The economic significance of the phytoextraction of nickel, cobalt and gold from metalliferous soils : a thesis in partial fulfilment of the requirements for the degree of Master of Science at Massey University

Phytoextraction of heavy metals is a relatively new technology that has potential applications for the remediation of many contaminated sites around the world. The technology has significant applications in the minerals industry for the treatment of low-grade ores and metalliferous mine waste. This study concerns the investigation of the potential to remove heavy metals, in particular nickel, cobalt and gold, from artificial and lateritic substrates. Four experiments comprise this study of the phytoextraction of nickel, cobalt and gold using both accumulator and non-accumulator species. Nickel and cobalt bioavailability was determined by ammonium acetate extraction for both artificial and laterite substrates. It was found that ammonium acetate extractability was predictive for nickel accumulation from a nickel-only artificial substrate. Cobalt bioavailability did not predict the accumulation response of either Alyssum bertolonii or Berkheya coddii grown of artificial substrates. The potential for phytoextraction of nickel and cobalt was investigated using the known nickel hyperaccumulators A. bertolonii and B. coddii, grown on artificially prepared substrates. The substrates were nickel-only (4 mg/kg to 1000 mg/kg), cobalt-only (4 mg/kg to 1000 mg/kg) and nickel-cobalt mixed (1:1 ratio, 4 mg/kg to 500 mg/kg) amendments of sulphates to commercial potting mix. Hyperaccumulation from nickel-only and cobalt-only substrates resulted in typical logarithmic metal uptake by both species. The cobalt-only substrates were phytotoxic to B. coddii above a concentration of 15-20 mg/kg. Phytotoxicity significantly reduced biomass production in B. coddii without effecting the bioaccumulation coefficient. No corresponding cobalt phytotoxicity was observed in A. bertolonii over the experimental range, although biomass production appears to favour substrate concentrations below 30 mg/kg. The bioavailability and hyperaccumulation of cobalt from the mixed nickel-cobalt substrates dramatically reduced the nickel accumulation potential of both species at substrate concentrations below 300 mg/kg. At higher substrate metal concentrations both species return to nickel dominant hyperaccumulation. Induced gold accumulation in B. coddii and Iberis intermedia was investigated using, sequential ammonium thiocyanate and ammonium thiosulphate chelation to, a 5 mg/kg gold artificial substrate. An attempt to determine gold bioavailability by ammonium thiocyanate and ammonium thiosulphate extraction was made on the substrate. It was found that neither chelator extraction could be correlated with plant accumulation induced by the same concentration of the reagent. Ammonium thiocyanate induction resulted in plant gold accumulation at or below the substrate concentration. Ammonium thiosulphate induced gold accumulation in I. Intermedia reached 48.8 mg/kg when treatment with a 1% solution. B. coddii accumulated 9.3 mg/kg gold for the same treatment. Five consignments of metalliferous lateritic materials from Western Australia were investigated. Three substrates originated from Project Murrin Murrin nickel and cobalt mine operated by Anaconda Nickel Ltd. and two substrates originated from Boddington Gold Mine operated by Worsley Alumina Ltd. Nickel and cobalt accumulation by A. bertolonii and B. coddii was found to be significantly lower than observed using artificial substrates. Nickel and cobalt bioavailability, determined by ammonium acetate extraction, failed to predict the accumulation responses from laterite substrates. This is attributed to elemental interference by, and possibly ammonium acetate chelation of, other mobile heavy metals in these substrates. A hypothesis deserved of further research. Hyperaccumulation of nickel was observed for both species on the Anaconda Nickel Ltd. SAP substrate only. Appreciable cobalt accumulation (≈90 mg/kg) was observed on the SAP substrate for both species and on the Boddington Gold Mine B5 substrate for B. coddii. Phytomining scenarios were determined for both species grown on the SAP substrate. A. bertolonii could produce 13 kg of nickel and 0.8 kg of cobalt per hectare with a value of US$163. B. coddii could produce 23.8 kg of nickel and 2.1 kg of cobalt per hectare at a value of US$ 319. These levels of production could be improved by fertilisation and/or substrate acidification. A preliminary investigation into induced gold accumulation from laterite substrates by I. Intermedia, A. longiflora, Brassica juncea and Limum usitatissimum was made using the acid biased chelator ammonium thiocyanate. It was found that an acidified amendment of ammonium thiocyanate greatly improved the phytoaccumulation of gold from the lateritic substrates. An amendment of 2M HC1 produced appreciable gold mobility and phytoaccumulation and indicates that gold solubility is the primary control on plant uptake. Analysis of various plant tissues indicated that Acacia longiflora stored significant gold in its roots compared to foliar components. All plant-substrate combinations indicated a trend towards increasing acidification and gold phytoaccumulation. No plant-substrate-treatment combination produced an economically viable phytomining scenario

