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Laboratory investigations of Mars: chemical and spectroscopic characteristics of a suite of clays as Mars soil analogs.

Two major questions have been raised by prior explorations of Mars. Has there ever been abundant water on Mars? Why is the iron found in the Martian soil not readily seen in the reflectance spectra of the surface? The work reported here describes a model soil system of Mars Soil Analog Materials, MarSAM, with attributes which could help resolve both of these dilemmas. The first set of MarSAM consisted of a suite of variably iron/calcium-exchanged montmorillonite clays. Several properties, including chemical composition, surface-ion composition, water adsorption isotherms, and reflectance spectra, of these clays have been examined. Also, simulations of the Viking Labeled Release Experiment using the MarSAM were performed. The results of these studies show that surface iron and adsorbed water are important determinants of clay behavior as evidenced by changes in reflectance, water absorption, and clay surface reactions. Thus, these materials provide a model soil system which reasonably satisfies the constraints imposed by the Viking analyses and remote spectral observations of the Martian surface, and which offers a sink for significant amounts of water. Finally, our initial results may provide insights into the mechanisms of reactions that occur on clay surfaces as well as a more specific approach to determining the mineralogy of Martian soils.

Aluminum Silicates↗

ToF-SIMS depth profiling analysis of the uptake of Ba2+ and Co2+ ions by natural kaolinite clay.

The sorption behavior of Ba(2+) and Co(2+) ions on a natural clay sample rich in kaolinite was studied using time-of-flight secondary ion mass spectrometry (ToF-SIMS). Depth profiling at 10-A steps was performed up to a 70-A matrix depth of the clay prior to and following sorption. The results showed that Co(2+) is sorbed in slightly larger quantities than Ba(2+), with significant numbers of ions fixed on the outermost surface of the clay. Depletion of the ions K(+), Mg(2+), and Ca(2+) from the clay lattice was observed to accompany enrichment with Co(2+) and Ba(2+) ions. The data obtained using X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) indicated insignificant structural and morphological changes in the lattice of the clay upon sorption of both Ba(2+) and Co(2+) ions. Analysis using energy dispersive X-ray spectroscopy (EDS) showed that the average atomic percentage (+/-S.D.) of Ba and Co on kaolinite surface were 0.49 +/- 0.11 and 0.61 +/- 0.19 , respectively, indicating a limited uptake capacity of natural kaolinite for both ions.

Aluminum Silicates↗

Paraquat adsorption onto clays and organoclays from aqueous solution.

Clays were compared with organoclays for the sorption of paraquat from aqueous solution. Sepiolite (S), bentonite (B), and illite (I) were used as clay samples. Organoclays were prepared by the modification of the clays with nonyl- and dodecylammonium chlorides, denoted as NS, DS, NB, DB, NI, and DI, respectively. Specific surface area and pore size distribution of the samples were determined by N2 adsorption-desorption at 77 K using the BET method. X-ray powder diffraction analysis of the samples was used to determine the effects of modifying agents on the layer structure of the clays. In the adsorption experiments, C(m) values increased from 0.038 mmol/g for DS to 0.223 mmol/g for NI. Kd0.3 values ranged from 0.177 for DS to 0.843 for NI. The adsorption data indicated that illite and NI are the most effective adsorbents among these clays and organoclay samples, respectively.

Adsorption↗

Sorption study of an acid dye from an aqueous solutions using modified clays.

The removal of the pollutant Supranol Yellow 4GL (S.Y.4GL) was studied by using different clays: clay exchanged with sodium (BNa+) and hydroxyaluminic polycation pillared clays in the presence or absence of non-ionic surfactant. While decomposing the surfactant at 500 degrees C, the surface of the clay changed significantly. The study of the behaviour of the three clays with respect to coloring solutions, allowed to determine the equilibrium time and the rate-determining step of the dye S.Y.4GL adsorption. Two simplified kinetic models, were tested to investigate the adsorption mechanisms in terms of pseudo-first order and pseudo-second order equations. Besides, the adsorption capacity data were fitted to Langmuir and Freundlich equations as well. A better fixation was obtained with an acidic pH. The effect of temperature on the adsorption of dye has been also studied and the thermodynamic parameters DeltaG degrees , DeltaH degrees and DeltaS degrees were determined.

Adsorption↗

Removal of methylene blue from aqueous solution by fibrous clay minerals.

