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Environmentally friendly pretreatment of double refractory gold ores (DRGO) to improve gold recovery without emitting pollutant gas is challenging. Sequential biotreatment, including iron-oxidizing microorganisms to decompose sulfides, followed by the enzymatic decomposition of carbonaceous matter, was recently developed. The effect of acid washing by 1 M HCl for 24 h between two bioprocesses was evaluated using a real double refractory gold ore from the Syama mines, Mali, which includes 24 g/t of Au and 5.27 wt% of carbon with a relatively higher graphitic degree. The addition of the acid washing process significantly improved gold recovery by cyanidation to yield to 84.9 ± 0.7% from 64.4 ± 9.2% (n = 2). The positive effects of acid washing can be explained by chemical alteration of carbonaceous matter to facilitate the accessibility for lignin peroxidase (LiP) and manganese peroxidase (MnP) in cell-free spent medium (CFSM), although the agglomeration was enhanced by an acid attack to structural Fe(III) in clay minerals. Sequential treatment of DRGO basically consists of the oxidative dissolution of sulfides and the degradation of carbonaceous matter prior to the extraction of gold; however, the details should be modified depending on the elemental and mineralogical compositions and the graphitic degree of carbonaceous matter.

Double refractory gold ore was sequentially pretreated to oxidize sulfides by thermophilic archaeon Acidianus brierleyi and then to decompose carbonaceous matters using the cell-free spent medium (CFSM) from white-rot fungus Phanerochaete chrysosporium. The pretreatment by A. brierleyi significantly improved the gold recovery from 25% to 77%. Additionally, the crude lignin-degrading enzymes in the CFSM converted the carbonaceous matters into more easily degradable substances, which were removed by alkaline washing, leading to a final gold recovery of 92%. These mineralogical alterations were confirmed by differential thermogravimetric analysis and quantitative evaluation of minerals with scanning electron microscopy. Based on the results, gold grains were mostly liberated after bio-oxidation of sulfides, and in following CFSM treatment, large particles of carbonaceous aluminosilicate were formed from the aggregation of clay minerals, gold grains and with partially decomposed carbonaceous matters acting as binders.

Sequential treatment was applied to carbonaceous Au-Ag-bearing ore concentrate to maximize the Au and Ag recovery. In the preliminary test, the present carbonaceous ore had well liberated and exposed type of gold grains, which are not refractory, but included mainly three types of Ag presented as electrum, hessite (Ag2Te) and Ag-bearing other minerals. Au recovery was ∼100% without any treatment, meanwhile Ag recovery was only 33.3%. The sequential treatment comprises two oxidation steps: (a) mixed culture of iron- and sulfur-oxidizing microorganisms at pH 1.2, followed by (b) cell-free spent medium (CFSM) at pH 4.0 from a white rot-fungus, Phanerochaete chrysosporium, which includes lignin-degrading enzymes. As a result, Ag recovery was 55.5% after the first step and greatly improved to ∼100%, including the dissolved Ag+ concentration in the first step of acid treatment. Although the acidophilic iron-oxidizing microorganisms were inhibited by dissolved Ag+ and Cd2+ ions, the strong acidic conditions dissolved hessite and Ag-bearing oxide minerals. However, the remaining carbonaceous matter acted to sorb Ag(CN)2− in cyanidation, causing the recovery loss. In the next step the lignin-degrading enzymes degraded carbonaceous matter in the ore. This step is necessary to avoid the adsorption of Ag(CN)2− on graphitic carbonaceous matter, leading a mostly perfect recovery of the remaining Ag in the solid residues, without necessity of alkaline washing. The sequential treatment including enzymatic lignin-degrading process was also effective in carbonaceous silver ore avoiding the emission of air pollutants.

Double refractory gold ore (DRGO) not only include ppt levels of gold grains locked in sulfide minerals but also a problematic amount of carbonaceous matter. This causes a significant recovery loss of gold during cyanidation because of the strong affinity of the Au(CN)2− with the carbonaceous matter. Combustion decreases the carbonaceous matter content, but also emits pollutant gases like CO2, SO2 and As2O3. Therefore, environmentally-friendly solutions have been explored by using biotechnology. Due to the very small amount of the above targets in the ore, it is challenging to show evidential changes in solid-phase before and after the biomineral processing of DRGO. This chapter introduces the mineralogical and chemical changes in the various solid residues produced during a sequential biotreatment, consisting of the liberation of gold from sulfides by an iron-oxidizer and decomposition of carbonaceous matter by lignin-degrading enzymes (lignin peroxidase, manganese peroxidase, laccase) secreted from a white rot-fungus, which successfully improved of gold recovery to over 90%. In addition, further development of biotechnology in the recovery of gold from DRGO is addressed.

