｎｍ过渡矿物相对增多。（３）土壤的络合态铁、铝和非晶形铁，铝含量随海拔升高明显增大。（４）土壤的可变电荷量，阴离子交换量，交换性酸和铝饱和度等均随海拔     

珠江三角洲平原不同种植年限土壤铁氧化物特征研究

珠江三角洲平原具有上千年的围垦历史,其土壤发生演变过程深受人为作用影响,开展此区域不同种植年限土壤中铁氧化物形态特征和分布规律的研究,能够揭示人为耕种下土壤发生演变过程。以珠江三角洲平原不同种植年限的土壤剖面为对象,研究了滨海沉积物、河流冲积物和三角洲沉积物发育的土壤及黏粒中全铁、游离铁含量变化及其影响因素。结果表明:随着种植年限的增加,河流冲积物、三角洲沉积物发育土壤中游离铁(Fe_d)向土体下部淀积深度逐渐增加,黏粒中游离铁(Fe_(d(clay)))含量在水耕氧化还原层中呈减小趋势,而滨海沉积物发育的土壤Fe_d含量及淀积深度均有所减小。随着种植年限的增加,滨海沉积物发育的土壤全铁(Fe_t)和游离铁(Fe_d)在黏粒中的富集程度呈增大趋势,而河流冲积物、三角洲沉积物发育的土壤Fe_t和Fe_d富集程度逐渐减小。土壤Fe_d与Fe_t、黏粒游离铁(Fe_(d(clay)))与黏粒全铁(Fe_(t(clay)))均呈极显著正相关;全铁富集率(Fe_(t(clay))/Fe_t)、游离铁富集率(Fe_(d(clay))/Fe_d)均与Fe_(t(clay))、Fe_(d(clay))、黏粒铁游离度(Fe_(d(clay))/Fe_(t(clay)))呈极显著正相关,与Fe_t、Fe_d、土壤铁游离度(Fe_d/Fe_t)、黏粒含量呈极显著负相关,且Fe_(t(clay))/Fe_t与Fe_(d(clay))/Fe_d呈极显著正相关,表明土壤铁氧化物在黏粒中的富集以Fe_d为主,且铁氧化物的富集程度受土壤黏粒含量的影响。     

Contribution of Iron and Aluminum Oxides to Electrokinetic Characteristics of Variable Charge Soils in Relation to Surface Charge

The contribution of iron and aluminum oxides to electrokinetic characteristics of variable charge soils was studied through determination of electrophoretic mobilities of the red soils treated with either removal of iron oxides or coating of aluminum oxides,and of those deferrated under natural conditions.After removal of the iron oxides,zeta potentials of the latosol and the red earth decreased obviously with a shift of IEP to a lower pH,from 6.4 to 5.3 and 4.1 to 2.4 for the former and the latter,respectively,and the electrokinetic change for the latosol was greater than for the red earth.Zeta potentials of the kaolinite sample increased markedly after coated with iron oxides.The striking effect of iron oxides on electrokinetix properties of the soils was also demonstrated by the electrokinetic differences between the samples from the red and white zones of a plinthitic horizon formed naturally,and between the samples from the gley and bottom horizons of a paddy soil derived from a red earth.The coatings of aluminum oxides on the latosol and the yellow earth made their zeta potentials rise pronouncedly and their IEFs move toward higher pHs,from 6.2 to 6.8 and 4.3 to 5.3 for the former and the latter,respectively.The samples with different particle sizes also exhibited some electrokinetic variation.The experiment showed that the effects of iron and aluminum oxides were closely related to the pH and type of the soils.     

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.     

