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 PO43- ν1 symmetric stretching mode. Low intensity Raman bands at 1152, 1263 and 1277 cm-1 are assigned to the PO43- ν3 antisymmetric stretching vibrations. Raman bands at 497 and 552 cm-1 are attributed to the PO43- 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 PO43- ν2 bending modes. The values for the OH stretching vibrations provide hydrogen bond distances of 2.728Å (3267 cm-1), 2.781Å (3374cm-1), 2.868Å (3479 cm-1), and 2.918Å (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.

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 PO43−, 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.

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.

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(NH4)Na(PO4)•4H2O 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 PO43-, H2O, 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.

Thermal stability of newberyite Mg(PO3OH)•3H2O – a cave mineral from Skipton lava tubes, Victoria, Australia.

The mineral newberyite Mg(PO3OH)•3H2O is a mineral that has been found in caves such as the Skipton Lava Tubes (SW of Ballarat, Victoria, Australia), Moorba cave, Jurien Bay, Western Australia, and in the Petrogale Cave (Madura , Eucla, Western Australia). Because these minerals contain water, the minerals lend themselves to thermal analysis. The mineral newberyite is found to decompose at 145°C with a water loss of 31.96%, a result which is very close to the theoretical value. The result shows that the mineral is not stable in caves where the temperature exceeds this value. The implication of this result rests with the removal of kidney stones, which have the same composition as newberyite. Point heating focussing on the kidney stone results in the destruction of the kidney stone.

Thermal stability of stercorite H(NH4)Na(PO4)·4H2O – a cave mineral from Petrogale Cave, Madura, Eucla, Western Australia

Thermogravimetric analysis has been used to determine the thermal stability of 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. The mineral is formed by the reaction of bat guano chemicals on calcite substrates. Upon thermal treatment the mineral shows a strong decomposition at 191°C with loss of water and ammonia. Other mass loss steps are observed at 158, 317 and 477°C. Ion current curves indicate a gain of CO2 at higher temperature and are attributed to the thermal decomposition of calcite impurity.

Thermal stability of crandallite CaAl3(PO4)2(OH)5•(H2O) – a ‘cave’ mineral from the Jenolan Caves

Thermogravimetry combined with evolved gas mass spectrometry has been used to characterise the mineral crandallite CaAl3(PO4)2(OH)5•(H2O) and to ascertain the thermal stability of this ‘cave’ mineral. X-ray diffraction proves the presence of the mineral and identifies the products after thermal decomposition. The mineral crandallite is formed through the reaction of calcite with bat guano. Thermal analysis shows that the mineral starts to decompose through dehydration at low temperatures at around 139°C while dehydroxylation occurs over the temperature range 200 to 700°C with loss of OH units. The critical temperature for OH loss is around 416°C and above this temperature the mineral structure is altered. Some minor loss of carbonate impurity occurs at 788°C. This study shows the mineral is unstable above 139°C. This temperature is well above the temperature in caves, which have a maximum temperature of 15°C. A chemical reaction for the synthesis of crandallite is offered and the mechanism for the thermal decomposition is given.

Vibrational spectroscopy of synthetic archerite (K,NH4)H2PO4 : and in comparison with the natural cave mineral

In order to mimic the formation of archerite in cave minerals, the mineral analogue has been synthesised. The cave mineral is formed by the reaction of the chemicals in bat guano with calcite substrates. X-ray diffraction proves that the synthesised archerite analogue was pure. The vibrational spectra of the synthesised mineral are compared with that of the natural cave mineral. Raman and infrared bands are assigned to H2PO4-, OH and NH stretching and bending vibrations. The Raman band at 917 cm-1 is assigned to the HOP stretching vibration of the H2PO4- units. Bands in the 1200 to 1800 cm-1 region are associated with NH4+ bending modes. Vibrational spectroscopy enables the molecular structure of archerite to be analysed.