Ferrihydrite: A review of structure,properties and occurrence in relation to soils

Ferrihydrite occurs in soils undergoing rapid weathering, and in soils containing soluble silicate or organic anions which inhibit the formation of more crystalline iron oxides. Because of its very high specific surface area and adsorptive capacity (analogous to allophane), ferrihydrite can profoundly influence soil properties, even if present in only low concentrations. Ferrihydrite was recognised as a mineral by the International Mineralogical Association in 1975. Its structure and chemical formula, however, are not yet clearly understood. Most evidence to date indicates hexagonal-close-packed layers of O²′, OH, and H₂O with Fe(III) occupying octahedral positions and giving a trigonal unit cell (a=0.508 nm; c=0.94 nm). Some samples appear to have only a partially ordered structure and uncertainty exists as to how to name such material. Natural ferrihydrites commonly contain up to about 9% Si and the role and location of silicate are subjects of active research. At concentrations greater than 5-10%, ferrihydrite in soils can usually be identified by X-ray diffraction. At lower concentrations, a combination of methods can be indicative. Acid-oxalate-extractable iron is a convenient and often useful indicator of the presence and quantity of ferrihydrite in a soil, though it cannot be regarded as a means of positive identification.     

共沉淀引发的溶解性有机质在水铁矿/水界面的分子分馏特性

土壤矿物与溶解性有机质（DOM）的相互作用会引起DOM在矿物/水界面的结构分馏,进而影响DOM在土壤中的长期保存及其环境行为。水铁矿在环境中广泛存在,可通过两种不同方式（表面吸附或共沉淀）与DOM结合。目前,鲜有研究从分子尺度上揭示共沉淀反应诱发的DOM在水铁矿/水界面的结构分馏特性。针对此,通过共沉淀方式在C/Fe不同的溶液中制备水铁矿-DOM复合体,将传统光谱手段（如,紫外（UV）-可见光光谱、Fe K边X射线吸收光谱（XAS）等）和近年来兴起的电喷雾-傅立叶变换-离子回旋共振质谱（ESI-FT-ICR-MS）相结合,从分子水平解析共沉淀过程中DOM在水铁矿/水界面的结构分馏行为。结果显示：水铁矿-DOM复合体中Fe主要以水铁矿的形式存在,所占比例与C/Fe值有关,介于68.0%~95.9%之间。UV和ESI-FT-ICR-MS分析共同表明在共沉淀过程中,水铁矿优先固定DOM中具有高分子量的富含氧的芳香性组分（主要燃烧过程中产生的致密多环芳香类物质和维管植物来源的多酚类物质）,该分子分馏特性与前人报道的因表面吸附引发的DOM在水铁矿/水界面的分馏现象基本一致,表明无论表面吸附还是共沉淀,水铁矿均倾向于固定芳香性强的高分子量组分。此外,本研究率先发现水铁矿对DOM的结构选择性随反应时间呈一定动态变化,表现为：燃烧过程中产生的致密多环芳香类组分优先被固定在复合体中,随着反应推进,维管植物来源的多酚类组分被固定。本研究结果有助于深入理解水铁矿形成过程中,通过共沉淀作用影响DOM环境地球化学行为的分子分馏机制。     

