Sorption and desorption of cobalt by soils and soil components

The sorption of Co by individual soil components was studied at solution Co concentrations that were within the range found in natural soil solutions. Soil-derived oxide materials sorbed by far the greatest amounts of Co although substantial amounts were also sorbed by organic materials (humic and fulvic acids). Clay minerals and non-pedogenic iron and manganese oxides sorbed relatively little Co. It is considered that clay minerals are unlikely to have a significant influence on the sorption of Co by whole soils. Cobalt sorbed by soil oxide material was not readily desorbed back into solution and, in addition, rapidly became non-isotopically exchangeable with solution Co. In contrast, Co was relatively easily desorbed from humic acid and a large proportion of the Co sorbed by humic acid remained isotopically exchangeable. Cobalt sorbed by montmorillonite was more easily desorbed than that sorbed by soil oxide but less easily than that sorbed by humic acid. Cobalt sorption isotherms for whole soils at low site coverage were essentially linear and the gradients of isotherms increased with pH. A comparison of isotherm gradients for whole soils and individual soil components supported the suggestion that Co sorption in whole soils is largely controlled by soil oxide materials.     

Phosphate sorption by calcareous Vertisols and Inceptisols as evaluated from extended P-sorption curves

The plant availability of phosphate applied to calcareous soils is affected by precipitation and adsorption reactions, the relative significance of which is not well known. We used extended P-sorption curves obtained at phosphate addition rates up to 340 mmol P kg^?1 soil to examine the relative contribution of precipitation and adsorption by 24 calcareous Spanish Vertisols and Inceptisols. Adsorption was dominant at 1 day and at small rates of addition (10–35 mmol P kg^?1). With increasing clay and Fe and Al oxides contents of the soil, more phosphate was sorbed before the sorption curve bent upwards, as a result of Ca phosphate precipitation. Sorption curves showed a nearly vertical intermediate region, the length of which increased with time, suggesting that a Ca phosphate buffered the concentration of P in solution. The buffering concentration decreased with time, suggesting a progressive transformation of more to less soluble forms of Ca phosphate. A phase less soluble than octacalcium phosphate seemed to control the concentration of P in solution at 180 days in most soils. The apparent solubility of this phase decreased with increasing carbonate content in the soil. Precipitation of poorly soluble Ca phosphates apparently predominated up to a P addition dose ranging from about 30 mmol P kg^?1 in some soils to more than 340 mmol P kg^?1 in others. At larger doses, the way additional P was bound to the solid phase was different; phosphate was probably adsorbed, at least in part, to low-affinity sites on silicate clays and oxides. The proportion of sorbed phosphate that was isotopically exchangeable decreased with time, soil carbonate content and P addition dose for doses <100 mmol P kg^?1. This is consistent with the idea that P in Ca phosphates is less isotopically exchangeable than P adsorbed on mineral surfaces. At larger additions of P, isotopic exchangeability was unrelated to the soil properties measured, probably because there was a variety of sorbed P forms influenced in turn by different soil components.     

DESORPTION AND ISOTOPIC EXCHANGE RELATIONSHIPS OF PHOSPHATE SORBED BY SOILS AND HYDROUS FERRIC OXIDE GEL

Sorption of added inorganic phosphate (P) was irreversible in four contrasting soils and hydrous ferric oxide gel during 16 h desorption after 40 h sorption at the same (iso)pH. Irreversibility increased with increasing time of desorption above 30 h. When the amount of P which was chemisorbed during the sorption step was subtracted from the amount desorbed, the latter fell on the isotherm describing the more-physical, potential-determining sorption. No pH change occurred during desorption and net negative charge decreased by 1 equivalent per mole P desorbed. These results suggested that only more-physically sorbed P was desorbed at the iso-pH. The more-physically sorbed P was also reversible with respect to changes in the ionic strength and cation species of the desorbing solution. The isotopic exchangeability of the more-physically sorbed P was at least ten times greater than that of chemisorbed P. With increasing sorption time, both the ease of desorption and exchangeability of sorbed P decreased. Subsequent to desorption, the exchangeability of the remaining sorbed P also decreased. These observations are interpreted in terms of the concurrent changes in the amounts of chemisorbed and more-physically sorbed P.     

