Growth rates in modern speleothems from Santana Cave, Brazil, by the Pb-210-method

The Santana Cave is located at the Upper Ribeira Touristic State Park (PETAR-Parque Estadual Turistico do Alto Ribeira) in southern São Paulo State, Brazil. This paper describes Pb-210 activity concentration data in soda straw stalactites samples collected at Salao das Flores in Santana Cave that is a fossil tributary of the cave river. Non-expensive alpha counting following some analytical steps for extracting and depositing Pb-210 were used for providing the Pb-210 data. In the analyzed samples, Pb-210 values of increasingly older samples fitted an exponential curve, thus suggesting that the production of Pb-210 has been constant with time. Also, the near-ideal fit indicated that the growth was uniform and there was no break in the continuous growth. The soda straw growth rates were determined from the best fit to the exponential curve through the Pb-210 activity concentration. The results of the measurements allowed estimate a longitudinal rate corresponding to 1.3 mm/yr and a lateral rate of 0.01 mm/yr, which permitted calculate times of 70 years and 317-498 years for their formation, respectively. The lateral growth rate is compatible with values from studies of chemical weathering rates held under laboratory and natural conditions. (C) 2011 Elsevier Ltd. All rights reserved.

Assessment of effective doses from radon levels for tour guides at several galleries of Santana Cave, Southern Brazil, with CR-39 detectors: preliminary results

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Speleoclimate dynamics in Santana Cave (PETAR, S(a)over-tildeo Paulo State, Brazil): general characterization and implications for tourist management

Show caves provide tourists with the opportunity to have close contact with natural underground spaces. However, visitation to these places also creates a need for management measures, mainly the definition of tourist carrying capacity. The present work describes the results of climate monitoring and atmospheric profiling performed in Santana Cave (Alto Ribeira State and Tourist Park - PETAR, Brazil) between 2008 and 2011. Based on the results, distinct preliminary zones with different levels of thermal variation were identified, which classify Santana Cave as a warm trap. Two critical points along the tourist route (Cristo and Encontro Halls) were identified where the temperature of the locality increased by 1.3 degrees C when tourists were present. Air flow from the inner cave to the outside occurs during the austral summer, and the opposite flow occurs when the outside environment is colder than the air inside the cave during the austral winter. The temperature was used to establish thresholds to the tourist carrying capacity by computing the recovery time of the atmospheric conditions after the changes caused by the presence of tourists. This method suggests a maximum limit of approximately 350 visits per day to Santana Cave. The conclusion of the study is that Santana Cave has an atmosphere that is highly connected with the outside; daily variations in temperature and, to a lesser extent, in the relative humidity occur throughout the entire studied area of the cave. Therefore, the tourist carrying capacity in Santana Cave can be flexible and can be implemented based on the climate seasonality, the tourism demand and other management strategies.

Capacidade de carga real (ccr) da caverna de santana, parque estadual turístico do alto ribeira (Petar) - sp, e indicações para o seu manejo turístico

The tourist use of Santana cave provides a row of environmental damages, compromising partially the pristine conditions. Among the measures adopted to avoid this situation, this issue presents a contribution for the physical limits to tourist visitation and the indications for speleotouristic management. It was used the Cifuentes Carrying Capacity method and some basic principles of Visitors Impact Management Framework - VIM. The results show a Real Carrying Capacity (CCR) about 120 visits daily on the cave. The discussions raise a few hypotheses about the alteration in the method used and the temporal frequency between visitors groups, suggesting a provisional CCR of 117 and 135 visitors daily, respectively, during the week and in the weekends and holidays. The conclusions appoint the necessity of a conceptual revision in the Carrying Capacity methods, mainly about its adaptation for tourist management in caves. In the case studied, it is suggested the immediate beginning of environmental monitoring of the cave, to verify the plausibility from proposed visitation limits and the possible contributions for to mitigate the environmental impacts from speleotourism.

