Platinum-group mineral formation: Evidence of an interchange process from the entropy of activation values

Small grains of Ru–Os–Ir sulfides or alloys that formed in the early stages of the crystallization of basaltic magmas occur as inclusions in chromitites from many ophiolite complexes, Ural/Alaskan-type and layered intrusions. The nature of platinum-group elements is debated, i.e., whether they originally occurred in a metallic state or bonded with sulfur or other ligands. The application of kinetics and suggestions regarding the mechanisms of PGE formation may contribute to a better understanding of the genetic processes for platinum-group mineral (PGM) formation. The aim of the present study is to investigate the type of mechanism (associative, dissociative or interchange) and the possibility of direct formation of PGM from the reaction of free metals with sulfur, defining also the structure of possible intermediate species.The literature on the grain sizes (r) of platinum-group minerals (PGM) and their formation temperatures (range between 700 and 1100 °C) reveals an Arrhenius temperature dependence. The activation energy was estimated to be 450 ± 45 kJ mol⁻¹. Applying the Eyring equation to the same data, a linear relationship between 2.5ln(r) + ln(T) versus 1/T was obtained, leading to an estimation of the free energy of activation, ΔG^≠ = 440 ± 43 kJ mol⁻¹. The thermodynamic relation ΔG^≠ = ΔH^≠ − TΔS^≠, used together with the relation ΔΗ^≠ = E_act − RT leads to the calculation of ΔS^≠ at various temperatures. The estimated entropy of activation at various temperatures being almost zero, we suggest an interchange mechanism for PGM formation.The possibility of PGM formation from the direct reaction of free metals with sulfur would be inconsistent with the estimated entropy of activation values (ΔS^≠  0) at various temperatures. In the cases of PGMs of known r, the formation temperatures can be estimated, and then the free energy of activation obtained, applying 2.5ln(r) + ln(T) versus 1/T (straight line). From that value, the entropy of activation can be calculated [ΔS^≠ = −R + (E_act − ΔG^≠)/T], and an interchange mechanism is proposed. Furthermore, applying the relation of 2.5ln(r) + ln(T) versus 1/T on PGM grains of known r and T, an interchange mechanism for their formation can be suggested if they fit the above line.     

Mechanical stratigraphy as a factor controlling the development of a sandbox transfer zone: a three-dimensional analysis

In thrust belts, fold–fault terminations are common features of the structural architecture and can pose complicated problems to unravel, in particular when two or more terminations are in close proximity. Such terminations usually reflect pre-existing attributes. Amongst the many factors, lateral variations in the mechanical stratigraphy can control along-strike geometry and kinematics of fault-related folds.A displacement transfer zone was produced in a compressional sandbox model by means of two adjacent, mechanically different stratigraphic domains. The experiment allowed two discrete chains to develop in the different domains, so that a complex structural setting occurred in the connecting area. Periclinal folds, oblique thrust fronts and oblique ramps developed in the resulting transfer zone. The interaction between periclines in the transfer zone produced lateral culminations in the folded structures. The analysis of displacement across the structural domains revealed that a significant loss of slip along the faults occurred in the relay zone. In this area, imbricate faulting was partially replaced by layer-parallel shortening. A linear relationship appears to exist between the bed length of the thrust sheet and the related fault slip.     

Resonance-centrifugal effects as a factor in the formation of solar magnetic arcades

The development of magnetohydrodynamical centrifugal instability is considered as a possible mechanism for the formation of solar magnetic arcades. The computations show that the plasma in a cylindrical, magnetized, rotating layer can develop two families of waveguide-resonance instability modes. These are gyroscopic resonance modes of the rotating, cylindrical layer and harmonics of fast magnetoacoustic waves that propagate along the forming cylindrical layer and initiate resonance instability in the layer. The joint action of these two mechanisms is able to produce the observed morphology of solar magnetic arcades.     