The pretreatment of carbonaceous material in double refractory gold ores (DRGO) is necessary to decrease preg-robbing of gold and maximize gold recovery. DRGO contains of carbonaceous matter and gold grains encapsulated in sulfide minerals, which typically results in very poor gold recovery. However, there is growing interest in DRGO because some estimates show that it makes up about a third of the total available gold for production by mining. This can be achieved by chemical and biological techniques, however, the chemical techniques like flotation, surface passivation and chemical oxidation have received more extensive study and either have to be retooled or modified to be applied to the carbonaceous matter in the DRGO. In comparison, the biological techniques are relatively unknown with significant gaps in the knowledge about the bio-treatment mechanism, byproducts and avenues for scaling up like bioreactor design. This study reviews the enzymatic pretreatment of DRGO to facilitate gold recovery and minimize reagent consumption. It focuses on the potential for application of oxidative enzymes like lignin peroxidase, manganese peroxidase and laccase to pretreat carbonaceous matter in DRGO with or without an additional step of sulfide oxidation and addresses characterization of byproducts of the enzymatic decomposition. Further, potential bioreactor configurations for the enzymatic decomposition without direct contact of ore with microorganisms are considered, both in terms of understanding the mechanisms within the pretreatment and in terms of application.

Thermal degradation characteristics of a Japanese oil sand at different heating rates (10, 20, and 30 °C/min), and 30 ml/min air flow rate have been investigated. The kinetic parameters have been calculated based on three stages of weight loss and/or the conversion of the sample. These include, stage 1 (SI): volatilization of moisture content and the light hydrocarbon (20–227 °C), stage 2 (SII): combustion of heavy hydrocarbon (227–527 °C), and stage 3 (SIII): oxidative decomposition of carbonaceous organic matter (502–877 °C). The results showed that the rate of change of the oil sand conversion with time dαdt was affected by the heating rate. The time taken by the system to reach 0.99 conversion was observed as 85, 50, and 35 min at the heating rates of 10, 20, and 30 °C/min, respectively. The frequency factor, A, at SI was between 0.09 and 0.54 min−1, while the activation energy, Ea, was 11.2–12.5 KJmol−1 (the percentage weight loss, Wt, was 0–3.6 %w/w; and the conversion, α, was 0–0.2.). At SII, the values of A and Ea were 2.1–5.5 min−1 and 17.6–19 KJmol−1, respectively (Wt = 3.1–15.88 %w/w; α = 0.17–0.86.). The value of A at SIII was 5.5E11–1.1E13 min−1, while Ea was 160–200 KJmol−1 (Wt = 15.33–17.99 %w/w; and α = 0.84–0.99). Keywords: Thermogravimetric and differential thermal analysis (TG-DTA), Thermal degradation, Heating rates, Kinetics parameters

Several efforts are made to find various green alternatives for carbonaceous matter (CM) degradation in carbonaceous gold ores. The deleterious effect of CM is observed during cyanidation, where CM adsorbs Au(CN)2- behaving like activated carbon, an effect called pre-robbing. Thus, biotechnological approaches like enzyme degradation of CM to reduce Au(CN)2- adsorption are currently being studied. In the present work, the potential of CM degradation and gold preg-robbing reduction by laccase-mediator system (LMS) oxidation was evaluated using powder activated carbon (PAC) as CM surrogate material through model experiments. Based upon gas chromatography-mass spectrometry (GC-MS) analysis of extracted by-products from bio-treated PAC, LMS treatment after seven days physically and chemically altered the surface of PAC by the reduction of specific surface area and pore volume, the disruption of aromatic moieties into aliphatic compounds, and the formation of oxygen-containing functional groups. Subsequently, under the studied condition, the adsorption capacity of Au(CN)2- on the surface-degraded PAC was dramatically decreased from 46 μmol/g to 7.36 μmol/g. The present findings provide a new outlook of an alternative pre-treatment process of carbonaceous gold ore in mineral processing.

The bio-treatment of double refractory gold ores (DRGO) to reduce preg-robbing needs to account for the heterogeneity of the ore so as to acquire a much more complete picture of the system. To this end, the effects of ferrous ion additives on the degradation of powdered activated carbon (PAC) by cell-free spent medium (CFSM) was studied. Au(CN)2- adsorption and Raman spectrometric results suggest that the ferrous salt could have possibly reacted with some biogenic hydrogen peroxide to aid in the degradation of PAC. The bio-treatment produced mixed solid residues containing some partially degraded aromatic compounds which were soluble in alkaline solutions. Ultimately, biodegradation of PAC using CFSM in the presence of 50 µM FeSO4.7H2O for 7 days followed by washing with 3 mM NaOH reduced Au(CN)2- uptake by 80%.

