土壤和粘粒矿物对亚硒酸盐的吸附和解吸

本文研究了三种土壤(砖红壤、红壤和黄棕壤)、高岭土和两种合成氧化铁(无定形氧化铁和针铁矿)对亚硒酸盐的吸附和解吸作用。讨论了亚硒酸盐的吸附特征,以及土壤中氧化铁对亚硒酸盐吸附和解吸的影响,根据实验资料与吸附等温方程式的拟合情况,作者认为以Freundlich和Langmuir公式为宜。此外,供试样品对亚硒酸盐的吸附和解吸结果表明,Se的吸附量随Se的添加量的增加而增加,但由于矿物组成各异,吸附量的差异显著。其吸附量的大小顺序为:无定形氧化铁>针铁矿>砖红壤>红壤>黄棕壤>高岭土;而被吸附Se的解吸能力则是高岭土>黄棕壤>红壤>砖红壤>针铁矿>无定形氧化铁。实验结果还表明,在各种矿物组成中,亚硒酸盐的吸附和解吸受氧化铁的影响很明显,三个土壤样品的吸附等温线都表现出氧化铁在初始阶段对亚硒酸盐吸附快而强烈的特征,而在去除氧化铁以后,这一特征也随之消失,硒的吸附量显著降低,而解吸率则明显上升。     

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。     

pH对酸性土壤中铝的溶出和铝离子形态分布的影响

ＰＨ对酸性土壤中铝的溶出和土壤溶液中铝离子形态分布的影响的研究结果表明,土壤中铝的溶出量随ＰＨ降低而增加,ＰＨ对不同土壤中铝的溶出的影响不同,三种土壤中铝的溶出量受ＰＨ影响的大小顺序是：红壤〉赤红壤〉砖红壤,说明不同类型土壤中铝的溶出对外来酸的敏感和程度不同。     

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。     

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.     

粘粒矿物和有机质对土壤胶体比表面的影响

分别从黑土、黄绵土、黄棕壤、红壤和砖红壤提取<2nm的胶体,测定去有机质前后土壤胶体比表面;并用猪粪中提取的胡敏酸与上述5种土壤胶体相作用,由泥炭中提取的胡敏酸与蒙脱石、伊利石、高岭石相作用,测定其复合胶体的比表面;研究了粘粒矿物类型和胡敏酸对土壤胶体比表面的影响。结果表明,土壤胶体比表面大小与其所含主要粘粒矿物类型密切相关。5种土壤胶体比表面大小为:黑土>黄棕壤>黄绵土>红壤>砖红壤。砖红壤胶体去游离氧化铁后,胶体比表面明显降低;但黄棕壤胶体去游离氧化铁后比表面反而增加。有机质对土壤胶体比表面的影响因土壤类型不同而异,去除有机质后,黑土、黄绵土和黄棕壤胶体的比表面增加;而红壤、砖红壤胶体的比表面无明显变化。黑土和黄棕壤胶体与猪粪胡敏酸复合后,比表面降低;而砖红壤胶体与猪粪胡敏酸复合后反而增加。泥炭胡敏酸与蒙脱石、伊利石胶体复合后比表面降低;而高岭石却增加。     

氧化还原条件下有机物料对酸性土壤pH、铁形态和铜吸附解吸的影响

研究了添加有机物料对水稻土、红壤和砖红壤在干湿交替一次以后土壤pH、铁的形态和对铜吸附解吸行为的影响。结果表明,添加有机物料使得土壤pH升高,且随着有机物料加入量的增加而升高。与对照相比,添加有机物料可使水稻土、红壤和砖红壤的pH分别上升1.55、0.8和1.33个pH单位。红壤和砖红壤中无定形氧化铁含量增加,而水稻土中变化不大。在铜的平衡浓度为0.2 mmol/L时,添加有机物料培养可使水稻土、红壤和砖红壤铜的吸附量分别增加6.7、10.3和3.6 mmol/kg。     

Interaction of silicon,iron, and manganese in rice (oryza sativa L.) rhizosphere at low ph in relation to rice growth

Rice (Oryza Sativa L.) nutrition is influenced by the interactions of (Iron) Fe, (Manganese) Mn, and (Silicon) Si in the rhizosphere. A greenhouse experiment was carried out with rice grown in four low‐pH soils (a granitic lateritic red earth, a paddy soil from the red earth, a basaltic latosol, and a paddy soil from the latosol). Rice was grown in pots with the roots confined in rhizobags and the rhizosphere soil and nonrhizosphere soil were analyzed separately for active Si, Fe, and Mn by Tamm's solution. Silicon and Mn concentrations were lower in the rhizosphere soil indicating a depletion which was higher for the basaltic soils and for the paddy soils. Iron concentrations were higher in the rhizosphere soil indicating an accumulation that was higher for granitic soils and for the upland soils. Plant growth response was due mostly to Mn with the basaltic soils supplying toxic amounts and the granitic soils being deficient. Iron accumulation in the rhizosphere caused lower plant uptake of Si, phosphorus (P), and calcium (Ca) and higher Fe and aluminum (Al) absorption leading to the conclusion that Fe deposition on plant roots and in rhizosphere may block the uptake of other nutrients.     

