Flotation and depression control of arsenopyrite through pH and pulp redox potential using xanthate as the collector

The role of pH and pulp redox potential (E_H) to control the flotation and depression of arsenopyrite has been investigated through studies on microflotation of arsenopyrite crystals and batch flotation of an arsenopyritic ore using isopropyl xanthate as collector. The transition between flotation and depression of arsenopyrite is established by the reversible potential of the xanthate/dixanthogen couple. Adsorption of arsenate ions on ferric hydroxide has been studied through electrokinetics to delineate mechanisms involved in the depression of arsenopyrite using oxidants. Chemical binding between arsenate species and ferric hydroxide sites on arsenopyrite is suggested as the mechanism responsible for depression of arsenopyrite. E_H conditions are given for the flotation and depression of arsenopyite at various pH values for the arsenopyritic ore.     

The relation between electric and redox potential: evidence from laboratory and field measurements

In field and laboratory experiments the relationship of redox, electric, and total potential was studied. This was carried out by using different arrangements of Pt and Ag/AgCl electrodes. The total potential is obtained by placing a Pt and an Ag/AgCl electrode at considerable distance apart on the rock. The studies indicate that the total potential yields the sum of redox and electric potential. Deviations larger than a couple of mV are caused by extensive fluid–rock interactions. In the laboratory it is seen that the magnitude of the electric potential is generally not larger than the artificially produced difference of the redox potential. The former is most likely attributed to a diffusion or membrane potential. At field scale the electric potential is designated as self potential. Redox potential measurements in the field may supply information from remnants of pore fluid of the rock and thereby may be suitable to support the exploration of concealed metal deposits. Detectable are in particular the fast H⁺ ions which are released by electrochemical reactions and transported by electromigration, both of which are attributed to the presence of the so called geobattery.     

The emergence of life from iron monosulphide bubbles at a submarine hydrothermal redox and pH front

Here we argue that life emerged on Earth from a redox and pH front at c. 4.2 Ga. This front occurred where hot (c. 150 degrees C), extremely reduced, alkaline, bisulphide-bearing, submarine seepage waters interfaced with the acid, warm (c. 90 degrees C), iron-hearing Hadean ocean. The low pH of the ocean was imparted by the ten bars of CO2 considered to dominate the Hadean atmosphere/hydrosphere. Disequilibrium between the two solutions was maintained by the spontaneous precipitation of a colloidal FeS membrane. Iron monosulphide bubbles comprising this membrane were inflated by the hydrothermal solution upon sulphide mounds at the seepage sites. Our hypothesis is that the FeS membrane, laced with nickel, acted as a semipermeable catalytic boundary between the two fluids, encouraging synthesis of organic anions by hydrogenation and carboxylation of hydrothermal organic primers. The ocean provided carbonate, phosphate, iron, nickel and protons; the hydrothermal solution was the source of ammonia, acetate, HS-, H2 and tungsten, as well as minor concentrations of organic sulphides and perhaps cyanide and acetaldehyde. The mean redox potential (delta Eh) across the membrane, with the energy to drive synthesis, would have approximated to 300 millivolts. The generation of organic anions would have led to an increase in osmotic pressure within the FeS bubbles. Thus osmotic pressure could take over from hydraulic pressure as the driving force for distension, budding and reproduction of the bubbles. Condensation of the organic molecules to polymers, particularly organic sulphides, was driven by pyrophosphate hydrolysis. Regeneration of pyrophosphate from the monophosphate in the membrane was facilitated by protons contributed from the Hadean ocean. This was the first use by a metabolizing system of protonmotive force (driven by natural delta pH) which also would have amounted to c. 300 millivolts. Protonmotive force is the universal energy transduction mechanism of life. Taken together with the redox potential across the membrane, the total electrochemical and chemical energy available for protometabolism amounted to a continuous supply at more than half a volt. The role of the iron sulphide membrane in keeping the two solutions separated was appropriated by the newly synthesized organic sulphide polymers. This organic take-over of the membrane material led to the miniaturization of the metabolizing system. Information systems to govern replication could have developed penecontemporaneously in this same milieu. But iron, sulphur and phosphate, inorganic components of earliest life, continued to be involved in metabolism.     

