SELECTIVE EXTRACTION OF AMORPHOUS IRON OXIDES BY EDTA FROM SOILS FROM DENMARK AND TANZANIA

Soils from Denmark and Tanzania were extracted with EDTA solutions of different concentrations and pH. After extraction for 3 months there was no significant (95% level) further increase in amounts of iron (and aluminium, calcium, and magnesium) during longer extraction periods. X-ray diffraction showed no change of the crystalline minerals caused by the extraction, which is believed to be specific for amorphous iron oxides. The EDTA method may thus serve as a reference method for the determination of amorphous iron oxides in soils. Although the difference between EDTA-extractable iron and that extracted during 2 h by ammonium oxalate at pH 3.0 in the dark may be high, the ammonium oxalate method is considered to give a fast and often fair estimate of amorphous iron oxides.     

SELECTIVE EXTRACTION OF AMORPHOUS IRON OXIDES BY EDTA FROM A DANISH SANDY LOAM

EDTA extracts (pH 7.5–10.5) from a Danish sandy loam showed no significant (95% level) increase in amounts of aluminium, calcium, iron, and magnesium between three and nine months' shaking. The amounts were independent of the soil: solution ratio (1:10–1:50), the EDTA concentration (0.01 M–0.2 M), and crushing the soil (< 0.25 mm or < 2 mm). IR spectroscopy and X-ray diffraction showed no change in the mineral composition of the soil during the extraction. The extracted iron was equal to that extracted after 2 h by ammonium oxalate at pH 3.0. EDTA extraction at pH > 7.5 seems to extract selectively iron oxides with solubility products > ～ 10^?41.     

应用穆斯堡尔谱和X射线法研究红壤性水稻土的氧化铁矿物

应用穆斯堡尔谱和X射线法分析研究红壤性水稻土的氧化铁矿物,研究结果表明,红壤性水稻土的氧化铁矿物组成、特性及其形成转化与起源土壤具有明显的差异。水稻土的成土条件不利于赤铁矿的形成。红壤的粘粒氧化铁矿物以赤铁矿和高铝替代(>20摩尔%)的针铁矿为主。经淹水种稻后,赤铁矿逐渐被转化为低铝替代的针铁矿或其它形态氧化铁。渗育型水稻土P层的赤铁矿含量比相应的母土低,其针铁矿铝替代量较其它水型的水稻土高。而潴育型水稻土W层和潜育型水稻土G层粘粒氧化铁矿物均以针铁矿为主,其铝同晶替代量低(<15摩尔%),且颗粒细小,结晶度较低。这些结果反映了水稻土的成土条件和发生特点,同时对水稻土发生分类具有重要的意义。     

Influence of iron oxides on the non-specific anion (chloride) adsorption by soil

Soils from Denmark and Tanzania were extracted with ammonium acetate (controls), EDTA to dissolve amorphous iron oxides, and dithionite-EDTA (DE) to dissolve crystalline iron oxides. The amounts of chloride adsorbed by the extracted soils from 1 m NaCl at pH 5 and pH 7 were determined. The differences (ΔCl) between chloride adsorption at pH 5 and pH 7, attributed to variably charged groups, decreased when iron oxides were removed by EDTA and DE extraction. Close correlations (P>0.001), with negligible intercepts, were found (i)between EDTA-extractable iron (amorphous iron oxides) and the decrease in ΔCl following EDTA extraction, and (ii) between the difference between DE-extracted iron and EDTA-extractable iron (crystalline iron oxides) and the further decrease in ΔCL following DE extraction. The difference between ΔCl for acetate-extracted and DE-extracted samples was calculated from the contents and specific surfaces of amorphous and crystalline iron oxides, together with ΔCl per m² for synthetic iron oxides. Calculated and measured values were in very good agreement, indicating that soil iron oxides, in relation to chloride adsorption, may be treated as if they consist of only two fractions.     