Composition and Characteristics of Organo—Mineral Complexes of Red Soils in South China

The objective of the present study is to reveal the composition and characteristics of organo-mineral complexes in red soils (red soil,lateritic red soil and latosol) of south China in terms of chemical dissolution and fractional peptization methos.In the combined humus,most of the extractable humus could dissolve in 0.1 M NaOH extractant and belonged to active humus (H1),and there was only a small amount of humus which could be further dissolved in 0.1 M Na4P2O7 extractant at pH 13 and was stably combined humus (H2).The H1/H2 ratio ranged from 3.3 to 33.8 in red soils,and the proportions of both H1 and total extractable organic carbon (H1 H2) in total soil organic carbon and the ratios of H1 to H2 and H1 to (H1 H2) were all higher in lateritic red soil and latosol than in red soil.The differences of combined humus composition in various red soils were directly related to the content of Fe and Al oxides.In organo-mineral complexes,the ratio of Na-dispersed fraction (G1) to Na-ground-dispersed fraction (G2) was generally smaller than 1 for red soils,but there was a higher G1/G2 ratio in red soil than in lateritic red soil and latosol.G1 fraction had a higher content of fulvic acid (FA),but G2 fraction had a higher content of humic acid (HA).The ratios of H1 to H2 and HA to FA were higher in G2 than in G1.The differences in the composition and activity of humus between G1 and G2 fractions were related to the content of free Fe and Al oxides.The quantities of complex Fe and Al,the Fe/C and Al/C atomic ratios were higher in G2 than in G1,and the ratio of Al/C was much higher than that of Fe/C.It may be deduced that aluminum plays a more important role than iron in the formation process of organo-mineral complexes in red soils.     

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.     

可变电荷土壤对SO42-的吸附

本文研究了三种带可变电荷的红壤在恒定pH和Cl^-离子存在条件下对SO₄^2-的吸附.三种红壤的OH^-释放量分别仅占SO₄^2-吸附量的12%,14%和20%.砖红壤在pH5.0时的电荷变化占所吸附的SO₄^2-的64-82%.作者认为大部分SO₄^2-以置换水合基的方式被吸附.     

土壤对铜离子的专性吸附及其特征的研究

供试土壤专性吸附铜的等温线均符合Langmuir方程。红壤吸附量最低,砖红腹与黄泥土最大吸附量相近,但在铜浓度低时砖红壤吸铜量远低于黄泥土,而在高浓度则反之。土壤专性吸附铜是在溶液中Na⁺浓度比Cu²⁺高8.3—100倍条件下,Na⁺离子仍不足以与之竞争的那些专性吸附点所吸持的铜。按其解吸条件区分为松结合铜(可为N NH₄Cl解吸)和紧结合铜(仅能为0.1 N HCl解吸)两种。紧结合铜受平衡溶液铜浓度影响很小,所占据的吸附点对Cu²⁺有较强亲和力。松结合铜则随平衡铜溶液浓度增大而增加,符合Langmuir方程。对于砖红壤和黄泥土,在铜浓度低时紧结合铜>松结合铜;浓度高时则反之。红壤专性吸附铜始终以松结合铜为主。三种土壤比较,紧结合铜是砖红壤>黄泥土>红壤;松结合铜则是黄泥土>砖红壤>红壤。造成这些差别的原因可能与土壤性质、氧化物、有机质和粘土矿物组成等不同有关。用平衡法研究三种土壤专性吸附铜在不同浓度NH₄Cl和HCl溶液中的解吸表明,可进一步区分为三或四种不同的结合状况。红壤对铜吸附容量最小,且最易解吸。     

氧化铝对红壤正、负电荷的影响

用人工合成氧化铝包被土壤的方法研究了氧化铝(三水铝石)对红壤地区五种土壤的电荷性质的影响.结果发现,土壤包被氧化铝后正电荷有不同程度的增加,但其增加量随pH的升高而减少,pH7左右时几乎为零.人工氧化铝对负电荷的影响因土而异.带负电荷少的砖红壤包铝后在pH<7范围内负电荷稍有减少;带负电荷多的黄壤和红壤包铝后在低pH时负电荷明显减少,而高pH时负电荷明显增大;另外两个赤红壤包铝后负电荷也有类似的变化趋势,但变幅较小.四种土壤的负电荷由减小转变到增大时转变点的pH值各土不同,在pH3.6-6.2之间.包铝后土壤净电荷的变化趋势与该土壤的负电荷相似.包铝后土壤的ZPNC都有所升高,升高的幅度因土而异,在0.4-1pH单位之间.     

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.     

