Comparison and classification of the effects of simple ions and molecules upon the transformation of ferrihydrite into more crystalline products

The effects of various simple ions and molecules on the extent and products of the conversion of ferrihydrite into more crystalline products are compared. These ions and molecules can be classified according to how strongly they retard the transformation of ferrihydrite, whether they favour the formation of haematite relative to goethite or whether they retard the formation of goethite more strongly than that of haematite and finally, whether foreign ions can replace a proportion of Fe in the goethite structure. Simple ions and molecules operate through two mechanisms. They adsorb on ferrihydrite and stabilize it and they also act by hindering the nucleation of goethite in solution. Adsorption on ferrihydrite retards the transformation to a far greater extent than does interference in solution.     

The Contrasting Effect of Goethite and Hematite on Phosphate Sorption and Desorption by Terre Rosse

Phosphate sorption and desorption in soils are markedly influenced by iron oxides, although little is known on how the common iron oxides differ in their behaviour towards added phosphate. In this study, we investigated phosphate sorption and desorption in the clay fractions of 12 Terre Rosse that ranged widely in Fe oxide content, had very low contents of oxalate-extractable Fe oxides and different hematite/goethite ratios. Phosphate sorption at an equilibrium concentration of 1 mg P 1^?1 was correlated with the goethite but not with the hematite content of the clay fractions. When phosphate was desorbed by electro-ultrafiltration, the difference in desorption half-time between untreated and deferrified clays was positively correlated with the goethite but not with the hematite content. These results suggest that goethite is more active than hematite in phosphate sorption and retention by soils.     

Transformations induced in ferrihydrite by oven-drying

Synthetic ferrihydrite preparations are metastable and on oven-drying are shown to undergo significant transformation to more stable crystalline products the composition of which depends on the properties of the initial ferrihydrite. For a poorly ordered sample produced by rapid neutralization of a ferric nitrate solution, the dominant product was well-crystalline hematite (α-Fe₂O₃), the amount depending on the temperature at which drying was accomplished. Freeze-drying prevented alteration of the ferrihydrite to more crystalline forms and, compared with any of the oven dried samples, minimized the change in rate of dissolution in acid ammonium oxalate solution. For a more ordered ferrihydrite produced by slow neutralization, oven-drying caused the formation of some goethite (α-FeOOH) with little or no hematite. The different transformation pathway for the more ordered ferrihydrite is attributed to 1) formation of larger polymers by slow growth during neutralization, resulting in a limited supply of the very small polymers which transform readily to hematite on heating, and 2) the probability of concomitant growth of goethite nuclei within the ferrihydrite allowing preferred transformation to goethite during oven-drying.     

Iron hydroxides in soils: A review of publications

Iron hydroxides are subdivided into thermodynamically unstable (ferrihydrite, feroxyhyte, and lepidocrocite) and stable (goethite) minerals. Hydroxides are formed either from Fe³⁺ (as ferrihydrite) or Fe²⁺ (as feroxyhyte and lepidocrocite). The high amount of feroxyhyte in ferromanganic concretions is proved, which points to the leading role of variable redox conditions in the synthesis of hydroxides. The structure of iron hydroxides is stabilized by inorganic elements, i.e., ferrihydrite, by silicon; feroxyhyte, by manganese; lepidocrocite, by phosphorus; and goethite, by aluminum. Ferrihydrite and feroxyhyte are formed with the participation of biota, whereas the abiotic formation of lepidocrocite and goethite is possible. The iron hydroxidogenesis is more pronounced in podzolic soils than in chernozems, and it is more pronounced in iron-manganic nodules than in the fine earth. Upon the dissolution of iron hydroxides, iron isotopes are fractioned with light-weight ⁵⁴Fe atoms being dissolved more readily. Unstable hydroxides are transformed into stable (hydr)oxides, i.e., feroxyhyte is spontaneously converted to goethite, and ferrihydrite, to hematite or goethite.     

