The Diavik Waste Rock Project: Particle size distribution and sulfur characteristics of low-sulfide waste rock

Three large-scale instrumented waste rock piles were constructed at the Diavik Diamond Mine in the Northwest Territories, Canada. These experimental waste rock piles (test piles) are 15 m high and are part of an integrated field and laboratory research program to characterize and compare low-sulfide waste rock and drainage at various scales. During test pile construction, samples of the <50 mm fraction of waste rock were collected from two types of waste rock that are segregated during mining operations based on S content. The samples were analyzed for S content and particle size distribution. One test pile contained waste rock with an average of 0.035 wt.% S in the <50 mm fraction, within the operational S target of <0.04 wt.% S for the lower S waste rock type. The second test pile contained waste rock with an average of 0.053 wt.% S in the <50 mm fraction, lower than the operational S target of >0.08 wt.% S for the higher S waste rock type. The third test pile has a low permeability till layer and a low sulfide waste rock thermal layer covering a core of waste rock with average 0.082 wt.% S in the <50 mm fraction, which is within the operational S target of >0.08 wt.% S for the higher S waste rock. Particle size distributions for the lower and higher S waste rock are similar, but the higher S waste rock has a higher proportion of fine-grained particles. Sulfur determinations for discrete particle sizes of the <50 mm fraction illustrate higher S concentrations in smaller particles for both the lower S waste rock and the higher S waste rock. Similarly, S concentrations calculated for the >10 m scale, from composite blast hole cuttings, are lower than those calculated for the <50 mm scale. Acid–base accounting using standard methods and site-specific mineralogical information was used to calculate the ratio of neutralization potential to acid generating potential. A comparison of calculation approaches to pH and alkalinity data from humidity cell and test pile effluent suggest that ratios are very sensitive to the calculation method. The preferred calculation method was selected by comparing calculation results to pH and alkalinity data from humidity cell effluent collected over 95 weeks and test pile effluent collected over five field seasons. The preferred acid–base accounting values were obtained by calculating the average neutralization potential divided by the average acid potential of a sample set. This approach indicates that waste rock with >0.05 wt.% S is of uncertain acid-generating potential and effluent data indicate this waste rock generates acidic effluent; whereas lower S waste rock does not produce acidic effluent, consistent with the acid–base accounting predictions.     

Influence of freeze–thaw dynamics on internal geochemical evolution of low sulfide waste rock

Continuous monitoring of a 15 m high heavily instrumented experimental waste rock pile (0.053 wt.% S) since 2006 at the Diavik diamond mine in northern Canada provided a unique opportunity to study the evolution of fresh run-of-mine waste rock as it evolved over annual freeze–thaw cycles. Samples were collected from soil water solution samplers to measure pore water properties, from twelve 4 to 16 m² basal collection lysimeters to measure basal leachate properties in the region underlying the crest of the pile (the core), and from basal drains to measure aggregate total pile leachate properties. By 2012, monitoring of pore water geochemistry within the core structure of the test pile revealed an apparent steady state with respect to weathering geochemistry, represented by (i) a flush of pre-existing blasting residuals and applied tracers, (ii) declining pH, (iii) a stepwise progression and subsequent equilibrium with acid-neutralizing phases (depletion of available carbonates; equilibrium with respect to aluminum hydroxide phases and subsequent iron (III) hydroxide phases), and (iv) concordant release of SO₄, major cations (Ca, Mg, K, Na, Si), and trace metals (Al, Fe, Ni, Co, Cu, Zn). Distinct, high concentration ‘spring flushes’, characteristic of drainage in northern environments and primarily explained by a combination of fluid residence time and the build-up of oxidation products over the winter, were released from core drainage each season. Following the initial flush, the concentration of all dissolved constituents steadily declined, with distinct minimums prior to freeze-up. The opposite trend was observed in the cumulative pile drainage, in which early season leachate dominated by snowmelt and batter flow had low concentrations and late season leachate dominated by contributions from the core of the pile (indicated by season end merging of core and cumulative drainage geochemistry) had higher concentrations. Northern waste rock pile drainage geochemistry is strongly influenced by freeze–thaw cycling and varying core and batter subsystem contributions to total drainage. A comprehensive understanding of thermal cycling in waste rock piles is an important component of temporal predictions of drainage water composition based on up-scaling or reactive transport modeling.     

