The solubility of iron sulphides in synthetic and natural waters at ambient temperature

A critical evaluation of literature values for the solubility products, K _sp ^NBS = [Fe²⁺][HS^–] Fe²⁺ HS^– (H _NBS ⁺ )^–1, of various iron sulphide phases results in consensus values for the pKs of 2.95 ± 0.1 for amorphous ferrous sulphide, 3.6 ± 0.2 for mackinawite, 4.4 ± 0.1 for greigite, 5.1 ± 0.1 for pyrrhotite, 5.25 ± 0.2 for troilite and 16.4 ± 1.2 for pyrite.Where the analogous ion activity products have been measured in anoxic freshwaters in which there is evidence for the presence of solid phase FeS, the values lie within the range of 2.6–3.22, indicating that amorphous iron sulphide is the controlling phase. The single value for a groundwater of 2.65 (2.98 considering carbonate complexation) agrees. In seawater four values range between 3.85 to 4.2, indicating that mackinawite or greigite may be the controlling phase. The single low value of 2.94 is in a situation where particularly high fluxes of Fe (II) and S (–II) may result in the preferential precipitation of amorphous iron sulphide. Formation of framboidal pyrite in these sulphidic environments may occur in micro-niches and does not appear to influence bulk concentrations. Calculations show that the formation of Fe₂S₂ species probably accounts for very little of the iron or sulphide in most natural waters. Previously reported stability constants for the formation of Fe (HS)₂ and (Fe (HS)₃)^– are shown to be suspect, and these species are also thought to be negligible in natural waters. In completely anoxic pore waters polysulphides also have a negligible effect on speciation, but in tidal sediments they may reach appreciable concentrations and lead to the direct formation of pyrite. Concentrations of iron and sulphide in pore waters can be controlled by the more soluble iron sulphide phase. The change in the IAP with depth within the sediment may reflect ageing of the solid phase or a greater flux of Fe (II) and S (–II) nearer the sediment surface. This possible kinetic influence on the value of IAPs has implications for their use in geochemical studies involving phase formation.     

The Mordor Alkaline Igneous Complex,Central Australia: PGE-enriched disseminated sulfide layers in cumulates from a lamprophyric magma

The Mordor Alkaline Igneous Complex (MAIC) is a composite intrusion comprising a body of syenite and a funnel-shaped layered mafic–ultramafic intrusion of lamprophyric parentage, the Mordor Mafic–Ultramafic Intrusion or MMUI. The MMUI is highly unusual among intrusions of lamprophyric or potassic parentage in containing primary magmatic platinum-group element (PGE)-enriched sulfides. The MMUI sequence consists largely of phlogopite-rich pyroxenitic cumulates, with an inward dipping conformable layer of olivine-bearing cumulates divisible into a number of cyclic units. Stratiform-disseminated sulfide accumulations are of two types: disseminated layers at the base of cyclic units, with relatively high PGE tenors; and patchy PGE-poor disseminations within magnetite-bearing upper parts of cyclic units. Sulfide-enriched layers at cycle bases contain anomalous platinum group element contents with grades up to 1.5 g/t Pt+Pd+Au over 1-m intervals, returning to background values of low parts per billion (ppb) on a meter scale. They correspond to reversals in normal fractionation trends and are interpreted as the result of new magma influxes into a continuously replenished magma chamber. Basal layers have decoupled Cu and PGE peaks reflecting increasing PGE tenors up-section, due to increasing R factors during the replenishment episode, or progressive mixing of between resident PGE-poor magma and more PGE-enriched replenishing magma. The presence of PGE enriched sulfides in cumulates from a lamprophyric magma implies that low-degree partial melts do not necessarily leave sulfides and PGEs in the mantle restite during partial melting. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Brine-pool deposition for the Zn–Pb–Cu massive sulphide deposits of the Bathurst mining camp, New Brunswick, Canada. II. Ocean anoxia during mineralisation