Carbonaceous matter in refractory gold ore is known to be one of the primary causes of gold recovery loss. Model experiments were conducted to simulate the bio-modification of carbonaceous matter using powdered activated carbon (PAC) as a surrogate and cell-free spent medium (CFSM) of Phanerochaete chrysosporium. The CFSM was used because of the lignin peroxidase and manganese peroxidase secreted by the microbe during its incubation. In the present work, an investigation was conducted to determine the physical and chemical alterations in PAC after enzymatic treatment and its effect on Au(CN)2− uptake. Characterization of the solid residues of PAC by 13C NMR and N2 adsorption after bio-modification revealed that the treatment had decomposed poly-aromatic carbons into aliphatic carbons and also reduced the specific surface area from 1430 m2/g to 697 m2/g in 14 days. As a result, Au(CN)2− uptake decreased from 100% (0.048 mmol/g) to 43% within 12 h primarily due to the enzyme treatment and adsorption of CFSM components. It further decreased to 26% due to surface passivation by bio-chemicals derived from CFSM and/or decomposed aliphatic hydrocarbons from aromatic carbons between 7 days and 14 days. These findings may contribute to efforts to decrease preg-robbing in hydrometallurgical processing of refractory gold ores.

Natural carbonaceous matter aided the bioleaching of Cu from chalcopyrite concentrates. The oxidative dissolution of chalcopyrite was enhanced more significantly by anthracite than carbonaceous matter in double refractory gold ore (DRGO). This was achieved through Galvanic interactions between the chalcopyrite and natural carbonaceous matter. Measurement of impedance verified that the electro-resistance is smaller in anthracite, which has a greater graphitic degree than carbonaceous matter in DRGO. The electron shuttle between chalcopyrite and the Fe3+ /Fe2+ redox couple was facilitated not only by the amounts of carbonaceous matter but also the degree of graphitization of carbonaceous matter. A higher graphitization degree increased the electron conductivity of the carbonaceous matter to help mediate Cu bioleaching while avoiding direct contact of thermophile cells with refractory copper sulfides.

The detailed mechanism behind the bio-decomposition of carbonaceous matter in refractroy goold ore byPhanerocheate chrysosporiumto facilitate improved cyanidation of gold is as yet undersdtood. To gain a better understanding of this mechanism, the present work model experiments using powdery activated carbon (PAC) and cell-free extracts ofP.chrysosporiumto simulate and focus on the biotransformation of carbonaceous matters in refractory gold ores. The results of solid characterization using SEM and XRD indicated a more non-uniform surface and smaller crystal sizes for PAC treaded with cell-free extracts for 72 hours. The significant decomposition of aromatic compounds into aliphatic compounds were observed in13C-NMR and FTIR results for the high ratio of cell-free extract volume to mass of PAC. This results support the theory that one of the fundamental mechanisms behind the bio-decomposition process is aromatic bond cleavage by biomolecules produced byP.chrysosporium.

Sulfides and carbonaceous matter in double refractory gold ore (DRGO) were bio-treated sequentially using an iron-oxidizing archaeon Acidianus brierleyi followed by lignin peroxidase-dominating crude enzymes released from the white-rot fungus Phanerochaete chrysosporium to significantly improve gold recovery from 24% to 92%. Transformation of the carbonaceous matter in the sequential bio-treatment was interpreted with Quantitative Evaluation of Materials by Scanning Electron Microscopy (QEMSCAN), Raman spectroscopy and three-dimensional fluorescence spectrometry. Firstly, microbiological sulfide oxidation did not affect carbonaceous matter but decreased the arsenic content in the solid residue, facilitating the following enzymatic reaction. Next, the crude enzymes predominantly decomposed the defect-bearing graphitic carbon into humic-like substances. The humic-like substances were not completely soluble under pH 4 but were instead retained in the solid residue as a part of a newly formed carbonaceous aluminosilicate (C–Si–Al) phase. Due to a wide pKa range of humic-like substances, it is proposed that at pH 4, electrostatic interaction between humic substances and illite, with and without heavy metals, might have enabled the agglomeration of fine aluminosilicate particles. Some gold grains trapped in C–Si–Al agglomerates were released by the dissolution of humic-like substances in 1 M NaOH, resulting in a further increase in gold recovery of approximately 15%.