Clay Surface Chemistry Research Articles

Advanced solid-liquid separation for dewatering fine coal tailings by combining chemical reagents and solid bowl centrifugation

Solid-liquid separation to dewater mine tailings is critical to transforming tailings dams that are hazardous to the environment and surrounding communities into safer and sustainable disposal storages by dry stacking and co-disposals. Current tailings dewatering by thickening and filtration has experienced big challenges due to the presence of fine clay minerals with complex surface properties and gelation caused by their swelling characteristics. They retain water in their structure, settle very slowly in thickeners, and pass through filter media during filtration. Here, we have systematically investigated the effect of clay mineral surface chemistry on settling, flocculation, and dewatering using pure clay samples and coal tailings samples. Our results indicate the critical role of clay surface charge in the successful dewatering of the clay samples. A two-step procedure including neutralizing the clay surface charge by salts and then flocculating by salt-resistant flocculants can be significantly effective in the dewatering. The newly-developed dewatering technique by combining chemical reagents and mechanical force of solid bowl centrifugation can deliver successful dewatering outcomes by achieving the required final moisture of dewatered tailings and providing improved water quality for recycling. This paper highlights the importance of clay surface chemistry in controlling clay interactions with chemical reagents, and solid-liquid separation to dewater the clay-rich tailings inherently present in the mining industry.

Dynamics of carbohydrate strands in water and interactions with clay minerals: influence of pH, surface chemistry, and electrolytes.

Carbohydrate hydrogels are extensively used in pharmaceuticals and engineered biomaterials. Molecular conformations, assembly, and interactions of the carbohydrate strands with stabilizers such as clay minerals in aqueous solution are difficult to quantify in experiments and the hydrogel properties remain largely a result of trial-and-error studies. We analyzed the assembly of gellan gum in aqueous solution and interactions with dispersed clay minerals in all-atomic detail using molecular dynamics simulation, atomic force microscopy (AFM), and comparisons to earlier measurements. Gellan strands associate at low pH values of 2 and gradually disassemble to double strands with weak association of -0.4 kcal per mole carbohydrate ring as the pH values increases to 9. Ionization of the carbonic acid side groups in the backbone extends the chains and accelerates the conformational dynamics via rapidly changing intramolecular ion bridges. Gellan interactions with clay minerals depend on the strength of electric triple layers between clay, cations, and anionic polymer strands, as well as weaker hydrogen bonds along the edges, which are tunable as a function of the clay surface chemistry, local ionic strength, and pH values. Interaction energies range from -4 to +6 kcal per mol carbohydrate ring and were most favorable for electric triple layers with high charge mobility, which can be achieved for intermediate cation exchange capacity of the clay mineral and high pH values to increase ionization of the clay edges and of the polymer. The findings provide understanding and help control the dynamics and stabilization of carbohydrate hydrogels by clay minerals.

Comparisons of structural iron reduction in smectites by bacteria and dithionite: II. A variable-temperature Mössbauer spectroscopic study of Garfield nontronite

The reduction of structural Fe in smectite may be mediated either abiotically by reaction with chemical reducing agents or biotically by reaction with various bacterial species. The effects of abiotic reduction on clay surface chemistry are much better known than the effects of biotic reduction, and differences between them are still in need of investigation. The purpose of the present study was to compare the effects of dithionite (abiotic) and bacteria (biotic) reduction of structural Fe in nontronite on the clay structure as observed by variable-temperature Mössbauer spectroscopy. Biotic reduction was accomplished by incubating Na-saturated Garfield nontronite (sample API 33a) with Shewanella oneidensis strain MR-1 (FeII/total Fe achieved was ~17 %). Partial abiotic reduction (FeII/total Fe ~23 %) was achieved using pH-buffered sodium dithionite. The nontronite was also reduced abiotically to FeII/total Fe ~96 %. Parallel samples were reoxidized by bubbling O2 gas through the reduced suspensions at room temperature prior to Mössbauer analysis at 77 and 4 K. At 77 K, the reduction treatments all gave spectra composed of doublets for structural FeII and FeIII in the nontronite. The spectra for reoxidized samples were largely restored to that of the unaltered sample, except for the sample reduced to 96 %. At 4 K, the spectrum for the 96 % reduced sample was highly complex and clearly reflected magnetic order in the sample. When partially reduced, the spectrum also exhibited magnetic order, but the features were completely different depending on whether reduced biotically or abiotically. The biotically reduced sample appeared to contain distinctly separate domains of FeII and FeIII within the structure, whereas partial abiotic reduction produced a spectrum representative of FeII–FeIII pairs as the dominant domain type. The 4 K spectra of the partially reduced, fully reoxidized samples were virtually the same as at 77 K, whereas reoxidation of the 96 % reduced sample produced a spectrum consisting of a magnetically ordered sextet with a minor contribution from a FeII doublet, indicating significant structural alterations compared to the unaltered sample.