电解质种类和浓度影响磷酸根解吸的机理研究

本文研究了吸附性阳离子、电解质浓度和组成影响几种矿物和土壤吸附态磷的解吸的机理。结果表明,吸附性阳离子影响磷酸根解吸与离子桥有关。桥接静电场愈强,被束缚磷的释放就愈困难。电解质阳离子对磷酸根解吸的影响则取决于其对表面负电荷的屏蔽效应。阳离子电价高,屏蔽作用大,磷解吸就少。电解质浓度影响吸附态磷的解吸主要与表面电位的变化有关。当pH>PZC值时,提高电解质浓度降低表面负电位,从而减少磷的吸附;当pH<PZC时,提高电解质浓度则降低表面正电位,促进磷的解吸。磷酸根解吸盐效应零点(P_PZSE)值一般都介于土壤或矿物样品吸附磷酸根前后测得的两个PZC值之间。不同浓度电解质溶液中磷解吸量之差与吸附层电位变化量(△ψ_x)呈正相关。     

高岭石,蒙脱石和针铁矿对泥炭腐殖酸的吸附和分离

Sorption of humic acid (HA) on mineral surfaces has a profound interest regarding the fate of hydrophobic organic contaminants (HOCs) and carbon sequestration in soils. The objective of our study is to determine the fractionation behavior of HA upon sorption on mineral surfaces with varying surface properties. HA was coated sequentially on kaolinite (1:1 clay), montmorillonite (2:1 clay), and goethite (iron oxide) for four times. The unadsorbed HA fractions were characterized by elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), and solid state ¹³C nuclear magnetic resonance spectroscopy (NMR). The mineral-HA complexes were characterized by DRIFT. Polarity index [(N+O)/C] revealed higher polarity of the unadsorbed HA fractions after coating on kaolinite, reflecting that relatively higher polarity fractions of HA remain unadsorbed. Sorption of aliphatic alcohol fraction along with carbohydrate was prominent on kaolinite surface. DRIFT results of the unadsorbed HA fractions indicated more sorption of aliphatic moieties on both kaolinite and montmorillonite. DRIFT results of the unadsorbed HA fractions after sorption on kaolinite and goethite showed the sorption of the proteinaceous fractions of HA. The HA fractions obtained after coating on goethite showed significant sorption of carboxylic moieties. The results mentioned above comply reasonably well with the DRIFT spectra of the mineral-HA complexes. ¹³C NMR results showed higher sorption of anomeric C on kaolinite surface. Higher sorption of paraffinic fraction was observed on montmorillonite. NMR data inferred the sorption of carboxylic moieties on goethite surface. Overall, this study showed that aliphatic moieties of HA preferentially sorbed on kaolinite and montmorillonite, while carboxylic functional groups play a significant role in sorption of HA on goethite. The sorbed fractions of HA may modify the mineral surface properties, and thus, the interaction with organic contaminants.     

Phosphate desorption from the surface of soil mineral particles by a phosphate-solubilizing fungus

High phosphate (Pi) sorption in soils is a serious limiting factor for plant productivity and Pi fertilization efficiency, particularly in highly weathered and volcanic ash soils. In these soils, the sorbed Pi is so strongly held on the surfaces of reactive minerals that it is not available for plant root uptake. The use of phosphate-solubilizing microorganisms (PSM) capable of Pi desorption seems to be a complementary alternative in the management of these soils. The aim of this study was to evaluate the effectiveness of the soil fungus Mortierella sp., a known PSM, to desorb Pi from four soil minerals differing in their Pi sorption capacity. The fungus was effective in desorbing Pi from all tested minerals except from allophane, and its desorption depended on the production of oxalic acid. The effectiveness of the fungus to desorb Pi was ranked as montmorillonite > kaolinite > goethite > allophane. The quantity of desorbed Pi increased by increasing the amount of sorbed Pi. The Pi sorption capacity expressed as P_0.2 value (amount of P required to increase a solution P concentration up to 0.2 mg L^?1) was a good indicator of the effectiveness of Mortierella sp. to desorb Pi from soil minerals.     

