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.

4D GPR tracking of water infiltration in fractured high-porosity limestone

Three thousand liters of water were infiltrated from a 4 m diameter pond to track flow and transport inside fractured carbonates with 20-40 % porosity. Sixteen time-lapse 3D Ground Penetrating Radar (GPR) surveys with repetition intervals between 2 hrs and 5 days monitored the spreading of the water bulb in the subsurface. Based on local travel time shifts between repeated GPR survey pairs, localized changes of volumetric water content can be related to the processes of wetting, saturation and drainage. Deformation bands consisting of thin sub vertical sheets of crushed grains reduce the magnitude of water content changes but enhance flow in sheet parallel direction. This causes an earlier break through across a stratigraphic boundary compared to porous limestone without deformation bands. This experiment shows how time-lapse 3D GPR or 4D GPR can non-invasively track ongoing flow processes in rock-volumes of over 100 m3.

Optimization studies on limestone beneficiation

Limestone rejects from Bagalkot mines have been beneficiated by froth flotation with a view to reducing the magnesia content. In order to ascertain the effect of the main parameters such as sodium oleate concentration, sodium silicate concentration and pH on the MgO content, statistically designed experiments have been performed. The results indicate that under the optimum conditions arrived at limestone rejects could be beneficiated to produce a concentrate with magnesia. content meeting the specifications for cement manufacture.

Colonization and development of Oribatida mite communities (Acari: Oribatida) in the forest reclaimed limestone mine dumps

In order to study the colonization and development of moss mites (Oribatida) communities in a Scots pine forest of a reclaimed limestone mine dump in Northern Poland, 3 plots from the dump were chosen. The selected plots differed in age, 5 years old, 35 and 50 years old. From a total of 30 samples 499 mites (Acari) were extracted in Tullgren funnel from which 262 were Oribatida. Abundance (N) was analyzed in all mites and after determining the species of both, juvenile and adult stages of oribatids, the following indices were analyzed: Abundance (N), Dominance (D), Species diversity (S), Species richness (s) and Shannon’s diversity index (H). Regarding to the results obtained; oribatid mites were dominant with the highest abundance in all assemblages (Plot 1: 139 Oribatida /299 Acari. Plot 2: 40/55 and Plot 3: 83/145). Tectocepheus velatus showed a very high dominance (45,99%) in plot 1; the highest value for Shannon’s diversity index belonged to plot 3. On the other hand, juvenile’s percentage was significantly higher than adult’s percentage, especially at plot 2 (95,02%). These results made us to conclude that the high abundance of oribatids in the youngest forest is due to T. velatus’s high abundance and that plot 3 is the best habitat for mites. Finally, the high occurrence of juvenile stages requires keeping on studying the area.

Metasomatism and magmatic assimilation at a gabbro-limestone contact, Christmas Mountains, Big Bend region, Texas

A composite stock of alkaline gabbro and syenite is intrusive into limestone of the Del Carmen, Sue Peake and Santa Elena Formations at the northwest end of the Christmas Mountains. There is abundant evidence of solution of wallrock by magma but nowhere are gabbro and limestone in direct contact. The sequence of lithologies developed across the intrusive contact and across xenoliths is gabbro, pyroxenite, calc-silicate skarn, marble. Pyroxenite is made up of euhedral crystals of titanaugite and sphene in a leucocratic matrix of nepheline, Wollastonite and alkali feldspar. The uneven modal distribution of phases in pyroxenite and the occurrence' of nepheline syenite dikes, intrusive into pyroxenite and skarn, suggest that pyroxenite represents an accumulation of clinopyroxene "cemented" together by late-solidifying residual magma of nepheline syenite composition. Assimilation of limestone by gabbroic magma involves reactions between calcite and magma and/or crystals in equilibrium with magma and crystallization of phases in which the magma is saturated, to supply energy for the solution reaction. Gabbroic magma was saturated with plagioclase and clinopyroxene at the time of emplacement. The textural and mineralogic features of pyroxenite can be produced by the reaction 2( 1-X) CALCITE + AN_XAB_l-X = (1-X) NEPHELINE+ 2(1-X) WOLLASTONITE+ X ANORTHITE+ 2(1-X) CO₂. Plagioclase in pyroxenite has corroded margins and is rimmed by nepheline, suggestive of resorption by magma. Anorthite and wollastonite enter solid solution in titanaugite. For each mole of calcite dissolved, approximately one mole of clinopyroxene was crystallized. Thus the amount of limestone that may be assimilated is limited by the concentration of potential clinopyroxene in the magma. Wollastonite appears as a phase when magma has been depleted in iron and magnesium by crystallization of titanaugite. The predominance of mafic and ultramafic compositions among contaminated rocks and their restriction to a narrow zone along the intrusive contact provides little evidence for the generation of a significant volume of desilicated magma as a result of limestone assimilation.