Leaching potential and redox transformations of arsenic and selenium in sediment microcosms with fly ash

The unintended release of coal ash to the environment is a concern due to the enrichment of contaminants such as arsenic (As) and selenium (Se) in this solid waste material. Current risk assessments of coal ash disposal focus on pH as the primary driver of leaching from coal ash. However, redox speciation of As and Se is a major factor for their mobilization potential and has received much less attention for risk assessments, particularly in disposal scenarios where coal ash will likely be exposed to microbially-driven redox gradients. The aim of this study was to demonstrate the differences of aerobic and anaerobic conditions for the leaching of As and Se from coal ash. Batch sediment-ash slurry microcosms were performed to mimic an ash spill scenario and were monitored for changes in As and Se speciation and mobilization potential. The results showed that the dissolved As concentrations were up to 50 times greater in the anaerobic microcosms relative to the aerobic microcosms during the two week incubation. This trend was consistent with As redox speciation determined by X-ray absorption spectroscopy, which indicated that 55% of the As in the solid phase at the end of the experiment was present as As(III) (a more leachable form of arsenic relative to As(V)). In the aerobic microcosms, only 13% of the As was As(III) and the rest was As(V). More than half of the Se was present as Se(IV) in the original fly ash and in the aerobic microcosms, while in the anaerobic microcosms Se was gradually transformed to less soluble Se(0) species. Likewise, dissolved Se concentrations were up to 25 times greater in the aerobic microcosms relative to anaerobic conditions. While the overall observations of As and Se mobilization potential from coal ash were consistent with expectations for aqueous and solid phase speciation of these elements, the findings directly show the relevance of these processes for coal ash disposal. These results highlight the need to select appropriate environmental parameters to include in risk assessments as well as provide potential geochemical monitoring tools through the use of dissolved Se/As ratios to determine the redox conditions of ash storage and spill sites.     

Predictability of bacterial activity and denitrification in aquatic sediments with continuous measurements of redox potential

Redox potential has been adopted as a qualitative parameter for interpreting solubility changes of nutrients and contaminants and the biological activity within wetland systems for several decades. The majority of studies considering the redox geochemistry in sediments used measurements of bulked material and single point measurement of biogeochemical parameters for interpretation, yet it remains questionable whether this information is reliable for environments that are very dynamic, such as wetlands. In this study it is evaluated whether variations in redox potential reflect dynamics of denitrification and overall bacterial respiration using continuous measurements of redox potential in time-series experiments in laboratory microcosms, in which the biogeochemical variation was enhanced by bioturbation. The results presented here suggest that measurements of redox potential have predictive potential in approximating rates of denitrification and overall bacterial respiration in aquatic sediments. The data clearly suggest that, while sediment bulk measurements and measurements of single profiles of redox potential, denitrification and bacterial activity often fail to provide ecological relevant information in dynamic systems, measurements of spatial and temporal redox potential profiles provide a useful parameter that reflects biogeochemical processes and functioning of sediments.     

Obtaining stable redox potential readings in gneiss groundwater and mine water: difficulties,meaningfulness, and potential improvement

Natural samples were run in three parallel flow-through cells in the laboratory in order to study the difficulties of obtaining stable redox potential readings, especially in gneiss groundwater and mine water with little redox buffer capacity. Redox potentials were recorded every 2 min for up to 5 days. Measured redox potentials were compared to means of partial potentials, modeled based on species-selective determinations of the most predominant redox-sensitive elements iron and nitrogen. Redox potentials stabilized reproducibly within minutes for a synthetic redox buffer solution and two well-buffered acid mine water samples at pH 2.3 and 3.5. For waters in redox disequilibrium, species-selective analytics might still be the better alternative compared to measuring the redox potential as summary parameter for modeling species distribution. In cases where the redox potential is the only readily available parameter, filtration and possibly acidification is recommended for quicker stabilization of redox potential readings and less deviations between measured and modeled values. A minimum of 2% was achieved in the samples investigated, however, often after measuring significantly longer than the previously suggested 30 min. Final stabilization could take up to several hours in waters with low buffer capacity.

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Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.

