Pyrite oxidation inhibition by a cross-linked lipid coating

The effect of a diacetylene-containing phospholipid on the oxidation of pyrite, FeS₂, was investigated. Earlier work reported by our research group showed that the adsorption of l,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphocholine on pyrite suppressed the extent of its oxidation by about 75% over a specific time period. Results presented here show that the pre-exposure to UV radiation of this lipid after sorption onto pyrite results in a 90% suppression. Attenuated total reflection (ATR) Fourier transform infra-red spectroscopy (FTIR) suggests that the UV irradiation of the lipid does not result in degradation of the adsorbed layer. It is believed that the UV exposure results in the cross-linking and polymerization of the adsorbed phospholipid into a relatively impermeable barrier that separates the pyrite from the aqueous phase. The results of this study might have implications for the protection of pyrite from oxidation in the environment.     

Pyrite framboids and their development: a new conceptual mechanism

It has been suggested that the two morphologies of sedimentary pyrite, framboids and euhedra, may reflect two distinct pathways of pyrite formation. Framboids form indirectly via iron monosulphides, whereas euhedra form from direct precipitation from solution. A third pathway which is bridging these two forms is proposed here, namely the continuous growth from a monosulphide globule through framboids to a euhedral single crystal. It is also suggested that framboids probably occur over a range of three orders of magnitude, from the least complex microframboids through framboids to polyframboids.Dedicated to Professors G. C. Amstutz and L. G. Love for their unrivalled contribution to the knowledge of pyrite framboids     

Pyrite oxidation in the tertiary sands of the London Basin aquifer

Possible groundwater quality changes related to pyrite oxidation during artificial groundwater recharge and its storage in the Tertiary sands of the London Basin are investigated. Pyrite textures in the Tertiary sands are examined by scanning electron microscopy while an experimental approach is used to study mechanisms of pyrite oxidation and of some associated chemical reactions. In the Tertiary sands of the London Basin aquifer, pyrite occurs as aggregates made of discrete individual crystals 0.5–5 μm in size or, in a cryptocrystalline form, often as pseudomorphs of biogenic debris. It can expose a very large specific surface area to porefluids. Although ferric iron, which can be an oxidising agent of pyrite, is abundant in the solid phase of the Tertiary sands, it does not appear to take a significant part in this case. Pyrite oxidation seems to rely on a supply of oxygen. Leaching experiments using a 0.001 M H₂SO₄ solution were carried out to examine interactions between mildly acidic groundwater resulting from pyrite oxidation at a moderate rate and the host-sediment. In the presence of CaCO₃ in the solid phase, H⁺ is rapidly buffered by CaCO₃ dissolution. Oscillations of this reaction around equilibrium appear to trigger cation-exchange reactions on clay mineral surfaces, resulting in the release of major cations (e.g. K and Mg) into solution. In the absence of CaCO₃ in the solid phase, H⁺ buffering occurs less efficiently solely through exchange of cations for H⁺ on clay minerals surfaces. If the rate of pyrite oxidation in the Tertiary sands becomes high enough for the buffering capacity of the system to be exceeded, the groundwater pH begins to fall. Interactions between low pH (2) groundwaters and the host sediments were examined by leaching solid material in 0.01 M and 0.1 M H₂SO₄ solutions. Concentrations of Fe, Mg and K increase in solution throughout the experiment, indicating partial dissolution of clay minerals. The composition of the porefluid thus depends on the geochemical composition and surface area of the different clay minerals present.     

Pyrite oxidation related to pyritic minesite spoils and its controls: A review

Pyrite oxidation is considered to be a main contribution to the acidification of minesite spoils and the generation of the Acid Mine Drainage (AMD) which has become the greatest threat to the ecological environment. In this paper, pyrite oxidation and its controls are reviewed with respect to the latest literature. Conceptual model and empirical rate law model with reference to indoor experiments are classified and presented to describe pyrite oxidation in heterogeneous minesite spoil piles. The influences of Thiobacillus (T) ferrooxidans on pyrite oxidation are simply summarized. In order to prevent the generation of the AMD, three approaches including the addition of alkali to minesite spoil, use of dry covers, and coating on the minesite spoil surface, are discussed.     