石灰石成土过程中Zn在土壤中的演化和重新分布

The long-term redistribution of Zn in a naturally Zn-enriched soil during pedogenesis was quantified based on mass balance calculations. According to their fate, parent limestones comprised three Zn pools: bound to calcite and pyritesphalerite grains, bound to phyllosilicates and bound to goethite in the inherited phosphate nodules. Four pedological processes, i.e., carbonate dissolution, two stages of redox processes and eluviation, redistributed Zn during pedogenesis. The carbonate dissolution of limestones released Zn bound to calcite into soil solution. Due to residual enrichment, Zn concentrations in the soil are higher than those in parent limestones. Birnessite, ferrihydrite and goethite dispersed in soil horizon trapped high quantities of Zn during their formation. Afterwards, primary redox conditions induced the release of Zn and Fe into soil solution, and the subsequent individualization of Fe and Mn into Zn-rich concretions. Both processes and subsequent aging of the concretions formed induced significant exportation of Zn through the bottom water table. Secondary redox conditions promoted the weathering of Fe and Mn oxides in cements and concretions. This process caused other losses of Zn through lateral exportation in an upper water table. Concomitantly, eluviation occurred at the top of the solum. The lateral exportation of eluviated minerals through the upper water table limited illuviation. Eluviation was also responsible for Zn loss, but this Zn bound to phyllosilicates was not bioavailable.     

Effect of Cadmium(Ii) and Anion Type on the Ageing of Ferrihydrite and its Subsequent Leaching under Neutral and Alkaline Conditions

The effect of cadmium(II) on the transformation of ferrihydrite[with Cd(II):Fe(III) ratios ranging from 0 to 5 mole %] in neutral and alkaline media (pH 7-11), combined with the effects of electrolyte type (NO₃ ^-, Cl^-, and SO₄ ^-2), was investigated at 20 °C over a period of 1 yr. The presence of Cd(II) strongly retards the conversion of ferrihydrite into hematite and/or goethite at pH 7–10, with decreases in the rate of transformation dependent on the amountof Cd(II). At a Cd(II):Fe(III) mole ratio of 1%, the transformation rate is NO₃ ^- > Cl^- > SO₄ ^-2, which correlates with the relative affinitiesof the anions for the ferrihydrite surface. The presence of Cd(II) promotes hematite formation at pH 9 and 10, whereas atpH 11 goethite is almost the sole product. With increasinginitial Cd(II) concentrations, increasing incorporationof Cd(II) into the products is observed. For 5 mole %Cd(II), ～ 2.5 mole % of Cd(II) is included in thetransformation products, principally hematite, while at pH 11, with 1 mole % Cd(II), all of the Cd(II) incorporates into thegoethite lattice. Transmission electron micrographs show that the presence of Cd(II) leads to a reduction in size and promotesthe twinning of goethite crystals, and can result in ellipsoidal-shaped hematite crystals. Leachability of Cd(II) fromfresh and aged coprecipitated Cd(II)-ferrihyrdite is dependent onthe extent of transformation of the ferrihydrite, with 70–90% of the Cd(II) leachable from ferrihydrite, while goethite is ableto incorporate and remove more Cd(II) than hematite.     

Factors Affecting the Formation,Nature, and Properties of Iron Precipitation Products at the Soil–Root Interface

Abstract

A number of iron oxides (hematite, goethite, lepidocrocite, maghemite, and magnetite) or short‐range ordered precipitates (ferrihydrite) may be found in soil environments, but in the rhizosphere the presence of organic ligands released by plants (exudates) or microorganisms promote the formation of ferrihydrite. Iron ions are liberated into soil solution by acidic weathering of minerals and then precipitated either locally or after translocation in soil environments. Humic and fulvic acids as well as organic substances produced by plants and microorganisms are involved in the weathering of primary minerals. Organic compounds play a very important role in the hydrolytic reactions of iron and on the formation, nature, surface properties, reactivity, and transformation of Fe oxides. Organic substances present in the rhizosphere interact with Fe promoting the formation of ferrihydrite and organo‐mineral complexes. The solubility of Fe precipitation products is usually low. However, the formation of soluble complexes of Fe(II) or Fe(III) with organic ligands, usually present in the rhizosphere increases the solubility of Fe‐oxides. Mobilization of Fe from Fe oxides by siderophores is of great importance in natural systems. They can form stable Fe(III) complexes (pK up to 32) and thus mobilize Fe from Fe(III) compounds. These higher Fe concentrations are important for the supply of Fe to plant roots which excrete organic acids at the soil–root interface. Iron oxides adsorb a wide variety of organic and inorganic anions and cations, which include natural organics, nutrients, and xenobiotics. There is competition between anions and cations for the surfaces of Fe‐oxides. Root exudates suppress phosphate or sulfate adsorption on Fe‐oxides. This is a mechanism by which plant roots mobilize adsorbed phosphate and improve their phosphate supply. Anions adsorption on iron oxides modify their dispersion/flocculation behavior and thus their mobility in the soil system. That can increase or decrease the possibility of contact between Fe‐oxides and organics or organisms able to dissolve them.     

