Chemical and colloidal stability of sols in the Al2O3-Fe2O3-SiO2-H2O system: their role in podzolization

Concentrations of dialysable silica in equilibrium with Al₂O₃-SiO₂-H₂O sols at pH 4.5–5.0 confirm the formation of a poorly ordered non-dialysable proto-imogolite species with an Al : Si ratio near 2, close to that of imogolite. Sols with Al : Si>2 give nearly constant levels of free silica in solution in the range 2–6 μg/cm³, indicating equilibrium between proto-imogolite and aluminium hydroxide species. These findings indicate that imogolite-like precipitates in acid soils will buffer silica in solution to within this range during leaching episodes. Imogolite is more stable than a previous estimate suggested, and a revised value for its free energy of formation is proposed: ΔG⁰_f(298.15) = -2929.7 kJ/mol. In Fe₂O₃-SiO₂-H₂O sols, the Fe : Si ratio of the non-dialysable species varies smoothly from 11 to 3 as free silica in solution ranges from 4 to 35 μg/cm³. Such sols are much less colloidally stable than hydroxyaluminium silicate sols, but mixed Al₂O₃—Fe₂O₃—SiO₂—H₂O sols are almost as stable as iron-free sols up to a Fe : Al ratio of 1.5. Thus migration of Al and Fe as mixed hydroxide sols can account for the almost constant ratio of Al to Fe with depth in oxalate extracts from Bs horizons of podzols.     

NH4F-extrahierbares P in Pelosolen und Basalt-Braunerden

NH₄-F extractable P in Pelosols and Cambisols The percentage of “Al-P” of the extractable inorganic P (∑“Al”-+“Fe”-+“Ca-P”, following the Chang and Jackson method) was assumed to be higher at the same pH in soils from basaltic parent material (as a result of an early Al supply from tektosilicates and slow clay formation) than in soils from clay-stone parent material. Contrary to this assumption, the percentage was (with one exception) not higher, probably because of an “Antivariscite-effect” by the 2:1 (clay) minerals.     

A reassessment of podzol formation processes

Translocated (oxalate-soluble) Al and Fe are present predominantly in inorganic forms in the B₂ horizons of the five pcdzol profiles examined: A1 as imogolite and proto-imogolite allophanes, and Fe as a separate oxide phase. Below the top few cm of the B₂ horizon, over 75 per cent of the extractable (acid-plus alkali-soluble) organic matter is present as Al-fulvates, largely sorbed on allophanic material. The Bh horizons of the Iron Humus Podzol and Iron Podzol intergrades are distinguished by very high levels of organically bound Fe (soluble in EDTA solution), five to ten times more than in immediately adjacent A₂ or B₂ horizons, and also by larger humic acid contents than in comparable B₂, levels in typical Iron Podzols. Inorganic forms of translocated Al and Fe are probably absent from two of the three Bh horizons examined, and also from the Bhg horizon overlying the thin iron pan in the Peaty Podzol. The organic matter in this Bhg horizon is saturated with Al rather than Fe. Chemical and physical processes which could lead to evolution of a profile along the genetic sequence, Iron Podzol, Iron Humus Podzol, Peaty Podzol, are postulated. During the formation of an Iron Podzol, positively charged inorganic sols carry aluminium, silicon and iron from the A₂ and deposit them in the B₂ horizon; subsequently, with the development of an H layer, colloidal humus migrates through the A₂ and precipitates on the positive colloids at the top of the B₂ horizon to form a Bh horizon, in which remobilized ferric species are trapped by the organic matter. In higher rainfall areas, occasional waterlogging above the oxide-impregnated B₂ leads to a thin iron pan, separating permanently oxidizing conditions below from seasonally waterlogged and reducing conditions above.     