Kinetics and equilibrium processes of the methylene blue (MB) retention from aqueous solution by a mixture of fibrous clay minerals, which was isolated from a naturally occurring clay, were investigated. For these purposes, the effects of contact time, initial adsorbate concentration, adsorbent content, pH and ionic strength were determined. The results show that the MB retention obeys a pseudo-first order equation and the process is a diffusion controlled solid-state reaction. Moreover, the isotherm data fitted the Langmuir equation and the MB binding process became more energetic with the increase of the adsorbent concentration. In addition, the augmentation of the clay content or the initial MB concentration reduced the adsorption capacity, presumably because of the clay particles microaggregation and/or the occurrence of MB deriving species. On the other hand, it is observed that the MB uptake limit is reduced in low acid pH, particularly below the PZC, as well as in ionic strengthen solutions. These facts are linked to the silanol group protonation and to the reduction of the electrostatic forces induced by the clay particles, respectively.

Adsorption↗

Modeling the long-term leaching behavior of (137)Cs, (60)Co, and (152,154)Eu radionuclides from cement-clay matrices.

Leaching characteristics of some radionuclides that are commonly encountered in radioactive waste streams from immobilized waste matrices in different cement-clay grouts have been assessed to investigate the influence of the clay additives on the leaching behavior of the solid waste matrices. The International Atomic Energy's Agency (IAEA) standard leach method has been employed to study the leach pattern of (137)Cs, (60)Co, and (152,154)Eu radionuclides immobilized in ordinary Portland cement (OPC), OPC-bentonite, and OPC-red clay grouts. The examination of the leaching data revealed that adding clays to OPC reduces the leach pattern as OPC-bentonite<OPC-red clay<OPC for all studied radionuclides. The controlling leaching mechanism has been found to be diffusion and the mean apparent diffusion coefficients and leachability indices have been calculated for the studied waste matrices. Simplified analytical models have been derived to predict the cumulative leach fraction (CLF) of radionuclides over the studied experimental period. These simplified research models could be used as a screening tool to assess the performance of the waste matrix under repository conditions.

Aluminum Silicates↗

Effect of coal mine dust and clay extracts on the biological activity of the quartz surface.

Modification of the quartz surface by aluminium salts and metallic iron have been shown to reduce the biological activity of quartz. This study aimed to investigate the ability of water soluble extracts of coal mine dust (CMD), low aluminium clays (hectorite and montmorillonite) and high aluminium clays (attapulgite and kaolin) to inhibit the reactivity of the quartz surface. DQ12 induced significant haemolysis of sheep erythrocytes in vitro and inflammation in vivo as indicated by increases in the total cell numbers, neutrophil cell numbers, MIP-2 protein and albumin content of bronchoalveolar lavage (BAL) fluid. Treatment of DQ12 with CMD extract prevented both haemolysis and inflammation. Extracts of the high aluminium clays (kaolin and attapulgite) prevented inhibition of DQ12 induced haemolysis, and the kaolin extract inhibited quartz driven inflammation. DQ12 induced haemolysis by coal mine dust and kaolin extract could be prevented by pre-treatment of the extracts with a cation chellator. Extracts of the low aluminium clays (montmorillonite and hectorite) did not prevent DQ12 induced haemolysis, although the hectorite extract did prevent inflammation. These results suggest that CMD, and clays both low and rich in aluminium, all contain soluble components (possibly cations) capable of masking the reactivity of the quartz surface.

Administration, Inhalation↗

Effect of clay and organic matter type on the ecotoxicity of zinc and cadmium to the potworm Enchytraeus albidus.

Clay and organic matter are considered as important parameters influencing bioavailability and ecotoxicity of metals in soils. As there exists a large variation in the type of clay and organic matter in field soils, the quantity of these variables alone may not be good indicators of metal bioavailability. To test this hypothesis, toxicity experiments with the potworm Enchytraeus albidus were conducted in artificial soils with three types of clay and seven types of organic matter, while the soil pH was kept constant. The 14d LC50 of zinc and cadmium varied from 83.0 to 1,140 mg Zn/kg D.W. and from 55.2 to 704 mg Cd/kg D.W., respectively, depending on the type of clay and organic matter that were used. Simultaneous measurements of the cation exchange capacity showed that this soil parameter is a better indicator of the bioavailability as it takes into account the type of clay and organic matter as well as other adsorption phases such as metal oxyhydroxides.

Adsorption↗

Effects of humidity and soil organic matter on the sorption of chlorinated methanes in synthetic humic-clay complexes.