Pyrite oxidation by Acidithiobacillus ferrooxidans at various concentrations of dissolved oxygen

Pyrite oxidation rates were examined at various concentrations of dissolved oxygen (DO) in the presence of the sulfur and iron oxidizer Acidithiobacillus ferrooxidans. Five different batch experiments were performed at room temperature for 75 days under various DO levels (273, 129, 64.8, 13.2, and ≤ 0.006 μM), containing pyrite grains (particle size 63–250 μm) and a modified 9K nutrient medium at pH 3. The reactors were inoculated with A. ferrooxidans. In all experiments, pH decreased with time and sulfur and iron were released to the solution, indicating pyrite oxidation at all DO levels. Pyrite oxidation rates (ca. 5 × 10^− 10 mol m^− 2 s^− 1 at 273 μM DO) from all experiments showed positive correlation with DO, Fe(III), and bacterial concentration. These rates were significantly slower than rates presented in other published studies, but this is probably due to the significantly greater Fe(III) concentration at lower pH in these previous studies. The results obtained in this study suggest that ferric iron reduction at the pyrite surface is the primarily mechanism for microbial pyrite oxidation in the presence of DO. The results from our study support the indirect mechanism of sulfide oxidation, where A. ferrooxidans oxidizes ferrous iron in the presence of DO, which then oxidizes pyrite.     

Pyrite (FeS2) oxidation: A sub-micron synchrotron investigation of the initial steps

Pyrite is an environmentally significant mineral being the major contributor to acid rock drainage. Synchrotron based SPEM (scanning photoelectron microscopy) and micro-XPS (X-ray photoelectron spectroscopy) have been used to characterise fresh and oxidised pyrite (FeS₂) with a view to understanding the initial oxidation steps that take place during natural weathering processes. Localised regions of the pyrite surface containing Fe species of reduced coordination have been found to play a critical role. Such sites not only initiate the oxidation process but also facilitate the formation of highly reactive hydroxyl radical species, which then lead the S oxidation process.Four different S species are found to be present on fresh fractured pyrite surfaces: S₂²⁻_(bulk) (4-fold coordination), S₂²⁻_(surface) (3-fold coordination), S²⁻ and S⁰/S_n²⁻ (metal deficient sulfide and polysulfide respectively). These species were found to be heterogeneously distributed on the fractured pyrite surface. Both O₂ and H₂O gases are needed for effective oxidation of the pyrite surface. The process is initiated when O₂ dissociatively and H₂O molecularly adsorb onto the surface Fe sites where high dangling bond densities exist. H₂O may then dissociate to produce OH radicals. The adsorption of these species leads to the formation of Fe-oxy species prior to the formation of sulfoxy species. Evidence suggests that Fe-O bonds form prior to Fe-OH bonds. S oxidation occurs through interactions of OH radicals formed at the Fe sites, with formation of SO₄²⁻ occurring via S₂O₃²⁻/SO₃²⁻ intermediates. The pyrite oxidation process is electrochemical in nature and was found to occur in patches, where site specific adsorption of O₂ and H₂O has occurred. Fe and S oxidation was found to occur within the same area of oxidation probably in atomic scale proximity. Furthermore, the O in SO₄²⁻ arises largely from H₂O; however, depending on the surface history, SO₄²⁻ formed early in the oxidation process may also contain O from O₂.     

Roof bolting in underground mining: a state-of-the-art review

Conclusions With continuing investigations and developments, roof bolting today can in most cases successfully reinforce the mine roof in underground mining. In order to cope with the increasing use of roof bolts, efforts should be made to maximize the safety and minimize the cost. With regard to mechanical bolting, two important parameters need more advanced improvements and study, namely, optimum design of the shape and type of expansion shell and optimum bolt tension for a specific bolt pattern. For the fully grouted resin bolt, the most critical requirement is to develop a fast-setting, low-cost, intoxic, inflammable grouting material that can be used in the high speed mining cycle. It should be noted that geological conditions such as the strata type, rock properties,in situ stress, and planes of weakness play an important role in the successful application of any roof bolting system. These factors should be specified as accurately and quantitatively as possible in the design of any roof bolting system. Finally, proper and careful installation and continuous monitoring are imperative for the success of any roof bolting system.     

Pyrite formation and the drowning of a palaeosol

Palaeosols may be modified in a variety of ways during burial diagenesis but significant alteration can take place during the earliest phases of burial caused by rising groundwaters. A calcrete palaeosol, the Heatherslade Geosol, from the Lower Carboniferous of South Wales, contains abundant pyrite which overprinted the original soil fabrics. The pyrite is interpreted as the product of anaerobic conditions caused by drowning during the early stages of a marine transgression. Unusual diamond-shaped forms of pyrite occur which possibly represent pseudomorphs after gypsum.     

