Effects of Organic Anions on Phosphate Adsorption and Desorption from Variable-Charge Clay Minerals and Soil

Effects of citrate and tartrate on phosphate adsorption and desorption from kaolinite, goethite, amorphous Al-oxide and Ultisol were studied. P adsorption was significantly decreased as the concentration of the organic anions increased from 10-5 to 10-1 M. At 0.1 M and pH 7.0, tartrate decreased P adsorption by 27.6% - 50.6% and citrate by 37.9 - 80.4%, depending on the kinds of adsorbent. Little Al and/ or Fe were detected in the equilibrium solutions, even at the highest concentration of the organic anions. Effects of the organic anions on phosphate adsorption follow essentially the competitive adsorption mechanism.The selectivity coefficients for competitive adsorption can be used to compare the effectiveness of different organic anions in reducing P adsorption under given conditions.Phosphate desorption was increased by 3 to 100 times in the presence of 0.001 M citrate or tartrate compared to that in 0.02 M KC1 solution alone. However, for all the soil and clay minerals studied the amount of P desorbed by citrate or tartrate was generally lower than or close to that of isotopically exchangeable P. The effect of organic anions on phosphate desorption arises primarily from ligand exchange.

Physical Experiments and Mechanism Study on the Occurrence State of Hydrogen in Clay Minerals

In recent years,natural hydrogen has been discovered in various geological environments both domestically and internationally,which has sparked a global interest among geologists and led to a surge in the exploration of hydrogen gas(Klein et al.,2019;Prinzhofer et al.,2019;Moretti and Webber,2021;Scott,2021;Bezruchko,2022).However,there is a lack of research on the occurrence state of natural hydrogen gas,which hinders a deeper understanding of its behavior in underground storage and migration.

Study of Adsorption Properties and Enriching RE on Clay Minerals by Ouantum Chemical Calculation

The order of adsorbability of three kinds of clay minerals and their selectivity of adsorption to common cations and RE ions have been studied by quantum chemical calculation.They are as follows: montmorilionite>halloysite>kaolinite,RE^(3+)>Al^(3+)>Ca^(2+)>Mg^(2+)>K^+>NH_4^+>Na^+,Sc^(3+)>La^(3+)> Ce^(3+)>Pr^(3+)>Nd^(3+)>Sm^(3+)>Eu^(3+)>Gd^(3+)>Tb^(3+)>Dy^(3+)>Ho^(3+)>Y^(3+)>Er^(3+)>Tm^(3+)>Yb^(3+)>Lu^(3+).Based on these orders,the facts that RE is preferentially adsorbed in weathered residual type of clay mineral and light RE and heavy RE are enriched at the upper layer and at the lower layer respectively in ore body have been explained.

A Preliminary Stndy on Identification of Clay Minerals in Soils with Reference to Reflectance Spectra

The characteristics of the reflectance spectra of clay minerals and their influences on the reflectancespectra of soils are dealt with in the paper. The results showed that dominant clay minerals in soils couldbe distinguished in light of the spectral-form parameters of the reflectance spectra of soils, thus making itpossible to develop a quick method to determine clay minerals by means of reflectance spectra of soils in thelab. and providing a theoretic basis for retnote sensing of clay minerals in soils with a high resolution imagingspectrometer.

Main Clay Minerals in Soils of Fujian Province, China

The clay minerals of more than 200 soil samples collected from various sites of Fujian Province were studied by the X-ray diffraction method and transmission electron microscopy to study their distribution and evolution. Montmorillonite was found in coastal solonchak, paddy soils derived from marine deposit, lacustrine deposit and river deposit, and some latentic red soil, red soil and yellow soil with a low weathering degree. Chlorite existed mainly in coastal solonchak and paddy soil developed from marine deposit. 1.4 nm intergradient mineral appeared frequently in yellow soil, red soil and latentic red soil. The content of l.4 nm intergradient mineral increased with the decrease of weathering degree from latentic red soil to red soil to yellow soil. Hydrous micas were more in coastal solonchak, paddy soils derived from marine deposit, lacustrine deposit and river deposit, and purple soil from purple shale than in other soils. Kaolinite was the most important clay mineral in the soils in this province. The higher the soil weathering degree, the more the kaolinite existed. From yellow soil to red soil to latentic red soil, kaolinite increased gradually. Kaolinite was the predominant clay mineral accompanied by few other minerals in typical latentic red soil. Tubular halloysite was a widespread clay mineral in soils of Fujian Province with varying quantities. The soil derived from the parent rocks rich in feldspar contained more tubular halloysite. Spheroidal halloysite was found in a red soil and a paddy soil developed from olivine basalt. Gibbsite in the soils in this district was largely 'primary gibbsite' which formed in the early weathering stage. Gibbsite decreased with the increase of weathering degree from yellow soil to red soil to latentic red soil. Goethite also decreased in the same sequence while hematite increased.