Characterization of zinc in contaminated soils: complementary insights from isotopic exchange,batch extractions and XAFS spectroscopy

Isotopic exchange (IE) of trace metals is an established method for characterizing metal reactivity in soils, but it is still unclear which metal species are isotopically exchangeable. In this study, we used IE to quantify ‘labile’ zinc (Zn) in 51 contaminated soils that were previously studied by Zn K‐edge X‐ray absorption fine structure (XAFS) spectroscopy and sequential extraction (SE). All soils had been contaminated by runoff water from 17‐ to 74‐year‐old galvanized power‐line towers. They covered a wide range in pH (4.0–7.7), organic carbon (0.9–10.2%), clay (3.8–45.1%) and Zn concentrations (251–30 090 mg kg^?1). Isotopic exchange was also performed on selected Zn minerals used as references for linear combination fitting of XAFS spectra. The isotopically exchangeable fraction (%E) of Zn generally decreased with increasing pH, but small %E values were also observed for acidic soils with a large fraction of Zn in hydroxy‐interlayered minerals (Zn‐HIM). The fraction of Zn identified by XAFS spectroscopy as (tetrahedrally and octahedrally coordinated) ‘sorbed Zn’ agreed reasonably well with the isotopically exchangeable fraction but was in many cases larger than the %E, indicating that some ‘sorbed Zn’ may be isotopically non‐exchangeable, such as Zn sorbed in micropores of Fe oxyhydroxides. Zinc identified by XAFS spectroscopy as Zn precipitates (Zn phyllosilicates, Zn‐layered double hydroxide (Zn‐LDH) or hydrozincite) or as Zn‐HIM was largely isotopically non‐exchangeable (‘non‐labile’). Comparison between IE and extraction results suggested that the isotopically exchangeable Zn was mainly extracted in the first two fractions of the SE. However, non‐labile Zn was also extracted in these first two fractions for some soils, including a hydrozincite‐containing soil. Despite the presence of Zn‐LDH and/or Zn phyllosilicates in almost all soils, the Zn concentrations in solution and labile Zn increased with increasing soil total Zn at a given pH, which contradicts the concept of precipitation control by a single phase. Solution Zn was well predicted from the labile Zn following a sorption model.     

Potassium release on drying of soil samples from a variety of weathering regimes and c clay mineralogy in China

Thirty two soil samples from China were analyzed for exchangeable K before and after drying. Most soil samples were higher in exchangeable K after air-drying and ovendrying (60°C) than when wet. Soil clay minerals, especially clay-size mica, affected K released in air-dry and oven-dry samples. According to composition of clay minerals of air-dried samples, five classes were recognized. Soil samples with high mica and montmorillonite have the highest exchangeable K. Samples that contained higher kaolinite than mica had lower exchangeable K. Samples with higher kaolinite than quartz and mica had still lower exchangeable K. Samples of sandy soils contained very low exchangeable K. When quartz was the main mineral, the samples that had kaolinite and gibbsite as the main clay minerals had very low exchangeable K. The degree of weathering (weathering mean) bore an inverse relationship to the amount of K released on drying in air or at 60°C. Udults and Udalfs (Red Earths) of southeastern China, because of their high K release on being dried, are inferred to have received fine mica from the Western Desert dust rainout, reported to Liu et al. (1981).     