Vapor-phase sorption is the most influential process governing the transport and the fate of volatile organic compounds in soil. To understand the influence of both soil organic content and the humidity of soil on the vapor sorption is an important process for degradation processes. The single-pellet moment technique was used to investigate sorption and diffusion of trichloromethane (TCM) and carbon tetrachloride (CTC) at varying relative humidities (0-80%) of synthetic humic-clay complex pellets consisting of clay (montmorillonite) and different amounts of organic matter (humic acid). The effective diffusivities of TCM and CTC did not show a noticeable change with moisture and humic acid content. On the other hand, with increasing humic acid content of clay at 0% relative humidity, an appreciable decrease of the equilibrium sorption constants of the tracers (TCM, CTC) was found because of the blockage of some sites of the mineral surfaces and especially micropores by the humic acid. The presence of water also reduced dramatically the sorption of TCM and CTC on synthetic humic-clay complexes. Above 20% relative humidity, the sorption coefficient of TCM and CTC varied only slightly with humic acid content. It was concluded that the sorption of TCM and CTC in synthetic humic-clay complexes was strongly effected by the moisture and humic acid content.

Adsorption↗

Interaction of nonionic polymers at a clay interface.

The structure and dynamics at the interface of swelling clays (smectites) are crucial to such diverse applications as drilling for oil, cosmetics, paints, water treatment, or chemical reactions. From our previous NMR studies on clay suspensions, we have shown how the orientation of interfacial molecules is affected by the clay structure1, by the nature of counterions 2, or by the composition of the liquid phase3. These results have been mainly obtained from the analysis of residual quadrupolar splittings of nuclei from interfacial species. In this work, we report our studies on a clay montmorillonite suspended in aqueous solutions of non ionic polymers. The polymer perturbs the structure within the interfacial region as deduced from the variations of the splittings of water quadrupolar nuclei and of sodium-23 relaxation parameters in terms of the polymer concentration. Proton self-diffusion coefficients and carbon-13 relaxation times are measured to describe the influence of the clay on the polymer mobility. The dependence of the polymer nature on these parameters is also investigated.

Aluminum Silicates↗

Influence of natural organic matter on the adsorption of metal ions onto clay minerals.

The influence of natural organic matter (NOM) on the adsorption of Al, Fe, Zn, and Pb onto clay minerals was investigated. Adsorption experiments were carried out at pH = 5 and pH = 7 in the presence and absence of NOM. In general, the presence of NOM decreased the adsorption of metal ions onto the clay particles. Al and Fe were strongly influenced by NOM, whereas Zn and Pb adsorption was only slightly altered. The interaction of the metal ions with the minerals and the influence of NOM on this interaction was investigated by coupling SdFFF with an inductively coupled plasma mass spectrometer (ICPMS) or an inductively coupled plasma atomic emission spectrometer (ICPAES). Quantitative atomization of the clay particles in the ICP was confirmed by comparing elemental content determined by direct injection of the clay into the ICPMS with values from acid digestion. Particle sizes of the clays were found to be between 0.1 and 1 microm by sedimentation field-flow fractionation (SdFFF) with UV detection. Aggregation of particles due to metal adsorption was observed using SdFFF-ICPMS measurements. This aggregation was dependent on the specific metal ion and decreased in the presence of NOM and at higher pH value.

Adsorption↗

Heterogeneous decomposition of CHF2OCH2CF3 and CHF2OCH2C2F5 over various standard aluminosilica clay minerals in air at 313 K.

The heterogeneous decomposition of CHF2OCH2C2F5, a potential substitute for hydrofluorocarbons, over aluminosilica clay minerals in air, was confirmed to occur at 313 K in a closed-circulation reactor. HC(O)OCH2C2F5, the gaseous main product was produced through hydrolytic elimination of F atoms from the CHF2OCH2- group. CHF2OCH2CF3 also decomposed to HC(O)OCH2CF3 over the clay minerals. The pseudo-first-order rate constants were determined for the decompositions over eight types of clay minerals (19 samples). The various clay minerals had different abilities to decompose these hydrofluoroethers. The decomposition rates per Brunauer-Emmett-Teller surface area and the conversion ratios to HC(O)OCH2C2F5 or HC(O)OCH2CF3 for the reactions over kaolinite, halloysite, and illite were high in comparison to those for the same reactions over montmorillonite, hectorite, and nontronite. The dependence of this heterogeneous reaction on temperature and relative humidity indicates that, in the environment, the reaction could be important only in hot, dry regions. The results did not suggest that sunlight would directly accelerate the decay of CHF2OCH2CF3 or CHF2OCH2C2F5. In the presence of clay-containing soils in arid areas, this hydrolytic oxidation reaction may significantly affect both the lifetime and the degradation products of CHF2OCH2CF3 and CHF2OCH2C2F5 in the troposphere.