the effect of phosphate on the transformation of ferrihydrite into crystalline products in alkaline media

The presence of phosphate retards the transformation of ferrihydrite into crystalline products. Increasing phosphate from 0 to 1 mole % results in an order of magnitude decrease in the rate of transformation of ferrihydrite at pH 12. Levels of phosphate of ～1 mol % suppress the formation of goethite (α-FeO(OH)) and result in the formation of a product consisting ofη-Fe₂O₃. Higher levels of phosphate result in the ferrihydrite remaining amorphous, even after several hundred hours. Phosphate prevents formation of goethite by hindering the dissolution of ferrihydrite rather than by interfering with nucleation and growth of goethite in solution. The transformation rate of pure ferrihydrite is also strongly inhibited in the presence of dissolved phosphate. This is due to surface complexation. The transformation rate was measured at temperatures of 60 °C and 70 °C. The rate of transformation was found to be described by either (i) a solid-state reaction equation for powdered compacts or (ii) a zero-order reaction controlled by desorption. The transformation of the ferrihydrite matrix was accompanied by the loss of the phosphate trace component. X-ray diffraction indicates that no solid solution involving phosphate substitution intoη-Fe₂O₃ is formed. Transmission electron microphotographs of the original precipitates containing phosphate confirm the presence of the phosphate and demonstrate its involvement in linking together extremely small particles of ferrihydrite.     

水耕人为土磁性矿物的生成转化机制研究回顾与展望

随着环境问题的日益突出,人为活动对土壤的影响越来越深刻,需加强对"人为作用"的研究以便解释现代土壤磁性的过程和变化。水耕人为土在发育过程中人为作用的方式多种多样,明确其磁性矿物的生成和转化机制及其影响因素有利于理解人为活动对现代土壤磁性的作用。但目前水耕人为土磁学研究还比较零散,缺乏系统性,已有研究结果有待深入梳理。本文对已有的相关研究报道,包括水耕人为土磁性参数的演变特征、磁性矿物的生成转化机制以及对成土因素的响应等进行综合评述。最后,对当前研究的不足和存在问题进行总结,并对研究方向进行了展望,以期有助于环境磁学的发展。     

Characterization of iron oxides in Fe-rich concretions from an imperfectly-drained Greek soil: a study by selective-dissolution techniques and X-ray diffraction

Fe-rich concretions commonly occur in Greek soils with alternating drying and waterlogging periods. This study was conducted to characterize the iron oxides in Fe-rich concretions from the upper solum of an Alfisol with seasonal perched water table by the combination of selective dissolution and X-ray diffraction (XRD) techniques. The results showed that more than 75% of the total iron (Fet) was associated with the crystalline and the amorphous Fe oxides, indicating a strong accumulation of free iron oxides (Fed) in concretions. Amorphous iron compounds (Feo) was present at high concentrations and fluctuated with profile depth. The active Fe ratio (Feo/Fed) values that ranged from 0.35 to 0.41 reflected an association of poorly crystalline goethite with some ferrihydrite. The XRD data showed that the Fe-rich concretions consisted of quartz, feldspars, illite and gypsum. The mineralogy of iron oxides in concretions was determined by comparison of XRD patterns for dithionite-citrate-bicarbonate (DCB) treated (deferrated) and untreated (non-deferrated) samples. Poorly crystalline goethite as demonstrated by broad lines in the diffraction patterns and ferrihydrite were the iron oxides detected in the concretions. This mineral assemblage appears to be related to the pedoenvironmental conditions in which the concretions were formed and indicates that the mechanisms governing the formation of crystalline Fe oxides from ferrihydrite are retarded by the presence of crystallization inhibitors.     