Unravelling the formation histories of placer gold and platinum-group mineral particles from Corrego Bom Successo,Brazil: A window into noble metal cycling

Gold and platinum-group-metals (PGM) are cycled through Earth’s environments by interwoven geological, physical, chemical and biological processes leading to the trans/neoformation of metallic particles in placers. The placer deposit at Corrego Bom Successo (CBS, Brazil) is one of the few localities worldwide containing secondary gold- and PGM-particles. Placer gold consists of detrital particles from nearby hydrothermal deposits that were transformed in the surface environment. Processes that have affected these particles include short-distance transport, chemical de-alloying of the primary gold‑silver, and (bio)geochemical dissolution/re-precipitation of gold leading to the formation of pure, secondary gold and the dispersion of gold nanoparticles. The latter processes are likely mediated by non-living organic matter (OM) and bacterial biofilms residing on the particles. The biofilms are largely composed of metallophillic β- and γ-Proteobacteria. Abundant mobile gold and platinum nanoparticles were detected in surface waters, suggesting similar mobilities of these metals. Earlier hydrothermal processes have led to the formation of coarsely-crystalline, arborescent dendritic potarite (PdHg). On potarite surfaces, biogeochemical processes have then led to the formation of platinum- and palladium-rich micro-crystalline layers, which make up the botryoidal platinum‑palladium aggregates. Subsequently potarite was dissolved from the core of many aggregates leaving voids now often filled by secondary anatase (TiO₂) containing biophilic elements. The presence of fungal structures associated with the anatase suggests that fungi may have contributed to its formation. For the first time a primary magmatic PGM-particle comprising a mono-crystalline platinum‑palladium-alloy with platinum‑iridium‑osmium inclusions was described from this locality, finally defining a possible primary source for the PGM mineralisation. In conclusion, the formation of modern-day placer gold- and PGM-particles at CBS began 100s of millions of years ago by magmatic and hydrothermal processes. These provided the metal sources for more recent biogeochemical cycling of PGEs and gold that led to the trans/neoformation of gold- and PGM-particles.     

The platinum-group element distribution in the Dumont Sill,Quebec. Implications for the formation of ni-sulfide mineralization

Summary The Dumont Sill is an Archaean komatiitic intrusion, whichDuke (1986) subdivided into a mafic (MZ) and ultramafic zone (UMZ). The UMZ comprises an upper (UPZ) and a lower peridotite subzone (LPZ) consisting of olivine + chromite cumulates and a dunite subzone (DZ) between them, consisting of olivine ± sulfide cumulates.Three sulfide-rich layers in the DZ are delineated by anomalously high Ni, Cu, S and Se concentrations (Ni 0.95 wt %, Cu 0.07 wt.%, S 1.0 wt.%, Se 2.7 ppm). They also contain elevated contents of noble metals (Au 31.5 ppb, Pd 210 ppb, Pt 180 ppb, Ir 8.4 ppb, Os 6 ppb). Unmineralized samples contain 3–8 ppb Pd, 1–20 ppb Pt, 0.2–3.6 ppb Au, 0.5–6 ppb Ir, and 1–6 ppb Os.Samples belonging to the LPZ and UPZ and lying above and beneath the mineralized horizons have rather high Ir contents, generally between 2.9 to 4.4 ppb. In contrast, Ir contents of sulfide-free samples from the DZ and UPZ which lie immediately above the mineralized zones have significantly lower Ir concentrations, ranging from 0.1 to 1.5 ppb. This zone of Ir depletion coincides with a zone of Ni-depleted olivine and sulfide which crystallized just above sulfide-rich horizons in the DZ (Duke, 1986). It is suggested that Ir and Ni depletion in cumulates which lie between or above sulfide-rich zones are due to the lower Ir and Ni contents in olivine which crystallized from a silicate magma from which a sulfide liquid had already been segregated. Alternatively, if metal alloys control the distribution of Ir and Os in the DZ, the Ir depletion in the cumulates above the ore' horizons implies that crystallization of the metal phase ceased. This would be the case if, due to the segregation of sulfides, the Ir concentration in the silicate liquid falls below the solubility limit of the metal phase.The sulfide mineralization probably formed by fractional segregation of a sulfide/ oxide liquid, as the PGE concentrations in the sulfide liquid and PGE/Se, or PGE/S ratios tend to decrease from the bottom to the top in the mineralized zones.Duke (1986) proposed that sulfide saturation was caused by mixing of primitive komatiite magma with fractionated interstitial liquid, which was squeezed out of the cumulate pile. Sulfide segregation at the floor of the magma chamber is likely to have been a very localized event implying low R-factors. The small PGE-enrichment in the sulfide horizons of the Dumont Sill and the narrow zones of Ir-depletion just above the sulfide zones are consistent with the proposed process.