Charge Properties and Clay Mineral Composition of Tianbao Mountains Soils

The clay mineral association, oxides of clay fraction and surface charge properties of 7 soils, which are developed from granite, located at different altitudes of the Tianbao Mountains were studied. Results indicate that with the increase in altitude, 1) the weathering process and desilicification of soil clay minerals became weaker, whereas the leaching depotassication and the formation process of hydroxy-aluminum interlayer got stronger; 2) the contents of amorphous and complex aluminum and iron, and the activity of aluminum and iron oxides for soil clay fraction increased; and 3) the amount of variable negative charge, anion exchange capacity and the values of PZC and PZNC also increased. The activity of aluminum and iron oxides, the accumulation of aluminum, and surface charge characteristics and their relation to clay oxides of the vertical zone soils were observed and recorded.

Potassium forms in calcareous soils as affected by clay minerals and soil development in Kohgiluyeh and Boyer-Ahmad Province,Southwest Iran

Potassium（K） is known as one of the essential nutrients for the growth of plant species. The relationship between K and clay minerals can be used to understand the K cycling, and assess the plant uptake and potential of soil K fertility. This study was conducted to analyze the K forms（soluble, exchangeable, non-exchangeable and structural） and the relationship of K forms with clay minerals of calcareous soils in Kohgiluyeh and Boyer-Ahmad Province, Southwest Iran. The climate is hotter and drier in the west and south of the province than in the east and north of the province. A total of 54 pedons were dug in the study area and 32 representative pedons were selected. The studied pedons were mostly located on calcareous deposits. The soils in the study area can be classified into 5 orders including Entisols, Inceptisols, Mollisols, Alfisols and Vertisols. The main soil clay minerals in the west and south of the study area were illite, chlorite and palygorskite, whereas they were smectite, vermiculite and illite in the north and east of the province. Due to large amount of smectite and high content of organic carbon in soil surface, the exchangeable K in surface soils was higher than that in subsurface soils. It seems that organic matter plays a more important role than smectite mineral in retaining exchangeable K in the studied soils. Non-exchangeable K exhibited close relationships with clay content, illite, vermiculite and smectite. Although the amount of illite was the same in almost all pedons, amounts of structural and non-exchangeable K were higher in humid regions than in arid and semi-arid regions. This difference may be related to the poor reservoir of K~＋ minerals like palygorskite and chlorite together with illite in arid and semi-arid regions. In humid areas, illite was accompanied by vermiculite and smectite as the K~＋ reservoir. Moreover, the mean cumulative non-exchangeable K released by CaCl_2 was higher than that released by oxalic acid, which may be due to the high buffering capacity resulting from high carbonates in soils.

Clay mineral expansion of black cotton soil based on interlayer cation hydration

To analyze the water swelling characteristics of black cotton soil(BCS),X-ray fluorescence and X-ray diffraction characterizations were performed to investigate the chemical compositions and types of clay minerals in BCS.A montmorillonite crystal lattice was established to simulate the hydration of interlayer cations by applying the SPC/E potential energy model,universal force field,algorithm of charge balance,and periodic boundary.Results indicated that the main clay mineral found in the BCS was montmorillonite(32.6%)with small amounts of interstratified illite-montmorillonite(10.9%),illite(2.3%),and kaolinite(1.5%).The high expansive potential of BCS comes from the strong adsorption property of montmorillonite with a high content of magnesium and sodium ions to water molecules.The exchangeable cations of Na^(+)in BCS were only 3.73%,but they enhanced the adsorption capacity of clay to water molecules and accelerated the hydration of Mg^(2+)(47.1%)and Ca^(2+)(4.78%).The free swell index can be used as a classification index of the swelling potential of BCS.