Aluminum Silicates↗

Use of ferrocenyl surfactants of varying chain lengths to study electron transfer reactions in native montmorillonite clay.

A series of ferrocenyl surfactants was tested as model compounds to study electron transfer reactions involving structural Fe(III) in clay minerals. The surfactants contain trimethylammonium headgroups, ferrocene tail groups, and intervening hydrocarbon chain lengths of one, six, or 11 carbons. Two factors considered to be decisive for electron transfer were addressed: (1) physical access of the surfactant ferrocene to the reactive sites through hexagonal holes in the clay lattice by X-ray diffraction (XRD) and small-angle X-ray scattering (SAXS) and (2) thermodynamic favorability of the overall oxidation/reduction reaction based on experimentally determined oxidation/reduction potentials. In suspensions of clay with the longer chain surfactants, (ferrocenylhexyl)trimethylammonim (FHTMA+) and (ferrocenylundecyl)trimethylammonium (FUTMA+), where electron transfer may be expected to be favored by both factors, physical accessibility, and thermodynamic favorability, ferroecene oxidation was observed by diffuse reflectance infrared spectroscopy (DRIFT), ultraviolet-visible spectroscopy (UV-vis), and visual color changes. In contrast, the shorter chain length surfactant, (ferrocenylmethyl)trimethylammonium (FMTMA+), did not participate in electron transfer with the clay, as substantiated by UV-vis and no visible color changes. Rigid conformation and/or higher oxidation/reduction potential than clay Fe can accountforthe lack of reaction. The utility and limitations of using these surfactants as model compounds is discussed.

Aluminum Silicates↗

Investigating the molecular interactions of oxytetracycline in clay and organic matter: insights on factors affecting its mobility in soil.

The interactions of oxytetracycline with model clay adsorbents were investigated as a function of suspension pH. The clay adsorbents used were native montmorillonite (SWy-2), Na-montmorillonite (Na-SWy-2), and hexadecyl trimethylammonium-montmorillonite (HDTMA-montmorillonite). The adsorption of oxytetracycline to the clay could be described by Freundlich-type adsorption isotherms. It was observed that the adsorption of oxytetracycline in the native and sodium forms of montmorillonite decreases with increasing pH in the order pH 1.5 > 5.0 > 8.7 > 11.0. This trend is consistent with cationic exchange interactions that are dominant at lower pH values when oxytetracycline has a net positive charge. On the other hand, hydrophobic interactions when oxytetracycline is zwitterionic (at pH 5.0) are predominant over other mechanisms, as evident from the FT-IR spectrum of the HDTMA-montmorillonite and humic acid-montmorillonite adsorbed with oxytetracycline. The presence of a large amount of dissolved organic matter (DOM) was also found to decrease the sorption of oxytetracycline to clay, suggesting that DOM may increase its mobility in the natural environment. Several mechanisms of interaction of oxytetracycline in clay are proposed based on the adsorption isotherms and the results from X-ray diffraction (XRD) and Fourier transform-infrared (FT-IR) analyses.

Adsorption↗

Origin of PCDDs in ball clay assessed with compound-specific chlorine isotope analysis and radiocarbon dating.

Polychlorinated dibenzo-p-dioxins (PCDDs) of high concentrations in a ball clay deposit from the Mississippi Embayment were found to be consistent with a natural abiotic and non-pyrogenic origin by investigation with bulk radiocarbon analysis, compound-specific chlorine isotope analysis (CSIA-delta37Cl) of octachlorodibenzo-p-dioxin (OCDD), and black carbon (BC) analysis. The conventional radiocarbon date of total organic carbon from a depth of approximately 10 m in three parallel cores ranged from 14 700 years to >48 000 years, indicating that the strata with elevated levels of PCDDs have remained isolated from recent anthropogenic input in these >40 Ma old clay sediments. The CSIA-delta37Cl of OCDD yielded a delta37Cl of -0.2 per thousandth, which is significantly higher than the postulated range for biotic chlorination by chloroperoxidase enzymes, -11 to -10 per thousandth, and falls within the known range for abiotic organochlorines, -6 to +3 per thousandth. The absence of correlations between concentrations of PCDDs and corresponding pyrogenic black carbon (BC), together with estimations of BC sorptive loadings and the absence of polychlorinated dibenzofurans (PCDFs), suggest that vegetation fires did not form these ball-clay PCDDs. Results from this study indicate that the high levels of the toxic and carcinogenic PCDDs found in kaolinite-bearing clays may result from natural abiotic formation via in situ surface-promoted reactions on the clay mineral, including a so-far unknown organic precursor, rather than being the result of anthropogenic contamination.

