Loc V. Duong

Infrared spectroscopy of goethite dehydroxylation: III. FT-IR microscopy of in situ study of the thermal transformation of goethite to hematite

Fourier transform infrared microscopy has been used to investigate in situ dehydroxylation of goethite to form hematite. The characterisation was based on the behaviour of hydroxyl units, which were observed in the hydroxyl stretching and hydroxyl deformation and water bending regions, and the Fe-O vibrations of the newly formed hematite during the thermal dehydroxylation process. Two hydroxyl stretching modes (v1 and v2), and three bending (V(bending-1, 2, 3)) and two deformation (V(deformation-1, 2)) modes were observed for goethite. The characteristic vibration at 916 cm(-1) was observed together with the residuals of the v1 and v2 bands in hematite spectrum. The structural transformation between goethite and hematite through thermal dehydroxylation was interpreted in order to provide criteria that can be used for the characterisation of thermally activated bauxite and their conversion to activated alumina phases.

Infrared spectroscopy of goethite dehydroxylation. II. Effect of aluminium substitution on the behaviour of hydroxyl units

Dehydroxylation of goethite as affected by aluminium substitution was investigated using Fourier transform infrared spectroscopy (FT-IR) in conjunction with X-ray diffraction (XRD), thermogravimetric analysis (TGA) and differential thermogravimetric analysis (DTGA). The band intensities of hydroxyl vibrations were indicative of the degree of dehydroxylation and the changes in band parameters due to aluminium substitution were observed. The effect of aluminium substitution on band parameters of FT-IR spectra of goethite and its partially and fully dehydroxylated products, the mixture of goethite/hematite and hematite, were interpreted. The results of this study have confirmed that aluminium substituted goethite is thermally more stable than non-substituted goethite and is in harmony with the results of XRD and DTGA. A larger amount of non-stoichiometric hydroxyl units is associated with a higher aluminium substitution. A shift to a higher wavenumber of bending and hydroxyl stretching vibrations is attributed to the effects of aluminium substitution associated with non-stoichiometric hydroxyl units on the a-b plane relative to the b-c plane of goethite. The results provide information for the characterisation of activated bauxite containing hematite and goethite.

Far-infrared spectroscopy of alumina phases

Far-infrared spectroscopy (FIR) has been used to distinguish alumina phases boehmite, diaspore, gibbsite and bayerite. The pellets of samples were prepared by mixing alumina phases with polyethylene at a ratio of 1:50, and the spectra were recorded between 50 and 400 cm(-1). The spectrum of boehmite resembles that of diaspore in the 300-400 cm(-1) region. Boehmite has two characteristic FIR bands at 366 and 323 cm(-1), while diaspore has five at 354, 331, 250, 199 and 158 cm(-1). The spectrum of gibbsite resembles that of bayerite in the 230-300 cm(-1) region. Gibbsite shows three characteristic FIR bands at 371, 279 and 246 cm(-1), whereas bayerite shows six at 383, 345, 326, 296, 252 and 62 cm(-1). The overlapping bands were resolved, and the spectra were manipulated appropriately using band analysis techniques. The FIR spectra are in harmony with the FT-Raman spectra. Far-infrared spectroscopy allows the study and differentiation of the stretching of AlO4 units to characterize these four alumina phases. Far-IR spectroscopy complements the mid-IR and near-IR for distinguishing alumina phases in bauxites.

Molecular assembly in secondary minerals: Raman spectroscopy of the arthurite group species arthurite and whitmoreite

Two members of the arthurite mineral group, arthurite and whitmoreite A(Fe3+) 2 (XO 4 ) 2 (O,OH) 2 .4(H 2 O) where A = Cu(II), Zn(II), Pb(II) or Fe(II) and X = As, P, S have been studied using Raman spectroscopy. The minerals are based upon the combination of a divalent cation such as Cu(II), Zn(II), Pb(II) or Fe(II) and the trivalent cation, Fe(III), with counterbalancing of hydroxyl, arsenate, phosphate and sulphate anions. Such minerals lend themselves to analysis by Raman spectroscopy. For arthurite Cu(Fe 3 + ) 2 (AsO 4 ,PO 4 ,SO 4 ) 2 (O,OH) 2 .4(H 2 O), arsenate and hydroxyl anions are observed as well as minor phosphate and significant carbonate anions. For whitmoreite FeFe 2 (PO 4 ) 2 (OH) 2 .4(H 2 O), hydroxyls and phosphate are the major anions with significant sulphate and some carbonate. Raman spectroscopic analysis of two whitmoreite samples from the same mineral field suggests that differentiation by concentration of the anions occurs in the molecular assembly of the anions as crystallisation occurs as a function of the equilibrium conditions. Changing solution conditions are reflected in the varying compositions in the lattice.

Raman spectroscopic and SEM study of cinnabar from Herod’s palace and its likely origin

Mineral samples of cinnabar were obtained from the ancient mining sites of Tarna and Almaden in Spain and from Hunan province in China. A comparison is made using a combination of scanning electron microscopy and Raman spectroscopy with the cinnabar coated on the wall of Herods palace. Scanning electron microscopy shows that the cinnabar samples from Spain were impure, whereas the sample from the wall of Herods palace was highly pure. No conclusion can be drawn as to the likely origin of the Herods palace cinnabar and the mineral is just as likely to have originated in Tuscany or China as Spain.