The effect of cadmium on the transformation of ferrihydrite into crystalline products at pH 8

Ferrihydrite, prepared in the presence of 0 to 20 mole % Cd in the solution, was used to study the transformation of ferrihydrite into crystalline products. The result showed that the presence of Cd strongly retards the transformation of ferrihydrite into crystalline products, suppressing the formation of goethite and leading to a product which eventually consists entirely of hematite at pH 8 and at 70 °C. The fraction of hematite in the transformation products increased with increasing level of Cd in the system. When 9 mole % Cd was present, the transformation product consisted entirely of hematite. The chemical analysis and XRD data showed that Cd was incorporated into the lattice of iron oxides, Cd-hematite and Cd-goethite being formed. The mole % Cd which replaced iron in the iron oxides increased with increasing level of Cd in the system below 9 mole % Cd. Above this value, but below 20 mole % the mole % of Cd incorporated in the lattice of iron oxides was constant at about 2.9 mole %. The volume of the unit cell of Cd-goethite increased with increasing level of Cd in the system until the goethite production was entirely suppressed. The volume of the unit cell of Cd-hematite also increased with increasing level of Cd, below 9 mole % of Cd in the system. Above this value, it was constant. Scanning electron microscopic examination showed that the presence of Cd affected the morphology of hematite more than that of goethite. The goethite grew from ferrihydrite as acicular crystals independent of the amount of Cd in the system. The shape of hematite particles varied from irregular platelets with lower Cd level, to ellipsoids, with higher Cd level in the system, and it also suggested that Cd prevented the formation of goethite by hindering the dissolution of ferrihydrite rather than by interfering with nucleation and growth of goethite from solution. The rate of transformation was studied at pH 8, 50 °C and 70 °C. The transformations were first order reactions at both temperatures.     

Iron speciation in soils and soil aggregates by synchrotron-based X-ray microspectroscopy (XANES,μ-XANES)

Iron speciation in soils is still poorly understood. We have investigated inorganic and organic standard substances, diluted mixtures of common Fe minerals in soils (pyrite, ferrihydrite, goethite), soils in a forested watershed which constitute a toposequence with a hydrological gradient (Dystric Cambisol, Dystric Planosol, Rheic Histosol), and microsites of a dissected soil aggregate by X‐ray Absorption Near Edge Spectroscopy (XANES) at the iron K‐edge (7112 eV) to identify different Fe(II) and Fe(III) components. We calculated the pre‐edge peak centroid energy of all spectra and quantified the contribution of different organic and inorganic Fe‐bearing compounds by Linear Combination Fitting (LCF) conducted on the entire spectrum (E = 7085–7240 eV) and on the pre‐edge peak. Fe‐XANES conducted on organic and inorganic standards and on synthetic mixtures of pyrite, ferrihydrite and goethite showed that by calculating the pre‐edge peak centroid energy, the Fe(II)/Fe(III) ratio of different Fe‐bearing minerals (Fe sulphides, Fe oxyhydroxides) in mineral mixtures and soils can be quantified with reasonable accuracy. A more accurate quantification of the Fe(II)/Fe(III) ratio was possible with LCF conducted on the entire XANES spectrum. For the soil toposequence, an increased groundwater influence from the Cambisol to the Histosol was reflected in a larger contribution of Fe(II) compounds (Fe(II) silicate, Fe monosulphide, pyrite) and a smaller contribution of Fe(III) oxyhydroxides (ferrihydrite, goethite) to total iron both in the topsoil and the subsoil. In the organic topsoils, organically bonded Fe (33–45% of total Fe) was 100% Fe(III). For different microsites in the dissected aggregate, spatial resolution ofμ‐XANES revealed different proportions of Fe(II) and Fe(III) compounds. Fe K‐edge XANES andμ‐XANES allows an approximate quantification of Fe(II) and Fe(III) and different Fe compounds in soils and (sub)micron regions of soil sections, such as mottles, concretions, and rhizosphere regions, thus opening new perspectives in soil research.     

