Rare earth element geochemistry of scleractinian coral skeleton during meteoric diagenesis: A sequence through neomorphism of aragonite to calcite

Rare earth element geochemistry in carbonate rocks is utilized increasingly for studying both modern oceans and palaeoceanography, with additional applications for investigating water–rock interactions in groundwater and carbonate diagenesis. However, the study of rare earth element geochemistry in ancient rocks requires the preservation of their distribution patterns through subsequent diagenesis. The subjects of this study, Pleistocene scleractinian coral skeletons from Windley Key, Florida, have undergone partial to complete neomorphism from aragonite to calcite in a meteoric setting; they allow direct comparison of rare earth element distributions in original coral skeleton and in neomorphic calcite. Neomorphism occurred in a vadose setting along a thin film, with degradation of organic matter playing an initial role in controlling the morphology of the diagenetic front. As expected, minor element concentrations vary significantly between skeletal aragonite and neomorphic calcite, with Sr, Ba and U decreasing in concentration and Mn increasing in concentration in the calcite, suggesting that neomorphism took place in an open system. However, rare earth elements were largely retained during neomorphism, with precipitating cements taking up excess rare earth elements released from dissolved carbonates from higher in the karst system. Preserved rare earth element patterns in the stabilized calcite closely reflect the original rare earth element patterns of the corals and associated reef carbonates. However, minor increases in light rare earth element depletion and negative Ce anomalies may reflect shallow oxidized groundwater processes, whereas decreasing light rare earth element depletion may reflect mixing of rare earth elements from associated microbialites or contamination from insoluble residues. Regardless of these minor disturbances, the results indicate that rare earth elements, unlike many minor elements, behave very conservatively during meteoric diagenesis. As the meteoric transformation of aragonite to calcite is a near worst case scenario for survival of original marine trace element distributions, this study suggests that original rare earth element patterns may commonly be preserved in ancient limestones, thus providing support for the use of ancient marine limestones as proxies for marine rare earth element geochemistry.

Super-orbital re-entry in Australia : laboratory measurement, simulation and flight observation

There are large uncertainties in the aerothermodynamic modelling of super-orbital re-entry which impact the design of spacecraft thermal protection systems (TPS). Aspects of the thermal environment of super-orbital re-entry flows can be simulated in the laboratory using arc- and plasma jet facilities and these devices are regularly used for TPS certification work [5]. Another laboratory device which is capable of simulating certain critical features of both the aero and thermal environment of super-orbital re-entry is the expansion tube, and three such facilities have been operating at the University of Queensland in recent years[10]. Despite some success, wind tunnel tests do not achieve full simulation, however, a virtually complete physical simulation of particular re-entry conditions can be obtained from dedicated flight testing, and the Apollo era FIRE II flight experiment [2] is the premier example which still forms an important benchmark for modern simulations. Dedicated super-orbital flight testing is generally considered too expensive today, and there is a reluctance to incorporate substantial instrumentation for aerothermal diagnostics into existing missions since it may compromise primary mission objectives. An alternative approach to on-board flight measurements, with demonstrated success particularly in the ‘Stardust’ sample return mission, is remote observation of spectral emissions from the capsule and shock layer [8]. JAXA’s ‘Hayabusa’ sample return capsule provides a recent super-orbital reentry example through which we illustrate contributions in three areas: (1) physical simulation of super-orbital re-entry conditions in the laboratory; (2) computational simulation of such flows; and (3) remote acquisition of optical emissions from a super-orbital re entry event.

The development of an observation tool for use with parents with psychiatric disability and their preschool children

Community-based treatment and care of people with psychiatric disabilities has meant that they are now more likely to engage in the parenting role. This has led to the development of programs designed to enhance the parenting skills of people with psychiatric disabilities. Evaluation of these programs has been hampered by a paucity of evaluation tools. This study's aim was to develop and trial a tool that examined the parent-child interaction within a group setting, was functional and easy to use, required minimum training and equipment, and had acceptable levels of reliability and validity. The revised tool yielded a single scale with acceptable reliability. It had discriminative validity and concurrent validity with non-independent global ratings of parenting. Sensitivity to change was not investigated. The findings suggest that this method of evaluating parenting is likely to have both clinical and research utility and further investigation of the psychometric properties of the tool is warranted.