有机阴离子对磷酸根吸附的影响

在中性条件下,低浓度的柠檬酸、草酸、酒石酸和胡敏酸阴离子都能显著降低针铁矿、非晶氧化铝、高岭石和红壤对磷酸根的吸附,尤其在低磷吸附饱和度下效果更好。有机阴离子抑制磷酸根吸附的能力因有机酸的种类和性质、以及固相的表面特性而异。有机阴离子存在下吸附的磷酸根具有较高的同位素³²P交换活性和解吸率。测定了吸附平衡溶液中铁和铝的浓度。结果表明,在实验条件下(pH 7.0),即使较高浓度的有机酸根(10^-2mol)也只能溶解极少量的铁和铝。有机阴离子络溶作用不足以说明固相吸附磷能力的显著下降。可见,有机阴离子降低磷酸根吸附的机制主要是竞争专性吸附。有机阴离子占据了一部分高亲和力的吸附位,从而降低了土壤固相吸附磷的量,增加了吸附态磷的活性。     

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.     

中国土壤胶体研究 Ⅵ.西藏高原几种主要土壤的粘土矿物组成和演变

西藏高原突起于我国西南,绝大部分地面的海拔高度在4000米以上,为世界上最高的大高原。它大致在第三纪开始形成,后来曾受第四纪冰川的深刻作用,高山顶部至今仍是冰川的活动场所^[1,2]。高原为昆仑山、唐古拉山、喜马拉雅山和横断山等大山脉所盘踞。     

Phosphate sorption in some representative soils of Bangladesh

An experiment was conducted to observe the phosphate sorption potential of some soils of Bangladesh. Three soil series of calcareous origin, namely Sara (Aquic Eutrochrept), Gopalpur (Aquic Eutrochrept) and Ishurdi (Aeric Haplaquept), and two soil series of non-calcareous origin, namely Tejgaon (Rhodic Paleustult) and Ghatail (Aeric Haplaquept), were selected. The soils were equilibrated with dilute solution of calcium chloride containing graded concentrations of phosphate (0, 1, 2, 5, 10, 25 and 50?μg?P?mL^?1), and the amount of phosphate sorbed or desorbed was determined. Although all the soils showed potential for sorbing phosphate from applied phosphorus, their ability to sorb phosphorus differed. Increasing rates of phosphate application increased the amount of P sorption but reduced phosphate sorption percentage in all soils except Tejgaon. Phosphate was sorbed by the soils in the order: Tejgaon > Ghatail > Ishurdi > Gopalpur > Sara at 50?μg?P?mL^?1 application. Soils possessing higher amounts of free iron oxide and clay sorbed more phosphate from applied phosphorus.     

STUDIES ON SOIL COPPER

A method based on that used by McAuliffe et al. (1948) for phosphorus was developed for determining isotopically exchangeable copper in soils using the radioisotope ⁶⁴Cu. The authors are confident that, with a few exceptions, isotopic equilibrium in soil/solution systems is attained rapidly enough to overcome possible difficulties resulting from the short half-life of this isotope. For the twenty-four soils examined, amounts of isotopically exchangeable copper were found to be between 0.19 and 12-24 μg g^-I and represented between 2 and 21 per cent of the total soil copper. A correlation test and an experiment involving fractionation of labelled soils both demonstrated that the bulk of the isotopically exchangeable copper was located in the organic-bound fraction. Not all copper specifically adsorbed by organic matter was readily exchangeable with ⁶⁴Cu : for one sample of organic material examined only 20 per cent of the adsorbed copper was isotopically exchangeable after 24 hours equilibration. The corresponding figures for clay materials and oxide material were found to be between 75 and 60 per cent.     

Relationship of soil properties to p‐fixing capacity of soils in northern Idaho

Abstract

Phosphorus sorption studies were conducted on volcanic ash influenced surface horizons of 29 northern Idaho soils. Results show that the amount of P sorbed was significantly correlated with citrate‐dithionite extractable aluminum (r = .64**), but not with Fe. Other significantly correlated soil properties were: percent base saturation (r = ‐.73**), percent clay (r = .42**), and exchangeable acidity (r = .39*).     

