Martin Pentrák

A review of microbial redox interactions with structural Fe in clay minerals

Abstract Virtually all 2:1 clay minerals contain some Fe in their crystal structure, which may undergo redox reaction with surrounding redox-active species causing potentially significant changes in the chemical and physical properties of the clay mineral and its surrounding matrix. This phenomenon was originally of interest mostly as a laboratory experiment using strong inorganic reduction agents, but the discovery that the structural Fe could be reduced by microorganisms in natural soils and sediments opened the way for this to become a practical method for altering the chemical and physical properties of soils and sediments in situ. The purpose of this report was to review the body of literature that has been published since the inception of this field of inquiry and to complement, update, and complete three other reviews that have been published during the intervening years. Studies of microbial reduction of structural Fe in smectites have revealed the extent of reduction, effects on chemical and physical properties, reversibility (or lack thereof) of microbial reduction, stoichiometry, possible reaction mechanism, and types of organisms involved. Some organisms are also capable of oxidizing structural Fe, such as in biotite or reduced smectite, while one appears to be able to do both. Illitic layers resist reduction by microorganisms, but this can be partially overcome by the presence of an electron shuttle compound such as anthraquinone-2,6- disulfonate, which also enhances the extent of reduction in smectites. Microorganisms may be employed as an in situ reducing agent to drive redox cycles for structural Fe in constituent clay minerals of soils and sediments, which in turn can serve as an abiotic source for redox-mediated remediation of environmental contaminants.

Biological Redox Cycling of Iron in Nontronite and Its Potential Application in Nitrate Removal

Biological redox cycling of structural Fe in phyllosilicates is an important but poorly understood process. The objective of this research was to study microbially mediated redox cycles of Fe in nontronite (NAu-2). During the reduction phase, structural Fe(III) in NAu-2 served as electron acceptor, lactate as electron donor, AQDS as electron shuttle, and dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens CN32 as mediator in bicarbonate- and PIPES-buffered media. During the oxidation phase, biogenic Fe(II) served as electron donor and nitrate as electron acceptor. Nitrate-dependent Fe(II)-oxidizing bacterium Pseudogulbenkiania sp. strain 2002 was added as mediator in the same media. For all three cycles, structural Fe in NAu-2 was able to reversibly undergo three redox cycles without significant dissolution. Fe(II) in bioreduced samples occurred in two distinct environments, at edges and in the interior of the NAu-2 structure. Nitrate reduction to nitrogen gas was coupled with oxidation of edge-Fe(II) and part of interior-Fe(II) under both buffer conditions, and its extent and rate did not change with Fe redox cycles. These results suggest that biological redox cycling of structural Fe in phyllosilicates is a reversible process and has important implications for biogeochemical cycles of carbon, nitrogen, and other nutrients in natural environments.

Near-infrared spectroscopic analysis of acid-treated organo-clays

The potential use of near-infrared (NIR) spectroscopy as a characterization tool for organo-clays would be a great asset but little work has been done in this regard because the application of NIR to clay mineral studies is a relatively new phenomenon. The purpose of this study was to use NIR spectroscopy to investigate the effect of alkylammonium cations on the acid dissolution of a high-charge montmorillonite (SAz-1). Detailed analysis of the spectra of Li+-, TMA+- (tetramethylammonium), and HDTMA+- (hexadecyltrimethylammonium) saturated SAz-1 montmorillonite in the NIR region was achieved by comparing the first overtone (2ν) and combination (ν+δ) bands of XH groups (X = O, C) with the fundamental stretching (ν) and bending (δ) vibrations observed in the mid-infrared (MIR) region. Comprehensive analysis of the vibrational modes of CH3-N, CH3-C, and -CH2-C groups of TMA+ and HDTMA+ cations detected in the MIR and NIR regions was also performed. Both MIR and NIR spectra demonstrated that exchange of Li+ by TMA+ only slightly improved the resistance of SAz-1 layers to dissolution in 6 M HCl at 80°C, while exchange by the larger HDTMA+ cations almost completely protected the montmorillonite layers from acid attack. Use of NIR spectra in reaching these conclusions was crucial. Only in the NIR region could the creation of SiOH groups be monitored, which is an important indicator of the acidification of the montmorillonite surface. The OH-overtone region in the spectra of Li-SAz-1 and TMA-SAz-1 revealed that the SiOH band near 7315 cm−1 increases in intensity with enhanced acid treatment. In contrast, no SiOH groups were identified in the NIR spectra of HDTMA-SAz-1 treated in HCl, indicating that HDTMA+ completely covers the inner and outer surfaces of the montmorillonite and hinders access ofprotons to the Si-O− bonds created upon acid treatment.

