Adsorption,activity, and kinetics of acid phosphatase as influenced by selected oxides and clay minerals

Abstrac

The effects of 3 oxides (Fe, Al, and Mn oxides) and 3 clay minerals (kaolin, montmorillonite, and allophane) on the adsorption and subsequent kinetic properties of acid phosphatase were compared. The amount of enzyme adsorbed by the oxides and clay minerals followed the order: montmorillonite ? kaolin > Mn oxide > Fe oxide > Al oxide ? allophane. The adsorption isotherms of the enzyme on the oxides and clay minerals, except for montmorillonite and allophane, fitted the Langmuir equation. The activity of the enzyme immobilized by the inorganic components studied was in the order of allophane > kaolin > Fe oxide > montmorillonite > Al oxide ≒ Mn oxide. Compared to the free enzyme, the V _max, K_m, and V _max / K _m values of the immobilized enzyme decreased, increased, and decreased, respectively. Among the oxides or clay minerals, the higher the ability of the inorganic components to adsorb the enzyme, the lower the value of the V _max / K _m ratio of the immobilized enzyme. These findings suggest that the catalytic efficiency of the enzyme complexes formed is determined by the adsorbability of the inorganic components for the enzyme.     

Radiocesium interception potential (RIP) of smectite and kaolin reference minerals containing illite (micaceous mineral) as impurity

Cesium-137 (¹³⁷Cs) is strongly adsorbed on clay minerals, especially on illite. The adsorption of Cs⁺ on reference clay minerals, however, has not been fully investigated in relation to the presence of illite. The objective of this study was to clarify the effect of impurities (i.e., illite and vermiculite), present in reference smectite group minerals and kaolin minerals, on the retention of Cs⁺. The clay mineralogy of the reference minerals was characterized by X-ray diffraction (XRD). The radiocesium interception potential (RIP) was measured as an index of the Cs⁺ retention ability of clays. The content of illite in clay was represented by the total potassium (K) content given that illite is a major source of K in the clay fraction. The content of vermiculite in clay was represented by the Cs fixation capacity induced by Cs saturation followed by heating of samples at 110°C. Metabentonite and beidellite gave extremely high RIP values compared with other smectite group minerals, although a peak for illite (at 1.0 nm) was not observed in XRD analysis. The reference smectite and kaolin minerals showed a range of RIP values, even though their RIP values are theoretically zero. The RIP values had a significant positive correlation with the total K content of all the reference clay minerals (r_s = 0.621*). This indicated that the retention ability for ¹³⁷Cs depended more on the content of illite, as impurity, rather than the type of bulk mineral. Hence, the contribution of illite to the magnitude of the RIP was elucidated by the combination of measurement of total K content and XRD analysis.     

根瘤菌存在下土壤胶体和矿物对镉的吸附

Experiments were conducted to study the adsorption of Cd on two soil collids(red soil and yellowbrown soil) and three variable-charge minerals (goethite,noncrystalline Fe oxide and kaolin) in the absence and presence of rhizobia.The tested strain Rhizobium fredii C6,tolerant to 0.8 mmol L^-1 Cd,was selected from 30 rhizobial strains.Results showed that the isotherms for the adsorption of Cd by examined soil colloids and minerals in the presence of rhizobia could be described by Langmuir equation.Within the range of the numbers of rhizobial cells studied,the amount of Cd adsorbed by each system increased with increasing rhizobial cells,Greater increases for the adsorption of Cd were found in red soil and kaolin systems.Rhizobia influence on the adsorption of Cd by examined soil colloids and minerals was different from that on the adsorption of Cu.The presence of rhizobia increased the adsorption affinity of soil colloids and minerals for Cd,particularly for the goethite and kaolin systems.The discrepancies in the influence of rhizobia on the adsorbability and affinity of selected soil colloids and minerals for Cd suggesed the different interactions of rhizobia with various soil components.It is assumed that bacterial biomass plays an important role in controlling the mobility and bioavailability of Cd in soils with kaolinite and goethite as the major colloidal compnents,such as in variable-charge soil.     

