Chalcophile element geochemistry of the Boggy Plain Zoned Pluton, southeastern Australia : a S-saturated barren compositionally diverse magma

The behavior of the platinum group elements (PGE) and Re in felsic magmas is poorly understood due to scarcity of data. We report the concentrations of Ni, Cu, Re, and PGE in the compositionally diverse Boggy Plain zoned pluton (BPZP), which shows a variation of rock type from gabbro through granodiorite and granite to aplite with a SiO2 range from 52 to 74 wt %. In addition, major silicate and oxide minerals were analyzed for Ni, Cu, and Re, and a systematic sulfide study was carried out to investigate the role of silicate, oxide, and sulfide minerals on chalcophile element geochemistry of the BPZP. Mass balance calculation shows that the whole rock Cu budget hosted by silicate and oxide minerals is <13 wt % and that Cu is dominantly located in sulfide phases, whereas most of the whole rock Ni budget (>70 wt %) is held in major silicate and oxide minerals. Rhenium is dominantly hosted by magnetite and ilmenite. Ovoid-shaped sulfide blebs occur at the boundary between pyroxene phenocrysts and neighboring interstitial phases or within interstitial minerals in the gabbro and the granodiorite. The blebs are composed of pyrrhotite, pyrite, chalcopyrite, and S-bearing Fe-oxide, which contain total trace metals (Co, Ni, Cu, Ag, Pb) up to ~16 wt %. The mineral assemblage, occurrence, shape, and composition of the sulfide blebs are a typical of magmatic sulfide. PGE concentrations in the BPZP vary by more than two orders of magnitude from gabbro (2.7–7.8 ppb Pd, 0.025–0.116 ppb Ir) to aplite (0.05 ppb Pd, 0.001 ppb Ir). Nickel, Cu, Re, and PGE concentrations are positively correlated with MgO in all the rock types although there is a clear discontinuity between the granodiorite and the granite in the trends for Ni, Rh, and Ir when plotted against MgO. Cu/Pd values gradually increase from 6,100 to 52,600 as the MgO content decreases. The sulfide petrology and chalcophile element geochemistry of the BPZP show that sulfide saturation occurred in the late gabbroic stage of magma differentiation. Segregation and distribution of these sulfide blebs controlled Cu and PGE variations within the BPZP rocks although the magma of each rock type may have experienced a different magma evolution history in terms of crustal assimilation and crystal fractionation. The sulfide melt locked in the cumulate rocks must have sequestered a significant portion of the chalcophile elements, which restricted the availability of these metals to magmatic-hydrothermal ore fluids. Therefore, we suggest that the roof rocks that overlay the BPZP were not prospective for magmatic-hydrothermal Cu, Au, or Cu–Au deposits.

Imaging of human lens lipids by desorption electrospray ionization mass spectrometry

The lipid composition of the human lens is distinct from most other tissues in that it is high in dihydrosphingomyelin and the most abundant glycerophospholipids in the lens are unusual 1-O-alkyl-ether linked phosphatidylethanolamines and phosphatidylserines. In this study, desorption electrospray ionization (DESI) mass spectrometry-imaging was used to determine the distribution of these lipids in the human lens along with other lipids including, ceramides, ceramide-1-phosphates, and lyso 1-O-alkyl ethers. To achieve this, 25 μm lens slices were mounted onto glass slides and analyzed using a linear ion-trap mass spectrometer equipped with a custom-built, 2-D automated DESI source. In contrast to other tissues that have been previously analyzed by DESI, the presence of a strong acid in the spray solvent was required to desorb lipids directly from lens tissue. Distinctive distributions were observed for [M + H]+ ions arising from each lipid class. Of particular interest were ionized 1-O-alkyl phosphatidylethanolamines and phosphatidylserines, PE (18:1e/18:1), and PS (18:1e/18:1), which were found in a thin ring in the outermost region of the lens. This distribution was confirmed by quantitative analysis of lenses that were sectioned into four distinct regions (outer, barrier, inner, and core), extracted and analyzed by electrospray ionization tandem mass spectrometry. DESI-imaging also revealed a complementary distribution for the structurally-related lyso 1-O-alkyl phosphatidylethanolamine, LPE (18:1e), which was localized closer to the centre of the lens. The data obtained in this study indicate that DESI-imaging is a powerful tool for determining the spatial distribution of human lens lipids. © 2010 American Society for Mass Spectrometry.