Controlled time–temperature oxidation reaction in a synthetic Mg-hercynite

The oxidation of a synthetic hercynite with composition Fe²⁺ _0.699Mg_0.301Al_1.941Fe³⁺ _0.059O₄ was investigated by X-ray single-crystal diffraction. Heating runs at 500°C up to 212 h did not produce detectable oxidation, but only a small variation in oxygen coordinate u, consistent with very limited reordering of Mg and Al in tetrahedral (T) and octahedral (M) sites, respectively. Oxidation began after the first run at 600°C, producing progressive decreases in u, cell parameter a and the mean atomic number in T site. After 1,842 h at 600°C, the transformation was close to equilibrium, with about 70% of ferrous iron transformed into ferric. This produced about 0.17 vacancies per formula unit, and caused a great increase in the displacement parameters of oxygen and M sites. Vacancies were strongly ordered in M sites, and the oxygen displacement parameter becames anisotropic, unlike stoichiometric spinels—because some of the oxygen coordination polyhedra have a vacancy instead of a cation in one vertex. The behaviour of displacement parameters in this case supports the calculated point defect distribution.     

Chemical oxidation of N,N-diethyl-m-toluamide by sulfate radical-based oxidation: kinetics and mechanism of degradation

A study was undertaken in order to understand the kinetics and mechanism of the chemical oxidation of N,N-diethyl-m-toluamide, an insect repellent, by sulfate radical. In this experiment, sulfate radical was generated using peroxymonosulfate with iron(II) and cobalt(II) as activator. The second-order rate constant for the reaction of the sulfate radical with N,N-diethyl-m-toluamide was found to be (1.9 ± 0.1) × 10⁹ M^?1 s^?1 at pH 7 and a temperature of 25 °C. Experiments for the chemical oxidation of N,N-diethyl-m-toluamide in river water and secondary wastewater revealed that the percentage of the removal of N,N-diethyl-m-toluamide was slightly influenced by the water matrices. However, the selected oxidation systems are not effective for the removal of N,N-diethyl-m-toluamide in seawater. Transformation by-products of N,N-diethyl-m-toluamide generated using peroxymonosulfate/iron(II) sulfate, peroxymonosulfate/iron(II) chloride, peroxymonosulfate/cobalt(II) sulfate and peroxymonosulfate/cobalt(II) chloride systems were identified. The results indicated that there are slight differences in the distributions of the transformation by-products detected depending on the activator. The common transformation by-products detected in all selected oxidation systems are N,N-diethylbenzamide, N-ethyl-m-toluamide, N,N-dimethyl-m-toluamide, N-ethyl-N-acetyl-m-toluamide, 2-(diethylamino)-1-m-tolylethanone, monohydroxylated N-ethyl-m-toluamide, and dihydroxylated N,N-diethyl-m-toluamide. Monohydroxylated N,N-diethyl-m-toluamide were detected only when the peroxymonosulfate/iron(II) system was applied. For the peroxymonosulfate/cobalt(II) systems, additional isomers of monohydroxylated N-ethyl-m-toluamide were detected. Peroxymonosulfate/cobalt(II) also transformed 2-(diethylamino)-1-m-tolylethanone into N-ethyl-N-(2-oxo-2-m-tolylethyl)acetamide and monohydroxylated 2-(ethyl(vinyl)amino)-1-m-tolylethanone as transformation by-products.     

Magmatism in the Iberian Pyrite Belt: petrological constraints on a metallogenic model