Size and charge characteristics of kaolinitic soils in SE Queensland

Some kaolinitic soils derived from basaltic material contain 2:1 minerals as a discrete phase and/or interstratified with kaolin as determined by X-ray diffraction (XRD) and by chemical analysis of DCB-treated clays, while others show little or no evidence of 2:1 minerals. Mineral impurities were not detected by electron diffraction in the latter group. There is good agreement between the interpretation of XRD traces and the SiO₂/Al₂O₃ ratio given by chemical analysis. Some kaolin is seen by electron microscopy to be of very small particle size, and two distinct morphological types have been recognized. High surface area measurements are consistent with fine particular size. These profiles contain kaolin with higher than normal CEC and permanent negative charges which cannot be accounted for by the presence of 2:1 clay minerals alone and which are attributed to a degree of isomorphous substitution. This substitution and/or mineral impurities may have limited kaolin crystal growth during neoformation.     

Contribution of organic matter and clay minerals to the cation exchange capacity of soils

Abstract

The cation exchange capacity (CEC) at pH 7 was measured for samples of 347 A horizons and 696 B horizons of New Zealand soils. The mean CEC was 22.1 cmolc/kg for the A horizons and 15.2 cmolc/kg for the B horizons. Multiple regressions were carried out for CEC against organic carbon (C), clay content, and the content of seven groups of clay minerals. The results, significant at p <0.001, were consistent with most of the CEC arising from soil organic matter. For the samples of A horizon, the calculated CEC was 221 cmolc/kg per unit C and for the B horizons was 330 cmolc/kg C. There was also a contribution from sites on clay minerals. Multiple regression indicated that smectite had a higher CEC (70 cmolc/kg) than other minerals but it was not as high as that of type smectites; kaolin minerals had the lowest CEC. There was a significant effect of interaction between organic matter and some clay minerals on the CEC. Samples from B horizons containing allophane had lower CEC than those not containing allophane which is consistent with allophane reacting with carboxyl groups on organic matter. For the samples from the A horizons, however the CEC was higher when allophane was present.     

Biodegradation of clay minerals under the influence of cyanobacterial-actinomycetal associations

The capacity of associations of cyanobacteria and actinomycetes to transform the structure of clay minerals (kaolin, vermiculite, mica, and montmorillonite) was experimentally revealed. First, easily weatherable vermiculite and biotite were transformed. The rate of transformation of micas to mixed-layered minerals depended on their structure: trioctahedral mica (biotite, the component of vermiculite) was changed much faster than dioctahedral mica (the component of kaolin). The lattices of all the phyllosilicates were altered (disordered and disaggregated) under the influence of the cyanobacterial-actinomycetal associations.     

Crystalline clay minerals of the soils derived from recent volcanic ashes in Hokkaido,Japan

For the past ten years much work has been carried out on clay minerals of volcanic ash soils. Most investigators have reported that allophane is dominant among clay minerals of volcanic ash soils and crystallizes to halloysite or meta-halloysite with the advance of weathering (1–8). On the other hand, UCHIYAMA, MASUI and ONIKURA (1960) found that montmorillonite predominates in the clay fraction of volcanic ash soil in Kawatabi (9). Furthermore, MASUI, SHOJI and UCHIYAMA (1966) showed that the major crystalline clay minerals of volcanic ash soils in the Tohoku district are montmorillonite, vermiculite, intergradient montmorillonite-vermiculite and chlorite (10). They also showed that these minerals increase with the advance of weathering and that kaolin minerals are minor constituents.     

Influence of pH on the formation of the hydroxy Al-montmorillonite complex

The presence of so-valled chlorite-like minerals has been reported in many soils of not only acid but also of alkaline reaction (1). The minerals have been designated by, many terms, for example, dioctahedral vermiculite (2), dioctahedral analogue of vermiculite (3), 14A mineral (4), chlorite-like mineral (5), interstratified chlorite-vermiculite (6), intergradient chlorite-expansible 2:1 layer silicate, intergradient chlorite-vermiculite, intergradient chlorite-vermiculite-montmorillonite, intergrade, or interlayered vermiculite (7), and 2: 1-2: 2 intergrade (1). The minerals designated by these terms are evidently of the same category, and some of them are synonymous. Although they are of intermediate properties, between true chlorite and true vermiculite or montomorillonite, they could be regarded as an independent group of minerals in the course of pedochemical weathering. Jackson (1), for instance, has given the minerals the position of “weathering index 9”, placing them between vermiculite and kaolin as equivalent to montmorillonite, or secondary chlorite and kaolin in his weathering sequence. An explanation of the diagenesis of the minerals has been recently attempted by synthesis of the chlorite-like structures from montmorillonite (8), (9) and vermiculite (10) and mineralogical analyses of soil clay fractions (7).     

