Clay-mineral composition and biogenic opal content of Late Neogene to Quaternary sediments of the Antarctic Peninsula region

Clay-mineral composition and biogenic opal content in upper Miocene to Quaternary drift sediments recovered at two Ocean Drilling Program (ODP) sites from the continental rise in the Bellingshausen Sea had been analyzed in order to reconstruct the climatic and glacial history of the Antarctic Peninsula. The clay mineral composition at both sites is dominated by smectite, illite, and chlorite, and alternates between a smectite-enriched and a chlorite-enriched assemblage throughout the last 9.3 my. The spatial distribution of clay minerals in Holocene sediments west of the Antarctic Peninsula facilitates the identification of particular source areas, and thus the reconstruction of transport pathways. The similarity to clay mineral variations reported from upper Quaternary sequences suggests that the short-term clay-mineralogical fluctuations in the ODP cores reflect glacial-interglacial cyclicity. Thus, repeated ice advances and retreats in response to a varying size of the Antarctic Peninsula ice cap are likely to have occurred throughout the late Neogene and Quaternary. The clay minerals in the drift sediments exhibit only slight long-term variations, which are caused by local changes in glacial erosion and in supply of source rocks, rather than by major climatic changes. The opal records at the ODP sites are dominated by long-term variations since the late Miocene. We infer that the opal content in the drift sediments, although it is influenced by dissolution in the water column and the sediment column and by the burial with lithogenic detritus, provides a signal of paleoproductivity. Because the annual sea-ice coverage is regarded as the main factor controlling biological productivity, the opal signal helps to reconstruct paleoceanographic changes in the Bellingshausen Sea. Slightly enhanced opal deposition during the late Miocene indicates slightly warmer climatic conditions in the Antarctic Peninsula area than at present. During the early Pliocene, enhanced opal deposition in the Pacific sector of the Southern Ocean and coinciding high opal concentrations in sedimentary sequences from the Atlantic and Indian sectors document a strong reduction of sea-ice cover and relatively warm climatic conditions. Thereby, the early onset of the Pliocene warmth in the Bellingshausen Sea points to a positive feedback of regional Antarctic climate on the global thermohaline circulation. A decrease of opal deposition between 3.1 and 2.6 Ma likely reflects sea-ice expansion in response to reduced supply of northern-sourced deep-waters to the Southern Ocean, caused by the onset of Northern Hemisphere glaciation. Throughout the Quaternary, a relatively constant level of opal deposition on the Antarctic continental margin indicates relatively stable climatic conditions.

The feasibility of vibration analysis as a technique to detect osseointegration of transfemoral implants