Collective pairing of resonantly coupled microcavity polaritons

We consider the possible phases of microcavity polaritons tuned near a bipolariton Feshbach resonance. We show that, as well as the regular polariton superfluid phase, a "molecular" superfluid exists, with (quasi-)long-range order only for pairs of polaritons. We describe the experimental signatures of this state. Using variational approaches we find the phase diagram (critical temperature, density and exciton-photon detuning). Unlike ultracold atoms, the molecular superfluid is not inherently unstable, and our phase diagram suggests it is attainable in current experiments.Comment: paper (4 pages, 3 figures), Supplemental Material (7 pages, 8 figures

Absorption, Photoluminescence and Resonant Rayleigh Scattering Probes of Condensed Microcavity Polaritons

We investigate and compare different optical probes of a condensed state of microcavity polaritons in expected experimental conditions of non-resonant pumping. We show that the energy- and momentum-resolved resonant Rayleigh signal provide a distinctive probe of condensation as compared to, e.g., photoluminescence emission. In particular, the presence of a collective sound mode both above and below the chemical potential can be observed, as well as features directly related to the density of states of particle-hole like excitations. Both resonant Rayleigh response and the absorption and photoluminescence, are affected by the presence of quantum well disorder, which introduces a distribution of oscillator strengths between quantum well excitons at a given energy and cavity photons at a given momentum. As we show, this distribution makes it important that in the condensed regime, scattering by disorder is taken into account to all orders. We show that, in the low density linear limit, this approach correctly describes inhomogeneous broadening of polaritons. In addition, in this limit, we extract a linear blue-shift of the lower polariton versus density, with a coefficient determined by temperature and by a characteristic disorder length.Comment: 16 pages, 11 figures; minor correction

Exotic attractors of the non-equilibrium Rabi-Hubbard model

We explore the phase diagram of the dissipative Rabi-Hubbard model, as could be realized by a Raman-pumping scheme applied to a coupled cavity array. There exist various exotic attractors, including ferroelectric, antiferroelectric, and inccomensurate fixed points, as well as regions of persistent oscillations. Many of these features can be understood analytically by truncating to the two lowest lying states of the Rabi model on each site. We also show that these features survive beyond mean-field, using Matrix Product Operator simulations.Comment: 5pages, 3 figures, plus supplementary material. Final version, as publishe

The church and religion in the Anglo Scottish border counties, 1534 to 1572

The 16th century Borders have been viewed traditionally as violent, feudal and catholic, but their feudalism is now questioned. The verdict on their religion seems often to be based either on general impressions or on lack of evidence. Recently the value of studying the social and political life of the English and Scottish Borders together has been recognised, and this approach is also viable for their religious life. The scattered evidence shows that in terms of material wealth and personnel the Border church was badly served, and that the changes of the Reformation often made the situation worse. Moreover it suffered from too close an association with the violent aspects of Border society. Popular religion in the area seems to have been more concerned with the magical aspect of the church's ceremonies than with orthodox Catholicism or Protestantism. At the same time there was a realisation of the problems, and there were educative and civilising influences at work. By the end of this period they were beginning to have some little effect, while at the same time the weakened traditional Catholicism was declining through lack of organised support. The 1569 revolt, which at first sight might suggest that the situation had changed little since 1536, in fact by its failure demonstrates the changes which had occurred. However the problems of the Border ' church went too deep to be solved easily, and the Borderers' independence in matters social, political, and religious would have to be overcome to achieve any great measure of success. Throughout this period both English and Scottish governments were by turn unable or unwilling to effect the necessary changes, and the inadequate church organisations were left to struggle on alone