Effects of NaHCO3 on photosynthetic characteristics,and iron and sodium transfer in pomegranate

In order to study effects of sodium bicarbonate (NaHCO₃) stress in irrigation water on photosynthetic characteristics and iron (Fe) and sodium (Na⁺) translocation content of pomegranate plants, a factorial experiment was conducted based on completely randomized design with three cultivars of pomegranate (“Gorch-e-Dadashi,” “Zagh-e-Yazdi,” and “Ghermez-e-Aliaghai”) and four concentrations of NaHCO₃ (0, 5, 10, and 15 mM), with three replications. The results of plant analysis indicated that NaHCO₃ affected chlorophyll index, F_v/F_m, and performance index (PI) in upper and lower leaves of shoots and also the translocation of Na⁺ and Fe. The results also showed that Fe translocation from root to shoot reduced at 15 mM level of NaHCO₃. The highest Na translocation and the lowest Fe translocation were observed in Zagh-e-Yazdi and Ghermez-e-Aliaghai cultivars, respectively. The ratio of sodium/potassium (Na⁺/K⁺) in stems was higher than that in roots and leaves, and the observed chlorophyll content of upper leaves was also lower than that of lower leaves. Based on the measured parameters Gorch-e-Dadashi cultivar showed less relative sensitivity than other cultivars to NaHCO₃ of irrigation water through maintaining the lower Na⁺ transport to the shoots, and improvement of Fe transport to shoots.     

Behavior of iron‐supplying materials in incubated calcareous soils 1

Two Fe chlorosis‐inducing calcareous soils were incubated for up to 5 months, at room temperature and field capacity, with Fe‐EDDHA, Fe‐DTPA, FeSO₄, an amino acid chelate “Fe‐Metalosate”;, an oxide “Micronized‐Iron”;, and a precipitated Fe‐S compound “Iron‐Sul”;. Other treatments included DTPA chelate alone, elemental S and H₂SO₄ at comparable rates. Both water‐soluble, and DTPA‐extractable Fe fractions were measured periodically from each sample. All water‐soluble sources decreased with time. Soluble Fe was highest after Fe‐EDDHA addition but was not detectable after “Fe‐Metalosate”; and FeSO₄. Acidification to neutralize CaCO₃ significantly increased DTPA‐extractable Fe, which remained high with increasing incubation time. “Micronized‐Iron”; and S had only a slight effect on DTPA‐ extractable Fe. Though Fe‐EDDHA is the most efficient Fe material, pelleted acidified Fe sources, i.e., “Iron‐Sul”;, may be more economical for some crops in the long term.     

Movement of aluminium as an inorganic complex in some podzolised soils,New Zealand

Chemical and mineralogical data are presented for three Spodosols (podzols) and a related Inceptisol (yellow-brown loam). Allophane with an Al/Si atomic ratio close to two is identified in the B horizons of all four soils, and minor amounts of imogolite are present in association with allophane in all but one soil where small-particle gibbsite occurs. Parent materials for these soils are essentially non-vitric. Allophane (Al/Si = 2) has been estimated quantitatively in all soils using oxalate-extractable Si (Si₀) and is selected clay fractions using both Si₀ and infrared spectroscopy. Maximum concentrations of allophane (Al/Si = 2) range from 5% to 18% of fine earth (< 2 mm) fractions and all occur in B horizons. Fe₀ values are low relative to Al₀ values except for the upper horizons of the Inceptisol. Al₀ values peak in B horizons and the ratio pyrophosphate-extractable Al to Al₀ decreases from about 1 in A and upper B horizons to 0.1–0.4 in lower B horizons.An interpretation of the data is consistent with recent proposals that the movement of Al in podzolisation is due primarily to the formation of inorganic complexes with Si. Chemical criteria for spodic horizons should be consistent with the total illuviation of Al and Fe (and perhaps Si), rather than just the organic-bound fraction of Al and Fe in these horizons as indicated by amounts in extractants such as pyrophosphate.     

Extractability of manganese and iron oxides in typical Japanese soils by 0.5 mol L−1 hydroxylamine hydrochloride (pH 1.5)

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 HH_mBCR, which is Step 2 (used for the reducible fraction) of the modified BCR (Community Bureau of Reference) sequential extraction procedure. The HH_mBCR 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 HH_mBCR 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 HH_mBCR from Andisols.     

