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.     

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.     

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.     

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.     

Differenzierung oxalatlöslicher Eisenoxide

Differentiation of oxalate soluble iron oxides According to their mode of formation the oxalate soluble Fe(III)-oxides show different rates of dissolution especially within the first 30 min of oxalate extraction. Precipitates formed by bacterial or oxidative decomposition of ferric citrate have a very high dissolution rate with more than 90 percent being dissolved within 30 min. Ferrihydrites prepared by alkaline hydrolysis of Fe(III) salts, after slow drying, dissolve to about 60 to 80 percent within this period, whereas similar products quenched with liquid N₂ dissolve more rapidly. A plot of (Fe₃₀/Fe_o) vs. (Fe_o/Fe_d) allows to draw a boundary line between the field of podzol values and the field of the other pedogenic iron oxides, as from brown earths and black earths (chernozems).     

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.     

SELECTIVE EXTRACTION OF AMORPHOUS IRON OXIDE BY EDTA FROM A MIXTURE OF AMORPHOUS IRON OXIDE, GOETHITE, AND HEMATITE

Iron (III) was extracted by EDTA and ammonium oxalate from a model substance consisting of amorphous iron oxide, goethite, and hematite precipitated in the presence of quartz sand. Even by varying the EDTA concentration between 0.02 and 0.1 M, pH between 4.40 and 6.00, the solid:solution ratio between I:25 and I:250, and using extraction times up to go days, it was found that EDTA was able to extract only a limited amount of iron. In contrast, 0.2 M ammonium oxalate at pH 3.0 is able to dissolve all the iron compounds if the extraction time is sufficient. Nevertheless, the amount of EDTA-extractable iron is equal to the amount of iron extracted after 4–5 hours with ammonium oxalateat pH 3.0. From X-ray analysis, DTA curves, a solubility product determination, and a kinetic investigation, it is concluded that the EDTA-extractable fraction consists of X-ray amorphous iron oxide, less soluble than polymeric iron hydroxide, and presumably only one compound. Therefore, it is concluded that it may be possible by means of EDTA to carry out a selective extraction of X-ray amorphous iron oxides mixed with goethite and hematite.     

Sodium hypochlorite oxidation reduces soil organic matter concentrations without affecting inorganic soil constituents

Oxidative treatment can isolate a stable organic matter pool in soils for process studies of organic matter stabilization. Wet oxidation methods using hydrogen peroxide are widely used for that purpose, but are said to modify poorly crystalline soil constituents. We investigated the effect of a modified NaOCl oxidation (pH 8) on the mineral composition of 12 subsoils (4.9–38.2 g organic C kg^?1) containing varying amounts of poorly crystalline mineral phases, i.e. 1.1–20.5 g oxalate‐extractable Fe kg^?1, and of different phyllosilicate mineralogy. Post‐oxidative changes in mineral composition were estimated by (i) the determination of elements released into the NaOCl solution, (ii) the difference in dithionite‐ and oxalate‐extractable Si, Al and Fe, and (iii) the specific surface areas (SSAs) of the soils. The NaOCl procedure reduced the organic C concentrations by 12–72%. The amounts of elements released into the NaOCl extracts were small (≤ 0.14 g kg^?1 for Si, ≤ 0.13 g kg^?1 for Al, and ≤ 0.03 g kg^?1 for Fe). The SSA data and the amounts of dithionite‐ and oxalate‐extractable elements suggest that the NaOCl oxidation at pH 8 does not attack pedogenic oxides and hydroxides and only slightly dissolves Al from the poorly crystalline minerals. Therefore, we recommend NaOCl oxidation at pH 8 for the purpose of isolating a stable organic matter pool in soils for process studies of organic matter stabilization.     