Current models of massive sulphide ore genesis in the Bathurst mining camp, New Brunswick, involve settling of sulphide particles from a stagnating, low-salinity hydrothermal plume spreading laterally in an anoxic ocean layer with minimal sulphate content. There is fragmentary evidence of ocean anoxia in the form of local fine lamination in the shales that host some of the deposits but the total organic carbon, S, Fe, U/Th, Ni/Co, V/Ni and V/Cr relationships indicate deposition under oxic or dysoxic conditions. Vanadium and Mn values range from oxic to anoxic and sulphate-reducing to non-sulphate reducing but Mn may be anomalously low due to derivation by erosion of acidic volcanic rocks. The somewhat equivocal physical and chemical data, combined with the likely disturbing effects of penecontemporaneous volcanism, considerably weaken the case for an anoxic bottom layer in a static ocean. The presence of barite with ambient seawater ³⁴S values in Brunswick no. 12 ore, and the abundance of sulphate in modern euxinic basin waters, make a sulphate-free layer unlikely, even if anoxic. Sulphate-bearing, low-salinity fluids mixing with seawater would lead to growth of barite-bearing chimneys and baritic rubble mounds, which are not observed. A model involving brine-pool deposition better explains the major features of the Bathurst ores.     

广西佛子冲铅锌矿田成岩成矿时代研究

广西佛子冲铅锌矿田位于桂东南博白-岑溪多金属成矿带的NE端,区内发育燕山期花岗岩、花岗闪长岩、二长花岗斑岩和英安质凝灰熔岩等;其中花岗闪长岩和二长花岗斑岩与铅锌成矿关系密切,成矿岩体形成时代分别为156Ma和127Ma。     

Fluid sources for the La Guitarra epithermal deposit (Temascaltepec district, Mexico): Volatile and helium isotope analyses in fluid inclusions

The La Guitarra deposit (Temascaltepec district, South-Central Mexico), belongs to the low/intermediate sulfidation epithermal type, has a polymetallic character although it is currently being mined for Ag and Au. The mineralization shows a polyphasic character and formed through several stages and sub-stages (named I, IIA, IIB, IIC, IID, and III). The previous structural, mineralogical, fluid inclusion and stable isotope studies were used to constrain the selection of samples for volatile and helium isotope analyses portrayed in this study. The N₂/Ar overall range obtained from analytical runs on fluid inclusion volatiles, by means of Quadrupole Mass Spectrometry (QMS), is 0 to 2526, and it ranges 0 to 2526 for stage I, 0 to 1264 for stage IIA, 0 to 1369 for stage IIB, 11 to 2401 for stage IIC, 19 to 324 for stage IID, and 0 to 2526 for stage III. These values, combined with the CO₂/CH₄ ratios, and N₂-He-Ar and N₂-CH₄-Ar relationships, suggest the occurrence of fluids from magmatic, crustal, and shallow meteoric sources in the forming epithermal vein deposit. The helium isotope analyses, obtained by means of Noble Gas Mass Spectrometry, display R/Ra average values between 0.5 and 2, pointing to the occurrence of mantle-derived helium that was relatively diluted or “contaminated” by crustal helium. These volatile analyses, when correlated with the stable isotope data from previous works and He isotope data, show the same distribution of data concerning sources for mineralizing fluids, especially those corresponding to magmatic and crustal sources. Thus, the overall geochemical data from mineralizing fluids are revealed as intrinsically consistent when compared to each other.The three main sources for mineralizing fluids (magmatic, and both deep and shallow meteoric fluids) are accountable at any scale, from stages of mineralization down to specific mineral associations. The volatile and helium isotope data obtained in this paper suggest that the precious metal-bearing mineral associations formed after hydrothermal pulses of predominantly oxidized magmatic fluids, and thus it is likely that precious metals were carried by fluids with such origin. Minerals from base-metal sulfide associations record both crustal and magmatic sources for mineralizing fluids, thus suggesting that base metals could be derived from deep leaching of crustal rocks. At the La Guitarra epithermal deposit there is no evidence for an evolution of mineralizing fluids towards any dominant source. Rather than that, volatile analyses in fluid inclusions suggest that this deposit formed as a pulsing hydrothermal system where each pulse or set of pulses accounts for different compositions of mineralizing fluids.The positive correlation between the relative content of magmatic fluids (high N₂/Ar ratios) and H₂S suggests that the necessary sulfur to carry mostly gold as bisulfide complexes came essentially from magmatic sources. Chlorine necessary to carry silver and base metals was found to be abundant in inclusion fluids and although there is no evidence about its source, it is plausible that it may come from magmatic sources as well.     

