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1.
Eleven horizons of acidic soils in mid-Wales developed from Lower Palaeozoic sedimentary rocks were examined. Selective extraction of Al and Si provided evidence against the occurrence of significant quantities of poorly ordered Al-silicates. Fe0 was weakly correlated with Al0, but very closely correlated with Al0 minus Al extracted by cold 5% Na2CO3, implying that poorly ordered Al occurs in part as a substituent in Fe oxide and in part in a form unassociated with Fe oxide. Support for this was obtained by analysis of oxide fractions concentrated from aqueous suspensions by sequential ultracentrifugation and through the examination of synthetic Al-substituted Fe oxides. Fe oxide containing Al substituted at an almost constant level was the dominant constituent of the poorly ordered fraction in four of the five Bs horizons examined. The occurrence of Al in this form is an important mechanism by which Al is retained in aerobic but highly acidic Bs horizons.  相似文献   

2.
The effect of liming the A and B horizons of a number of acid soils on the subsequent adsorption of phosphate by soils retained moist or allowed to dry was investigated. Air-drying increased the phosphate adsorption capacity but the reason was not clear. When A horizons were maintained moist, incubation with lime for six weeks increased phosphate adsorption by four samples and had no effect on another. When A horizons were air-dried, the effect was considerably reduced or reversed. For B horizons, which had considerably greater phosphate adsorption capacities than A horizons, liming decreased phosphate adsorption irrespective of whether the soils remained moist or were dried. The relative decrease in adsorption was, however, greater when the soils were dried. In a more detailed study using one acid soil it was shown that incubation of the soil with lime for six weeks had no effect on phosphate adsorption by moist A and B horizons but after 36 weeks incubation liming decreased adsorption by the moist samples. If soils were dried then liming decreased phosphate adsorption after six or 36 weeks incubation. Such relative effects of liming on phosphate adsorption were confounded by the fact that air-drying greatly increased the phosphate adsorption capacity of the unlimed soil. The drying effect was at least partially reversible following rewetting of the soil. Results were interpreted in terms of the lime-induced increase in soil pH causing (i) the surface charge conferred on soil oxide surfaces to become more negative (thus decreasing phosphate adsorption) and (ii) the precipitation of exchangeable Al as hydroxy-Al polymers resulting in the formation of new, highly active, adsorbing surfaces (thus increasing phosphate adsorption). Phosphate adsorption by moist limed soils can, therefore, be increased, decreased or unaffected depending on the relative magnitudes of these two processes. It is suggested that after liming, and/or air-drying, crystallization of amorphous materials progressively decreases their surface area and adsorbing capacity. Thus, liming tends to decrease phosphate adsorption when the soils are dried.  相似文献   

3.
The study about the adsorption of phosphate on four variable charge soils and some minerals revealed that two stage adsorption appeared in the adsorption isotherms of phosphate on 4 soils and there was a maximum adsorption on Al-oxide-typed surfaces between pH 3.5 to pH 5.5 as suspension pH changed from 2 to 9, but the adsorption amount of phosphate decreased continually as pH rose on Fe-oxide typed surfaces. The adsorption amount of phosphate and the maximum phosphate adsorption pH decreased in the order of yellow-red soil > lateritic red soil > red soil > paddy soil, which was coincided with the content order of amorphous Al oxide. The removement of organic matter and Fe oxide made the maximum phosphate adsorption pH rise from 4.0 to 5.0 and 4.5, respectively. The desorption curves with pH of four soils showed that phosphate desorbed least at pH 5. Generally the desorption was contrary to the adsorption with pH changing.  相似文献   

4.
The phosphate adsorption capacity (Pmax) 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 Pmax 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 Pmax 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 Pmax. In contrast, the influence of organic matter on the crystallinity of the iron oxides, and therefore on their capacity to adsorb phosphate, seemed limited.  相似文献   

5.
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.  相似文献   

6.