Collective Dynamics of Bose--Einstein Condensates in Optical Cavities

Recent experiments on Bose--Einstein condensates in optical cavities have reported a quantum phase transition to a coherent state of the matter-light system -- superradiance. The time dependent nature of these experiments demands consideration of collective dynamics. Here we establish a rich phase diagram, accessible by quench experiments, with distinct regimes of dynamics separated by non-equilibrium phase transitions. We include the key effects of cavity leakage and the back-reaction of the cavity field on the condensate. Proximity to some of these phase boundaries results in critical slowing down of the decay of many-body oscillations. Notably, this slow decay can be assisted by large cavity losses. Predictions include the frequency of collective oscillations, a variety of multi-phase co-existence regions, and persistent optomechanical oscillations described by a damped driven pendulum. These findings open new directions to study collective dynamics and non-equilibrium phase transitions in matter-light systems.Comment: 5 pages, 5 figure

Enhanced vaccine control of epidemics in adaptive networks

We study vaccine control for disease spread on an adaptive network modeling disease avoidance behavior. Control is implemented by adding Poisson distributed vaccination of susceptibles. We show that vaccine control is much more effective in adaptive networks than in static networks due to an interaction between the adaptive network rewiring and the vaccine application. Disease extinction rates using vaccination are computed, and orders of magnitude less vaccine application is needed to drive the disease to extinction in an adaptive network than in a static one

Modelling the spread of American foulbrood in honeybees

We investigate the spread of American foulbrood (AFB), a disease caused by the bacterium Paenibacillus larvae, that affects bees and can be extremely damaging to beehives. Our dataset comes from an inspection period carried out during an AFB epidemic of honeybee colonies on the island of Jersey during the summer of 2010. The data include the number of hives of honeybees, location and owner of honeybee apiaries across the island. We use a spatial SIR model with an underlying owner network to simulate the epidemic and characterize the epidemic using a Markov chain Monte Carlo (MCMC) scheme to determine model parameters and infection times (including undetected ‘occult’ infections). Likely methods of infection spread can be inferred from the analysis, with both distance- and owner-based transmissions being found to contribute to the spread of AFB. The results of the MCMC are corroborated by simulating the epidemic using a stochastic SIR model, resulting in aggregate levels of infection that are comparable to the data. We use this stochastic SIR model to simulate the impact of different control strategies on controlling the epidemic. It is found that earlier inspections result in smaller epidemics and a higher likelihood of AFB extinction

Social encounter networks : collective properties and disease transmission

A fundamental challenge of modern infectious disease epidemiology is to quantify the networks of social and physical contacts through which transmission can occur. Understanding the collective properties of these interactions is critical for both accurate prediction of the spread of infection and determining optimal control measures. However, even the basic properties of such networks are poorly quantified, forcing predictions to be made based on strong assumptions concerning network structure. Here, we report on the results of a large-scale survey of social encounters mainly conducted in Great Britain. First, we characterize the distribution of contacts, which possesses a lognormal body and a power-law tail with an exponent of −2.45; we provide a plausible mechanistic model that captures this form. Analysis of the high level of local clustering of contacts reveals additional structure within the network, implying that social contacts are degree assortative. Finally, we describe the epidemiological implications of this local network structure: these contradict the usual predictions from networks with heavy-tailed degree distributions and contain public-health messages about control. Our findings help us to determine the types of realistic network structure that should be assumed in future population level studies of infection transmission, leading to better interpretations of epidemiological data and more appropriate policy decisions

Interpreting the seasonal cycles of atmospheric oxygen and carbon dioxide concentrations at American Samoa Observatory

We present seven years of atmospheric O2/N2 ratio and CO2 concentration data measured from flask samples collected at American Samoa. These data are unusual, exhibiting higher short-term variability, and seasonal cycles not in phase with other sampling stations. The unique nature of atmospheric data from Samoa has been noted previously from measurements of CO2, methyl chloroform, and ozone. With our O2 data, we observe greater magnitude in the short-term variability, but, in contrast, no clear seasonal pattern to this variability. This we attribute to significant regional sources and sinks existing for O2 in both hemispheres, and a dependence on both the latitudinal and altitudinal origins of air masses. We also hypothesize that some samples exhibit a component of "older" air, demonstrating recirculation of air within the tropics. Our findings could be used to help constrain atmospheric transport models which are not well characterized in tropical regions