Interactive Sorption of Metal Ions and Humic Acids onto Mineral Particles

The sorption of metal ions (Pb2+, Zn2+ and Cu2+) and soil humic acids (HA) from aqueous solutions onto mineral particles (sand, calcite and clay) was investigated using a batch equilibrium system. The sorption reactions in two- component systems (heavy metals-mineral particles and humic acids- mineral particles), as well as interactions in three-component system (heavy metals-humic acids-mineral particles) were examined. Results showed that the presence of humic acids, dissolved or bound onto mineral surfaces, considerably influenced the fixation of heavy metals. The various effects, depending on mineral type, humic concentration and specific metal-ion, were observed in three- component system. Sorption of Cu2+-ions on all minerals studied rapidly increased as the concentration of dissolved HA increased. The amount of Pb2+-ions sorbed on sand slightly decreased, while on kaolin increased between 15 and 20%. Sorption of Zn2+-ions on all minerals studied decreased at pH 4. At pH 5.5 the sorption of Zn2+-ions onto calcite decreased, while on kaolin and sand increased as a function of the humic acid concentration giving the curve with maximum at c(HA) = 2.5 mmol C L-1. At pH 6.5 sorption onto kaolin and sand increased. This effect occurs as a result of the conditional stability constant of Zn-HA complexes increasing at higher pH which in turn promotes the chelation of Zn2+-ions to mineral- bound humic substances. The enhanced sorption of metal ions from the aqueous phase in three-component systems is not only the result of mineral sorption of free metals but also the result of chelation with HA sorbed on the mineral surface.     

土壤和粘粒矿物对亚硒酸盐的吸附和解吸

本文研究了三种土壤(砖红壤、红壤和黄棕壤)、高岭土和两种合成氧化铁(无定形氧化铁和针铁矿)对亚硒酸盐的吸附和解吸作用。讨论了亚硒酸盐的吸附特征,以及土壤中氧化铁对亚硒酸盐吸附和解吸的影响,根据实验资料与吸附等温方程式的拟合情况,作者认为以Freundlich和Langmuir公式为宜。此外,供试样品对亚硒酸盐的吸附和解吸结果表明,Se的吸附量随Se的添加量的增加而增加,但由于矿物组成各异,吸附量的差异显著。其吸附量的大小顺序为:无定形氧化铁>针铁矿>砖红壤>红壤>黄棕壤>高岭土;而被吸附Se的解吸能力则是高岭土>黄棕壤>红壤>砖红壤>针铁矿>无定形氧化铁。实验结果还表明,在各种矿物组成中,亚硒酸盐的吸附和解吸受氧化铁的影响很明显,三个土壤样品的吸附等温线都表现出氧化铁在初始阶段对亚硒酸盐吸附快而强烈的特征,而在去除氧化铁以后,这一特征也随之消失,硒的吸附量显著降低,而解吸率则明显上升。     

Clay minerals of sediments in the Yatsushiro bay

Since three decades ago it has been established by numerous investigators⁴,⁷,⁹⁾ that the general Process of formation of clay minerals is different between the marine and terrestrial conditions, and that the clays of the marine origin are, in general, of illitic type, whereas those of the terrestrial are of kaolin group. In previous communications,¹,²⁾ it was reported that clay fractions of the soil and mud from the Ariake Sea are characterized by the abundance of minerals of illite-montmorin series (montmorin refers to montmorillonite group after Jackson and Sherman⁸⁾, being different from most terrestrial soils in Kyushu. The matter seems to be of some importance because the Presence of montmorin, even in a relatively small quantity, is likely to exercise a considerable, influence on the behaviour and properties of the clay and the fertility of the soil. The soils of the reclaimed land of the Sea are not only productive, Whether they are clayey or sandy, but also they have been approved to be powerful improving materials for the degraded paddy soils, so-called “Akiochi” soils by several field experiments.     

Crystallinity of kaolin minerals and their weathering sequence in some soils from Nigeria,Brazil and Colombia

A study of the clay mineralogy of a number of soils from West Africa and South America has enabled the construction of a generalized weathering/crystallinity sequence for the 1:1 layer silicates. The kaolin minerals appear to weather via halloysite and disordered kaolin to a well-ordered kaolinite characterized by large flakes and a high crystallinity index. Further weathering results in a reversal of the sequence via small flakes of highly disordered kaolin to gibbsite and ultimately perhaps to amorphous materials. The changes in the value of the crystallinity index as weathering proceeds are shown, together with changes downprofile and downslope.     

