A vibrational spectroscopic study of hydrated Fe3+ hydroxyl-sulphates; polymorphic minerals butlerite and parabutlerite

Raman and infrared spectra of two polymorphous minerals with the chemical formula Fe3+(SO4)(OH)•2H2O, monoclinic butlerite and orthorhombic parabutlerite, are studied and the spectra assigned. Observed bands are attributed to the (SO4)2- stretching and bending vibrations, hydrogen bonded water molecules, stretching and bending vibrations of hydroxyl ions, water librational modes, Fe-O and Fe-OH stretching vibrations, Fe-OH bending vibrations and lattice vibrations. The O-H...O hydrogen bond lengths in the structures of both minerals are calculated from the wavenumbers of the stretching vibrations. One symmetrically distinct (SO4)2- unit in the structure of butlerite and two symmetrically distinct (SO4)2- units in the structure of parabutlerite are inferred from the Raman and infrared spectra. This conclusion agrees with the published crystal structures of both mineral phases.

A vibrational spectroscopic study of the mixed anion mineral sanjuanite Al2(PO4)(SO4)(OH)•9H2O

The mineral sanjuanite Al2(PO4)(SO4)(OH)•9H2O has been characterised by Raman spectroscopy complimented by infrared spectroscopy. The mineral is characterised by an intense Raman band at 984 cm-1, assigned to the (PO4)3- ν1 symmetric stretching mode. A shoulder band at 1037 cm-1 is attributed to the (SO4)2- ν1 symmetric stretching mode. Two Raman bands observed at 1102 and 1148 cm-1 are assigned to (PO4)3- and (SO4)2- ν3 antisymmetric stretching modes. Multiple bands provide evidence for the reduction in symmetry of both anions. This concept is supported by the multiple sulphate and phosphate bending modes. Raman spectroscopy shows that there are more than one non-equivalent water molecules in the sanjuanite structure. There is evidence that structural disorder exists, shown by the complex set of overlapping bands in the Raman and infrared spectra. At least two types of water are identified with different hydrogen bond strengths. The involvement of water in the sanjuanite structure is essential for the mineral stability.

Raman spectroscopic study of the minerals diadochite and destinezite Fe3+2(PO4,SO4)2(OH)•6H2O – implications for soil science

The two minerals diadochite and destinezite of formula Fe2(PO4,SO4)2(OH)•6H2O have been characterised by Raman spectroscopy and complimented with infrared spectroscopy. These two minerals are both found in soils and are identical except for their morphology. Diadochite is amorphous whereas destinezite is highly crystalline. The spectra of diadochite are broad and ill-defined, whereas the spectra of destinezite are intense and well defined. Bands are assigned to phosphate and sulphate stretching and bending modes. Two symmetric stretching modes for both the phosphate and sulphate symmetric stretching modes support the concept of non-equivalent phosphate and sulphate units in the mineral structure. Multiple water bending and stretching modes imply that non-equivalent water molecules in the structure exist with different hydrogen bond strengths.

A Raman spectroscopic study of bukovskýite Fe2(AsO4)(SO4)(OH)•7H2O-a mineral phase with a significant role in arsenic migration

The Raman spectrum of bukovskýite, Fe3+2(OH)(SO4)(AsO4)•7H2O has been studied and compared with the Raman spectrum of an amorphous gel containing specifically Fe, As and S elements and is understood as an intermediate product in the formation of bukovskýite. Observed bands are assigned to the stretching and bending vibrations of (SO4)2- and (AsO4)3- units, stretching and bending vibrations and librational modes of hydrogen bonded water molecules, stretching and bending vibrations of hydrogen bonded (OH)- ions and Fe3+-(O,OH) units. Approximate range of O-H...O hydrogen bond lengths is inferred from the Raman spectra. Raman spectra of crystalline bukovskýite and of the amorphous gel differ in that the bukovskýite spectrum is more complex, observed bands are sharp, the degenerate bands of (SO4)2- and (AsO4)3- are split and more intense. Lower wavenumbers of  H2O bending vibration in the spectrum of the amorphous gel may indicate the presence of weaker hydrogen bonds compared with those in bukovskýite.