Heavy metal sorption on soil minerals affected by the siderophore desferrioxamine B: the role of Fe(III) (hydr)oxides and dissolved Fe(III)

Phytoextraction of heavy metals from polluted soils has often been found to be limited by the bioavailability of the pollutants. Inorganic or organic ligands are occasionally used as complexing agents to enhance the mobility of the heavy metals. However, the opposite effect is also possible. We studied the influence of the hydroxamate siderophore desferrioxamine B (DFOB) on the sorption of Cu, Zn and Cd to clay minerals, with the emphasis on the role of dissolved Fe(III) and Fe(III) minerals. Depending on the surface charge of the minerals and on pH, sorption of heavy metals can be either enhanced or diminished. We show here that this effect of DFOB disappears if dissolved Fe(III) is added to suspensions of clay minerals in excess to DFOB. We found that the solid Fe(III) phases ferrihydrite and goethite did not impede the effect of DFOB on the sorption of heavy metal, however. Between pH 4 and 10, DFOB completely prevented Cu sorption on ferrihydrite. A strong mobilizing effect was also observed for Zn, but not for Cd. In presence of goethite, concentrations of dissolved Cu, Zn and Cd were enhanced only above approximately pH 5, 7 and 8, respectively. Below these pH values the binding of these metals to goethite was even stronger with than without DFOB. In the absence of heavy metals, DFOB‐promoted dissolution of ferrihydrite was much faster than that of goethite due to the larger surface area of ferrihydrite. In the alkaline pH range, where sorption of DFOB on the surfaces of the iron oxides was greater, dissolution of both minerals was reduced.     

Precipitation of iron in a poorly drained alluvial soil

Abstract

Ferruginous deposits from the outfall and backfill of a newly‐installed drainage scheme in a poorly drained alluvial soil have been characterised using selective chemical dissolution, X‐ray diffraction, and chemical analysis and compared with the iron (Fe) deposits found in various micro‐environments within the soil profile. In the drainage ditch and on the permeable backfill around the drainage pipes, the mineralogy of the ferruginous deposits is dominated by the poorly ordered mineral, ferrihydrite, whereas within the soil environment the hydrous iron oxides display a wider range of structural order. It is probable that the initial precipitation product is poorly‐ordered material but that within the soil transformation to a more well ordered mineral, goethite, can occur.     

Iron oxide‐humic acid coprecipitates as iron source for cucumber plants

In soil, iron (Fe) solubility depends on complex interactions between Fe minerals and organic matter, but very little is known about plant availability of Fe present in Fe oxides associated with humic substances. For this purpose, this study investigates the effect of Fe mineral crystallinity in the presence of humic acids (HA) on Fe availability to plants. Four Fe–HA mineral coprecipitates were prepared, either in the presence or absence of oxygen, i.e., two goethite (G)‐HA samples containing large amounts of Fe as nanocrystalline goethite and ferrihydrite mixed phases, and two magnetite (M)‐HA samples containing crystalline magnetite. Bioavailability studies were conducted in hydroponic systems on cucumber plants (Cucumis sativus L.) grown under Fe deficient conditions and supplied with the Fe–HA coprecipitates containing goethite or magnetite. Results showed that plants grown in the presence of Fe–HA coprecipitates exhibited a complete recovery from Fe deficiency, albeit less efficiently than plants resupplied with Fe‐chelate fertilizer used as control (Fe‐diethylene triamine penta acetic acid, Fe‐DTPA). However, the supply with either G‐ or M–HA coprecipitates produced different effects on plants: G–HA‐treated plants showed a higher Fe content in leaves, while M–HA‐treated plants displayed a higher leaf biomass and SPAD (Soil–Plant Analysis Development) index recovery, as compared to Fe‐DTPA. The distribution of macronutrients in the leaves, as imaged by micro X‐ray fluorescence (µXRF) spectroscopy, was different in G–HA and M–HA‐treated plants. In particular, plants supplied with the poorly crystalline G–HA coprecipitate with a lower Fe/HA ratio showed features more similar to those of fully recovered plants (supplied with Fe‐DTPA). These results highlight the importance of mineral crystallinity of Fe–HA coprecipitates on Fe bioavailability and Fe uptake in hydroponic experiments. In addition, the present data demonstrate that cucumber plants can efficiently mobilize Fe, even from goethite and ferrihydrite mixed phases and magnetite, which are usually considered unavailable for plant nutrition.     

