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Cations as mediators of the adsorption of nucleic acids on clay surfaces in prebiotic environments.

Monovalent ([Na+] > 10 mM) and divalent ([Ca2+], [Mg2+] > 1.0 mM) cations induced the precipitation of nucleic acid molecules. In the presence of clay minerals (montmorillonite and kaolinite), there was adsorption instead of precipitation. The cation concentration needed for adsorption depended on both the valence of the cations and the chemical nature of the nucleic acid molecules. Double-stranded nucleic acids needed higher cation concentrations than single-stranded ones to be adsorbed to the same extent on clay. Divalent cations were more efficient than monovalent ones in mediating adsorption. Adsorption to the clay occurred only when both nucleic acids and cations were present. However, once the complexes were formed, the cations could not be removed from the system by washing, indicating that they are directly involved in the association between nucleic acids and mineral surfaces. These observations indicate that cations take part directly in the formation of nucleic acid-clay complexes, acting as a 'bridge' between the negative charges on the mineral surface and those of the phosphate groups of the genetic polymer. The relatively low cation concentrations needed for adsorption and the ubiquitous presence of clay minerals in the environment suggest that the adsorption of nucleic acids on mineral surfaces could have taken place in prebiotic habitats. This may have played an important role in the formation and preservation of nucleic acids and/or their precursor polymers.

Adsorption↗

Implementation of a best management practice (BMP) system for a clay mining facility in Taiwan.

The present paper describes the planning and implementation of a best management practice (BMP) system for a clay mining facility in Northern Taiwan. It is a challenge to plan and design BMPs for mitigating the impact of clay mining operations due to the fact that clay mining drainage typically contains very high concentrations of suspended solids (SS), Fe-ions, and [H+] concentrations. In the present study, a field monitoring effort was conducted to collect data for runoff quality and quantity from a clay mining area in Northern Taiwan. A BMP system including holding ponds connected in series was designed and implemented and its pollutant removal performance was assessed. The assessment was based on mass balance computations and an analysis of the relationship between BMP design parameters such as pond depth, detention time, surface loading rate, etc. and the pollutant removal efficiency. Field sampling results showed that the surface-loading rate is exponential related to the removing rate. The results provide the basis for a more comprehensive and efficient BMP implementation plan for clay mining operations.

Aluminum Silicates↗

Microorganisms metabolizing on clay grains in 3-km-deep Greenland basal ice.

We have discovered > 10(8) microbial cells/cm3 attached to clay grains in the bottom 13 m of the GISP2 (Greenland Ice Sheet Project) ice core. Their concentration correlates with huge excesses of CO2 and CH4. We show that Fe-reducing bacteria produce most of the excess CO2 and methanogenic archaea produce the excess CH4. The number of attached cells per clay grain is proportional to grain perimeter rather than to area, which implies that nutrients are accessed at grain edges. We conclude that Fe-reducing microbes immobilized on clay surfaces metabolize via "shuttle" molecules that transport electrons to grain edges, where they reduce Fe(III) ions at edges to Fe(II) while organic acid ions are oxidized to CO2. Driven by the concentration gradient, electrons on Fe(II) ions at grain edges "hop" to Fe(III) ions inward in the same edges and oxidize them. The original Fe(III) ions can then attach new electrons from shuttle molecules at the edges. Our mechanism explains how Fe-reducers can reduce essentially all Fe(III) in clay minerals. We estimate that the Fe(III) in clay grains in the GISP2 silty ice can sustain Fe-reducing bacteria at the ambient temperature of -9 degrees C for approximately 10(6) years. F420 autofluorescence imaging shows that > 2.4% of the cells are methanogens, which account for the excess methane.

Aluminum Silicates↗

Adsorption of liposomes by clay.

The interaction between liposomes and clay was investigated. Lecithin liposomes were adsorbed by montmorillonite, and aggregation of the clay particles occurred. From studies using differential scanning calorimetry (DSC), the transition temperature (Tc) from a gel to a liquid-crystalline state of this phospholipid increased by several degrees on adsorption by the clay. Although a lecithin molecule as a whole seems to have no net charge, liposomes were considered to have been adsorbed by the clay via the choline positive charge, which occupies the outermost part of the liposome membrane, as the clay is known to be negatively charged.

Adsorption↗

Comparison of clay mineral stratigraphy to other proxy palaeoclimate indicators in the Mesozoic of NW Europe.

