Raman spectroscopic study of the hydroxy-phosphate mineral plumbogummite PbAl3(PO4)2(OH,H2O)6.

Plumbogummite PbAl(3)(PO(4))(2)(OH,H(2)O)(6) is a mineral of environmental significance and is a member of the alunite-jarosite supergroup. The molecular structure of the mineral has been investigated by Raman spectroscopy. The spectra of different plumbogummite specimens differ although there are many common features. The Raman spectra prove the spectral profile consisting of overlapping bands and shoulders. Raman bands and shoulders observed at 971, 980, 1002 and 1023 cm(-1) (China sample) and 913, 981, 996 and 1026 cm(-1) (Czech sample) are assigned to the ν(1) symmetric stretching modes of the (PO(4))(3-), at 1002 and 1023 cm(-1) (China) and 996 and 1026 cm(-1) to the ν(1) symmetric stretching vibrations of the (O(3)POH)(2-) units, and those at 1057, 1106 and 1182 (China) and at 1102, 1104 and 1179 cm(-1) (Czech) to the ν(3) (PO(4))(3-) and ν(3) (PO(3)) antisymmetric stretching vibrations. Raman bands and shoulders at 634, 613 and 579 cm(-1) (China) and 611 and 596 cm(-1) (Czech) are attributed to the ν(4) (δ) (PO(4))(3-) bending vibrations and those at 507, 494 and 464 cm(-1) (China) and 505 and 464 cm(-1) (Czech) to the ν(2) (δ) (PO(4))(3-) bending vibrations. The Raman spectrum of the OH stretching region is complex. Raman bands and shoulders are identified at 2824, 3121, 3249, 3372, 3479 and 3602 cm(-1) for plumbogummite from China, and at 3077, 3227, 3362, 3480, 3518 and 3601 cm(-1) for the Czech Republic sample. These bands are assigned to the ν OH stretching modes of water molecules and hydrogen ions. Approximate O-H⋯O hydrogen bond lengths inferred from the Raman spectra vary in the range >3.2-2.62Å (China) and >3.2-2.67Å (Czech). The minority presence of some carbonate ions in the plumbogummite (China sample) is connected with distinctive intensity increasing of the Raman band at 1106 cm(-1), in which may participate the ν(1) (CO(3))(2-) symmetric stretching vibration overlapped with phosphate stretching vibrations.

Identification of montgomeryite mineral [Ca4MgAl4(PO4)6·(OH)4·12H2O] found in the Jenolan Caves-Australia.

In this paper, we report on many phosphate containing natural minerals found in the Jenolan Caves - Australia. Such minerals are formed by the reaction of bat guano and clays from the caves. Among these cave minerals is the montgomeryite mineral [Ca(4)MgAl(4)(PO(4))(6)·(OH)(4)·12H(2)O]. The presence of montgomeryite in deposits of the Jenolan Caves - Australia has been identified by X-ray diffraction (XRD). Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the crystal structure of montgomeryite. The Raman spectrum of a standard montgomeryite mineral is identical to that of the Jenolan Caves sample. Bands are assigned to H(2)PO(4)(-), OH and NH stretching vibrations. By using a combination of XRD and Raman spectroscopy, the existence of montgomeryite in the Jenolan Caves - Australia has been proven. A mechanism for the formation of montgomeryite is proposed.

Is the mineral borickyite (Ca,Mg)(Fe3+,Al)4(PO4,SO4,CO3)(OH)(8)·3-7.5H2O the same as delvauxite CaFe4(3+)(PO4,SO4)2(OH)(8)·4-6H2O?

The two minerals borickyite and delvauxite CaFe(4)(3+)(PO(4),SO(4))(2)(OH)(8)·4-6H(2)O 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.

Raman spectroscopy of the multianion mineral gartrellite-PbCu(Fe3+,Cu)(AsO4)2(OH,H2O)2.

The multianion mineral gartrellite PbCu(Fe3+,Cu)(AsO4)2(OH,H2O)2 has been studied by a combination of Raman and infrared spectroscopy. The vibrational spectra of two gartrellite samples from Durango and Ashburton Downs were compared. Gartrellite is one of the tsumcorite mineral group based upon arsenate and sulphate anions. Crystal symmetry is either triclinic in the case of an ordered occupation of two cationic sites, triclinic due to ordering of the H bonds in the case of species with 2 water molecules per formula unit, or monoclinic in the other cases. Characteristic Raman spectra of the minerals enable the assignment of the bands to specific vibrational modes. These spectra are related to the structure of gartrellite. The position of the hydroxyl and water stretching vibrations are related to the strength of the hydrogen bond formed between the OH unit and the AsO4 anion.