The Diavik waste rock project: Initial geochemical response from a low sulfide waste rock pile

Three large-scale experimental waste rock piles (test piles) were constructed and instrumented at the Diavik Diamond Mine in the Northwest Territories, Canada, as part of an integrated field and laboratory study to measure and compare physical and geochemical characteristics of experimental, low sulfide waste rock piles at various scales. This paper describes the geochemical response during the first season from a test pile containing 0.053 wt.% S. Bulk drainage chemistry was measured at two sampling points for pH, Eh, alkalinity, dissolved cations and anions, and nutrients. The geochemical equilibrium model MINTEQA2 was used to interpret potential mineral solubility controls on water chemistry. The geochemical response characterizes the initial flushing response of blasting residues and oxidation products derived from sulfides in waste rock exposed to the atmosphere for less than 1 year. Sulfate concentrations reached 2000 mg L⁻¹ when ambient temperatures were >10 °C, and decreased as ambient temperatures declined to <0 °C. The pH decreased to <5, concomitant with an alkalinity minimum of <1 mg L⁻¹ (as total CaCO₃), suggesting all available alkalinity is consumed by acid-neutralizing reactions. Concentrations of Al and Fe were <0.36 and <0.11 mg L⁻¹, respectively. Trends of pH and alkalinity and the calculated saturation indices for Al and Fe (oxy)hydroxides suggest that dissolution of Al and Fe (oxy)hydroxide phases buffers the pH. The effluent water showed increased concentrations of dissolved Mn (<13 mg L⁻¹), Ni (<7.0 mg L⁻¹), Co (<1.5 mg L⁻¹), Zn (<0.5 mg L⁻¹), Cd (<0.008 mg L⁻¹) and Cu (<0.05 mg L⁻¹) as ambient temperatures increased. Manganese is released by aluminosilicate weathering, Ni and Co by pyrrhotite [Fe_1−xS] oxidation, Zn and Cd by sphalerite oxidation, and Cu by chalcopyrite [CuFeS₂] oxidation. No dissolved metals appear to have discrete secondary mineral controls. Changes in SO₄, pH and metal concentrations indicate sulfide oxidation is occurring and effluent concentrations are influenced by ambient temperatures and, possibly, increasing flow path lengths that transport reaction products from previously unflushed waste rock.     

The Diavik waste rock project: Water flow through mine waste rock in a permafrost terrain

A field experiment is being carried out at the Diavik diamond mine in northern Canada to investigate the influence of unsaturated flow behavior on the quality of drainage from mine waste rock piles in a region of continuous permafrost. This paper is part of a series describing processes affecting the weathering of waste rock and transport of reaction products at this site; here the focus is on unsaturated water flow and its role in mass loading. Two 15 m-high instrumented test piles have been built on 60 m by 50 m collection systems, each consisting of lysimeters and a large impermeable high-density polyethylene (HDPE) liner. Collection lysimeters are installed nearby to investigate infiltration in the upper 2 m of the waste rock. Porosity, water retention curves, and hydraulic conductivity functions are estimated from field measurements and for samples ranging in size from 200 cm³ to 16 m³. Net infiltration in 2007 is estimated to have been 37% of the rainfall for mean annual rainfall conditions. Early-season infiltration freezes and is remobilized as the waste rock thaws. Wetting fronts migrate at rates of 0.2–0.4 m d⁻¹ in response to common rainfall events and up to 5 m d⁻¹ in response to intense rainfall. Pore water and non-reactive solutes travel at rates of <10⁻² to 3 × 10⁻² m d⁻¹ in response to common rainfall events and up to 0.7 m d⁻¹ in response to intense rainfall. Time-varying SO₄ mass loading from the base of the test piles is dictated primarily by the flow behavior, rather than by changes in solute concentrations.     

The Diavik Waste Rock Project: Measurement of the thermal regime of a waste-rock test pile in a permafrost environment

The interior thermal regime of a field-scale experimental waste rock pile in the Northwest Territories, Canada, was studied. Test pile construction was completed in the summer 2006, and temperature data was collected continuously since that time to February 2009. The temperature data indicates the test pile cooled over the study period, with an average heat energy release of −2.5 × 10⁴ and −2.6 × 10⁴ MJ in 2007 and 2008, respectively. The mean annual air temperature (MAAT) at the site was −8.9 °C during the period between 2006 and 2009, with a permafrost table at a depth of 4 m in bedrock away from the pile. Because of this cold environment, the upward movement rate of the 0 °C isotherm into the test pile at its base was approximately 1.5 m a⁻¹ during 2007 and 2008. Thermistor strings installed immediately below the base of the test pile showed the test-pile basal temperatures remained near and below 0 °C during the study period. Furthermore, due to low rates of sulfide mineral oxidation, elevated temperatures in the interior of the test pile were not observed. The average air velocity in the pore space in July 2007 and 2008 was about one third of that during January of each year based on temperature distributions. Therefore, due to higher air velocity during the winter, it is expected that heat transfer is greater during winter.     

