Vibrational spectroscopy of the sulphate mineral sturmanite from Kuruman manganese deposits, South Africa

The mineral sturmanite is a hydrated calcium iron aluminium manganese sulphate tetrahydroxoborate hydroxide of formula Ca6(Fe, Al, Mn)2(SO4)2(B(OH)4)(OH)12•26H2O. We have studied the mineral sturmanite using a number of techniques, including SEM with EPMA and vibrational spectroscopy. Chemical analysis shows a homogeneous phase, composed by Ca, Fe, Mn, S, Al and Si. B is not determined in this EPMA technique. An intense Raman band at 990 cm−1 is assigned to the SO42− symmetric stretching mode. Raman spectroscopy identifies multiple sulphate symmetric stretching modes in line with the three sulphate crystallographically different sites. Raman spectroscopy also identifies a band at 1069 cm−1 which may be attributed to a carbonate symmetric stretching mode, indicating the presence of thaumasite. Infrared spectra display two bands at 1080 and 1107 cm−1 assigned to the SO42− antisymmetric stretching modes. The observation of multiple bands in this ν4 spectral region offers evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 3622 cm−1 is assigned to the OH unit stretching vibration and the broad feature at around 3479 cm−1 to water stretching bands. Infrared spectroscopy shows a set of broad overlapping bands in the OH stretching region. Vibrational spectroscopy enables an assessment of the molecular structure of sturmanite to be made.

A vibrational spectroscopic study of the phosphate mineral rimkorolgite (Mg,Mn2+)5(Ba, Sr)(PO4)4·8H2O from Kovdor massif, Kola Peninsula, Russia

We have studied aspect of the molecular structure of the phosphate mineral rimkorolgite from Zheleznyi iron mine, Kovdor massif, Kola Peninsula, Russia, using SEM with EDX and vibrational spectroscopy. Qualitative chemical analysis shows a homogeneous phase, composed by P, Mg, Ba, Mn and Ca. Small amounts of Si were also observed. An intense Raman peak at 975 cm−1 is assigned to the PO43− ν1 symmetric stretching mode. The Raman band at 964 cm−1 is attributed to the HPO42− ν1 symmetric stretching vibration. Raman bands observed at 1016, 1035, 1052, 1073, 1105 and 1135 cm−1 are attributed to the ν3 antisymmetric stretching vibrations of the HPO42− and PO43− units. Complexity in the spectra of the phosphate bending region is observed. The broad Raman band at 3272 cm−1 is assigned to the water stretching vibration. Vibrational spectroscopy enables aspects on the molecular structure of rimkorolgite to be undertaken.

A vibrational spectroscopic study of the silicate mineral analcime – Na2(Al4SiO4O12)·2H2O : a natural zeolite

We have studied the mineral analcime using a combination of scanning electron microscopy with energy dispersive spectroscopy and vibrational spectroscopy. The mineral analcime Na2(Al4SiO4O12)·2H2O is a crystalline sodium silicate. Chemical analysis shows the mineral contains a range of elements including Na, Al, Fe2+ and Si. The mineral is characterized by intense Raman bands observed at 1052, 1096 and 1125 cm−1. The infrared bands are broad; nevertheless bands may be resolved at 1006 and 1119 cm−1. These bands are assigned to SiO stretching vibrational modes. Intense Raman band at 484 cm−1 is attributed to OSiO bending modes. Raman bands observed at 2501, 3542, 3558 and 3600 cm−1 are assigned to the stretching vibrations of water. Low intensity infrared bands are noted at 3373, 3529 and 3608 cm−1. The observation of multiple water bands indicate that water is involved in the structure of analcime with differing hydrogen bond strengths. This concept is supported by the number of bands in the water bending region. Vibrational spectroscopy assists with the characterization of the mineral analcime.

