Relationships between phosphate sorption and iron oxides in Alfisols from a river terrace sequence of Mediterranean Spain

Phosphate sorption isotherms for samples of the A- and upper B-horizons of Alfisols situated on a sequence of terraces of the River Guadalquivir, southern Spain, showed that phosphate sorbed at an equilibrium concentration of 0.3 μg P ml^?1 was correlated with several soil properties. Crystalline Fe-oxides (goethite and hematite) appeared to be the most important P-sorbing components of the soil samples. Sorption was highly correlated with percent clay and with dithionite soluble Fe. This last property was as good a property to predict sorption as the specific surface of crystalline Fe-oxides (which was estimated by line profile analysis of the X-ray diffractograms), probably because the range of surface areas for goethite and hematite was relatively narrow in the samples and because of the limited accuracy of the method of line profile analysis.Well drained and imperfectly drained soils differed little in sorption properties. In imperfectly drained, hematite-free soils, chroma was correlated with sorption. This is promising for it would allow rapid field estimation of sorption.The sorption maximum, calculated from the fitted Langmuir isotherm, was about 1.7 μmol P m^?2 of Fe-oxides, a value similar to those reported in the literature for natural and synthetic oxides.     

Types of Crystalline Iron Oxides and Phosphate Adsorption in Variable Charge Soils

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.     

Phosphate sorption by red mediterranean soils from Greece

Abstract

In nineteen surface horizons of red Mediterranean soils from various locations of Greece, phosphorus (P) sorption experiments were conducted and the sorption characteristics were studied in relation to soil properties. Phosphate sorption data were fitted both to the Langmuir and Freundlich equations. From these equations, the following P sorption parameters were determined from the Freundlich equation, X = ACⁿ, the parameters A (the phosphate sorbed at C = 1 mg P/L), n (the P sorption intensity), the P sorption index (PS = X/log C) and maximum P sorption (Xmfr). From the Langmuir equation, C/X = 1/KXm + C/Xm, the parameters K (showing the bonding energy), maximum P sorption (Xmla), the quantity of P adsorbed at a standard concentration of 0.2 mg P/L (P0.2), and P maximum buffering capacity (PMBC). The Freundlich parameter A was strongly correlated to the clay and sesquioxides ("free”; iron and aluminum oxides and amorphous iron oxides) content. Seventy‐four percent of the variance of this parameter was explained by clay and “free”; iron (Fe) content. The Freundlich parameter n was significantly correlated with pH and amorphous iron oxides content, while 52% of its variance was explained by amorphous Fe and dithionite extrac‐table aluminum (Al). The P sorption maxima calculated from the Freundlich equation were in general lower than those calculated by the Langmuir equation. Both these parameters were strongly correlated with clay and more slightly with sesquioxides content. About 50% of their variance was explained by clay content of the soils. The P sorption index was strongly correlated with the clay content and less strongly with dithionite‐extractable Fe and Al. The P‐buffering capacity calculated from the data of Langmuir equation was also strongly correlated with these two parameters. In addition, clay content and dithionite‐extractable Fe and Al were well correlated to the amounts of P required to obtain an equilibrium concentration of 0.2 mg P/L while 61% of the variation of this parameter was explained by the clay and the dithionite‐extractable Fe content. From these findings, it seems that for the red Mediterranean soils from Greece, P sorption is affected by clay content and iron and aluminum oxide contents.     

THE COVARIANCE OF PHOSPHATE SORPTION WITH OTHER SOIL PROPERTIES IN SOME BRITISH AND TROPICAL SOILS

Phosphate sorption capacity estimated by Piper's (1942) ‘anion exchange capacity’ and Bache and Williams's (1971) phosphate sorption index were correlated with soil pH, clay, organic matter, ‘free iron oxides’ and ‘extractable aluminium’ (McLean et al., 1958) for topsoil and subsoil samples from twenty tropical and twenty British acidic soil profiles. These two groups of soils did not differ significantly in phosphate sorption. Extractable aluminium and free iron oxide were well correlated with phosphate sorption, free iron oxide being superior to aluminium in freely drained British soils but not in poorly drained ones. Organic matter content correlated well with phosphate sorption for the poorly drained British soils, and for the tropical soils when sorption capacitywas measured using a high phosphate concentration.     