Background

Glyphosate (GLP) is a widely used herbicide with possible adverse effects on human health and the environment. In soils, GLP strongly adsorbs on clay-sized minerals, depending on pH, the amount of organic carbon, as well as the contents and properties of Al and Fe oxyhydroxides and clay minerals. Many clay-sized minerals have already been investigated regarding GLP adsorption behavior, but information on minerals commonly found in volcanic soils is still lacking.

Aim

The aim of this study was to investigate for the first time the pH-dependent adsorption of GLP on allophane and halloysite, typical minerals found in volcanic soils.

Methods

GLP adsorption was studied in batch experiments at three pH values (5, 6, and 7). Synthetic allophanes with two different initial Al:Si ratios (1.4 and 1.8) and a halloysite were used as adsorbents.

Results

The adsorption capacity (AC) increased with rising Al:Si ratio and decreasing pH. The AC of allophane was significantly higher than that of halloysite. GLP adsorption on allophane was larger than that reported for other clay minerals and Al and Fe oxyhydroxides, especially at low pH. The AC of halloysite was higher than reported for most other clay minerals.

Conclusion

Different mineral formation pathways in volcanic soils, notably the formation of halloysite versus allophanes, strongly affect the soils’ retention capacity for GLP. The high AC of allophanes may induce the low mobility of GLP in allophane-containing soils. Long-term use of GLP may accumulate the herbicide in these soils with potential effects on biodiversity and ecosystem services.  相似文献   

7.
Forest and grassland soils that contained varying amounts of Fe and Al were collected from England and Wales. Fractionation of free Fe and Al was accomplished to determine which components affected sulfate adsorption. Organic Fe and Al were the dominant fractions in most soil horizons and high amounts of these organically bound metals and, to some extent, crystalline Fe oxide were associated with high sulfate adsorption potentials. These adsorption potentials reflected naturally occurring amounts of absorbed sulfate and ester sulfate. Overall, the C content exhibited a positive relationship with sulfate adsorption potentials. Soils with a high C content also exhibited high rates of organic S formation. The rate of organic S mobilization was greater in soils with higher amounts of soluble sulfate. Organic S was the largest pool and, typically, sulfonate S was the most abundant constituent of the organic pool.  相似文献   

8.
LIUFAN  XUFENG-LIN 《土壤圈》1994,4(1):35-46
The types,contents and morphologies of crystalline Fe oxides and their relations to phosphate adsorption on the clay fractions in soils with varable charge in southern China were investigated by means of XRD,TEM,EMA and chemical analysis methods.Results indicated that the types and contents of crystalline Fe oxides varied with the soils examined.The dominant crystaline Fe oxide was hematite in the latosols and goethites in the red soils.In yellow-brown soils,the only crystalline Fe oxide was goethite.The difference between Ald and Alo came mainly from the Al Substituting for Fe in the Fe oxides.The crystal morphology of goethite appeared mainly as subrounded flat or iso-dimensional rather than acicular particles,Hematities occurred in plates of various thickness,Their MCDa/MCDc ratios in the latosols and red soils were generally above 1.5 and below 1.5,respectively.The MCD values of goethites and hematites were 15-25nm and 20-35nm,and their specific surface areas were 80-120m^2/g and 35-75m^2/g,respectively.The goethite crystals were generally smaller,Variations of the total amounts of crystalline Fe oxides in clay fractions were not related to plhophats adsorption.The types,contents and morphologies of crystalline Fe oxides in the soils remarkably affected phosphate adsorption characteristics of the soils.The phosphate adsorption of goethite was much greater than that of hematite,The higher th MCDa/MCDc ratio of hematite,the lower the phosphate adsorption.  相似文献   