Phosphatases in soils

Most studies on phosphatase activity in soils have been concerned with acid phosphatase. This study was conducted to determine the activity of phosphomonoesterases (acid and alkaline phosphatases), phosphodiesterase, and “phosphotriesterase”. The results indicate that acid phosphatase is predominant in acid soils and that alkaline phosphatase is predominant in alkaline soils. With universal buffer, the pH optima of phosphodiesterase and phosphotriesterase were at pH 10. The activities of these phosphatases in soils were much lower than those of the acid and alkaline phosphatases. Studies on the effects of various soil treatments on the activity of phosphatases in soils indicated that air-drying increased the activity of acid phosphatase and phosphotriesterase, decreased the activity of alkaline phosphatase, but did not affect the activity of phosphodiesterase. Steam sterilization of soils at 121 C for 1 h inactivated alkaline phosphatase, phosphodiesterase, and phosphotriesterase, but did not completely inactivate acid phosphatase. Addition of toluene to the incubation mixture did not markedly affect the activity of acid phosphatase, alkaline phosphatase, phosphodiesterase, but increased the activity of phosphotriesterase in soils.Studies of the kinetic parameters of phosphatases in the soils studied showed that the K_m values ranged from 1.11 to 3.40 mm for acid phosphatase. from 0.44 to 4.94 mm for alkaline phosphatase, and from 0.25 to 1.25 mm for phosphodiesterase. Expressed as μg p-nitrophenol released·h^?1·g^?1 soil, the V_max values ranged from 200 to 625 for acid phosphatase, from 124 to 588 for alkaline phosphatase, and from 46 to 127 for phosphodiesterase. The substrate of phosphotriesterase (tris-p-nitrophenyl phosphate) is insoluble in water; hence, the K_m and V_max values of this enzyme in soils could not be determined.     

Sulfur in soils

Sulfur (S) deficiency of crops, which has been reported with increasing frequency over the past two decades on a worldwide scale, is a factor that reduces yield and affects the quality of harvested products. Especially in Western European countries, incidence of S deficiency has increasingly been reported in Brassicaceae. For this reason, more attention should be paid to the optimization of S‐fertilizer application, in order to cover plant S requirements whilst minimizing environmental impacts. In soils, S exists in inorganic and organic forms. While sulfate (SO ), which is a direct S source for plants, contributes up to 5% of total soil S, generally more than 95% of soil S are organically bound. Organic S is divided into sulfate ester and carbon‐bonded S. Although not directly plant‐available, organically bound S may potentially contribute to the S supply of plants, especially in deficiency situations. Sulfur turnover involves both biochemical and biological mineralization. Biochemical mineralization, which is the release of SO from the ester sulfate pool through enzymatic hydrolysis, is controlled by S supply, while the biological mineralization is driven by the microbial need for organic C to provide energy.     

Phenols in rice soils

In a laboratory study on the distribution of phenols in rice soils, a humus-rich acid sulphate soil liberated more alkali-extractable phenols than an alluvial soil under both flooded and nonflooded conditions. Nonflooded conditions appeared to favour the release of phenols from the acid sulphate soil whereas in the alluvial soil no difference was apparent under the two water regimes. The addition of calcium carbonate to the acid sulphate soil further increased the production of phenols. Analysis of the solvent extract of the soils by thin-layer chromatography showed that both the soils contained vanillic acid and two unidentified phenols.     

还原态蒙脱石结构Fe（Ⅱ）催化水铁矿转化特性及影响因素

还原条件下土壤中Fe(Ⅱ)催化水铁矿转化在调控营养元素和污染物的生物地球化学过程中具有重要作用。然而,作为土壤中Fe(Ⅱ)存在的主要形态之一,蒙脱石结构中Fe(Ⅱ)催化水铁矿转化的特性及其影响因素目前尚不清楚。以化学还原的蒙脱石为研究对象,探究还原态蒙脱石(rSWy-2)结构中Fe(Ⅱ)催化水铁矿转化的特性及其影响因素。结果表明,贫铁的蒙脱石结构中Fe(Ⅱ)可催化水铁矿向纤铁矿转化,反应96 h后水铁矿转化量达到83.3%。X射线衍射(XRD)、高分辨透射(HRTEM)、球差电镜(STEM)和表面吸附态Fe(Ⅱ)含量分析表明,rSWy-2结构Fe(Ⅱ)催化水铁矿转化主要经历矿物间固相吸附、电子传递和水铁矿转化三个阶段,形成的纤铁矿呈板状纳米片,尺寸大小为100～200 nm。溶液中Na+和Cl–离子对rSWy-2催化水铁矿转化影响较弱,而Ca²⁺、SO₄^2-、有机质和As(Ⅲ)均对水铁矿转化具有明显的抑制作用。     