Phosphate sorption characteristics of major soils in Okinawa,Japan

Abstract

Phosphate sorption isotherms were determined for 16 representative major soils developed from different parent materials on Okinawa. Phosphate sorption characteristics were satisfactorily described by the Langmuir equation, which was used to determine phosphorus (P) sorption maxima of the soils. Phosphate sorption maxima ranged from 630 to 2208 mg P kg^‐1 soil (mean 1,362 mg P kg^‐1). The standard P requirement (i.e., the amount of P required to attain 0.2 mg P L^‐1 equilibrium solution) followed the same trend as sorption maximum (r =0.94***), with values ranging from 132 to 1,020 mg P kg^‐1 soil (mean 615 mg P kg^‐1). This mean value corresponds to fertilizer addition of 923 kg P ha^‐1 indicating that the soils have high P fertilizer requirements. Results of simple linear regression analysis indicated that sorption maximum was significantly correlated with clay content, organic matter, oxalate iron (Fe), pyrophosphate Fe, DCB aluminum (Al), oxalate Al, and pyrophosphate Al, but not with DCB Fe, pH, or available P content. The best regression model for predicting sorption maximum was the combination of clay, organic matter, pyrophosphate Fe, and DCB Al which altogether explained 79% of the variance in sorption maximum. The equation obtained could offer a rapid estimation of P sorption in Okinawan soils.     

海南岛北部玄武岩上土壤发生研究Ⅱ.铁氧化物特征

研究了海南岛北部玄武岩上发育的不同风化成土年代土壤系列的铁氧化物特征。研究表明,随风化成土时间增加,土壤发生过程中形成的游离铁（Fed）以及铁游离度（Fed/Fet）增大,铁活化度（Feo/Fed）降低。穆斯堡尔谱分析显示风化成土时间从9×104a、64×104a至 181× 104a,土壤黏粒中形成的赤铁矿含量占铁氧化物的比例从16％、25％增至 48％。风化成土时间越短,土壤中针铁矿结晶程度越差。X-射线衍射结果表明土壤细土和黏粒中赤铁矿含量与风化成土时间呈正比增加。同时,土壤有磁铁矿含量减少、磁赤铁矿增加的趋势。     

Origin of red-yellow mottling in a Ferric Acrisol of southern Spain

We studied the spatial distribution of the amount and types of Fe oxides in a Ferric Acrisol having a red-yellow mottled horizon. Red mottles contain hematite and goethite; yellow mottles have goethite but in amounts markedly smaller than those of the contiguous red mottles. We think that reductive dissolution caused the disappearance of the hematite and part of the goethite in the yellow mottles. This is supported by the experimental dissolution of the iron oxides of the clay fractions: hematite dissolved, on the average, at a rate twice of that of goethite.     

Properties and distribution of iron oxides and their association with minor elements in the soils of south-western Australia

Iron oxides from 39 soils derived from various parent materials in south-western Australia have been studied using a variety of techniques. Goethite and hematite were the only two Fe oxides present. The goethite/(goethite+hematite) ratio ranged from 0.18 to 1.0, and was highest in soils on acidic igneous rocks, decreasing for soils on alluvial and mafic parent materials. In a few soils derived from acid rocks only goethite was present. The redness rating of soils increased linearly with increasing amount of hematite. Al substitution in goethite ranged from 13 to 35 mol%, with higher values for soils on acid igneous rocks (median value = 26 mol%) than for soils on mafic (19 mol%) and alluvial (17 mol%) parent materials. Substitution of A1 in hematite ranged from 4 to 23 mol%, and was greatest in soils on mafic parent materials (median value = 12 mol% A1). A1 substitution in hematite was about half of that in associated goethite. The dehydroxylation temperature for goethite increased linearly with increasing A1 substitution. Goethite and hematite had similar crystal sizes (c. 20 nm), and both were in the form of irregular plates. Dissolution with 1 M HCl of iron oxides concentrated from the soils by 5 M NaOH digestion could be described both by the Cube Root Law and by Kabai's equation. Only one straight line was obtained for the dissolution data using Kabai's equation for samples containing both goethite and hematite, in contrast to the results of other workers. Major proportions of the Co, Cr, Cu, Mn, Ni and Zn in the soils were concentrated with the iron oxides, and the dissolution kinetics of these elements indicate that some may be present in the structure of the iron oxides.     