Numerical modeling of contaminated neutral drainage from a waste-rock field test cell

Contaminated drainage related to the leaching of soluble metals under near-neutral conditions, known as contaminated neutral drainage (CND), may arise when metal species are soluble at neutral pH. Such a phenomenon has been sporadically observed in effluent from the Tio mine waste-rock pile in Quebec, Canada, particularly from older sections of the pile, where Ni concentrations are increasing with time. It has been postulated that Ni is retained within the fresh waste rock as sorbed species, but as the rock ages, sorption sites become saturated and more Ni is released to the effluent. A field test program was initiated to evaluate the geochemical behavior of the waste rock. This paper presents a numerical analysis of CND generation from waste-rock field test cells including water flow and multi-component transport with geochemical reactions (e.g. sulfide oxidation, pH neutralization, and Ni sorption), using the code MIN3P. The model was able to represent the delay before Ni is seen in the effluent, as caused by sorption of Ni onto Fe-oxide particles. Once the sorption sites are saturated, the model allows Ni release into the effluent by millerite dissolution, expressed by the shrinking core model. A sensitivity analysis indicated that sorption parameters significantly affected the simulated results, so their selection should be based on sound independent field or experimental data.     

Response of 1 × 2 pile group under eccentric lateral loading

A large scale model test of a 1 × 2 pile group was conducted in silts to investigate its behavior under eccentric lateral loading. The model pile group consisted of two well instrumented steel piles and was installed in a large soil tank with a close spacing of three-pile diameters on centers. The test results revealed that the eccentricity of lateral loads had limited effect on the overall performances of the 1 × 2 pile group, but significantly contributed to the unevenness of internal forces of the individual piles. The coupling effect between the lateral deflection and torque gave rise to the substantial increase in the torsional resistance of individual piles within the group, comparing to that of a torsionally loaded single pile. The contribution provided by the torsional resistances of individual piles in resisting the external torque continually decreased when the applied lateral load increased. In addition, a three-dimensional finite-element analysis for the pile group was performed and the simulated response was found to be in good agreement with the measured test results. Based on the same model, more cases with different loading conditions were further analyzed. It could be concluded from the analyses that the layout of individual piles within the group obviously affected the behavior of the 1 × 2 pile group under eccentric lateral loads.     

The Diavik Waste Rock Project: Geochemical and microbiological characterization of low sulfide content large-scale waste rock test piles

Two experimental waste-rock piles (test piles), each 15 m in height × 60 m × 50 m, were constructed at the Diavik diamond mine in Northern Canada to study the behavior of low-sulfide content waste rock, with a similarly low acid-neutralization potential, in a continuous permafrost region. One test pile with an average of 0.035 wt.% S (<50 mm fraction; referred to as Type I) and a second test pile with an average of 0.053 wt.% S (<50 mm fraction; referred to as Type III) were constructed in 2006. The average carbon content in the <50 mm fraction of waste rock in the Type I test pile was 0.031 wt.% as C and in the Type III test pile was 0.030 wt.% as C. The NP:AP ratio, based on the arithmetic mean of particle-size weighted NP and AP values, for the Type I test pile was 12.2, suggesting this test pile was non-acid generating and for the Type III test pile was 2.2, suggesting an uncertain acid-generating potential. The Type I test pile maintained near-neutral pH for the 4-year duration of the study. Sulfate and dissolved metal concentrations were low, with the exception of Ni, Zn, Cd, and Co in the fourth year following construction. The pore water in the Type III test pile contained higher concentrations of SO₄²⁻ and dissolved metals, with a decrease in pH to <4.7 and an annual depletion of alkalinity. Maximum concentrations of dissolved metals (20 mg L⁻¹ Ni, 2.3 mg L⁻¹ Cu, 3.7 mg L⁻¹ Zn, 35 μg L⁻¹ Cd, and 3.8 mg L⁻¹ Co) corresponded to decreases in flow rate, which were observed at the end of each field season when the contribution of the total outflow from the central portion of the test pile was greatest. Bacteria were present each year in spite of annual freeze/thaw cycles. The microbial community within the Type I test pile included a population of neutrophilic S-oxidizing bacteria. Each year, changes in the water quality of the Type III test-pile effluent were accompanied by changes in the microbial populations. Populations of acidophilic S-oxidizing bacteria and Fe-oxidizing bacteria became more abundant as the pH decreased and internal test pile temperatures increased. Irrespective of the cold-climate conditions and low S content of the waste rock, the geochemical and microbiological results of this study are consistent with other acid mine drainage studies; indicating that a series of mineral dissolution–precipitation reactions controls pH and metal mobility, and transport is controlled by matrix-dominated flow and internal temperatures.     