Vibrational spectroscopic study of the 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 determination of the structure of these minerals. Among this group of minerals is pitticite, simply described as (Fe, AsO(4), SO(4), H(2)O). In this work, the analogue of the mineral pitticite has been synthesised. The objective of this research is to determine the molecular structure of the mineral pitticite using vibrational spectroscopy. Raman and infrared bands are attributed to the AsO(4)(3-), SO(4)(2-) and water stretching and bending vibrations. The Raman spectrum of the pitticite analogue shows intense peaks at 845 and 837cm(-1) assigned to the AsO(4)(3-) stretching vibrations. Raman bands at 1096 and 1182cm(-1) are attributed to the SO(4)(2-) antisymmetric stretching bands. Raman spectroscopy offers a useful method for the analysis of such colloidal minerals.

Raman spectroscopy of the multi-anion mineral schlossmacherite (H3O,Ca)Al3(AsO4,PO4,SO4)2(OH)6.

The mineral schlossmacherite (H(3)O,Ca)Al(3)(AsO(4),PO(4),SO(4))(2)(OH)(6), a multi-cation-multi-anion mineral of the beudantite mineral subgroup has been characterised by Raman spectroscopy. The mineral and related minerals functions as a heavy metal collector and is often amorphous or poorly crystalline, such that XRD identification is difficult. The Raman spectra are dominated by an intense band at 864cm(-1), assigned to the symmetric stretching mode of the AsO(4)(3-) anion. Raman bands at 809 and 819cm(-1) are assigned to the antisymmetric stretching mode of AsO(4)(3-). The sulphate anion is characterised by bands at 1000cm(-1) (ν(1)), and at 1031, 1082 and 1139cm(-1) (ν(3)). Two sets of bands in the OH stretching region are observed: firstly between 2800 and 3000cm(-1) with bands observed at 2850, 2868, 2918cm(-1) and secondly between 3300 and 3600 with bands observed at 3363, 3382, 3410, 3449 and 3537cm(-1). These bands enabled the calculation of hydrogen bond distances and show a wide range of H-bond distances.

Vibrational spectroscopy of synthetic stercorite H(NH4)Na(PO4)·4H2O--a comparison with the natural cave mineral.

In order to mimic the chemical reactions in cave systems, the analogue of the mineral stercorite H(NH(4))Na(PO(4))·4H(2)O has been synthesised. X-ray diffraction of the stercorite analogue matches the stercorite reference pattern. A comparison is made with the vibrational spectra of synthetic stercorite analogue and the natural Cave mineral. The mineral in nature is formed by the reaction of bat guano chemicals on calcite substrates. A single Raman band at 920 cm(-1) (Cave) and 922 cm(-1) (synthesised) defines the presence of hydrogen phosphate in the mineral. In the synthetic stercorite analogue, additional bands are observed and are attributed to the dihydrogen and phosphate anions. The vibrational spectra of synthetic stercorite only partly match that of the natural stercorite. It is suggested that natural stercorite is more pure than that of synthesised stercorite. Antisymmetric stretching bands are observed in the infrared spectrum at 1052, 1097, 1135 and 1173 cm(-1). Raman spectroscopy shows the stercorite mineral is based upon the hydrogen phosphate anion and not the phosphate anion. Raman and infrared bands are found and assigned to PO(4)(3-), H(2)O, OH and NH stretching vibrations. Raman spectroscopy shows the synthetic analogue is similar to the natural mineral. A mechanism for the formation of stercorite is provided.

Raman spectroscopy of the multi-anion mineral mallestigite Pb3Sb(5+)(SO4)(AsO4)(OH)6·3H2O: a mineral of archaeological significance.

Some minerals are formed which show poorly defined X-ray diffraction patterns. Vibrational spectroscopy offers one of the few methods for the assessment of the structure of the oxyanions in such minerals. Among this group of minerals is mallestigite with formula Pb(3)Sb(5+)(SO(4))(AsO(4))(OH)(6)·3H(2)O. The objective of this research is to determine the molecular structure of the mineral mallestigite using vibrational spectroscopy. Raman and infrared bands are attributed to the AsO(4)(3-), SO(4)(2-) and water stretching vibrations. Mallestigite is a mineral formed in ancient waste dumps such as occurs at Mallestiger, Carinthia, Austria and as such is a mineral of archaeological significance.

Vibrational spectroscopic analysis of taranakite (K,NH4)Al3(PO4)3(OH)·9(H2O) from the Jenolan Caves, Australia.