This paper reviews the opportunities and pitfalls associated with using clay mineralogical analysis in palaeoclimatic reconstructions. Following this, conjunctive methods of improving the reliability of clay mineralogical analysis are reviewed. The Mesozoic succession of NW Europe is employed as a case study. This demonstrates the relationship between clay mineralogy and palaeoclimate. Proxy analyses may be integrated with clay mineralogical analysis to provide an assessment of aridity-humidity contrasts in the hinterland climate. As an example, the abundance of kaolinite through the Mesozoic shows that, while interpretations may be difficult, the Mesozoic climate of NW Europe was subject to great changes in rates of continental precipitation. We may compare sedimentological (facies, mineralogy, geochemistry) indicators of palaeoprecipitation with palaeotemperature estimates. The integration of clay mineralogical analyses with other sedimentological proxy indicators of palaeoclimate allows differentiation of palaeoclimatic effects from those of sea-level and tectonic change. We may also observe how widespread palaeoclimate changes were; whether they were diachronous or synchronous; how climate, sea level and tectonics interact to control sedimentary facies and what palaeoclimate indicators are reliable.

Aluminum Silicates↗

Late Precambrian oxygenation; inception of the clay mineral factory.

An enigmatic stepwise increase in oxygen in the late Precambrian is widely considered a prerequisite for the expansion of animal life. Accumulation of oxygen requires organic matter burial in sediments, which is largely controlled by the sheltering or preservational effects of detrital clay minerals in modern marine continental margin depocenters. Here, we show mineralogical and geochemical evidence for an increase in clay mineral deposition in the Neoproterozoic that immediately predated the first metazoans. Today most clay minerals originate in biologically active soils, so initial expansion of a primitive land biota would greatly enhance production of pedogenic clay minerals (the "clay mineral factory"), leading to increased marine burial of organic carbon via mineral surface preservation.

Aluminum Silicates↗

Effect of proteins on reovirus adsorption to clay minerals.

Organic matter in sewage, soil, and aquatic systems may enhance or inhibit the infectivity of viruses associated with particulates (e.g., clay minerals, sediments). The purpose of this investigation was to identify the mechanisms whereby organic matter, in the form of defined proteins, affects the adsorption of reovirus to the clay minerals kaolinite and montmorillonite and its subsequent infectivity. Chymotrypsin and ovalbumin reduced the adsorption of reovirus to kaolinite and montmorillonite homoionic to sodium. Lysozyme did not reduce the adsorption of the virus to kaolinite, but it did reduce adsorption to montmorillonite. The proteins apparently competed with the reovirus for sites on the clay. As lysozyme does not adsorb to kaolinite by cation exchange, it did not inhibit the adsorption of reovirus to this clay. The amount of reovirus desorbed from lysozyme-coated montmorillonite was approximately 38% less (compared with the input population) than that from uncoated or chymotrypsin-coated montmorillonite after six washings with sterile distilled water. Chymotrypsin and lysozyme markedly decreased reovirus infectivity in distilled water, whereas infectivity of the virus was enhanced after recovery from an ovalbumin-distilled water-reovirus suspension (i.e., from the immiscible pelleted fraction plus supernatant). The results of these studies indicate that the persistence of reovirus in terrestrial and aquatic environments may vary with the type of organic matter and clay mineral with which the virus comes in contact.

Adsorption↗

Adhesion of the clay minerals montmorillonite, kaolinite, and attapulgite reduces respiration of Histoplasma capsulatum.

The respiration of three phenotypes of Histoplasma capsulatum, the causal agent of histoplasmosis in humans, was markedly reduced by low concentrations of montmorillonite but was reduced less by even higher concentrations of kaolinite or attapulgite (palygorskite). The reduction in respiration followed a pattern that suggested saturation-type kinetics: an initial sharp reduction that occurred with low concentrations of clay (0.01 to 0.5% [wt/vol]), followed by a more gradual reduction with higher concentrations (1 to 8%). Increases in viscosity (which could impair the movement of O2) caused by the clays were not responsible for the reduction in respiration, and the clays did not interfere with the availability of nutrients. Scanning electron microscopy after extensive washing showed that the clay particles were tightly bound to the hyphae, suggesting that the clays reduced the rate of respiration of H. capsulatum by adhering to the mycelial surface and, thereby, interfered with the movement of nutrients, metabolites, and gases across the mycelial wall.