One of the main causes of above knee or transfemoral amputation (TFA) in the developed world is trauma to the limb. The number of people undergoing TFA due to limb trauma, particularly due to war injuries, has been increasing. Typically the trauma amputee population, including war-related amputees, are otherwise healthy, active and desire to return to employment and their usual lifestyle. Consequently there is a growing need to restore long-term mobility and limb function to this population. Traditionally transfemoral amputees are provided with an artificial or prosthetic leg that consists of a fabricated socket, knee joint mechanism and a prosthetic foot. Amputees have reported several problems related to the socket of their prosthetic limb. These include pain in the residual limb, poor socket fit, discomfort and poor mobility. Removing the socket from the prosthetic limb could eliminate or reduce these problems. A solution to this is the direct attachment of the prosthesis to the residual bone (femur) inside the residual limb. This technique has been used on a small population of transfemoral amputees since 1990. A threaded titanium implant is screwed in to the shaft of the femur and a second component connects between the implant and the prosthesis. A period of time is required to allow the implant to become fully attached to the bone, called osseointegration (OI), and be able to withstand applied load; then the prosthesis can be attached. The advantages of transfemoral osseointegration (TFOI) over conventional prosthetic sockets include better hip mobility, sitting comfort and prosthetic retention and fewer skin problems on the residual limb. However, due to the length of time required for OI to progress and to complete the rehabilitation exercises, it can take up to twelve months after implant insertion for an amputee to be able to load bear and to walk unaided. The long rehabilitation time is a significant disadvantage of TFOI and may be impeding the wider adoption of the technique. There is a need for a non-invasive method of assessing the degree of osseointegration between the bone and the implant. If such a method was capable of determining the progression of TFOI and assessing when the implant was able to withstand physiological load it could reduce the overall rehabilitation time. Vibration analysis has been suggested as a potential technique: it is a non destructive method of assessing the dynamic properties of a structure. Changes in the physical properties of a structure can be identified from changes in its dynamic properties. Consequently vibration analysis, both experimental and computational, has been used to assess bone fracture healing, prosthetic hip loosening and dental implant OI with varying degrees of success. More recently experimental vibration analysis has been used in TFOI. However further work is needed to assess the potential of the technique and fully characterise the femur-implant system. The overall aim of this study was to develop physical and computational models of the TFOI femur-implant system and use these models to investigate the feasibility of vibration analysis to detect the process of OI. Femur-implant physical models were developed and manufactured using synthetic materials to represent four key stages of OI development (identified from a physiological model), simulated using different interface conditions between the implant and femur. Experimental vibration analysis (modal analysis) was then conducted using the physical models. The femur-implant models, representing stage one to stage four of OI development, were excited and the modal parameters obtained over the range 0-5kHz. The results indicated the technique had limited capability in distinguishing between different interface conditions. The fundamental bending mode did not alter with interfacial changes. However higher modes were able to track chronological changes in interface condition by the change in natural frequency, although no one modal parameter could uniquely distinguish between each interface condition. The importance of the model boundary condition (how the model is constrained) was the key finding; variations in the boundary condition altered the modal parameters obtained. Therefore the boundary conditions need to be held constant between tests in order for the detected modal parameter changes to be attributed to interface condition changes. A three dimensional Finite Element (FE) model of the femur-implant model was then developed and used to explore the sensitivity of the modal parameters to more subtle interfacial and boundary condition changes. The FE model was created using the synthetic femur geometry and an approximation of the implant geometry. The natural frequencies of the FE model were found to match the experimental frequencies within 20% and the FE and experimental mode shapes were similar. Therefore the FE model was shown to successfully capture the dynamic response of the physical system. As was found with the experimental modal analysis, the fundamental bending mode of the FE model did not alter due to changes in interface elastic modulus. Axial and torsional modes were identified by the FE model that were not detected experimentally; the torsional mode exhibited the largest frequency change due to interfacial changes (103% between the lower and upper limits of the interface modulus range). Therefore the FE model provided additional information on the dynamic response of the system and was complementary to the experimental model. The small changes in natural frequency over a large range of interface region elastic moduli indicated the method may only be able to distinguish between early and late OI progression. The boundary conditions applied to the FE model influenced the modal parameters to a far greater extent than the interface condition variations. Therefore the FE model, as well as the experimental modal analysis, indicated that the boundary conditions need to be held constant between tests in order for the detected changes in modal parameters to be attributed to interface condition changes alone. The results of this study suggest that in a clinical setting it is unlikely that the in vivo boundary conditions of the amputated femur could be adequately controlled or replicated over time and consequently it is unlikely that any longitudinal change in frequency detected by the modal analysis technique could be attributed exclusively to changes at the femur-implant interface. Therefore further development of the modal analysis technique would require significant consideration of the clinical boundary conditions and investigation of modes other than the bending modes.

Palaeoecology of the Mount Etna bat fauna, coastal Eastern Queensland

Global warming is already threatening many animal and plant communities worldwide, however, the effect of climate change on bat populations is poorly known. Understanding the factors influencing the survival of bats is crucial to their conservation, and this cannot be achieved solely by modern ecological studies. Palaeoecological investigations provide a perspective over a much longer temporal scale, allowing the understanding of the dynamic patterns that shaped the distribution of modern taxa. In this study twelve microchiropteran fossil assemblages from Mount Etna, central-eastern Queensland, ranging in age from more than 500,000 years to the present day, were investigated. The aim was to assess the responses of insectivorous bats to Quaternary environmental changes, including climatic fluctuations and recent anthropogenic impacts. In particular, this investigation focussed on the effects of increasing late Pleistocene aridity, the subsequent retraction of rainforest habitat, and the impact of cave mining following European settlement at Mount Etna. A thorough examination of the dental morphology of all available extant Australian bat taxa was conducted in order to identify the fossil taxa prior to their analysis in term of species richness and composition. This detailed odontological work provided new diagnostic dental characters for eighteen species and one genus. It also provided additional useful dental characters for three species and seven genera. This odontological analysis allowed the identification of fifteen fossil bat taxa from the Mount Etna deposits, all being representatives of extant bats, and included ten taxa identified to the species level (i.e., Macroderma gigas, Hipposideros semoni, Rhinolophus megaphyllus, Miniopterus schreibersii, Miniopterus australis, Scoteanax rueppellii, Chalinolobus gouldii, Chalinolobus dwyeri, Chalinolobus nigrogriseus and Vespadelus troughtoni) and five taxa identified to the generic level (i.e., Mormopterus, Taphozous, Nyctophilus, Scotorepens and Vespadelus). Palaeoecological analysis of the fossil taxa revealed that, unlike the non-volant mammal taxa, bats have remained essentially stable in terms of species diversity and community membership between the mid-Pleistocene rainforest habitat and the mesic habitat that occurs today in the region. The single major exception is Hipposideros semoni, which went locally extinct at Mount Etna. Additionally, while intensive mining operations resulted in the abandonment of at least one cave that served as a maternity roost in the recent past, the diversity of the Mount Etna bat fauna has not declined since European colonisation. The overall resilience through time of the bat species discussed herein is perhaps due to their unique ecological, behavioural, and physiological characteristics as well as their ability to fly, which have allowed them to successfully adapt to their changing environment. This study highlights the importance of palaeoecological analyses as a tool to gain an understanding of how bats have responded to environmental change in the past and provides valuable information for the conservation of threatened modern species, such as H. semoni.