我国几种地带性土壤无机胶体的表面电荷特性

研究了用返滴定法测定我国七个不同地带土壤无机胶体的表面电荷特性。结果表明 :( 1 )返滴定法测定的供试土壤无机胶体可变电荷量随纬度升高而逐渐上升。这主要与供试土壤粘土矿物、铁铝氧化物组成及含量有关。一般来说 ,土壤层状硅酸盐粘土含量越多 ,永久负电荷量和其可变负电荷量越大 ;铁铝氧化物含量越高 ,可变负电荷量越低。( 2 )七个地带性土壤无机胶体的Qv pH曲线上在pH5左右有一峰值 ,这可能与供试土壤胶体中铁铝氧化物的ZPC及供试土样层状硅酸盐的边面Si OH基吸附H 及Al OH基离解H 有关     

海南岛琼山热带土壤中重金属分布和矿物特征的关系

本文探讨了海南岛玄武岩上发育的热带地球化学景观中土壤重金属与机械组成,矿物成分和矿物组合之间的关系。结果表明,砖红壤粘粒并不富集重金属元素,这与砖红壤各粒级矿物分布特征有关,在其粉粒级和砂粒级中有大量氧化铁矿物,面粘粒级中主要是高岭石和三水铝矿。此外,水稻土随粒径变大,重金属含量减少,这同水稻土随粒径增大,粘土矿物迅速减少,长石、石英增多有关。这和一般土壤重金属在不同粒级中分布规律相符合。     

Retention of dissolved organic matter by illitic soils and clay fractions: Influence of mineral phase properties

The dependency of the retention of dissolved organic carbon (DOC) on mineral phase properties in soils remains uncertain especially at neutral pH. To specifically elucidate the role of mineral surfaces and pedogenic oxides for DOC retention at pH 7, we sorbed DOC to bulk soil (illitic surface soils of a toposequence) and corresponding clay fraction (< 2 μm) samples after the removal of organic matter and after removal of organic matter and pedogenic oxides. The DOC retention was related to the content of dithionite‐extractable iron, specific surface area (SSA, BET‐N₂ method) and cation exchange capacity (pH 7). The reversibility of DOC sorption was determined by a desorption experiment. All samples sorbed 20–40 % of the DOC added. The DOC sorption of the clay fractions explained the total sorption of the bulk soils. None of the mineral phase properties investigated was able to solely explain the DOC retention. A sorption of 9 to 24 μg DOC m^–2 indicated that DOC interacted only with a fraction of the mineral surface, since loadings above 500 μg m^–2 would be expected for a carbon monolayer. Under the experimental conditions used, the surface of the silicate clay minerals seemed to be more important for the DOC sorption than the surface of the iron oxides. The desorption experiment removed 11 to 31 % of the DOC sorbed. Most of the DOC was strongly sorbed.     

Influence of iron oxides on cobalt adsorption by soils

Eleven soils from Denmark and Tanzania were extracted with ammonium acetate (controls), EDTA, and dithionite-EDTA (DE) to fractionate iron (and manganese) oxides. The amounts of cobalt adsorbed and acidity desorbed by the extracted soils as well as by two synthetic iron oxides were determined, using 0.85 mM cobalt in 0.2 m NaNO₃.
No significant correlations were found between cobalt adsorption and the contents of extractable manganese or organic matter, presumably because of their low contents. The major part of the cobalt adsorption (by DE-extracted samples) was due to the clay fraction and was associated with the release of approximately one proton per adsorbed Co. The remaining cobalt adsorption was attributed to the iron oxides. This portion of adsorbed cobalt was well described by considering soil iron oxides composed of only two fractions, an EDTA-extractable fraction of high reactivity and a less reactive fraction corresponding to the difference between DE-extractable iron and EDTA-extractable iron. Approximately 1.7 protons were released per Co adsorbed by these iron oxide fractions and by the synthetic iron oxides.
The amounts of cobalt adsorbed by the soil iron oxides were well predicted from the contents and specific surfaces of the two iron oxide fractions together with the specific cobalt adsorption of synthetic iron oxides.     

福建三个垂直带谱中土壤氧化铁的研究

应用穆斯堡尔谱分析、化学分析和光学显微镜分析，对福建三条最有代表性的土壤垂直带谱中的粗粒及粘粒氧化铁矿物进行研究。结果表明，赤铁矿从黄壤－黄红壤－红壤－赤红壤逐渐增多而针铁矿逐步减少，粗粒原生矿物组合类型从复杂趋向简单。铁的游离度及晶胶比从黄壤－黄红壤－红壤逐渐升高而活化度逐渐下降，但赤红壤例外，这可能与其成土年龄有关。本文还讨论了土壤分类的有关问题。