Siderophores are low molecular weight organic ligands synthesized by aerobic microorganisms to acquire Fe. In addition to Fe(III), siderophores may complex other metals such as Pb and Cd. This study compared the effects of the trihydroxamate siderophores desferrioxamine-B (DFO-B), desferrioxamine-D1 (DFO-D1), desferrioxamine-E (DFO-E), and the monohydroxamate siderophore-like ligand acetohydroxamic acid (aHA) on Pb and Cd (except for DFO-E) adsorption to kaolinite (KGa-1b) at pH 4.5 to 9, in 0.1 M NaClO4, at 22°C, in the dark. At pH >6, all of the studied ligands decreased Pb adsorption to kaolinite: aHA by 5–40% and DFO-B, DFO-D1 and DFO-E by 30–75%; the greater effects were at higher pH. The studied ligands decreased Cd adsorption to kaolinite at pH >8: aHA by 5–20% and the trihydroxamates by as much as 80%. We also observed enhancement of Pb adsorption in the presence of DFO-B at pH ≈5–6.0, probably due to adsorption of the doubly positively charged H3Pb (DFO-B)2+ complex, although spectroscopic evidence is needed.

The interaction of cytochromes (heme proteins) with mineral surfaces is important from an environmental perspective (e.g. heavy metal remediation and reductive dehalogenation reactions), for designing biosensors and bioanalytical systems, and for emerging photovoltaic applications. In addition, the cytochrome studied here shares properties with some cytochromes from Fe-reducing bacteria and its general behavior sheds light on how other cytochromes might behave during Fe(III) reduction. The objectives of this study were to characterize the direct electrochemistry and sorption mechanism of horse heart ferricytochrome c (a mitochondrial cytochrome referred to as Hcc) on hematite surfaces as a function of pH, time of sorption and ionic strength. Hcc sorption on hematite mainly occurs between pH 8 and 10, the pH range in which hematite surfaces and Hcc are oppositely charged. Calculated net attractive forces correspond closely with the pH range of peak sorption, suggesting that sorption is mainly electrostatically controlled. Hcc sorption with ionic strength is consistent with this conclusion. The pH-dependent conformation of Hcc sorbed on hematite appears to be different from that in solution as indicated by UV-visible spectroscopy and its more negative reduction potential compared to native Hcc. Sorption kinetics were rapid and pH-independent across the pH range 3–10 with slow conformational changes occurring at >60 h. Our results suggest that the electrostatic attraction of the cytochrome towards the surface orient the cytochrome for favorable electron transfer between the heme group of the cytochrome and hematite.

This study was undertaken to investigate the changes in flocculation properties of Fe-rich smectite (nontronite, NAu-1) suspensions, including settling velocity, aggregate size and floc architecture associated with microbial Fe(III)-reduction in the smectite structure. The dissimilatory Fe-reducing bacterium Shewanella oneidensis MR-1 was incubated with lactate as the electron donor and structural Fe(III) as the sole electron acceptor for 3, 12, 24 and 48 h in an anaerobic chamber. Two controls were prepared; the first was identical to the experimental treatments except that heat-killed cells were used (non-reduced control), and the second control was the same as the first except that the incubation was carried out in an aerobic environment. The extent of Fe(III) reduction for the 48 h incubation was observed to reach up to 18%. Neither the non-reduced control nor the aerobically inoculated sample showed Fe(III) reduction. Compared with the non-reduced control, there was a 2.7 μm increase in mean aggregate size and a 30-fold increase in average settling velocity in the bioreduced smectite suspensions as measured using a Micromeritics Sedigraph®. The aerobically inoculated smectite showed a similar aggregate-size distribution to that of the non-reduced control. Significant changes in physical properties of smectite suspensions induced by microbial Fe(III) reduction were measured directly using transmission electron microscopy. The floc architecture of bioreduced smectite revealed less open structures compared to those of a non-reduced control. The aspect ratio (thickness/length) of individual smectite particle increased from 0.11 for the non-reduced control to 0.18 on average for the bioreduced smectite suspensions. The effects of pH on the clay flocculation were minimal in this study because the value of pH remained nearly constant at pH = 7.0–7.3 before and after the experiments. We therefore suggest that the increase in net negative charge caused by microbial Fe(III) reduction significantly promoted clay flocculation by increasing the electrochemical attraction in the smectite suspensions.