GENESIS OF RED AND BLACK SOILS ON BASALT ON THE DARLING DOWNS, QUEENSLAND, AUSTRALIA

Shallow friable red soils (euchrozems) and shallow cracking clays (black earths) occur in close proximity on basalt hills of the Darling Downs of Queensland. The euchrozems are mainly restricted to fiat hill crests and are associated with lithosols; the shallow black earths occur on upper pediment slopes, on small convex crests and on depressions on flat crests. The euchrozems are moderately leached and contain kaolin minerals and hematite with minor montmorillonite, while the black earths are dominantly montmorillonite with minor kaolin and hematite. It is proposed that the euchrozems have developed by long continued weathering under stable well-drained conditions while the black earths have formed in sites prone to erosion and in situations with less water available for weathering. The weathering products produced in each situation have ensured continuation of the processes. The presence of two red soils in anomalous positions have been ascribed to (a) soil formation on exposed ‘bole’ (compacted red clay) layers and (b) local peculiarities of parent material controlling the course of weathering.     

Clay minerals of red-yellow soils derived from pleistocene sediments in Japan

Red-Yellow soils are widely developed on terraces and hilly lands in the south-western half of Japan. They do not show any evidence of bleaching in the lower part of the A horizon, and are characterized by an extremely strong acid reaction, and a very low base-status⁹⁾. There are few studies on clay mineralogy of Red-Yellow soils in Japan. Egawa et al⁴⁾. have reported on clay mineralogy of soils derived from the Pleistocene and the Tertiary sediments most of which may be regarded as Red-Yellow soils. Matsui and Katô¹⁰⁾ have described clay minerals of Red-Yellow soils derived from the Pleistocene sediment in the environs of Shinjobara, Shizuoka Prefecture. These investigations indicated that clay minerals of Red-Yellow soils derived from the Pleistocene sediments consisted mainly of kaolin minerals, whereas those of Red-Yell ow soils derived from the Tertiary sediments were of the kaolin-illite association.     

Selective removal of heavy metals from contaminated kaolin by chelators

The competitive desorption/dissolution of kaolin-adsorbed heavy metal mixtures and mixtures of adsorbed Cd with Mg and/or Ca by four chelators (NTA, EDTA, EGTA, and DCyTA) was investigated. Metals were adsorbed on kaolin at pH 7 and the effects of chelator type and concentration on the extent of metal dissolution was studied at a solution pH of 10. EGTA addition. EGTA was the most effective chelator in selectively removing Cd from kaolin in the presence of adsorbed alkaline-earth metals. Approximately 90% of the adsorbed Ca and Mg were retained on the kaolin until almost all (> 80%) of the cadmium was dissolved by EGTA chelator. NTA was the least effective chelator in selectively dissolving Cd from kaolin contaminated with both Cd and Ca (≈ 45% of the adsorbed Cd could not be removed). All four chelators exhibited some desorption/dissolution selectivity for Cd, Cu, and Pb adsorbed on kaolin. When the concentration of chelator in solution was insufficient to dissolve all adsorbed metals, the observed metal ordering for chelation and dissolution was Cd > Cu > Pb (for EGTA), Cd > Pb > Cu (for EDTA and DCyTA), and Cu > Cd > Pb (for NTA).     

Mercury porosimetry of compacted clay minerals

The clay minerals, kaolin and montmorillonite, were compacted at different pressures up to 300 MPa. The textural characteristics (pore radius, surface area and porosity) of the clay minerals were measured after compaction and related to the particle size and the cation exchange capacity of these clays. Kaolins and montmorillonites with and without compaction were characterized by mercury intrusion using a porosimeter within the range 0.1 MPa to 200 MPa. A negative linear correlation was obtained between the mean pore radius of compacted clays and the cation exchange capacity. A larger percentage of fine particles originated compacts with small pore sizes. The pore radius and the porosity of the clay minerals diminished with increasing compaction pressure, whereas the surface area increased.     

Clay minerals from diallage in a warm and humid climate

In the course of chemical weathering, rockforming minerals release constituent ions changing into secondary minerals by alteration or recrystallization. Minerals formed in this way are primarily of colloidal nature, and are the most active portion in soils together with humus. The chemical weathering has dual meaning for soil fertility, that is, it provides soils with nutrients released and inorganic colloids formed, namely clay minerals. It has been well established that climate, vegetation, parent material, topography and time influence the formation of soils. Generally speaking, Japanese soils have developed under a warm and humid climate which causes leaching of released bases resulting in acid reactions, and a predominance of kaolin in soils. Accumulated information pertaining to Japanese soils, however, has disclosed that physical, chemical, and mineralogical properties of parent rocks are still obviously reflected in the clay minerals of soils.     