Many phosphate containing minerals are found in the Jenolan Caves. Such minerals are formed by the reaction of bat guano and clays from the caves. Among these cave minerals is the mineral taranakite (K,NH(4))Al(3)(PO(4))(3)(OH)·9(H(2)O) which has been identified by X-ray diffraction. Jenolan Caves taranakite has been characterised by Raman spectroscopy. Raman and infrared bands are assigned to H(2)PO(4), OH and NH stretching vibrations. By using a combination of XRD and Raman spectroscopy, the existence of taranakite in the caves has been proven.

Raman spectroscopy of the multi anion mineral arsentsumebite Pb2Cu(AsO4)(SO4)(OH) and in comparison with tsumebite Pb2Cu(PO4)(SO4)(OH).

The mineral arsentsumebite Pb(2)Cu(AsO(4))(SO(4))(OH), a copper arsenate-sulphate hydroxide of the brackebuschite group has been characterised by Raman spectroscopy. The brackebuschite mineral group are a series of monoclinic arsenates, phosphates and vanadates of the general formula A(2)B(XO(4))(OH,H(2)O), where A may be Ba, Ca, Pb, Sr, while B may be Al, Cu(2+),Fe(2+), Fe(3+), Mn(2+), Mn(3+), Zn and XO(4) may be AsO(4), PO(4), SO(4),VO(4). Bands are assigned to the stretching and bending modes of SO(4)(2-) AsO(4)(3-) and HOAsO(3) units. Raman spectroscopy readily distinguishes between the two minerals arsentsumebite and tsumebite. Raman bands attributed to arsenate are not observed in the Raman spectrum of tsumebite. Phosphate bands found in the Raman spectrum of tsumebite are not found in the Raman spectrum of arsentsumebite. Raman spectroscopy readily distinguishes the two minerals tsumebite and arsentsumebite.

Vibrational spectroscopy of the multi-anion mineral zykaite Fe4(AsO4)(SO4)(OH)·15H2O-implications for arsenate removal.

Some minerals are colloidal and are poorly diffracting. Vibrational spectroscopy offers one of the few methods for the assessment of the structure of these types of minerals. Among this group of minerals is zykaite with formula Fe(4)(AsO(4))(SO(4))(OH)·15H(2)O. The objective of this research is to determine the molecular structure of the mineral zykaite using vibrational spectroscopy. Raman and infrared bands are attributed to the AsO(4)(3-), SO(4)(2-) and water stretching vibrations. The sharp band at 3515 cm(-1) is assigned to the stretching vibration of the OH units. This mineral offers a mechanism for the formation of more crystalline minerals such as scorodite and bukovskyite. Arsenate ions can be removed from aqueous systems through the addition of ferric compounds such as ferric chloride. This results in the formation of minerals such as zykaite and pitticite (Fe(3+), AsO(4), SO(4), H(2)O).

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 Na(2)(PO(3)OH)·2H(2)O 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 PO(3) and POH stretching vibrations. Bands at 991, 1066 and 1141 cm(-1) are assigned to the ν(3) antisymmetric stretching modes. Raman bands at 393, 413 and 448 cm(-1) and 514, 541 and 570 cm(-1) are attributed to the ν(2) and ν(4) bending modes of the HPO(4) 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.

Vibrational spectroscopic analysis of the mineral crandallite CaAl3(PO4)2(OH)5·(H2O) from the Jenolan Caves, Australia.

The mineral crandallite CaAl(3)(PO(4))(2)(OH)(5)·(H(2)O) has been identified in deposits found in the Jenolan Caves, New South Wales, Australia by using a combination of X-ray diffraction and Raman spectroscopic techniques. A comparison is made between the vibrational spectra of crandallite found in the Jenolan Caves and a standard crandallite. Raman and infrared bands are assigned to PO(4)(3-) and HPO(4)(2-) stretching and bending modes. The predominant features are the internal vibrations of the PO(4)(3-) and HPO(4)(2-) groups. A mechanism for the formation of crandallite is presented and the conditions for the formation are elucidated.

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 (SO(4))(2-) and (AsO(4))(3-) units, stretching and bending vibrations of hydrogen bonded (OH)(-) ions and Cu(2+)-(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 (SO(4))(2-) and (AsO(4))(3-) are split and more intense. Lower wavenumbers of δ H(2)O bending vibration in the spectrum may indicate the presence of weaker hydrogen bonds compared with those in different leogangite samples. The formation of leogangite offers a mechanism for the removal of arsenic from the environment.

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.

Vibrational spectroscopic study of the mineral tsumebite Pb2Cu(PO4,SO4)(OH).

