The distribution and paragenesis of low temperature nickel/iron/cobalt sulphides in central Britain

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Geochemistry of some sulphides and sulpho-salts from Parys Mountain, Anglesey

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Sulphide ore minerals:surface chemical properties

The surfaces of iron-containing sulphide minerals were oxidised by a range of inorganic oxidants, and the resultant surface alteration products studied using various spectroscopic techniques. The characterisation of surface oxidation is relevant to the alteration of ores in nature and their behaviour during flotation and leaching, of importance to the metallurgical industry. The sulphides investigated included pyrite (FeS2), hexagonal pyrrhotine (Fe9S10), monoclinic pyrrhotine (Fe7Se), violarite (FeNi2S4), pentlandite ((FeiNi)9Se), chalcopyrite (CuFeS2) and arsenopyrite (FeAsS). The surfaces were oxidised by various methods including acid (sulphuric), alkali (ammonium hydroxide), hydrogen peroxide, steam, electrochemical and air/oxygen (in a low-temperature (150ºC) furnace), The surfaces were examined using surface sensitive chemical spectroscopic methods including x-ray photoelectron spectroscopy (ms), Auger electron spectroscopy (LES) and conversion electron Mössbauer spectroscopy (CEKS). Physical characterisation of the surfaces was undertaken using scanning electron microscopy (SM), spectral reflectance measurements and optical microscopy. Bulk characterisation of the sulphide minerals was undertaken using x-ray diffraction and electron microprobe techniques. Observed phases suggested to form in most of the sulphide surfaces include Fe204, Fe1-x0, Fe202, Fe00H, Fe(OH)3, with iron II & III oxy-sulphates. The iron sulphides show variable extents of oxidation, indicating pyrite to be the most stable. Violarite shows stability to oxidation, suggested to result from both its stable spinel crystal structure, and from the rapid formation of sulphur at the surface protecting the sub-surface from further oxidation. The phenomenon of sub-surface enrichment (in metals), forming secondary sulphides, is exhibited by pentlandite and chalcopyrite, forming violarite and copper sulphides respectively. The consequences of this enrichment with regard to processing and leaching are discussed. Arsenopyrite, often a hindrance in ore processing, exhibits the formation of arsenic compounds at the surface, the dissolution of which is discussed in view of the possible environmental hazard caused by the local pollution of water systems. The results obtained allow a characterisation of the sulphides in terms of their relative stability to oxidation, and an order of stability of the sulphide surfaces is proposed. Models were constructed to explain the chemical compositions of the surfaces, and the inter-relationships between the phases determined at the surface and in the sub-surface. These were compared to the thermo-chemically predicted phases shown in Eh/pH and partial pressure diagrams! The results are discussed, both in terms of the mineralogy and geochemistry of natural ores, and the implications for extraction and processing of these ore minerals.