9.
R.J. Haynes  R.S. Swift 《Geoderma》1985,35(2):145-157
The effects of air-drying field-moist soils on the adsorption and desorption of added phosphate and on the levels of extractable native soil phosphate were examined using the A and B horizons of a group of four acid soils.Air-drying increased the capacity of all the soil samples to adsorb phosphate. At an equilibrium solution concentration of 0.5 μg P ml?1, the increase in the quantity of phosphate adsorbed following drying ranged from 23% to 70% of that adsorbed by the moist samples. Considerable hysteresis in phosphate adsorption—desorption isotherms was observed for both moist and dried soil samples indicating that the additional phosphate adsorbed by the dried samples was held with the same strength as that held by the moist samples.Air-drying the soil samples caused a small decrease in soil pH of approximately 0.1 pH unit and a general increase in levels of EDTA-extractable Fe, Al and organic matter. Quantities of native soil phosphate extractable with EDTA, resin and NaHCO3 were also increased. Concentrations of oxalate- and pyrophosphate-extractable Fe and Al and exchangeable Al were, however, unaffected by drying.It was also shown that when the phosphate content of NaHCO3 extracts is measured using the conventional molybdenum blue method, orthophosphate plus a differing amount of acid-hydrolysable organic P present in the extract is measured.  相似文献   

10.
Chemical reactions and fate of the toxins of Bacillus thuringiensis(Bt) in the soil environment are causing increasing concerns due to the large-scale cultivation of transgenic Bt plants.In this study,the effect of ionic strength(0-1 000 mmol kg 1) adjusted by NaCl or CaCl 2 on adsorption of Bt toxin by a lateritic red soil,a paddy soil and these soils after chemical removal of organic-bound or free Fe and Al oxides,as well as by pure minerals(goethite,hematite and gibbsite) which are widespread in these soils,were studied.The results indicated that when the supporting electrolyte was NaCl,the adsorption of Bt toxin by the lateritic red soil and paddy soil increased rapidly until the ionic strength reached 250 mmol kg 1 and then gradually slowed down with the increase of ionic strength;while in case the supporting electrolyte was CaCl 2,the adsorption of Bt toxin enhanced significantly at low ionic strength(< 10 mmol kg 1) and then decreased as the ionic strength increased.The adsorption of Bt toxin by the tested minerals and soils after the removal of organic-bound or free Fe and Al oxides also increased with increasing ionic strength controlled by NaCl.Removing organic-bound Fe and Al oxides obviously increased the adsorption of Bt toxin in the tested soils.Differently,removing free Fe and Al oxides increased the Bt adsorption by the paddy soil,but decreased the adsorption by the lateritic red soil.The study indicated that the varieties of ionic strength and the presence of Fe and Al oxides affected the adsorption of Bt toxin by the soils,which would contribute to the further understanding of the fate of Bt toxin in the soil environment and provide references for the ecological risk assessment of transgenic Bt plants.  相似文献   

11.
An isotopic exchange method was used to characterize quantitatively the fixation and plant availability of phosphate previously sorbed by soils. In general, the exchangeability of the sorbed phosphate was much higher than its desorbability for both soils and clay minerals. Isotopic exchangeability of the sorbed phosphate increased with sorption saturation during the initial stage (15–60% saturation), but the increase was less with increasing saturation from 60–90% for all soils tested. Therefore a sorption saturation of 60% was recommended as the upper limit of P fertilization in terms of economical efficiency. For clay minerals, with increasing sorption saturation, the isotopic exchangeability of the sorbed P increased significantly for kaolinite and sesquioxides, but decreased for montmorillonite. Most of the phosphate sorbed by montmorillonite and kaolinite was found to be isotopically exchangeable, but only a small amount of the P sorbed by goethite could be exchanged. The P sorbed by Al oxide exhibited isotopic exchangeability between that of kaolinite and Fe oxide. The isotopically exchangeable phosphate pool could readily account for the P uptake of plants and the available P determined by some commonly used chemical methods, such as Olsen-P and Bray-P.  相似文献   