Mining and (sustainable) local communities : transforming Ravensthorpe, Western Australia

This chapter examines local community experiences, understandings and changes attending the presence of mining activity, in particular as occurred in the Shire of Ravensthorpe in the South West of Western Australia (WA). It does so by drawing on an extensive ethnographic study spanning the development, opening, and closure of BHP Billiton’s Ravensthorpe Nickel Operation (RNO). Given that the negative consequences of mining activity are most evident and complex at the local level, it is crucial that we understand and address how communities (and the individuals and families who are both part of and are shaped by communities) experience the impacts of mining. Though difficult to measure, social and cultural dimensions of mining at the local scale, as this chapter demonstrates, are central to our understanding of mining as a curse or cure.

Configurations of Gender, Class and Rurality in Resource Affected Rural Australia

Historically, class has been a key concern in studies of resource affected communities (e.g., Williamson 1982, Warwick and Littlejohn 1992). While work continues, particularly in Britain, today it reflects the rationalization of the British mining sector, and thus focuses largely on mining heritage (e.g., Strangleman et al. 1999, Dicks 2008). In contrast, this chapter examines class relations as manifest in a contemporary setting in rural Australia. This site, the Ravensthorpe Shire in the south west of Western Australia, relied largely on agriculture until 2004 when BHP Billiton commenced construction of a nickel mine in the area. This affected the entire Shire as well as the two rural communities of Ravensthorpe and Hopetoun. The mine, which was officially opened in June 2008, is one of a large number of new mineral and energy developments being established in non metropolitan areas of the country as high international demand for resources fuels significant growth in the sector. In a single six month period in 2009, for example, 15 major minerals and energy projects were completed across the nation and a further 74 projects were at advanced stages (Australian Bureau of Agricultural Economics 2009). A number of these were, as was the case in Ravensthorpe, in what had been traditionally agricultural communities.

Plasma-driven self-organization of Ni nanodot arrays on Si(100)

The results of the combined experimental and numerical study suggest that nonequilibrium plasma-driven self-organization leads to better size and positional uniformity of nickel nanodot arrays on a Si(100) surface compared with neutral gas-based processes under similar conditions. This phenomenon is explained by introducing the absorption zone patterns, whose areas relative to the small nanodot sizes become larger when the surface is charged. Our results suggest that strongly nonequilibrium and higher-complexity plasma systems can be used to improve ordering and size uniformity in nanodot arrays of various materials, a common and seemingly irresolvable problem in self-organized systems of small nanoparticles. © 2008 American Institute of Physics.

Plasma-assisted self-organized growth of uniform carbon nanocone arrays

The self-organized growth of uniform carbon nanocone arrays using low-temperature non-equilibrium Ar + H 2 + CH 4 plasma-enhanced chemical vapor deposition (PECVD) is studied. The experiment shows that size-, shape-, and position-uniform carbon nanocone arrays can develop even from non-uniformly fragmented discontinuous nickel catalyst films. A three-stage scenario is proposed where the primary nanocones grow on large catalyst particles during the first stage, and the secondary nanocones are formed between the primary ones at the second stage. Finally, plasma-related effects lead to preferential growth of the secondary nanocones and eventually a uniform nanopattern is formed. This does not happen in a CVD process with the same gas feedstock and surface temperature. The proposed three-stage growth scenario is supported by the numerical experiment which generates nanocone arrays very similar to the experimentally synthesized nanopatterns. The self-organization process is explained in terms of re-distribution of surface and volumetric fluxes of plasma-generated species in a developing nanocone array. Our results suggest that plasma-related self-organization effects can significantly reduce the non-uniformity of carbon nanostructure arrays which commonly arises from imperfections in fragmented Ni-based catalyst films.

Stoichiometry, crystallinity, and nano-scale surface morphology of the graded calcium phosphate-based bio-ceramic interlayer on Ti-Al-V

A plasma-assisted concurrent Rf sputtering technique for fabrication of biocompatible, functionally graded CaP-based interlayer on Ti-6Al-4V orthopedic alloy is reported. Each layer in the coating is designed to meet a specific functionality. The adherent to the metal layer features elevated content of Ti and supports excellent ceramic-metal interfacial stability. The middle layer features nanocrystalline structure and mimics natural bone apatites. The technique allows one to reproduce Ca/P ratios intrinsic to major natural calcium phosphates. Surface morphology of the outer, a few to few tens of nanometers thick, layer, has been tailored to fit the requirements for the bio-molecule/protein attachment factors. Various material and surface characterization techniques confirm that the optimal surface morphology of the outer layer is achieved for the process conditions yielding nanocrystalline structure of the middle layer. Preliminary cell culturing tests confirm the link between the tailored nano-scale surface morphology, parameters of the middle nanostructured layer, and overall biocompatibility of the coating.