The influence of iron oxides on the surface area of soil

Soils from Denmark and Tanzania have been extracted with ammonium acetate (controls), EDTA to dissolve amorphous iron oxides, and dithionite-EDTA (DE) to dissolve crystalline iron oxides. The surface areas of the extracted soils have been determined by applying the BET equation to nitrogen adsorption and by water adsorption at 19 percent relative humidity. High correlations (P < 0.001) were found (i) between EDTA-extractable iron (amorphous iron oxides) and the decrease in the surface area following EDTA extraction, and (ii) between the difference between DE-extractable iron and EDTA-extractable iron (crystalline iron oxides) and the further decrease in the surface area following DE extraction. The calculated specific surfaces of both the amorphous and the crystalline iron oxides varied from soil to soil but without any definite trend. The means of all the soils investigated may therefore serve as reasonable estimates of the specific surfaces of amorphous and crystalline iron oxides in soil.     

The influence of iron oxides on phosphate adsorption by soil

Soils from Denmark and Tanzania were extracted with ammonium acetate (controls), EDTA to dissolve amorphous iron oxides, and dithionite-EDTA (DE) to dissolve crystalline iron oxides. The phosphate adsorption capacities of the extracted soils were taken as the maximum quantity of phosphate adsorbed computed from the Langmuir equation. The decreases in the phosphate adsorption capacity following EDTA extraction and DE extraction were attributed to the removal of iron oxides. Close correlations (P<0.001) were found (i) between EDTA-extractable iron (amorphous iron oxides) and the decrease in phosphate adsorption capacity following EDTA extraction, and (ii) between the difference between DE-extractable iron and EDTA-extractable iron (crystalline iron oxides) and the further decrease in phosphate adsorption capacity following DE extraction. The phosphate adsorption capacity, estimated to be approximately 2.5 μmol P m^?2, was in good agreement with the capacity of various synthetic iron oxides. The calculated phosphate adsorption capacity of soil iron oxides, obtained from the contents and specific surfaces of amorphous and crystalline iron oxides together with the phosphate adsorption capacity per m² for synthetic iron oxides, compared favourably with the measured phosphate adsorption capacity.     

EXCHANGEABLE PHOSPHORUS, ESTIMATES OF IT FROM AMORPHOUS IRON OXIDES, AND SOIL SOLUTION PHOSPHORUS, IN RELATION TO PHOSPHORUS TAKEN UP BY MAIZE

Amounts of phosphorus taken up by maize plants during 23 days from an Entisol, two Alfisols and an Ultisol from Nigeria, each with three histories of management, were related to the concentration of soil phosphorus extracted in 0.01 m CaCl₂; but the relationships differed between kinds of management. Phosphorus in plants 51 days old was not related to concentration. Relationships of plant phosphorus with isotopically exchangeable phosphorus, and with phosphorus extracted from the soils by anion exchange resin, were poor in young plants but were good in the older plants, irrespective of field management. Amounts of phosphorus in the older plants were also well related to estimates of exchangeable phosphorus computed from P in solution and amounts of amorphous iron oxides extracted by ammonium oxalate from the soils, using equations derived in an earlier investigation with a larger group of soils. Thus estimates of exchangeable phosphorus made from simple measurements of the soil constituents that largely control it, and from extraction by resins, are potentially useful to indicate the ability of soils to supply phosphate to crops, and hence to guide fertilizer policies.     

Fractionation of extractable aluminum in acid soils: A review and a proposed procedure

Abstract

Different forms of soil aluminum (Al) are involved in the retention of anions and cations, phytotoxicity of Al in acid soils, CEC reduction and soil physical properties such as aggregate stability and water infiltration. Therefore it is desirable to quantify the different forms of Al in soil especially acidic soils. A rationale was developed from a literature survey to identify the following fractions of Al: (a) exchangeable quantified by 1M KC1 extraction; (b) organic bound quantified by 0.1M CuCl₂ + 0.5M KCl extraction; (c) sorhed Al extractable with 1M NE₄OAc at pH 4.0; (d) amorphous Al oxide and hydroxide and amorphous aluminosilicates (if present) extractable with 0.2M ammonium oxalate at pH 3.0; and (e) interlayered Al extractable with 0. 33M sodium citrate at pH 7.3. Pools (a), (b), and (c) are extracted sequentially. Amorphous Al oxide and hydroxide (pool d) is calculated from ammonium oxalate extractable Al minus (a + b + c). Interlayered Al is calculated from sodium citrate extractable Al minus ammonium oxalate extractable Al. The latter two extractions are done on separate subsamples of soils. From preliminary studies and data for 13 soil samples it is suggested that this fractionation of soil Al is more meaningful than that obtained by the KCl ‐> K₄P₂O₇ ‐> ammonium oxalate > citrate‐bicarbonate‐dithionite extraction sequence.     