Effect of pulsed current on the electrodeposition of chromium and copper

This research was concerned with the effects of pulsed current on the electrodeposition of chromium and copper. In the case of the latter metal, a novel application has been studied and a theory proposed for the ability to improve throwing power by the joint use of organic additives and pulsed reverse current. During the course of the research, several improvements were made to the pulse plating unit.Chromium. A study was made of the effect of square wave pulsed current on various physical properties of deposits from three hard chromium plating electrolytes. The effect of varying frequency at a duty cycle of 50% on the mean bulk internal stress, visual appearance, hardness, crack characteristics and surface topography of the electrodeposits was determined. X-ray diffraction techniques were used to study the phases present in the deposits. The effect of varying frequency on the cathodic efficiencies of the electrolytes was also determined. It was found that pulsed current reduced the internal stress of deposits from the sulphate catalysed electrolyte. It also reduced or eliminated cracking of deposits and reduced deposit brightness. Under certain conditions, pulsed current was found to induce the co-deposition of hydrides of chromium. Deposit hardness was found to be reduced by the use of pulsed current. Cathodic efficiencies of the high efficiency electrolytes were reduced by use of pulsed current although this effect was minimised at high frequencies. The sulphate catalysed electrolyte showed an increase in efficiency over the frequency range where hydrides were co-deposited.Copper. The polarisation behaviour of acid copper solutions containing polyethers, sulphopropyl sulphides and chloride ions was studied using both direct and pulse reverse current. The effect of these additives on the rest potentials of copper deposits immersed in the electrolyte was also studied. Hole Throwing Power on printed circuit boards was determined using a specially designed test cell. The effect of pulsed reverse current on the hole throwing power of commercially produced printed circuit boards was also studied. Polyethers were found to have an inhibiting effect on the deposition of copper whereas the sulphopropyl sulphides produced a stimulating (i.e. depolarising) effect. Studies of rest potentials made when both additives were present indicated that the sulphopropyl sulphide was preferentially adsorbed. The use of pulsed reverse current in solutions containing both polyether and sulphopropyl sulphide was found to cause desorption of the sulphopropyl sulphide at the cathode surface. Thus, at higher current densities, the inhibiting effect of the polyether produced an increase in the cathodic polarisation potential. At lower current densities, the depolarisation effect of the sulphopropyl sulphide could still occur. On printed circuit boards, this effect was found to produce an increase in the `hole throwing power' due to depolarisation of the holes relative to the surface of the boards. Typically, using direct current, hole/surface thickness ratios of 40% were obtained when plating 0.6 mm holes in a 3.2 mm thick board at a current density of 3 A/dm2 whereas using pulsed reverse current, ratios of 80% could be obtained at an equivalent rate of deposition. This was observed both in laboratory tests and on commercially plated boards.

The performance of cement stabilised minestone

This study is concerned with the durability of cement stabilised minestone (CSM). Minestone is dominated by the clay-bearing mudrocks and shales of the Coal Measures. Consequently, engineering problems are often encountered due to the likelihood of these rocks undergoing volume change and degradation when exposed to fluctuations in moisture content. In addition, iron sulphides (chiefly pyrite) are frequently present in minestone as diagenetic minerals which on excavation have the potential to oxidise forming sulphate minerals. The oxidation of sulphides may in itself contribute to volume increase in pyritic rocks and sulphate minerals may combine with the products of cement hydration to produce further expansion. The physical and chemical properties of a wide range of minestones are determined and attempts are made to correlate these with the engineering performance of cement stabilised specimens subjected to short-term immersion in water. Criteria, based on these raw material indices are proposed with a view to eliminating minestones which are unsuitable. A long-term durability study is also described. In this, the geochemical stability of pyrite in CSM was examined together with the role played by the sulphur bearing mineralogy in determining the engineering performance of CSM's exposed to conditions of increased moisture availability. The nature of a number of disrupted CSM pavements which have been examined are also discussed.

Palaeozoic volcanogenic mineral deposits at Parys Mountain, Avoca, and S.E. Canada: a comparative study. Available in 2 volumes.

The sulphide mineralisation at Avoca and Parys Mountain is intimately related to volcanism and is of volcanogenic sedimentary type. The associated volcanics are predominantly pyroclastics of rhyodacitic composition and of Upper Ordovician age. They were erupted from discrete small volcanic centres, products of single local volcanic events, whose spatial distribution was related to fractures in the sialic basement of the paratectonic Caledonides of the British Isles. These fractures resulted in linear controls on volcanic, plutonic and tectonic features; they are the result of predominantly strikeslip stresses generated in this part of the European plate during closure of the Iapetus ocean. The mineralisation, predominantly pyritic, consists of a siliceous footwall zone containing bedded and cross-cutting sulphides and an overlying non-siliceous zone of bedded sulphides which may show vertical zoning of metal ratios. The sulphides are associated with chert and iron formation and have been affected by slumping. Mineralisation developed near the vents during intense fumarolic activity accompanying strong volcanism; at Parys Mountain, fumarolic activity commenced prior to, and continued after, the rnain volcanic event. Comparison with similar deposits in Newfoundland and at Bathurst, in the Canadian Appalachians, shows that mineralisation can be associated with any discrete pulse of acid magmatism in shallow subaqueous conditions. Local features of the sulphides and associated sediments are similar, although in more distal deposits (with respect to a volcanic centre) footwall alteration and mineralisation are less well developed. The nature of the basement and the presence or absence of earlier volcanics are not critical, although establishment of a local tensional regime at the time of ore formation may be important. The volcanics hosting mineralisation are rhyodacitic pyroclastics, generally related to a small centre and representing a single episode of volcanism.

