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.

Limestone and speleothem trace element geochemistry as tools for palaeoclimatic reconstruction, Mount Etna region, central-coastal Queensland

This study investigated potential palaeoclimate proxies provided by rare earth element (REE) geochemistry in speleothems and in clay mineralogy of cave sediments. Speleothem and sediment samples were collected from a series of cave fill deposits that occurred with rich vertebrate fossil assemblages in and around Mount Etna National Park, Rockhampton (central coastal Queensland). The fossil deposits range from Plio- Pleistocene to Holocene in age (based on uranium/thorium dating) and appear to represent depositional environments ranging from enclosed rainforest to semi-arid grasslands. Therefore, the Mount Etna cave deposits offer the perfect opportunity to test new palaeoclimate tools as they include deposits that span a known significant climate shift on the basis of independent faunal data. The first section of this study investigates the REE distribution of the host limestone to provide baseline geochemistry for subsequent speleothem investigations. The Devonian Mount Etna Beds were found to be more complex than previous literature had documented. The studied limestone massif is overturned, highly recrystallised in parts and consists of numerous allochthonous blocks with different spatial orientations. Despite the complex geologic history of the Mount Etna Beds, Devonian seawater-like REE patterns were recovered in some parts of the limestone and baseline geochemistry was determined for the bulk limestone for comparison with speleothem REE patterns. The second part of the study focused on REE distribution in the karst system and the palaeoclimatic implications of such records. It was found that REEs have a high affinity for calcite surfaces and that REE distributions in speleothems vary between growth bands much more than along growth bands, thus providing a temporal record that may relate to environmental changes. The morphology of different speleothems (i.e., stalactites, stalagmites, and flowstones) has little bearing on REE distributions provided they are not contaminated with particulate fines. Thus, baseline knowledge developed in the study suggested that speleothems were basically comparable for assessing palaeoclimatically controlled variations in REE distributions. Speleothems from rainforest and semi-arid phases were compared and it was found that there are definable differences in REE distribution that can be attributed to climate. In particular during semiarid phases, total REE concentration decreased, LREE became more depleted, Y/Ho increased, La anomalies were more positive and Ce anomalies were more negative. This may reflect more soil development during rainforest phases and more organic particles and colloids, which are known to transport REEs, in karst waters. However, on a finer temporal scale (i.e. growth bands) within speleothems from the same climate regime, no difference was seen. It is suggested that this may be due to inadequate time for soil development changes on the time frames represented by differences in growth band density. The third part of the study was a reconnaissance investigation focused on mineralogy of clay cave sediments, illite/kaolinite ratios in particular, and the potential palaeoclimatic implications of such records. Although the sample distribution was not optimal, the preliminary results suggest that the illite/kaolinite ratio increased during cold and dry intervals, consistent with decreased chemical weathering during those times. The study provides a basic framework for future studies at differing latitudes to further constrain the parameters of the proxy. The identification of such a proxy recorded in cave sediment has broad implications as clay ratios could potentially provide a basic local climate proxy in the absence of fossil faunas and speleothem material. This study suggests that REEs distributed in speleothems may provide information about water throughput and soil formation, thus providing a potential palaeoclimate proxy. It highlights the importance of understanding the host limestone geochemistry and broadens the distribution and potential number of cave field sites as palaeoclimate information no longer relies solely on the presence of fossil faunas and or speleothems. However, additional research is required to better understand the temporal scales required for the proxies to be recognised.

Imaging fluid solid interactions in hydrocarbon reservoir rocks

The environmental scanning electron microscope (ESEM) has been used to image liquid hydrocarbons in sandstones and oil shales. Additionally, the fluid sensitivity of selected clay minerals in hydrocarbon reservoirs was assessed via three case studies: HCl acid sensitivity of authigenic chlorite in sandstone reservoirs, freshwater sensitivity of authigenic illite/smectite in sandstone reservoirs, and bleach sensitivity of a volcanic reservoir containing abundant secondary chlorite/corrensite. The results showed the suitability of using ESEM for imaging liquid hydrocarbon films in hydrocarbon reservoirs and the importance of simulating in situ fluid-rock interactions for hydrocarbon production programmes. In each case, results of the ESEM studies greatly enhanced prediction of reservoir/borehole reactions and, in some cases, contradicted conventional wisdom regarding the outcome of potential engineering solutions. (C) 1993 Wiley-Liss, Inc.

