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.

A vibrational spectroscopic study of the mineral hinsdalite (Pb,Sr)Al3(PO4)(SO4)(OH)6

The objective of this research is to determine the molecular structure of the mineral hinsdalite using vibrational spectroscopy. The mineral hinsdalite (Pb,Sr)Al3(PO4,SO4)2(OH)6 is a hydroxy phosphate-sulphate mineral belonging to the beudantite subgroup of alunites. The mineral is interesting because it contains two oxyanions, phosphate and sulphate, which is unusual. The formation of hinsdalite offers a mechanism for the removal of phosphate from the environment. The mineral has been characterised by Raman spectroscopy and infrared spectroscopy. The spectra are then related to the molecular structure of the mineral. Bands at various wavenumbers are assigned to the different vibrational modes of hinsdalite, which were then associated to the molecular structure of the mineral. Bands were primarily assigned to phosphate and sulphate stretching and bending modes. The Raman spectrum is characterised by an intense sharp band at 982 cm-1 with a component band at 997 cm-1 assigned to the ν1 (PO4)3- symmetric stretching 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. Hinsdalite is characterised by disordered phosphate/sulphate tetrahedra and non-equivalent phosphate units are observed in the vibrational spectrum of hinsdalite.

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.

A Raman spectroscopic study of the mono-hydrogen phosphate mineral dorfmanite Na2(PO3OH)•2H2O – and in comparison with brushite

Aspects of the molecular structure of the mineral dorfmanite Na2(PO3OH)•2H2O were determined by Raman spectroscopy. The mineral originated from the Kedykverpakhk Mt., Lovozero, Kola Peninsula, Russia. Raman bands are assigned to the hydrogen phosphate units. The intense Raman band at 949 cm-1 and the less intense band at 866 cm-1 are assigned to the PO3 and POH stretching vibrations. Bands at 991, 1066 and 1141 cm-1 are assigned to the ν3 antisymmetric stretching modes. Raman bands at 393, 413 and 448 cm-1 and 514, 541 and 570 cm-1 are attributed to the ν2 and ν4 bending modes of the HPO4 units, respectively. Raman bands at 3373, 3443 and 3492 cm-1 are assigned to water stretching vibrations. POH stretching vibrations are identified by bands at 2904, 3080 and 3134 cm-1. Raman spectroscopy has proven very useful for the study of the structure of the mineral dorfmanite.

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.

Molecular structural studies of the amorphous mineral pitticite Fe, AsO4, SO4, H2O

Some minerals are colloidal and show no X-ray diffraction patterns. Vibrational spectroscopy offers one of the few methods for the assessment of the structure of these types of mineral. Among this group of minerals is pitticite simply described as Fe, AsO4, SO4, H2O. The objective of this research is to determine the molecular structure of the mineral pitticite using vibrational spectroscopy. Raman microscopy offers a useful method for the analysis of such colloidal minerals. Raman and infrared bands are attributed to the , and water stretching vibrations. The Raman spectrum is dominated by a very intense sharp band at 983 cm−1 assigned to the symmetric stretching mode. A strong Raman band at 1041 cm−1 is observed and is assigned to the antisymmetric stretching mode. Low intensity Raman bands at 757 and 808 cm−1 may be assigned to the antisymmetric and symmetric stretching modes. Raman bands observed at 432 and 465 cm−1 are attributable to the doubly degenerate ν2(SO4)2- bending mode.