Diagenetic processes in ore formation with special reference to the Zambian copperbelt and permian marl slate.

This thesis is concerned with the role of diagenesis in forming ore deposits. Two sedimentary 'ore-types' have been examined; the Proterozoic copper-cobalt orebodies of the Konkola Basin on the Zambian Copperbelt, and the Permian Marl Slate of North East England. Facies analysis of the Konkola Basin shows the Ore-Shale to have formed in a subtidal to intertidal environment. A sequence of diagenetic events is outlined from which it is concluded that the sulphide ores are an integral part of the diagenetic process. Sulphur isotope data establish that the sulphides formed as a consequence of the bacterial reduction of sulphate, while the isotopic and geochemical composition of carbonates is shown to reflect changes in the compositions of diagenetic pore fluids. Geochemical studies indicate that the copper and cobalt bearing mineralising fluids probably had different sources. Veins which crosscut the orebodies contain hydrocarbon inclusions, and are shown to be of late diagenetic lateral secretion origin. RbiSr dating indicates that the Ore-Shale was subject to metamorphism at 529 A- 20 myrs. The sedimentology and petrology of the Marl Slate are described. Textural and geochemical studies suggest that much of the pyrite (framboidal) in the Marl Slate formed in an anoxic water column, while euhedral pyrite and base metal sulphides formed within the sediment during early diagenesis. Sulphur isotope data confirm that conditions were almost "ideal" for sulphide formation during Marl Slate deposition, the limiting factors in ore formation being the restricted supply of chalcophile elements. Carbon and oxygen isotope data, along with petrographic observations, indicate that much of the calcite and dolomite occurring in the Marl Slate is primary, and probably formed in isotopic equilibrium. A depositional model is proposed which explains all of the data presented and links the lithological variations with fluctuations in the anoxicioxic boundary layer of the water column.

Gold mineralisation in the Caledonides of the British Isles with special reference to the Dolgellau Gold-belt, North Wales and the Southern Uplands, Scotland. Available in 2 volumes.

