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Mineralogical characterisation showed the deportment of Ni to be similar in the Vale and Glencore tailings, with 60% of the total Ni locked in pyrrhotite, and the balance 40% associated with pentlandite. Nickel leaching was correlated with the dissolution extents of pyrrhotite and pentlandite as functions of four leaching regimes: ‘anoxic acid’ (with and without pH control), ‘oxic acid’ (oxygen sparging), ‘oxic acid’ (air sparging), and ‘oxic ferric’ (air sparging). The results showed that the maximum Ni dissolution was obtained during the pH controlled oxic acid leach with oxygen sparging at pH 1.5, while the anoxic acid leach at pH 1.5 resulted in minimum Ni dissolution (10–15%) from pyrrhotite. An overall Ni mass balance showed that pyrrhotite and pentlandite dissolve simultaneously in the presence of Fe(III) and oxygen, in contrast to the preferential dissolution of pyrrhotite in the absence of Fe(III). Elemental sulphur yield increased with increasing temperature, but no observable trend coul...

The recovery of valuable base metals from mining rejects presents an economical alternative to conventional hydrometallurgical processes. The reject of interest investigated in the present work is a nickeliferous, upgraded pyrrhotite tailings produced by Vale Base Metals in the Sudbury Basin of Ontario. A QEMSCAN™ analysis of the tailings showed a total Ni content of 1 wt%, with 59% of the total Ni deported to pyrrhotite and 40% associated with pentlandite. The initial part of this study involved the development of a selective dissolution protocol to quantify the differential dissolution extents of the two Ni-bearing minerals. Application of this protocol to the pyrrhotite tailings sample showed that an acidity of 15 wt% HCl, and a temperature of 80 °C was adequate to selectively dissolve 96% of pyrrhotite from the tailings. Subsequently, an anoxic acidic leach of the tailings at pH 1.5, and at 5% (w/v) solids loading showed minimal dissolution of Fe and Ni from pentlandite in tests with and without pH control. The extent of Ni dissolution was next evaluated as a function of pH during an oxic acid leach. The testing protocol involved leaching the tailings under two pH regimes: fixed and uncontrolled pH. The results showed that operation at a fixed pH increases the extent of Ni dissolution due to the higher concentration of the oxidant Fe(III) in solution. Finally, an oxic ferric leach showed that the terminal dissolution extents of pyrrhotite and pentlandite were comparable at 46% total Ni extraction.

The increasing availability of the genome sequences of microorganisms involved in important bioremediation processes makes it feasible to consider developing genome‐scale models that can aid in predicting the likely outcome of potential subsurface bioremediation strategies. Previous studies of the in situ bioremediation of uranium‐contaminated groundwater have demonstrated that Geobacter species are often the dominant members of the groundwater community during active bioremediation and the primary organisms catalysing U(VI) reduction. Therefore, a genome‐scale, constraint‐based model of the metabolism of Geobacter sulfurreducens was coupled with the reactive transport model HYDROGEOCHEM in an attempt to model in situ uranium bioremediation. In order to simplify the modelling, the influence of only three growth factors was considered: acetate, the electron donor added to stimulate U(VI) reduction; Fe(III), the electron acceptor primarily supporting growth of Geobacter; and ammonium, a key nutrient. The constraint‐based model predicted that growth yields of Geobacter varied significantly based on the availability of these three growth factors and that there are minimum thresholds of acetate and Fe(III) below which growth and activity are not possible. This contrasts with typical, empirical microbial models that assume fixed growth yields and the possibility for complete metabolism of the substrates. The coupled genome‐scale and reactive transport model predicted acetate concentrations and U(VI) reduction rates in a field trial of in situ uranium bioremediation that were comparable to the predictions of a calibrated conventional model, but without the need for empirical calibration, other than specifying the initial biomass of Geobacter. These results suggest that coupling genome‐scale metabolic models with reactive transport models may be a good approach to developing models that can be truly predictive, without empirical calibration, for evaluating the probable response of subsurface microorganisms to possible bioremediation approaches prior to implementation.

The activity of microorganisms often plays an important role in dynamic natural attenuation or engineered bioremediation of subsurface contaminants, such as chlorinated solvents, metals, and radionuclides. To evaluate and/or design bioremediated systems, quantitative reactive transport models are needed. State-of-the-art reactive transport models often ignore the microbial effects or simulate the microbial effects with static growth yield and constant reaction rate parameters over simulated conditions, while in reality microorganisms can dynamically modify their functionality (such as utilization of alternative respiratory pathways) in response to spatial and temporal variations in environmental conditions. Constraint-based genome-scale microbial in silico models, using genomic data and multiple-pathway reaction networks, have been shown to be able to simulate transient metabolism of some well studied microorganisms and identify growth rate, substrate uptake rates, and byproduct rates under different growth conditions. These rates can be identified and used to replace specific microbially-mediated reaction rates in a reactive transport model using local geochemical conditions as constraints. We previously demonstrated the potential utility of integrating a constraint-based microbial metabolism model with a reactive transport simulator as applied to bioremediation of uranium in groundwater. However, that work relied on an indirect coupling approach that was effective for initial demonstration but may not be extensible to more complex problems that are of significant interest (e.g., communities of microbial species and multiple constraining variables). Here, we extend that work by presenting and demonstrating a method of directly integrating a reactive transport model (FORTRAN code) with constraint-based in silico models solved with IBM ILOG CPLEX linear optimizer base system (C library). The models were integrated with BABEL, a language interoperability tool. The modeling system is designed in such a way that constraint-based models targeting different microorganisms or competing organism communities can be easily plugged into the system. Constraint-based modeling is very costly given the size of a genome-scale reaction network. To save computation time, a binary tree is traversed to examine the concentration and solution pool generated during the simulation in order to decide whether the constraint-based model should be called. We also show preliminary results from the integrated model including a comparison of the direct and indirect coupling approaches and evaluated the ability of the approach to simulate field experiment.

Background Geobacter sulfurreducens is a member of the Geobacter species, which are capable of oxidation of organic waste coupled to the reduction of heavy metals and electrode with applications in bioremediation and bioenergy generation. While the metabolism of this organism has been studied through the development of a stoichiometry based genome-scale metabolic model, the associated regulatory network has not yet been well studied. In this manuscript, we report on the implementation of a thermodynamics based metabolic flux model for Geobacter sulfurreducens. We use this updated model to identify reactions that are subject to regulatory control in the metabolic network of G. sulfurreducens using thermodynamic variability analysis. Findings As a first step, we have validated the regulatory sites and bottleneck reactions predicted by the thermodynamic flux analysis in E. coli by evaluating the expression ranges of the corresponding genes. We then identified ten reactions in the metabolic network of G. sulfurreducens that are predicted to be candidates for regulation. We then compared the free energy ranges for these reactions with the corresponding gene expression fold changes under conditions of different environmental and genetic perturbations and show that the model predictions of regulation are consistent with data. In addition, we also identify reactions that operate close to equilibrium and show that the experimentally determined exchange coefficient (a measure of reversibility) is significant for these reactions. Conclusions Application of the thermodynamic constraints resulted in identification of potential bottleneck reactions not only from the central metabolism but also from the nucleotide and amino acid subsystems, thereby showing the highly coupled nature of the thermodynamic constraints. In addition, thermodynamic variability analysis serves as a valuable tool in estimating the ranges of ΔrG' of every reaction in the model leading to the prediction of regulatory sites in the metabolic network, thereby characterizing the regulatory network in both a model organism such as E. coli as well as a non model organism such as G. sulfurreducens.