Petrology, geochemistry and the mechanisms determining the distribution of platinum-group element and base metal sulphide mineralisation in the Platreef at Overysel, northern Bushveld Complex, South Africa

Platinum-group element (PGE) mineralisation within the Platreef at Overysel is controlled by the presence of base metal sulphides (BMS). The floor rocks at Overysel are Archean basement gneisses, and unlike other localities along the strike of the Platreef where the floor is comprised of Transvaal Supergroup sediments, the intimate PGE–BMS relationship holds strong into the footwall rocks. Decoupling of PGE from BMS is rare and the BMS and platinum-group mineral assemblages in the Platreef and the footwall are almost identical. There is minimal overprinting by hydrothermal fluids; therefore, the mineralisation style present at Overysel may represent the most ‘primary’ style of Platreef mineralisation preserved anywhere along the strike. Chondrite-normalised PGE profiles reveal a progressive fractionation of the PGE with depth into the footwall, with Ir, Ru and Rh dramatically depleted with depth compared to Pt, Pd and Au. This feature is not observed at Sandsloot and Zwartfontein, to the south of Overysel, where the footwall rocks are carbonates. There is evidence from rare earth element abundances and the amount of interstitial quartz towards the base of the Platreef pyroxenites that contamination by a felsic melt derived from partial melting of the gneissic footwall has taken place. Textural evidence in the gneisses suggests that a sulphide liquid percolated down into the footwall through a permeable, inter-granular network that was produced by partial melting around grain boundaries in the gneisses that was induced by the intrusion of the Platreef magma. PGE were originally concentrated within a sulphide liquid in the Platreef magma, and the crystallisation of monosulphide solid solution from the sulphide liquid removed the majority of the IPGE and Rh from it whilst still within the mafic Platreef. Transport of PGE into the gneisses, via downward migration of the residual sulphide liquid, fractionated out the remaining IPGE and Rh in the upper parts of the gneisses leaving a ‘slick’ of disseminated sulphides in the gneiss, with the residual liquid becoming progressively more depleted in these elements relative to Pt, Pd and Au. Highly sulphide-rich zones with massive sulphides formed where ponding of the sulphide liquid occurred due to permeability contrasts in the footwall. This study highlights the fact that there is a fundamental floor rock control on the mechanism of distribution of PGE from the Platreef into the footwall rocks. Where the floor rocks are sediments, fluid activity related to metamorphism, assimilation and later serpentinisation has decoupled PGE from BMS in places, and transport of PGE into the footwall is via hydrothermal fluids. In contrast, where the floor is comprised of anhydrous gneiss, such as at Overysel, there is limited fluid activity and PGE behaviour is controlled by the behaviour of sulphide liquids, producing an intimate PGE–BMS association. Xenoliths and irregular bands of chromitite within the Platreef are described in detail for the first time. These are rich in the IPGE and Rh, and evidence from laurite inclusions indicates they must have crystallised from a PGE-saturated magma. The disturbed and xenolithic nature of the chromitites would suggest they are rip-up clasts, either disturbed by later pulses of Platreef magma in a multi-phase emplacement or transported into the Platreef from a pre-existing source in a deeper staging chamber or conduit.     

Aeromagnetic signatures over western Marie Byrd Land provide insight into magmatic arc basement, mafic magmatism and structure of the Eastern Ross Sea Rift flank

