Raman spectroscopic study of the hydroxy-arsenate mineral pharmacolite Ca(HAsO4)•2H2O : implications for aquifer and sediment remediation

The removal of arsenate anions from aqueous media, sediments and wasted soils is of environmental significance. The reaction of gypsum with the arsenate anion results in pharmacolite mineral formation, together with related minerals. Raman and infrared spectroscopy have been used to study the mineral pharmacolite Ca(HAsO4)•2H2O. The mineral is characterised by an intense Raman band at 865 cm-1 assigned to the (AsO4)3- symmetric stretching mode. The equivalent infrared band is found at 864 cm-1. The low intensity Raman band at 886 cm-1 provides evidence for (AsO3OH)2-. A series of overlapping bands in the 300 to 450 cm-1 are attributed to ν2 and ν4 bending modes. Prominent Raman bands at around 3187 cm-1 are assigned to water OH stretching vibrations and the two sharp bands at 3425 and 3526 cm-1 to the OH stretching vibrations of (HOAsO3) units.

Implications for the design of a digital stethoscope for anaesthetic preadmission consultations

Background This research addresses the development of a digital stethoscope for use with a telehealth communications network to allow doctors to examine patients remotely (a digital telehealth stethoscope). A telehealth stethoscope would allow remote auscultation of patients who do not live near a major hospital. Travelling from remote areas to major hospitals is expensive for patients and a telehealth stethoscope could result in significant cost savings. Using a stethoscope requires great skill. To design a telehealth stethoscope that meets doctors’ expectations, the use of existing stethoscopes in clinical contexts must be examined. Method Observations were conducted of 30 anaesthetic preadmission consultations. The observations were video- taped. Interaction between doctor, patient and non-human elements in the consultation were “coded” to transform the video into data. The data were analysed to reveal essential aspects of the interactions. Results The analysis has shown that the doctor controls the interaction during auscultation. The conduct of auscultation draws heavily on the doctor’s tacit knowledge, allowing the doctor to treat the acoustic stethoscope as infrastructure – that is, the stethoscope sinks into the background and becomes completely transparent in use. Conclusion Two important, and related, implications for the design of a telehealth stethoscope have arisen from this research. First, as a telehealth stethoscope will be a shared device, doctors will not be able to make use of their existing expertise in using their own stethoscopes. Very simply, a telehealth stethoscope will sound different to a doctor’s own stethoscope. Second, the collaborative interaction required to use a telehealth stethoscope will have to be invented and refined. A telehealth stethoscope will need to be carefully designed to address these issues and result in successful use. This research challenges the concept of a telehealth stethoscope by raising questions about the ease and confidence with which doctors could use such a device.

National health and hospital network for Australia's future : Implications for emergency medicine

The proposals arising from the agreement reached between the Rudd government and the States and Territories (except Western Australia) in April 2010 represent the most fundamental realignment of health responsibilities since the creation of Medicare in 1984. They will change the health system, and the structures that will craft its future direction and design. These proposals will have a significant impact on Emergency Medicine; an impact from not only the system-wide effects of the proposals but also those that derive from the specific recommendations to create an activity-based funding mechanism for EDs, to implement the four hour rule and to develop a performance indicator framework for EDs. The present paper will examine the potential impact of the proposals on Emergency Medicine to inform those who work within the system and to help guide further developments. More work is required to better evaluate the proposals and to guide the design and development of specific reform instruments. Any such efforts should be based upon a proper analysis of the available evidence, and a structured approach to research and development so as to deliver on improved services to the community, and on improved quality and safety of emergency medical care.