Acid and alkali treatment of kaolins

Abstract Two kaolins containing kaolinites of different crystallinity, as confirmed by the Aparicio-Galán-Ferrell index, were treated in HCl and KOH solutions at 95° and 80°C, respectively, for periods up to 36 h. Changes resulting from the treatments have been characterized by several methods. Fe occurs in the octahedral sheets of both kaolinites and dissolves similarly to Al. Lower structural ordering, more structural defects and particles of smaller average size and less regular shape are responsible for faster dissolution of KGa-2 in comparison to well ordered Gold Field (Tanzania) kaolinite. More Si than Al is dissolved in KOH from both kaolins after any dissolution time. An aluminosilicate (feldspathoid) phase is thought to occur in the material prepared from KGa-2 in KOH. Near-IR spectra provide very useful information on changes in the mineral structure upon the treatments, on the solid reaction products and on the adsorbed water molecules.

Sorption of heavy metal cations on rhyolitic and andesitic bentonites from Central Slovakia

Sorption of heavy metal cations on rhyolitic and andesitic bentonites from Central Slovakia The main purpose of this work was to determine adsorption characteristics of heavy metal cations on two Slovak bentonites. Adsorption of Pb2+, Zn2+, Cu2+ and Cd2+ on Jelšový Potok (JP) and Lieskovec (L) bentonites was studied by the batch equilibration technique using solutions of different concentrations. Higher smectite content (81 mass %) and higher cation exchange capacity (CEC) (105 mmol M+/100 g) of JP bentonite cause higher adsorption of all heavy metals in comparison with L bentonite. JP adsorbed heavy metals in the order Pb2+ » Cd2+ > Zn2+ > Cu2+ while sorption on L was slightly different, Pb2+ » Cd2+ > Cu2+ ≥ Zn2+. The Freundlich model of adsorption is more appropriate for adsorption of Pb2+ and Cd2+ while lower uptake of Cu2+ and Zn2+ is better described by the Langmuir model. Negative ΔG° values indicate that the adsorption process of all cations on both bentonites is feasible, spontaneous and exothermic. The decrease in the d001 spacings from 14.8-14.9 Å in natural dominantly Ca2+-saturated samples to 13.2-12.6 Å for both bentonites saturated with four heavy metal cations shows the effect of less hydrated exchangeable cations on interlayer spacing. Jelšový Potok bentonite of higher montmorillonite content and greater CEC is the more effective candidate for removal of Pb2+, Zn2+, Cu2+ and Cd2+ from waste water than Lieskovec bentonite.