Chemical characterization of conducive and suppressive soils for potato scab in Hokkaido,Japan

Potato common scab induced by Streptomyces scabies is a serious constraint for potato-producing farmers and the incidence of potato scab depends on the soil chemical properties. We examined the chemical characteristics of conducive and suppressive soils to potato common scab with reference to the chemical properties of nonallophanic Andosols, recently incorporated into the classification system of cultivated soils in Japan. Allophanic Andosols with a ratio of pyrophosphate-extractable aluminum (Al_p) to oxalate-extractable aluminum (Al_o) of less than 0.3–0.4 were “conducive” soils with a high allophane content of more than 3%. On the other hand, nonallophanic Andosols with a Al_p/Al_a ratio higher than this critical value were “suppressive” soils, and their allophane content was less than 2%. The concentration of water-soluble aluminum (AI) was also a useful index for separating conducive from suppressive soils as well as the Al_p/Al_a value and allophane content. The suppressive soils showed a much higher concentration of water-soluble Al at pH 4.5 to 5.5 than the conducive soils. The high concentration of water-soluble Al may be responsible for the control of the incidence of potato common scab in Andosols.     

Interference by organic complexation of Fe and A1 on the SO2-4 adsorption in Spodic B horizons in Sweden

The relations between pH, different fractions of Fe and A1 and Na₄P₂O₇-soluble C and the amount of adsorbed SO^2-₄ were assessed by analysing 63 soil samples from 14 podsolized soils in Sweden. The amount of adsorbed SO^2-₄ was significantly better correlated with the calculated amount of the inorganic fraction of Fe and A1 oxides obtained by subtracting Na₄P₂O₇-soluble Fe and A1 from oxalate-soluble Fe and Al than with the oxalate extraction alone. There was a close correlation between C and organically-bound S in the Na₄P₂O₇ extract which shows that the C:S ratio of the extracted fulvic acids is about constant in the soils studied. It was found that, as the proportion of organically-complexed Fe and Al increases, the ability of the soil to adsorb SO^2-₄ decreases. The amount of adsorbed SO^2-₄ expressed on the basis of the amounts of oxalate-soluble Fe and Al was generally smaller in areas with low S deposition (< 60 mmol m^-2 a^-1). The ratio between pyrophosphate-soluble C and oxalate-extractable Fe and Al was negatively correlated with pH in water. It was concluded that Fe and Al associated with organic matter cannot adsorb SO^2-₄ and that the degree of this association is pH dependent. These observations have important implications regarding the effects of anthropogenic acidification.     

The Determination of Soil Boron Fractions,Their Relationships to Soil Properties and the Availability to Olive (Olea europea L.) Trees

This study was conducted to investigate the various boron fractions in olive tree grown soils. The correlations between boron fractions in leaves, fruits and soil properties were examined. For this purpose cv “Gemlik” olive (Olea europaea L.) orchards were visited. Soil samples from 0–30 cm and 30–60 cm deep, the leaf and fruit samples were collected. The greatest proportion of total soil boron is present in residual form (85–88%). It is followed by organically bound B (2.84–4.50%), specifically adsorbed on soil colloid surfaces (0.93–1.31%), oxides (manganese oxyhydroxides, amorphous Fe and Al oxides, crystalline Fe and Al oxides) bound B (7.27–8.31%). The smallest one readily soluble (extracting plant available) boron values were composed of only 0.40–0.50% of total boron ranging. To determine readily soluble boron five different extraction solutions were in the order Hot water ? 0.01 M CaCl₂ ? 1 M NH₄OAc ? 0.1 M KCl ? 0.005 M DTPA. Fruit boron concentration and soil boron fractions showed close correlations than leaf boron concentration.     

Related Characteristics and Multivariate Analyses in the Evaluation of White Oat Aluminum Tolerance

Standard white oat genotypes were subjected to different methods and aluminum (Al) levels under hydroponic conditions to verify the relationship between plantlet characteristics and their Al tolerance using multivariate analyses. A completely randomized design with three replications was used, adopting three evaluation protocols: “complete nutrient solution” with 0, 8, 16, and 32 mg L^?1 of Al supplied as aluminum sulfate [Al₂(SO₄)₃·18H₂O]; “complete nutrient solution” with 0, 8, 16 and 32 mg L^?1 of Al supplied as aluminum chloride (Al₂Cl₃?6H₂O); and the “minimum nutrient solution” with 0, 1, 3, and 5 mg L^?1 of Al supplied as Al₂Cl₃?6H₂O. The performance of white oat plantlet genotypes subjected to excess Al in hydroponic conditions is greatly associated with root length, where the nutrient solution composition and the Al sources interfere in these associations. The study based on the joint analysis of characteristics at plantlet level does not allow an efficient discrimination of Al-tolerant and Al-sensitive white oat genotypes.     