Characterization of Soil Clay Minerals of the River Nile Sediments, Sohag Region, Egypt： Decomposition of X-Ray Diffraction Patterns

Up till now all the clay mineral studies on the soils of the River Nile flood plain in Egypt could not trace the very rapid mineral change observed in these soils. So, the clay mineralogy of the River Nile flood plain soils in Sohag region, Egypt, has been studied using the method of numerical analysis of X-ray diffraction recordings （curve decomposition） as a new, powerful tool for precise mineral identification. The X-ray patterns of the studied soil clay fraction show that 2：1 clay minerals are much more abundant than kaolinite and that this clay fraction contains fair amounts of K-feldspar and quartz. XRD pattems obtained on the 〈 2 μm fraction of the River Nile sediments indicate the presence of smectite, mixed-layer illite-expanding minerals, kaolinite, mica-illite and chlorite. The decomposed XRD patterns reveal significant changes in the mineralogy of the clays. The major clay phases present in the 4-11 20 range are well crystallized illite （10 A）, poorly crystallized illite （10.2-10.4 A）, two mixed-layer I-S （illite/smectite） minerals, one with a peak near 13.5 A （rich-smectite） and the other near 11 A （rich-illite）.

Characterization and Modification of a Clay Mineral Used in Adsorption Tests

Clay minerals are widespread in natural systems and have been widely used for the removal of pollutants. In this study, natural expanded vermiculite was used in adsorption tests to remove ammonium nitrogen from landfill leachate. The modification of vermiculite was carried out using NaOH and HCl, and for both modifications the best concentration was 0.1 mol/L. The results produced by XRD (X-ray diffraction) showed that Al replaced K after modification of the vermiculite using HCl and that Mg and Na replaced K after modification using NaOH. It was observed that the adsorption capacity increased as the percentage in mass of K diminished. The Langmuir is the isotherm that presents the best fit of the data, and the values of RL (the Langmuir coefficient) suggest that the adsorption is linear. The thermodynamic parameters indicate that the process is spontaneous and endothermic, that there is a high affinity between the adsorbate and the adsorbent, and that physical adsorption is prevalent.

Adsorption Characteristics of Zinc (Zn²⁺) from Aqueous Solution by Natural Bentonite and Kaolin Clay Minerals: A Comparative Study

Clay minerals are one of the potential good adsorbent alternatives to activated carbon because of their large surface area and high cation exchange capacity. In this work the adsorptive properties of natural bentonite and kaolin clay minerals in the removal of zinc (Zn2+) from aqueous solution have been studied by laboratory batch adsorption kinetic and equi- librium experiments. The result shows that the amount of adsorption of zinc metal ion increases with initial metal ion concentration, contact time, but decreases with the amount of adsorbent and temperature of the system for both the ad- sorbents. Kinetic experiments clearly indicate that adsorption of zinc metal ion (Zn2+) on bentonite and kaolin is a two-step process: a very rapid adsorption of zinc metal ion to the external surface is followed by possible slow decreas- ing intraparticle diffusion in the interior of the adsorbent. This has also been confirmed by an intraparticle diffusion model. The equilibrium adsorption results are fitted better with the Langmuir isotherm compared to the Freundlich model. The value of separation factor, RL from Langmuir equation give an indication of favourable adsorption. Finally from thermodynamic studies, it has been found that the adsorption process is exothermic due to negative ?H0 accompa- nied by decrease in entropy change and Gibbs free energy change (?G0). Overall bentonite is a better adsorbent than kaolin in the the removal of Zn2+ from its aqueous solution.

Changes of Clay Mineral Association After High-Gradient Magnetic Separation

The changes of clay mineral association after high-gradient magnetic separation (HGMS) treatment, and the effects of chemical and physical technologies on concentrating Fe oxides for main soils in central and southern China were investigated by means of X-ray diffraction (XRD) and chemical analysis methods. Results indicated that the concentrating times of Fe oxides by HGMS treatment were the largest for 0.2-2 μmsize fractions in the examined soils. For the soils in which 2: 1 phyllosilicates were dominant, concentrating times of iron oxides by HGMS treatment were larger than by 5 mol L-1 NaOH treatment. Phyllosili-cates were decreased after HGMS treatment; however, the decrease was less than that of kaorolinite. The goet bite / (goethite + hematie) values in Fe oxides of the soils kept virtually constant after HGMSt reatment.