Adhesiveness↗

Sm-Nd dating of Fig Tree clay minerals of the Barberton greenstone belt, South Africa.

Sm-Nd isotopic data from carbonate-derived clay minerals of the 3.22-3.25 Ga Fig Tree Group, Barberton greenstone belt, South Africa, form a linear array corresponding to an age of 3102 +/- 64 Ma, making these minerals the oldest dated clays on Earth. The obtained age is 120-160 m.y. younger than the depositional age determined by zircon geochronology. Nd model ages for the clays range from approximately 3.39 to 3.44 Ga and almost cover the age variation of the Barberton greenstone belt rocks, consistent with independent evidence that the clay minerals are derived from material of the belt. The combined isotopic and mineralogical data provide evidence for a cryptic thermal overprint in the sediments of the belt. However, the highest temperature reached by the samples since the time of clay-mineral formation was <300 degrees C, lower than virtually any known early Archean supracrustal sequence.

Aluminum Silicates↗

Analyses of the 1990 chest health survey of china clay workers.

During 1990 all present and retired china clay workers in the United Kingdom were invited to take part in a chest health survey. A total of 4401 china clay workers participated representing over 70% of current employees and 17% of pensioners. The survey consisted of a chest x ray film, lung function measurements, and a questionnaire on respiratory symptoms and smoking habits. The chest x ray films were read by three readers to the International Labour Office (ILO) 1980 classification. Full details of occupational history for each participant were available and for each employee an estimate of total exposure to china clay dust was derived from representative dust concentrations for each location and job. These were based on measured dust concentrations after 1978 and on estimates before 1978. Analyses of the data were carried out to investigate the relations between exposure, x ray film category, lung function, and respiratory symptoms. The percentage of people with small opacities greater than major x ray film category 1 was 0.8% (lower than in previous studies). Dust concentrations have been reduced in recent years, averaging 1.7 mg m-3 for dryers in 1990 compared with 3.5 mg m-3 in 1978. The lower effect of exposure after 1971, compared with earlier exposure, was confirmed by the analyses. After 1971 the milling of dried china clay (Atritor mills) was found to be the occupation with the highest effect on x ray film category. The relation between total exposure to china clay dust and x ray film category is such that a typical non-smoker worker employed in the most dusty of current occupations may expect to reach the lower limit of category 1 after about 42 years continuous employment in that job at current exposures. Both forced vital capacity (FVC) and forced expiratory volume in one second (FEV1) were found (as in other studies) to decline with age, more rapidly for smokers than non-smokers at the rates for FVC of 0.035 l/y and 0.033 l/y, whereas for FEV1 the rates are 0.039 l/y for smokers and 0.034 l/y for non-smokers. Changes in x ray film category are also related to lung function , a change of one major category being equivalent to about six years of aging in its effect on FEV1.

Adult↗

Synthesis of polymer latex particles decorated with organically-modified laponite clay platelets via emulsion polymerization.

We report a new route to colloidal nanocomposites consisting of polymer latex particles covered with Laponite clay nanoplatelets. These composite particles are prepared by seeded emulsion (co)polymerization of styrene and butyl acrylate from Laponite clay suspensions previously functionalized by ion exchange using either a free radical initiator: 2,2-azobis (2-methylpropionamidine) hydrochloride (AIBA) or a cationic vinyl monomer: 2-(methacryloyloxy) ethyl trimethyl ammonium chloride (MADQUAT). The successful intercalation of the cationic reactive molecules was confirmed by elemental analysis, FTIR, 13C solid-state NMR and WAXD. The organically-modified clays were dispersed into water with the help of tetrasodium pyrophosphate and an anionic surfactant. stable latexes, produced under different experimental conditions, were successfully obtained from the clay suspensions. Cryo-TEM images of the resulting latexes showed spherical composite particles with diameters in the 50-250 nm range with clay sheets located on their surface. This paper reports on the effect of the processing conditions on the particle morphology and latex stability, and describes the mechanism of formation of the nanocomposite particles.

Aluminum Silicates↗

Percolation of clay liners of ash landfills in short and long time perspectives.