Removal of epoxy-attached thin-sections from glass slides by plasma-etching

Thin-sectioned samples mounted on glass slides with common petrographic epoxies cannot be easily removed (for subsequent ion-milling) by standard methods such as heating or dissolution in solvents. A method for the removal of such samples using a radio frequency (RF) generated oxygen plasma has been investigated for a number of typical petrographic and ceramic thin sections. Sample integrity and thickness were critical factors that determined the etching rate of adhesive and the survivability of the sample. Several tests were performed on a variety of materials in order to estimate possible heating or oxidation damage from the plasma. Temperatures in the plasma chamber remained below 138°C and weight changes in mineral powders etched for 76 hr were less than ±4%. A crystal of optical grade calcite showed no apparent surface damage after 48 hr of etching. Any damage from the oxygen plasma is apparently confined to the surface of the sample, and is removed during the ion-milling stage of transmission electron microscopy (TEM) sample preparation.

Vibrational spectroscopy of natural cave mineral monetite CaHPO4 and the synthetic analog

Monetite is a phosphate mineral formed by the reaction of the chemicals in bat guano with calcite substrates and is commonly found in caves. The analog of the mineral monetite CaHPO4 has been synthesized and the Raman and infrared spectra of the natural monetite originating from the Murra-el-elevyn Cave, Eucla, Western Australia, compared. Monetite is characterized by a complex set of phosphate bands that arise because of two sets of pairs of phosphate units in the unit cell. Raman and infrared bands are assigned to HPO4(2-), OH stretching and bending vibrations. Infrared bands at 1346 and 1402 cm−1 are assigned to POH deformation modes. Vibrational spectroscopy confirms the presence of monetite in the cave system.

Carbonate cementation in sandstones of the Plover Formation, North West Shelf, W.A

Ancient sandstones include important reservoirs for hydrocarbons (oil and gas), but, in many cases, their ability to serve as reservoirs is heavily constrained by the effects of carbonate cements on porosity and permeability. This study investigated the controls on distribution and abundance of carbonate cements within the Jurassic Plover Formation, Browse Basin, North West Shelf, Australia. Samples were analysed petrographically with point counting of 59 thin sections and mineralogically with x-ray diffraction from two wells within the Torosa Gas Field. Selected samples were also analysed for stable isotopes of O and C. Sandstones are classified into eleven groups. Most abundant are quartzarenites and then calcareous quartzarenites. Lithology ranged between sandstones consisting of mostly quartz with scant or no carbonate in the form of cement or allochems, to sandstones with as much as 40% carbonate. The major sources of carbonate cement in Torosa 1 and Torosa 4 sandstones were found to be early, shallow marine diagenetic processes (including cementation), followed by calcite cementation and recrystallisation of cements and allochems during redistribution by meteoric waters. Blocky and sparry calcite cements, indicative of meteoric environments on the basis of stable isotope values and palaeotemperature assessment, overprinted the initial shallow marine cement phase in all cases and meteoric cements are dominant. Torosa 4 was influenced more by marine settings than Torosa 1, and thus has the greater potential for calcite cement. The relatively low compaction of calcite-cemented sandstones and the stable isotope data suggest deep burial cementation was not a major factor. Insufficient volcanic rock fragments or authigenic clay content infers alteration of feldspars was not a major source of calcite. Very little feldspar is present, altered or otherwise. Hence, increased alkalinity from feldspar dissolution is not a contributing factor in cement formation. Increased alkalinity from bacterial sulphate reduction in organic–rich fine sediments may have driven limited cementation in some samples. The main definable and significant source of diagenetic marine calcite cement originated from original marine cements and the nearby dissolution of biogenic sources (allochems) at relatively shallow depths. Later diagenetic fluids emplaced minor dolomite, but this cement did not greatly affect the reservoir quality in the samples studied.

Trace-element modeling of the magmatic evolution of rare-earth-rich carbonatite from the Miaoya deposit, Central China