Defektverbindung und fremdionen-dotierung bei der ausfällung von eisen(II)- und eisen(III)- phosphaten

The products obtained by precipitation of iron(III)-phosphates in the pH-range from 2 to 13.35 differ in their composition from the ones reported in the literature, e.g. FePO₄2H₂O or FeH₂(OH)₂PO₄, except at low pH values.The molar ratio of 1 : 1 for P and Fe is disturbed to a significant extent and foreign ions are also incorporated as integral parts of the precipitation products.The change of the P/Fe ratio within the pH-range from 2 to 11 is the result of continuous substitution of OH^? for PO₄^? ions. This exchange may be explained as a transition between phosphate- and hydroxide-“Defektserie” (reference is to sets of compounds which form partial rather than complete isomorphous series), whereby the critical composition and the critical precipitation product are defined by the inflection point of the exchange curve.During the hydrothermal recrystallization of amorphous precipitation products, crystalline iron phosphate (strengite) is formed at low pH values, and crystalline iron hydroxide is formed at high pH values. The precipitation products formed at intermediate pH values have a heterogeneous composition and fail to crystallize under these conditions.     

Effects of aerobic conditions in the rhizosphere of rice on the dynamics and availability of phosphorus in a flooded soil – A model experiment

The secretion of O₂ by rice roots results in aerobic conditions in the rhizoshere compared to the bulk flooded soil. The effect of this phenomenon on the adsorption/desorption behavior and on the availability of phosphorus (P) in a flooded soil was investigated in a model experiment. An experimental set‐up was developed that imitates both O₂ release and P uptake by the rice root. The results showed that O₂ secretion significantly reduced P adsorption/retention and increased P desorption/release in the “rhizosphere” soil, compared to the anaerobic bulk soil. The P uptake by an anion exchange resin from both unfertilized and P‐amended soil was significantly increased. The results confirm that the O₂ secretion is an important mechanism to enhance P availability and P uptake of rice under flooded conditions, where the “physico‐chemical” availability of P in the anaerobic bulk soil is strongly reduced. The decrease of P availability in the P‐amended flooded bulk soil was mainly associated with the almost complete transformation of the precedingly enriched Al‐P fraction into Fe‐bound P with extremely low desorption/release characteristics during the subsequent flooding.     

Chemical and mineralogical properties of sandy and loamy-sandy ochreous brown earths in relation to incipient podzolization in a brown earth—podzol evolutive sequence

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.     

土壤有机矿质复合体研究 Ⅶ．土壤结合态腐殖质的形成特点及其结合特征

本文系统剖析了熊毅－傅积平改进区分的土壤结合态腐殖质的形成特点，胡，富组成及其结合特征。结果表明：（１）用０．１ｍｏｌ／ＬＮａＯＨ及０．１ｍｏｌ／ＬＮａＯＨ＋０．１ｍｏｌ／ＬＮａ４Ｐ２Ｏ７混合液连续浸提的松结态（Ｈ１）和稳结态（Ｈ２）腐殖质所占的比例随土壤ｐＨ升高分别呈减少和增加趋势。统计分析显示Ｈ１与游离态铁，铝呈极显著的正相关，与交换性钙呈极显著负相关，Ｈ２则与交换性钙呈极显著正相关，而与游离     

Dissolved organic matter sorption by mineral constituents of subsoil clay fractions