Instrumental Characterization of Pretoria Clay Soil by XRF, XRD and SEM

The products of refractory materials are used for lining furnace, incinerators and kilns among other uses and they have the potential of withstanding high temperature without deformation. The objective of the research was to charac-terize the clay soil sample collected from Tshwane University of Technology in Pretoria. The sample, collected from a location Latitude 25.0969°S and Longi-tude 28.1624°E, was oven-dried, pulverized and sieved in the laboratory. Min-eralogical and elemental compositions of the sample were determined by using X-Ray Diffraction (XRD), X-Ray Fluorescence (XRF) and Scanning Electron Microscopy (SEM) analytical methods. The XRF analysis revealed Fe2O3, Al2O3 and SiO2 as the major constituents, while the other elements occur in minor quantities. Mineralogically, the three samples contain Montmorillonite, Kaolinite and Bentonite, while Samples A contained Quartz in addition to ear-lier mentioned minerals, samples B and C contained Albite.

Adsorption of fluoride on clay minerals and their mechanisms using X-ray photoelectron spectroscopy

This research investigates the adsorptionmechanisms of fluoride(F)on four clay minerals(kaolinite,montmorillonite,chlorite,and illite)underdifferent F^(-)concentrations and reaction times by probingtheir fluoride superficial layer binding energies and elementcompositions using X-ray photoelectron spectroscopy(XPS).At high F^(-)concentrations(C_(0)=5-1000 mg·L^(-1)),the amount of F^(-)adsorbed(Q_(F)),amount of hydroxidereleased by clay minerals,solution F^(-)concentration,andthe pH increase with increasing C_(0).The increases areremarkable at C_(0)>50 mg·L^(-1).The QF increases significantlyby continuously modifying the pH level.At C_(0)<5-100 mg·L^(-1),clay minerals adsorb H+to protonatealuminum-bound surface-active hydroxyl sites in thesuperficial layers and induce F^(-)binding.As the C_(0)increases,F^(-),along with other cations,is adsorbed toform a quasi-cryolite structure.At C_(0)>100 mg·L^(-1),newminerals precipitate and the product depends on the criticalAl^(3+)concentration.At[Al^(3+)]>10^(-11.94)mol·L^(-1),cryoliteforms,while at[Al^(3+)]<10^(-11.94)mol·L^(-1),AlF_(3) is formed.At low C_(0)(0.3-1.5 mg·L^(-1)),proton transfer occurs,andthe F^(-)adsorption capabilities of the clay minerals increasewith time.

Adsorption of Naphthalene on Clay and Sandy Soil from Aqueous Solution

The adsorption behavior of naphthalene using clay and sandy soil as adsorbents is examined under ambient conditions. The adsorption equilibrium of naphthalene on clay and sandy soil was evaluated by the Langmuir, Freundlich and Tempkin isotherms. The results showed that the equilibrium data for naphthalene fitted the Freundlich model best within the concentration range studied for both clay and sandy soil. Experimental results showed that the time taken to attain adsorption equilibrium for naphthalene was 26 hrs and 20 hrs for clay and sandy soil, respectively. Among the tested kinetic models in this study, the pseudo-second order successfully predicted the adsorption process.

Adsorption of Benzene in Batch System in Natural Clay and Sandy Soil

The adsorption potential of clay and sandy soil to remove benzene from liquid-phase system was examined. A series of batch adsorption tests were carried out for various concentrations of benzene (50 - 250 mg/l) in tightly corked 1000 ml flasks for clay and sandy soil, respectively. Equilibrium and kinetics data were obtained from the batch experiments. Adsorption increased with increasing initial benzene concentration. The equilibrium data obtained from the adsorption of benzene were well fitted to the Freundlich isotherm model. The adsorption kinetics process showed that the kinetic model of pseudo second-order was the best fit to the experimental data. The results showed that clay and sandy soil had good potential for the removal of aromatic hydrocarbon, benzene from aqueous solution.