Are the ‘cave’ minerals archerite (K,NH4)H2PO4 and biphosphammite (K,NH4)H2PO4 identical? A molecular structural study

The molecular structure of the mineral archerite ((K,NH4)H2PO4) has been determined and compared with that of biphosphammite ((NH4,K)H2PO4). Raman spectroscopy and infrared spectroscopy has been used to characterise these ‘cave’ minerals. Both minerals originated from the Murra-el-elevyn Cave, Eucla, Western Australia. The mineral is formed by the reaction of the chemicals in bat guano with calcite substrates. Raman and infrared bands are assigned to H2PO4-, OH and NH stretching vibrations. The Raman band at 981 cm-1 is assigned to the HOP stretching vibration. Bands in the 1200 to 1800 cm-1 region are associated with NH4+ bending modes. The molecular structure of the two minerals appear to be very similar, and it is therefore concluded that the two minerals are identical.

Molecular Structure of the mineral woodhouseite CaAl3(PO4,SO4)2(OH)6

The mineral woodhouseite CaAl3(PO4,SO4)2(OH)6 is a hydroxy phosphate-sulphate mineral belonging to the beudantite subgroup of alunites, and has been characterised by Raman spectroscopy, complimented with infrared spectroscopy. Bands at various wavenumbers were assigned to the different vibrational modes of woodhouseite, which were then associated to the molecular structure of the mineral. Bands were primarily assigned to phosphate and sulphate stretching and bending modes. Two symmetric stretching modes for both phosphate and sulphate supported the concept of non-equivalent phosphate and sulphate units in the mineral structure. Bands in the OH stretching region enabled hydrogen bond distances to be calculated.

Raman spectroscopic study of the magnesium carbonate mineral– hydromagnesite Mg5[(CO3)4(OH)2]•4H2O

Magnesium minerals are important for the understanding of the concept of geosequestration. One method of studying the hydrated hydroxy magnesium carbonate minerals is through vibrational spectroscopy. A combination of Raman and infrared spectroscopy has been used to study the mineral hydromagnesite. An intense band is observed at 1121 cm-1 attributed CO32- ν1 symmetric stretching mode. A series of infrared bands at 1387, 1413, 1474 cm-1 are assigned to the CO32- ν3 antisymmetric stretching modes. The CO32- ν3 antisymmetric stretching vibrations are extremely weak in the Raman spectrum and are observed at 1404, 1451, 1490 and 1520 cm-1. A series of Raman bands at 708, 716, 728, 758 cm-1 are assigned to the CO32- ν2 in-plane bending mode. The Raman spectrum in the OH stretching region is characterised by bands at 3416, 3516 and 3447 cm-1. In the infrared spectrum a broad band is found at 2940 cm-1 assigned to water stretching vibrations. Infrared bands at 3430, 3446, 3511, 2648 and 3685 cm-1 are attributed to MgOH stretching modes.

A Raman spectroscopic study of the different vanadate-groups in solid-state compounds, model case : mineral phases vésigniéite, BaCu3(VO4)2(OH)2, and volborthite, Cu3V2O7(OH)2•2H2O

Raman spectroscopy has been used to study vanadates in the solid state. The molecular structure of the vanadate minerals vésigniéite [BaCu3(VO4)2(OH)2] and volborthite [Cu3V2O7(OH)2·2H2O] have been studied by Raman spectroscopy and infrared spectroscopy. The spectra are related to the structure of the two minerals. The Raman spectrum of vésigniéite is characterized by two intense bands at 821 and 856 cm−1 assigned to ν1 (VO4)3− symmetric stretching modes. A series of infrared bands at 755, 787 and 899 cm−1 are assigned to the ν3 (VO4)3− antisymmetric stretching vibrational mode. Raman bands at 307 and 332 cm−1 and at 466 and 511 cm−1 are assigned to the ν2 and ν4 (VO4)3− bending modes. The Raman spectrum of volborthite is characterized by the strong band at 888 cm−1, assigned to the ν1 (VO3) symmetric stretching vibrations. Raman bands at 858 and 749 cm−1 are assigned to the ν3 (VO3) antisymmetric stretching vibrations; those at 814 cm−1 to the ν3 (VOV) antisymmetric vibrations; that at 508 cm−1 to the ν1 (VOV) symmetric stretching vibration and those at 442 and 476 cm−1 and 347 and 308 cm−1 to the ν4 (VO3) and ν2 (VO3) bending vibrations, respectively. The spectra of vésigniéite and volborthite are similar, especially in the region of skeletal vibrations, even though their crystal structures differ.