Optimum conditions for extraction of Al,Fe, and Si from soils with acid oxalate

Abstract

Acid oxalate reagent was used at various concentrations, pH values, shaking times, and soil to solution ratios to find the optimum conditions for the extraction of Al, Fe, and Si from short‐range‐order materials in soils and stream‐bed deposits. The optimum conditions vary with the nature of the soil sample and its components. For most soils maximum amounts of Al, Fe, and Si were extracted with 0.15M acid oxalate reagent at pH 3.0 with a soil to solution ratio of 1:100 and shaking for 4 h in the dark at 20°C. Soils with more than 5% oxalate‐extractable Al or Fe require a 0.20M oxalate solution at pH 3.0 with a soil to solution ratio of 1:200.

Allophane is extracted by acid oxalate reagent after shaking for 2 h and it may be estimated from the 4 h oxalate‐extractable Si values. Ferrihydrite is extracted after shaking for 4 h, and it may be estimated from the oxalate‐extractable Fe values. Either sodium oxalate or ammonium oxalate may be used     

The formation of maghemite and hematite from lepidocrocite and goethite in a Cambisol from Corsica,France

The influence of a recent forest fire on the iron oxide phases, present in the A and the B horizon of a brown earth from Corsica, was examined by X-ray diffraction and chemical analysis. In the B horizon goethite and lepidocrocite, in the A horizon maghemite and hematite were identified. From the Al/(Al+Fe) ratio, which was determined for all four minerals by XRD, it was concluded that goethite was the precursor of hematite and lepidocrocite the precursor of maghemite respectively. The proportion of maghemite formed in the A horizon was calculated from the difference in Fe_d between the untreated sample and that free of maghemite. Because of substantial dissolution of clay minerals even after 5 citrate-bicarbonate treatments, it was not possible to determine Al_d correctly.     

第四纪红土的磁性与氧化铁矿物学特征及其古环境意义

应用矿物磁测,Ｘ－衍射和电镜技术对浙江省第四纪红土的磁性与氧化铁矿物学特征进行了研究。结果表明,均质层和网纹层的磁化率（χ）、频率磁化率（χｆｄ）、软剩磁（ＳｏｆｔＩＲＭ）、非滞后剩磁（ＡＲＭ）、饱和等温剩磁（ＳＩＲＭ）和剩磁矫顽力（（Ｂｏ）ｃｋ）等磁性参数存在明显差异,均质层的磁化率和饱和等温剩磁分别是网纹层的６倍和４倍;第四纪红土的磁化率主要由风化成土作用产生的超顺磁性颗粒（ＳＰ）和稳定单畴颗     

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.     

Iron oxide mineralogy of some soils of two river terrace sequences in Spain

The iron oxides of soils of two river terrace sequences in Spain which show an increasing degree of redness with age were studied. Clay fractions contained only small amounts of oxalate-extractable Fe. Goethite and hematite, the only crystalline Fe-oxides identified, were determined quantitatively by X-ray diffraction (XRD) after concentrating the Fe-oxides by boiling in $\text{5N}$ NaOH and subtracting the step-counted diffractogram of the deferrated clay from that of the non-deferrated clay, obtaining thus a “pure” Fe-oxide diffractogram. EDTA extracted hematite preferentially to goethite as is seen by loss of red colour and by XRD. A good correlation was found between the content of hematite in the fine earth and a redness rating based on Munsell notations.In the Guadalquivir River sequence, Fe_d and Fe_d/Fe_t increased with age. The amount of both goethite and hematite formed from silicate-Fe increased with soil age but hematite increased more than goethite, possibly due to the xeric soil environment. Also, goethite increased in crystallinity as indicated by a decrease in XRD line broadening and Fe_o/Fe_d ratios. No such trends were found in the Esla River sequence, possibly because the initial alluvium was already highly weathered as shown by high Fe_d/Fe_t values (0.8) irrespective of terrace level.Al substitution in goethite calculated from XRD increased with soil age, reflecting the increasing acidity of the soils. Al substitution in hematite was markedly lower.     