Raman spectroscopy of decrespignyite (Y,REE)4Cu(CO3)4Cl(OH)5•2(H2O) and in relation with other halogenated carbonates including bastnasite, hydroxybastnasite, parisite and northupite

Raman spectroscopy complimented with infrared spectroscopy has been used to study the rare earth based mineral decrespignyite (Y,REE)4Cu(CO3)4Cl(OH)5•2(H2O) 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 decrespignyite displays three bands are at 1056, 1070 and 1088 cm-1 attributed to the CO32- symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of CO32- symmetric stretching vibration varies with mineral composition. Raman bands of decrespignyite show bands at 1391, 1414, 1489 and 1547 cm-1. 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 are observed at 791, 815, 837 and 849 cm-1and assigned to the (CO3)2- ν2 bending modes. Raman bands are observed for decrespignyite at 694, 718 and 746 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. Multiple bands are observed in the OH stretching region for decrespignyite, bastnasite and parisite indicating the presence of water and OH units in the mineral structure.

It’s not me, it’s you : a participant observation case study of the self-publishing musician in the 21st century

This thesis explores the business environment for self-publishing musicians at the end of the 20th century and the start of the 21st century from theoretical and empirical standpoints. The exploration begins by asking three research questions: what are the factors affecting the sustainability of an Independent music business; how many of those factors can be directly influenced by an Independent musician in the day-to-day operations of their musical enterprise; and how can those factors be best manipulated to maximise the benefit generated from digital music assets? It answers these questions by considering the nature of value in the music business in light of theories of political economy, then quantitative and qualitative examinations of the nature of participation in the music business, and then auto-ethnographic approaches to the application of two technologically enabled tools available to Independent musicians. By analyzing the results of five different examinations of the topic it answers each research question with reference to four sets of recurring issues that affect the operations of a 21st century music business: the musicians’ personal characteristics, their ability to address their business’s informational needs; their ability to manage the relationships upon which their business depends; and their ability to resolve the remaining technological problems that confront them. It discusses ways in which Independent self-publishing musicians can and cannot deal with these four issues on a day-to-day basis and highlights aspects for which technological solutions do not exist as well as ways in which technology is not as effective as has been claimed. It then presents a self-critique and proposes some directions for further study before concluding by suggesting some common features of 21st century Independent music businesses. This thesis makes three contributions to knowledge. First, it provides a new understanding of the sources of musical value, shows how this explains changes in the music industries over the past 30 years, and provides a framework for predicting future developments in those industries. Second, it shows how the technological discontinuity that has occurred around the start of the 21st century has and has not affected the production and distribution of digital cultural artefacts and thus the attitudes, approaches, and business prospects of Independent musicians. Third, it argues for new understandings of two methods by which self-publishing musicians can grow a business using production methods that are only beginning to be more broadly understood: home studio recording and fan-sourced production. Developed from the perspective of working musicians themselves, this thesis identifies four sets of issues that determine the probable success of musicians’ efforts to adopt new technologies to capture the value of the musicians’ creativity and thereby foster growth that will sustain an Independent music business in the 21st century.

Controlling Minimally-Actuated Vehicles for Applications in Ocean Observation

Establishing a persistent presence in the ocean with an AUV to observe temporal variability of large-scale ocean processes requires a unique sensor platform. In this paper, we propose a strategy that utilizes ocean model predictions to increase the autonomy and control of Lagrangian or profiling floats for precisely this purpose. An A* planner is applied to a local controllability map generated from predictions of ocean currents to compute a path between prescribed waypoints that has the highest likelihood of successful execution. The control to follow the planned path is computed by use of a model predictive controller. This controller is designed to select the best depth for the vehicle to exploit ambient currents to reach the goal waypoint. Mission constraints are employed to simulate a practical data collection mission. Results are presented in simulation for a mission off the coast of Los Angeles, CA USA, and show surprising results in the ability of a Lagrangian float to reach a desired location.