Igneous formations associated with massive sulphide deposits in the Iberian Pyrite Belt (IPB) are essentially composed of basic lavas and dolerites, and dacitic to rhyolitic volcanites; intermediate lavas are subordinate. The basic rocks show variable geochemical characteristics: lavas and dolerites comparable to recent within-plate alkaline basalts seem restricted to the western and southern parts of the IPB, whereas basic rocks comparable to continental tholeiites or arc-related basalts occur across the whole belt. The felsic rocks are classified as calc-alkaline and belong to the “low-Al₂O₃ and high-Yb type”. At given SiO₂, Al₂O₃ and TiO₂ contents, they show variable Zr, Nb, and HREE contents. Heavy-rare-earth element fractionation decreases from the dacites to the rhyolites ([Gd/Yb]_N ∼ 1), whereas the negative Eu-anomaly becomes more pronounced. The characteristics of the rhyolites are typical of sulphide-fertile volcanic packages. Trace-element modelling suggests that the felsic rocks evolved from a dacitic parent magma through fractional crystallization of hornblende and plagioclase. Partial melting of an amphibolite protolith, which appears as the most probable model for the origin of this dacitic magma, requires a high T/P gradient in the crust. The occurrence of alkaline basalts and continental tholeiites is consistent with formation of the IPB in a tensional tectonic setting. However, the associated island-arc tholeiites suggest a location in a domain of plate convergence. Emplacement in a fore-arc basin over a recently accreted crustal segment is envisaged as a possible hypothesis to account for the geological and petrological constraints. A high geothermal gradient and eruption in a submarine tensional basin could have been two key ingredients for the development of massive sulphide deposits within the IPB.

---

Resumen (translated by E. Pascual) Las formaciones ígneas asociadas con los depósitos de sulfuros masivos de la Faja Pirítica Ibérica (IPB) se componen esencialmente de doleritas y lavas básicas y de rocas volcánicas dacíticas a riolíticas; las lavas intermedias son poco abundantes. Las rocas básicas muestran caracteres geoquímicos variables: lavas y doleritas comparables a basaltos alcalinos intraplaca recientes parecen hasta ahora restringidos a las partes W y S de la IPB, mientras que rocas básicas de caracteres comparables a las de toleítas continentales o basaltos relacionados con arcos aparecen en toda la zona. Las rocas ácidas se clasifican como calcoalcalinas del tipo “low-Al₂O₃, high-Yb”. Para un contenido dado en SiO₂, Al₂O₃ y TiO₂, muestran contenidos variables en Zr, Nb y REE. El contenido en tierras raras pesadas decrece de dacitas a riolitas ([Gd/Yb]_N ∼ 1), al tiempo que la anomalía de Eu se hace más pronunciada. La modelización de elementos trazas sugiere que las rocas evolucionaron a partir de un magma parental dacítico mediante cristalización fraccionada de hornblenda y plagioclasa. La fusión parcial de un protolito anfibolítico, que parece el modelo más plausible para el origen del magma dacítico, requiere un elevado gradiente T/P en la corteza. La existencia de basaltos alcalinos y de toleítas continentales es congruente con la formación de la IPB en un entorno tectónico distensivo. El emplazamiento en una cuenca “fore-arc”, en un segmento cortical de reciente acreción, se contempla como una hipótesis posible para explicar los caracteres geológicos y petrológicos. Un alto gradiente térmico, junto con la erupción en una cuenca submarina extensional, pueden haber sido los dos ingredientes clave en el desarrollo de los depósitos de sulfuros masivos en la IPB.

---

---

Received: 3 March 1996 / Accepted: 7 April 1997     

层间氧化作用:一种分散元素(Re、Se)新的富集成矿机制

文章分析了分散元素成矿机制研究现状,在简要概括世界主要地区砂岩型铀矿床中分散元素富集状况的基础上,以我国511层间氧化带砂岩型铀矿床为例,阐述了分散元素Re、Se在砂岩型铀矿中的超常富集特征,论证和分析了砂岩型铀矿中分散元素超常富集的相对独立性,以及层间氧化作用机制下分散元素(Re、Se、Ge、Ga)独立成矿的可能性。认为在矿源条件具备的表生环境下,层间氧化作用促使分散元素超常富集并独立成矿是可能的。提出层间氧化作用是一种分散元素成矿新机制、新类型。建议加强分散元素基础成矿理论和检测技术方法等方面的研究。     

Copula函数在水文水资源中的研究进展与述评

Copula函数是一种灵活构造多变量联合分布和处理多变量问题的有效工具,在水文水资源领域应用广泛;随着研究的广度和深度不断推进,显示出其良好的适用性和不可替代的优越性。重点综述了近10年来Copula函数在水文事件多变量频率分析、水文事件遭遇组合分析、水文随机模拟、水文模型与预报以及其他问题中的最新应用研究进展与不足。从应用条件、参数估计、不对称性、拟合优选、尾部特性、多变量重现期选取、成果抽样误差等方面阐述了Copula函数应用需要注意的问题。展望了未来Copula函数在水文水资源领域应用中的研究重点和发展方向,为今后的研究提供借鉴和参考。     