Soil solution aluminium activity related to theoretical A1 mineral solubilities in four Australian soils

Four soils were treated with HNO₃, CaCO₃ and K₂SO₄ to enable observation of the response of the soil solution composition and the solution A1 ion activity (Al³⁺) to the treatments and to time. The clay fraction of three of the soils was dominated by illite, kaolinite and quartz. The fourth was minated by kaolinite and iron oxides. The initial pH in 0.01 M CaCl₂ varied between 4.0 and 5.0 and the organic carbon content from 0.7 to 1.1%. The soil solutions from soils dominated by kaolinite, illite and quartz were generally supersaturated with respect to quartz and well ordered kaolinite, and unsaturated with respect to illite. The soil solutions from the soil dominated by kaolin and iron oxide were generally unsaturated with respect to quartz but still saturated with respect to ell crystallized kaolin. Within mineral groups such as Al₂SiO₅ compounds, A1₂Si₂O₅(OH)₄ (kaolinite group), and Al(OH)₃ (A1 oxide) minerals, the more soluble forms became less supersaturated or unsaturated with time for many treatments. Lime treatment usually increased the ion activity product of AI(OH)₃ in all soils, and of minerals with the composition, Al₂SiO₅, in the illite/kaolinite soils. Acid treatment reduced the apparent solubility of Al(OH)₃, and the A1 silicates in the Al₂SiO₅, and Al₂, Si₂, O₅,(OH)₄, mineral groups on all soils. These results are interpreted to indicate that lime treatment led to the formation of trace quantities of more soluble A1 minerals that subsequently controlled (Al³⁺), whereas acid treatment dissolved trace quantities of such minerals leaving less soluble minerals to control (Al³⁺). The results suggest that, in mineral soils such as these, (Al³⁺) is under the control of inorganic dissolution and precipitation processes. These processes conform to expectations given the free energy of various inorganic aluminium compounds. Furthermore the sequence of dissolution and formation processes appears to be governed by the Gay-Lussac—Ostwald step rule.     

Intensive kaolinization during a lateritic weathering event in South-West Spain: Mineralogical and geochemical inferences from a relict paleosol

This study documents the mineralogical and geochemical record of a lateritic weathering event during the Pliocene in South-west Spain. The paleoweathering profile derived from arkosic sands and comprises a white sandy clayey saprolite, a red mottled clay zone overlain by a thick soft layer, and a ferruginous pisolitic hardcap partially dismantled by erosive processes. Kaolinite, quartz and degraded K-feldspars are the major minerals forming the saprolite, along with Al-goethite (mottled zone) as well as gibbsite and boehmite (soft layer), while the pisolitic duricrust is essentially composed of quartz grains embedded in a matrix of Fe oxy-hydroxides (hematite, goethite, and/or maghemite). Besides quartz, the phases most resistant to alteration were a variety of heavy minerals (mostly titanium oxides) that are present as minor impurities in the residual kaolin deposit.     

Effects of associations between humic acids and iron or aluminium on the flocculation and aggregation of kaolin and quartz

The aggregative effect of organic matter on soil particles is conditioned by its composition and concentration and the degree to which it is associated with metal ions and oxides in the soil. We treated suspensions of kaolin or quartz substrates at pH 5 with metal (Fe or Al; c. 3 to 23 mg g^?1 of substrate) or humic acid (HA; 7 to 53 mg g^?1 of substrate) or both. In the absence of added Fe or Al, the proportion of HA retained by the substrate decreased from 98.5 to 50.8% for kaolinitic samples, and from 35.8 to 23.4 for quartz-based samples, as the HA dose increased. In the presence of Fe or Al, the proportion of HA removed from solution increased and was always >91%. Untreated kaolin flocculated between pH 2.0 and 4.5. This flocculation interval narrowed as the dose of HA increased, widened as the dose of HA-A1 increased, but was barely affected by HA-Fe. Similarly, the aggregative effect of HA-Fe associations on kaolin was smaller than that of HA-A1 associations, which induced formation of aggregates >100 μm that were essentially absent in the untreated substrate. There was a similar but less marked difference between the aggregative effects of HA-Fe and HA-A1 on quartz.