Reply to the discussion by Karen Johannesson on “Rare earth element geochemistry of scleractinian coral skeleton during meteoric diagenesis: a sequence through neomorphism of aragonite to calcite” by Webb et al., Sedimentology, 56, 1433-1463

Webb et al. (2009) described a late Pleistocenecoral sample wherein the diagenetic stabilization of original coral aragonite to meteoric calcite was halted more or less mid-way through the process, allowing direct comparison of pre-diagenetic and post-diagenetic microstructure and trace element distributions. Those authors found that the rare earth elements (REEs) were relatively stable during meteoric diagenesis, unlike divalent cations such as Sr,and it was thus concluded that original, in this case marine, REE distributions potentially could be preserved through the meteoric carbonate stabilization process that must have affected many, if not most, ancient limestones. Although this was not the case in the analysed sample, they noted that where such diagenesis took place in laterally transported groundwater, trace elements derived from that groundwater could be incorporated into diagenetic calcite, thus altering the initial REE distribution (Banner et al., 1988). Hence, the paper was concerned with the diagenetic behaviour of REEs in a groundwater-dominated karst system. The comment offered by Johannesson (2011) does not question those research results, but rather, seeks to clarify an interpretation made by Webb et al. (2009) of an earlier paper, Johannesson et al. (2006).

Discriminating stromatolite formation modes using rare earth element geochemistry: Trapping and binding versus in situ precipitation of stromatolites from the Neoproterozoic Bitter Springs Formation, Northern Territory, Australia

Stromatolites consist primarily of trapped and bound ambient sediment and/or authigenic mineral precipitates, but discrimination of the two constituents is difficult where stromatolites have a fine texture. We used laser ablation-inductively coupled plasma-mass spectrometry to measure trace element (rare earth element – REE, Y and Th) concentrations in both stromatolites (domical and branched) and closely associated particulate carbonate sediment in interspaces (spaces between columns or branches) from bioherms within the Neoproterozoic Bitter Springs Formation, central Australia. Our high resolution sampling allows discrimination of shale-normalised REE patterns between carbonate in stromatolites and immediately adjacent, fine-grained ambient particulate carbonate sediment from interspaces. Whereas all samples show similar negative La and Ce anomalies, positive Gd anomalies and chondritic Y/Ho ratios, the stromatolites and non-stromatolite sediment are distinguishable on the basis of consistently elevated light REEs (LREEs) in the stromatolitic laminae and relatively depleted LREEs in the particulate sediment samples. Additionally, concentrations of the lithophile element Th are higher in ambient sediment samples than in stromatolites, consistent with accumulation of some fine siliciclastic detrital material in the ambient sediment but a near absence in the stromatolites. These findings are consistent with the stromatolites consisting dominantly of in situ carbonate precipitates rather than trapped and bound ambient sediment. Hence, high resolution trace element (REE + Y, Th) geochemistry can discriminate fine-grained carbonates in these stromatolites from coeval non-stromatolitic carbonate sediment and demonstrates that the sampled stromatolites formed primarily from in situ precipitation, presumably within microbial mats/biofilms, rather than by trapping and binding of ambient sediment. Identification of the source of fine carbonate in stromatolites is significant, because if it is not too heavily contaminated by trapped ambient sediment, it may contain geochemical biosignatures and/or direct evidence of the local water chemistry in which the precipitates formed.

Assessment of flood-related recharge to alluvial aquifers of an irrigated catchment following extended drought conditions using 3D visualisation and environmental tracers, Lockyer Valley, southeast Queensland, Australia.