Top covers of waste landfills conventionally contain a drain layer over a 1(low-permeable clay liner usually containing smectite minerals. The rate of percolation of the clay liner, which may require tens of years to become water-saturated, determines the downward transport of ions released from the underlying waste to and through the bottom clay liner. The percolation rate is controlled by the composition and density of the tipper liner, which should be as tight as possible. This implies a high density and therefore a high swelling potential which must be moderated by proper design. The bottom clay liner is a less effective and reliable barrier since cation exchange will increase the hydraulic conductivity and cause a significant rise in percolation rate and risk of chemical attack by the percolate. The top liner will undergo very moderate strain if the ash fill is effectively compacted and undergoes little self-compaction. Processes that may cause degradation are freezing and drying and require proper design. In this paper the authors examine the performance of ash-fills isolated by clay liners and conclude that the most important issue is to design and construct the top liner to be as impermeable as possible paying less attention to the tightness of the bottom layer.

Aluminum Silicates↗

Photostabilization of an entomopathogenic fungus using composite clay matrices.

To provide photostabilization for entomopathogenic fungi by anionic dyes, composite matrices based on clay-biopolymer combinations were prepared. In the first step, the negative surface charge of various clays (montmorillonite, attapulgite, bentonite and kaolinite) was reversed to positive by adsorption to the polycationic biopolymer chitosan. The second step involved adsorption of the toxicologically safe anionic dyes fast green (FG) and naphthol yellow S (NYS) to the clay complexes. Compared with cytotoxic photoprotectants like berberine, palmatine and acriflavine, the anionic dyes have no adverse effects up to a concentration of 1 M. In assays using various clay-chitosan-dye matrices and UV irradiation from a lamp source, it was evident that both FG and NYS provided considerable photostabilization for conidia of the entomopathogenic fungus Aschersonia spp. that served as a model biocontrol agent. Apparently, because of the light-dispersing property, bentonite and attapulgite per se provided significant photoprotection. All clay matrices containing FG provided a substantial photostabilization effect.

Aluminum Silicates↗

Preparation of a clay-modified carbon paste electrode based on 2-thiazoline-2-thiol-hexadecylammonium sorption for the sensitive determination of mercury.

A montmorillonite from Wyoming-USA was used to prepare an organo-clay complex, named 2-thiazoline-2-thiol-hexadecyltrimethylammonium-clay (TZT-HDTA-clay), for the purpose of the selective adsorption of the heavy metals ions and possible use as a chemically modified carbon paste electrode (CMCPE). Adsorption isotherms of Hg2+, Pb2+, Cd2+, Cu2+, and Zn2+ from aqueous solutions as a function of the pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The organo-clay complex was very selective to Hg(II) in aqueous solution in which other metals and ions were also present. The accumulation voltammetry of Hg(II) was studied at a carbon paste electrode chemically modified with this material. The mercury response was evaluated with respect to the pH, electrode composition, preconcentration time, mercury concentration, "cleaning" solution, possible interferences and other variables. A carbon paste electrode modified by TZT-HDTA-clay showed two peaks: one cathodic peak at about 0.0 V and an anodic peak at 0.25 V, scanning the potential from -0.2 to 0.8 V (0.05 M KNO3 vs. Ag/AgCl). The anodic peak at 0.25 V presents excellent selectivity for Hg(II) ions in the presence of foreign ions. The detection limit was estimated as 0.1 microg L(-1). The precision of determination was satisfactory for the respective concentration level.

Adsorption↗

Irrigation with effluents: effects of prewetting rate and clay content on runoff and soil loss.

Stability of soil surface aggregates and irrigation water quality significantly affect runoff and soil erosion. Slow wetting of aggregates prevents slaking. We hypothesized that wetting rate will affect a soil's susceptibility to seal formation and soil erosion, and that this susceptibility will differ between effluent- and fresh water (FW)-irrigated soils. Effects of prewetting rate (2, 4, 8, and 64 mm h(-1)) on runoff and interrill erosion from five Israeli soils exposed to 60 mm of simulated rain were studied in the laboratory. Soils were taken from fields irrigated with FW or effluents for >15 yr. In general, for effluent- and FW-irrigated samples, runoff and soil loss were greatest for the soil with 22.5% clay; at lower or higher clay contents, less runoff and soil losses were noted. Runoff and soil loss decreased with decreasing prewetting rate (PWR) mainly in soils with clay content > or =38%. Total runoff and soil loss were higher in effluent-irrigated soils than in FW-irrigated ones in the loamy sand (8% clay) only. Greater soil losses occurred from effluent-irrigated soils exposed to fast PWR (64 m h(-1)) compared with FW-irrigated soils. In general, PWR had similar effects on total runoff and soil loss for effluent- and FW-irrigated soils. Use of wetting rates < or =8 mm h(-1) to prevent aggregate slaking decreased runoff and soil loss from loam and clayey soils exposed to simulated rainfall of high kinetic energy (15.9 kJ m(-3)). Long term irrigation with effluents in soils containing >20% clay did not seem to adversely affect soil susceptibility to runoff and soil loss in soils exposed to simulated rainfall, beyond that observed in FW-irrigated soils.

