雷州半岛和海南岛北部玄武岩发育土壤的表面电化学性质及其演变

利用采自雷州半岛和海南岛北部不同年代喷发的玄武岩发育的6种土壤,研究了土壤的游离氧化铁、铁的游离度、CEC和土壤胶体动电电位与成土母岩年龄的关系,探讨土壤表面化学性质与成土的时间和空间因素的关系。结果表明:土壤游离铁和铁的游离度与母岩年龄间存在很好的线性相关性,铁的游离度与母岩年龄间的相关性更高,土壤全铁与母岩年龄间没有相关性。土壤CEC随母岩年龄增加而降低,土壤IEP呈相反变化趋势。进一步对2个地区土壤CEC和IEP与岩石年龄进行分析表明,空间因素对这2个地区土壤性质的影响更为明显,尤其对IEP。     

Comparison of the surface chemical properties of four soils derived from Quaternary red earth as related to soil evolution

The surface chemical properties of soil samples i.e., surface charge and zeta potential, and the mineralogy of soil clay fraction were investigated with reference to soil weathering extent for four different soils derived from Quaternary red earth using the ion adsorption method, a micro-electrophoresis method and the X-ray diffraction analysis. Results indicated that all these soil samples contained kaolinite and gibbsite. The Ultisols from Guizhou, Hunan and Jiangxi possessed the 2:1 type clay minerals of mica and vermiculite. Hematite and magnetite were found in the Ultisols from Guangxi, Hunan and Jiangxi. Goethite was found in the Ultisols from Jiangxi, Hunan and Guizhou. The positive surface charge for these soils decreased with the order: the Ultisol from Guangxi ≅ the Ultisol from Guizhou > the Ultisols from Hunan and Jiangxi from south to north when pH < 5.0. This is consistent with the content of free Fe/Al oxides present in these soils. On the other hand, the value of negative surface charge on the Ultisol from Guangxi was found much lower than the other soils perhaps because of the intensive weathering of the soil. Both permanent and variable negative charges for the former were also lower than the latter, whereas the point of zero salt effect (PZSE) for the former was greater than that of the latter. The variability of soil negative surface charge followed the order: the Ultisol from Guangxi > the Ultisol from Guizhou > the Ultisol from Jiangxi ≅ the Ultisol from Hunan. The zeta potential and isoelectric point (IEP) of soil colloids and soil net surface charge followed the same order: the Ultisol from Guangxi > the Ultisol from Guizhou > the Ultisols from Hunan and Jiangxi. A good correlation between zeta potential and net surface charge of these soils was observed. Therefore, the magnitudes of the PZSE, IEP and zeta potential of these soils were in agreement with the weathering extent of the soils and can be employed as reference criteria for classification and evolution of soils.     

典型热带土壤时间序列的电荷零点变化特征及其土壤发生意义

本研究选取海南岛北部玄武岩上不同发育时间的土壤进行研究,通过电位滴定法测定土壤的电荷零点,并结合XRD衍射测定土壤中的黏土矿物,探讨热带地区电荷零点随土壤发育程度的变化及其指示意义。结果表明:热带地区土壤电荷零点随土壤发育时间延长而升高,土壤中黏土矿物含量的变化和金属氧化物的增加是导致这一现象的主要原因,另外黏土矿物的种类和结晶程度也会影响到电荷零点的大小。电位滴定曲线的数据表明,随着土壤发育程度的加深,土壤永久负电荷减少,土壤的缓冲性能和保肥能力下降。对比其他指示土壤发育程度的指标,电荷零点大小能更好地表征热带地区土壤发育时间的长短,评估土壤发育程度强弱。     

Charge characteristics in relation to free iron and organic matter of soils from Bambouto Mountains, Western Cameroon

We have examined the charge characteristics, with special emphasis on the role of free Fe and organic matter, of humid tropical soils from Bambouto Mountains, Western Cameroon. The soils, which are formed from tuff, basalt and trachyte, are dominated by kaolinite and sesquioxides. The amounts of Fe oxides in them increase somewhat with depth. Open 2:1 phyllosilicates are present in trace amounts. The point of zero charge of the variable charge components, pH₀, is around 4 in the topsoil (0–20 cm) and around 6 at 100–150 cm depth. In the subsoils, pH₀ exceeds soil pH presumably because of large quantities of Fe oxides. Deferration increases both soil pH and pH₀, but diminishes the anion exchange capacity. Oxides and oxyhydrates of Fe have positive surface charge, so their removal from the soils would result in overall loss of positive charge. Increases in soil pH would bring about an increase in the cation exchange capacity of the soils. Hence, management practices that reduce soil acidity should reduce loss of essential basic cations via leaching.     

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。     

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.     