Australia and New Zealand CBNG development and environmental implications

Following the success of Coalbed Natural Gas (CBNG) operations in the United States, companies in Australia and New Zealand have been actively exploring and developing this technology for the last two decades. In particular, the Bowen and Surat basins in Queensland, Australia, have undergone extensive CBNG development. Unfortunately, awareness of potential environmental problems associated with CBNG abstraction has not been widespread and legislation has at times struggled to keep up with rapid development. In Australia, the combined CBNG resource for both the Bowen and Surat basins has been estimated at approximately 10,500 PJ with gas content as high as 10 m3/tonne of coal. There are no official estimates for the magnitude of the CBNG resource in New Zealand but initial estimates suggest this could be up to 1,300 PJ with gas content ranging from 1 to 5 m3/tonne of coal. In Queensland, depressurization of the Walloon Coal Measures to recover CBNG has the potential to induce drawdown in adjacent deep aquifer systems through intraformational groundwater flow. In addition, CBNG operators have been disposing their co-produced water by using large unlined ponds, which is not the best practice for managing co-produced water. CBNG waters in Queensland have the typical geochemical signature associated with CBNG waters (Van Voast, 2003) and thus have the potential to impair soils and plant growth where land disposal is considered. Water quality from exploration wells in New Zealand exhibit the same characteristics although full scale production has not yet begun. In general, the environmental impacts that could arise from CBNG water extraction depend on the aquifer system, the quantity and quality of produced water, and on the method of treatment and disposal being used. Understanding these impacts is necessary to adequately manage CBNG waters so that environmental effects are minimized; if properly managed, CBNG waters can be used for beneficial applications and can become a valuable resource to stakeholders.

Population ageing in a globalizing labour market : implications for older workers

This article concerns the changing nature of the relationship between age and the labour market. Global demographic, economic and technological changes potentially pose major challenges for older workers trying to maintain a secure attachment to the labour market. Recent public policy has responded by defining concepts such as 'active ageing' which encourage older workers to participate fully within society, including maintaining workforce participation. Older workers' ability to secure quality work within a volatile labour market is considered. While activation approaches are currently popular among policymakers, the notion that older workers will easily avoid a diminution of their employment prospects is challenged.

Treating an unhealthy organisational culture : the implications of the Bundaberg Hospital inquiry for managerial ethical decision making

This paper explores the interplay between individual values, espoused organisational values and the values of the organisational culture in practice in light of a recent Royal Commission in Queensland, Australia, which highlighted systematic failures in patient care. The lack of congruence among values at these levels impacts upon the ethical decision making of health managers. The presence of institutional ethics regimes such as the Public Sector Ethics Act 1994 (Qld) and agency codes of conduct are not sufficient to counteract the negative influence of informal codes of practice that undermine espoused organisational values and community standards. The ethical decision-making capacity of health care managers remains at the front line in the battle against unethical and unprofessional practice. What is known about the topic? Value congruence theory focusses on the conflicts between individual and organisational values. Congruence between individual values, espoused values and values expressed in everyday practice can only be achieved by ensuring that such shared values are an ever-present factor in managerial decision making. What does this paper add? The importance of value congruence in building and sustaining a healthy organisational culture is confirmed by the evidence presented in the Bundaberg Hospital Inquiry. The presence of strong individual values among staff and strong espoused values in line with community expectations and backed up by legislation and ethics regimes were not, in themselves, sufficient to ensure a healthy organisational culture and prevent unethical, and possibly illegal, behaviour. What are the implications for practitioners? Managers must incorporate ethics in decision making to establish and maintain the nexus between individual and organisational values that is a vital component of a healthy organisational culture.

Mapping social enterprise in Australia : conceptual debates and their operational implications

In the last ten years, there has been growing interest in social enterprise by governments, the not for profit sector and philanthropy in Australia The drivers of this interest have been variously understood to be: increasing demands for innovative responses to social and environmental problems; pressures on non-profit organisations to diversify their income sources; and increasing emphases by government on the role of civil society actors in partnering around social policy agendas. Whatever its genesis, very little is known about the scale and scope of the emerging social enterprise sector. In order to research the scope of the sector, an important first step involves understanding just what social enterprise is, and how it may be operationalised. This paper presents the findings from the first stage of a national research project conducted by the authors in conjunction with a new social enterprise development company. The purpose of the project was to provide a comprehensive snapshot of the social enterprise sector in Australia. In this paper, we focus on the definitional debates arising from our workshop discussions, what these mean for understanding contemporary discourses of social enterprise, and their implications for research, policy and practice.