Effect of the Organoclay Preparation on the Extent of the Intercalation/Exfoliation and the Barrier Properties in Polyamide-6/Montmorillonite Nanocomposites

This paper shows the importance of the clay surface chemistry in the preparation of nanocomposite materials. An Argentinean montmorillonite was used for preparing two modified clays. The filosilicate was intercalated with a quaternary ammonium salt derived from ε- caprolactam to obtain an organofilic material. The other modification was introduced by mixing the clay with hexadecyl trimethyl ammonium chloride. Thus, the polyamide 6 ability in dispersing clays was applied to prepare composites with the intercalated clays. The polyamide 6/clay dry composites with 3 wt % of filler were prepared by melt processing in a mixer chamber. Composites of polyamide 6/organoclay were characterized by X-ray diffraction, transmission and scanning electron microscopy and thermogravimetry. The barrier properties were determined by cyclohexane pervaporation. The results show that the dispersion and degree of delamination depend on a proper chemical treatment and the clay content influences the polyamide 6 nanocomposites solvent pervaporation resistance.

Comparisons of Structural Fe Reduction in Smectites by Bacteria and Dithionite: An Infrared Spectroscopic Study

AbstractThe reduction of structural Fe in smectite is mediated either abiotically, by reaction with dithionite, or biotically, by Fe-reducing bacteria. The effects of abiotic reduction on clay-surface chemistry are much better known than the effects of biotic reduction. Since bacteria are probably the principal agent for mediating redox processes in natural soils and sediments, further study is needed to ascertain the differences between biotic and abiotic reduction processes. The purpose of the present study was to compare the effects of dithionite (abiotic) and bacteria (biotic) reduction of structural Fe in smectites on the clay structure as observed by infrared spectroscopy. Three reference smectites, namely, Garfield nontronite, ferruginous smectite (SWa-1), and Upton, Wyoming, montmorillonite, were reduced to similar levels by either Shewanella oneidensis or by pH-buffered sodium dithionite. Each sample was then analyzed by Fourier transform infrared spectroscopy (FTIR). Parallel samples were reoxidized by bubbling O2 gas through the reduced suspension at room temperature prior to FTIR analysis. Redox states were quantified by chemical analysis, using 1, 10-phenanthroline. The reduction level achieved by dithionite was controlled to approximate that of the bacterial reduction treatment so that valid comparisons could be made between the two treatments. Bacterial reduction was achieved by incubating the Na-saturated smectites with S. oneidensis strain MR-1 in a minimal medium including 20 mM lactate. After redox treatment, the clay was washed four times with deoxygenated 5 mM NaCl. The sample was then prepared either as a self-supporting film for OH-stretching and deformation bands or as a deposit on ZnSe windows for Si-O stretching bands and placed inside a controlled atmosphere cell also fitted with ZnSe windows. The spectra from bacteria-treated samples were compared with dithionite-treated samples having a similar Fe(II) content. The changes observed in all three spectral regions (OH stretching, M2-O-H deformation, and Si-O stretching) for bacteria-reduced smectite were similar to results obtained at a comparable level of reduction by dithionite. In general, the shift of the structural OH vibration and the Si-O vibration, and the loss of intensity of OH groups, indicate that the bonding and/or symmetry properties in the octahedral and tetrahedral sheets changes as Fe(III) reduces to Fe(II). Upon reoxidation, peak positions and intensities of the reduced smectites were largely restored to the unaltered condition with some minor exceptions. These observations are interpreted to mean that bacterial reduction of Fe modifies the crystal structures of Fe-bearing smectites, but the overall effects are modest and of about the same extent as dithionite at similar levels of reduction. No extensive changes in clay structure were observed under conditions present in our model system.