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Résumé Afin d’étudier les difficultés à obtenir des lectures stables des potentiels redox, notamment sur les eaux souterraines présentes dans des gneiss et dans les mines, qui présentent un faible pouvoir tampon, des échantillons ont été prélevés régulièrement en laboratoire, dans trois cellules d’écoulement parallèles. Les potentiels redox ont été enregistrés toutes les deux minutes durant cinq jours. Ces potentiels redox mesurés ont été comparés aux moyennes des potentiels partiels, modélisés à partir des déterminations sélectives des espèces chimiques des éléments sensibles aux conditions redox les plus prédominants, le fer et l’azote. Les potentiels redox se sont systématiquement stabilisés en quelques minutes pour une solution tampon synthétique et pour deux échantillons d’eaux de mines acides bien tamponnées à pH 2.3 à 3.5. Pour les eaux en déséquilibre redox, des analyses sélectives des espèces chimiques seraient toujours la meilleure alternative aux mesures sommaires du potentiel redox, pour modéliser la distribution des espèces. Dans les cas où le potentiel redox est le seul paramètre directement disponible, une filtration et éventuellement une acidification sont recommandées pour obtenir une stabilisation plus rapide des lectures des potentiels redox, et pour réduire les écarts entre les valeurs mesurées et modélisées. Un minimum de 2% a été atteint parmi les échantillons étudiés, mais en prolongeant souvent les mesures au-delà des 30 minutes suggérées initialement. La stabilisation finale pourrait prendre jusqu’à plusieurs heures dans des eaux à faible pouvoir tampon.

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Resumen Se han llevado a cabo experimentos en laboratorio sobre tres muestras naturales en tres células de flujo paralelas, para estudiar las dificultades en la obtención de medidas de potencial redox estables, especialmente en aguas subterráneas procedentes de gneisses y en agua de minas con capacidades tampón redox bajas. Los potenciales redox fueron medidos cada dos minutos durante más de cinco días. Los potenciales redox medidos fueron comparados con medias de potenciales parciales, modelizados en base a determinaciones selectivas de especies de hierro y nitrógeno, los elementos predominantes redox-sensitivos. Los potenciales redox se estabilizaron de forma reproducible en minutos en una solución redox tampón y dos muestras de agua ácida de pozos de mina a pH 2.3 y 3.5. Para aguas en desequilibrio redox los análisis selectivos por especies deberían ser todavía la mejor alternativa comparados con la medida del potencial redox como una suma de parámetros para modelizar la distribución de especies. En casos en los que el potencial redox sea el único parámetro fácilmente obtenible, se recomienda una filtración y una posible acidificación para una estabilización más rápida de las medidas de potencial redox y que haya menos desviaciones entre los valores medidos y los del modelo. En las muestras investigadas se consiguió un mínimo de un 2%, sin embargo, a menudo incluso después de medidas significativamente más largas que las previamente sugeridas de 30 minutos. La estabilización final tuvo lugar después de más de varias horas en aguas con capacidad tampón baja.

     

Structure of colloid particles in groundwaters on the territory of the Mayak production association and its impact on the colloid transport of radionuclides in subsoil environments

Colloid particles were examined in groundwaters sampled at the large contamination area of the subsoil environment at the Mayak production association in the Southern Urals. Colloid particles were separated from groundwater samples by ultrafiltration, and their composition and structure were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger spectroscopy (AS). Our results indicate that the chemical composition of the particles significantly varies at their surface and along their radii, from the peripheries to the cores of the particles. The data are used to estimate the possibility of utilizing properties of colloid particles contained in groundwaters (the composition, structure, and zeta potential of such particles) to numerically simulate the spreading of radioactive contamination with groundwaters with regard to the colloid mode of radionuclide transport. It is demonstrated that, along with transmitting electron spectroscopy (TEM) coupled with X-ray microprobe analysis and electron diffraction, the XPS and AS techniques make it possible to obtain information on heterogeneity in the distribution and modes of occurrence of various elements in colloid particles.     