Effect of chemical composition and swelling on acid dissolution of 2 : 1 clay minerals

Dissolution of fine fractions of three clays, containing as the main minerals a montmorillonite, a mixed-layer illite/smectite and an illite, in 6 mol dm−3 HCl at 95°C was investigated. The extent of dissolution was followed by chemical analysis of the reaction liquids. The solid materials were characterised by X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy in mid- and near-IR regions and by determination of cation exchange capacities. The objective was to compare the effects of chemical composition and swelling ability of three dioctahedral clay minerals from the montmorillonite–illite series on their dissolution in HCl. Montmorillonite with swelling interlayers (Jelšový Potok, Slovakia) was completely dissolved within 18 h, whereas the residues of illite could be distinguished in both illitic samples with prevailing non-swelling interlayers treated for 36 h. Chemical composition of dioctahedral clay minerals has greater effect on the dissolution rate than swellability. Greater substitution of Mg and Fe for Al in the octahedral sheets and of Al for Si in the tetrahedral sheets in the layers of Ca-illite from Morris (Illinois, USA) makes it more easily soluble in HCl than the mixed-layer illite/smectite mineral (Dolná Ves, Slovakia) with 30% swelling interlayers. FTIR spectroscopy in both mid- and near-IR regions provides complex information on dissolution of dioctahedral clay minerals.

Oriented inclusions in apatite in a post-UHP fluid-mediated regime (Tromsø Nappe, Norway)

We report pyrrhotite, anhydrite and dolomite crystal rods in fluorapatite occurring in silicate-bearing carbonate rocks associated with UH P eclogites in the Tromso Nappe of the Scandinavian Caledonides in Norway. The apatite-rich rock (up to 10 vol. %) is composed of Mg-rich calcite-dolomite exsolutions, almandine-grossular garnet, low-jadeite clinopyroxene, magnesiohornblende, phlogopite, and accessory minerals represented mainly by zircon, Fe-Ti oxides and allanite. Fluorapatite occurring as euhedral crystals in the carbonate matrix and as inclusions in garnet and clinopyroxene shows up to 45 mol. % of the hydroxylapatite component, traces of CO 3 2− , probably CN − and small amounts of the britholite and ellestadite components. Pyrrhotite occurs as crystallographically oriented rods parallel to the c axis of the host hydroxyl-bearing fluorapatite either as a dense trellis or in the form of scarce inclusions. Precipitation of pyrrhotite in the fluorapatite was probably facilitated by a volatile sulphur phase ( e.g ., H 2 S), which was enclosed within the apatite nano-channels and interacted with Fe in apatite. Anhydrite and dolomite rods have also been identified in the apatite, pointing to the presence of HCO 3 − in the fluids. The anhydrite is also trapped by exsolved dolomite from calcite in the carbonate matrix. Crystallisation of anhydrite, and probably also the associated pyrrhotite, at about 550–650°C was deduced from calcite–dolomite thermometry. At these amphibolite-facies, post-UH P conditions rapid pyrrhotite precipitation in the host apatite is presumed. Relaxation of the fluorapatite structure in the a -axis direction during decompression facilitated the formation of the oriented inclusions in apatite.

Methods for handling redox-sensitive smectite dispersions

Abstract Redox activation (reduction of structural Fe) of smectites greatly alters their chemical reactivity and physical properties, which may be exploited for various environmental, agricultural or industrial purposes. Their re-oxidation during preparation, characterization, and use is, however, a significant risk to their utility. In this study, methods and apparatus were developed and described which mitigated reoxidation. Ferruginous smectite (sample SWa-1, Na saturated) was used as the model smectite. It was reduced with sodium dithionite in a citrate-bicarbonate buffer solution at 70°C for 4 h, which achieved a maximum Fe(II)/total Fe ratio of 0.9113±0.0048. The first step in rendering reduced samples useful is to remove from them the reducing agents and other solutes present during reduction. This was accomplished in the present study by reducing the sample in an inert-atmosphere reaction tube (IRT) (a 50 mL centrifuge tube equipped with a removable septum cap), then removing solutes from the suspension by centrifuge washing. The washing steps were performed with the aid of a controlled-atmosphere liquid exchanger (CALE) which provided connections between the sample suspension and deoxygenated solutions. The reduced state was measured by 1,10-phenanthroline or by Mössbauer spectroscopy at 77 K to give Fe(II)/total Fe ratios. Some samples were freeze dried after washing. Results revealed that if reduced smectites are washed without protection from atmospheric O2, the extent of reoxidation is on the order of 40 to 60%. If the sample is subsequently dried, reoxidation increases to more than 76%. If the sample is protected using the IRT and the CALE, however, reoxidation is decreased to less than 2%. Freeze drying in a glove box allowed reoxidaton to increase to slightly more than 10%. These results indicate that more reoxidation occurred during the drying stage than during the washing stage. These observations lead to the conclusions that (1) protection of reduced samples from atmospheric O2 is essential if extensive reoxidation is to be prevented, and (2) the methods and apparatus described herein are effective for accomplishing that purpose in abiotically reduced smectites. They may also be effective if applied to microbially reduced smectites.

