clay and vermiculite

The adsorption of thallium (Tl) onto phyllosilicate minerals plays a critical role in the retention of Tl in soils and sediments and the potential transfer of Tl into plants and groundwater. Especially micaceous minerals are thought to strongly bind monovalent Tl(I), in analogy to their strong binding of Cs. To advance the understanding of Tl(I) adsorption onto phyllosilicate minerals, we studied the adsorption of Tl(I) onto Na- and K-saturated illite and Na-saturated smectite, two muscovites, two vermiculites and a naturally Tl-enriched soil clay mineral fraction. Macroscopic adsorption isotherms were combined with the characterization of the adsorbed Tl by X-ray absorption spectroscopy (XAS). In combination, the results suggest that the adsorption of Tl(I) onto phyllosilicate minerals can be interpreted in terms of three major uptake paths: (i) highest-affinity inner-sphere adsorption of dehydrated Tl

Topics: Adsorption; Aluminum Silicates; Cesium; Clay; Minerals; Silicates; Siloxanes; Soil; Thallium

The geochemistry of copper (Cu) is generally assumed to be controlled by organic matter in soils. However, the role of clay and iron oxide minerals may be understated. Soil density fractionation, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS) were combined to assess the long-term behavior of Cu in an agricultural soil subject to organic waste application. Two unprecedented molecular environments of natural Cu (i.e. Cu inherited from the parent rock) in soils are reported: Cu dimer in the interlayer of vermiculite and Cu structurally incorporated within hematite. Moreover, the soil naturally containing Cu-vermiculite, Cu-hematite, but also Cu-kaolinite (Cu

Topics: Aluminum Silicates; Animals; Clay; Copper; Ferric Compounds; Kaolin; Minerals; Soil; Soil Pollutants; Sulfides; Swine

The retention of radioactive cesium (Cs) in soil is significantly related to the types of clay minerals, while the weathering process affects the irreversible adsorption sites in clay minerals. In this study, the effect of weathering (exposure duration of Cs and repeated wetting and drying cycles) on fractionation of Cs in soils was investigated using fractionation analysis by the sequential extraction. The residual fraction of Cs increased slowly with exposure time but increased rapidly by repeated wetting and drying cycles. XRD analysis shows that a 1.43 nm of interlayer size for vermiculite is shortened to 1.00 nm, i.e., similar to that of illite. The change implies the potential that the structure of expandable clay minerals is transformed to the non-expandable structure by weathering process after Cs retention. Based on the result, the residual fraction of Cs, most stable form of Cs in the soil, reached relatively rapidly to a maximum. However, the process is much slower kinetically in the field because the bench-scale weathering process used in this study is more aggressive. This study implies that Cs fractionations in the soil are converted into a more stable fraction by weathering processes in the soil. Therefore, Cs removal should be conducted as soon as possible after accidental release of Cs in an environmental side.

Topics: Adsorption; Aluminum Silicates; Cesium Radioisotopes; Chemical Fractionation; Clay; Minerals; Soil; Soil Pollutants, Radioactive; Wettability

Radiocesium is well-known to be stabilized by clay minerals in soils, while volcanic soils could typically be poor in micaceous clays that fix

Topics: Aluminum Silicates; Cesium Radioisotopes; Clay; Forests; Fukushima Nuclear Accident; Japan; Minerals; Radiation Monitoring; Soil; Soil Pollutants, Radioactive

Some microorganisms in the environment make siderophores, which are low molecular chelators, to take up minerals from soil. Eleven bacteria were separated from the root of white clover by chlome azrol S (CAS) assay. Each bacterium was incubated in casamino acid (CAA) culture, and siderophores in CAA culture were purified. These extractions were applied to biotite or vermiculite spiked with Cs. From each clay mineral, 57.1-72.8% (5100 ppm), 55.6-63.8% (920 ppm) and 48.6-54.3% (2300 ppm), 31.6-34.4% (520 ppm) was eluted, respectively. To understand elution behaviour, Cs desorption ratio of each clay was measured every 30 min. The results indicate Cs elution was occurred quickly.