Carbonatites are known to contain the highest concentrations of rare-earth elements (REE) among all igneous rocks. The REE distribution of carbonatites is commonly believed to be controlled by that of the rock forming Ca minerals (i.e., calcite, dolomite, and ankerite) and apatite because of their high modal content and tolerance for the substitution of Ca by light REE (LREE). Contrary to this conjecture, calcite from the Miaoya carbonatite (China), analyzed in situ by laser-ablation inductively-coupled-plasma mass-spectrometry, is characterized by low REE contents (100–260 ppm) and relatively !at chondrite-normalized REE distribution patterns [average (La/Yb)CN=1.6]. The carbonatite contains abundant REE-rich minerals, including monazite and !uorapatite, both precipitated earlier than the REE-poor calcite, and REE-fluorocarbonates that postdated the calcite. Hydrothermal REE-bearing !uorite and barite veins are not observed at Miaoya. The textural and analytical evidence indicates that the initially high concentrations of REE and P in the carbonatitic magma facilitated early precipitation of REE-rich phosphates. Subsequent crystallization of REE-poor calcite led to enrichment of the residual liquid in REE, particularly LREE. This implies that REE are generally incompatible with respect to calcite and the calcite/melt partition coefficients for heavy REE (HREE) are significantly greater than those for LREE. Precipitation of REE-fluorocarbonates late in the evolutionary history resulted in depletion of the residual liquid in LREE, as manifested by the development of HREE-enriched late-stage calcite [(La/Yb)CN=0.7] in syenites associated with the carbonatite. The observed variations of REE distribution between calcite and whole rocks are interpreted to arise from multistage fractional crystallization (phosphates!calcite!REE-!uorocarbonates) from an initially REE-rich carbonatitic liquid.

Discerning the timing and cause of historical mortality events in modern Porites from the Great Barrier Reef

The life history strategies of massive Porites corals make them a valuable resource not only as key providers of reef structure, but also as recorders of past environmental change. Yet recent documented evidence of an unprecedented increase in the frequency of mortality in Porites warrants investigation into the history of mortality and associated drivers. To achieve this, both an accurate chronology and an understanding of the life history strategies of Porites are necessary. Sixty-two individual Uranium–Thorium (U–Th) dates from 50 dead massive Porites colonies from the central inshore region of the Great Barrier Reef (GBR) revealed the timing of mortality to have occurred predominantly over two main periods from 1989.2 ± 4.1 to 2001.4 ± 4.1, and from 2006.4 ± 1.8 to 2008.4 ± 2.2 A.D., with a small number of colonies dating earlier. Overall, the peak ages of mortality are significantly correlated with maximum sea-surface temperature anomalies. Despite potential sampling bias, the frequency of mortality increased dramatically post-1980. These observations are similar to the results reported for the Southern South China Sea. High resolution measurements of Sr/Ca and Mg/Ca obtained from a well preserved sample that died in 1994.6 ± 2.3 revealed that the time of death occurred at the peak of sea surface temperatures (SST) during the austral summer. In contrast, Sr/Ca and Mg/Ca analysis in two colonies dated to 2006.9 ± 3.0 and 2008.3 ± 2.0, suggest that both died after the austral winter. An increase in Sr/Ca ratios and the presence of low Mg-calcite cements (as determined by SEM and elemental ratio analysis) in one of the colonies was attributed to stressful conditions that may have persisted for some time prior to mortality. For both colonies, however, the timing of mortality coincides with the 4th and 6th largest flood events reported for the Burdekin River in the past 60 years, implying that factors associated with terrestrial runoff may have been responsible for mortality. Our results show that a combination of U–Th and elemental ratio geochemistry can potentially be used to precisely and accurately determine the timing and season of mortality in modern massive Porites corals. For reefs where long-term monitoring data are absent, the ability to reconstruct historical events in coral communities may prove useful to reef managers by providing some baseline knowledge on disturbance history and associated drivers.

Identification of allanite (Ce, Ca, Y)2(Al, Fe3+)3(SiO4)3OH found in marble from Chillagoe, Queensland using Raman spectroscopy

Samples of marble from Chillagoe, North Queensland have been analyzed using scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) and Raman spectroscopy. Chemical analyses provide evidence for the presence of minerals other than limestone and calcite in the marble, including silicate minerals. Some of these analyses correspond to silicate minerals. The Raman spectra of these crystals were obtained and the Raman spectrum corresponds to that of allanite from the Arizona State University data base (RRUFF) data base. The combination of SEM with EDS and Raman spectroscopy enables the characterization of the mineral allanite in the Chillagoe marble.

Raman spectroscopy of pyrite in marble from Chillagoe, Queensland

Samples of marble from Chillagoe, North Queensland have been analysed using scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS) and Raman spectroscopy. Different types of marble were studied including soft white marble, hard white marble and a black marble. In this work, we try to ascertain why the black marble has this colour. Chemical analyses provide evidence for the presence of minerals other calcite in the marble, including the pyrite mineral. Some of these chemical analyses correspond to pyrite minerals in the black marble. The Raman spectra of these crystals were obtained and the Raman spectrum corresponds to that of pyrite from the RRUFF data base. The combination of SEM with EDS and Raman spectroscopy enables the characterisation of the mineral pyrite in Chillagoe black marble.