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.

A vibrational spectroscopic study of the mineral hinsdalite (Pb,Sr)Al3(PO4)(SO4)(OH)6

The objective of this research is to determine the molecular structure of the mineral hinsdalite using vibrational spectroscopy. The mineral hinsdalite (Pb,Sr)Al3(PO4,SO4)2(OH)6 is a hydroxy phosphate-sulphate mineral belonging to the beudantite subgroup of alunites. The mineral is interesting because it contains two oxyanions, phosphate and sulphate, which is unusual. The formation of hinsdalite offers a mechanism for the removal of phosphate from the environment. The mineral has been characterised by Raman spectroscopy and infrared spectroscopy. The spectra are then related to the molecular structure of the mineral. Bands at various wavenumbers are assigned to the different vibrational modes of hinsdalite, which were then associated to the molecular structure of the mineral. Bands were primarily assigned to phosphate and sulphate stretching and bending modes. The Raman spectrum is characterised by an intense sharp band at 982 cm-1 with a component band at 997 cm-1 assigned to the ν1 (PO4)3- symmetric stretching modes. Two symmetric stretching modes for both phosphate and sulphate supported the concept of non-equivalent phosphate and sulphate units in the mineral structure. Bands in the OH stretching region enabled hydrogen bond distances to be calculated. Hinsdalite is characterised by disordered phosphate/sulphate tetrahedra and non-equivalent phosphate units are observed in the vibrational spectrum of hinsdalite.

Molecular structural studies of the amorphous 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 assessment of the structure of these types of mineral. Among this group of minerals is pitticite simply described as Fe, AsO4, SO4, H2O. The objective of this research is to determine the molecular structure of the mineral pitticite using vibrational spectroscopy. Raman microscopy offers a useful method for the analysis of such colloidal minerals. Raman and infrared bands are attributed to the , and water stretching vibrations. The Raman spectrum is dominated by a very intense sharp band at 983 cm−1 assigned to the symmetric stretching mode. A strong Raman band at 1041 cm−1 is observed and is assigned to the antisymmetric stretching mode. Low intensity Raman bands at 757 and 808 cm−1 may be assigned to the antisymmetric and symmetric stretching modes. Raman bands observed at 432 and 465 cm−1 are attributable to the doubly degenerate ν2(SO4)2- bending mode.

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.

Vibrational spectroscopic study of the copper silicate mineral ajoite (K,Na)Cu7AlSi9O24(OH)6•3H2O

Ajoite (K,Na)Cu7AlSi9O24(OH)6•3H2O is a mineral named after the Ajo district of Arizona. Raman and infrared spectroscopy were used to characterise the molecular structure of ajoite. The structure of the mineral shows disorder which is reflected in the difficulty of obtaining quality Raman spectra. The Raman spectrum is characterised by a broad spectral profile with a band at 1048 cm-1 assigned to the ν1 (A1g) symmetric stretching vibration. Strong bands at 962, 1015 and 1139 cm-1 are assigned to the ν3 SiO4 antisymmetric stretching vibrations. Multiple ν4 SiO4 vibrational modes indicate strong distortion of the SiO4 tetrahedra. Multiple AlO and CuO stretching bands are observed. Raman spectroscopy and confirmed by infrared spectroscopy clearly shows that hydroxyl units are involved in the ajoite structure. Based upon the infrared spectra, water is involved in the ajoite structure, probably as zeolitic water.