Estudo da dinâmica atmosférica subterrânea na determinação da capacidade de carga turística na caverna de Santana (Petar, Iporanga, SP)

Pós-graduação em Geociências e Meio Ambiente - IGCE

The'cave' mineral oxammite: a high resolution thermogravimetry and Raman spectroscopic study

The thermal decomposition of natural ammonium oxalate known as oxammite has been studied using a combination of high resolution thermogravimetry coupled to an evolved gas mass spectrometer and Raman spectroscopy coupled to a thermal stage. Three mass loss steps were found at 57, 175 and 188°C attributed to dehydration, ammonia evolution and carbon dioxide evolution respectively. Raman spectroscopy shows two bands at 3235 and 3030 cm-1 attributed to the OH stretching vibrations and three bands at 2995, 2900 and 2879 cm-1, attributed to the NH vibrational modes. The thermal degradation of oxammite may be followed by the loss of intensity of these bands. No intensity remains in the OH stretching bands at 100°C and the NH stretching bands show no intensity at 200°C. Multiple CO symmetric stretching bands are observed at 1473, 1454, 1447 and 1431cm-1, suggesting that the mineral oxammite is composed of a mixture of chemicals including ammonium oxalate dihydrate, ammonium oxalate monohydrate and anhydrous ammonium oxalate.

Prehistoric hand stencils at Fern Cave, North Queensland (Australia): environmental and chronological implications of Raman spectroscopy and FT-IR imaging results

Raman spectroscopy and FT-IR imaging analyses of cave wall pigment samples from north Queensland (Australia) indicate that some hand stencils were undertaken during a dry environmental phase indicating late Holocene age. Other, earlier painting episodes also took place during dry environmental periods of the terminal Pleistocene and/or early Holocene. These results represent a rare opportunity to attain chronological information for rock art in conditions where insufficient carbon is present for radiocarbon dating.

A Raman spectroscopic study of the ‘cave’ mineral ardealite Ca2(HPO4)(SO4)•4H2O

The mineral ardealite Ca2(HPO4)(SO4)•4H2O is a ‘cave’ mineral and is formed through the reaction of calcite with bat guano. The mineral shows disorder and the composition varies depending on the origin of the mineral. Raman spectroscopy complimented with infrared spectroscopy has been used to characterise the mineral ardealite. The Raman spectrum is very different from that of gypsum. Bands are assigned to SO42- and HPO42- stretching and bending modes.

Thermal stability of the ‘cave’ mineral brushite CaHPO4•2H2O -mechanism of formation and decomposition

Thermogravimetry combined with evolved gas mass spectrometry has been used to ascertain the stability of the ‘cave’ mineral brushite. X-ray diffraction shows that brushite from the Jenolan Caves is very pure. Thermogravimetric analysis coupled with ion current mass spectrometry shows a mass loss at 111°C due to loss of water of hydration. A further decomposition step occurs at 190°C with the conversion of hydrogen phosphate to a mixture of calcium ortho-phosphate and calcium pyrophosphate. TG-DTG shows the mineral is not stable above 111°C. A mechanism for the formation of brushite on calcite surfaces is proposed, and this mechanism has relevance to the formation of brushite in urinary tracts.

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 the ‘cave’ mineral ardealite Ca2(HPO4)(SO4)•4H2O

Thermogravimetry combined with evolved gas mass spectrometry has been used to characterise the mineral ardealite and to ascertain the thermal stability of this ‘cave’ mineral. The mineral ardealite Ca2(HPO4)(SO4)•4H2O is formed through the reaction of calcite with bat guano. The mineral shows disorder and the composition varies depending on the origin of the mineral. Thermal analysis shows that the mineral starts to decompose over the temperature range 100 to 150°C with some loss of water. The critical temperature for water loss is around 215°C and above this temperature the mineral structure is altered. It is concluded that the mineral starts to decompose at 125°C, with all waters of hydration being lost after 226°C. Some loss of sulphate occurs over a broad temperature range centred upon 565°C. The final decomposition temperature is 823°C with loss of the sulphate and phosphate anions.

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.