Dark Fe oxides and sulfides are major discoloring impurities in mined commercial white kaolin clay. In order to evaluate the potential influence of Fe-cycle bacteria on Fe cycling during post-depositional clay-weathering alteration, Fe(III)-reducing and/or Fe(II)-oxidizing microorganisms were examined in open-pit, subsurface mine samples from kaolin lenses and smectite formations collected from sites in central Georgia. Samples of varying age were examined, including late Eocene smectite overburden, hard kaolin of Middle Eocene age, soft gray kaolin from the late Paleocene, and soft tan kaolin of late Cretaceous age. These clays contained 0.06–5.33% organic carbon, which included various potential organic electron donors for bacterial metabolism: formate (1.1–30.6 mmol/kg), acetate (0–40.5 mmol/kg), lactate (0–12.1 mmol/kg), pyruvate (0.4–78 mmol/kg), oxalate (0–141.7 mmol/kg), and citrate (0–1.4 mmol/kg). All clay samples studied had small concentrations of ‘bio-available’ Fe(III) (0.5 M HCl-extractable Fe, 0.5–2.8 mmol/kg) compared to total Fe (HF-extractable, 25–171.9 mmol/kg). The highest Fe(III)/[Fe(II)+Fe(III)] ratio and the lowest organic carbon content were in kaolin samples in which Fe(III) reduction was determined to be the dominant terminal electron accepting process by hydrogen analysis. All clay samples showed greater numbers of Fe(II)-oxidizing bacteria (22–22,000 cells/g) than Fe(III)-reducing bacteria (3–410 cells/g) as determined by MPN analysis. The Fe(III)-reducing activity in clays could be stimulated with the addition of 1 mM of the Fe(III) chelator, nitrilotriacetic acid. The addition of nitrate stimulated anaerobic Fe(II) oxidation. These results suggest that anaerobic bacteria involved in both oxidation and reduction of Fe exist in these subsurface clay formations, and might have had an influence on post-depositional weathering reactions.

Sorption and transformation of 1-naphthol by a K-smectite (K-SWy-2) were studied using batch sorption isotherms, Fourier-transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The sorbents included three preparations of the reference smectite clay (SWy-2): (1) whole clay containing naturally occurring carbonate impurities, (2) SWy-2 with the removal of carbonate impurities, and (3) the carbonate-free SWy-2 fraction amended with calcite. For the whole clay and carbonate-free clay amended with calcite, >80% of added 1-naphthol disappeared from aqueous solution within 24 h, corresponding to a sorbed concentration of ≥2 mg/g of clay. In contrast, only 35% of the added 1-naphthol disappeared from solution in the carbonate-free clay after 24 h of exposure. For the clays from the three preparations in this study, <1% of sorbed 1-naphthol could be recovered by methanol extraction from the clays. The XRD data suggested that 1-naphthol was intercalated in the smectite, but was not conclusive because the 1-naphthol sorption range (1.5–2.8 mg/g of clay) in this study had relatively minor effects on the XRD patterns. The FTIR spectra of sorbed 1-naphthol-clay complexes demonstrated structural Fe3+ reduction. The spectra also showed evidence of the transformation of 1-naphthol. It suggests that reduction of structural Fe3+ may be coupled to oxidation/polymerization of 1-naphthol. Further transformation of oxidized 1-naphthol, such as by oxidative coupling reactions, is implicated by formation of a dark gray color on the clay and the inability to extract sorbed 1-naphthol.

Interaction between metal Fe and a variety of natural and synthetic smectite samples with contrasting crystal chemistry was studied by scanning electron microscopy and X-ray diffraction from experiments conducted at 80°C. These experiments demonstrate an important reactivity contrast as a function of smectite crystal chemistry. An XRD method involving the use of an internal standard allowed quantification of the relative proportion of smectite destabilized as a function of initial pH conditions as well as of smectite structural parameters. In mildly acidic to neutral pH conditions, a significant proportion of metal Fe is corroded to form magnetite without smectite destabilization. Under basic pH conditions, smectite and metal Fe are partly destabilized to form magnetite and newly-formed 1:1 phyllosilicate phases (odinite and crondstedtite). More specifically, systematic destabilization of both metal Fe and smectite is observed for dioctahedral smectites while trioctahedral smectites are essentially unaffected under similar experimental conditions. In addition, smectite reactivity is enhanced with increasing Fe3+ content and with the presence of Na+ cations in smectite interlayers. A conceptual model for smectite destabilization is proposed. This model involves first the release of protons from smectite structure, MeFe3+OH groups being deprotonated preferentially and metal Fe acting as proton acceptor. Corrosion of metal Fe results from its interaction with these protons. The Fe2+ cations resulting from this corrosion process sorb on the edges of smectite particles to induce the reduction of structural Fe3+ and migrate into smectite interlayers to compensate for the increased layer-charge deficit. Interlayer Fe2+ cations subsequently migrate to the octahedral sheet of smectite because of the extremely large layer-charge deficit. At low temperature, this migration is favored by the reaction time and by the absence of protons within the di-trigonal cavity. Smectite destabilization results from the inability of the tetrahedral sheets to accommodate the larger dimensions of the newly formed trioctahedral domains resulting from the migration of Fe2+ cations.