Cu–(Ni–Co–Au)-bearing massive sulfide deposits associated with mafic–ultramafic rocks of the Main Urals Fault,South Urals: Geological structures,ore textural and mineralogical features,comparison with modern analogs

Cu-rich massive sulfide deposits associated with mafic–ultramafic rocks in the southern portion of the Main Urals Fault (MUF) are characterized by variable enrichments in Ni (up to 0.45 wt.%), Co (up to 10 wt.%) and Au (up to 16 ppm in individual hand-specimens). The Cu (Ni–Co)-rich composition of MUF deposits, as opposed to the Cu (Zn)-rich composition of more eastward massive sulfide deposits of broadly similar age along the western flank of the Magnitogorsk arc, reflects the abundance of seafloor-exposed, Ni–Co-rich ultramafic rocks in the most external portion of the Early-Devonian Magnitogorsk forearc. Morphological, textural, and compositional differences between individual deposits are interpreted to be the result of the sulfide deposition style and, in part, of the original subseafloor lithology. One deposit produced by dominantly on-seafloor hydrothermal processes is characterized by pyrite–marcasite ≫ pyrrhotite, not so low Zn grades (occasionally up to 2 wt.%), abundant clastic facies and periodical superficial oxidation. Deposits produced by dominantly subseafloor hydrothermal processes are characterized by pyrrhotite > pyrite, very low Zn (generally < to ≪ 0.1 wt.%), volumetrically minor clastic facies, and multi-layer deposit morphology. Very low Ni/Co ratios in the on-seafloor deposit may indicate a dominant metal contribution from a mafic rather than ultramafic source. The sulfide mineralization was associated with extensive hydrothermal alteration of the host ultramafic and mafic rocks, leading to formation of abundant talc, talc–carbonate and chlorite rocks. Occurrence of large volumes of such altered lithotypes in ophiolitic belts may be considered as a potential searching criteria for MUF-type (Cu, Co, Ni)-deposits. In spite of the contrasting geodynamic environment, geological, geochemical, textural and mineralogical peculiarities of the MUF deposits in many respects are similar to those of ultramafic-hosted massive sulfide deposits along the Mid-Atlantic Ridge. In geological time, supra subduction-zone settings appear to have been more effective than mid-ocean ridge settings for preservation of ultramafic-hosted massive sulfide deposits.     

Estimation of potential pollution of waste mining dumps at Peña del Hierro (Pyrite Belt,SW Spain) as a base for future mitigation actions

Peña del Hierro is an abandoned mine site located in the catchment area of the Tinto river (Pyrite Belt, SW Spain). As leaching from the spoils affect the quality of the stream water, the waste dumps have been characterized for mineralogy, geochemistry and granulometry to obtain an estimate of the potential pollution. Waste rock dumps in Peña del Hierro are very heterogeneous and are mainly composed of acid volcanic tuffs > gossan > shales > roasted pyrite ashes > floated pyrite. The volcanic tuffs, the gossan and the shales coexist in the same piles. The roasted pyrite ashes and the floated pyrite form more homogeneous dumps. The dissolution of pyrite concentrated in pyrite ashes and floated pyrite units can generate acid mine drainage. Nevertheless, acid volcanic tuffs, which are rich in pyrite and have no neutralizing minerals, are the main source of these acidic effluents. Only muscovite might partially neutralize the acidity, but the dissolution of this mineral is too slow to compensate for acidity. The occurrence of jarosite in the <2 mm fraction indicates that extreme acid mine drainage occurs. The gossan and roasted pyrite ashes have high contents of trace elements. According to their concentration, As (46–1710 ppm), Pb (113–3455 ppm) and Hg (0–53) are some of the most important toxic trace elements in these wastes. In dumps mainly composed of volcanic tuffs most of the trace elements derive from the gossan mixed in the piles. Gossan is stable in an oxidizing environment, but acidic effluents (pH < 2) can dissolve Fe oxyhydroxides from them and release high amounts of trace elements to the stream water. This research contributes to estimating the production of acid mine drainage and the actual contamination risk of potentially toxic elements in soils and waters of this area, and could be the base for possible future mitigation actions in other areas affected by mining wastes.     

