A Record Of Assimilation Preserved By Exotic Minerals In The Lowermost Platinum-Group Element Deposit Of The Bushveld Complex: The Volspruit Sulphide Zone

 This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this record Low-grade platinum-group element mineralisation in the Volspruit Sulphide Zone is sulphide-poor (<5 vol. %), distributed over a ~60 m-thick horizon in the lowermost cumulates of the northern limb of the Bushveld Complex. Unlike any other platinum-group element (PGE) deposit of the Bushveld Complex, the Volspruit Sulphide Zone is hosted exclusively within harzburgitic and dunitic cumulates in the Lower Zone of the Rustenburg Layered Suite. Here, we present a petrological investigation on the distribution of PGEs and chalcophile metals in mineralised pyroxenite cumulates from the Volspruit Sulphide Zone, to determine the origin of the PGE mineralisation in ultramafic cumulates and evaluate whether Volspruit-style mineralisation could occur in the stratigraphically lowest, ultramafic portions of other layered intrusions. Electron microscopy of pyroxenite cumulates revealed (1) chromite inclusions containing dolomite, albite, monazite, Pb-chlorides, base metal sulphides and Pt-As minerals, (2) the presence of exotic microxenocrysts (<300 μm diameter) in the pyroxenite matrix such as grains of CaCO3, U-Th-oxide and Mn-ilmenite, and (3) base metal sulphide assemblages enclosing grains of primary galena, sphalerite and Pb-chlorides. Systematic mapping of high-density mineral assemblages in pyroxenite cumulates across the Volspruit Sulphide Zone identified 196 precious metal mineral grains (Pt-, Pd-, Rh-, Au- or Ag-minerals), 98 Pb-sulphide grains (± Se, Cl), 27 Pb-chloride grains (± K, Se, Te, S), as well as 1 grain of Pb-telluride, 1 monazite grain and 1 grain of U–Pb-Th oxide. Trace element analyses of base metal sulphides reveal the highest S/Se values in pyrrhotite and chalcopyrite yet recorded in the Bushveld Complex. While some base metal sulphides are enriched in PGEs, the overall low-grade of the deposit and inferred fertile ultramafic magma(s) require relatively low R-factors (mass of silicate to sulphide melt) compared to other sulphide-poor PGE deposits, with a calculated R factor of ~500–3000. We consider that the presence of exotic inclusions in chromite, exotic microxenocrysts, and Pb/Zn/Cl grains enclosed within primary base metal sulphide assemblages provide strong evidence for crustal contamination in the Volspruit Sulphide Zone. The Malmani dolomite and the Black Reef quartzite within the lower Chuniespoort Group (2.2–2.4 Ga) are the most likely source of xenocrysts, assimilated in a staging chamber beneath the main Grasvally chamber, in which the Volspruit Sulphide Zone developed. It is possible that the Malmani dolomite contained an enrichment of Pb, Zn, Cl, and S minerals prior to assimilation. The assimilation of dolomite and limestone would locally increase the fO2 of the magma, triggering chromite crystallisation. The sudden removal of Fe from the melt, coupled with the addition of external sulfur triggered saturation of an immiscible sulphide melt in the ultramafic Volspruit magma. Chromite and base metal sulphides were subsequently emplaced into the main Grasvally magma chamber as a crystal-bearing slurry. Therefore, we consider it is possible for PGE mineralisation to occur in the ultramafic portion of any layered intrusion intruding in the vicinity of carbonate units. Even if this style of mineralisation in the lowermost portions of layered intrusions is sub-economic, it may reduce the grade or opportunity for PGE mineralisation higher up in the local magmatic stratigraphy, or in later magma emplacement events sourced from the same reservoir. The technique of specifically searching for microxenocrysts could be applied beyond layered intrusion research, to identify the range of crustal contaminants in other magmatic systems where macro-scale xenoliths are neither sampled nor preserved.National Environment Research CouncilUniversity of WollongongClaude Leon FoundationCentre of Excellence for Integrated Mineral & Energy Resource Analysis (CIMERA) at the Universities of Witwatersrand and Johannesburg

High Energy Secondaries for the Quantitative Secondary Ion Mass Spectrometric Analysis of Minerals