The impact of redox conditions on the rare earth element signature of redoximorphic features in a soil sequence developed from limestone

Redox processes, which are widespread in soils, need to be quantified for an improved comprehension of the dynamics of Fe- and Mn-oxides and their associated trace elements. The classical methodology used to study these redox processes generally relies on the quantification of all mineral species in the various pedological features that can be related to different redox stages. However, this approach usually encounters the difficulty of precisely quantifying the different forms of poorly crystallised Fe- and Mn-oxides.In this study, we use the signature of rare earth elements (REEs) to visualise and, eventually, quantify the importance of redox processes in soils. Our approach relies on that developed by Laveuf et al. (2008) and the idea that the relative contribution to the mobilisation of REEs that is made by the primary minerals reactive to redox conditions depends on the following factors: (i) their initial proportion in the different pedological features that can be related to various redox processes, (ii) their relative mobilisation during the redox process in question, and (iii) their initial REE signatures.The catena studied is characterised by two stages of redox conditions: the first is related to the formation and subsequent dissolution of Fe–Mn concretions, and the second is related to the bleaching of the soil matrix due to morphological degradation. In this soil, the main minerals reactive to redox conditions are Mn-oxides, ferrihydrite, goethite and (fluor)apatite. The results indicate that the primary redox conditions can be characterised by a positive Ce anomaly on the REE pattern, which has been attributed to a preferential immobilisation of this element, due to its association with Mn-oxides. The results also indicate that the secondary redox conditions can be characterised by depletion in medium REEs (MREEs) in the REE pattern, which has been attributed to a preferential release of these elements during the dissolution of (fluor)apatite and, to a lesser extent, of ferrihydrite.These results emphasise the potential of REE signatures of the visualisation of the various redox processes that have been active in a soil. Additionally, REE signatures are a proxy of the frequency and intensity of the redox conditions.     

Transformation of haematite and Al-poor goethite to Al-rich goethite and associated yellowing in a ferralitic clay soil profile of the middle Amazon Basin (Manaus, Brazil)

The red and yellow colours of ferralitic soils in the tropics have for long intrigued pedologists. We have investigated the upward yellowing in a 10-m thick profile representative of the Ferralsols of the plateaux of the Manaus region of Brazil. We determined changes in the nature and crystal chemistry of their Fe oxides by optical and Mössbauer spectroscopy as well as Rietveld refinement of X-ray diffraction patterns. We attribute the upward yellowing of the soil to a progressive transformation of the Fe oxides at nearly invariant iron contents. Aluminium in contrast is strongly mobilized in the uppermost clay-depleted topsoil where there is preferential dissolution of kaolinite and crystallization of gibbsite. Haematite decreases from 35 to 10% of the Fe oxides from the bottom to the top of the profile and the particles become smaller (75–10 nm). Its Al for Fe-substitution remains almost unchanged (10–15 mol %). The average Al-substitution rate of goethite increases from 25 to 33 mol %, and its mean crystal diameter remains in the range 20–40 nm. The proportion of Al-rich goethite (33 mol %) increases at the expense of less Al-substituted Fe oxides (haematite and goethite). This conversion with restricted transfer of iron means that the amount of Al stored in Fe oxides gradually increases. Kaolinite, haematite and Al-poor goethite are thus witnesses of earlier stages of ferralitization of the soil. In contrast, Al-rich goethite and gibbsite initiate the alitization (or bauxitization) of the soil. They correspond to the last generation of soil minerals, which most likely reflects the present-day weathering conditions. The progressive replacement of kaolinite, haematite and Al-poor goethite by new generations of Al-rich goethite and gibbsite attests to greater activities of water and aluminium and smaller activity of aqueous silica in the topsoil than in the subsoil. We interpret this as a consequence of longer periods of wetting in the topsoil that could result from soil aging, more humid climate or both.     