The structure of the mineral leogangite Cu10(OH)6(SO4)(AsO4)4•8H2O–implications for arsenic accumulation and removal

The objective of this research is to determine the molecular structure of the mineral leogangite. The formation of the types of arsenosulphate minerals offers a mechanism for arsenate removal from soils and mine dumps. Raman and infrared spectroscopy have been used to characterise the mineral. Observed bands are assigned to the stretching and bending vibrations of (SO4)2- and (AsO4)3- units, stretching and bending vibrations of hydrogen bonded (OH)- ions and Cu2+-(O,OH) units. The approximate range of O-H...O hydrogen bond lengths is inferred from the Raman spectra. Raman spectra of leogangite from different origins differ in that some spectra are more complex, where bands are sharp and the degenerate bands of (SO4)2- and (AsO4)3- are split and more intense. Lower wavenumbers of  H2O bending vibration in the spectrum may indicate the presence of weaker hydrogen bonds compared with those in a different leogangite samples. The formation of leogangite offers a mechanism for the removal of arsenic from the environment.

The mixed anion mineral parnauite Cu9[(OH)10|SO4|(AsO4)2]•7H2O – a Raman spectroscopic study

The mixed anion mineral parnauite Cu9[(OH)10|SO4|(AsO4)2].7H2O from two localities namely Cap Garonne Mine, Le Pradet, France and Majuba Hill mine, Pershing County, Nevada, USA has been studied by Raman spectroscopy. The Raman spectrum of the French sample is dominated by an intense band at 975 cm-1 assigned to the ν1 (SO4)2- symmetric stretching mode and Raman bands at 1077 and 1097 cm-1 may be attributed to the ν3 (SO4)2- antisymmetric stretching mode. Two Raman bands 1107 and 1126 cm-1 are assigned to carbonate CO32- symmetric stretching bands and confirms the presence of carbonate in the structure of parnauite. The comparatively sharp band for the Pershing County mineral at 976 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode and a broad spectral profile centered upon 1097 cm-1 is attributed to the ν3 (SO4)2- antisymmetric stretching mode. Two intense bands for the Pershing County mineral at 851 and 810 cm-1 are assigned to the ν1 (AsO4)3- symmetric stretching and ν3 (AsO4)3- antisymmetric stretching modes. Two Raman bands for the French mineral observed at 725 and 777 cm-1 are attributed to the ν3 (AsO4)3- antisymmetric stretching mode. For the French mineral, a low intensity Raman band is observed at 869 cm-1 and is assigned to the ν1 (AsO4)3- symmetric stretching vibration. Chemical composition of parnauite remains open and the question may be raised is parnauite a solid solution of two or more minerals such as a copper hydroxy-arsenate and a copper hydroxy sulphate.

The molecular structure of the mineral sarmientite Fe2(AsO4,SO4)2(OH)6•5H2O : implications for arsenic accumulation and removal

Sarmientite is an environmental mineral; its formation in soils enables the entrapment and immobilisation of arsenic. The mineral sarmientite is often amorphous making the application of X-ray diffraction difficult. Vibrational spectroscopy has been applied to the study of sarmientite. Bands are attributed to the vibrational units of arsenate, sulphate, hydroxyl and water. Raman bands at 794, 814 and 831 cm−1 are assigned to the ν3 (AsO4)3− antisymmetric stretching modes and the ν1 symmetric stretching mode is observed at 891 cm−1. Raman bands at 1003 and 1106 cm−1 are attributed to vibrations. The Raman band at 484 cm−1 is assigned to the triply degenerate (AsO4)3− bending vibration. The high intensity Raman band observed at 355 cm−1 (both lower and upper) is considered to be due to the (AsO4)3−ν2 bending vibration. Bands attributed to water and OH stretching vibrations are observed.

Infrared transmission and emission spectroscopic study of selected Chinese palygorskites

Infrared and infrared emission spectroscopy were used to analyze the difference in structure and thermal behavior of two Chinese palygorskites. The position of the main bands identified in the infrared spectra of the palygorskites studied is similar for these two Chinese samples, but there are some differences in their intensity, which is significant. This discrepancy is attributed to various geological environments in different regions and the existence of impurities. The infrared emission spectra clearly show the structural changes and dehydroxylation of the palygorskites when the temperature is raised. The dehydration of the palygorskites is followed by the loss of intensity of the OH stretching vibration bands in the region 3600-3200 cm-1. Dehydroxylation is followed by the decrease in intensity in the bands between 3700 and 3550 cm-1. Dehydration of pure palygorskite was completed by 600 °C. Partial loss of coordinated water was observed at 400 °C. Infrared emission spectroscopy is an effective method to determine the stability of the mineral.