Topics: Aluminum Silicates; Bacteria; Cesium Radioisotopes; Clay; Ferrous Compounds; Medicago; Minerals; Plant Roots; Siderophores; Soil Microbiology; Soil Pollutants, Radioactive

Prediction of water and solute migration in natural clay-based materials requires a detailed understanding of the roles played by different porosity types (around or inside clay particles) on the overall transfer process. For smectite, a reference material for the design of migration models, this discrimination is complex because of osmotic swelling of the structure under water-saturated conditions. Diffusion experiments with a water tracer (HDO) were conducted on 0.1-0.2, 1-2, and 10-20 μm size fractions of Na-vermiculite, a swelling clay mineral with no osmotic swelling. Results obtained for the two finest fractions suggest that osmotic swelling and the associated impact on pore structure are responsible for the low D

Topics: Aluminum Silicates; Clay; Diffusion; Minerals; Porosity; Water

Many studies have shown that the adsorption of ions like K and Cs on 2:1 clay minerals can prompt the collapse of their interlayers and render the adsorbing ions nonexchangeable. This study sought to better understand this unique adsorption mechanism through the generation of an adsorption envelope for Cs adsorption on vermiculite and the exploration of the kinetics of interlayer collapse. The collapse of the vermiculite interlayer was confirmed via X-ray diffraction (XRD), and the timing of interlayer collapse was determined by placing Cs in competition with K at different time intervals. The adsorption envelope for Cs on vermiculite showed that although H competition does affect the adsorption of Cs on vermiculite, the effect of this competition is quite limited, even at very low pH values. This hypothesis is supported by the fact that XRD demonstrated a significant decrease in interlayer dimension after Cs adsorption. Finally, kinetics experiments showed that the irreversible adsorption of K and the collapse of the interlayer may take place on a much longer time scale than previously considered.

Topics: Adsorption; Aluminum Silicates; Cesium Radioisotopes; Clay; Hydrogen-Ion Concentration; Ion Exchange; Kinetics; Models, Chemical; X-Ray Diffraction

Pharmaceutical residues presence in the environment is among nowadays top emergent environmental issues. For removal of such pollutants, adsorption is a generally efficient process that can be complementary to conventional treatment. Research of cheap, widely available adsorbents may make this process economically attractive. The aim of the present work was to evaluate the capacity of two clay materials (exfoliated vermiculite, LECA) to adsorb gemfibrozil, mefenamic acid and naproxen in lab-scale batch assays. Results show that both adsorbents are able to remove the pharmaceuticals from aqueous medium. Although vermiculite exhibited higher adsorption capacities per unit mass of adsorbent, LECA yielded higher absolute removals of the pharmaceuticals due to the larger mass of adsorbent. Quantum chemistry calculations predicted that the forms of binding of the three molecules to the vermiculite surface are essentially identical, but the adsorption isotherm of naproxen differs substantially from the other two's. The linear forms of the latter impose limits at lower concentrations to the removal efficiencies of these pharmaceuticals by vermiculite, thereby electing LECA as more efficient. Notwithstanding, vermiculite's high specific adsorption capacity and also its much faster adsorption kinetics suggest that there may be some benefits in combining both materials as a composite adsorbent solution.

Topics: Adsorption; Aluminum Silicates; Clay; Computer Simulation; Drug Residues; Gemfibrozil; Kinetics; Mefenamic Acid; Models, Molecular; Naproxen; Particle Size; Pharmaceutical Preparations; Thermodynamics; Waste Disposal, Fluid

The effects of clay minerals on microbial degradation of phenol under unfavorable environmental conditions were investigated. Degradation of phenol by Sphingomonas sp. GY2B adsorbed on kaolinite, montmorillonite, and vermiculite were evaluated in comparison with free bacteria under optimal conditions. Kaolinite was found to be the most effective in accelerating degradation rate (reducing the degradation time) as well as improving degradation efficiency (increasing the percentage of phenol degraded), with GY2B/kaolinite complex achieving a degradation efficiency of 96% within 6 h. GY2B adsorbed on kaolinite was more competent than free GY2B in degradation under conditions with high phenol concentrations and at alkaline pH. Kaolinite reduced the time required for degradation by 8-12 h and improved the degradation efficiency by as much as 82% at high phenol concentrations. Meanwhile, the GY2B/kaolinite complex reduced the degradation time by 24 h and improved the degradation efficiency by 46% at pH 12. The improvement was partially due to the buffering effects of kaolinite. It was also shown that Cr(VI) and kaolinite synergistically enhanced the degradation by GY2B, with Cr(VI) and kaolinite both increasing the degradation rate and kaolinite being primarily responsible for enhanced degradation efficiency. These results showed one of the common clay minerals, kaolinite, is able to significantly improve the microbial degradation performance, and protect microorganisms against unfavorable environment. Kaolinite can collaborate with Cr(VI) to further improve the microbial degradation performance. It is implied that clay minerals have great potential to be applied in enhancing the biodegradation of phenol.