Kinetics of selenium release in mine waste from the Meade Peak Phosphatic Shale,Phosphoria Formation,Wooley Valley,Idaho, USA

Phosphorite from the Meade Peak Phosphatic Shale member of the Permian Phosphoria Formation has been mined in southeastern Idaho since 1906. Dumps of waste rock from mining operations contain high concentrations of Se which readily leach into nearby streams and wetlands. While the most common mineralogical residence of Se in the phosphatic shale is elemental Se, Se(0), Se is also an integral component of sulfide phases (pyrite, sphalerite and vaesite–pyrite_ss) in the waste rock. It may also be present as adsorbed selenate and/or selenite, and FeSe₂ and organo-selenides.Se release from the waste rock has been observed in field and laboratory experiments. Release rates calculated from waste rock dump and column leachate solutions describe the net, overall Se release from all of the possible sources of Se listed above. In field studies, Se concentration in seepage water (pH 7.4–7.8) from the Wooley Valley Unit 4 dump ranges from 3600 µg/L in May to 10 µg/L by Sept. Surface water flow, Q, from the seep also declines over the summer, from 2 L/s in May to 0.03 L/s in Sept. Se flux ([Se] ? Q) reaches a steady-state of < 150 mg/day in 1–4 months, depending upon the volume of Q. Se release (mg/L) follows a first order reaction with a rate constant, k, = 1.35 – 6.35e?3 h^? 1 (11.8–55.6 yr^? 1).Laboratory experiments were performed with the waste shale in packed bed reactors; residence time varied from 0.09 to 400 h and outlet pH ～ 7.5. Here, Se concentration increased with increasing residence time and release was modeled with a first order reaction with k = 2.19e?3 h^? 1 (19.2 yr^? 1).Rate constants reported here fall within an order of magnitude of reported rate constants for oxidation of Se(0) formed by bacterial precipitation. This similarity among rate constants from both field and laboratory studies combined with the direct observation of Se(0) in waste shales of the Phosphoria Formation suggests that oxidation of Se(0) may control steady-state Se concentration in water draining the Wooley Valley waste dump.     

Pile and pile group response to tunnelling using a large diameter slurry shield – Case study in Shanghai

The study investigates the disturbance to piles and pile groups caused by multiple nearby drives of a large diameter slurry shield-driven tunnelling machine in Shanghai. The minimum distance between the slurry shield tunnel (with diameter D = 15.43 m) and the adjacent pile groups of Metro Line 3 and Yixian Elevated Road is 1 m. The nonlinear finite element (FE) software program ABAQUS was used to analyse the movement of the pile groups caused by the process of shield tunnelling. A field investigation was conducted before the multiple crossings to study the impact (movement and excess pore water pressure) on the surrounding soil and piles caused by the tunnelling process. The field investigation is divided into two sections: (i) free-field tunnelling, and (ii) tunnelling close to trial piles pre-installed in the section. For the full-scale test, tunnelling variable, including slurry pressure and grouting pressure, are adjusted during construction to reduce the disturbance during tunnelling close to pile groups supporting two elevated bridges. The FE simulation of the multiple crossings includes two steps: (a) shield tunnelling along the south bound tunnel approaching the working shaft at the western bank of the Huangpu River, and passing separately between two adjacent pile groups of each bridge; (b) return tunnel passing again between the pile groups of the two bridges along the north bound tunnel. Three different FE models are generated: (1) free-field tunnelling process, (2) tunnelling close to trial piles, and (3) multiple tunnel passes adjacent to pile groups supporting the two elevated bridges. Most of the relevant factors in tunnelling are taken into consideration in the FE models including (a) slurry pressure, (b) grouting pressure, (c) grouting material hardening, and (d) soil-pile interaction.     