The adsorption of plutonium IV and V on goethite

The adsorption of Pu(IV) and Pu(V) on goethite (αFeOOH) from NaNO₃ solution shows distinct differences related to the different hydrolytic character of these two oxidation states. Under similar solution conditions, the adsorption edge of the more strongly hydrolyzable Pu(IV) occurs in the pH range 3 to 5 while that for Pu(V) is at pH 5 to 7. The adsorption edge for Pu(V) shifts with time to lower pH values and this appears to be due to the reduction of Pu(V) to Pu(IV) in the presence of the goethite surface. These results suggest that redox transformations may be an important aspect of Pu adsorption chemistry and the resulting scavenging of Pu from natural waters.Increasing ionic strength (from 0.1 M to 3 M NaCl or NaNO₃ and 0.03 M to 0.3 M Na₂SO₄) did not influence Pu(IV) or Pu(V) adsorption. In the presence of dissolved organic carbon (DOC), Pu(V) reduction to Pu(IV) occurred in solution. Pu(IV) adsorption on goethite decreased by 30% in the presence of 240 ppm natural DOC found in Soap Lake, Washington waters. Increasing concentrations of carbonate ligands decreased Pu(IV) and Pu(V) adsorption on goethite, with an alkalinity of 1000 meq/l totally inhibiting adsorption.The Pu-goethite adsorption system provides the data base for developing a thermodynamic model of Pu interaction with an oxide surface and with dissolved ligands, using the MINEQL computer program. From the model calculations we determined equilibrium constants for the adsorption of Pu(IV) hydrolysis species. The model was then applied to Pu adsorption in carbonate media to see how the presence of CO₃^?2 could influence the mobility of Pu. The decrease in adsorption appears to be due to formation of a Pu-CO₃ complex. Model calculations were used to predict what the adsorption curves would look like if Pu-CO₃ complexes formed.     

Mobilisation of arsenic from bauxite residue (red mud) affected soils: Effect of pH and redox conditions

The tailings dam breach at the Ajka alumina plant, western Hungary in 2010 introduced ∼1 million m³ of red mud suspension into the surrounding area. Red mud (fine fraction bauxite residue) has a characteristically alkaline pH and contains several potentially toxic elements, including arsenic. Aerobic and anaerobic batch experiments were prepared using soils from near Ajka in order to investigate the effects of red mud addition on soil biogeochemistry and arsenic mobility in soil–water experiments representative of land affected by the red mud spill. XAS analysis showed that As was present in the red mud as As(V) in the form of arsenate. The remobilisation of red mud associated arsenate was highly pH dependent and the addition of phosphate to red mud suspensions greatly enhanced As release to solution. In aerobic batch experiments, where red mud was mixed with soils, As release to solution was highly dependent on pH. Carbonation of these alkaline solutions by dissolution of atmospheric CO₂ reduced pH, which resulted in a decrease of aqueous As concentrations over time. However, this did not result in complete removal of aqueous As in any of the experiments. Carbonation did not occur in anaerobic experiments and pH remained high. Aqueous As concentrations initially increased in all the anaerobic red mud amended experiments, and then remained relatively constant as the systems became more reducing, both XANES and HPLC–ICP-MS showed that no As reduction processes occurred and that only As(V) species were present. These experiments show that there is the potential for increased As mobility in soil–water systems affected by red mud addition under both aerobic and anaerobic conditions.     

The effect of subduction on the sulphur,carbon and redox budget of lithospheric mantle

Subduction of hydrated lithospheric mantle introduces HO, ferric iron, oxidized carbon and sulphur to the subduction zone system. The fate of these components is poorly known, but is intimately linked to the global geochemical cycles of iron, carbon and sulphur, the genesis of arc‐related ore deposits, the temporal evolution of mantle redox state and subduction‐related earthquakes and magmatism. thermocalc is used to provide first‐order constraints on the effect of subduction zone metamorphism on metamorphic redistribution of iron, carbon, sulphur and water in ultramafic rocks via construction of P?T and T‐X(O) pseudosections with open system calculation of the effect of fluid loss. The calculations replicate observed mineral assemblages in high‐P to low‐T ultramafic rocks at P?T conditions consistent with those suggested by other workers. The results are consistent with open system fluid loss without significant fluid infiltration. Water loss is complete by 850 C, the corresponding depth of fluid loss being consistent with that inferred for earthquakes in subducting slabs. Losses of carbon and sulphur are relatively minor, at around <5% and <1%, respectively, so it is envisaged that most carbon and sulphur subducted in ultramafic lithologies is transported to >5 GPa, below the depths of the source zone for arc volcanoes. Oxygen activity for rocks in closed systems that evolve with a fixed redox budget is calculated to change from ΔFMQ ?1 at 350 C to over ΔFMQ +3 at 850 C. This result emphasizes the need to consider redox budget as well as oxygen activity when the results of experiments performed at fixed oxygen activity relative to some buffer are interpreted in the context of natural systems. In open systems, devolatilization is calculated to increase the redox budget and oxygen activity of the residue via loss of methane and HS at the brucite‐out and serpentine‐out reactions respectively. No fluid‐induced mechanism for oxidation of sub‐arc mantle by transfer of redox budget from hydrated ultramafic lithologies to the overlying sub‐arc mantle was identified, although further thermodynamic data on fluid species such as S are required to confirm this.     