The major hurdle in quantitative analysis by SIMS is the inconsistency and non-predictability of ion yields, particularly their sensitivity to sample matrix. High energy (100-500 eV) secondary ions have been shown to be considerably less susceptible to matrix effects than low energy secondary ions, particularly in mineral analysis. Therefore ion yields of some sixty elements were measured utilizing very high energy secondaries (~ 500 eV), from a standard silicate glass. They show a broad ionization potential dependence and a mass (or velocity) dependency which is not removed by the application of a M½ or M factor. The modification of yields with conventional thermodynamic partition functions, improves but does not clearly define agreement with the inverse exponential relationship observed by others, for low energy secondaries sputtered from oxygen rich matrices. The reproducibility of ion yields of high energy secondaries suggests empirical approaches to quantitative analysis are well justified; however the poor agreement of ion yields with an inverse exponential relationship, suggests that ion yielding mechanisms are somewhat different to those proposed in the low energy regime

Advances in Ambulatory Oxygen workshop and Longterm Oxygen therapy in real-life practice.

The practical workshop presented recent advances in the field of ambulatory oxygen (AO), with experts discussing identification of patients who would benefit from AO, as well as current trials to measure specific benefits of AO in chronic patients. In particular, AO prescription in clinical practice and developments in pulsed-dose delivery of AO as a more efficient method of oxygen delivery were extensively discussed. After audience questions, the attendees had the opportunity to handle the AO systems on display in order to gain greater insight into their functionality and wearability, which should assist them in providing the most appropriate device for each patient. The symposium addressed considerations required when prescribing long-term oxygen therapy (LTOT). Dr Kampelmacher reviewed current indications for LTOT, emphasising the importance of accurate assessment of patients for LTOT, optimisation of oxygen dose, and patient education. Dr Vivodtzev discussed the evidence for LTOT in patients with exercise-induced desaturation, the role of portable oxygen concentrators, and the optimisation necessary to benefit from their use. The symposium concluded with a health economic study presented by Dr Little, demonstrating the cost benefits of a reform of the Scottish healthcare oxygen supply service

Development of Stresses in Cohesionless Poured Sand

The pressure distribution beneath a conical sandpile, created by pouring sand from a point source onto a rough rigid support, shows a pronounced minimum below the apex (`the dip'). Recent work of the authors has attempted to explain this phenomenon by invoking local rules for stress propagation that depend on the local geometry, and hence on the construction history, of the medium. We discuss the fundamental difference between such approaches, which lead to hyperbolic differential equations, and elastoplastic models, for which the equations are elliptic within any elastic zones present .... This displacement field appears to be either ill-defined, or defined relative to a reference state whose physical existence is in doubt. Insofar as their predictions depend on physical factors unknown and outside experimental control, such elastoplastic models predict that the observations should be intrinsically irreproducible .... Our hyperbolic models are based instead on a physical picture of the material, in which (a) the load is supported by a skeletal network of force chains ("stress paths") whose geometry depends on construction history; (b) this network is `fragile' or marginally stable, in a sense that we define. .... We point out that our hyperbolic models can nonetheless be reconciled with elastoplastic ideas by taking the limit of an extremely anisotropic yield condition.Comment: 25 pages, latex RS.tex with rspublic.sty, 7 figures in Rsfig.ps. Philosophical Transactions A, Royal Society, submitted 02/9

Homogenisation of sulphide inclusions within diamonds: A new approach to diamond inclusion geochemistry