Raman spectroscopic study of the minerals apophyllite-(KF) KCa4Si8O20F.8H2O and apophyllite-(KOH) KCa4Si8O20(F,OH).8H2O

Raman spectroscopy complimented with infrared spectroscopy has been used to study the variation in molecular structure of two minerals of the apophyllite mineral group, namely apophyllite-(KF)KCa4Si8O20F.8H2O and apophyllite-(KOH) KCa4Si8O20(F,OH).8H2O. apophyllite-(KF) and apophyllite-(KOH) are different minerals only because of the difference in the percentage of fluorine to hydroxyl ions. The Raman spectra are dominated by a very intense sharp peak at 1059 cm -1. A band at around 846 cm -1 is assigned to the water librational mode. It is proposed that the difference between apophyllite-(KF) and apophyllite-(KOH) is the observation of two Raman bands in the OH stretching region at around 3563 and 3625 cm -1. Multiple water stretching and bending modes are observed showing that there is much variation in hydrogen bonding between water and the silicate surfaces.

The phosphate mineral sigloite Fe3+Al2(PO4)2(OH)3·7(H2O), an exception to the paragenesis rule – a vibrational spectroscopic study

The secondary phosphate mineral sigloite Fe3+Al2(PO4)2(OH)3·7H2O is the exception to the rule that phosphate mineral paragenesis is related to the final phase of hydrothermal mineralization at low temperatures. Sigloite was formed as an oxidation pseudomorph after paravauxite, during the last supergene paragenetic stage. We have studied the secondary phosphate mineral sigloite Fe3+Al2(PO4)2(OH)3·7H2O using vibrational spectroscopic techniques. Because the mineral is a phosphate mineral, it is readily studied by spectroscopic techniques as the phosphate and hydrogen phosphate units are readily measured. Indeed, sigloite shows the presence of both phosphate and hydrogen phosphate units in its structure. Raman bands at 1009 cm−1 with shoulders at 993 and 1039 cm−1 are assigned to stretching vibrations of and units. The Raman band at 993 cm−1 is assigned to the ν1 symmetric stretching mode of the POH units, whereas the Raman band at 1009 cm−1 is assigned to the ν1 symmetric stretching mode. Raman bands observed at 506, 528, 571, 596, 619 and 659 cm−1 are attributed to the ν4 out of plane bending modes of the PO4 and H2PO4 units. The Raman bands at 2988, 3118 and 3357 cm−1 are assigned to water stretching vibration. The series of bands at 3422, 3449, 3493, 3552 and 3615 cm−1 are assigned to the OH stretching vibrations of the hydroxyl units. The observation of multiple bands gives credence to the non-equivalence of the OH units in the sigloite structure.

Infrared and Raman spectroscopic characterization of the carbonate mineral huanghoite - and in comparison with selected rare earth carbonates

Raman spectroscopy complimented with infrared spectroscopy has been used to study the rare earth based mineral huanghoite with possible formula given as BaCe(CO3)2F and compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of huanghoite displays three bands are at 1072, 1084 and 1091 cm−1 attributed to the symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of symmetric stretching vibration varies with mineral composition. Infrared spectroscopy of huanghoite show bands at 1319, 1382, 1422 and 1470 cm−1. No Raman bands of huanghoite were observed in these positions. Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 cm−1 assigned to the ν3 (CO3)2− antisymmetric stretching mode. The observation of additional Raman bands for the ν3 modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands for huanghoite are observed at 687, 704, 718 and 730 cm−1and assigned to the (CO3)2− ν2 bending modes. Raman bands are observed for huanghoite at around 627 cm−1 and are assigned to the (CO3)2− ν4 bending modes. Raman bands are observed for the carbonate ν4 in phase bending modes at 722 cm−1 for bastnasite, 736 and 684 cm−1 for parisite, 714 cm−1 for northupite. Raman bands for huanghoite observed at 3259, 3484 and 3589 cm−1 are attributed to water stretching bands. Multiple bands are observed in the OH stretching region for bastnasite and parisite indicating the presence of water and OH units in their mineral structure. Vibrational spectroscopy enables new information on the structure of huanghoite to be assessed.