Modelling of pH and inorganic aluminium after termination of liming in 3000 Swedish lakes

Significant resources are spent on counteracting the effects of acidification, mainly by liming. Due to lower S and N deposition in Europe and North America, authorities are changing directives and strategies for remediation and reducing liming. However, as the acid–base buffer capacity differs in different water bodies, the desirable reduction of the lime dose is variable. In this study, a geochemical model is used to predict pH and inorganic monomeric Al (Al_i) when liming is reduced and finally terminated in the 3000 Swedish lakes currently treated with lime. To estimate Ca and Mg concentrations not affected by liming for use in the model, the Ca/Mg ratio in nearby unlimed reference lakes was used. For the modelling of pH and inorganic Al the Visual MINTEQ program including the Stockholm Humic Model recently calibrated for Swedish fresh water was used. The predictions were validated with modelling results from six monitored lakes, in which liming had been terminated. The use of geochemical modelling appeared to be a promising tool for the calculation of accurate lime requirements in acid waters. For simulations in which liming was completely terminated, the pH value decreased by, on average, 1 pH unit to pH 5.7, whereas Al_i increased by 17 μg L⁻¹ to 32 μg L⁻¹. If liming was reduced by half, the pH would drop only 0.3 pH units and Al_i would increase by 2 μg L⁻¹. Lakes in the south-western part of Sweden were predicted to reach a lower pH and higher Al_i, which would be expected due to their greater historical S deposition. The results indicate that liming can be terminated in certain areas and in other areas be reduced without increases in the lake acidity.     

The geochemistry of plutonium in fresh and marine water environments

The chemical behaviour of plutonium in the hydrosphere is a subject of both great practical and intrinsic importance. The production and eventual disposal of Pu and other artificial radionuclides dictates that this be the case. The main objective of this paper is to provide a synthesis and critical examination of currently published data and interpretations on the geochemistry of Pu in natural waters and sediments. Where appropriate, an attempt is made to reinterpret published data with the aim of establishing the relationships between geochemical and biological processes and the distribution, concentration and speciation of Pu. Particular attention is paid to the question of the potential for the chemical remobilization of Pu from the solid to the aqueous phase. Approximately one third of the text deals with freshwaters (mostly lakes) while two thirds discusses the estuarine, coastal and open ocean environments.     

Long-term continuous in situ potentiometrically measured redox potential in anoxic groundwater with high methane and iron contents

The in situ redox potential (Eh) in anoxic groundwater with high methane and iron contents (approximately 12.3 and 28.4 mg/L, respectively) was potentiometrically measured to identify the processes that control Eh. The measured Eh ranged from −213 to −187 mV; it had an inverse correlation with the concentration of methane and no correlation with that of iron. The saturation indices indicate that goethite and amorphous FeS were nearly at solubility equilibrium. A comparison of the measured Eh with those calculated for the particular redox pairs indicates that either Fe²⁺/FeOOH or CH₄/CO₂, but not sulfur redox pairs, controlled the measured Eh. The inverse relationship between measured Eh and methane concentration suggests possible control of the redox conditions by the CH₄/CO₂ redox pair. Furthermore, the equilibrium solubility state of goethite, which has higher crystallinity and lower solubility than Fe(OH)₃ indicates that the iron reaction was electrochemically irreversible. This further supports the contribution of the CH₄/CO₂ pair to controlling the measured Eh of groundwater.     