Gel structures in soils

The colloidal structures in soils were studied by scanning and transmission electron microscopy. Small-angle neutron scattering was used in the pioneering study of the colloidal soil structures and their rearrangements under the effect of different factors. It was found that colloidal particles are fixed apart in a gel matrix formed by organic molecules. The results obtained suggest that the organomineral gel is composed of soil humus occurring, at least in part, in a gel-like status and reinforced by organic and inorganic colloidal particles. In the interaction with water, the reinforced humus gel behaves as many polymers: it swells, absorbing water and increasing in volume; it shrinks under drying conditions. Different impacts on the soil affect the status of the reinforced humus gel, which results in the observed changes of the soil properties.     

Hard-setting soils

Abstract. Hard-setting soils are widespread in dry regions. Their properties are described and a physical explanation for hard-setting behaviour is given. The limitations on soil management and physical fertility caused by hard-setting depend on timing of rainfall or irrigation with respect to cultivations and crop development, and much research is needed to quantify reductions in crop yield imposed by these limitations.     

Plant Opal in Japanese soils

Several years ago the writers (6) found peculiar amorphous grains having a low refractive index (n = 1.45) in the tine sand fraction of Japanese volcanic-ash soils, especially in the A horizons of glassy-ash soils (Onji type). These grains have been considered PELE's tears (liquid lava drops) or bead-like glassy grains on the basis of their relative abundance in volcanic-ash soils. Their morphological, and chemical characteristics have been reported elsewhere by the authors (6). Furthermore, it has been noticed that many of red-yellow soils and paddy soils contain varying amounts of these grains. Some Japanese agronomists and phytopathologists have previously pointed out that silica cells in leaves of Oryza sativa have the effective power of resistance to blast (Imochi disease).     

Speciation of iodine in soils

In order to analyze the behavior and phytoxicity of iodine in soil, the chemical forms of soil iodine must be identified. Therefore, a method for quantitative speciation of iodine in soil was proposed. Iodine extracted from soil samples with tetrametBPyIammonium hydroxide (TMAH) was separated into humic and fnalvic acid fractions at pH4 1.5 after the addition of ascorbic acid into the TMAH extract to reduce iodate into iodide. Since the iodide in the TMAH extract was recovered in the fdvic acid fraction by this procedure, iodine contained in the haamic acid fraction was considered to be organically bound. Podine in the fulvic acid fraction was separated into organic iodine bound to fnlvic acids and the total inorganic iodine. Furthermore, iodine soluble from soil in 0.1 mol L^-1 potassium chloride was assumed to correspond to the amount of total iodide in soil, and from the difference in the concentration of total inorganic iodine and soluble iodide, the amount of iodate was calculated. By the application of this method, iodine in soil was separated into four fractions: organic iodine bound to humic acids, organic iodine bound to fulvic acids, iodate, and iodide. This speciation method was applied to two soils. It was found that s Barge proportion of iodine in soil occurred in an organicalPy bound form.     

Iron minerals in urban soils

Technogenically contaminated urban soils contain a substantial amount of magnetite Fe₃O₄, whereas another ferrimagnetic, i.e., maghemite αFe₂O₃, more often prevails in unpolluted soils. The content of magnetite may exceed the content of another iron oxide, hematite, in contaminated soils. In the town of Chusovoi, where emissions from a single enterprise, a metallurgical plant, predominate among pollutants, the upper soil horizons are contaminated with magnetite of one type. In the much larger city of Perm, the polluting sources are diverse, which results in a wide variation of magnetic susceptibility of technogenic magnetite. The difference in magnetite properties may depend on the composition and the content of heavy metals associated with this mineral. A considerable amount of oxalate-soluble magnetite in technogenically contaminated soils produces two important consequences. Schwertmann’s criterion Fe_ox: Fe_dit as a gleying index turns out to be overestimated and, therefore, does not work in technogenically contaminated soils. The second consequence is that Tamm’s reagent is inapplicable to extracting heavy metals bound to amorphous iron compounds from contaminated soils. On the other hand, a high solubility (30–60%) of technogenic magnetite by oxalate favors the use of Tamm’s reagent for the complete extraction of iron (hydr)oxides and heavy metals bound to them.     