Agriculture↗

Structural and sorption characteristics of adsorbed humic acid on clay minerals.

Clay-humic complexes are commonly distributed in natural environments. They play very important roles in regulating the transport and retention of hydrophobic organic contaminants in soils and sediments. This study examined the structural changes of humic acid (HA) after adsorption by clay minerals and determined phenanthrene sorption by clay-humic complexes. Solid- and liquid-state 13C nuclear magnetic resonance (NMR), for the first time, provided direct evidence for HA fractionation during adsorption on mineral surfaces, that is, aliphatic fractions were preferentially adsorbed by clay minerals while aromatic fractions were left in the solution. The ratio of UV absorbance of HA at 465 and 665 nm (E4 to E6 ratio), which is related to aromaticity, corroborated with the NMR results. For both montmorillonite and kaolinite, adsorbed HA fractions had higher sorption linearity (N) and affinity (K(oc)) than the source HA. The K(oc) of adsorbed HA for the clay-humic complexes could be up to several times higher than that of the source HA. This large increase may be contributed by the low polarity of the bound HA. Moreover, for each mineral, the N values of adsorbed HA increased with increasing HA loading. It is believed that HA may develop a more condensed structure on mineral surface at lower HA loading level due to the stronger interactions between HA and mineral surface as a result of close contacts.

Adsorption↗

Clay-enhanced DNA separation in low-molecular-weight poly(N,N-dimethylacrylamide) solution by capillary electrophoresis.

The effect of the separation medium in capillary electrophoresis consisting of a low-molecular-mass poly(N,N-dimethylacrylamide) (PDMA) solution on the DNA separation by adding a small amount of montmorillonite clay into the polymer matrix is presented. On the separation of the pBR322/HaeIII digest, both the resolution and the efficiency were increased by adding 2.5-5.0 x 10(-5) g/mL clay into the 5% w/v PDMA with a molecular mass of only 100 K. Moreover, there was no increase in the migration time of DNA fragments. Similar results were observed by using a C-terminated pGEM-3Zf(+) sequencing DNA sample in a sequencing buffer. Experimental data also showed that the addition of clay increased the viscosity of the polymer solution. We attribute this effect to the structural change of the polymer matrix caused by the exfoliated clay sheets, whereby the thin clay sheets function like a "dynamic cross-linking plate" for the PDMA chains and effectively increase the apparent molecular mass of PDMA.

Acrylamides↗

Interactions of cimetidine and ranitidine with aluminum-containing antacids and a clay-containing gastric-protective drug in an "artificial stomach-duodenum" model.

Interactions of cimetidine and ranitidine with aluminum-containing antacids and clay-containing gastric-protective drugs were analyzed in vitro by using an artificial stomach-duodenum model. The model reproduced near-physiologic conditions, taking into account gastric and duodenal flux variations and interactions between gastric mucosa and drugs added to the gastric content. Clay bound cimetidine in acid medium, but the drug was released when the pH increased, resulting in cimetidine amounts in the duodenal site close to those in controls. In contrast, clay bound ranitidine in acid medium and did not release it in the duodenal site. Aluminum-containing antacids did not significantly modify the amount of cimetidine or ranitidine available for absorption. Several factors play a role in the interactions of cimetidine and ranitidine with aluminum-containing antacids and clay-containing gastric-protective drugs: the structure of the antisecretory drugs, gastroduodenal pH, interactions of the antacid and clay with the gastric mucosa, and release of aluminum that could adsorb the drugs or prevent their adsorption by the mucosa. These phenomena are intricate and difficult to analyze without using a physicochemical approach.

Aluminum↗