Factors affecting phosphate sorption along a Mediterranean, dolomitic soil and vegetation chronosequence

Phosphate sorption by calcareous soils has been studied mainly on heavily fertilized agricultural soils and soils with calcite as the main carbonate mineral. We examined factors affecting phosphate adsorption in the soils of a semi-arid, mediterranean, dolomitic, soil and vegetation chrono-sequence in southeastern Spain. The youngest soils are highly eroded, Sandy Regosols (Typic Xerorthents) under gorse-scrubland vegetation. These have small P sorption capacities, large Mg-Ca carbonate contents but small amounts of Fe and Al oxides. Small total P (HNO₃/HClO₄ digestion) concentrations (30–130 μg P g^?1), of which up to 90% is Ca-bound (HCl-extractable), are typical of these young soils. P sorption markedly increased when Ca²⁺ was added to the solution. The fractionation of previously sorbed P indicates that the fate of most of this extra-sorbed P is the labile-P fraction sorbed on to (carbonate) surfaces and the apatite-like fraction (NaHCO₃-extractable and HCl-extractable fractions). At the other extreme, older more-intensively weathered, sandy-clay-loam rendzinas (Entic Haploxerolls), supporting dense mature garrigue, have a much greater P adsorption capacity and larger clay and Fe and Al oxide concentrations. They have more total P (ca 400 μg P g^?1), much of it in occluded form (residual fraction). These soils show no significant differences in P sorption whether or not CaCl₂ was used as a background electrolyte. Considering the overall variations within the chronosequence, dithionite extractable Fe and Al are the properties best correlated with P sorption. This support the general finding that crystalline Fe-oxides (e.g. goethite and haematite) appear to be the most important P-sorbing component for soils in the Mediterranean region, rather than amorphous Fe-oxides (e.g. ferrihydrite) as is reported for more mesic areas. Stepwise multiple regression and fractionation data, however, suggest that, provided the soil solution is rich in Ca²⁺, carbonate may also be a significant contributing factor to P sorption, especially in the youngest of these dolomitic soils.     

Retention of dissolved organic matter by illitic soils and clay fractions: Influence of mineral phase properties

The dependency of the retention of dissolved organic carbon (DOC) on mineral phase properties in soils remains uncertain especially at neutral pH. To specifically elucidate the role of mineral surfaces and pedogenic oxides for DOC retention at pH 7, we sorbed DOC to bulk soil (illitic surface soils of a toposequence) and corresponding clay fraction (< 2 μm) samples after the removal of organic matter and after removal of organic matter and pedogenic oxides. The DOC retention was related to the content of dithionite‐extractable iron, specific surface area (SSA, BET‐N₂ method) and cation exchange capacity (pH 7). The reversibility of DOC sorption was determined by a desorption experiment. All samples sorbed 20–40 % of the DOC added. The DOC sorption of the clay fractions explained the total sorption of the bulk soils. None of the mineral phase properties investigated was able to solely explain the DOC retention. A sorption of 9 to 24 μg DOC m^–2 indicated that DOC interacted only with a fraction of the mineral surface, since loadings above 500 μg m^–2 would be expected for a carbon monolayer. Under the experimental conditions used, the surface of the silicate clay minerals seemed to be more important for the DOC sorption than the surface of the iron oxides. The desorption experiment removed 11 to 31 % of the DOC sorbed. Most of the DOC was strongly sorbed.     

Iron oxide mineralogy of some soils of two river terrace sequences in Spain

The iron oxides of soils of two river terrace sequences in Spain which show an increasing degree of redness with age were studied. Clay fractions contained only small amounts of oxalate-extractable Fe. Goethite and hematite, the only crystalline Fe-oxides identified, were determined quantitatively by X-ray diffraction (XRD) after concentrating the Fe-oxides by boiling in $\text{5N}$ NaOH and subtracting the step-counted diffractogram of the deferrated clay from that of the non-deferrated clay, obtaining thus a “pure” Fe-oxide diffractogram. EDTA extracted hematite preferentially to goethite as is seen by loss of red colour and by XRD. A good correlation was found between the content of hematite in the fine earth and a redness rating based on Munsell notations.In the Guadalquivir River sequence, Fe_d and Fe_d/Fe_t increased with age. The amount of both goethite and hematite formed from silicate-Fe increased with soil age but hematite increased more than goethite, possibly due to the xeric soil environment. Also, goethite increased in crystallinity as indicated by a decrease in XRD line broadening and Fe_o/Fe_d ratios. No such trends were found in the Esla River sequence, possibly because the initial alluvium was already highly weathered as shown by high Fe_d/Fe_t values (0.8) irrespective of terrace level.Al substitution in goethite calculated from XRD increased with soil age, reflecting the increasing acidity of the soils. Al substitution in hematite was markedly lower.     