Within 60 m of the intrusive contact with the gabbro, nodular chert in the Santa Elena Limestone reacted with the enveloping marble to form spherical nodules of high-temperature calc-silicate minerals. The phases wollastonite, rankinite, spurrite, tilleyite and calcite, form a series of sharply-bounded, concentric monomineralic and two-phase shells which record a step-wise decrease in silica content from the core of a nodule to its rim. Mineral zones in the nodules vary 'with distance from the gabbro as follows:

0-5 m CALCITE + SPURRITE + RANKINITE + WOLLASTONITE
5-16 m CALCITE + TILLEYITE ± SPURRITE + RANKINITE + WOLLASTONITE
16-31 m CALCITE + TILLEYITE + WOLLASTONITE
31-60 m CALCITE + WOLLASTONITE
60-plus CALCITE + QUARTZ

The mineral of a one-phase zone is compatible with the phases bounding it on either side but these phases are incompatible in the same volume of P-T-X_CO2.

Growth of a monomineralio zone is initiated by reaction between minerals of adjacent one-phase zones which become unstable with rising temperature to form a thin layer of a new single phase that separates the reactants and is compatible with both of them. Because the mineral of the new zone is in equilibrium with the phases at both of its contacts, gradients in the chemical potentials of the exchangeable components are established across it. Although zone boundaries mark discontinuities in the gradients of bulk composition, two-phase equilibria at the contacts demonstrate that the chemical potentials are continuous. Hence, Ca, Si and CO₂ were redistributed in the growing nodule by diffusion. A monomineralic zone grows at the expense of an adjacent zone by reaction between diffusing components and the mineral of the adjacent zone. Equilibria between two phases at zone boundaries buffers the chemical potentials of the diffusing species. Thus, within a monomineralic zone, the chemical potentials of the diffusing components are controlled external to the local assemblage by the two-phase equilibria at the zone boundaries.

Mineralogically zoned calc-silicate skarn occurs as a narrow band that separates pyroxenite and marble along the intrusive contact and forms a rim on marble xenoliths in gabbro. Skarn consists of melilite or idocrase pseudomorphs of melili te, one or two . stoichiometric calcsilicate phases and accessory Ti-Zr garnet, perovskite and magnetite. The sequence of mineral zones from pyroxenite to marble, defined by a characteristic calc-silicate, is wollastonite, rankinite, spurrite, calcite. Mineral assemblages of adjacent skarn zones are compatible and the set of zones in a skarn band defines a facies type, indicating that the different mineral assemblages represent different bulk compositions recrystallized under identical conditions. The number of phases in each zone is less than the number that might be expected to result from metamorphism of a general bulk composition under conditions of equilibrium, trivariant in P, T and u_CO2. The "special" bulk composition of each zone is controlled by reaction between phases of the zones bounding it on either side. The continuity of the gradients of composition of melilite and garnet solid solutions across the skarn is consistent with the local equilibrium hypothesis and verifies that diffusion was the mechanism of mass transport. The formula proportions of Ti and Zr in garnet from skarn vary antithetically with that of Si Which systematically decreases from pyroxenite to marble. The chemical potential of Si in each skarn zone was controlled by the coexisting stoichiometric calc-silicate phases in the assemblage. Thus the formula proportion of Si in garnet is a direct measure of the chemical potential of Si from point to point in skarn. Reaction between gabbroic magma saturated with plagioclase and clinopyroxene produced nepheline pyroxenite and melilite-wollastonite skarn. The calcsilicate zones result from reaction between calcite and wollastonite to form spurrite and rankinite.

Ecological study of chalk and limestone streams. Annual Report October 1974 to September 1975

Few detailed studies have been made on the ecology of the chalk streams. A complex community of plants and animals is present and much more information is required to achieve an understanding of the requirements and interactions of all the species. It is important that the rivers affected by this scheme should be studied and kept under continued observation so that any effects produced by the scheme can be detected. The report gives a brief synopsis of work carried out during the second year of a four year ecological study sponsored jointly by the Thames Water Authority and the Central Water Planning Unit. It assumes some familiarity with the investigations carried out on the River Lambourn during the preceding three years which was sponsored jointly by the Thames Conservancy and Water Resources Board (immediate predecessors of the present sponsoring organisations). (PDF contains 31 pages)

Ecological study of chalk and limestone stream. Annual report October 1975 to September 1976

Few detailed studies have been made on the ecology of the chalk streams. A complex community of plants and animals is present and much more information is required to achieve an understanding of the requirements and interactions of all the species. It is important that the rivers affected by this scheme should be studied and kept under continued observation so that any effects produced by the scheme can be detected. The report gives a brief synopsis of work carried out during the third year of a four year ecological study sponsored jointly by the Thames Water Authority and the Central Water Planning Unit. It assumes . It assumes some familiarity with the investigations carried out on the River Lambourn during the preceding three years which was sponsored jointly by the Thames Conservancy and Water Resources Board (immediate predecessors of the present sponsoring organisations). (PDF contains 35 pages)