The Lockyer Valley in southeast Queensland, Australia, hosts an economically significant alluvial aquifer system which has been impacted by prolonged drought conditions (~1997 to ~ 2009). Throughout this time, the system was under continued groundwater extraction, resulting in severe aquifer depletion. By 2008, much of the aquifer was at <30% of storage but some relief occurred with rains in early 2009. However, between December 2010 and January 2011, most of southeast Queensland experienced unprecedented flooding, which generated significant aquifer recharge. In order to understand the spatial and temporal controls of groundwater recharge in the alluvium, a detailed 3D lithological property model of gravels, sands and clays was developed using GOCAD software. The spatial distribution of recharge throughout the catchment was assessed using hydrograph data from about 400 groundwater observation wells screened at the base of the alluvium. Water levels from these bores were integrated into a catchment-wide 3D geological model using the 3D geological modelling software GOCAD; the model highlights the complexity of recharge mechanisms. To support this analysis, groundwater tracers (e.g. major and minor ions, stable isotopes, 3H and 14C) were used as independent verification. The use of these complementary methods has allowed the identification of zones where alluvial recharge primarily occurs from stream water during episodic flood events. However, the study also demonstrates that in some sections of the alluvium, rainfall recharge and discharge from the underlying basement into the alluvium are the primary recharge mechanisms of the alluvium. This is indicated by the absence of any response to the flood, as well as the observed old radiocarbon ages and distinct basement water chemistry signatures at these locations. Within the 3D geological model, integration of water chemistry and time-series displays of water level surfaces before and after the flood suggests that the spatial variations of the flood response in the alluvium are primarily controlled by the valley morphology and lithological variations within the alluvium. The integration of time-series of groundwater level surfaces in the 3D geological model also enables the quantification of the volumetric change of groundwater stored in the unconfined sections of this alluvial aquifer during drought and following flood events. The 3D representation and analysis of hydraulic and recharge information has considerable advantages over the traditional 2D approach. For example, while many studies focus on singular aspects of catchment dynamics and groundwater-surface water interactions, the 3D approach is capable of integrating multiple types of information (topography, geological, hydraulic, water chemistry and spatial) into a single representation which provides valuable insights into the major factors controlling aquifer processes.

Assessment of interactions between alluvial, Great Artesian Basin (GAB) and volcanic aquifers using 3D visualisation and environmental tracers, Lockyer Valley, southeast Queensland, Australia

A detailed 3D lithological model framework was developed using GOCAD software to understand interactions between alluvial, volcanic and GAB aquifers and the spatial and temporal distribution of groundwater recharge to the alluvium of the Lockyer Valley. Groundwater chemistry, isotope data (H20-δ2H and δ18O , 87Sr/86Sr, 3H and 14C) and groundwater level time-series data from approximately 550 observation wells were integrated into the catchment-wide 3D model to assess the recharge processes involved. This approach enabled the identification of zones where recharge to the alluvium primarily occurs from stream water during episodic flood events. Importantly, the study also demonstrates that in some sections of the alluvium recharge is also from storm rainfall and seepage discharge from the underlying GAB aquifers. These other sources of recharge are indicated by (a) the absence of a response of groundwater levels to flooding in some areas, (b) old radiocarbon ages, and (c) distinct bedrock water chemistry and δ2H and δ18O signatures in alluvial groundwater at these locations. Integration of isotopes, water chemistry and time-series displays of groundwater levels before and after the 2010/2011 flood into the 3D model suggest that the spatial variations in the alluvial groundwater response are mostly controlled by valley morphology and lithological (i.e. permeability) variations within the alluvium. Examination of the groundwater level variations in the 3D model also enabled quantification of the volumetric change of groundwater stored in the unconfined alluvial aquifer prior to and post-flood events.

Observation of new particle formation in subtropical urban environment

The aim of this study was to characterise the new particle formation events in a subtropical urban environment in the southern hemisphere. The study measured the number concentration of particles and its size distribution in Brisbane, Australia during 2009. The variation of particle number concentration and nucleation burst events were characterised as well as the particle growth rate which was first reported in urban environment of Australia. The annual average NUFP, NAitken and NNuc were 9.3 x 103, 3.7 x 103 and 5.6 x 103 cm-3, respectively. Weak seasonal variation in number concentration was observed. Local traffic exhaust emissions were a major contributor of the pollution (NUFP) observed in morning which was dominated by the Aitken mode particles, while particles formed by secondary formation processes contributed to the particle number concentration during afternoon. Overall, 65 nucleation burst events were identified during the study period. Nucleation burst events were classified into two groups, with and without particles growth after the burst of nucleation mode particles observed. The average particle growth rate of the nucleation events was 4.6 nm hr-1 (ranged from 1.79 – 7.78 nm hr-1). Case studies of the nucleation burst events were characterised including i) the nucleation burst with particle growth which is associated with the particle precursor emitted from local traffic exhaust emission, ii) the nucleation burst without particle growth which is due to the transport of industrial emissions from the coast to Brisbane city or other possible sources with unfavourable conditions which suppressed particle growth and iii) interplay between the above two cases which demonstrated the impact of the vehicle and industrial emissions on the variation of particle number concentration and its size distribution during the same day.