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1.
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.  相似文献   

2.
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.  相似文献   

3.
The extraction of soil organic phosphorus by the NaOH–EDTA procedure was assessed in detail for a tropical forest soil (clay‐loam, pH 4.3, total carbon 2.7%). Optimum conditions for the quantification of soil organic phosphorus and characterization of its composition by solution 31P NMR spectroscopy were extraction in a solution containing 0.25 m NaOH and 50 mm Na2EDTA in a 1:20 solid to solution ratio for 4 hours at ambient laboratory temperature. Replicate analyses yielded a coefficient of variation of 3% for organic phosphorus as a proportion of the spectral area. There was no significant difference in total phosphorus extraction from fresh and air‐dried soil, although slightly more organic phosphorus and less paramagnetic ions were extracted from dried soil. The procedure was not improved by changing the concentration of NaOH or EDTA, extraction time, or solid to solution ratio. Pre‐extraction with HCl or Na2EDTA did not increase subsequent organic phosphorus extraction in NaOH–EDTA or improve spectral resolution in solution 31P NMR spectroscopy. Post‐extraction treatment with Chelex resin did not improve spectral resolution, but removed small concentrations of phosphorus from the extracts. Increasing the pH of NaOH–EDTA extracts (up to 1.0 m NaOH) increased the concentration of phosphate monoesters, but decreased DNA to an undetectable level, indicating its hydrolysis in strong alkali. The standardized NaOH–EDTA extraction procedure is therefore recommended for the analysis of organic phosphorus in tropical forest soils.  相似文献   

4.
One technique for cleansing heavy metal contaminated soils is to wash the excavated soil with an extraction solution of a chelating agent. The rate of extraction is an important parameter when considering the length of time needed for soil clean-up and the amount and concentration of wash solution required. The extraction kinetics of copper, zinc, iron and manganese from a contaminated sediment of the Clark Fork River in western Montana, U.S.A., with Disodiun Ethylenediaminetetraacetate (Na2EDTA) as the extraction agent, were investigated. The results showed the extraction process consisted of rapid extraction in the first minutes followed by much slower extraction for the remainder of the experiment. The rate of extraction, particularly in the rapid phase, demonstrated clear pH dependence: the lower the pH, the faster the extraction rate. In the EDTA concentration range of 0.01 M to 0.05 M, the effect of the EDTA concentration on the extraction rate was not important compared with that of the solution pH. Extraction kinetics for different size particles were similar, although in the first few minutes, EDTA extracted more metals from clay and silt than sand. The two reaction, diffusion, and two-constant kinetic models were compared to experimental results. The two reaction model did not fit any of the data well, and only iron extraction could be described with a simple diffusion model. In general the extraction rates can be well described by the two-constant model, C=A t B, up to 600 minutes and under different conditions such as solution pH, EDTA concentration, and different sediment particle size.  相似文献   

5.
Abstract

Soil extraction techniques to measure the status of available micronutrients for plants are important in the diagnosis of deficiency or toxicity. Mehlich 3 (M3), EDTA (pH=8.2), DTPA‐TEA, and Soltanpour and Schwab (SS) solutions were confronted for their ability to extract simultaneously copper (Cu), zinc (Zn), manganese (Mn), and iron (Fe). Argentinean soils from different taxonomic orders with widely varying properties were investigated. The values obtained showed that DTPA‐TEA and SS solutions extracted similar amounts of Zn, Fe, and Mn, while EDTA dissolved comparatively higher amounts of Fe and Mn. Mehlich 3 yielded the highest extractions for the four micronutrients. Soil pH not only affected the extraction of Mn by DTPA‐TEA, SS, and EDTA extractions, but also the extraction of Fe by EDTA. The organic carbon affected the determination of Fe and Zn in all cases. The correlations of the different tests for Cu, Zn, Mn, and Fe were significant. The results suggest that for the determination of the bioavailable status of micronutrients, any of the studied tests could be applied using the soil edaphic properties as factors to improve the correlations between them and standardize the methods.  相似文献   