A combined fluid inclusion and S–Pb isotope study of the Neoproterozoic Pingshui volcanogenic massive sulfide Cu–Zn deposit,Southeast China

The Pingshui Cu–Zn deposit is located in the Jiangshan–Shaoxing fault zone, which marks the Neoproterozoic suture zone between the Yangtze block and Cathaysia block in South China. It contains 0.45 million tons of proven ore reserves with grades of 1.03 wt.% Cu and 1.83 wt.% Zn. This deposit is composed of stratiform, massive sulfide ore bodies, which contain more than 60 vol.% sulfide minerals. These ore bodies are hosted in altered mafic and felsic rocks (spilites and keratophyres) of the bimodal volcanic suite that makes up the Neoproterozoic Pingshui Formation. Metallic minerals include pyrite, chalcopyrite, sphalerite, tennantite, tetrahedrite and magnetite, with minor galena. Gangue minerals are quartz, sericite, chlorite, calcite, gypsum, barite and jasper. Three distinct mineralogical zones are recognized in these massive sulfide ore bodies: a distal zone composed of sphalerite + pyrite + barite (zone I); an intermediate zone characterized by a pyrite + sphalerite + chalcopyrite assemblages (zone II); and a proximal zone containing chalcopyrite + pyrite + magnetite (zone III). A thin, layer of exhalative jaspilite overlies the sulfide ore bodies except in the proximal zone. The volcanic rocks of the Pingshui Formation are all highly altered spilites and keratophyres, but their trace element geochemistry suggests that they were generated by partial melting of the depleted mantle in an island arc setting. Homogenization temperatures of the primary fluid inclusions in quartz from massive sulfide ores are between 217 and 328 °C, and their salinities range from 3.2 to 5.7 wt.% NaCl equivalent. Raman spectroscopy of the fluid inclusions showed that water is the dominant component, with no other volatile components. Fluid inclusion data suggest that the ore-forming fluids were derived from circulating seawater. The δ³⁴S values of pyrite from the massive sulfide ores range from − 3.6‰ to + 3.4‰, indicating that the sulfur was primarily leached from the arc volcanic rocks of the Pingshui Formation. Both pyrite from the massive sulfide ores and plagioclase from the spilites have similar lead isotope compositions, implying that the lead was also derived from the Pingshui Formation. The low lead contents of the massive sulfide ores and the geochemistry of their host rocks are similar to many VMS Cu–Zn deposits in Canada (e.g., Noranda) and thus can be classified as belonging to the bimodal-mafic subtype. The presence of magnetite and the absence of jaspilite and barite at the − 505 m level in the Pingshui deposit suggest that this level is most likely the central zone of the original lateral massive sulfide ore bodies. If this interpretation is correct, the deep part of the Pingshui Cu–Zn deposit may have significant exploration potential.     

Sulfur and lead isotopic compositions of massive sulfides from deep-sea hydrothermal systems: Implications for ore genesis and fluid circulation

Studies of sulfur and lead isotopic compositions in hydrothermal deposits are an important tool to determine the source and processes of both sulfur and lead, and to understand the origin of hydrothermal ore deposits. Here, the sulfur and lead isotopic compositions of sulfide minerals have been studied for different hydrothermal fields in the East Pacific Rise (EPR), Mid-Atlantic Ridge (MAR), Central Indian Ridge (CIR), Southwest Indian Ridge (SWIR), and North Fiji Basin (NFB). The sulfur isotopic compositions of the studied sulfide samples are variable (δ³⁴S 0.0 to 9.6‰, avg. δ³⁴S 4.7‰; n = 60), being close to the associated igneous rocks (~ 0‰ for, e.g., basalt, serpentinized peridotite), which may reflect the S in the sulfide samples is derived mainly from the associated igneous rocks, and a relatively small proportion (< 36%) of seawater sulfur incorporated into these sulfides during mixing between seawater (δ³⁴S 21‰) and hydrothermal fluid. In contrast for a mixed origin for the source of S, the majority of the lead isotopic compositions (²⁰⁶Pb/²⁰⁴Pb 17.541 ± 0.004 to 19.268 ± 0.001, ²⁰⁷Pb/²⁰⁴Pb 15.451 ± 0.001 to 15.684 ± 0.001, ²⁰⁸Pb/²⁰⁴Pb 37.557 ± 0.008 to 38.988 ± 0.002, n = 21) of the sulfides possess a basaltic Pb isotopic composition, suggesting that the lead in the massive sulfide is mainly leached from local basaltic rocks that host the sub-seafloor hydrothermal systems in sediment-free mid-ocean ridges and mature back-arc basins. Furthermore, sulfide minerals in the super-fast and fast spreading mid-ocean ridges (MORs) exhibit less spread in their the δ³⁴S values compared to sulfides from super-slow, and slow spreading MORs, which is most easily explained as a lesser degree of fluid-rock interaction and hydrothermal fluid-seawater mixing during hydrothermal ore-forming process. Additionally, the S and Pb isotope compositions of sulfides are controlled by the fluid processes for forming seafloor massive sulfide deposits. We demonstrate that the variable sulfur and lead isotopic compositions exhibit a relationship with the sulfur and lead sources, fluid–rock interaction, and fluid–seawater mixing.     