Strategic entrepreneurship in New Zealand's state-owned enterprises : underlying elements and financial implications

The concept of strategic entrepreneurship has received increased attention over the past ten yeras. Viewed as the intersection of entrepreneurship and strategy this field of research is populated by conceptual studies which focus mainly on the nature and perceived benefits of strategic entrepreneurship. Similarly the study of entrepreneurship in a public sector context has gained increasing support in recent years but also remains underexplored. To address these gaps this thesis considers : what are the underlying elements and financial implications of strategic entrepreneurship in New Zealand's state-owned enterprises, New Zealand's SOE sector comprising 17 government-owned,commercially focused organisations, is considered to be a prime subject for this research. Well known for their implementation of new public management, many New Zealand SOEs have also been publicly recognised as both innovative and entrepreneurial. The research question is addressed by first developing a preliminary framework of strategic entrepreneurship from literature on entrepreneurhsip and strategy. The framework is then examined in the context of case studies on activity.

Examining the covert nature of product placement : implications for public policy

As consumers become better educated and more skeptical of traditional advertising, alternate forms of marketing communication have emerged that aim to influence audiences unobtrusively. One such example is product placement. Product placement has attracted ongoing debate as to whether it is covert, unethical, and influences consumption. The current article examines the nature and practice of product placement in this light. This taxonomy of product placement attributes is based on current marketing practice and examines whether this is, indeed, a covert marketing strategy. Further, it presents a conceptualization of the influence of product placement on consumer welfare. We highlight that the many forms of product placement necessitate independent evaluation to determine ethical and regulatory standards. Operational solutions for developing public policy are offered.

The effect of red blood cell orientation on the electrical impedance of pulsatile blood with implications for impedance cardiography