Comparison of different models for phosphate sorption as a function of the iron and aluminium oxides of soils

Phosphate sorption on topsoil and subsoil samples from different soils located in the eastern part of Germany was studied. Two models were fitted to sorption data obtained after 4 and 40 d of gentle shaking. The models differ with respect to the fractions of iron and aluminium (hydr)oxides that are considered and whether the phosphate initially sorbed in the soil is taken into zccount. Oxalate-extractable P, (P_ox), appears to be a major part of the total soil P. The total P sorption measured, F, was predominantly related to the amounts of amorphous iron (Fe_ox) and aluminium (Al_ox). A significant relation between crystalline iron (Fe_d– Fe_ox) and total P sorption was not found. Reversibly adsorbed phosphate (P_i), measured after 40 d reaction time, was a function of clay content and content of amorphous iron and aluminium (hydr)oxides.     

台湾红壤及森林土壤中之氧化铁

本文综合汇整近年来在台湾，应用高梯度磁场分离技术，配合一般化学分析，Ｘ－射线衍射法，磁测分析，电子显微镜观察与电子衍射鉴定，以及铁－５７穆期堡尔谱学分析等方法，研究红壤与森林土壤中，氧化铁的分布及其结构性质之成果回顾；关于氧化铁之分布情形，其研究结果显示：台湾红壤中普遍存在有赤铁矿与针铁矿等氧化铁矿物，而在化育自大屯山更新世纪安山岩母质与澎湖列岛更新世纪玄武岩母质的红壤中，以及兰屿绿岛海边之银白色     

Zinc sorption–desorption by sand,silt and clay fractions in calcareous soils of Iran

Zinc sorption–desorption by sand, silt and clay fractions of six representative calcareous soils of Iran were measured. Sand, silt and clay particles were fractionated after dispersion of soils with an ultrasonic probe. Zinc sorption analysis was performed by adding eight rates of Zn from 6 to 120 μmol g^?1. For the desorption experiment, samples retained after the measurement of Zn sorption were resuspended sequentially in 0.01 M NaNO₃ solution and shaken for 24 h. Results indicated that Zn sorption by soil fractions increased in the order clay > silt > sand, and correlated negatively with CaCO₃ content and positively with cation exchange capacity (CEC) and smectite content. Results indicated that for all fractions, the Langmuir equation described the sorption rates fairly well. In contrast to sorption, Zn desorption from soil fractions increased in the order sand > silt > clay, and correlated positively with CaCO₃ content, CEC and smectite content. Results showed that parabolic diffusion and two constant equations adequately described the reaction rates of Zn desorption. In general, for all soils studied, the coarser the particle size, the less Zn sorption and more Zn desorption, and this reflects much higher risk of Zn leaching into groundwater or plant uptake in contaminated soils.     

Adsorption and Desorption of Copper in Pasture Soils

Abstract

Copper (Cu) is bound strongly to organic matter, oxides of iron (Fe) and manganese (Mn), and clay minerals in soils. To investigate the relative contribution of different soil components in the sorption of Cu, sorption was measured after the removal of various other soil components; organic matter and aluminum (Al) and Fe oxides are important in Cu adsorption. Both adsorption and desorption of Cu at various pH values were also measured by using diverse pasture soils. The differences in the sorption of Cu between the soils are attributed to the differences in the chemical characteristics of the soils. Copper sorption, as measured by the Freundlich equation sorption constants [potassium (K) and nitrogen (N)], was strongly correlated with soil properties, such as silt content, organic carbon, and soil pH. The relative importance of organic matter and oxides on Cu adsorption decreased and increased, respectively, with increasing solution Cu concentrations. In all soils, Cu sorption increased with increasing pH, but the solution Cu concentration decreased with increasing soil pH. The cumulative amounts of native and added soil Cu desorbed from two contrasting soils (Manawatu and Ngamoka) during desorption periods showed that the differences in the desorbability of Cu were a result of differences in the physico‐chemical properties of the soil matrix. This finding suggests that soil organic matter complexes of Cu added through fertilizer, resulted in decreased desorption. The proportions of added Cu desorbed during 10 desorption periods were low, ranging from 2.5% in the 24‐h to 6% in the 2‐h desorption periods. The desorption of Cu decreased with increasing soil pH. The irreversible retention of Cu might be the result of complex formation with Cu at high pH.     

Poorly crystalline iron and aluminium oxides contribute to the carbon saturation and sorption of dissolved organic carbon in the soil

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.     