A vibrational spectroscopic study of the borate mineral takedaite Ca3(BO3)2

We have studied the mineral takedaite Ca3(BO3)2, a borate mineral of calcium using SEM with EDX and vibrational spectroscopy. Chemical analysis shows a homogeneous phase, composed of Ca. Boron was not detected. A very intense Raman band at 1087 cm−1 is assigned to the BO stretching vibration of BO3 units. Additional Raman bands may be due to isotopic splitting. In the infrared spectrum, bands at 1218 cm−1 and at 1163, 1262 and 1295 cm−1 are assigned to the trigonal borate stretching modes. Raman bands at 712 and 715 cm−1 are assigned to the in-plane bending modes of the BO3 units. Vibrational spectroscopy enables aspects of the molecular structure of takedaite to be assessed.

A vibrational spectroscopic study of the silicate mineral pectolite – NaCa2Si3O8(OH)

The mineral pectolite NaCa2Si3O8(OH) is a crystalline sodium calcium silicate which has the potential to be used in plaster boards and in other industrial applications. Raman bands at 974 and 1026 cm−1 are assigned to the SiO stretching vibrations of linked units of Si3O8 units. Raman bands at 974 and 998 cm−1 serve to identify Si3O8 units. The broad Raman band at around 936 cm−1 is attributed to hydroxyl deformation modes. Intense Raman band at 653 cm−1 is assigned to OSiO bending vibration. Intense Raman bands in the 2700–3000 cm−1 spectral range are assigned to OH stretching vibrations of the OH units in pectolite. Infrared spectra are in harmony with the Raman spectra. Raman spectroscopy with complimentary infrared spectroscopy enables the characterisation of the silicate mineral pectolite.

A vibrational spectroscopic study of the silicate mineral lomonosovite Na5Ti2(Si2O7)(PO4)O2

The mineral lomonosovite has been studied using a combination of scanning electron microscopy with energy dispersive X-ray analysis and vibrational spectroscopy. Qualitative chemical analysis gave Si, P, Na and Ti as the as major elements with small amounts of Mn, Ca, Fe and Al. The mineral lomonosovite has a formula Na5Ti2(Si2O7)(PO4)O2. Raman bands observed at 909, 925 and 939 cm−1 are associated with phosphate units. Raman bands found at 975, 999, 1070, 1080 and 1084 cm−1 are attributed to siloxane stretching vibrations. The observation of multiple bands in both the phosphate stretching and bending regions supports the concept that the symmetry of the phosphate anion in the structure of lomonosovite is significantly reduced. Infrared spectroscopy identifies bands in the water stretching and bending regions, thus suggesting that water is involved with the structure of lomonosovite either through adsorption on the surface or by bonding to the phosphate units.

The molecular structure of the phosphate mineral kidwellite NaFe93+(PO4)6(OH)11⋅3H2O – a vibrational spectroscopic study

The mineral kidwellite, a hydrated hydroxy phosphate of ferric iron and sodium of approximate formula NaFe93+(PO4)6(OH)11⋅3H2O, has been studied using a combination of electron microscopy with EDX and vibrational spectroscopic techniques. Raman spectroscopy identifies an intense band at 978 cm−1 and 1014 cm−1. These bands are attributed to the PO43− ν1 symmetric stretching mode. The ν3 antisymmetric stretching modes are observed by a large number of Raman bands. The series of Raman bands at 1034, 1050, 1063, 1082, 1129, 1144 and 1188 cm−1 are attributed to the ν3 antisymmetric stretching bands of the PO43− and HOPO32− units. The observation of these multiple Raman bands in the symmetric and antisymmetric stretching region gives credence to the concept that both phosphate and hydrogen phosphate units exist in the structure of kidwellite. The series of Raman bands at 557, 570, 588, 602, 631, 644 and 653 cm−1are assigned to the PO43− ν2 bending modes. The series of Raman bands at 405, 444, 453, 467, 490 and 500 cm−1 are attributed to the PO43− and HOPO32− ν4 bending modes. The spectrum is quite broad but Raman bands may be resolved at 3122, 3231, 3356, 3466 and 3580 cm−1. These bands are assigned to water stretching vibrational modes. The number and position of these bands suggests that water is in different molecular environments with differing hydrogen bond distances. Infrared bands at 3511 and 3359 cm−1 are ascribed to the OH stretching vibration of the OH units. Very broad bands at 3022 and 3299 cm−1 are attributed to the OH stretching vibrations of water. Vibrational spectroscopy offers insights into the molecular structure of the phosphate mineral kidwellite.