Identification of mixite minerals – an SEM and Raman spectroscopic analysis

Abstract Two mixites from Boss Tweed Mine, Tintic District, Juab County, Utah and Tin Stope, Majuba Hill, Pershing County, Nevada, USA, were analysed by scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis and by Raman spectroscopy. The SEM images show the mixite crystals to be elongated fibres up to 200 μm long and 2 μm wide. Detailed images of the mixite crystals show the mineral to be composed of bundles of fibres. The EDX analyses depend on the crystal studied, though the Majuba mixite gave analyses which matched the formula BiCu6(AsO4)3(OH)6·3H2O. Raman bands observed in the 880-910 cm-1 and 867-870 cm-1 regions are assigned to the AsO-stretching vibrations of (HAsO4)2- and (H2AsO4)- units, whilst bands at 803 and 833 cm-1 are assigned to the stretching vibrations of uncomplexed (AsO4)3- units. Intense bands observed at 473.7 and 475.4 cm-1 are assigned to the ν4 bending mode of AsO4 units. Bands observed at 386.5, 395.3 and 423.1 cm-1 are assigned to the ν2 bending modes of the HAsO4 (434 and 400 cm-1) and the AsO4 groups (324 cm-1). Raman spectroscopy lends itself to the identification of minerals on host matrices and is especially useful for the identification of mixites.

Electron microscopy study of biosorbents from marine macro alga Durvillaea potatorum

Biosorbents derived from the biomass of marine algae have shown to have high uptake capacities for heavy metals and the internal structure has been generally assumed to be pseudo-homogenous. In this paper, the microstructures of biosorbents derived from Australian marine alga Durvillaea poratorum were analysed using scanning electron microscopy. The structural components of the biosorbent resembled fiber-like cylinders. The internal structure was a highly connected network of cylinders with varying sizes. Methods of drying and pre-treatment of the biomass also affected the details of the internal structure. Calcium chloride followed by thermal treatment provided the most uniform cylinder networks for the biosorbents. Heavy metal Cu2+ and Cd2+ binding in the biomass was confirmed by using an electron probe microanalyser.

Raman microscopy of the molybdate minerals koechlinite, iriginite and lindgrenite

A series of molybdate bearing minerals including wulfenite, powellite, lindgrenite and iriginite have been analysed by Raman microscopy. These minerals are closely related and often have related paragenesis. Raman microscopy enables the selection of individual crystals of these minerals for spectroscopic analysis even though several of the minerals can be found in the same matrix because of the paragenetic relationships between the minerals. The molybdenum bearing minerals lindgrenite, iriginite and koechlinite were studied by scanning electron microscopy and compositionally analysed by EDX methods using an electron probe before Raman spectroscopic analyses. The Raman spectra are assigned according to factor group analysis and related to the structure of the minerals. These minerals have characteristically different Raman spectra.

Synthesis and characterization of K2Ca5(SO4)6· H2O, the equivalent of görgeyite, a rare evaporite mineral

Abstract Görgeyite, K2Ca5(SO4)6·H2O, is a very rare monoclinic double salt found in evaporites related to the slightly more common mineral syngenite. At 1 atmosphere with increasing external temperature from 25 to 150 °C, the following succession of minerals was formed: first gypsum and K2O, followed at 100 °C by görgeyite. Changes in concentration at 150 °C due to evaporation resulted in the formation of syngenite and finally arcanite. Under hydrothermal conditions, the succession is syngenite at 50 °C, followed by görgyeite at 100 and 150 °C. Increasing the synthesis time at 100 °C and 1 atmosphere showed that initially gypsum was formed, later being replaced by görgeyite. Finally görgeyite was replaced by syngenite, indicating that görgeyite is a metastable phase under these conditions. Under hydrothermal conditions, syngenite plus a small amount of gypsum was formed, after two days being replaced by görgeyite. No further changes were observed with increasing time. Pure görgeyite showed elongated crystals approximately 500 to 1000 μm in length. The infrared and Raman spectra are mainly showing the vibrational modes of the sulfate groups and the crystal water (structural water). Water is characterized by OH-stretching modes at 3526 and 3577 cm-1, OH-bending modes at 1615 and 1647 cm-1, and an OH-libration mode at 876 cm-1. The sulfate ν1 mode is weak in the infrared but showed strong bands at 1005 and 1013 cm-1 in the Raman spectrum. The ν2 mode also showed strong bands in the Raman spectrum at 433, 440, 457, and 480 cm-1. The ν3 mode is characterized by a complex set of bands in both infrared and Raman spectra around 1150 cm-1, whereas ν4 is found at 650 cm-1.

Nondestructive identification of arsenic and cobalt minerals from Cobalt City, Ontario, Canada: arsenolite, erythrite and spherocobaltite on pararammelsbergite

A Ni-Co-As ore sample from Cobalt City, Ontario, Canada, was examined with scanning electron microscopy and energy dispersive X-ray analysis. In addition to cobaltian pararammelsbergite with variable cobalt content, for which Cobalt City is the type locality, and erythrite, one new mineral was observed for this locality. Well-formed crystals of arsenolite, As2O3, were found embedded in what appears to be fibrous spherocobaltite, CoCO3. Additional information was obtained by Raman microscopy, confirming the identification of the arsenolite. Both are considered to be secondary minerals formed by exposure to air resulting in oxidation and the formation of secondary carbonates.