Comparison of Prewashing Procedures for the Assessment of Phosphate Rock Dissolution in Soils

When evaluating phosphate rock (PR) dissolution, previous to the extraction with sodium hydroxide (NaOH), dry soil samples with PR were extracted with three solutions to remove exchangeable and solution calcium (Ca) [sodium chloride (NaCl) 1 M, buffered NaCl with ethylenediaminetetraacetic acid (EDTA) (NaCl–EDTA), and NaCl buffered at pH 7 with triethanolamine (TEA) (NaCl–TEA)] for comparison with the extraction of soil samples without any prewash. In acidic soils, up to 51% of applied P was recovered during the NaCl extraction because of the high exchangeable acidity released during the extraction. In soils with exchangeable Ca>2 cmol₍₊₎kg^?1, high EDTA quantities also promoted PR dissolution. The NaCl–TEA solution efficiently removed Ca, avoiding PR dissolution and P retention by calcium hydroxide [Ca(OH)₂] during the NaOH extraction. Thus, when evaluating PR dissolution we recommend the use of NaCl–TEA to remove Ca. We also recommend the same procedure when applying the Chang and Jackson fractionation to calcareous soils and soils submitted to PR application.     

Minerals controlling arsenic distribution in floodplain soils

As a consequence of intensive mining of the western Erzgebirge since medieval times, floodplain soils of the Mulde river contain large concentrations of arsenic (As) (>50 mg kg⁻¹). Arsenic in soil is often bound to poorly crystalline Fe and Mn (hydr)oxides, which may dissolve under reducing conditions. Part of the As may also exist in primary minerals, predominately sulphides, or in secondary minerals formed upon weathering. In order to better understand the impact of seasonal flooding, we surveyed As‐bearing mineral phases, especially of iron (Fe) (hydr)oxides. Because Fe (hydr)oxides are clay‐sized, soil samples were fractionated into six particle‐size fractions. The fractions were digested with aqua regia for determination of total element concentrations, extracted with hydroxylammonium chloride (NH₃OHCl; selective for Mn (hydr)oxides and NH₄ oxalate), and analysed by X‐ray diffraction and scanning electron microscopy. The largely similar distribution of As and lead (Pb) suggested the potential co‐existence of the two elements in primary or secondary mineral phases. However, neither As–Pb minerals nor any other As mineral were detected. Association with Mn oxides was negligible. The predominant As‐bearing phases were poorly crystalline Fe (hydr)oxides, which also incorporated large amounts of Pb and were affected by redox dynamics.     

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.     

What Constitutes Plant-Available Molybdenum in Sandy Acidic Soils?

Molybdenum (Mo) is critical for the function of enzymes related to nitrogen cycling. Concentrations of Mo are very low in sandy, acidic soils, and biologically available Mo is only a small fraction of the total pool. While several methods have been proposed to measure plant-available Mo, there has not been a recent comprehensive analytical study that compares soil extraction methods as predictors of plant Mo uptake. A suite of five assays [total acid microwave digestion, ethylenediamenetetraaacetic acid (EDTA) extraction, Environmental Protection Agency (EPA) protocol 3050B, ammonium oxalate extraction, and pressurized hot water] was employed, followed by the determination of soil Mo concentrations via inductively coupled mass spectroscopy. The concentrations of soil Mo determined from these assays and their relationships as predictors of plant Mo concentration were compared. The assays yielded different concentrations of Mo: total digest > EPA > ammonium oxalate ≥ EDTA > pressurized hot water. Legume foliar Mo concentrations were most strongly correlated with ammonium oxalate–extractable Mo from soils, but an oak species showed no relationship with any soil Mo fraction and foliar Mo. Bulk fine roots in the 10- to 30-cm soil horizon were significantly correlated with the ammonium oxalate Mo fraction. There were significant correlations between ammonium oxalate Mo and the oxides of iron (Fe), manganese (Mn), and aluminum (Al). Results suggest that the ammonium oxalate extraction for soil Mo is the best predictor of plant-available Mo for species with high Mo requirements such as legumes and that plant-available Mo tracks strongly with other metal oxides in sandy, acidic soils.     