Convergence in the gender wage gap in Australia over the 1980s : identifying the role of counteracting forces via the Juhn, Murphy and Pierce decomposition

The paper utilises the Juhn Murphy and Pierce (1991) decomposition to shed light on the pattern of slow male-female wage convergance in Australia over the 1980s. The analysis allows one to distinguish between the role of wage structure and genderspecific effects. The central question addressed is whether rising wage inequality counteracted the forces of increased female investment in labour market skills, i.e. education and experience. The conclusion is that in contrast to the US and the UK, Australian women do not appear to have been swimming against a tide of adverse wage structure changes.

Development of modified inorganic adsorbents for radioactive iodine removal and biomolecule adsorption

Development and application of inorganic adsorbent materials have been continuously investigated due to their variability and versatility. This Master thesis has expanded the knowledge in the field of adsorption targeting radioactive iodine waste and proteins using modified inorganic materials. Industrial treatment of radioactive waste and safety disposal of nuclear waste is a constant concern around the world with the development of radioactive materials applications. To address the current problems, laminar titanate with large surface area (143 m2 g−1) was synthesized from inorganic titanium compounds by hydrothermal reactions at 433 K. Ag2O nanocrystals of particle size ranging from 5–30 nm were anchored on the titanate lamina surface which has crystallographic similarity to that of Ag2O nanocrystals. Therefore, the deposited Ag2O nanocrystals and titanate substrate could join together at these surfaces between which there forms a coherent interface. Such coherence between the two phases reduces the overall energy by minimizing surface energy and maintains the Ag2O nanocrystals firmly on the outer surface of the titanate structure. The combined adsorbent was then applied as efficient adsorbent to remove radioactive iodine from water (one gram adsorbent can capture up to 3.4 mmol of I- anions) and the composite adsorbent can be recovered easily for safe disposal. The structure changes of the titanate lamina and the composite adsorbent were characterized via various techniques. The isotherm and kinetics of iodine adsorption, competitive adsorption and column adsorption using the adsorbent were studied to determine the iodine removal abilities of the adsorbent. It is shown that the adsorbent exhibited excellent trapping ability towards iodine in the fix-bed column despite the presence of competitive ions. Hence, Ag2O deposited titanate lamina could serve as an effective adsorbent for removing iodine from radioactive waste. Surface hydroxyl group of the inorganic materials is widely applied for modification purposes and modification of inorganic materials for biomolecule adsorption can also be achieved. Specifically, γ-Al2O3 nanofibre material is converted via calcinations from boehmite precursor which is synthesised by hydrothermal chemical reactions under directing of surfactant. These γ-Al2O3 nanofibres possess large surface area (243 m2 g-1), good stability under extreme chemical conditions, good mechanical strength and rich surface hydroxyl groups making it an ideal candidate in industrialized separation column. The fibrous morphology of the adsorbent also guarantees facile recovery from aqueous solution under both centrifuge and sedimentation approaches. By chemically bonding the dyes molecules, the charge property of γ-Al2O3 is changed in the aim of selectively capturing of lysozyme from chicken egg white solution. The highest Lysozyme adsorption amount was obtained at around 600 mg/g and its proportion is elevated from around 5% to 69% in chicken egg white solution. It was found from the adsorption test under different solution pH that electrostatic force played the key role in the good selectivity and high adsorption rate of surface modified γ-Al2O3 nanofibre adsorbents. Overall, surface modified fibrous γ-Al2O3 could be applied potentially as an efficient adsorbent for capturing of various biomolecules.

A vibrational spectroscopic study of the arsenate mineral bayldonite (Cu,Zn)3Pb(AsO3OH)2(OH)2 : a comparison with other basic arsenates

We have studied the vibrational spectra of the mineral bayldonite, a hydroxy arsenate of copper and lead of formula Cu3Pb(AsO3OH)2(OH)2 from the type locality, the Penberthy Croft Mine, St Hilary, Mount's Bay District, Cornwall, England.and relate the spectra to the mineral structure. Raman bands at 896 and 838 cm-1are assigned to the (AsO4)3- ν1 symmetric stretching mode and the second to the (AsO4)3- ν3 antisymmetric stretching mode. It is noted that the position of the symmetric stretching mode is at a higher position than the antisymmetric stretching mode. It is proposed that the Raman bands at 889 and 845 cm-1 are symmetric and antisymmetric stretching modes of the (HOAsO3)2- units. Raman bands of bayldonite at 490 and 500 cm-1 are assigned to the (AsO4)3- ν4 bending modes. Raman bands for bayldonite are noted at 396, 408 and 429 cm-1 and are assigned to the (AsO4)3- ν2 bending modes. A comparison is made with spectra of the other basic copper arsenate minerals, namely cornubite, olivenite, cornwallite.