Topics: Adsorption; Aluminum Silicates; Bentonite; Biodegradation, Environmental; Chromium; Clay; Environmental Pollutants; Kaolin; Phenol; Phenols; Sphingomonas

Procedures for removing harmful radiation from interior and exterior surfaces of homes and businesses after a nuclear or radiological disaster may generate large volumes of radiologically contaminated waste water. Rather than releasing this waste water to potentially contaminate surrounding areas, it is preferable to treat it onsite. Retention barrels are a viable option because of their simplicity in preparation and availability of possible sorbent materials. This study investigated the use of aluminosilicate clay minerals as sorbent materials to retain (137)Cs, (85)Sr, and (152)Eu. Vermiculite strongly retained (137)Cs, though other radionuclides displayed diminished affinity for the surface. Montmorillonite exhibited increased affinity to sorb (85)Sr and (152)Eu in the presence of higher concentrations of (137)Cs. To simulate flow within retention barrels, vermiculite was mixed with sand and used in small-scale column experiments. The GoldSim contaminate fate module was used to model breakthrough and assess the feasibility of using clay minerals as sorbent materials in retention barrels. The modeled radionuclide breakthrough profiles suggest that vermiculite-sand and montmorillonite-sand filled barrels could be used for treatment of contaminated water generated from field operations.

Topics: Adsorption; Aluminum Silicates; Bentonite; Clay; Kinetics; Models, Theoretical; Radioactive Hazard Release; Radioisotopes; Wastewater; Water Pollutants, Radioactive

Batch experiments were conducted to evaluate Tween 80 sorption by oxides, aluminosilicates, and soils. For oxides, the sorption by silica and alumina follow linear isotherms, and that by hematite follows a Langmuir isotherm. Considering isotherm type and surface coverage, Tween 80 may partition into the silica/alumina-water interface, whereas it may bind to hematite surface sites. Among aluminosilicates, montmorillonite shows the greatest sorption due to the absorption of Tween 80 into interlayers. For other aluminosilicates, it sorbs to surfaces, with the sorption increasing as plagioclase

Topics: Adsorption; Aluminum Silicates; Clay; Kaolin; Kinetics; Micelles; Minerals; Organic Chemicals; Oxygen; Particle Size; Polysorbates; Soil; Soil Pollutants; Surface-Active Agents; X-Ray Diffraction

Geochemical mobility of Hg(II) species is strongly affected by the interactions of these compounds with naturally occurring adsorbents such as humic acids, clay minerals, oxides, etc. Interactions among these sorbents affect their affinity for Hg(II) and a full understanding of these processes is still lacking. The present work describes the influence of a humic acid (HA) sample on the adsorption of Hg(II) by vermiculite (VT). Adsorption isotherms were constructed to evaluate the affinity of Hg(II) by VT, HA, VT modified with humic acid (VT-HA), and VT-HA in presence of soluble humic acid (VT-HA + HA). All experiments were made at pH 6.0 ± 0.1 in 0.02 M NaNO3 and 25.0 ± 0.5 °C for initial Hg(II) concentrations from 1.0 to 100 μM. Determinations of Hg(II) were made by square wave voltammetry automated by sequential injection analysis, an approach that enables the determination of the free plus labile fractions of Hg(II) in HA suspensions without the need for laborious separation steps. The adsorption isotherms were fitted to Langmuir and Freundlich equations, showing that HA was the material with the higher adsorption capacity (537 ± 30 μmol g(-1)) in comparison with VT and VT-HA (44 ± 3 and 51 ± 11 μmol g(-1), respectively). Adsorption order was HA >> VT-HA + HA > VT = VT-HA. At pH 6.0 the interaction of HA with VT is weak and only 14% of C initially added to the suspension was effectively retained by the mineral. Desorption of Hg(II) in acidic medium (0.05 M HCl) was higher in binary (VT-HA) and ternary (VT-HA + HA) systems in comparison with that of VT and HA alone, suggesting that interactions between VT and HA are facilitated in acidic medium, weakening the binding to Hg(II).

Topics: Adsorption; Aluminum Silicates; Clay; Environmental Pollutants; Humic Substances; Hydrogen-Ion Concentration; Mercury; Nitrates

The performance of two bacteria, Arthrobacter viscosus and Streptococcus equisimilis, and the effect of the interaction of these bacteria with four different clays on the retention of diethylketone were investigated in batch experiments. The uptake, the removal percentages and the kinetics of the processes were determined. S. equisimilis, by itself, had the best performance in terms of removal percentage, for all the initial diethylketone concentrations tested: 200, 350 and 700 mg/L. The uptake values are similar for both bacteria. A possible mechanism to explain the removal of diethylketone includes its degradation by bacteria, followed by the adsorption of the intermediates/sub-products by the functional groups present on the cells' surfaces. The assays performed with bacteria and clays indicated that the uptake values are similar despite of the clay used, for the same microorganism and mass of clay, but in general, higher values are reached when S. equisimilis is used, compared to A. viscosus. Kinetic data were described by pseudo-first- and pseudo-second-order models.