Characteristics and alteration origins of matrix minerals in volcaniclastic kimberlite of the Muskox pipe (Nunavut, Canada)

The matrix of volcaniclastic kimberlite (VK) from the Muskox pipe (Northern Slave Province, Nunavut, Canada) is interpreted to represent an overprint of an original clastic matrix. Muskox VK is subdivided into three different matrix mineral assemblages that reflect differences in the proportions of original primary matrix constituents, temperature of formation and nature of the altering fluids. Using whole rock X-ray fluorescence (XRF), whole rock X-ray diffraction (XRD), microprobe analyses, back-scatter electron (BSE) imaging, petrography and core logging, we find that most matrix minerals (serpentine, phlogopite, chlorite, saponite, monticellite, Fe-Ti oxides and calcite) lack either primary igneous or primary clastic textures. The mineralogy and textures are most consistent with formation through alteration overprinting of an original clastic matrix that form by retrograde reactions as the deposit cools, or, in the case of calcite, by precipitation from Ca-bearing fluids into a secondary porosity. The first mineral assemblage consists largely of serpentine, phlogopite, calcite, Fe-Ti oxides and monticellite and occurs in VK with relatively fresh framework clasts. Alteration reactions, driven by deuteric fluids derived from the juvenile constituents, promote the crystallisation of minerals that indicate relatively high temperatures of formation (> 400 °C). Lower-temperature minerals are not present because permeability was occluded before the deposit cooled to low temperatures, thus shielding the facies from further interaction with fluids. The other two matrix mineral assemblages consist largely of serpentine, phlogopite, calcite, +/- diopside, and +/- chlorite. They form in VK that contains more country rock, which may have caused the deposit to be cooler upon emplacement. Most framework components are completely altered, suggesting that larger volumes of fluids drove the alteration reactions. These fluids were likely of meteoric provenance and became heated by the volcaniclastic debris when they percolated into the VK infill. Most alteration reactions ceased at temperatures > 200 °C, as indicated by the absence or paucity of lower-temperature phases in most samples, such as saponite. Recognition that Muskox VK contains an original clastic matrix is a necessary first step for evaluating the textural configuration, which is important for reconstructing the physical processes responsible for the formation of the deposit.

Inhibition by poly(acrylic acid) and morphological changes in calcium carbonate and calcium carbonate/calcium sulfate crystallization on silica fibers

An intrinsic exposed core optical fiber sensor (IECOFS) made from fused silica was used to monitor the crystallization of calcium carbonate (CaCO3) and CaCO3/calcium sulfate (CaSO4) composite at 100 and 120 °C in the absence and presence of low-molar-mass (Mn ≤ 2000) poly(acrylic acid) (PAA) with different end groups. The IECOFS responded only to deposition and growth processes on the fiber surface rather than changes occurring in the bulk of the solution. Hexyl isobutyrate-terminated PAA (Mn = 1400) and hexadecyl isobutyrate-terminated PAA (Mn = 1700) were the most effective species in preventing CaCO3 deposition. Phase transformation from vaterite to aragonite/calcite decreased with increasing hydrophobicity of the PAA end group. Low-molar-mass PAA at 10 ppm showed very significant inhibition of CaCO3/CaSO4 composite formation for all end groups investigated.

Study of Pinna nobilis growth from inner record: How biased are posterior adductor muscle scars estimates?

Previous studies have shown that the external growth records of the posterior adductor muscle scar (PAMS) of the bivalve Pinna nobilis are incomplete and do not produce accurate age estimations. We have developed a new methodology to study age and growth using the inner record of the PAMS, which avoids the necessity of costly in situ shell measurements or isotopic studies. Using the inner record we identified the positions of PAMS previously obscured by nacre and estimated the number of missing records in adult specimens with strong abrasion of the calcite layer in the anterior portion of the shell. The study of the PAMS and inner record of two shells that were 6 years old when collected showed that only 2 and 3 PAMS were observed, while 6 inner records could be counted, thus confirming our working methodology. Growth parameters of a P. nobilis population located in Moraira, Spain (western Mediterranean) were estimated with the new methodology and compared to those obtained using PAMS data and in situ measurements. For the comparisons, we applied different models considering the data alternatively as length-at-age (LA) and tag-recapture (TR). Among every method we tested to fit the Von Bertalanffy growth model, we observed that LA data from inner record fitted to the model using non-linear mixed effects and the estimation of missing records using the calcite width was the most appropriate. The equation obtained with this method, L = 573*(1 - e(-0.16(t-0.02))), is very similar to that calculated previously from in situ measurements for the same population.