A TECHNIQUE FOR SELECTIVE SOLUTION OF IRON OXIDES IN THIN SECTIONS OF SOIL

A technique to study optically the effects of three different extraction procedures for removing iron from thin sections of soil is described. The distribution of iron in each section is recorded before treatment. Silicone grease is then applied to all parts of the sections except those to be treated. The areas selected for treatment are immersed for 24 hours in one of three beakers containing dithionite-citrate-bicarbonate, 02M ammonium oxalate at pH₃ and 01M K-pyrophosphate at pH10. After treatment, the sections are degreased and the effects of the various treatments examined optically.     

COMPARISON OF AQUEOUS ACETYLACETONE AND POTASSIUM PYROPHOSPHATE SOLUTIONS FOR SELECTIVE EXTRACTION OF ORGANIC-BOUND Fe FROM SOILS

Seven samples of iron oxyhydroxides, characterised by crystallinity and surface area (monolayer water content), were examined for solubility in aqueous acetylacetone (0.68 M), potassium pyrophosphate pH 10 (0.1 M) and acid ammonium oxalate pH 3 (0.2 M). Solubilities in acetylacetone and oxalate were dependent on surface area, being 30 per cent Fe or more for non-crystalline oxides in 40 h. Solubility in pyrophosphate was 2 per cent Fe or less in 40 h even when surface area was 300 m²/g. Pyrophosphate solution was more suitable than aqueous acetylacetone for selective extraction of iron-organic complexes from soils which contain amorphous or poorly crystalline 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。     

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.     

Dissolution of Poorly Crystalline Iron Oxides in Soils by EDTA and Oxalate

Poorly crystalline iron oxides in soils are often estimated by 2 hours oxalate extraction at pH 3 and less often by 3–7 months EDTA extraction at pH 7.5–10.5. Calculated solubility products (Ksp) of iron oxides in equilibrium with EDTA and oxalate showed EDTA to dissolve only iron oxides with Ksp > 10^?40-10^?41 at pH > 10, whereas at pH 3 oxalate (and EDTA) should theoretically dissolve all iron oxides. The different pHs could largely account for the great difference in extraction speed between the two methods. Although EDTA and oxalate seem to act by surface complexation, where the adsorbed ligand by attenuating lattice Fe-O bonds causes iron detachment, the mechanisms are considered to be different. Possibly EDTA forms tetranuclear surface complexes, which are considered to inhibit dissolution of well crystallized but not poorly crystallized iron oxides due to differences in bond strengths. Oxalate forming binuclear and mononuclear surface complexes can probably also act as an electron bridge between iron(II) in solution and surface iron(III) leading to iron(II) catalyzed dissolution of iron oxides. This mechanism is obviously of particular importance in the dissolution of magnetite and maghemite. Despite the great theoretical differences the published methods with EDTA and oxalate dissolve comparable amounts of iron from many soils and the dissolved iron corresponds to poorly crystalline (highly reactive) iron oxides, mainly ferrihydrite.     

浙江省三种红、紫色砂页岩发育土壤的矿物学研究

本文用Ｘ射线衍射分析,红外光谱分析、透射电镜及Ｘ射线荧光分析对浙江省三种红、紫色砂页岩发育的红砂土、紫砂土和红紫砂土的矿物进行了分析。     

土壤和氧化铁对氟化物的吸附和解吸

本文研究了两种土壤(砖红壤和黄棕壤)和两种合成氧化铁(无定形氧化铁和针铁矿)对氟化钠溶液的吸附和解吸现象,讨论了氟离子吸附的吸附等温线特征.根据实验资料和吸附等温线的拟合情况,我们认为,砖红壤和无定形氧化铁用Langmuir公式来描述,黄棕壤和针铁矿用Freundlich公式来描述更为适宜.氟离子的解吸量均低于吸附量.研究结果表明,由于水洗和醇洗,一部分以静电引力所吸附的氟离子被洗去,造成氟离子解吸量偏低.