---

Die Verteilung von Platingruppen-Elementen im Dumont Sill, Quebec und ihre Bedeutung für die Bildung von Ni-Sulfid MIneralisationen

Zusammenfassung Der Dumont Sill ist eine komatiitische Intrusion, die von Duke (1986) in eine mafische (MZ) und eine ultramafische (UMZ) Zone untergliedert wurde. Die UMZ setzt sich aus einer oberen (UPZ) und einer unteren (LPZ) peridotitischen Subzone, die aus Olivinund Chromft-Kumulaten besteht, und einer dunitischen Subzone (DZ), zwischen diese beiden eingeschaltet, zusammen. Letztere besteht aus Olivin- und Sulfid-Kumulaten.Drei sulfidreiche Lagen innerhalb der DZ sind durch anomal hohe Gehalte an Ni, Cu, S und Se (Ni 0.95 Gew. %, Cu 0.07 Gew. %, S 1.0 Gew. %, Se 2.7 ppm) charakterisiert. Erhöhte Gehalte an Edelmetallen (Au 31.5 ppb, Pd 210 ppb, Pt 180 ppb, Ir 8.4 ppb, Os 6 ppb) sind ebenfalls an diese Lagen gebunden. Unvererzte Proben enthalten < 3–8 ppb Pd, 1–20 ppb Pt, 0.2–3.6 ppb Au, 0.5–6 ppb Ir und 1–6 ppb Os.Proben aus der LPZ und UPZ und solche aus dem Hangenden und Liegenden der Mineralisationshorizonte zeigen relativ hohe Ir-Gehalte; im allgemeinen zwischen 2.9 und 4.4 ppb. Im Gegensatz dazu sind die Ir-Gehalte sulfidfreier Proben unmittelbar über vererzten Lagen deutlich erniedrigt; sie variieren zwischen 0.1–1.5 ppb. Diese an Ir verarmte Zone entspricht einer Zone nickelarmer Olivine und Sulfide, die unmittelbar oberhalb der sulfidreichen Horizonte in der DZ kristallisierten (Duke, 1986). Es wird vermutet, daß die Ir- und Ni-Abreicherung in den Kumulaten, die oberhalb und zwischen den sulfid-reichen Zonen liegen, mit den niedrigeren Ir- und Ni-Gehalten der Olivinen zusammenhängt. Die Olivine kristallisierten aus einem Silikatmagma, von dem sich bereits eine Sulfidschmelze abgeschieden hatte.Soferne metallische Verbindungen die Ir- und Os-Verteilung in der DZ kontrollieren, würde die Ir-Abreicherung in den Kumulaten oberhalb des Erzhorizontes auf ein Ende der Kristallisation einer metallischen Phase hinweisen. Dieser Fall könnte eintreten, sobald durch die Ausscheidung von Sulfiden, die Ir-Konzentration in der silikatischen Schmelze unter die Löslichkeitsgrenze der Metallphase fällt.Die Sulfidvererzung bildete sich wahrscheinlich infolge von fraktionierter kristallisation einer Sulfid/Oxidschmelze, da die PGE Konzentrationen der Sulfidschmelze, und das PGE/S Verhältnis vom Liegenden zum Hangenden hin in den mineralisierten Horizonten abnehmen. Duke (1986) schlug ein Modell vor, in dem die Sulfid-Sättigung der silikatischen Schmelze durch eine Vermischung eines komatiitischen Magmas mit einer fraktionierten, interstitialen, aus den Kumulaten ausgequetschten Schmelze erklärt wird. Die Sulfidausfällung an der Basis der Magmenkammer scheint ein lokal recht begrenztes Phänomen gewesen zu sein, die niedrige R-Faktoren bedingt. Die geringfügige PGE-Anreicherung in den Sulfidlagen des Dumont Sills und die schmale Zone der Ir-Abreicherung unmittelbar oberhalb dieser sulfidischen Zone stehen mit diesen vorgeschlagenen Prozessen im Einklang.