Topics: Absorption; Aluminum Silicates; Arthrobacter; Bentonite; Biodegradation, Environmental; Clay; Environmental Restoration and Remediation; Kaolin; Magnesium Silicates; Pentanones; Streptococcus; Wastewater; Water Pollutants, Chemical

The effect of different rice cultivation periods on the properties of selected soils in alluvial plain were studied in Mazandaran province (north of Iran) in 2004. Soils were sampled form 0, 6, 16, 26 and over 40 years rice cultivation fields. In each treatment three soil profiles and six nearby auger holes were studied. The present study results indicated that continuous rice cultivation have changed soil moisture regime from xeric to aquic, soil color from brown to grayish, surface horizons from mollic to ochric epipedon and soil structure changed from granular or blocky to massive. Therefore, the soil order has changed from Mollisols to Inceptisols. No illuviation and eluviation of clay minerals occurred as a consequence of rice cultivation. X-ray diffraction analysis showed that clay minerals in non-rice cultivated field were illite, vermiculite, montmorillonite, kaolinite and chlorite, but in rice field were illite, montmorillonite, kaolinite and chlorite, respectively. In contrast of montmorillonite, the amount of illite and vermiculite have been decreased by increasing periods of rice cultivation. The pH values of the saturated soil surface in six weeks past plantation have shifted toward neutrality. While Eh value of non-paddy soils were about +90 mv, surface horizons of paddy soils at field conditions had Eh value about +40, -12, -84, -122 mv, respectively. The amounts of organic matter and available Fe, Mn, Zn and Cu were increased whereas available K was decreased in paddy soils.

Topics: Agriculture; Aluminum Silicates; Bentonite; Chlorides; Clay; Hydrogen-Ion Concentration; Iran; Kaolin; Minerals; Oryza; Potassium; Soil; Time Factors; Water; X-Ray Diffraction

Vermiculite, a 2:1 clay mineral, was applied as adsorbent for removal of cadmium, zinc, manganese, and chromium from aqueous solutions. Parameters such as time of reaction, effect of pH and cation concentration were investigated. All isotherms were L type of the Gilles classification, except zinc (type S). The adsorbent showed good sorption potential for these cations. The experimental data was analyzed by Langmuir isotherm model showing reasonable adjustment. The quantity of adsorbed cations was 0.50, 0.52, 0.60, and 0.48 mmol g(-1) of Cd(2+), Mn(2+), Zn(2+), and Cr(3+), respectively.

Topics: Aluminum Silicates; Cadmium; Cations; Cesium; Chromium; Clay; Hydrogen-Ion Concentration; Manganese; Metals, Heavy; Models, Chemical; Thermodynamics; Time Factors; Water Pollutants; Water Purification; Zinc

Geochemical analyses using a sequential extraction method and lead adsorption studies were carried out in order to characterize the distribution and adsorption of lead on each genetic horizon of a Luvisol profile developed on a pelagic clayey aleurolite. Clay illuviation is the most important pedogenic process in the profile studied. Its clay mineralogy is characterized by chlorite/vermiculite species with increasing chlorite component downward. The amount of carbonate minerals strongly increases in the lower part of the profile resulting in an abrupt rise in soil pH within a small distance. The Pb content of the soil profile exceeds the natural geochemical background only in the Ao horizon, and its amount decreases with depth in the profile without correcting for differences in bulk density, suggesting the binding of Pb to soil organic matter. According to the sequential extraction analysis the organic matter and carbonate content of the soil have the most significant effect on lead distribution. This effect varies in the different soil horizons. Lead adsorption experiments were carried out on whole soil samples, soil clay fractions, as well as on their carbonate and organic matter free variant. The different soil horizons adsorb lead to different extents depending on their organic matter, clay mineral and carbonate content; and the mineralogical features of soil clays significantly affect their lead adsorption capacity. The clay fraction adsorbs 25% more lead than the whole soil, while in the calcareous subsoil a significant proportion of lead is precipitated due to the alkaline conditions. 10 and 5% of adsorbed Pb can be leached with distilled water in the organic matter and clay mineral dominated soil horizons, respectively. These results suggest that soil organic matter plays a decisive role in the adsorption of Pb, but the fixation by clay minerals is stronger.