12.
Soil minerals are known to influence the biological stability of soil organic matter (SOM). Our study aimed to relate properties of the mineral matrix to its ability to protect organic C against decomposition in acid soils. We used the amount of hydroxyl ions released after exposure to NaF solution to establish a reactivity gradient spanning 12 subsoil horizons collected from 10 different locations. The subsoil horizons represent six soil orders and diverse geological parent materials. Phyllosilicates were characterized by X-ray diffraction and pedogenic oxides by selective dissolution procedures. The organic carbon (C) remaining after chemical removal of an oxidizable fraction of SOM with NaOCl solution was taken to represent a stable organic carbon pool. Stable organic carbon was confirmed as older than bulk organic carbon by a smaller radiocarbon (14C) content after oxidation in all 12 soils. The amount of stable organic C did not depend on clay content or the content of dithionite–citrate-extractable Fe. The combination of oxalate-extractable Fe and Al explained the greatest amount of variation in stable organic C (R2 = 0.78). Our results suggest that in acid soils, organic matter is preferentially protected by interaction with poorly crystalline minerals represented by the oxalate-soluble Fe and Al fraction. This evidence suggests that ligand exchange between mineral surface hydroxyl groups and negatively charged organic functional groups is a quantitatively important mechanism in the stabilization of SOM in acid soils. The results imply a finite stabilization capacity of soil minerals for organic matter, limited by the area density of reactive surface sites.  相似文献   

13.
Chemical and mineralogical properties of ochreous brown earths have been studied with particular reference to: (1) the distribution within the profiles of Fe and Al compounds; (2) the occurrence of smectite-like clay minerals in surface horizons. Ochreous brown earths studied belong to a developmental sequence of forest soils, from acid brown earths to ferric podzols, developed on sandy or loamy-sandy acid parent materials. In such a soil sequence, both selective chemical and mineralogical data show clearly that podzolization is already active in ochreous brown earths, whereas such an incipient podzolization is quite undetectable by direct morphological observations. The distribution patterns of amorphous Fe and Al hydrous oxides and organic associations, clearly show the intergrade character of ochreous brown earths, when compared with the vertical distribution of Fe and Al forms in acid brown earths and podzolized soils. The Fe/Al ratio of both an NH4-oxalate extract and an NaOH/Na-tetraborate extract buffered at pH 9.7, measured in the A1B diagnostic horizon of ochreous brown earths, is a particularly appropriate and useful genetic criterion for the detection of incipient podzolization. Moreover, the presence of expansible clay minerals (degradation smectites) in the clay-sized fraction of the surface horizons of ochreous brown earths (A1 and A1B) can be considered as supplementary evidence of incipient podzolization.  相似文献   

14.
The release of hydroxyl ions from silica and ferric oxide gels on treatment with sodium fluoride solution is very small above pH values of 7.6 and 9 respectively. Hydroxyl release from alumina gel and poorly ordered aluminosilicates is appreciable at pH 9 and varies little with pH, but that from crystalline forms of alumina decreases with decrease of pH. For poorly ordered aluminosilicates, the ratio (OH′ released at pH 8.0): (OH′ released at pH 6.8) is directly proportional to the mole fraction Al/(Al+Si). The measurement of hydroxyl release at differing pH values may enable determination of hydrous alumina separately from the total poorly ordered inorganic gel material; moreover, the amount of hydroxyl released at high pH values is related to phosphate sorption capacity.  相似文献   