Whelanite Ca5Cu2(OH)2CO3,Si6O17•4H2O – A vibrational spectroscopic study

Whelanite Ca5Cu2(OH)2CO3,Si6O17•4H2O is a hydrated hydroxy mixed anion compound with both silicate and carbonate anions in the formula. The structural characterisation of the mineral whelanite remains incomplete. Whelanite is probably a neosilicate with Cu2+ in square planar coordination. Two Raman bands at 1070 and 1094 cm-1 are assigned to the ν1 symmetric stretching modes of the CO32- units. The observation of two symmetric stretching modes supports the concept of two non-equivalent CO32- units in the whelanite structure. The intense sharp Raman band at 1006 cm-1 is assigned to the ν1 (A1g) symmetric stretching vibration of the Si6O17 units. The splitting of the ν3 vibrational mode offers support to the concept that the SiO4 tetrahedron in whelanite is strongly distorted. A very intense Raman band observed at 666 cm-1 with a shoulder at 697 cm-1 is assigned to the ν4 vibrational modes. Intense Raman bands at 3534, 3556, 3550 and 3595 cm-1 are assigned to the stretching vibrations of the OH units. Low intensity Raman bands at 2910, 3187 and 3453 cm-1 are assigned to water stretching modes. Thus, vibrational spectroscopy has been used to characterise the molecular structure of whelanite. Whelanite is a mineral that could be conceived as a healing mineral

Raman spectroscopic study of the mineral arsenogorceixite BaAl3AsO3(OH)(AsO4,PO4)(OH,F)6

Arsenogorceixite BaAl3AsO3(OH)(AsO4,PO4)(OH,F)6 belongs to the crandallite mineral subgroup of the alunite supergroup. Arsenogorceixite forms a continuous series of solid solutions with related minerals including gorceixite, goyazite, arsenogoyazite, plumbogummite and philipsbornite. Two minerals from (a) Germany and (b) from Ashburton Downs, Australia were analysed by Raman spectroscopy. The spectra show some commonality but the intensities of the peaks vary. Sharp intense Raman bands for the German sample, are observed at 972 and 814 cm−1 attributed to the ν1 PO43− and AsO43− symmetric stretching modes. Raman bands at 1014, 1057, 1148 and 1160 cm−1 are attributed to the ν1 PO2 symmetric stretching mode and ν3 PO43− antisymmetric stretching vibrations. Raman bands at 764 and 776 cm−1 and 758 and 756 cm−1 are assigned to the ν3 AsO43− antisymmetric stretching vibrations. For the Australian mineral, the ν1 PO43− band is found at 973 cm−1. The intensity of the arsenate bands observed at 814, 838 and 870 cm−1 is greatly enhanced. Two low intensity Raman bands at 1307 and 1332 cm−1 are assigned to hydroxyl deformation modes. The intense Raman band at 441 cm−1 with a shoulder at 462 cm−1 is assigned to the ν2 PO43− bending mode. Raman bands at 318 and 340 cm−1 are attributed to the (AsO4)3−ν2 bending. The broad band centred at 3301 cm−1 is assigned to water stretching vibrations and the sharper peak at 3473 cm−1 is assigned to the OH stretching vibrations. The observation of strong water stretching vibrations brings into question the actual formula of arsenogorceixite. It is proposed the formula is better written as BaAl3AsO3(OH)(AsO4,PO4)(OH,F)6·xH2O. The observation of both phosphate and arsenate bands provides a clear example of solid solution formation.

Is the mineral borickyite (Ca,Mg)(Fe3+,Al)4(PO4,SO4,CO3)(OH)8•3-7.5H2O the same as delvauxite CaFe3+4(PO4,SO4)2(OH)8•4-6H2O?

The two minerals borickyite and delvauxite CaFe3+4(PO4,SO4)2(OH)8•4-6H2O have the same formula. Are the minerals identical or different? The minerals borickyite and delvauxite have been characterised by Raman spectroscopy. The minerals are related to the minerals diadochite and destinezite. Both minerals are amorphous. Delvauxite appears to vary in crystallinity from amorphous to semi-crystalline. The minerals are often X-ray non-diffracting. The minerals are found in soils and may be described as ‘colloidal’ minerals. Vibrational spectroscopy enables an assessment of the molecular structure of borickyite and delvauxite. Bands are assigned to phosphate and sulphate stretching and bending modes. Multiple water bending and stretching modes imply that non-equivalent water molecules in the structure exist with different hydrogen bond strengths. The two minerals show differing spectra and must be considered as different minerals.