Topics: Adsorption; Aluminum Silicates; Biological Availability; Carbonates; Chlorides; Clay; Environmental Monitoring; Lead; Minerals; Organic Chemicals; Soil; Soil Pollutants; Trees

We present recent dielectric data on the dynamics of water confined in molecular sieves with pore sizes 5 and 10 A. The dielectric measurements in the frequency and temperature ranges 10(-2)-10(6) Hz and 120-300 K show three relaxation processes for both samples. In the case of the 10 A pore the slowest process shows an Arrhenius temperature dependence at low temperatures (<220 K), while at high temperatures the relaxation appears to follow a more Vogel-Fulcher-Tammann (VFT) like behaviour. The relaxation time for this process is 100 s at about 170 K. The second slowest process is at low temperatures very similar to the main process of (bulk-like) water in a fully hydrated clay, but also this process seems to exhibit some kind of dynamical transition, in this case at T approximately 185 K. All the three processes in the 5 A pore exhibit Arrhenius temperature dependence, and two of them are considerably slower than the main relaxation in the hydrated clay. Thus, dynamics of bulk-like water is only observed in the 10 A molecular sieves, and most of the water molecules in both 5 and 10 A pores have considerably slower dielectric relaxation than has been observed for water confined in clay, most likely due to strong interactions with the considerably more hydrophilic inner surfaces of molecular sieves.

Topics: Aluminum Silicates; Clay; Dielectric Spectroscopy; Electric Impedance; Hydrophobic and Hydrophilic Interactions; Porosity; Water

We studied one sample of commercial sepiolite and two samples of commercial vermiculite--clay minerals proposed as replacements for asbestos--and tested in vitro their abilities to activate complement, to lyse erythrocytes, and to elicit the production of reactive oxygen species (ROS) with human polymorphonuclear leukocytes (PMN) or bovine alveolar macrophages (AM); their behavior was compared with that of asbestos fibers obtained from the Union International Contra Cancer (UICC) as reference standards, as well as with kaolinite and illite, main members of the clay mineral family. Since in short-term in vitro tests the biological activity of mineral particles seems especially related to the active sites on their surface, we first measured the specific surface area of each mineral. Sepiolite was unreactive in two of the three tests we used (complement activation and ROS production) and able to lyse a minimal percentage of red blood cells. Vermiculite was shown to be incapable of activating complement, to have a moderate hemolytic activity and a high ability to elicite ROS production, although lower than that of chrysotile. Sepiolite, therefore, might be of more interest than vermiculite, given the low level of biological effects detected during the tests used to compare both clay minerals with asbestos fibres. The ROS production does not seem to require phagocytosis. A high ROS production was observed with kaolinite: this result casts doubt on the ability of pathogenic mineral dusts in vitro to induce a greater release of ROS than nonpathogenic mineral dusts.

Topics: Acridines; Aluminum Silicates; Animals; Antacids; Antidiarrheals; Asbestos; Asbestos, Crocidolite; Asbestos, Serpentine; Carcinogens; Cattle; Clay; Complement Activation; Dose-Response Relationship, Drug; Erythrocytes; Hemolysis; Humans; Kaolin; Linear Models; Luminescent Measurements; Luminol; Macrophages, Alveolar; Magnesium Silicates; Minerals; Neutrophils; Reactive Oxygen Species; Tetradecanoylphorbol Acetate; Zymosan

Nitrate production by Nitrosomonas europaea in inorganic liquid medium containing ammonium was limited by reduction in pH. In the presence of montmorillonite and vermiculite, expanding clays with high cation-exchange-capacity (CEC), nitrite yield was increased, ammonia oxidation continued at pH values below those which inhibited growth in the absence of clays and growth was biphasic. The first phase was similar to that in the absence of clays, while the second was characterized by a lower rate of nitrite production. Illite, a non-expanding clay with low CEC, had no significant effect on ammonia oxidation, while oxidation of ammonia-treated vermiculite (ATV) occurred with no significant change in the pH of the medium. ATV, montmorillonite and vermiculite, but not illite, protected cells from inhibition by nitrapyrin at concentrations inhibitory to cells growing in suspended culture. This protection was maintained in ATV homo-ionic to Al3+, but montmorillonite made homo-ionic to Al3+ did not provide protection from inhibition. Attachment of cells to clays with high CEC is therefore advantageous in providing exchange at the clay surface of NH+4 and H+ produced by ammonia oxidation, in reducing pH toxicity, and in protecting cells from inhibition.

Topics: Aluminum Silicates; Ammonia; Bentonite; Clay; Hydrogen-Ion Concentration; Kinetics; Minerals; Nitrites; Nitrosomonas; Oxidation-Reduction; Picolines; Soil Microbiology