Aluminum Silicates↗

Organo-clay formulation of acetochlor for reduced movement in soil.

This study aimed to design ecologically acceptable formulations of acetochlor by adsorbing it on montmorillonite exchanged by a small organic cation, phenyltrimethylammonium (PTMA). Adsorption of acetochlor on the clay mineral exchanged with different organic cations and its release from these complexes were determined by GC and modeled by Langmuir equation. Interactions between acetochlor molecules and the exchanged organic cation on the clay surface were studied by Fourier transform infrared spectroscopy. Leaching of acetochlor in soil was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of acetochlor on montmorillonite exchanged by PTMA at a loading of 0.5 mmol/g of clay were higher than at a loading up to the cation-exchange capacity, i.e., 0.8 mmol/g, and were higher than obtained by using a clay mineral exchanged by other organic cations. Preloading montmorillonite by PTMA at 0.5 mmol/g yielded maximal shifts of the infrared peaks of the herbicide. The above formulation of acetochlor yielded slow release in water and showed improved weed control in field and greenhouse experiments in comparison with the commercial formulation. The PTMA-clay formulation of acetochlor maintained herbicidal activity in the topsoil and yielded the most significant reduction in herbicide leaching and persistence under field conditions. The application of this formulation can minimize the risk to groundwater and can reduce the applied rates.

Adsorption↗

Bioavailability of an organophosphorus pesticide, fenamiphos, sorbed on an organo clay.

Hydrolysis of an insecticide/nematicide, fenamiphos [ethyl-3-methyl-4-(methylthio)phenyl-(1-methylethyl)phosphoramidate], immobilized through sorption by cetyltrimethylammonium-exchanged montmorillonite (CTMA-clay) by a soil bacterium, Brevibacterium sp., was examined. X-ray diffraction analysis, infrared spectra, and a negative electrophoretic mobility strongly indicated that fenamiphos was intercalated within the bacterially inaccessible interlayer spaces of CTMA-clay. The bacterium hydrolyzed, within 24 h, 82% of the fenamiphos sorbed by the CTMA-clay complex. There was a concomitant accumulation of hydrolysis product, fenamiphos phenol, in nearly stoichiometric amounts. During the same period, in abiotic (uninoculated) controls, 4.6% of the sorbed insecticide was released into the aqueous phase as compared to 6.0% of the sorbed fenamiphos in another abiotic control where activated carbon, a sink for desorbed fenamiphos, was present. Thus, within 24 h, the bacterium hydrolyzed 77% more fenamiphos sorbed by organo clay than the amounts desorbed in abiotic controls. Such rapid degradation of an intercalated pesticide by a bacterium has not been reported before. Evidence indicated that extracellular enzymes produced by the bacterium rapidly hydrolyzed the nondesorbable fenamiphos, even when the enzyme itself was sorbed. Fenamiphos strongly sorbed to an organo clay appears to be readily available for exceptionally rapid degradation by the bacterium.

Adsorption↗

Sorption and catalytic hydrolysis of diethatyl-ethyl on homoionic clays.

Sorption and catalytic hydrolysis of the herbicide diethatyl-ethyl [N-chloroacetyl-N-(2,6-diethylphenyl)glycine ethyl ester] on homoionic Na(+)-, K(+)-, Ca(2+)-, and Mg(2+)-montmorillonite clays were studied in aqueous media. The Freundlich sorption coefficient, K(f), measured from isotherms on clay followed the order of Na(+) approximately K(+) > Mg(2+) approximately Ca (2+). Analysis of FT-IR spectra of diethatyl-ethyl sorbed on clay suggests probable bonding at the carboxyl and amide carbonyl groups of the herbicide. The rate of herbicide hydrolysis in homoionic clay suspensions followed the same order as that for sorption, indicating that sorption may have preceded and thus caused hydrolysis. Preliminary product identification showed that hydrolysis occurred via nucleophilic substitution at the carboxyl carbon, causing cleavage of the ester bond and formation of diethatyl and its dechlorinated derivative, and at the amide carbon, yielding an ethyl ester derivative and its acid. These pathways also suggest that hydrolysis of diethatyl-ethyl was catalyzed by sorption on the clay surface.

Adsorption↗