Glassy volcanic-ash soils in Japan

Introduction

In Tottori district, there can be seen an extensive sand-dune region, which develops on the coastal terrace of the volcanogenous diluvium running from east to west along the shore of the Japan Sea. There is about 9750 hectares in total area: 5265 hectares comprising numerous inter-dune depressions are used for tillage field, 1207 hectares afforested and 3278 hectares left barren.     

Nitrogen fixation in paddy soils

The 4 long-term experimental plots (Umbric haplaquept) with different fertilizer treatment at Cent. Agric. Exp. Sta. in Konosu City, Saitama Prefecture, were used for the sites of investigation. The 4 plots were NF (applied with no fertilizer), IF (applied with inorganic fertilizers), GM (applied with green manure and CaCO₂), and OM (applied with manure and inorganic fertilizers). Flooded water, floating weed, upper (0-2cm) and lower (2-10cm) parts of Apg horizon and rhizosphere were collected from each plot before flooding, during flooding, and after drainage. These samples were analyzed for N₂-fixing activity by acetylene reduction method, pH, Eh, and contents of Fe²⁺, NH₄ ⁺, chlorophyll-type compounds, and water-soluble carbohydrates.

The N₂-fixing activity of all samples showed almost the same pattern of change with time: very low before flooding, rapidly increased after flooding, the maximum value at the maximum tillering stage of rice plant, declined afterwards and reached a very low value after drainage.

Rough estimation of the “N₂-fixing capacity” of each part of the paddy field revealed that the most important site of the N₂ fixation was the reduced Apg horizon, that the importance of flooded water and/or the oxidized layer in the N₂ fixation was rather low except in infertile soil, and that the role of rhizosphere in the N₂ fixation could not be neglected also in Japan.

Reduced condition and content of easily decomposable organic substances were judged to be main factors which control the N₂-fixing activity in the flooded soil on the basis of correlations between the Nt-fixing activity and several analytical data of the paddy soils.     

Phosphomonoesterase activity in forest soils

Phosphatases are important in the mineralization of organically-bound phosphorous. Although phosphatases have been studied extensively in agricultural soils, there are few reports on phosphatase activity in forest soils, and no information on the effect of forest management practices, such as thinning and N-fertilization, on phosphomonoesterase (PME) activities. In the present study, the (PME) activity of forest soils from Shawnigan Lake and Jordan River (mg p-nitrophenol released g⁻¹ dry soil h⁻¹ was highest in the forest floor horizon (L-H) and decreased with depth to 60 cm in mineral soil horizons. Addition of orthophosphate and urea during the assay of PME demonstrated these chemicals competitively depressed PME activity. With Shawnigan Lake soil (L-H), the minimum rate (V_max) of PME activity was 5.71 mg p-nitrophenol released g⁻¹ dry soil h⁻¹. For Jordan River, V_max was 3.33 mg p-nitrophenol released g⁻¹h⁻¹. Incubation of L-H horizon of both soils, fumigated or non-fumigated, at 30°C for up to 40 days after rewetting resulted in an initial reduction in PME activity. Comparatively, the PME activity of Jordan River soil recovered faster than that of the Shawnigan Lake soil whose activity remained very low at the end of the incubation. In field plots where trees were thinned and urea and ammonium nitrate fertilizers had been applied 2 yr previously, assays for PME demonstrated that urea fertilization and thinning depressed PME activity while ammonium nitrate did not. This study demonstrated (1) PME activity depended on soil geographic location and depth, and (2) fertilization of forests with phosphates and urea appeared to reduce PME activity and thus may have the potential to depress the mineralization of organic-P.