---

---

With 6 Figures     

基于能量平衡法的黑河中游灌溉渠道蒸发量估算

干旱区绿洲农田需要通过渠道引水进行灌溉,在此过程中蒸发损失不可避免,尤其是在渠系广泛分布的情况下,蒸发损失量大,如何估算这部分量对于干旱区水资源管理至关重要. 以甘肃张掖绿洲灌溉渠道为研究对象,采用Mihara所提供的基于能量平衡理论的经验方程,对渠道蒸发量进行了估算.结果表明：蒸发率在晴天时白天大于夜间,阴天时白天和夜间相差不大,气温和相对湿度是影响蒸发率的主要因子.累计蒸发量在晴天时白天是夜间的2倍左右,阴天时白天和夜间相差不大,蒸发率是直接原因.     

On mantle drag force for the formation of a next supercontinent as estimated from a numerical simulation model of global mantle convection

Three‐dimensional spherical mantle convection was simulated to predict future continental motion and investigate the driving force of continental motion. Results show that both the time required (≥300 Ma from the present) and the process for the next supercontinent formation are sensitive to the choice of critical rheological parameters for mantle dynamics, such as a viscosity contrast between the upper and lower mantles and a yield strength of the lithosphere. From all the numerical models studied herein, mantle drag force by horizontal mantle flow beneath the continents may mostly act as a resistance force for the continental motion in the process of forming a new supercontinent. The maximum absolute magnitude of the tensional and compressional stress acting at the base of the moving continents is in the order of 100 MPa, which is comparable to a typical value of the slab pull force.     

The use of simultaneous R- and Q-mode factor analysis as a tool for assisting interpretation of mineral magnetic data

The paper demonstrates both the potential and possible limitations of the use of simultaneous R-and Q-mode factor analysis for the detection of multivariate patterns in mineral magnetic data sets. Two examples are presented: correlation of Quaternary age glacial sediments from the Isle of Man within the Irish Sea Basin, and secondly, sediment-source linkages in recent lake sediments from Bar Mere, Cheshire, England. In both examples, the factor analysis offers useful insights into the environmental processes involved. Also, it seems to offer a suitable method by which qualitative interpretations of mineral magnetic data can be underpinned by a more objective approach. Plots of both variable and sample factor loadings provide a simple visual impression of the underlying multivariate trends in the data set. Given the simplicity with which the factor approach used here can be performed, it appears that it could become routine practice for the analysis of suitable mineral magnetic data sets.     