Vibrational spectroscopic characterization of the sulphate–halide mineral sulphohalite – implications for evaporites

The mineral sulphohalite – Na6(SO4)2FCl is a rare sodium halogen sulphate and occurs associated with evaporitic deposits. Sulphohalite formation is important in saline evaporites and in pipe scales. Sulphohalite is an anhydrous sulphate–halide with an apparent variable anion ratio of formula Na6(SO4)2FCl. Such a formula with oxyanions lends itself to vibrational spectroscopy. The Raman band at 1003 cm−1 is assigned to the (SO4)2− ν1 symmetric stretching mode. Shoulders to this band are found at 997 and 1010 cm−1. The low intensity Raman bands at 1128, 1120 and even 1132 cm−1 are attributed to the (SO4)2− ν3 antisymmetric stretching vibrations. Two symmetric sulphate stretching modes are observed indicating at least at the molecular level the non-equivalence of the sulphate ions in the sulphohalite structure. The Raman bands at 635 and 624 cm−1 are assigned to the ν4 SO42− bending modes. The ν2 (SO4)2− bending modes are observed at 460 and 494 cm−1. The observation of multiple bands supports the concept of a reduction in symmetry of the sulphate anion from Td to C3v or even C2v. No evidence of bands attributable to the halide ions was found.

A Raman spectroscopic study of the arsenate mineral chenevixite Cu2Fe23+(AsO4)2(OH)4⋅H2O

We have studied the mineral chenevixite from Manto Cuba Mine, San Pedro de Cachiyuyo District, Inca de Oro, Chañaral Province, Atacama Region, Chile, using a combination of scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDX) and vibrational spectroscopy. Qualitative chemical analysis shows a homogeneous composition, with predominance of As, Fe, Al, Cu, Fe and Cu. Minor amounts of Si were also observed. Raman spectroscopy complimented with infrared spectroscopy has been used to assess the molecular structure of the arsenate minerals chenevixite. Characteristic Raman and infrared bands of the (AsO4)3− stretching and bending vibrations are identified and described. The observation of multiple bands in the (AsO4)3− bending region offers support for the loss of symmetry of the arsenate anion in the structure of chenevixite. Raman bands attributable to the OH stretching vibrations of water and hydroxyl units were analysed. Estimates of the hydrogen bond distances were made based upon the OH stretching wavenumbers.

Spectroscopic vibrations of austinite (CaZnAsO4⋅OH) and its mineral structure : Implications for identification of secondary arsenic-containing mineral

Austinite (CaZnAsO4⋅OH) is a unique secondary mineral in arsenic-contaminated mine wastes. The infrared and Raman spectroscopies were used to characterize the austenite vibrations. The IR bands at 369, 790 and 416 cm−1 are assigned to the ν2, ν3 and ν4 vibrations of AsO43− unit, respectively. The Raman bands at 814, 779 and 403 cm−1 correspond to the ν1, ν3 and ν4 vibrations of AsO43− unit respectively. The sharp bands at 3265 cm−1 for IR and 3270 cm−1 both reveals that the structural hydroxyl units exist in the austenite structure. The IR and Raman spectra both show that some SO4 units isomorphically replace AsO4 in austinite. X-ray single crystal diffraction provides the arrangement of each atom in the mineral structure, and also confirms that the conclusions made from the vibrational spectra. Micro-powder diffraction was used to confirm our mineral identification due to the small quantity of the austenite crystals.

A vibrational spectroscopic study of the silicate mineral harmotome – (Ba,Na,K)1-2(Si,Al)8O16⋅6H2O – A natural zeolite

The mineral harmotome (Ba,Na,K)1-2(Si,Al)8O16⋅6H2O is a crystalline sodium calcium silicate which has the potential to be used in plaster boards and other industrial applications. It is a natural zeolite with catalytic potential. Raman bands at 1020 and 1102 cm−1 are assigned to the SiO stretching vibrations of three dimensional siloxane units. Raman bands at 428, 470 and 491 cm−1 are assigned to OSiO bending modes. The broad Raman bands at around 699, 728, 768 cm−1 are attributed to water librational modes. Intense Raman bands in the 3100 to 3800 cm−1 spectral range are assigned to OH stretching vibrations of water in harmotome. Infrared spectra are in harmony with the Raman spectra. A sharp infrared band at 3731 cm−1 is assigned to the OH stretching vibration of SiOH units. Raman spectroscopy with complimentary infrared spectroscopy enables the characterization of the silicate mineral harmotome.