Charge Properties and Clay Mineral Composition of Tianbao Mountains Soils

The clay mineral association,oxides of clay fraction and surface charge properties of 7 soils,which are developed from granite,located at different altitudesof the Tianbao Mountains were studied.Results indicate that with the increase in altitude,1) the weathering process and desilicification of soil clay minerals became weaker,whereas the leaching depotassication and the formation process of hydroxy-aluminum interlayer got stronger;2)the contents of amorphous and complex aluminum and iron,and the activity of aluminum and iron oxides for soil clay fraction increased;and 3) the amount of variable negarive charge,anion exchange capacity and the values of PZC and PZNC also increased.The activity of aluminum and iron oxides,the accumulation of aluminum,and surface charge characteristics and their relation to clay oxides of the vertical zone soils were observed and recorded.     

土壤电化学性质的研究——Ⅸ.水稻土的某些表面电化学性质

水稻土的表面电化学性质与水稻土的肥力有密切关系。土壤在淹水种稻和排水落干的季节性交替过程中,其pH、Eh和养分离子浓度等都有颇大的变动,某些固相成份如铁、锰、铝等也发生形态的转化或数量的变动。这些变化都将对水稻土的表面电化学性质有明显影响。过去对水稻土的氧化还原性质已研究很多^[3],而对涉及固液相间的离子平衡的表面电化学性质则研究较少。本工作主要是选用几种代表性水稻土及其相应的母质,研究土壤的电荷性质及其对钾离子和氯离子的吸附、作为胶体电解质而表现出来的离解度的变化、和对钾离子的结合能等,以揭示不同类型的水稻土的表面电化学性质的特点,以及水稻土形成过程中表面电化学性质的变异。     

Lability of soil organic carbon in tropical soils with different clay minerals

Soil organic carbon (SOC) storage and turnover is influenced by interactions between organic matter and the mineral soil fraction. However, the influence of clay content and type on SOC turnover rates remains unclear, particularly in tropical soils under natural vegetation. We examined the lability of SOC in tropical soils with contrasting clay mineralogy (kaolinite, smectite, allophane and Al-rich chlorite). Soil was sampled from A horizons at six sites in humid tropical areas of Ghana, Malaysian Borneo and the Solomon Islands and separated into fractions above and below 250 μm by wet sieving. Basal soil respiration rates were determined from bulk soils and soil fractions. Substrate induced respiration rates were determined from soil fractions. SOC lability was significantly influenced by clay mineralogy, but not by clay content when compared across contrasting clay minerals. The lability of SOC was lowest in the allophanic and chloritic soil, higher in the kaolinitic soils and highest in the smectitic soil. Our results contrast with conventional concepts of the greater capacity of smectite than of kaolinite to stabilize SOC. Contents of dithionite-citrate-bicarbonate extractable Fe and Al were inversely related to SOC lability when compared across soil types. A stronger inverse correlation between content of ammonium-oxalate extractable Fe and SOC lability was found when considering the kaolinitic soils only and we conclude that the content of active Fe (hydr-) oxides controls SOC stabilization in the kaolinitic soils. Our results suggest that the validity of predictive models of SOC turnover in tropical soils would be improved by the inclusion of soil types and contents of Fe and Al (hydr-) oxides.     

上海地区水稻土氮素矿化模拟

Three types of paddy soils, derived from granite, Quaternary red clay and basalt, respectively, were selected to study the effects of Fe and Mn in paddy soils on methane production and emission through pot and incubation experiments. The results indicated that the difference of Fe and Mn in paddy soils was one of the important factors causing obvious differences in methane emission from different soil types. Soil Fe and Mn affecting methane emission from the paddy soils was likely through affecting soil Eh and forming Fe and Mn plaques on rice roots. Different rates and valences of added Fe and Mn significantly affected methane production from paddy soils. Therefore, this study enhanced understanding of processes controlling methane emission from paddy soils and may help to improve modeling and estimating regional and global methane emission from paddy soils.     

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。     

磷酸盐吸附对可变电荷土壤正负电荷的影响

本文研究了华南地区不同类型的可变电荷土壤，并对磷酸盐的吸附量和吸附磷后土壤的正、负电荷的变化，以及ｐＨ和游离氧化铁对这种变化的影响进行了研究。结果表明，土壤吸磷量与土壤游离氧化铁含量成良好的正相关。土壤吸磷后正电荷减少，负电荷增加，土壤电荷量与吸磷量之间呈抛物线状相关。吸附１摩尔磷酸盐对土壤净负电荷的贡献在０．３－１．０摩尔之间。土壤中的游离氧化铁使吸附的磷对土壤负电荷的贡献减少。     

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。     

可变电荷土壤中特殊化学现象及其微观机制的研究进展

综述了近年来可变电荷土壤化学研究的进展,着重总结了可变电荷土壤中的盐吸附、铁铝氧化物对土壤自然酸化的抑制作用和离子强度对离子专性吸附的影响等特殊化学现象及其微观机制的研究进展。用颗粒表面扩散层重叠导致有效电荷数量减小的原理解释了盐吸附现象和铁铝氧化物对土壤自然酸化的抑制作用。阐明了可变电荷土壤和矿物中介质离子强度影响离子专性吸附的机制,用四层吸附模型解释了离子专性吸附随离子强度增大而增加的现象,并根据胶体zeta电位随离子强度改变而变化的趋势进一步证明了离子强度增大使胶体专性吸附面上静电电位的绝对值减小,是离子专性吸附随离子强度增大而增加的主要原因。带电颗粒表面双电层结构和双电层相互作用的深入研究,有助于阐明可变电荷土壤中一些特殊化学现象的微观机理,从而进一步完善土壤化学理论。     