Two aspects of gold mineralisation in the Caledonides of the British Isles have been investigated: gold-telluride mineralisation at Clogau Mine, North Wales; and placer gold mineralisation in the Southern Uplands, Scotland. The primary ore assemblage at Clogau Mine is pyrite, arsenopyrite, cobaltite, pyrrhotine, chalcopyrite, galena, tellurbismuth, tetradymite, altaite, hessite, native gold, wehrlite, hedleyite, native bismuth, bismuthunite and various sulphosalts. The generalised paragenesis is early Fe, Co, Cu, As and S species, and later minerals of Pb, Bi, Ag, Au, Te, Sb. Electron probe micro-analysis (EPMA) of complex telluride-sulphide intergrowths suggests that these intergrowths formed by co-crystallisation/replacement processes and not exsolution. Minor element chemical variation, in the sulphides and tellurides, indicates that antimony and cadmium are preferentially partitioned into telluride minerals. Mineral stability diagrams suggest that during gold deposition log bf aTe2 was between -7.9 and -9.7 and log bf aS2 between -12.4 and -13.8. Co-existing mineral assemblages indicate that the final stages of telluride mineralisation were between c. 250 - 275oC. It is suggested that the high-grade telluride ore shoot was the result of remobilisation of Au, Bi, Ag and Te from low grade mineralisation elsewhere within the vein system, and that gold deposition was brought about by destabilisation of gold chloride complexes by interaction with graphite, sulphides and tellurbismuth. Scanning electron microscopy of planer gold grains from the Southern Uplands, Scotland, indicates that detailed studies on the morphology of placer gold can be used to elucidate the history of gold in the placer environment. In total 18 different morphological characteristics were identified. These were divided on an empirical basis, using the relative degree of mechanical attrition, into proximal and distal characteristics. One morphological characteristic (a porous/spongy surface at high magnification) is considered to be chemical in origin and represent the growth of `new' gold in the placer environment. The geographical distribution of morphological characteristics has been examined and suggests that proximal placer gold is spatially associated with the Loch Doon, Cairsphairn and Fleet granitoids. Quantitative EPMA of the placer gold reveals two compositional populations of placer gold. Examination of the geographical distribution of fineness suggests a loose spatial association between granitoids and low fineness placer gold. Also identified was chemically heterogeneous placer gold. EPMA studies of these heterogeneities allowed estimation of annealing history limits, which suggest that the heterogeneities formed between 150 and 235oC. It is concluded, on the basis of relationships between morphology and composition, that there are two types of placer gold in the Southern Uplands: (i) placer gold which is directly inherited from a hypogene source probably spatially associated with granitoids; and (ii) placer gold that has formed during supergene processes.

Genetic studies of Cu-Pb-Zn mineralisation in Triassic red beds of Western Europe

Continental red bed sequences are host, on a worldwide scale, to a characteristic style of mineralisation which is dominated by copper, lead, zinc, uranium and vanadium. This study examines the features of sediment-hosted ore deposits in the Permo-Triassic basins of Western Europe, with particular reference to the Cu-Pb-Zn-Ba mineralisation in the Cheshire Basin, northwest England, the Pb-Ba-F deposits of the Inner Moray Firth Basin, northeast Scotland, and the Pb-rich deposits of the Eifel and Oberpfalz regions, West Germany. The deposits occur primarily but not exclusively in fluvial and aeolian sandstones on the margins of deep, avolcanic sedimentary basins containing red beds, evaporites and occasionally hydrocarbons. The host sediments range in age from Permian to Rhaetian and often contain (or can be inferred to have originally contained) organic matter. Textural studies have shown that early diagenetic quartz overgrowths precede the main episode of sulphide deposition. Fluid inclusion and sulphur isotope data have significantly constrained the genetic hypotheses for the mineralisation and a model involving the expulsion of diagenetic fluids and basinal brines up the faulted margins of sedimentary basins is favoured. Consideration of the development of these sedimentary basins suggests that ore emplacement occurred during the tectonic stage of basin evolution or during basin inversion in the Tertiary. ð34S values for barite in the Cheshire Basin range from 13.8% to 19.3% and support the theory that the Upper Triassic evaporites were the principal sulphur source for the mineralisation and provided the means by which mineralising fluids became saline. In contrast, δ34S values for barite in the Inner Moray Firth Basin (mean δ34S = + 29%) are not consistent with simple derivation of sulphur from the evaporite horizons in the basin and it is likely that sulphur-rich Jurassic shales supplied the sulphur for the mineralisation at Elgin. Possible sources of sulphur for the mineralisation in West Germany include hydrothermal vein sulphides in the underlying Devonian sediments and evaporites in the overlying Muschelkalk. Textural studies of the deeply buried sandstones in the Cheshire Basin reveal widespread dissolution and replacement of detrital phases and support the theory that red bed diagenetic processes are responsible for the release of metals into pore fluids. The ore solutions are envisaged as being warm (60-150%C), saline (9-22 wt % equiv NaCl) fluids in which metals were transported as chloride complexes. The distribution of δ34S values for sulphides in the Cheshire Basin (-1.8% to + 16%), the Moray Firth Basin (-4.8% to + 27%) and the German Permo-Triassic Basins (-22.2% to -12.2%) preclude a magmatic source for the sulphides and support the contention that sulphide precipitation is thought to result principally from sulphate reduction processes, although a decrease in temperature of the ore fluid or reaction with carbonates may also be important. Methane is invoked as the principal reducing agent in the Cheshire Basin, whilst terrestrial organic debris and bacterial reduction processes are thought to have played a major part in the genesis of the German ore deposits.