15.
Major weathering sequences in soils are well established; however, knowledge on rates of mineral transformations remains unknown, because it is often difficult to date precisely soil processes. This work was carried out on soils developed on recent (< 188 y) sand dunes on the W coast of Oléron Island (France). The coast has been protected against marine and wind erosion by constructing five consecutives barriers close to the coastline since 1820 (1820, 1864, 1876, 1889, 1948) defining the maximum age of the soil parent material, as before the areas between the barriers were under water. Soils on the older dunes have low clay content (> 94% of sand) and exhibit a bleached E horizon that overlies a yellowish brown B horizon. The process responsible for their formation is podzolization promoted by the high permeability of the material and complexing organic matter produced by coniferous vegetation. Initial mineralogy of C horizons is homogenous and constituted of chlorite, illite, illite/smectite mixed‐layer minerals, and kaolinite, quartz, calcite (≈ 8% related to shell fragments), and feldspars. The initial clay‐mineral assemblage of the E horizons is dominated by illite (well‐crystallized WCI and poorly crystallized PCI) and chlorite. With progressive podzolization, poorly crystallized illite is first transformed to illite/smectite mixed‐layer minerals and in a further step into smectite. In addition, transformation of well‐crystallized illite leads to formation of ordered illite/smectite mixed‐layer minerals in the E horizons, which is not commonly described in soils. In the B horizons, illite/smectite mixed‐layer minerals are present with traces of smectite, as well as Al and Fe oxi‐hydroxides as revealed by DCB and oxalate chemical extractions. This chronosequence illustrates that over short distances and short time (< 188 y) intense mineral weathering and soil development occur. Major clay‐mineral changes occur between 132 and 188 y in agreement with development of the pine forest producing acidic litter.  相似文献   

16.
Billions of dollars are spent annually in Brazil on imported phosphorus (P) fertilizers for agricultural crops produced on Oxisols. Phosphate fixation by Oxisols is a main limitation to crop productivity because these highly weathered soils have a high phosphate adsorption capacity. The objective was to determine whether reaction of an Acric Oxisol with citrate increases P availability. Columns of P-amended subsoil material were leached with 1 mM citrate solution, and effluent was monitored. Solid-phase speciation was measured for different stages of leaching using X-ray absorption near edge structure (XANES) spectroscopy at the P K-edge. When soil columns were leached with up to 56 column pore volumes of 1 mM citrate solutions, no P was detected in column effluent samples, whereas aluminum (Al) and iron (Fe) increased up to 30 and 1.4 µmol L?1, respectively. The XANES analysis suggested that with increased leaching, a minor proportion of phosphate adsorbed on Fe-oxides increased as phosphate adsorbed on Al-oxides decreased. The results indicated that citrate tends to induce minor species redistribution of phosphate between Al- and Fe-oxide bound forms, but P mobilization was trivial compared with complexometric mobilization of Fe and Al.  相似文献   

17.
Knowledge is scarce about the composition of soils on Bellona and other Pacific atolls. Such knowledge is important as it is closely related to sustainable land use of these special soils formed on carbonatic/phosphatic materials. Therefore, the micromorphological, chemical and mineralogical composition of samples from genetic horizons in three dominant Bellonese soils (Malanga, Kenge Ungi and Kenge Toaha) and underlying rock (Tanahu) were investigated. Tanahu mainly consists of dolomite, but this mineral is absent in the three soils, which are dominated by phosphate-containing minerals. The Malanga soil is strongly dominated by Ca and P with minor amounts of Al, F and Fe present in fluorapatite, hydroxyapatite and crandallite. In contrast, Al, Fe and P dominate in the Kenge Ungi and Kenge Toaha soils in accordance with a mineralogy consisting of crandallite together with aluminum oxides (gibbsite/boehmite) and iron oxides, mainly goethite with minor contents of hematite. The observed carbonate for phosphate substitution in the apatites and crandallite is important as it indicates an increased phosphate availability in the soils. All three soil samples contain ≤ 1% Si and very little K and Mg. Total contents of essential microelements are considered adequate, but the rather high contents of Sr and U, especially in the Kenge Ungi soil may be problematic. Although the composition of the soils suggests substantial fertility and resilience, the lack of K-containing weatherable minerals (silicate minerals) is in line with a very low K (and low Mg) content and explains why fertilization may be needed to sustain future cultivation of these special soils. Due to a possible low bioavailability of Fe, Mn and maybe other micronutrients at the circumneutral pH of these carbonatic/phosphatic soils as well as the rather high contents of Sr and U, it may be recommended to test element availability using appropriate chemical soil tests supplemented by plant experiments to ensure safe and sustainable (optimal) soil use. However, according to the local farmers, the Malanga, Kenge Toaha and Kenge Ungi soils are considered well suited for production of the preferred crops.  相似文献   