Synthetic solid solutions formed between goethite and diaspore

The substitutional solid solutions of goethite (a-FeOOH) and diaspore (α-AlOOH) have been investigated by X-ray powder diffraction and chemical analysis in order to establish the solubility limits of aluminium in the goethite structure. α-Fe_1-xAI_xOOH samples were obtained by ageing of coprecipitated amorphous (Fe,Al) hydroxides at pH 13 in NaOH and Na[Al(OH)₄] solutions at 25°C (G25 series) and 70°C (G70 series), respectively. Chemical analysis reveals that the aluminium content of Al goethites is consistent with Al concentration in the coprecipitated hydroxides up to about 10 mol% Al. In Al goethites obtained from (Fe,Al) hydroxides with higher Al:Fe ratios, the relative Al content is considerably lower. It was found that pure ferrihydrite stored in the aluminate solution is also transformed into Al goethite. The X-ray diffraction results show a significant divergence of the unitcell parameters from Vegard's law. This points out the limited ranges of the solid solution between goethite and diaspore and suggests the formation of defect, cation-deficient structures.     

Soil development processes in an Aqualf-Ochrept sequence from loess with admixtures of tephra, New Zealand

The properties of contrasting soils occurring under a 1050–1600 mm rainfall gradient are described. The soils range, with increasing rainfall, from Typic Fragiaqualfs to Andic Dystrochrepts. Sand mineralogy of these soils indicates that they have formed in essentially similar parent materials consisting largely of quartzo-feldspathic loess with admixtures of rhyolitic and andesitic tephra. The Fragiaqualfs have high bulk density, impeded drainage in winter, degraded chlorite, argillic horizons, halloysite and vermiculite. The Dystrochrepts have lower bulk density, free drainage, ferrihydrite, allophane, humus-(Al, Fe) complexes and no argillic horizons. An hypothesis to explain differences between these soil groups proposes that the dense horizons in the Fragiaqualfs arise largely from hydraulic suctions exerted by roots during periods of high summer water deficits. The consequent loss of porosity leads to impeded drainage in winter causing gleying and enhanced clay formation. In the Dystrochrepts the summer deficits are lower, consequently the soils have lower bulk densities and remain free draining.     

Sorption of 2,4-D and other phenoxy herbicides to soil, organic matter, and minerals

Purpose

We review 2,4-dichlorophenoxyacetic acid (2,4-D) and other phenoxy herbicide sorption experiments.

Methods

A database with 469 soil–water distribution coefficients K _d (in liters per kilogram) was compiled: 271 coefficients are for the phenoxy herbicide 2,4-D, 9 for 4-(2,4-dichlorophenoxy)butyric acid, 18 for 2-(2,4-dichlorophenoxy)propanoic acid, 109 for 2-methyl-4-chlorophenoxyacetic acid, 5 for 4-(4-chloro-2-methylphenoxy)butanoic acid, and 57 for 2-(4-chloro-2-methylphenoxy)propanoic acid. The following parameters characterizing the soils, solutions, or experimental procedures used in the studies were also compiled if available: solution CaCl₂ concentration, pH, pre-equilibration time, temperature, soil organic carbon content (f _oc), percent sand, silt and clay, oxalate extractable aluminum, oxalate extractable iron (Oxalate Fe), dithionite–citrate–bicarbonate extractable aluminum, dithionite–citrate–bicarbonate extractable iron (DCB Fe), point of zero negative charge, anion exchange capacity, cation exchange capacity, soil type, soil horizon or depth of sampling, and geographic location. K _d data were also compiled characterizing phenoxy herbicide sorption to the following well-defined sorbent materials: quartz, calcite, α-alumina, kaolinite, ferrihydrite, goethite, lepidocrocite, soil humic acid, Fluka humic acid, and Pahokee peat.

Results

The data review suggests that sorption of 2,4-D can be rationalized based on the soil parameters pH, f _oc, Oxalate Fe, and DCB Fe in combination with sorption coefficients measured independently for humic acids and ferrihydrite, and goethite.

Conclusions

Soil organic matter and iron oxides appear to be the most relevant sorbents for phenoxy herbicides. Unfortunately, few authors report Oxalate Fe and DCB Fe data.