The retention of dissolved organic matter in soils is mainly attributed to interactions with the clay fraction. Yet, it is unclear to which extent certain clay‐sized soil constituents contribute to the sorption of dissolved organic matter. In order to identify the mineral constituents controlling the sorption of dissolved organic matter, we carried out experiments on bulk samples and differently pretreated clay‐size separates (untreated, organic matter oxidation with H₂O₂, and organic matter oxidation with H₂O₂ + extraction of Al and Fe oxides) from subsoil horizons of four Inceptisols and one Alfisol. The untreated clay separates of the subsoils sorbed 85 to 95% of the dissolved organic matter the whole soil sorbed. The sorption of the clay fraction increased when indigenous organic matter was oxidized by H₂O₂. Subsequent extraction of Al and Fe oxides/hydroxides caused a sharp decrease of the sorption of dissolved organic matter. This indicated that these oxides/hydroxides in the clay fraction were the main sorbents of dissolved organic matter of the investigated soils. Moreover, the coverage of these sorbents with organic matter reduced the amount of binding sites available for further sorption. The non‐expandable layer silicates, which dominated the investigated clay fractions, exhibited a weak sorption of dissolved organic matter. Whole soils and untreated clay fractions favored the sorption of ”︁hydrophobic” dissolved organic matter. The removal of oxides/hydroxides reduced the sorption of the lignin‐derived ”︁hydrophobic” dissolved organic matter onto the remaining layer silicates stronger than that of ”︁hydrophilic” dissolved organic matter.     

Aluminum compounds in soil solutions and their migration in podzolic soils on two-layered deposits

The fractional composition of aluminum compounds was studied in soil solutions obtained using vacuum lysimeters from loamy podzolic soils on two-layered deposits. The concentration of aluminum was estimated in brooks and a river draining the area with a predominance of these soils. In soil solutions, the concentration of aluminum was experimentally determined in the following compounds: (1) organic and inorganic monomers, (2) stable complexes with HAs and FAs together with polymers, and (3) the most stable complexes with HAs and FAs together with fine-crystalline and colloidal compounds. The total Al concentration in soil solutions from forest litter was 0.111–0.175 mmol/l and decreased with depth to 0.05 mmol/l and lower in solutions from the IIBD horizons. More than 90% of the Al in the solutions was bound into complexes with organic ligands. Some amount of Al in solution could occur in aluminosilicate sols. The translocation of Al complexes from the litter through the AE horizon to the podzolic horizon was accompanied by an increase in the ratio between the Al concentration in fraction 2 and the C concentration in the solution. The concentrations of Al_tot in the surface waters varied in the range from 0.015 to 0.030 mmol/l. Most of the Al came to the surface waters from the litter and AE horizons and partially from the podzolic horizon due to the lateral runoff along the waterproof IIBD horizon. Approximate calculations showed that the recent annual removal of Al from the AE and E horizons with the lateral runoff was 7 to 560 mg (3–21 mmol) from 1 m².     

Oxalate-soluble compounds of Al, Fe, and Si in soils of cold humid regions as a function of weathering

Original and published data on the contents of X-ray amorphous oxalate-soluble compounds of Al, Fe, and Si in mesomorphic eluvial soils of cold, moderately cold, and moderately warm continental humid and semihumid regions are generalized. The groups of soils developed from mafic igneous, metamorphic, and pyroclastic rocks are considered. It is shown that the content of oxalate-soluble oxides (OSOx) in the horizons of their maximal accumulation varies from less than 1% to 20–30%; the Al_ox/Fe_ox ratio varies from 1 to 6.5. The leading factor dictating the amount and quality of the OSOx in the soils is the presence or absence of volcanic glass in the parent materials. The boundary between the soils with and without volcanic glass corresponds to the OSOx content of 5% and the Al₂O_3ox/Fe₂O_3ox ratio equal to 2. These criteria are more reliable than the Al_ox/Fe_ox ratio used by foreign soil scientists to specify Andosols (Al_ox/Fe_ox > 2). The contents of oxalate-soluble oxides of Al and Fe do not depend on the total contents of these oxides in the parent material and seem to be related to the presence of these elements in minerals with different resistance to weathering. Under the natural conditions described in this paper, the content of OSOx shows a very weak response to zonal (temperature-controlled) climatic changes and/or to changes in the degree of humidity and the continentality of the climate.