Tetrahedral charge and Fe content in dioctahedral smectites

Abstract Natural aluminosilicates can contain Fe in tetrahedral or octahedral coordination. Amongst smectites, tetrahedral iron is known to occur in Fe-rich nontronites but few indications exist for the presence of tetrahedral Fe in smectites of the montmorillonite-beidellite series. A set of 38 different bentonites showed a correlation of tetrahedral charge and Fe content in their smectites. All materials with large tetrahedral charge were rich in Fe. This could be explained by a general tendency of Fe to enter the tetrahedral sheet. To investigate this correlation, nine materials were selected and investigated by Mössbauer, UV-Vis, Fe K pre-edge and EXAFS spectroscopy with respect to tetrahedral Fe (Fe[IV]). The latter two methods were at the detection limit but Mössbauer and UV-Vis spectroscopy provided consistent results indicating the significance of both methods in spite of some scatter caused by the overall small amount of tetrahedral Fe. The results indicate the absence of any relation between Fe content and tetrahedral Fe. Tetrahedral Fe can be present in Fe-poor smectites and absent in the case of Fe-rich materials. This means that Fe-rich montmorillonites have a larger tetrahedral charge which is not caused by Fe[IV] but by Al[IV]. A possible explanation for this indirect relation is based on: the coordination of Al3+ in the weathering/smectite-forming solutions determines the coordination in the precipitates; and the Al[IV/VI] ratio increases with increasing pH. The correlation could thus be explained if the pH of weathering solutions generally was higher in Fe-rich parent smectite rocks than in more acidic smectite parent rocks. The relation between tetrahedral charge and Fe content can probably be explained by different geochemical contexts throughout the formation of smectites which affect the coordination of dissolved Al.

Impacts of detrital nano- and micro-scale particles (dNP) on contaminant dynamics in a coal mine AMD treatment system

Pollutants in acid mine drainage (AMD) are usually sequestered in neoformed nano- and micro-scale particles (nNP) through precipitation, co-precipitation, and sorption. Subsequent biogeochemical processes may control nNP stability and thus long-term contaminant immobilization. Mineralogical, chemical, and microbiological data collected from sediments accumulated over a six-year period in a coal-mine AMD treatment system were used to identify the pathways of contaminant dynamics. We present evidence that detrital nano- and micron-scale particles (dNP), composed mostly of clay minerals originating from the partial weathering of coal-mine waste, mediated biogeochemical processes that catalyzed AMD contaminant (1) immobilization by facilitating heterogeneous nucleation and growth of nNP in oxic zones, and (2) remobilization by promoting phase transformation and reductive dissolution of nNP in anoxic zones. We found that dNP were relatively stable under acidic conditions and estimated a dNP content of ~0.1g/L in the influent AMD. In the AMD sediments, the initial nNP precipitates were schwertmannite and poorly crystalline goethite, which transformed to well-crystallized goethite, the primary nNP repository. Subsequent reductive dissolution of nNP resulted in the remobilization of up to 98% of S and 95% of Fe accompanied by the formation of a compact dNP layer. Effective treatment of pollutants could be enhanced by better understanding the complex, dynamic role dNP play in mediating biogeochemical processes and contaminant dynamics at coal-mine impacted sites.