Iron oxides in four Red Mediterranean soils on metarhyolite and metadolerite in Kilkis,Greece

The various iron fractions were quantified by selective dissolution (Fe_d, Fe_o, Fe_t) in four Red Mediterranean soils, developed on metarhyolite and metadolerite. They were similar in all profiles. A strong trend of iron removal from the surface horizon and of its subsequent illuvial translocation to the argillic horizons was observed. In all profiles, Fe_o was not related to the organic matter content indicating the Mediterranean xeric soil environment. The Fe_o/Fe_d ratio and the percentage of crystalline iron oxides (Fe_d-Fe_o) suggested that the pedoenvironment in which the profiles P1, P2 were formed, allowed the high crystallization of iron oxides. As indicated by the Fe_d/Fe_t values, the weathering process was more intense in the metarhyolite-developed soils. In contrast, the metadolerite-developed soils present conditions of poorly crystallized iron oxides and a lower degree of development.     

Influence of organic matter on phosphate adsorption by aluminium and iron oxides in sandy soils

The phosphate adsorption capacity (P_max) of samples from various horizons of five Danish podzolized soils were investigated before and after organic matter removal. Removal of organic matter had no direct influence on P_max suggesting that organic matter did not compete with phosphate for adsorption sites. In the soils investigated aluminium and iron oxides were the main phosphate adsorbents. Thus, more than 96% of the variation in P_max could be accounted for by poorly crystalline aluminium and iron oxides (extractable by oxalate) and by well-crystallized iron oxides (taken as the difference between dithionite-citrate-bicarbonate-extractable iron and oxalate-extractable iron). Organic matter affected phosphate adsorption indirectly by inhibiting aluminium oxide crystallization. The resulting poorly crystalline oxides had high P_max. In contrast, the influence of organic matter on the crystallinity of the iron oxides, and therefore on their capacity to adsorb phosphate, seemed limited.     

Selective sequential dissolution techniques for trace metals in arid‐zone soils: The carbonate dissolution step

Abstract

Dissolution capacity and kinetics of carbonates by sodium acetate (NaOAc)‐acetic acid (HOAc) at various pHs were studied. A comparative study of the selectivity, specificity, and effectivity of NaOAc‐HOAc solution on carbonate bound fraction during the sequential selective dissolution procedure was conducted by comparing the dissolution of major and trace elements from arid zone soils by this buffer solution at various pHs. The effect of the pH of NaOAc‐HOAc solution on the following fractions in the sequential selective dissolution procedure was also studied. NaOAc‐HOAc solution at pH 5.5 at a soil to solution ratio of 1:25, can dissolve all the carbonate from calcareous soils with 10–20% of carbonate; at pH 5.0 it can dissolve all the carbonate in soils with about 30–50% calcium carbonate (CaCO₃). A second extraction with fresh buffer solution at pH 5.0 is required for soils with more than 50% of carbonate. Six hours of extraction time is generally sufficient for complete carbonate dissolution. For most of agricultural soils in arid and semi‐arid zones, the attack of the buffer solution at pH 5.0 on other solid‐phases seems to be limited. But the buffer solution at pH 5.5 would be better for some forest soils with low carbonate content and high organic matter content. The part of carbonate fraction not be dissolved in this step is released in the following steps: easily reducible oxides fraction (ERO), organic matter fraction (OM), and reducible oxides fraction (RO), leading to gross misinterpretation of the elemental partitioning in arid zone 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.     

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.     

Extraction of inorganic forms of translocated Al, Fe and Si from a podzol Bs horizon

A range of extractants commonly used in soil studies, both to clean up the crystalline clay minerals by dissolving poorly ordered phases, and to assist in the classification of soils, has been used to assess their efficiency in extracting inorganic forms of translocated Al, Fe and Si from a podzol Bs horizon. A 4 h extraction with ammonium oxalate pH 3 is the most efficient single procedure for these phases. It is concluded that satisfactory characterization of a podzol B horizon requires the use of two extractants: acid oxalate to assess the total amounts of Al, Fe and Si in non-crystalline weathering products, and pyrophosphate to assess the amounts in organic forms. Dithionite-citrate-bicarbonate gives a measure of total free iron oxides, but extracts only an ill-defined fraction of the allophane-imogolite complex.