Iron-pillared clays (Fe-PILCs) were synthesized from hydrolyzed FeCl3 solutions added to NaOH solutions using different synthesis conditions. X-ray diffraction, N2 adsorption-desorption, chemical analysis, thermogravimetric analysis, differential thermal analysis, temperature-programmed desorption of ammonia and temperature-programmed reduction were used to characterize the resulting Fe-pillared clays (Fe-PILCs). A higher degree of pillaring was obtained when the Fe content was adjusted to 60 mmoles of Fe/g of clay. It was observed that higher values of this ratio led to worse acidity and textural characteristics, a consequence of the probable formation of Fe oxides that could not only deposit on the surface but also block the pores formed during the pillaring process. Likewise, it was found that the amount of Fe that can be introduced depended on the OH/Fe ratios. Total surface and micropore area decreased and Fe content increased with increasing pillaring solution concentrations. Finally, all pillared samples prepared here were thermally stable at temperatures up to 400°C.

MgO-clay nanocomposites were prepared from a synthetic smectite-type clay, TS, using three different non-ionic surfactants (Igepal CA-720, Brij 30 and Brij 56) and the resulting clay nanocomposites were impregnated with Ni for the methane reforming reaction with carbon dioxide to synthesis gas. A Ni/TS catalyst was also prepared for comparison. The prepared supports and catalysts were characterized by X-ray diffraction, X-ray fluorescence, thermogravimetric analysis and N2 adsorption/desorption isotherms. The thermal stability, pore structure and the surface area strongly influence the catalytic behavior of the catalysts. The methane conversions (at 700°C for 4 h) were 91, 95 and 97% for Ni/TSIGE, Ni/TSBR30 and Ni/TSBR56, respectively, indicating that the surface properties and the catalytic performance of the resulting solids slightly improved as the polyethylene oxide number of the surfactant increased. A reduced conversion (10%) and a rapid deactivation was observed in the Ni/TS catalyst, attributed to its Na content and low thermal stability, which led to sintering and coke deposition.

Study of the transformation of smectite to illite, chlorite or vermiculite via interstratified clay minerals needs precise qualitative and quantitative determinations of the different layers in the mixed-layer clays and is generally based on X-ray diffraction (XRD) patterns after specific treatments of the clay samples. Saturation with K or Mg followed by ethylene glycol (EG) solvation are classical methods used to identify high-charge smectite and vermiculite. These procedures have been applied to two experimental clays, one composed of smectite layers and the second, a mixture of vermiculite and smectite layers. Different methods of glycolation (EG vapor or liquid EG) produce significant differences in the XRD patterns. Comparison with literature data indicates that K-saturated, high-charge smectite (≈0.8 < total charge <1/unit-cell) and Mg-vermiculite (whatever its charge) do not expand in ethylene glycol vapor (d values ≈14–15 Å). Expansion to 17 Å in liquid ethylene glycol occurs for Mg-vermiculite with a total charge of <~1.2/unit-cell and for K-saturated, high-charge smectite, when the tetrahedral charge is <≈0.7/unit-cell. This study shows that: (1) glycolation procedures need to be standardized; (2) the use of saturation protocols using both liquid ethylene glycol and ethylene glycol vapor yields useful additional information about the distribution of charges in clay minerals.

Sudoite from diagenetic to very low-grade metaclastites of the Betic Cordillera was studied by X-ray diffraction and transmission/analytical electron microscopy. Sudoite formed directly from dickite, the assemblage dickite + sudoite + illite being replaced at increasing metamorphic grade by the assemblage pyrophyllite + sudoite + illite. Sudoite ranges in composition from Mg-rich to Fe-rich chemistries. In addition, a wide variety of mixed-layered structures (illite-sudoite, pyrophyllite-sudoite, and dickite-sudoite) was also identified. Mg-rich sudoite shows a mean chemical composition of (Al2.91Fe0.252+Mg1.80)(Si3.10Al0.90)O10(OH)8, and a IIb ordered structure with b = 9.055 Å. Intermediate Fe-Mg sudoite exhibits a very variable composition, the Fe-rich phases having a mean composition of (Al2.09Fe0.613+Fe0.872+Mg1.44)(Si3.31Al0.69O10(OH)8. These are disordered polytypes with b values ranging from 9.070 to 9.101 Å. Fe occurs in both octahedral sheets, according to two types of substitutions: Fe3+ for Al in the dioctahedral sheet and Fe2+ for Mg in the trioctahedral sheet. Sudoite with such a composition has not been described previously.