6.
Abstract

Alfisols, Vertisols, Inceptisols, Aridisols, Mollisols, and Entisols were sampled (0–30 cm) from 32 locations across Ethiopia. The soils were analyzed for copper (Cu), zinc (Zn), manganese (Mn), and iron (Fe) contents using 0.005 M diethylene triamine pentaacetic acid (DTPA), 0.05 M hydrochloric acid (HC1), and 0.02 M ethylene diamine tetraacetic acid (EDTA) extractants. EDTA extracted more of each micronutrient than DTPA, which extracted greater amounts than HC1. The quantities of EDTA and DTPA‐extractable micronutrients were significantly correlated, and were in the order: Mn>Fe>Cu>Zn. The order of HCl‐extractable micronutrients was Mn>Fe>Zn>Cu. Micronutrient contents of Mollisols, Vertisols, and Alfisols were usually greater than those of the other soils, and Entisols usually had the lowest micronutrient contents. The contents were mostly positively correlated with clay and Fe2O3 contents, but negatively correlated with soil pH and A12O3contents. While comparison of DTPA‐ and EDTA‐extractable micronutrients with critical levels showed that most soils had adequate amounts of the micronutrients for crops, the amounts extracted by HC1 were below critical levels in most soils. Since the critical levels that were used in the comparisons were not established in Ethiopia, calibration of the soil contents of these micronutrients with crops grown in Ethiopia is required to identify the most suitable extractant(s).  相似文献   

7.
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.  相似文献   

8.
A pre-lysis buffer washing procedure was introduced to DNA extraction from a forest soil with high organic matter and iron oxide contents. Sodium phosphate of 0.1 M (pH 7.5) was used as a buffer to wash soil samples when subsequent lysis buffer was phosphate, and 20 mM EDTA (pH 7.5) was used when subsequent lysis buffer included EDTA. Initial experiments were not successful because the DNA extracts could not be amplified by polymerase chain reaction (PCR). The consideration of introducing a pre-lysis washing procedure was based on the idea that the washing should promote soil dispersion and homogeneity, decrease DNA adsorption by soil components (e.g. iron oxides), and remove covalent cations and those easily-dissolving organic compounds from the soil samples. Results revealed that humic substance content decreased by 31%, but DNA yield increased by 24% in the DNA extracts of the pre-lysis washing procedures, compared to the non-washing procedures. DNA extracted by the pre-washing procedure needed less purification for subsequent 18S and 16S rDNA PCR amplifications. It was recommended that the pre-lysis buffer washing should be used for DNA extraction from those difficult environmental samples, such as the forest soil with high contents of organic matter and iron oxides.  相似文献   

9.
Abstract

Investigations have examined the effects of extraction period and soil:solution ratio on the extraction of zinc from some New Zealand soils by EDTA, DTPA, HCl, Ca(NO3)2 and CH3COONH4. A high proportion of the zinc extracted by EDTA, DTPA, HCl, and Ca(NO3)2 was extracted rapidly, within the first 0.5 h, followed by small increases over the next 15 h. An exception occurred with a soil containing iron/manganese concretionary material. In this soil, with both EDTA and DTPA, there were significant increases in the amount of zinc extracted between 1 and 8 h. The amounts of zinc extracted by CH3COONH4 increased gradually with the time of extraction up to approximately 4 h.

Substantial increases in the amounts of zinc extracted with HCl, Ca(NO3)2 and CH3COONH4 were obtained by increasing the soil:solution ratio from 1:2.5 to 1:10. However, soil:solution ratio has little effect on the amounts of zinc extracted by EDTA or DTPA.  相似文献   

10.
Abstract

We evaluated the validity of Tessier’s method as applied to the extraction of manganese (Mn) and iron (Fe) oxides in Japanese Andisols and other soil types in Japan. Using the original Tessier’s extractant mixture, 0.04 mol L?1 hydroxylamine hydrochloride in 25% acetic acid (0.04 mol L–1 NH2OH-HCl in 25% HOAc), we found that substantial amounts of short-range-ordered Fe oxides were not extracted from allophanic Andisol samples and that considerable amounts of total Fe oxides were not extracted from all soil types. Relatively high extraction pH and large amounts of short-range-ordered Fe oxides in the Andisol samples might be responsible for incomplete extraction. Stoichiometric calculation indicated that the concentration of NH2OH-HCl might be insufficient for complete extraction of Fe oxides. The extracted amounts of Mn and Fe increased with increasing concentration of NH2OH-HCl in the extractant, and most of the Mn and Fe oxides in the soil samples, including samples with as much as 5.6% Fe, were extracted with 0.6 mol L–1 NH2OH–HCl in 25% HOAc. As judged from the simultaneous dissolution of aluminum (Al) and silicon (Si) minerals, extraction selectivity of Fe oxides with 0.6 mol L–1 NH2OH-HCl in 25% HOAc was comparable to that of the original Tessier’s method and better than that of a modified Community Bureau of Reference (BCR) sequential extraction procedure or a method using an extractant consisting of a mixture of oxalate and ascorbate, especially for Andisol samples.  相似文献   