Impedance cardiography is an application of bioimpedance analysis primarily used in a research setting to determine cardiac output. It is a non invasive technique that measures the change in the impedance of the thorax which is attributed to the ejection of a volume of blood from the heart. The cardiac output is calculated from the measured impedance using the parallel conductor theory and a constant value for the resistivity of blood. However, the resistivity of blood has been shown to be velocity dependent due to changes in the orientation of red blood cells induced by changing shear forces during flow. The overall goal of this thesis was to study the effect that flow deviations have on the electrical impedance of blood, both experimentally and theoretically, and to apply the results to a clinical setting. The resistivity of stationary blood is isotropic as the red blood cells are randomly orientated due to Brownian motion. In the case of blood flowing through rigid tubes, the resistivity is anisotropic due to the biconcave discoidal shape and orientation of the cells. The generation of shear forces across the width of the tube during flow causes the cells to align with the minimal cross sectional area facing the direction of flow. This is in order to minimise the shear stress experienced by the cells. This in turn results in a larger cross sectional area of plasma and a reduction in the resistivity of the blood as the flow increases. Understanding the contribution of this effect on the thoracic impedance change is a vital step in achieving clinical acceptance of impedance cardiography. Published literature investigates the resistivity variations for constant blood flow. In this case, the shear forces are constant and the impedance remains constant during flow at a magnitude which is less than that for stationary blood. The research presented in this thesis, however, investigates the variations in resistivity of blood during pulsataile flow through rigid tubes and the relationship between impedance, velocity and acceleration. Using rigid tubes isolates the impedance change to variations associated with changes in cell orientation only. The implications of red blood cell orientation changes for clinical impedance cardiography were also explored. This was achieved through measurement and analysis of the experimental impedance of pulsatile blood flowing through rigid tubes in a mock circulatory system. A novel theoretical model including cell orientation dynamics was developed for the impedance of pulsatile blood through rigid tubes. The impedance of flowing blood was theoretically calculated using analytical methods for flow through straight tubes and the numerical Lattice Boltzmann method for flow through complex geometries such as aortic valve stenosis. The result of the analytical theoretical model was compared to the experimental impedance measurements through rigid tubes. The impedance calculated for flow through a stenosis using the Lattice Boltzmann method provides results for comparison with impedance cardiography measurements collected as part of a pilot clinical trial to assess the suitability of using bioimpedance techniques to assess the presence of aortic stenosis. The experimental and theoretical impedance of blood was shown to inversely follow the blood velocity during pulsatile flow with a correlation of -0.72 and -0.74 respectively. The results for both the experimental and theoretical investigations demonstrate that the acceleration of the blood is an important factor in determining the impedance, in addition to the velocity. During acceleration, the relationship between impedance and velocity is linear (r2 = 0.98, experimental and r2 = 0.94, theoretical). The relationship between the impedance and velocity during the deceleration phase is characterised by a time decay constant, ô , ranging from 10 to 50 s. The high level of agreement between the experimental and theoretically modelled impedance demonstrates the accuracy of the model developed here. An increase in the haematocrit of the blood resulted in an increase in the magnitude of the impedance change due to changes in the orientation of red blood cells. The time decay constant was shown to decrease linearly with the haematocrit for both experimental and theoretical results, although the slope of this decrease was larger in the experimental case. The radius of the tube influences the experimental and theoretical impedance given the same velocity of flow. However, when the velocity was divided by the radius of the tube (labelled the reduced average velocity) the impedance response was the same for two experimental tubes with equivalent reduced average velocity but with different radii. The temperature of the blood was also shown to affect the impedance with the impedance decreasing as the temperature increased. These results are the first published for the impedance of pulsatile blood. The experimental impedance change measured orthogonal to the direction of flow is in the opposite direction to that measured in the direction of flow. These results indicate that the impedance of blood flowing through rigid cylindrical tubes is axisymmetric along the radius. This has not previously been verified experimentally. Time frequency analysis of the experimental results demonstrated that the measured impedance contains the same frequency components occuring at the same time point in the cycle as the velocity signal contains. This suggests that the impedance contains many of the fluctuations of the velocity signal. Application of a theoretical steady flow model to pulsatile flow presented here has verified that the steady flow model is not adequate in calculating the impedance of pulsatile blood flow. The success of the new theoretical model over the steady flow model demonstrates that the velocity profile is important in determining the impedance of pulsatile blood. The clinical application of the impedance of blood flow through a stenosis was theoretically modelled using the Lattice Boltzman method (LBM) for fluid flow through complex geometeries. The impedance of blood exiting a narrow orifice was calculated for varying degrees of stenosis. Clincial impedance cardiography measurements were also recorded for both aortic valvular stenosis patients (n = 4) and control subjects (n = 4) with structurally normal hearts. This pilot trial was used to corroborate the results of the LBM. Results from both investigations showed that the decay time constant for impedance has potential in the assessment of aortic valve stenosis. In the theoretically modelled case (LBM results), the decay time constant increased with an increase in the degree of stenosis. The clinical results also showed a statistically significant difference in time decay constant between control and test subjects (P = 0.03). The time decay constant calculated for test subjects (ô = 180 - 250 s) is consistently larger than that determined for control subjects (ô = 50 - 130 s). This difference is thought to be due to difference in the orientation response of the cells as blood flows through the stenosis. Such a non-invasive technique using the time decay constant for screening of aortic stenosis provides additional information to that currently given by impedance cardiography techniques and improves the value of the device to practitioners. However, the results still need to be verified in a larger study. While impedance cardiography has not been widely adopted clinically, it is research such as this that will enable future acceptance of the method.

Raman spectroscopic study of the mineral thorikosite Pb3(OH)(SbO3,AsO3)Cl2 : a mineral of archaeological significance

The mineral thorikosite Pb3(OH)(SbO3,AsO3)Cl2 is named after the ancient city of Thorikos, in the region of Attica, where the ancient mine sites dating back to the bronze ages are found. Raman spectra of the antimonate bearing mineral thorikosite Pb3(OH)(SbO3,AsO3)Cl2 were studied, and related to the structure of the mineral. Two intense Raman peaks are observed at 596 and 730 cm-1 and are assigned to the Sb3+O3 and As3+O3 stretching vibrations. A peak at 1085 cm-1 is assigned to the Sb3+OH deformation mode. Raman band at 325 cm-1 is assigned to an OAsO bending vibration of the As3+O3 units and the bands at 269 and 275 cm-1 are attributed to the OSbO bending modes of the Sb3+O3 units. The intense Raman bands at 112 and 133 cm-1 are associated with PbCl stretching modes. Minerals such as nealite and thorikosite are minerals of archaeological significance. Yet no spectroscopic studies of these minerals have been undertaken.