A study of the effects metal residues in poly(9,9-dioctylfluorene) have on field-effect transistor device characteristics

The amount of metal residues from organometallic reagents used in preparation of poly(9,9-dioctylfluorene) by palladium catalysed Suzuki and nickel-induced Yamamoto polycondensations have been determined, and their effect upon the behaviour of the polymer in field-effect transistors (FETs) has been measured. The metal levels from material polymerised by Suzuki method were found to be much higher than from that made by the Yamamoto procedure. Simple treatment of the polymers with suitable metal trapping reagents lowered the metal levels significantly, with EDTA giving best results for nickel and triphenylphosphine for palladium. Comparison of the behaviour of FETs using polyfluorenes with varying levels of metal contamination, showed that the metal residues have little effect upon the mobility values, but often affect the degree of hysteresis, possibly acting as charge traps. Satisfactory device performances were obtained from polymer with palladium levels of 2000 μg/g suggesting that complete removal of metal residues may not be necessary for satisfactory device performance.

Investigations of ultrafine particles emitted by ships and other transport modes in the port of Brisbane

This research measured particle and gaseous emissions from ships and trains operating within the Port of Brisbane, and explored their influence on ambient air composition at a downwind suburban measurement site. The ship and train emission factor investigations resulted in the development of novel measurement techniques which permit the quantification of particle and gaseous emission factors using samples collected from post-emission exhaust plumes. The urban influence investigation phase of the project produced a new approach to identifying influences from ship emissions.

Adsorption and mobility of metals in build-up on road surfaces

The study investigated the adsorption and bioavailability characteristics of traffic generated metals common to urban land uses, in road deposited solids particles. To validate the outcomes derived from the analysis of field samples, adsorption and desorption experiments were undertaken. The analysis of field samples revealed that metals are selectively adsorbed to different charge sites on solids. Zinc, copper, lead and nickel are adsorbed preferentially to oxides of manganese, iron and aluminium. Lead is adsorbed to organic matter through chemisorption. Cadmium and chromium form weak bonding through cation exchange with most of the particle sizes. Adsorption and desorption experiments revealed that at high metal concentrations, chromium, copper and lead form relatively strong bonds with solids particles while zinc is adsorbed through cation exchange with high likelihood of being released back into solution. Outcomes from this study provide specific guidance for the removal of metals from stormwater based on solids removal.

Health consequences of exposure to e-waste : a systematic review

Background The population exposed to potentially hazardous substances through inappropriate and unsafe management practices related to disposal and recycling of end-of-life electrical and electronic equipment, collectively known as e-waste, is increasing. We aimed to summarise the evidence for the association between such exposures and adverse health outcomes. Methods We systematically searched five electronic databases (PubMed, Embase, Web of Science, PsycNET, and CINAHL) for studies assessing the association between exposure to e-waste and outcomes related to mental health and neurodevelopment, physical health, education, and violence and criminal behaviour, from Jan 1, 1965, to Dec 17, 2012, and yielded 2274 records. Of the 165 full-text articles assessed for eligibility, we excluded a further 142, resulting in the inclusion of 23 published epidemiological studies that met the predetermined criteria. All studies were from southeast China. We assessed evidence of a causal association between exposure to e-waste and health outcomes within the Bradford Hill framework. Findings We recorded plausible outcomes associated with exposure to e-waste including change in thyroid function, changes in cellular expression and function, adverse neonatal outcomes, changes in temperament and behaviour, and decreased lung function. Boys aged 8–9 years living in an e-waste recycling town had a lower forced vital capacity than did those living in a control town. Significant negative correlations between blood chromium concentrations and forced vital capacity in children aged 11 and 13 years were also reported. Findings from most studies showed increases in spontaneous abortions, stillbirths, and premature births, and reduced birthweights and birth lengths associated with exposure to e-waste. People living in e-waste recycling towns or working in e-waste recycling had evidence of greater DNA damage than did those living in control towns. Studies of the effects of exposure to e-waste on thyroid function were not consistent. One study related exposure to e-waste and waste electrical and electronic equipment to educational outcomes. Interpretation Although data suggest that exposure to e-waste is harmful to health, more well designed epidemiological investigations in vulnerable populations, especially pregnant women and children, are needed to confirm these associations. Funding Children's Health and Environment Program, Queensland Children's Medical Research Institute, The University of Queensland, Australia.