Public participation in policy making: the state-of-the-art in Canada

This paper critically reviews the current status of public participation in Canada. Postulating that public participation implies an open, democratic form of planning and policy making, the paper examines factors which have influenced the attainment of meaningful public input in practice. Public participation in Canada has evolved greatly in the past 15 years but several key issues remain unresolved: provisions for participation remain, in large part, discretionary; procedures for the funding of intervenors require further development; and the emphasis in many jurisdictions remains upon the operational level involvement of the lay public, with a public hearing as the final arbiter of public opinion. More attention to the formal evaluation of participatory exercises is essential to the resolution of these concerns. In particular, more attention should be given to the context within which participation occurs. Moreover, greater consideration should be given to public involvement at the normative and strategic levels of planning. The paper concludes by briefly exploring the implications for practice that the concept of ‘normative participation’ might have in Canada.     

莓状黄铁矿:环境与生命的示踪计

莓状黄铁矿这一奇妙的微晶(0.1~1 μm)矿物集合体(5~50 μm)自科学家首次发现(1923年)和冠名(1935年)至今一直是不同学科竞相研究的热点.主要从莓状黄铁矿的形成机制、莓状黄铁矿与环境的关系等方面回顾了莓状黄铁矿的生物成因说(1923-1969年)、非生物成因说(1969-2000年)和多元成因说(2000-现今)各研究阶段取得的进展和存在的问题,指出莓状黄铁矿作为表层生物圈、深部生物圈和地外环境与生命示踪计具有巨大潜力,提出从地球科学、生命科学、材料科学、化学和纳米科技以及凝聚态物理学融合的角度加强对莓状黄铁矿研究的建议.      

黄铁矿解抑活化机理研究现状及进展

含有黄铁矿的多金属矿物浮选分离一般先采用石灰抑制黄铁矿以更好地选别其他有用金属矿物,随后再综合回收黄铁矿。为获得较好的回收指标,需对受抑制的黄铁矿进行解抑活化处理。在矿业工程领域,关于石灰抑制过的黄铁矿解抑活化机理等相关内容得到了广泛研究并取得一定进展。本文综合评述了影响黄铁矿可浮性的主要因素、不同种类活化剂对黄铁矿的活化机理及黄铁矿机械活化效应等相关研究进展,为今后黄铁矿资源高效加工理论与应用研究的进一步发展提供参考。     

Rock fracturing by explosive energy: review of state-of-the-art

A study of the dynamic rock fracture initiation and propagation due to explosive energy is presented through a detailed state-of-the-art review. Explosive energy dissipation in crushing and fracturing is examined and the various means to enhance the explosive energy utilization for dynamic rock fracturing are reviewed. The study highlights the need for a better understanding of the dynamic fracturing process particularly in the presence of in situ stresses in the rock mass.     

The Iberian Pyrite Belt: a mineralized system dismembered by voluminous high-level sills

The Iberian Pyrite Belt is a world-ranking massive sulphide province in which a reassessment of the palaeovolcanology has dramatically changed understanding of the source of metals and mechanism of ore formation. In the northern sector, the deposits are hosted by a sill–sediment complex in which more than 90% of the sills post-date the sulphide sheets. Because of a very high sill/sediment ratio, these late intrusions dominate the host succession and have severely disrupted the post-mineralization configuration thus obscuring the true genetic relationships. For example, some oxide deposits have been separated by hectometric sills from sulphide deposits they originally capped, creating seemingly totally independent mineralizing systems. In addition, stratiform sulphide sheets without underlying stockworks are not necessarily allochthonous. An early timing for the mineralization with respect to volcanism means that metals had to be predominantly sourced from the sedimentary basin and the continental crust below the volcanogenic sequence.     

黄铁矿晶体形貌学研究进展

介绍了黄铁矿晶体形貌学、黄铁矿晶体表面微形貌学的研究内容;黄铁矿习见晶形在金矿床研究中的标型意义;近年来黄铁矿晶须形貌学研究进展;黄铁矿形貌的生长机制研究内容等.根据前人黄铁矿习见晶形研究成果的理论实践意义,分析认为纳-微米黄铁矿晶须形貌成因和生长地质过程研究,不仅在矿物结晶生长理论研究中有意义,在认知纳米矿物,理解纳米矿化现象等方面有启示,纳-微米黄铁矿晶须形貌学研究值得重视.