Allophanes are poorly crystalline and quasi-stable aluminosilicate minerals, the structures of which are sensitive to chemical treatment. In the present study, solid-state 27Al and 29Si nuclear magnetic resonance (NMR) spectra of allophane samples were monitored as they went through several purification procedures. It was confirmed that no significant structural changes were caused by boiling with 6% H2O2 to remove organic matter, by size fractionation (sonification), by sedimentation, by precipitation at pH 4.0, or by dithionite-citrate-bicarbonate treatment for the removal of Fe (hydr)oxides. Hot 5% Na2CO3 treatment for the removal of reactive silica-alumina gels and adsorbed citrate from allophane samples, however, decreased signal intensity corresponding to imogolite-like Si (Q33VIAl, −78 ppm in 29Si NMR) and increased signal intensities corresponding to IVAl (55 ppm in 27Al NMR) and possibly X-ray amorphous aluminosilicates (centered at −85 ppm in 29Si NMR). Cold (room temperature) 5% Na2CO3 treatment for 16 h proved to be effective in avoiding these structural changes.

The Plio-Pleistocene deposits of the Olduvai Basin in northern Tanzania consist of a sequence of lacustrine and fluvial sediments. They contain various amounts of zeolite minerals, the formation of which is related to an interaction of volcanic material or detrital clays with saline alkaline lake water and groundwater. Petrographic characteristics of zeolite occurrences provide information about their conditions of formation. They were studied for all four main stratigraphical units that are recognized at Olduvai (Beds I to IV), sampled in the southeastern part of the basin. In the lake-margin deposits of Bed I and the lower part of Bed II, chabazite is the dominant zeolite mineral accompanied by phillipsite and minor amounts of erionite and clinoptilolite. Chabazite commonly occurs as part of altered volcanic rock fragments, characterized by partial or complete dissolution of volcanic glass and the formation of chabazite inside vesicles, following the development of thin smectite coatings. It also formed within the sediment matrix, requiring extended periods of impregnation of the deposits by saline alkaline solutions. Chabazite also occurs extensively as coatings and infillings of pores, developed during periods of subaerial exposure which were characterized by high groundwater levels. Phillipsite formed at a later stage, from more evolved solutions, with higher K/Na ratios than during chabazite formation. The fluvial deposits of Bed IV, Bed III and the upper part of Bed II have a high analcime content. They also contain various amounts of chabazite, phillipsite and natrolite. All zeolite minerals mainly occur in pores. The predominance of analcime indicates a higher salinity and alkalinity than during the preceding period with sedimentation and diagenesis in a lake margin environment. Early development of zeolite occurrences, shortly after the deposits became exposed during breaks in sedimentation, is recorded for some intervals, where zeolites are covered by illuvial clay coatings or by sparitic carbonate cement. In most intervals, however, zeolites mainly formed at a later stage.

The Mevaiela kaolin deposits are located in the northern part of the anorthositic-gabbro massif within the Cunene complex (southern Angola) and were formed by the alteration of basic anorthosites and gabbros. The Mevaiela area is part of an elevated region which is located between two extensive NNW-SSE fracture systems. Several kaolinite samples were collected from a quarry (main excavation) and from drill-holes as well as from surficial occurrences in the Cunene complex. Chemical analyses, X-ray diffraction, differential thermal analysis, scanning electron microscopy and isotope analyses were performed in order to model the kaolinite occurrences. The alteration of the anorthosite to kaolin approaching the main excavation is characterized by significant decrease in alkaline-earth and transition metals (Ca, Mg, Fe, Co, Ni and Mn) between the average anorthosite and the kaolin. The crystallinity indices suggest that the kaolin contains kaolinite with a reasonably well ordered structure and near the transition between T (triclinic) and pM (pseudo monoclinic).

Mineral exploration tools have been evaluated during this study to assist in future kaolin exploration in the Cunene anorthosite complex.

Isotopic analysis of O and D indicates that Ca-feldspar alteration is essentially due to meteoric fluids, over a different range of temperatures. Furthermore, the presence of quartz-feldspar veinlets in the kaolinite bodies could be the result of hydrothermal activity linked to post-anorthosite granite intrusions of the so-called ‘red granite’. Kaolinite from Cunene plots on or close to the kaolinite line into the ‘warm temperature in tropical region’ area (surficial samples). Samples from drill-holes plot on the left and show the largest displacement from the KS line; these samples also have a relatively reduced δD range of values (−65 to −98%). However, if supergene processes take place in the presence of waters of meteoric origin at temperatures similar to typical surface temperatures, the clays thus formed should plot either in the vicinity of the KS line or be displaced towards lower δO18 and higher δD, depending on both the temperature and relative proportion of clay to water.