Facile dearomatisation of porphyrins using palladium-catalysed hydrazination: the 5,15-diiminoporphodimethenes and their redox products

The synthesis, electronic absorption and 1H NMR spectra of a suite of novel porphyrinoids derived from meso-bromoporphyrins by palladium-catalysed aminations using ethyl and tert-butylcarbazates are reported. Instead of the expected carbazate-substituted porphyrins, a facile oxidative dearomatisation of the porphyrin ring occurs in high yield, especially for the nickel(II) complexes, resulting in high yields of 5,15-diiminoporphodimethenes (DIPDs). The analogous zinc(II) and free base DIPDs were also characterised, the former by X-ray crystallography. The oxidation and reduction reactions of DIPDs and their precursor carbazate porphyrins were studied. Density Functional Theory (DFT) was used to calculate the optimised geometries and frontier molecular orbitals of DIPD Ni8c and bis(azocarboxylate) 19c, and Time Dependent DFT calculations allowed the prediction of electronic absorption spectra, whose characteristics corresponded well with those of the observed solution spectra. In the latter case, the calculated low-energy absorptions were unlike those of a typical porphyrin, due to the near-degeneracy of the highest filled frontier orbitals, and the wide energy separation between the unfilled orbitals. This feature was present in the observed spectrum.

Pentacene on Ni(111): room-temperature molecular packing and temperature-activated conversion to graphene

We investigate, using scanning tunnelling microscopy, the adsorption of pentacene on Ni(111) at room temperature and the behaviour of these monolayer films with annealing up to 700 °C. We observe the conversion of pentacene into graphene, which begins from as low as 220 °C with the coalescence of pentacene molecules into large planar aggregates. Then, by annealing at 350 °C for 20 minutes, these aggregates expand into irregular domains of graphene tens of nanometers in size. On surfaces where graphene and nickel carbide coexist, pentacene shows preferential adsorption on the nickel carbide phase. The same pentacene to graphene transformation was also achieved on Cu(111), but at a higher activation temperature, producing large graphene domains that exhibit a range of moiré superlattice periodicities.

A social licence to operate: Corporate social responsibility, local communities and the constitution of global production networks

This article contributes to the theorization of the role of informal regulation (undertaken by leading firms) in the ongoing organization of global production networks. It does so through a qualitative case study of BHP Billiton's Ravensthorpe Nickel Operation (RNO) in the rural Shire of Ravensthorpe in Western Australia. This less tangible, and to date under-researched, dimension of global production networks is foregrounded through a focus on the corporate social responsibility strategy implemented by RNO in the service of achieving and/or demonstrating a broader ‘social licence to operate’. This ‘licence’ functions – beyond the corporation – as a legitimated and legitimating multi-scalar mechanism through which to gain and maintain access to mineral resources and thus to establish viable and ongoing global production networks. Further, this informal regulation is shown to shape social relations and qualities of place conducive to competitive global mineral extraction and to facilitate the positioning of local communities and places in mineral global production networks.

The exhaustive reduction of formylporphyrins to methylporphyrins using dimethylformamide/water as reductant under microwave irradiation

The reduction of meso-formyl derivatives of 5,15-diaryl- and 5,10,15-triphenylporphyrin (and their nickel(II) complexes) to the corresponding meso-methyl porphyrins is achieved in high yield by microwave heating of the substrate in dimethylformamide (DMF) in the presence of acids such as trifluoroacetic acid, or even just with added water. The reactions are complete in less than 30 min at 250 °C. The reaction is strongly suppressed in very dry DMF in the absence of added acid. The meso-hydroxymethyl porphyrins are also reduced to the methyl derivatives, suggesting the primary alcohols may be intermediates in the exhaustive reduction. UV-visible spectra taken at intervals during reaction at 240 °C indicated that at least one other intermediate is present, but it was not identified. In d7-DMF, the methylporphyrin isolated was mainly Por-CD2H, showing that both of the added hydrogens arise from the solvent, and not from the added water or acid.