This is the final version of the article. Available from Elsevier via the DOI in this record.Base metal sulphide (BMS) inclusions in diamonds provide a unique insight into the chalcophile and highly siderophile element composition of the mantle. Entombed within their diamond hosts, these provide a more robust (closed system) sample, from which to determine the trace element, Re-Os and S-isotopic compositions of the mantle than mantle xenoliths or orogenic peridotites, as they are shielded from alteration during ascent to the Earth’s crust and subsequent surface weathering. However, at temperatures below 1100 °C some BMS inclusions undergo subsolidus re-equilibration from an original monosulphide solid solution (Mss) and this causes fractionation of the major and trace elements within the inclusions. Thus to study the subjects noted above, current techniques require the entire BMS inclusion to be extracted for analyses. Unfortunately, ‘flaking’ of inclusions during break-out is a frequent occurrence and hence the risk of accidentally under-sampling a portion of the BMS inclusion is inherent in current practices. This loss may have significant implications for Re-Os isotope analyses where incomplete sampling of a Re-rich phase, such as chalcopyrite that typically occurs at the outer margins of BMS inclusions, may induce significant bias in the Re-Os and 187Os/188Os measurements and resulting model and isochron ages. We have developed a method for the homogenisation of BMS inclusions in diamond prior to their break-out from the host stone. Diamonds are heated to 1100 °C and then quenched to chemically homogenise any sulphide inclusions for both major and trace elements. Using X-ray Computed Microtomography (µCT) we determine the shape and spatial setting of multiple inclusions within a host stone and crucially show that the volume of a BMS inclusion is the same both before and after homogenisation. We show that the homogenisation process significantly reduces the inherent variability of in situ analysis when compared with unhomogenised BMS, thereby widening the scope for multiple methods for quantitative analysis, even on ‘flakes’ of single BMS inclusions. Finally we show that the trace elements present in peridotite (P-type) and eclogitic (E-type) BMS are distinct, with P-type diamonds having systematically higher total platinum-group element (particularly Os, Ir, Ru) and Te and As concentrations. These distinctions suggest that the PGE and semi-metal budgets of mantle-derived partial melts will be significantly dependent upon the type(s) and proportions of sulphides present in the mantle source.HSRH gratefully acknowledges her current Postdoctoral Fellowship with the Claude Leon Foundation and the support of the CIMERA centre of excellence at the Universities of the Witwatersrand and Johannesburg. The Diamond Trading Company (a member of the DeBeers Group of Companies) is thanked for the donation to JWH of the diamonds used in this study. The analytical work in this study was supported by NERC SoS Consortium grant NE/M011615/1 “Te and Se Cycling and Supply” awarded to Cardiff University. The authors would like to thank Associate Editor Amy Riches and the three anonymous reviewers for their advice and comments that significantly improved the paper

Higher analogues of the discrete-time Toda equation and the quotient-difference algorithm

The discrete-time Toda equation arises as a universal equation for the relevant Hankel determinants associated with one-variable orthogonal polynomials through the mechanism of adjacency, which amounts to the inclusion of shifted weight functions in the orthogonality condition. In this paper we extend this mechanism to a new class of two-variable orthogonal polynomials where the variables are related via an elliptic curve. This leads to a `Higher order Analogue of the Discrete-time Toda' (HADT) equation for the associated Hankel determinants, together with its Lax pair, which is derived from the relevant recurrence relations for the orthogonal polynomials. In a similar way as the quotient-difference (QD) algorithm is related to the discrete-time Toda equation, a novel quotient-quotient-difference (QQD) scheme is presented for the HADT equation. We show that for both the HADT equation and the QQD scheme, there exists well-posed $s$-periodic initial value problems, for almost all \s\in\Z^2. From the Lax-pairs we furthermore derive invariants for corresponding reductions to dynamical mappings for some explicit examples.Comment: 38 page

Prison officer self-legitimacy and support for rehabilitation in Ghana

Legitimacy refers to the moral recognition of power, and prison legitimacy remains a principal issue for prison researchers and managers. However, the prison legitimacy literature tends to focus on the views held by individuals in custody. Research on prison officer Self-Legitimacy – that is, the powerholders’ belief that the authority vested in them is morally right – remains scanty. Drawing on data from a survey of 1,062 prison officers in Ghana, this study examined both the correlates of prison officer Self-Legitimacy and the links between Self-Legitimacy and Support for Rehabilitation of individuals in custody. The results of multivariate analyses showed that having good Relations with Colleagues and being treated fairly by supervisors enhance prison officers’ Self-Legitimacy. In turn, Self-Legitimacy was found to increase officers’ Support for Rehabilitation. Finally, perceived Fair Treatment by Supervisors and positive Relations with Individuals in Custody were associated with increased Support for Rehabilitation. The implications of these findings are discussed

Spectral sum rules and finite volume partition function in gauge theories with real and pseudoreal fermions

Based on the chiral symmetry breaking pattern and the corresponding low-energy effective lagrangian, we determine the fermion mass dependence of the partition function and derive sum rules for eigenvalues of the QCD Dirac operator in finite Euclidean volume. Results are given for $N_c = 2$ and for Yang-Mills theory coupled to several light adjoint Majorana fermions. They coincide with those derived earlier in the framework of random matrix theory.Comment: 22p., SUNY-NTG-94/18, TPI-MINN-94/10-