Copper retention by Danish Spodosols in relation to contents of organic matter and aluminum,iron, and manganese oxides

Abstract

The importance of various soil components on copper (Cu) retention by Spodosois was investigated. Copper sorption and extraction were conducted on samples from the B horizon from six Danish Spodosois. The investigation was conducted on untreated samples, on hydrogen peroxide‐treated samples (to remove organic matter), on oxalate‐treated samples [to remove amorphous to poorly crystalline aluminum (Al) and iron (Fe) oxides], on hydroxylamine‐treated samples [to remove manganese (Mn) oxides]. Subfractions treated with hydrogen peroxide (H₂O₂) were further treated with oxalate and citrate‐bicarbonate‐dithionite (CBD). Sorption of Cu from an initial 10^‐6 M solution after 48 hours was determined in the pH range 3 to 7 using 0.1M sodium nitrate (NaNO₃) as the background electrolyte. The pH‐dependent sorption curve (sorption edge) was shifted to a higher pH with decreasing Al oxide content in the soils, and for the treated sample after removal of organic matter and Al and Fe oxides. A negligible effect was seen after removal of the Mn oxides because of their low abundance. Extraction of sorbed Cu at pH 4 to 6 with 0.1M nitric acid (HNO₃) for 24 hours confirmed the sorption results, in inasmuch as removal of the Al (and Fe) oxides increased Cu extractability. Therefore, it was concluded that in the soils investigated, Cu retention is mainly determined by the oxalate‐extractable Al fraction with a minor contribution due to crystalline Fe oxides.     

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.     

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.     

不同作物对赤红壤酸铝毒害的响应研究

为评价赤红壤酸铝对作物的毒害作用,本文用氧化钙和硫酸铝将典型赤红壤pH值调节为4.01、4.52、5.02、5.52,研究了7种作物对不同酸铝土壤的响应。结果表明,不同酸铝土壤中,7种作物相对根长与相对根干重呈相似变化趋势,均表现为pH 5.02土壤>pH 4.52土壤>pH 4.01土壤,水稻的相对根长与相对根干重较大,而大麦较小,通菜、玉米、菜豆、豆角、大豆位于其中。铝溶液处理下不同作物的相对根伸长均以水稻、大豆、菜豆、豆角>玉米>通菜>大麦,与土培结果基本一致;作物根系的苏木精染色程度随酸铝毒害程度的上升而加深,与作物铝吸收结果趋势相同。大麦、水稻、豆角染色较深,但其相对根长差异显著,表明它们具有不同的耐铝机制。     

Adsorption of Potassium and Sodium Ions by Variable Charge Soils

Adsorption of potassium and sodium ions by four typical variable charge soils of South China was studied.The results indicated that the variable charge soils saturated with H and Al showed a much higher preference for potassium ions relative to sodium ions,and this tendence could not be changed by such factors as the pH,the concentration of the cations,the dielectric constant of solvent,the accompanying anions and the iron oxide content etc.,suggesting that this difference in affinity is caused by the difference in the nature of the two cations.It was observed that a negative adsorption of sodium ions by latosol and lateritic red soil in a mixed system containing equal amount of potassium and sodium ions at low pH,which is caused by a competitive adsorption of potassium and sodium ions and repulsion of positive charge on the surfaces of soil particles for cations.The adsorption of potassium and sodium ions increased with the decreases in the dielectric constant of solvent and the iron oxide content.Sulfate affected the adsorption of potassium and sodium ions through changing the surface properties of the soils.     

Effect of Low Molecular Weight Organic Anions on Adsorption of Aluminum by Variable Charge Soils

To examine the effect of organic anions on adsorption of Al by variable charge soils at different pH values, the adsorption by three soils in the presence of three low-molecular-weight aliphatic carboxylic acids was investigated. The results showed that the effect depended on pH, the type of organic anions and their concentration. The presence of citrate and oxalate led to an increase in the adsorption of Al at low pH and low concentration of organic anions, with citrate showing a stronger effect than oxalate. For example, the maximum increments of Al adsorption in the presence of citrate were 131.9, 104.8 and 32.9% in the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively, whereas in the presence of oxalate it was 36.1% in the Rhodic Ferralsol. At high pH or high concentration of organic anions, they showed an inhibiting effect on the adsorption of Al. For example, citrate caused the increase in Al adsorption by 164.0, 131.0 and 61.0% at pH3.85 and the decrease in Al adsorption by 15.2, 19.5 and 45.6% at pH 4.8 for the Hyper-Rhodic Ferralsol, the Rhodic Ferralsol and the Ferric Acrisol, respectively. In the citrate and oxalate systems, the adsorption of Al increased with the increase in the concentration of organic anions, reaching a maximum values at about 0.4 mmol L^?1, and then decreased. When the concentration of organic anions was higher than about 1.0 mmol L^?1, both citrate and oxalate inhibited the adsorption of Al. The ability of organic anions in increasing the adsorption at low pH and decreasing the adsorption at high pH followed the same order: citrate > oxalate > acetate. The increase of Al adsorption at low pH is caused by the increase in soil negative surface charge as a result of the adsorption of organic anions by variable charge soils, while the decrease of Al adsorption at high pH and high concentration of organic anions is related to the competition of organic ligands for aluminum ions with soil surface. After the removal of free iron oxides from the soil, Al adsorption decreased in the presence of citrate, the anion species most strongly adsorbed by variable charge soils and complexed with aluminum ions. For example, for the Rhodic Ferralsol and the Ferric Acrisol, the removal of free iron oxides caused a decrease in the adsorption of Al in the presence of citrate at pH4.4 by 26.2 and 21.9%, respectively.