Modelling the effects of ageing on Cd,Zn, Ni and Cu solubility in soils using an assemblage model

Ageing reactions can reduce trace metal solubility and can explain natural attenuation of contaminated soils. We modelled ageing reactions in soil with an assemblage model that considers slow reactions in Fe‐oxyhydroxides and reversible sorption on organic matter and clay minerals. Metal adsorption kinetics on Fe‐oxyhydroxides was obtained from data with synthetic oxyhydroxides. Metal solubility and isotopic exchangeability data were obtained from 28 soils amended with Ni, Zn, Cu and Cd metal salts and monitored for 850 days. The assemblage model was constructed in WHAM 6.0 and used soil properties and dissolved organic matter as input data. The model was first validated to predict dissolved metal concentrations, based on the concentration of isotopic exchangeable metals. The model overestimated metal solubility without parameter adjustment by mean factors of 4–7, and successful fits were obtained by increasing the specific surface area of Fe‐oxyhydroxides from measured values of synthetic systems to a value of 600 m² g^?1 recommended by other authors. The effect of ageing on the isotopic exchangeable metal fraction was subsequently modelled starting from the predicted fraction of metals present on Fe‐oxyhydroxides immediately after soil spiking. The observed isotopic exchangeable metal fractions of Ni, Zn and Cd agreed reasonably well with predicted values. The model predicts that ageing reactions are more pronounced at higher pH because metal sorption is increasingly directed to oxyhydroxide surfaces with increasing soil pH. Modelling fixation of Cu requires more information on fixation of that metal in organic matter.     

Sorption of isotopically exchangeable and non-exchangeable phosphate by some soils of Colombia and Brazil, and comparisons with soils of southern Nigeria

Fourteen soils from Colombia and Brazil provided a wide range of sorption characteristics. Curves of sorbed phosphate that was exchangeable to ³²P were described by Freundlich's equation, and of non-exchangeable phosphate by Temkin's equation. Exchangeable phosphate was associated with aluminium in poorly-crystalline oxides and in organic complexes. Non-exchangeable phosphate was related to aluminium in organic complexes, and especially to the ratio of AI/C in them. In Nigerian soils similar mechanisms controlled sorption of phosphate but oxides and organic complexes of iron were important. The concentration of phosphate in solution when affinities of soil for exchangeable and non-exchangeable phosphate are equal, and the importance of organic matter, are discussed in relation to soil management and to responses of crops to fertilizer phosphate. The results indicate that sorption curves should not be split into sections.     

Interactions of clay minerals with Arthrobacter crystallopoietes: starvation, survival and 2-hydroxypyridine catabolism

For bacterial inoculants to be effective in soil remediation, the bacterial strain must be capable of overcoming any negative effects of soil minerals on cellular processes. One class of minerals commonly encountered by soil bacteria is clays. Thus, the effect of commonly occurring clay minerals in soils on starvation, survival and 2-hydroxypyridine catabolism by Arthrobacter crystallopoietes was evaluated. Stationary phase A. crystallopoietes cells were suspended in 0.03M, pH7.0, phosphate buffer containing no clay or amended with 0.2% (wt/vol) montmorillonite, sodium montmorillonite or kaolinite. Marked effects of clay minerals on both survival rates and catabolic rates of 2-hydroxypyridine were noted. For example, after 14 weeks starvation, 4.6% of the initial cell population was viable with no clay present, compared to 0.8% (montmorillonite), 22.1% (kaolinite) and 54.1% (sodium montmorillonite) in the presence of the clay minerals. Acclimated and nonacclimated cell populations were used to evaluate 2-hydroxypyridine catabolism. Induction of 2-hydroxypyridine metabolism occurred in the unacclimated cells following starvation. Differential impact of the clay minerals on unacclimated cells was detected. Montmorillonite enhanced the capacity for induction of 2-hydroxypyridine catabolism and its decomposition rate after 0–3 days starvation. For acclimated cells, clay did not affect the metabolic activity prior to starvation, but the presence of clay resulted in increased activity during starvation. For example, after 3 days starvation, a nearly two fold increase in metabolism was detected in the presence of clay minerals. These data suggest that some clay minerals in soil alter the survival time and metabolic activity of soil-amended bacteria, thereby affecting the potential for bioremediation success. Received: 1 March 1996     