11.
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.  相似文献   

12.
Mössbauer and ESR spectroscopy have shown that the iron extracted from the Bh horizons of an iron humus podzol and an iron podzol by EDTA at pH 9.1 is predominantly in the form of complexes * 1 The use of the word ‘complex’ in this paper in the context of polymeric iron species and organic matter is not intended to imply any single specific type of complex, such as exists in Fe(II1) EDTA, for example, but to embrace many possible modes of association including salt formation, direct coordination, Van der Waal's adsorption, and electrostatic attraction.
of polymeric Fe(III) hydroxide and oxide with organic matter (O.M.). Small amounts of monomeric Fe(III)-O.M. and Fe(III)-EDTA complexes also occur. In contrast EDTA at pH 7 extracts iron from these podzols predominantly in the form of iron-EDTA complexes. Some monomeric Fe(III)-O.M. complex also occurs in a pH 9.1 NH4 OH extract of these horizons and in a pH 9.1 EDTA extract of the B3 horizon of a peaty podzol. Dialysis experiments show that the particle dimensions of the polymeric hydroxy Fe(III)-O.M. complex, which accounts for about 66% of the Fe extracted from the iron humus podzol and about 36% of that from the iron podzol, are greater than 2.4 nm. The thermal behaviour of the Mössbauer peaks indicated that the size of the iron cores was of the order of 5 nm, thus suggesting that the complex probably consists of hydroxyiron cores surrounded by large organic molecules. Results from XRD and IR suggest that these hydroxyiron cores may have structural organizations similar to those of goethite and ferrihydrite. The relationship between these forms of iron in the extracts and those in the soil is briefly discussed.  相似文献   

13.
A reliable soil test is needed for estimating mercury (Hg) availability to crop plants. In this study, four extraction procedures including 0.1 M hydrochloric acid (HCl), 1 M ammonium acetate (NH4OAc) (pH 7.0), 0.005 M diethylenetriaminepentaacetic acid (DTPA), and 0.1 M calcium chloride (CaCl2) (pH5.0) were compared for their adequacy in predicting soil Hg availability to crop plants of a rice–cabbage–radish rotation system. The amounts of Hg extracted by each of the four procedures increased with increasing equilibrium time. The optimal time required for extraction of soil Hg was approximately 30 min, though it varied slightly among the four extractants. The amounts of Hg extracted decreased with increasing soil/solution ratio, and a soil/solution ratio of 1:5 appeared to be adequate for soil Hg availability tests. The amounts of Hg extracted increased in the order of NH4OAc < CaCl2 < DTPA < HCl in silty loam soil (SLS) soil, and the order was NH4OAc < CaCl2 ≈ DTPA < HCl in yellowish red soil (YRS) soil. Significant positive correlations among the four extractants were obtained in SLS soil. In contrast, the correlations were poor in YRS soil, especially for HCl. There were significant correlations between concentrations of Hg in edible tissue of three plants and the amounts of soil Hg extractable to the four extractants for soil–rice system and soil–radish system, but not for soil–Chinese cabbage system. The 0.1M HCl extraction overall provided the best estimation of soil‐available Hg and could be used to predict phytoavailability of Hg in soil–crop systems.  相似文献   

14.
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15.
The more labile forms of aluminium in a range of soils from areas of permanent grassland were determined with a number of selective extractants. The amounts of exchangeable A1 extracted with molar KCl were dependent upon pH, while the amounts exchangeable with 0.3 M LaCl3, although much greater, were not well correlated with pH. There were good correlations between soil organic C content and A1 extracted by (i) 0.5 M EDTA and (ii) 0.1 M potassium pyrophosphate. Pyrophosphate extracted greater amounts than any of the other extractants (sodium citrate/dithionite, ammonium oxalate (dark), acid oxalate (UV radiation), as well as those already mentioned). It was concluded that much of the extractable A1 in soils was associated with organic matter. Addition of lime to one of the soils reduced the amount of A1 extracted by all reagents except dithionite and acid oxalate solutions. There were considerable differences between soils in their release of A1 to continuous leaching with 0.01 M CaCl2. Despite these differences between the soils in organically bound extractable Al, the differences in the amounts and patterns of release of A1 with CaCl2 did not appear to be related to organic matter contents, nor to the other determined properties.  相似文献   

16.