The mineral tsumebite Pb2Cu(PO4)(SO4)(OH), a copper phosphate-sulfate hydroxide of the brackebuschite group has been characterised by Raman and infrared spectroscopy. The brackebuschite mineral group are a series of monoclinic arsenates, phosphates and vanadates of the general formula A2B(XO4)(OH,H2O), where A may be Ba, Ca, Pb, Sr, while B may be Al, Cu2+,Fe2+, Fe3+, Mn2+, Mn3+, Zn and XO4 may be AsO4, PO4, SO4,VO4. Bands are assigned to the stretching and bending modes of PO4(3-) and HOPO3 units. Hydrogen bond distances are calculated based upon the position of the OH stretching vibrations and range from 2.759 Å to 3.205 Å. This range of hydrogen bonding contributes to the stability of the mineral.

A vibrational spectroscopic study of hydrated Fe(3+) hydroxyl-sulfates; 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.

Raman spectroscopy of stercorite H(NH4)Na(PO4)·4H2O--a cave mineral from Petrogale Cave, Madura, Eucla, Western Australia.

Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the mineral stercorite H(NH4)Na(PO4)·4H2O. The mineral stercorite originated from the Petrogale Cave, Madura, Eucla, Western Australia. This cave is one of many caves in the Nullarbor Plain in the South of Western Australia. These caves have been in existence for eons of time and have been dated at more than 550 million years old. The mineral is formed by the reaction of bat guano chemicals on calcite substrates. A single Raman band at 920 cm(-1) defines the presence of phosphate in the mineral. Antisymmetric stretching bands are observed in the infrared spectrum at 1052, 1097, 1135 and 1173 cm(-1). Raman spectroscopy shows the mineral is based upon the phosphate anion and not the hydrogen phosphate anion. Raman and infrared bands are found and assigned to PO4(3-), H2O, OH and NH stretching vibrations. The detection of stercorite by Raman spectroscopy shows that the mineral can be readily determined; as such the application of a portable Raman spectrometer in a 'cave' situation enables the detection of minerals, some of which may remain to be identified.

Raman spectroscopy of newberyite Mg(PO3OH)·3H2O: a cave mineral.

Newberyite Mg(PO3OH)·3H2O is a mineral found in caves such as from Moorba Cave, Jurien Bay, Western Australia, the Skipton Lava Tubes (SW of Ballarat, Victoria, Australia) and in the Petrogale Cave (Madura, Eucla, Western Australia). Because these minerals contain oxyanions, hydroxyl units and water, the minerals lend themselves to spectroscopic analysis. Raman spectroscopy can investigate the complex paragenetic relationships existing between a number of 'cave' minerals. The intense sharp band at 982 cm(-1) is assigned to the PO4(3-)ν1 symmetric stretching mode. Low intensity Raman bands at 1152, 1263 and 1277 cm(-1) are assigned to the PO4(3-)ν3 antisymmetric stretching vibrations. Raman bands at 497 and 552 cm(-1) are attributed to the PO4(3-)ν4 bending modes. An intense Raman band for newberyite at 398 cm(-1) with a shoulder band at 413 cm(-1) is assigned to the PO4(3-)ν2 bending modes. The values for the OH stretching vibrations provide hydrogen bond distances of 2.728 Å (3267 cm(-1)), 2.781 Å (3374 cm(-1)), 2.868 Å (3479 cm(-1)), and 2.918 Å (3515 cm(-1)). Such hydrogen bond distances are typical of secondary minerals. Estimates of the hydrogen-bond distances have been made from the position of the OH stretching vibrations and show a wide range in both strong and weak bonds.

Synthesis and vibrational spectroscopy of halotrichite and bilinite.

Near infrared (NIR), infrared (IR) spectroscopy and X-ray diffraction (XRD) have been applied to halotrichites of the formula FeAl(2)(SO(4))(4)·22H(2)O and Fe(2+)Fe(2)(3+)(SO(4))(4)·22H(2)O. Comparison of the halotrichites and their starting materials has been used to give a better understanding of the bonding involved in these types of minerals. The vibrational spectroscopy data has shown that Fe(2+) oxidises during the formation of halotrichite, no preventative measures were implemented to prevent oxidation, and this has been clearly shown by the position and broadness of electronic bands of transition metals in the NIR spectra (12,500-7500 cm(-1)). It is apparent from this region that Fe(3+) substitutes for Al(3+) in the synthesis of halotrichite. Due to the oxidation of Fe(2+) to Fe(3+) the halotrichite sample contains a small portion of bilinite. This has been confirmed by XRD, peaks at 9 and 14° 2θ were observed in the halotrichite sample and are identical to the XRD pattern obtained for bilinite. Substitution of aluminium for Fe(3+) has resulted in significant changes in the overall infrared and NIR spectral profiles. However, the lower wavenumber regions of the NIR spectra have very similar spectral profiles, which indicates a similar structure to halotrichite has formed for bilinite. This work has shown that iron halotrichites can be synthesised and characterised by infrared and NIR spectroscopy.