18.
Soil carbon (C) saturation implies an upper limit to a soil's capacity to store C depending on the contents of silt + clay and poorly crystalline Fe and Al oxides. We hypothesized that the poorly crystalline Fe and Al oxides in silt + clay fraction increased the C saturation and thus reduced the capacity of the soil to sorb additional C input. To test the hypothesis, we studied the sorption of dissolved organic carbon (DOC) on silt + clay fractions (<53 µm) of highly weathered oxic soils, collected from three different land uses (i.e., improved pasture, cropping and forest). Soils with high carbon saturation desorbed 38% more C than soils with low C saturation upon addition of DOC, whereas adsorption of DOC was only observed at higher concentration (>15 g kg?1). While high Al oxide concentration significantly increased both the saturation and desorption of DOC, the high Fe oxide concentration significantly increased the desorption of DOC, supporting the proposition that both oxides have influence on the DOC sorption in soil. Our findings provide a new insight into the chemical control of stabilization and destabilization of DOC in soil.  相似文献   

19.
P. Violante  M.J. Wilson 《Geoderma》1983,29(2):157-174
The mineralogy of four Italian Andosols - derived from volcanic material either oversaturated or undersaturated with respect to silica - has been investigated by XRD, EM and IR. The crystalline clay minerals in all four profiles are essentially similar, consisting of abundant halloysite with moderate illite and 14A intergrade material, minor kaolinite and occasional gibbsite. The soils also contain large amounts of imogolite and proto-imogolite allophane. With the exception of illite all these clay minerals are believed to be of pedogenic origin. Halloysite occurs in the dehydrated form in the surface horizons but becomes progressively more hydrated with depth. At depths of > 1.4 m the clay fraction consists almost entirely of fully hydrated halloysite, supporting the suggestion that halloysite forms best in a stagnant moisture regime where there is a depositional overburden acting as a silica source. EM observations show that the halloysite may have spherical morphology and may be intimately associated with gas vesicles in pumice grains where it probably forms by the transformation of allophanic material. It seems likely that dehydrated halloysite slowly converts to poorly crystallized kaolinite in the upper horizons of these profiles. The origin of the 2/1 minerals is more problematical. Illite is probably inherited from mica in the parent material but the 14A intergrade material is so poorly ordered that a pedogenic origin seems more likely than formation by inheritance or by transformation of pre-existing 2/1 silicates.  相似文献   

20.
The phytoavailability of soil phosphorus (P) depends on the different forms in which it occurs and how these forms change after the application of P fertiliser to the soil. Forms of P in the A, B and C horizons of eleven pedons that developed on mafic rocks were characterised by a fractionation method before and after fertilisation with single superphosphate, and a micropot experiment was conducted to assess the short-term use of P fertiliser by rye (Secale cereale L.). The main sources of P to the crop were (i) phosphate adsorbed on mineral surfaces and pedogenic Fe, Al or Ca phosphates in the A horizon and (ii) Ca-phosphates in B and C horizons. In the C horizons, poor in Fe/Al phases and clay, the precipitated Ca-P showed low solubility, resulting in a reduction in shoot biomass. The apparent P recovery by rye was similar in the A (36%) and B (29%) but decreased in the C (15%) horizons. The partial factor productivity (g g?1) decreased from the A (58) to B (11) and C (5) horizons. P phytoavailability decreased with increasing profile depth because the transformation of P fertiliser to poorly soluble Ca-P forms increased with depth.  相似文献   

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