Purpose

The purpose of the present study was to investigate the distribution of antimony (Sb) and its species in soil fractions in order to understand better the real risk associated with Sb in the environment.

Materials and methods

Nine surface soil samples contaminated from lead/zinc and iron smelting operations and coal fired power plants were examined using: (1) four-step sequential extraction procedure (BCR); (2) two-step sequential extraction including ethylenediaminetetraacetic acid (EDTA), sodium hydroxide (NaOH) and NH4F; and (3) single extraction with EDTA and NaOH. Liquid phase extraction was used for redox speciation of Sb. The distribution of Sb between soil fulvic and humic acids was determined after their chemical separation. The concentrations of Sb were measured by electrothermal atomic absorption spectrometry.

Results and discussion

The main part of total Sb (2.5–105 mg?kg?1) was associated with the residual fraction in all soils. The exchangeable/carbonate-bound concentrations were 0.83–4.7 % of total Sb. Up to 6.8 % was in the reducible and up to 1.4 % was in the oxidizable fraction. EDTA removed 7.2–11.4 % of total content. Sb(V) was the predominant form in acetic acid and EDTA extracts. Single extraction with 0.1 mol?l?1 NaOH released up to 13.7 % of soil antimony. The main part of Sb was complexed to the higher molecular weight fraction of soil-derived humic substances.

Conclusions

For highly contaminated soils, 4 % solubility in acetic acid could represent risk of contamination of ground water under specific conditions. Also, the relatively high phytoavailable Sb (7–11 %) can represent a significant proportion in highly polluted soils. Pentavalent antimony was the main antimony species extracted from soils. The main part of the organically antimony was found to be present as complexes with higher molecular weight humic acids fraction.  相似文献   

17.
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.  相似文献   

18.
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.  相似文献   

19.
We investigated the extractability of manganese (Mn) and iron (Fe) oxides from typical Japanese soils (Entisols, Inceptisols, and Andisols) by 0.5?mol?L?1 hydroxylamine hydrochloride (NH2OH-HCl) extraction (pH 1.5; 16?h shaking at 25°C; soil:solution ratio 1:40), referred as to HHmBCR, which is Step 2 (used for the reducible fraction) of the modified BCR (Community Bureau of Reference) sequential extraction procedure. The HHmBCR procedure extracted almost all Mn oxides from the non-Andisol samples, but failed to extract a part of the Mn oxides from some Andisol samples. The procedure extracted most short-range ordered Fe oxides from non-Andisol samples, but it extracted only 7.5% and 13% of the short-range ordered Fe oxides from allophanic and non-allophanic Andisol samples, respectively. This remarkably low extractability of Fe oxides suggests that the HHmBCR method is not suitable for extracting oxide-occluded heavy metals from Andisols. Since the extraction rate of short-range ordered Fe oxides from various soils with the extractant was negatively correlated with the amounts of oxalate- and pyrophosphate-extractable Al even when the variability of the extraction pH was reduced by increasing the soil:solution ratio from 1:40 to 1:500, the extractability of Fe oxides would be negatively affected by the presence of active Al, including allophane/imogolite, amorphous Al, and Al-humus complexes. Because these Al constituents are abundant in Andisols, they would be at least partially responsible for the lower extractability of Fe oxides by HHmBCR from Andisols.  相似文献   

20.
We assessed cadmium (Cd) and zinc (Zn) availability when applying reactive phosphate rock (RPR) in combination with lime and chicken manure on Indonesian acidic upland soils. Maize plants were grown on unamended soil and soils treated with several combinations of 2 tons dolomite ha–1, 2 tons of chicken manure ha–1, 1 ton ha–1 of RPRL (reactive phosphate rock containing 4 mg Cd kg–1 and 224 mg Zn kg–1), and 1 ton ha–1 of RPRH (RPR containing 69 mg Cd kg–1 and 745 mg Zn kg–1). In addition to its positive effect on plant yield, application of RPR in combination with chicken manure did not result in toxic Cd concentrations. Although liming is effective to reduce plant Cd concentrations, it results in more soil Cd accumulation and more plant Zn deficiency. Cadmium and Zn concentrations in shoots and grains can be predicted well from amounts extracted from the soil by 0.5 M ammonium (NH4) acetate + 0.02 M ethylenediaminetetraacetic acid (EDTA) at pH 4.65.  相似文献   

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