By design: The architecture of microbial redox cycling

The authors’ work on mine systems, combines field and laboratory integrated microbial geochemical investigation with high-resolution techniques enabling characterization and visualization at the bacterium scale (i.e. STXM). The results indicate a repeated motif of socially organized microbial cooperation occurring within microbial consortial macrostructures (pods). The pod structure directly enables the specific geochemical processes linked to the metabolic function of the consortial members. These microbially linked geochemical processes have important ramifications for bulk system geochemistry that were previously unknown. Results from two examples: (1) microbial metal interactions within AMD biofilms and (2) sulfur redox cycling by a novel consortia within mine waters, illustrate how the ecology of the pod consortia is linked to pod biogeochemical macrostructure as well as to the resulting geochemistry associated with pod metabolism. In both instances the pod structures enabled the associated consortia to carry out reactions not predicted by classic geochemical understanding of these systems. Investigation of AMD biofilm biogeochemical architecture capturing the micro-scale linkages amongst geochemical gradients, metal dynamics and depth resolved micro-organism community structure, illustrated a novel biomineralization process driven by biofilm associated pods controlling biofilm metal capture. Similarly, the groups’ recent discovery of an environmental S redox cycling, pod-forming, consortium revealed ecologically driven S cycling with previously unknown implications for both AMD mitigation and AMD carbon flux modeling. These results highlight how microbes cooperatively orchestrate their geochemical environment, underscoring the need to consider syntrophic community activity in environmental processes and the requirement for integrated, high-resolution techniques spanning geochemistry, molecular microbiology and imaging to reveal the biogeochemistry involved.     

The effect of microorganisms on Fe precipitation rates at neutral pH

The effect of microorganisms on Fe precipitation rates at neutral pH in the field was examined. The studied area was a cave having Fe-stalactites composed mainly of ferrihydrite and associated microorganisms. The microorganisms were covered with ferrihydrite. Water associated with stalactites was slightly supersaturated with respect to ferrihydrite, and had a dissolved oxygen concentration of 2 ppm, a pH of 6, and an Fe concentration of approximately 14 ppm. Fe precipitation rates were estimated from decreases in Fe concentrations in water during flowing through the Fe-stalactites. The estimated Fe precipitation rate in the field ranges from 6.8×10⁻⁸ to 4.0×10⁻⁷ mol/l/s. These values are in good agreement with bulk estimates of Fe-stalactite growth rates derived from the length increase (1.3 cm) of one formation over 30 days. The estimated Fe precipitation rates are faster by about four orders of magnitude than expected inorganic precipitation rates. On-site Fe precipitation experiments with sterilized and unsterilized Fe-stalactites and without Fe-stalactites indicate that microorganisms are the controlling factor accelerating Fe precipitation rates at neutral pH. These results suggest that microbially accelerated Fe precipitation rates are more likely related to exopolysaccharides and microbial surface properties than metabolic precipitation mechanisms.     

The association of gold with calcrete

The discovery that Au accumulates in calcrete (pedogenic carbonate or caliche) was made in 1987 by CSIRO. Calcrete is a general term describing accumulation of alkaline earth metals in soils of arid and semi-arid terrains around the world. The principal constituent of calcrete is calcite while Au is a noble metal. Calcrete has been a significant tool in a number of Au deposit discoveries, so understanding the mechanisms by which these diametrically different components come together is valuable for enhancing future discovery. Numerous laboratory experiments, case histories and exploration models have been published (most from Australia) yet we do not fully understand the mechanisms involved. It is timely, therefore, twenty-five years on since the first publication of this phenomenon, to review this highly unusual but economically important association.Critical to any review on Au in calcrete is to first consider calcretes themselves. The nature of a particular calcrete, where it has formed and mode of formation is relevant to how, where and why Au accumulates within it. This review commences with a background, nomenclature, history, classification and some examples of calcrete types found near Au deposits. How calcretes form, their origins and the role of biota is considered. Their locations in the regolith and landscape, as well as exploration models for Au in calcrete are discussed. A section on the chemistry of Au in calcretes details what we know about possible mechanisms of formation and considers what laboratory experiments on microorganisms and abiotic experiments tell us. Following on is a summary of practical aspects of identifying, collecting and analysing samples for exploration purposes. Selected mineral exploration case histories are described and how they fit into models of exploration and different regolith settings. Concluding sections include a summary and implications of this accumulated knowledge to discovering Au deposits.