A vibrational spectroscopic study of the copper bearing silicate mineral luddenite

The molecular structure of the copper–lead silicate mineral luddenite has been analysed using vibrational spectroscopy. The mineral is only one of many silicate minerals containing copper. The intense Raman band at 978 cm−1 is assigned to the ν1 (A1g) symmetric stretching vibration of Si5O14 units. Raman bands at 1122, 1148 and 1160 cm−1 are attributed to the ν3 SiO4 antisymmetric stretching vibrations. The bands in the 678–799 cm−1 are assigned to OSiO bending modes of the (SiO3)n chains. Raman bands at 3317 and 3329 cm−1 are attributed to water stretching bands. Bands at 3595 and 3629 cm−1 are associated with the stretching vibrations of hydroxyl units suggesting that hydroxyl units exist in the structure of luddenite.

Vibrational spectroscopy of the borate mineral priceite : implications for the molecular structure

Priceite is a calcium borate mineral and occurs as white crystals in the monoclinic pyramidal crystal system. We have used a combination of Raman spectroscopy with complimentary infrared spectroscopy and scanning electron microscopy with Energy-dispersive X-ray Spectroscopy (EDS) to study the mineral priceite. Chemical analysis shows a pure phase consisting of B and Ca only. Raman bands at 956, 974, 991, and 1019 cm−1 are assigned to the BO stretching vibration of the B10O19 units. Raman bands at 1071, 1100, 1127, 1169, and 1211 cm−1 are attributed to the BOH in-plane bending modes. The intense infrared band at 805 cm−1 is assigned to the trigonal borate stretching modes. The Raman band at 674 cm−1 together with bands at 689, 697, 736, and 602 cm−1 are assigned to the trigonal and tetrahedral borate bending modes. Raman spectroscopy in the hydroxyl stretching region shows a series of bands with intense Raman band at 3555 cm−1 with a distinct shoulder at 3568 cm−1. Other bands in this spectral region are found at 3221, 3385, 3404, 3496, and 3510 cm−1. All of these bands are assigned to water stretching vibrations. The observation of multiple bands supports the concept of water being in different molecular environments in the structure of priceite. The molecular structure of a natural priceite has been assessed using vibrational spectroscopy.

Development of a new regulatory model for occupational health and safety in the New South Wales coal industry: an issues paper for the New South Wales Department of Mineral Resources

This paper addresses the regulatory issues arising in developing a new regulatory model for the New South Wales Coal Industry. As such, it identifies the relevant literature on this subject, the options available for reform, and the experience of Australian and key international bodies responsible for the development of regulatory standards in this area. In particular it: Identifies the main shortcomings in the existing regulatory approach; Identifies the potential roles/main strengths and weaknesses of different types of standards (eg specification, performance, process and systems-based rules) and potential “best practice’ combinations of standards; Examines the appropriateness of the current regulatory regime whereby the general OHS legislation (including the general duty provisions) applies to mining in addition to the large body of regulation which is specific to mining; Identifies the importance of, and possible means of addressing, issues of worker participation within the coal mining industry; Draws on the literature on what motivates companies and individuals for the purpose of recommending key provisions for inclusion in new legislation to provide appropriate personal and organisational incentives; Draws on the literature on major hazards facilities to suggest the appropriate roles for OHS management systems and safety reports or comparable approaches (eg mine safety management plans); Draws on the United Kingdom (UK) and United States of America (USA) experience of coal mine safety and its regulation for comparative purposes, and for insights as to what sort of regulation most effectively reduces work related injury and disease in coal mining; Examines the relevant roles of International Labour Organisation (ILO) Conventions; Examines the extent to which different regulatory regimes would be appropriate to open cut and underground coal mining; and Examines options for reform. This paper is focussed specifically on the issues identified above.