Synthesis of biochar/clay mineral nanocomposites using oil shale semi-coke waste for removal of organic pollutants

Due to the poor surface/interfacial interaction and the large gaps in the size and microstructure between biomass and clay mineral,it was difficult to adjust the structure and performance of biochar/clay mineral composites at the molecular level.Herein,oil shale semi-coke composed of multi-minerals and organic matters was used as a promising precursor to prepare biochar/clay mineral nanocomposites via phosphoric acid-assisted hydrothermal treatment followed by KOH activation for removal of organic pollutants from aqueous solution.The results revealed that the nanocomposites presented well-defined sheet-like morphology,and the carbon species uniformly anchored on the surface of clay minerals.With the changes in the pore structure,surface charge and functional groups after two-step modification,the nanocomposites exhibited much better adsorption property toward organic pollutants than the raw oil shale semi-coke,and the maximum adsorption capacities of methylene blue,methyl violet,tetracycline,and malachite green were 165.30 mg g^(−1),159.02 mg g^(−1),145.89 mg g^(−1),and 2137.36 mg g^(−1),respectively.The adsorption mechanisms involved electrostatic attraction,π-πstacking and hydrogen bonds.After five consecutive adsorption-desorption,there was no obvious decrease in the adsorption capacity of malachite green,exhibiting good cyclic regeneration performance.It is expected to provide a feasible strategy for the preparation of biochar/clay mineral nanocomposites with the excellent adsorption performances for removal of organic pollutants based on full-component resource utilization of oil shale semi-coke.

Cr^(Ⅵ) adsorption on four typical soil colloids: equilibrium and kinetics

It is observed that the adsorption of chromium are greater on kaolinite minerals, red soil (R) and laterite (L) colloids than that on montmorillonite, indicotic black (IB) and yellow brown (YB) soil colloids. The adsorption process of Cr Ⅵ on these media can be further described by Langmuir or Freundlich equation quite well. The adsorption reaction of Cr Ⅵ is fast, and the adsorption equilibrium can be reached within the first two hours in moderate temperature. The adsorption quantity of Cr Ⅵ to kaolinite mineral increased with the increasing pH in the range of 2.0 to 7.0, then decreased at higher pH. But it showed some consistence among the four soil colloids. The lower the pH, the stronger the adsorption. The possible mechanisms are further discussed here. Meanwhile the influence of temperature on Cr Ⅵ adsorption on different soil colloid and clay minerals are also investigated.

Characterization of an Area Polluted by Copper and Zinc:the Relation between Soil Texture,Mineralogy and Pollutant Concentration

Twenty-four soil samples were collected at three depths from an approximately 2.5 acre contaminated site in southern Piedmont （Italy） and then analyzed. The main soil parameters determined were： pH, Cation Exchange Capacity （CEC）, particle size distribution, total organic carbon （TOC） content and retained metal concentration. The mineral phases were identified by X-Ray Powder Diffraction （XRPD）. All of the samples contained Zn and Cu resulting from industrial contamination during the last century, and those obtained at depths of 20-40 cm consistently showed the highest levels. To determine which size fraction was most active in the retention process, the samples were separated into four fractions （≤2 mm, ≤63 0m, ≤30 0m and ≤2 μm） and the amount of pollutant measured in each. It was found that metal retention was the highest in the clayey fraction, whose clay minerals were identified by XRPD after K＋ and Mg2＋ saturation, glycerol treatment and heating to 550℃. The clayey fraction was also the richest in TOC, and a direct correlation between TOC amount and metal retention was observed.

Use of flue gas desulfurization gypsum to reduce dissolved phosphorus in runoff and leachate from two agricultural soils

Controlling dissolved phosphorus(DP)loss from high P soil to avoid water eutrophication is a worldwide high priority.A greenhouse study was conducted in which flue gas desulfurization gypsum(FGDG)was applied by using different application methods and rates to two agricultural soils.Phosphorus fertilizer was incorporated into the soils at 2.95 g kg^(-1)to simulate soil with high P levels.The FGDG was then applied at amounts of 0,1.5,and 15 g kg^(-1)soil on either the soil surface or mixed throughout the soil samples to simulate no-tillage and tillage,respectively.Ryegrass was planted after treatment application.The study showed that FGDG reduced runoff DP loss by 33%and leachate DP loss 38%in silt loam soil,and runoff DP loss 46%and leachate DP loss 14%in clay loam soil,at the treatment of 15 g kg^(-1)FGDG.Mixing applied method(tillage)provided strong interaction with higher FGDG.To overall effect,the mixing-applied method performed better in controlling DP loss from silt loam soil,while surface-applied(no tillage)showed its advantage in controlling DP loss from clay loam soil.In practice it is necessary to optimize FGDG concentrations,application methods,and DP sources(runoff or leachate)to get maximized benefits of FGDG application.The FGDG application had no negative effects on the soil and ryegrass.