Hydraulic and mechanical behavior of GCLs in contact with leachate as part of a composite liner

When a geosynthetic clay liner (GCL) containing sodium bentonite is brought into contact with fluids and soils containing other cations, the latter may exchange with the sodium present between clay layers. This modification of clay surface chemistry may change the clay microstructure and its mechanical behavior. The influence of cation exchange on the potential for squeezing of bentonite was studied by submitting 10-cm-diameter GCL samples to squeezing tests. Those samples were part of 1-m-diameter GCL specimens that had intentionally been put in contact with leachate during a one year period through the discontinuity in a damaged geomembrane as part of a composite bottom liner, and an underlying soil containing calcium, thus generating cation concentration gradients through the GCL specimens. The impact of the hydration mode of the GCL on flow rate through the composite liner and cation exchange was studied. Results obtained tend to show that if pre-hydration of GCL on the whole surface under no load as compared to pre-hydration through the discontinuity in the geomembrane slightly prevented from cation exchange, it resulted in a larger flow rate in the composite liner. Consequently, based on the experiments presented in this paper, pre-hydration of GCLs prior to confining is discouraged. Furthermore, an increase in the calcium concentration combined with a decrease in potassium and ammonium concentrations at the surface of clay particles lead to a softening of bentonite resulting in a greater susceptibility to bentonite squeezing in the GCL samples.

Alterations in Geochemical Associations in Artificially Disturbed Deep-Sea Sediments

In view of the role of Sediment geochemistry in regulating the benthic ecosystem, diagenetic remobilization of dissolved constituents, bottom water redox, and regeneration of benthic fluxes, surficial sediments in and around the track disturbed by a “benthic disturber” were studied for metal variation in three phases: (1) before the disturbance, (2) immediately after the disturbance, and (3) during monitoring of restoration after ~44 months, from the same locations. Minor variations in metal concentrations before the disturbance ere noticed indicating the homogeneity in the area or supply from similar source areas. Terrigenous fraction determined normatively from titanium contents in these sediments ranges between 40 and 47%. Most of the elements analyzed showed reduced average concentrations immediately after the disturbance suggesting physical removal and resedimentation in other areas with the migration of the plume. All the elements showed positive relation and coherence in the sediments collected after the disturbance, irrespective of their susceptibility to changes in provenance and depositional environment, whereas elemental associations during the predisturbance and monitoring periods can be explained by the known geochemical processes. The changes in Al, Ti, excess aluminium contents, their interelement relations, and factor analyses, suggest the possible transformation of clay mineral type due to the benthic disturbance that would involve changes in surface chemistry of clays. Interelement relations among redox-sensitive elements have also changed with time. This includes decoupling of Co from Mn after 44 months, probably due to the varying oxidation kinetics of two major oxides, Fe and Mn. Model calculations suggest increased diagenetic remobilization rates of Mn during the monitoring phase. Substantial increase in redox-sensitive elements, especially Fe and Mn indicate oxygenation of bottom water due either to reduced activity of benthic burrowing organisms or to renewal of oxygen-rich Antarctic Bottom water (AABW). Increase in these elements is consistent with the results of the HEBBLE experiment, where the burrows seem to protect these elements from strong bottom currents. Restoration of predisturbance values in the terrigenous component is attributed to the influence of shifts in the direction of bottom flow and suggests that bottom currents would play a major role in restoring the lithogenic component by transporting it from other locations within the Basin during commercial mining operations.

Geosynthetic Clay Liner Interaction with Leachate: Correlation between Permeability, Microstructure, and Surface Chemistry

When a geosynthetic clay liner (GCL) containing sodium bentonite is brought into contact with fluids containing other cations, the latter may exchange with the sodium present between clay layers. This modification of clay surface chemistry may change the clay microstructure and hence its hydraulic conductivity. The influence of clay surface chemistry on microstructure and permeability, after prolonged contact between two GCLs (a natural sodium bentonite GCL and a sodium-activated calcium bentonite GCL) and different fluids in oedometer cells, was investigated using exchangeable-cation analysis, small-angle x-ray scattering, and transmission electron microscopy. Results suggest that calcium carbonate in the bentonite, formed during activation of the calcium bentonite, may redissolve during contact with a dilute permeant, releasing calcium ions that exchange with sodium in the clay. This exchange leads to obliteration of a so-called phase (beneficial in terms of low permeability) and to the development of a more permeable hydrated-solid phase. Sodium replacement by calcium during GCL contact with a 0.1 M CaCl2 solution was found to be virtually complete, with or without GCL prehydration with dilute water. No gel phase was observed in these samples. When in contact with real leachate, however, a gel phase appeared, especially when GCL samples were prehydrated. A correlation was observed between the level of hydraulic conductivity and the relative proportions of gel phase and clay interlayer occupation by sodium.