Vibrational spectroscopic study of multianion mineral clinotyrolite Ca2Cu9[(As,S)O4]4(OH)10•10(H2O)

The molecular structure of the mixed anion mineral Clinotyrolite Ca2Cu9[(As,S)O4]4(OH)10•10(H2O) has been determined by the combination of Raman and infrared spectroscopy. Characteristic bands associated with arsenate, sulphate and hydroxyl units are identified. Broad bands in the OH stretching region are observed and are resolved into component bands. Estimates of hydrogen bond distances were made using a Libowitzky function and both short and long hydrogen bonds are identified. Two intense Raman bands at 842 and ~796 cm-1 are assigned to the ν1 (AsO4)3- symmetric stretching and ν3 (AsO4)3- antisymmetric stretching modes. The comparatively sharp Raman band at 980 cm-1 is assigned to the ν1 (SO4)2- symmetric stretching mode and a broad Raman spectral profile centred upon 1100 cm-1 is attributed to the ν3 (SO4)2- antisymmetric stretching mode.

Molecular structure of the mineral svanbergite SrAl3(PO 4,SO4)2(OH)6 - A vibrational spectroscopic study

The mineral svanbergite SrAl 3(PO 4,SO 4) 2(OH) 6 is a hydroxy phosphate-sulphate mineral belonging to the beudantite subgroup of alunites and has been characterised by vibrational spectroscopy. Bands at various wavenumbers were assigned to the different vibrational modes of svanbergite, which were then associated with the 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. Comparison of the hydrogen bond distances and the calculated hydrogen bond distances from the structure models indicates that hydrogen bonding in svanbergite occurs between the two OH units rather than OH to SO42- units.

Vibrational spectroscopy of the multianion mineral kemmlitzite (Sr,Ce)Al3(AsO4)(SO4)(OH)6

Some minerals are colloidal and show no X-ray diffraction patterns. Vibrational spectroscopy offers one of the few methods for the assessment of the structure of these types of mineral. Among this group of minerals is kemmlitzite (Sr,Ce)Al3(AsO4)(SO4)(OH)6. The objective of this research is to determine the molecular structure of the mineral kemmlitzite using vibrational spectroscopy. Raman microscopy offers a useful method for the analysis of such colloidal minerals. Raman and infrared bands are attributed to the AsO43- , SO42- and water stretching vibrations. The Raman spectrum is dominated by a very intense sharp band at 984 cm-1 assigned to the SO42- symmetric stretching mode. Raman bands at 690, 772 and 825 cm-1 may be assigned to the AsO43- antisymmetric and symmetric stretching modes. Raman bands observed at 432 and 465 cm-1 are attributable to the doubly degenerate 2 (SO4)2- bending mode. Vibrational spectroscopy is important in the assessment of the molecular structure of the kemmlitzite, especially when the mineral is non-diffracting or poorly diffracting.

The borate mineral jeremejevite Al6(BO3)5(F,OH)3 – A vibrational spectroscopic study

Jeremejevite is a borate mineral of aluminium and is of variable colour, making the mineral and important inexpensive jewel. The mineral contains variable amounts of F and OH, depending on origin. A comparison of the vibrational spectroscopic data is made with the published data of borate minerals. Raman spectra were averaged over a range of crystal orientations. Two intense Raman bands observed at 961 and 1067 cm−1 are assigned to the symmetric stretching and antisymmetric stretching modes of trigonal boron. Infrared spectrum, bands observed at 1229, 1304, 1350, 1388 and 1448 cm−1 are attributed to BOH in-plane bending modes. Intense Raman band found at 372 cm−1 with other bands of significant intensity at 327 and 417 cm−1 is assigned to trigonal borate bending modes. A quite intense Raman band is found at 3673 cm−1 with other sharp Raman bands found at 3521, 3625 and 3703 cm−1 are assigned to the stretching modes of OH. Raman and infrared spectroscopy has been used to assess the molecular structure of the mineral jeremejevite. Such research is important in the study of borate based nanomaterials.