Trace elements as indicators of the physicochemical conditions of mineral formation in hydrothermal sulfide systems

The three-mode distribution of trace-element (TE) concentrations is observed in accordance with three main forms of TE occurrence in mineral: structural, surficial, and phase (native TE phases). Minerals of hydrothermally synthesized pyrite–pyrrhotite–magnetite–greenockite assemblage in the presence of Au and Mn are studied. Discrimination of modes is made, using the method of statistical sample of analytical data for single crystals (SSADSC), which is based on the postulate that individual crystals can contain predominantly one of possible forms. This is supported by study of Cd modes of occurrence by element thermorelease atomic-absorption spectrometry. X-ray photoelectron spectroscopy and atomic-force microscopy were used to examine the surficial TE forms. It has been confirmed that the dependence of the TE content on the crystal size in the sample is mainly due to surficial nonautonomous phases absorbing TEs. The effect of correspondence of chemical-component forms on the surfaces of coexisting minerals is also corroborated. This phenomenon is not related to the mutual contamination of phases but is due to the induction of the corresponding states of chemical forms in coexisting nonautonomous phases. It is possible to obtain true coefficients of interface distribution, characterizing structural TE impurities. These coefficients differ strongly from apparent distribution coefficients calculated from the bulk contents of impurities, except for Mn in pyrrhotite and magnetite, where its structural mode is predominant. The results obtained show that TEs can be used as quantitative geochemical indicators, which help to obtain correct information about the parameters of mineral formation and TE contents in the fluid phase.     

Sustainable development and the exploitation of mineral and energy resources: a review

Natural resources, e.g., metals, industrial minerals, water, and soil, are the essential basis for our economy and well-being. We have to know where these raw materials come from and how they are mined. Sustainable development requires the maintenance, rational use and enhancement of natural resources, as well as a balanced consideration of ecology, economy and social justice. Four general rules concerning the implementation of sustainable development for renewable and non-renewable resources are discussed. Examples of the consumption of selected materials from historical times to the present day are presented, as well as of regional distribution, usage (in contrast to consumption), lifetimes of resources, the supply-and-demand cycle, recycling and substitution in modern times. To fulfill the requirement of sustainable development, the efficiency with which resources are utilized has to be improved. The learning process, often driven by financial rewards, leads from one technology to a better one, thus increasing the efficiency of the use of a resource or commodity. Examples of learning curves are discussed. Industrial countries have to transfer their advanced technologies to developing countries in order to avoid undesirable development in the mining industry and use of natural resources in those regions. The use of the best available technology by the mining industry, taking into account economic considerations, and the necessity to establish environmental guidelines are essential if environmental impact of the production of non-renewable resources is to be minimized. Far more critical than the production of non-renewable resources under the aspect of sustainable development and the capacity of the pollutant sinks of the Earth is the element of natural attenuation with regard to the resources soil and water.     

Fidelity of the integrated kinetic energy factor as an indicator of storm surge impacts

Natural Hazards - After the devastating hurricane season of 2005, shortcomings with the Saffir–Simpson Hurricane Scale’s (SSHS) ability to characterize a tropical cyclone’s...     

The entropy and Gibbs free energy of formation of the aluminum ion

A reevaluation of the entropy and Gibbs free energy of formation of Al³⁺_(aq) yields ?308 ± 15 J/K·mol and 489.4 ± 1.4kj/mol for S⁰₂₉₈ and $\text{ΔG}{}^0{}_{\mathrm{?,298}}$ respectively. The standard electrode potential for aluminum is 1.691 ± 0.005 volts.     

Resonance centrifugal effects as a factor in the formation of solar magnetic arcades. Influence of dynamical radiative cooling

This article continues our studies of the development of an MHD, waveguide, centrifugalresonance instability as a possible mechanism for the formation of solar magnetic arcades; here, we take into account the non-isentropic nature of this process associated with the presence of dynamical radiative cooling. In contrast to the results of our previous study, our computational data show that five, rather than two, waveguide-resonance families of unstable modes are able to develop in a cylindrical, rotating layer of magnetized plasma. This substantially expands the spectrum of associated wave processes, so that the joint action of all these growing wave harmonics can lead in the non-linear stage of their development to morphologies close to those observed in solar magnetic arcades—to the formation both of the magnetic arcades themselves and of fine structure in such arcades.