Massive sulfides of Mount Jourdanne along the super-slow spreading Southwest Indian Ridge and their genesis

Modern massive sulfide deposits are known to occur in diverse tectonic settings and it is generally expected that hydrothermal deposits of similar geological settings shall have more or less similar mineralogical and geochemical signatures. However, the Mount Jourdanne sulfide deposits along the super-slow spreading Southwest Indian Ridge deviate from this common concept. These sulfide precipitates are Zn-rich (up to 35 wt.%) and are characterized by high concentrations of Pb (≤ 3.5 wt.%), As (≤ 1.1 wt.%), Ag (≤ 0.12 wt.%), Au (≤ 11 ppm), Sb (≤ 967 ppm), and Cd (≤ 0.2 wt.%) which are unusual for a modern sediment-free mid-oceanic ridge system. Therefore, we have reinvestigated the sulfide samples collected during the INDOYO cruise in 1998, in order to explain their unusual mineralogy and geochemical composition. The sulfide samples are polymetallic and are classified as: a) chimneys, b) mounds, and c) hydrothermal breccias. The chimneys are small tube-like symmetrical bodies (30–40 cm high; ~ 10 cm diameter) and consist mainly of sphalerite and less chalcopyrite, set in a matrix of late amorphous silica. The inner wall shows a late-stage colloform sphalerite containing co-precipitates of galena and/or Pb–As sulfosalts. In contrast, the mound samples are dominated either by Fe-sulfides (pyrite) or by a mixture of pyrite and chalcopyrite with less sphalerite, pyrrhotite, amorphous silica and barite. Both, the chimney and mound samples, are characterized by layering and mineral zonation. The hydrothermal breccias are highly altered and mineralogically heterogeneous. They consist of silicified basaltic material that are impregnated with sulfides and contain cm-sized chimney fragments within a matrix of low-temperature minerals such as sphalerite and pyrite. The latter fragments mainly consist of chalcopyrite with isocubanite lamellae. In addition, these breccias contain late-stage realgar, boulangerite, galena, Pb–As sulfosalts and barite that are mostly confined to vugs or fractures. At least five mineralogical associations are distinguished that indicate different thermal episodes ranging from black smoker mineralization conditions to cessation of the hydrothermal activity. Based on the mineralogical associations and established literature in this regard, it is inferred that the mineralization at Mt. Jourdanne occurred mainly in three temperature domains. Above 300 °C, the chalcopyrite (with isocubanite)–pyrrhotite association formed whereas the sphalerite dominated assemblage with much less chalcopyrite and pyrite formed around and below 300 °C. The late-stage mineralization (below 200 °C) contains colloform sphalerite, galena, Pb–As sulfosalts, realgar and barite. The unusual mineralogy and trace element chemistry for this modern VHMS deposit could be explained assuming hydrothermal leaching of some felsic differentiates underneath the basaltic cover and subsequent zone refining processes.     

Redox front penetration in the fractured Toki Granite,central Japan: An analogue for redox reactions and redox buffering in fractured crystalline host rocks for repositories of long-lived radioactive waste

Redox buffering is one important factor to be considered when assessing the barrier function of potential host rocks for a deep geological repository for long-lived radioactive waste. If such a repository is to be sited in fractured crystalline host rock it must be demonstrated that waste will be emplaced deeper than the maximum depth to which oxidizing waters can penetrate from the earth’s surface via fractures, during the assessment timeframe (typically 1 Ma). An analogue for penetration of such oxidizing water occurs in the Cretaceous Toki Granite of central Japan. Here, a deep redox front is developed along water-conducting fractures at a depth of 210 m below the ground surface. Detailed petrographical studies and geochemical analyses were carried out on drill core specimens of this redox front. The aim was to determine the buffering processes and behavior of major and minor elements, including rare earth elements (REEs), during redox front development. The results are compared with analytical data from an oxidized zone found along shallow fractures (up to 20 m from the surface) in the same granitic rock, in order to understand differences in elemental migration according to the depth below the ground surface of redox-front formation. Geochemical analyses by XRF and ICP-MS of the oxidized zone at 210 m depth reveal clear changes in Fe(III)/Fe(II) ratios and Ca depletion across the front, while Fe concentrations vary little. In contrast, the redox front identified along shallow fractures shows strong enrichments of Fe, Mn and trace elements in the oxidized zone compared with the fresh rock matrix. The difference can be ascribed to the changing Eh and pH of groundwater as it flows downwards in the granite, due to reactions with rock forming minerals, in particular feldspar dissolution. These observations give important insights into the processes that control the rates of redox front penetration in fractured crystalline rock. The findings of the study can be used to help build confidence among stakeholders that radioactive waste would be emplaced in such rocks at greater depth than that to which oxidizing water is likely to penetrate in future.     