Effect of processing on sulphur antioxidants in polyolefins

The effect of processing on the antioxidant activity of sulphur-containing compounds, with particular reference to nickel dialkyldithiophosphates and their corresponding di sulphides, were studied in polyolefins under melt, thermal and photo-oxidative conditions. These compounds were evaluated both at low (normal) and high (concentrates) concentrations. In general, the dithiophosphates were found to be very efficient melt stabilisers at normal concentrtion levels, and compare quite favourably with the best commercially available systems. The nickel dithiophosphates were also found to be very efficient thermal stabilisers for polyolefins, but their activity is highly dependent on the alkyl substituent in the molecule. The corresponding disulphides on the other hand showed very little activity under thermal oxidative conditions, and this was attributed to their inefficiency in scavenging alkyl peroxyl radicals since both compounds possess similar peroxidolytic activity. Furthermore, the nickel dithiophosphates were found to be excellent photo stabilisers for mildly-processed polyolefins while the corresponding disulphides only offer slight protection to the polymer. Oxidative processing of the disulphide, however, results in a dramatic improvement in their photo antioxidant activity. Thionophospho-ric acid, a major oxidation product of dithiophosphates, was also shown to have photo antioxidant activity similar to that of the disulphides. A combination of a U.V. absorber with the nickel complex and/or the disulphide resulted in a synergistic stabiliser system which was further augmented by oxidative processing. Moreover, the dilute analogues of such multicomponent stabiliser concentrates also showed excellent melt, thermal and photo-stabilising activity. The mechanistic studies carried out on the nickel complex and the corresponding disulphide clearly identified the thionophosphoric acid a a major transformation product although various triesters were formed as reaction intermediates. The mechanisms of the antioxidant action of the dithiophosphates, which is believed to involve a cyclical process similar to that shown for simple alkyl sulphides and nitroxyls, are discussed.

Onions:a global benefit to health

Onion (Allium cepa L.) is botanically included in the Liliaceae and species are found across a wide range of latitudes and altitudes in Europe, Asia, N. America and Africa. World onion production has increased by at least 25% over the past 10 years with current production being around 44 million tonnes making it the second most important horticultural crop after tomatoes. Because of their storage characteristics and durability for shipping, onions have always been traded more widely than most vegetables. Onions are versatile and are often used as an ingredient in many dishes and are accepted by almost all traditions and cultures. Onion consumption is increasing significantly, particularly in the USA and this is partly because of heavy promotion that links flavour and health. Onions are rich in two chemical groups that have perceived benefits to human health. These are the flavonoids and the alk(en)yl cysteine sulphoxides (ACSOs). Two flavonoid subgroups are found in onion, the anthocyanins, which impart a red/purple colour to some varieties and flavanols such as quercetin and its derivatives responsible for the yellow and brown skins of many other varieties. The ACSOs are the flavour precursors, which, when cleaved by the enzyme alliinase, generate the characteristic odour and taste of onion. The downstream products are a complex mixture of compounds which include thiosulphinates, thiosulphonates, mono-, di- and tri-sulphides. Compounds from onion have been reported to have a range of health benefits which include anticarcinogenic properties, antiplatelet activity, antithrombotic activity, antiasthmatic and antibiotic effects. Here we review the agronomy of the onion crop, the biochemistry of the health compounds and report on recent clinical data obtained using extracts from this species. Where appropriate we have compared the data with that obtained from garlic (Allium sativum L.) for which more information is widely available. Copyright © 2002 John Wiley & Sons, Ltd.