VERTICAL DISTRIBUTION OF EXTRACTABLE IRON AND ALUMINIUM IN SOIL PROFILES FROM A BROWN EARTH-PEATY PODZOL ASSOCIATION

Fe and Al extractable by 3 per cent oxalic acid and by 0.1M potassium pyrophosphate at pH 10 have been determined in horizon samples of two soil profiles of each of three subgroups (Brown Earth, Brown Podzolic Soil, and Peaty Podzol) developed in North Wales on parent materials derived from Silurian shales. The vertical distribution of Fe and Al together with the relationship between pyrophosphate-extractable (‘fresh’ hydrous oxides) and oxalic-extract-able Fe or Al (‘fresh’+‘aged’ hydrous oxides) can assist classification and interpretation of the course of podzolization in these soils. If podzolization is defined as sesquioxide transport, then its degree of development in the soils studied differs according to whether Al or Fe are used as the index element. The evidence supports continued recognition of soils of Brown Podzolic type as an intergrade subgroup.     

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.     

磷的吸附和表面电荷特征及其与华南地区某些土壤矿物的关系

The phosphate adsorption and surface charge characteristics of the tropical and subtropical soils derived from different parent materials in China were determined, and their relations to soil mineralogy were analysed. The results showed that all soil phosphate adsorption curves were well fitted by Freundlich equation and Langmuir equation. The maximum buffering capacity of P ranged from 66 to 9 880 mg kg^-1, with an increasing order of purple soil, skeletal soil, red soil, lateritic red soil, yellow soil and latosol; and the highest value was 149 times the lowest value, which indicated great differences among these soils in phosphate adsorption and supplying characteristics. The pH₀ (zero point of charge) values obtained by salt titration-potential titration varied from 3.03 to 5.49, and the highest value was found in the latosol derived from basalt whereas the lowest value was found in the purple soil. The correlation analysis indicated that the main minerals responsible for phosphate adsorption in the soils were gibbsite, amorphous iron oxide and kaolinite; and the pH₀ was mainly controlled by kaolinite, gibbsite and oxides.     

浙南易蚀土壤的团聚体稳定性及其稳定机理

土壤团聚体的数量和稳定性是衡量土壤质量和可蚀性的重要指标。应用常规湿筛法和Le Bissonnais法测定了紫砂岩母质发育的柑橘园土壤团聚体稳定性,分析了土壤团聚体稳定性与胶结物质组成的关系。结果表明,供试土壤团聚体稳定性差异较大,湿筛法测定的水稳性团聚体MWD在0.75～3.49mm,MWD干筛-湿筛为0.15～2.89mm;Le Bissonnais法测定的水稳性团聚体平均MWD为1.57～3.12mm,其平均MWD与湿筛法测定的0.25mm团聚体含量、MWD、5～2mm团聚体破坏率和MWD干筛-湿筛呈极显著相关,表明两种方法测定的结果具有可比性;5～2mm土壤团聚体经快速湿润(FW)、慢速湿润(SW)和预湿后扰动(WS)3种处理后,团聚体崩解产物的MWD表现为FWSWWS,团聚体崩解产物的粒级分布随处理方式不同而不同,经快速湿润处理后,大多数团聚体崩解,崩解成较小粒径的水稳性团聚体,表明崩解的主要机制是由于团聚体内部的闭塞空气产生的压力引起的;土壤团聚体的稳定性指标与黏粒和游离氧化铁含量呈显著正相关,而有机质主要影响水稳定性团聚体的数量,它与土壤中MWD呈极显著正相关。     

发育程度对海南玄武岩发育土壤吸附铬酸根和磷酸根的影响

选择海南岛北部3个不同年代喷发的玄武岩发育的土壤研究了其对铬酸根(CrO42-)和磷酸根(PO43-)的吸附特征,结果表明随着母岩年龄的增加,土壤发育程度提高,土壤游离氧化铁和表面正电荷数量增加,对2种阴离子的吸附量增加。土壤CrO42-的解吸率在19.8%~39.6%之间,表明土壤对CrO42-的吸附涉及静电吸附和专性吸附2种机制,且随着土壤发育程度增加,CrO42-静电吸附所占比例增加。土壤对PO43-的吸附以非静电吸附为主,吸附的PO43-的解吸量非常低,其解吸率不超过6%。吸附PO43-在去离子水中的解吸量高于在0.1 mol/L NaNO3和KNO3中的解析量,KNO3体系中的解吸量低于NaNO3体系中的,电解质主要通过改变胶体表面离子吸附面上的静电电位影响PO43-的解吸。     

我国几种地带性土壤无机胶体的表面电荷特性

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