Effects of iron oxidation states on the surface and structural properties of smectites

Abstract The oxidation state of iron (Fe) in the crystal structure of smectite clay minerals profoundly alters their physical-chemical properties. Among the properties affected are layer charge, cation exchange and fixation capacity, swelling in water, particle size, specific surface area, layer stacking order, magnetic exchange interactions, octahedral site occupancy, surface acidity, and reduction potential. Also affected is the surface chemistry of the clay, which alters clay–water and clay–organic interaction mechanisms. Rates and extents of degradation of pesticides are increased in the presence of reduced smectites compared to oxidized and reduced-reoxidized counterparts. A hypothesis regarding the mechanism for Fe reduction in clay minerals was first developed in 1963, and subsequent modifications have been proposed periodically through the present time. Recent studies clearly reveal that the process of Fe reduction involves more than the mere transfer of an electron to octahedral Fe(III) in the clay crystal. Ancillary reactions occur that produce significant structural modifications, some of which are reversible and others of which are not. Such changes in the crystal-chemical environment of structural Fe are thought to play a dominant role in altering the clay surface chemistry.

Fate of atrazine and alachlor in redox‐treated ferruginous smectite

AbstractThe oxidation state of structural iron (Fe) in clay minerals exerts a large influence on clay surface chemistry and may affect the adsorption and degradation of pesticides in the environment. This effect, however, has been little investigated. In the present study, herbicides atrazine and alachlor were reacted with ferruginous smectite (sample SWa‐1) in its oxidized, reduced (either chemically or bacterially), and reduced–reoxidized states. In some experiments the herbicide was labeled with 14C. Gas chromatography/mass spectrometry (GC‐MS) was also used to detect alachlor degradation products. Compared to oxidized clays, reduction by both chemical and microbial treatments decreased the concentration of both herbicides in the surrounding solution. Reoxidized clay exhibited behavior similar to the oxidized clay. Hydrolysis–dechlorination of atrazine occurred in the presence of chemically reduced SWa‐1, and GC‐MS analysis of alachlor revealed at least 14 degradation products after treatment with reduced clay and only two with the oxidized clay. Interaction of atrazine and alachlor with the clay may be through a H bond with the waters of hydration surrounding interlayer cations, the extent of which should increase with increasing acidity; but under reduced conditions, the validity of this model is unclear. Reduction of structural Fe may affect pH‐dependent phenomena in two ways: The increased surface charge density increases the number of hydrated interlayer cations, thereby enhancing surface acidity, and increased electron density at basal surface oxygens increases their Brønsted basicity. Atrazine could, therefore, adsorb and/or degrade through either acid or alkaline hydrolysis pathways. Increased reduction potential of the reduced clay surfaces may also promote degradation.

Fate of atrazine and alachlor in redox-treated ferruginous smectite.

The oxidation state of structural iron (Fe) in clay minerals exerts a large influence on clay surface chemistry and may affect the adsorption and degradation of pesticides in the environment. This effect, however, has been little investigated. In the present study, herbicides atrazine and alachlor were reacted with ferruginous smectite (sample SWa-1) in its oxidized, reduced (either chemically or bacterially), and reduced-reoxidized states. In some experiments the herbicide was labeled with 14C. Gas chromatography/mass spectrometry (GC-MS) was also used to detect alachlor degradation products. Compared to oxidized clays, reduction by both chemical and microbial treatments decreased the concentration of both herbicides in the surrounding solution. Reoxidized clay exhibited behavior similar to the oxidized clay. Hydrolysis-dechlorination of atrazine occurred in the presence of chemically reduced SWa-1, and GC-MS analysis of alachlor revealed at least 14 degradation products after treatment with reduced clay and only two with the oxidized clay. Interaction of atrazine and alachlor with the clay may be through a H bond with the waters of hydration surrounding interlayer cations, the extent of which should increase with increasing acidity; but under reduced conditions, the validity of this model is unclear. Reduction of structural Fe may affect pH-dependent phenomena in two ways: The increased surface charge density increases the number of hydrated interlayer cations, thereby enhancing surface acidity, and increased electron density at basal surface oxygens increases their Brønsted basicity. Atrazine could, therefore, adsorb and/or degrade through either acid or alkaline hydrolysis pathways. Increased reduction potential of the reduced clay surfaces may also promote degradation.