水溶性有机碳在各种粘土底土中的吸附：土壤性质的影响

Clay-rich subsoils are added to sandy soils to improve crop yield and increase organic carbon (C) sequestration; however, little is known about the influence of clay subsoil properties on organic C sorption and desorption. Batch sorption experiments were conducted with nine clay subsoils with a range of properties. The clay subsoils were shaken for 16 h at 4 ^oC with water-extractable organic C (WEOC, 1 224 g C L^-1) from mature wheat residue at a soil to extract ratio of 1:10. After removal of the supernatant, the residual pellet was shaken with deionised water to determine organic C desorption. The WEOC sorption was positively correlated with smectite and illite contents, cation exchange capacity (CEC) and total organic C, but negatively correlated with kaolinite content. Desorption of WEOC expressed as a percentage of WEOC sorbed was negatively correlated with smectite and illite contents, CEC, total and exchangeable calcium (Ca) concentrations and clay content, but positively correlated with kaolinite content. The relative importance of these properties varied among soil types. The soils with a high WEOC sorption capacity had medium CEC and their dominant clay minerals were smectite and illite. In contrast, kaolinite was the dominant clay mineral in the soils with a low WEOC sorption capacity and low-to-medium CEC. However, most soils had properties which could increase WEOC sorption as well as those that could decrease WEOC sorption. The relative importance of properties increasing or decreasing WEOC sorption varied with soils. The soils with high desorption had a low total Ca concentration, low-to-medium CEC and low clay content, whereas the soils with low desorption were characterised by medium-to-high CEC and smectite and illite were the dominant clay minerals. We conclude that WEOC sorption and desorption depend not on a single property but rather a combination of several properties of the subsoils in this study.     

Studies on the mechanisms of fixation and release of ammonium in paddy soils after flooding. I. Effect of iron oxides on ammonium fixation

Experiments were conducted with two typical paddy soils from China and a vermiculite to study the influence of iron oxides on the fixation and release of ammonium. Removing iron oxides, especially amorphous iron oxides, from the soils favoured the release of non-exchangeable NH₄-N and stimulated the fixation of NH₄-N in the presence of added (NH₄)₂SO₄. Addition of artificial goethite and hematite to the original soils or to the soils free of iron oxides reduced the fixation of NH₄⁺-ions. This effect was also observed with vermiculite. We conclude that the coating of clay minerals with iron oxides has an impact on the diffusion of NH₄⁺-ions into and out of the interlayers of the clay minerals. The reduction and dissolution of iron oxides induced by low redox potential (E_h) after flooding of paddy soils is assumed to be an important mechanism controlling NH₄⁺-fixation in paddy fields.     

三种铁氧化物的磷吸附解吸特性以及与磷吸附饱和度的关系

采用三种人工合成铁氧化物(针铁矿、赤铁矿和水铁矿)比较了结晶态和无定形铁氧化物对磷的吸附—解吸特性以及与磷吸附饱和度的关系。结果表明,三种铁氧化物的磷吸附特性均可用Langumir方程来描述,相关系数均大于0.9,达到极显著水平。从磷最大吸附量(Qm)、吸附反应常数(K)和最大缓冲容量(MBC)三项吸附参数综合考虑,水铁矿(无定形)对磷的吸附无论在容量还是强度方面均比结晶态铁氧化物针铁矿和赤铁矿大得多。水铁矿吸附的磷比针铁矿和赤铁矿所吸附的磷更难解吸;水铁矿的大量活性表面并没有表现出增加磷释放的作用。磷吸附饱和度有望作为评价土壤或铁氧化物磷吸附—解吸的强度和容量因子的一个综合指标。     

The cause of redness in some buried and non-buried soils in eastern England

Relationships were examined between colours and the amounts of extractable-iron or of individual iron oxides present in <2μm fractions of samples from buried and non-buried soils in eastern England. Colour was expressed in terms of a redness rating (RR). Oxalate-extractable iron (Fe_o), dithionite-extractable iron (Fe_d) and goethite contents were not significantly correlated with RR. There was, however, a strong correlation between RR and hematite content. These preliminary results provide some justification for the assumptions concerning relationships between reddish colours and hematite content, which are implicit in the paleo-argillic concept of the Soil Survey of England and Wales. However, reddish colours (particularly within the 7.5 YR and possibly the 5 YR hue range) should not be used in isolation as an indiscriminate indicator of pre-Devensian pedogenesis in Britain.