CLAY MINERAL DISTRIBUTION AND ORIGIN IN THE SOIL TYPES OF ISRAEL

The mineralogical composition of clays (< 2μm) in representative profiles of all soil types of Israel was investigated. The soils were classified according to their clay mineral assemblages into three groups. I. Montmorillonitic soils. Montmorillonite is the dominant mineral and exceeds 65 per cent of the total minerals found; each of the other minerals comprises less than 15 per cent. 2. Montmorillonitic-kaolinitic soils. The soil clay fractions contain 50-60 per cent montmorillonite and 15-25 per cent kaolinite, generally adding up to more than 75 per cent of the clay fraction. 3. Montmorillonitic-calcitic soils. The clays contain more than 10 per cent calcite. Montmorillonite is the dominant clay mineral (except for one soil type, mountain rendzina, where calcite is dominant). The first and second assemblages are typical of the soils of the Mediterranean zone, whereas the soils of the desert zone are characterized by the third assemblage. The origin of montmorillonite, kaolinite, and illite, the three main clay minerals, was found to be detritic, as was the origin of palygorskite which was mainly found in the calcite rich soils of the desert zone. The cation exchange capacity of montmorillonite seems to be higher under higher precipitation. Montmorillonite content and cation exchange capacity of the clays were found to be highly correlated. The carbonate content of the clay fraction and the amount of carbonate in the soil were also highly correlated.     

INFLUENCE OF ADSORBED SODIUM AND GYPSUM CONTENT ON PERMEABILITY OF GLACIAL TILL SOILS

The permeability of glacial till soils having mainly montmorillonite in the clay fraction was negligible when the exchangeable sodium percentage (ESP) exceeded 15 to 20. Relatively higher permeability values were obtained in soils containing gypsum, but water transmission through such soils was negligible above ESP of 30 to 35. The relative decrease in permeability with increase in exchangeable sodium depends not only on the ESP and electrolyte concentration in the soil solution but is affected by the types of clay minerals.     

广西水耕人为土黏粒矿物组成及其空间分布特征

黏粒矿物影响着土壤理化性质，可指示成土因素特征和土壤发生发育过程/强度，也是中国土壤系统分类的基层单元土族矿物学类型划分的重要依据。本研究选择了广西不同纬度和成土母质的18个代表性水耕人为土的剖面，应用X射线衍射（XRD）方法分析了其典型水耕氧化还原层（Br层）的黏粒矿物组成及其空间分布特征，并确定了其中“黏质”剖面的土族控制层段矿物学类型。结果表明：（1）供试土壤的黏粒矿物主要包括高岭石、伊利石、三水铝石、1.42 nm过渡矿物、蒙脱石和蛭石等，依次分别出现在100%、88.9%、72.2%、61.1%、44.4%和38.9%的剖面中。（2）黏粒矿物组成在纬度空间分布上具有明显规律性特征。随着纬度降低，土壤黏粒中的高岭石增加，伊利石、蒙脱石、1.42nm过渡矿物逐渐减少；纬度＞23°N区域内，成土母质对黏粒矿物组成影响明显。（3）纬度23°N是黏粒矿物组成和土族矿物学类型分界线，＜23°N区域，黏粒矿物均以高岭石为主，是“黏质”剖面的土族控制层段的主要矿物学类型；＞23°N区域，黏粒矿物组成以高岭石、蒙脱石、伊利石或1.42 nm过渡矿物为主，因成土母质不同而异，“黏质”剖面的土族控制层段矿物学类型包括高岭石混合型、混合型和伊利石型。