A possible energetic role of mineral surfaces in chemical evolution.

The postulated roles of clays and other minerals in chemical evolution and the origin of life are reconsidered in terms of the interaction of these minerals with penetrating sources of energy such as ionizing radiation and mechanical stress. This interaction, including such facets as excitation, degradation, storage, and transfer, is considered here with regard to its profound potential for altering the capabilities of minerals to serve both as substrates for prebiological chemistry and as inorganic prototypic life forms. The interaction of minerals and energy in relationship to surface chemistry is discussed in terms of the spectroscopic properties of minerals, the interaction of energy with condensed phases, some commonly accepted concepts of heterogeneous catalysis in the absence of electronic energy inputs, and some commonly accepted and novel means by which surface activity might be enhanced in the presence of energy inputs. An estimation is made of the potential contribution of two poorly characterized prebiotic energy sources, natural radioactive decay and triboelectric energy. These estimates place a conservative lower limit on their prebiotic abundance. Also some special properties of these energy sources, relative to solar energy, are pointed out which might give them particular suitability for driving reactions occurring under geological conditions. Skeletal support for this broadly defined framework of demonstrated and potential relationships between minerals, electronic excitation, and surface reactivity, as applied to chemical evolution, is provided from the results of our studies on 1/1 clays. We have discovered and partially characterized a number of novel luminescent properties of these clays, that indicate energy storage and transfer processes in clays. These luminescent properties are interpreted in relationship to the electron spin resonance phenomena, to provide a basis for estimating the potential significance of energy storage and transduction in monitoring or driving clay surface chemistry. Consideration of the electronic structure of abundant minerals in terms of band theory and localized defect centers provides a predictive theoretical framework from which to rationalize the capacity of these materials to store and transduce energy. The bulk crystal is seen as a collecting antenna for electronic energy, with the defect centers serving as storage sites. The clay properties produced by isomorphic substitution appear to be intimately associated with all of the life-mimetic chemical processes that have been attributed to clays.(ABSTRACT TRUNCATED AT 400 WORDS)

Surface Chemistry of Clays and Shales

The chemistry of clays and shales has been assuming increasing importance inthe petroleum industry, and two factors have greatly influenced this trend. Thefirst has been the growing evidence that the marine shales are source beds, andthat the petroleum compounds have migrated to the sand reservoirs overlying orunderlying these shales: the second has been the demand for drilling fluidsbetter adapted to penetrate these marine shales without difficulty andexpense. Origin and General Composition of Clays and Shales Clays, shales and surface soils are all closely related materials. They aremixtures of finely divided compounds formed during the weathering of the solidcrust of the earth. Their nature is essentially colloidal; that is, theirbehavior is determmed by the state of division of the materials and the surfacereactions of the smallest grains. Many of their chemical changes affect onlythe exposed areas and do not involve the interior of the grains of matter. Theextent of these reactions is more nearly proportional to the area of thesubstances than to their mass therefore it is possible for a small amount of amaterial in an extremely fine state of division to completely dominate thecharacter of the mixture. More than 83 per cent of the crust of the earth is composed of threeelements-oxygen, silicon and aluminum. Consequently, the corrosion products ofthe crust are predominantly aluminosilicates, or compounds of aluminum, siliconand oxygen. If we add the compounds of six elements-iron, calcium, sodium, potassium, magnesium and hydrogen-more than 98 per cent of the crust has been accountedfor. These six elements, together with the first three, also appear in soils, clays and shales. But direct chemical analysis is of little value in describing the nature ofsuch materials. Many chemical individuals may be present in variable amounts, and the extreme subdivision of anyone of the individuals may contributequalities that dominate the mixture. T.P. 1027