Simulated cataract and low contrast stimuli impair cognitive performance in older adults : implications for neuropsychological assessment and everyday function

Objective: To investigate how age-related declines in vision (particularly contrast sensitivity), simulated using cataract-goggles and low-contrast stimuli, influence the accuracy and speed of cognitive test performance in older adults. An additional aim was to investigate whether declines in vision differentially affect secondary more than primary memory. Method: Using a fully within-subjects design, 50 older drivers aged 66-87 years completed two tests of cognitive performance - letter matching (perceptual speed) and symbol recall (short-term memory) - under different viewing conditions that degraded visual input (low-contrast stimuli, cataract-goggles, and low-contrast stimuli combined with cataract-goggles, compared with normal viewing). However, presentation time was also manipulated for letter matching. Visual function, as measured using standard charts, was taken into account in statistical analyses. Results: Accuracy and speed for cognitive tasks were significantly impaired when visual input was degraded. Furthermore, cognitive performance was positively associated with contrast sensitivity. Presentation time did not influence cognitive performance, and visual gradation did not differentially influence primary and secondary memory. Conclusion: Age-related declines in visual function can impact on the accuracy and speed of cognitive performance, and therefore the cognitive abilities of older adults may be underestimated in neuropsychological testing. It is thus critical that visual function be assessed prior to testing, and that stimuli be adapted to older adults' sensory capabilities (e.g., by maximising stimuli contrast).

Customers behaving badly : a state of the art review, research agenda and implications for practitioners

The purpose of this paper is to highlight important issues in the study of dysfunctional customer behavior and to provide a research agenda to inspire, guide, and enthuse. Through a critical evaluation of existing research, the aim is to highlight key issues and to present potentially worthy avenues for future study.

Structure of selected basic zinc/copper (II) phosphate minerals based upon near-infrared spectroscopy : implications for hydrogen bonding

The NIR spectra of reichenbachite, scholzite and parascholzite have been studied at 298 K. The spectra of the minerals are different, in line with composition and crystal structural variations. Cation substitution effects are significant in their electronic spectra and three distinctly different electronic transition bands are observed in the near-infrared spectra at high wavenumbers in the 12000-7600 cm-1 spectral region. Reichenbachite electronic spectrum is characterised by Cu(II) transition bands at 9755 and 7520 cm-1. A broad spectral feature observed for ferrous ion in the 12000-9000 cm-1 region both in scholzite and parascholzite. Some what similarities in the vibrational spectra of the three phosphate minerals are observed particularly in the OH stretching region. The observation of strong band at 5090 cm-1 indicates strong hydrogen bonding in the structure of the dimorphs, scholzite and parascholzite. The three phosphates exhibit overlapping bands in the 4800-4000 cm-1 region resulting from the combinations of vibrational modes of (PO4)3- units.

Infrared and infrared emission spectroscopy of nesquehonite Mg(OH)(HCO3)•2H2O : implications for the formula of nesquehonite

The mineral nesquehonite Mg(OH)(HCO3)•2H2O has been analysed by a combination of infrared (IR) and infrared emission spectroscopy (IES). Both techniques show OH vibrations, both stretching and deformation modes. IES proves the OH units are stable up to 450°C. The strong IR band at 934 cm-1 is evidence for MgOH deformation modes supporting the concept of HCO3- units in the molecular structure. Infrared bands at 1027, 1052 and 1098 cm-1 are attributed to the symmetric stretching modes of HCO3- and CO32- units. Infrared bands at 1419, 1439, 1511, and 1528 cm-1 are assigned to the antisymmetric stretching modes of CO32- and HCO3- units. IES supported by thermoanalytical results defines the thermal stability of nesquehonite IES defines the changes in the molecular structure of nesquehonite with temperature. The results of IR and IES supports the concept that the formula of nesquehonite is better defined as Mg(OH)(HCO3)•2H2O.