Aeromagnetic signatures over the Edward VII Peninsula (E7) provide new insight into the largely ice-covered and unexplored eastern flank of the Ross Sea Rift (RSR). Positive anomalies, 10–40 km in wavelength and with amplitudes ranging from 50 to 500 nT could reveal buried Late Devonian(?)–Early Carboniferous Ford Granodiorite plutons. This is suggested by similar magnetic signature over exposed, coeval Admiralty Intrusives of the Transantarctic Mountains (TAM). Geochemical data from mid-Cretaceous Byrd Coast Granite, contact metamorphic effects on Swanson Formation and hornblende-bearing granitoid dredge samples strengthen this magnetic interpretation, making alternative explanations less probable. These magnetic anomalies over formerly adjacent TAM and western Marie Byrd Land (wMBL) terranes resemble signatures typically observed over magnetite-rich magmatic arc plutons. Shorter wavelength (5 km) 150 nT anomalies could speculatively mark mid-Cretaceous mafic dikes of the E7, similar to those exposed over the adjacent Ford Ranges. Anomalies with amplitudes of 100–360 nT over the Sulzberger Bay and at the margin of the Sulzberger Ice Shelf likely reveal mafic Late Cenozoic(?) volcanic rocks emplaced along linear rift fabric trends. Buried volcanic rock at the margin of the interpreted half-graben-like “Sulzberger Ice Shelf Block” is modelled in the Kizer Island area. The volcanic rock is marked by a coincident positive Bouguer gravity anomaly. Late Cenozoic volcanic rocks over the TAM, in the RSR, and beneath the West Antarctic Ice Sheet exhibit comparable magnetic anomaly signature reflecting regional West Antarctic Rift fabric. Interpreted mafic magmatism of the E7 is likely related to mid-Cretaceous and Late Cenozoic regional crustal extension and possible mantle plume activity over wMBL. Magnetic lineaments of the E7 are enhanced in maximum horizontal gradient of pseudo-gravity, vertical derivative and 3D Euler Deconvolution maps. Apparent vertical offsets in magnetic basement at the location of the lineaments and spatially associated mafic dikes and volcanic rocks result from 2.5D magnetic modelling. A rift-related fault origin for the magnetic lineaments, segmenting the E7 region into horst and graben blocks, is proposed by comparison with offshore seismic reflection, marine gravity, on-land gravity, radio-echo sounding, apatite fission track data and structural geology. The NNW magnetic lineament, which we interpret to mark the eastern RSR shoulder, forms the western margin of the “Alexandra Mountains horst”. This fundamental aeromagnetic feature lies on strike with the Colbeck Trough, a prominent NNW half-graben linked to Late Cretaceous(?) and Cenozoic(?) faulting in the eastern RSR. East–west and north–north–east to NE magnetic trends are also imaged. Magnetic trends, if interpreted as reflecting the signature of rift-related normal faults, would imply N–S to NE crustal extension followed by later northwest–southeast directed extension. NW–SE extension would be compatible with Cenozoic(?) oblique RSR rifting. Previous structural data from the Ford Ranges have, however, been interpreted to indicate that both Cretaceous and Cenozoic extensions were N–S to NE–SW directed.     

西秦岭中川花岗岩岩浆活动特征及地质效应

西秦岭中川花岗岩为3期5次侵入的复式岩体,其主侵入体为印支—燕山期黑云母同碰撞S型二长花岗岩。该岩浆活动在沉积建造中形成热变质作用带和岩浆侵位构造,并产生成矿地质效应。     

Characterisation of the 1997 Vulcanian explosions of Soufrière Hills Volcano,Montserrat, by video analysis

The activity of Convention at Montserrat Soufrière Hills Volcano, Montserrat, during the period 1995–1999 included numerous violent explosions. Two major cycles of Vulcanian explosions occurred in 1997: a first of 13 explosions between 4 and 12 August and a second of 75 between 22 September and 21 October. The explosions were short-lived events lasting a few tens of seconds during which partial fountain collapse generated pyroclastic surges and pyroclastic flows, and buoyant plumes ascended 3–15 km into the atmosphere. Each explosion discharged on average 3×10⁵ m³ (dense-rock equivalent, DRE) of magma, draining the conduit to depths of 1–2 km. The paper focuses on the first few seconds of three explosions of the 75 that occurred in September/October 1997: 6 October 1997 at 17:50, 7 October 1997 at 16:02 and 9 October 1997 at 12:32. Physical parameters such as exit velocities, magmatic water contents and magma pressures at fragmentation are estimated by following and modelling the ascent of individual momentum-dominated finger jets visible on videos during the initial stages of each explosion. The model treats each finger jet as an incompressible flow sustained by a steady flux of gas and particles during the few seconds of ascent, and produces results that compare favourably with those using a multiphase compressible code run using similar eruptive parameters. Each explosion reveals a progressive increase in eruptive intensity with time, jet exit velocities increasing from 40 m s^–1 at the beginning of the explosion up to 140 m s^–1 after a few seconds. Modelling suggests that the first magma to exit was largely degassed, whereas that discharged after a few seconds contained up to 2 wt% water. Magma overpressures up to ~10 MPa are estimated to have existed in the conduit immediately prior to each explosion. Progressive increases in jet exit velocity with time over the first few seconds of each explosion provide direct evidence for strong pre-eruptive gradients in water content and magma pressure in the upper reaches (probably 100–500 m) of the conduit. Fountain collapse occurred during the first 10–20 s of each explosion because the discharging jets had bulk densities up to 100 times that of the atmosphere and were unable to entrain enough air to become buoyant. Such high eruptive densities were due to the presence of partially degassed magma in the conduit.Editorial responsibility: A. Woods