Rock alteration in alkaline cement waters over 15 years and its relevance to the geological disposal of nuclear waste

The interaction of groundwater with cement in a geological disposal facility (GDF) for intermediate level radioactive waste will produce a high pH leachate plume. Such a plume may alter the physical and chemical properties of the GDF host rock. However, the geochemical and mineralogical processes which may occur in such systems over timescales relevant for geological disposal remain unclear. This study has extended the timescale for laboratory experiments and shown that, after 15 years two distinct phases of reaction may occur during alteration of a dolomite-rich rock at high pH. In these experiments the dissolution of primary silicate minerals and the formation of secondary calcium silicate hydrate (C–S–H) phases containing varying amounts of aluminium and potassium (C–(A)–(K)–S–H) during the early stages of reaction (up to 15 months) have been superseded as the systems have evolved. After 15 years significant dedolomitisation (MgCa(CO₃)₂ + 2OH⁻ → Mg(OH)₂ + CaCO₃ + CO₃²⁻_(aq)) has led to the formation of magnesium silicates, such as saponite and talc, containing variable amounts of aluminium and potassium (Mg–(Al)–(K)–silicates), and calcite at the expense of the early-formed C–(A)–(K)–S–H phases. This occured in high pH solutions representative of two different periods of cement leachate evolution with little difference in the alteration processes in either a KOH and NaOH or a Ca(OH)₂ dominated solution but a greater extent of alteration in the higher pH KOH/NaOH leachate. The high pH alteration of the rock over 15 years also increased the rock’s sorption capacity for U(VI). The results of this study provide a detailed insight into the longer term reactions occurring during the interaction of cement leachate and dolomite-rich rock in the geosphere. These processes have the potential to impact on radionuclide transport from a geodisposal facility and are therefore important in underpinning any safety case for geological disposal.     

Paleoproterozoic high-Mg low-Ti gabbro-granite series in eastern Sarmatia: Geochemistry and formation conditions

We present nomenclature and geochemical classification of Paleoproterozoic LILE-enriched high-Mg low-Ti mafic-granitoid rocks of the eastern margin of the Sarmatia paleocontinent and substantiate their tectonic position. Two differentiated rock series are recognized: (1) biotite-orthopyroxene melanorite-quartz-meladiorite-melagranodiorite and (2) hornblende-biotite quartz-diorite-tonalite-granodiorite. Both series correspond in chemical composition to calc-alkalic gabbro-diorites, diorites, tonalites, and granodiorites. As follows from their mineralogical and geochemical compositions, these are norite-diorite rocks (intrusive analogs of boninites) (SiO₂ = 52-65 wt.%, MgO = 5-20 wt.%, TiO₂ = 0.2-0.8 wt.%) and high-Mg granitoids (SiO₂ = 60-70 wt.%, Na₂O/K₂O = 0.65-1.33, MgO = 3.23-7.40 wt.%, K₂O = 1.9-4.0 wt.%), respectively. Their high Mg# values (67-87) and Cr contents (> 100 ppm), on the one hand, and their isotope-geochemical characteristics similar to those of the host metaterrigenous rocks, the magma enrichment in LILE, and the presence of Ni sulfide ores with a predominance of light sulfur isotopes, on the other, testify to crustal contamination of mantle magmas. The rock series are nearly of the same age and belong to the same magmatic system, where high-Mg granitoids are differentiates of parental high-Mg (boninite-like) norite-dioritic magma. This is confirmed by a gradual increase in SiO₂ and K₂O contents and a decrease in Mg# and Ni, Co, V, and Cr contents in the sequence from norites to granodiorites and by the facies and phase relationships between the series. Intrusion of rocks took place at shallow depths following the low-temperature metamorphism and folding under postcollisional collapse of the East Sarmatian orogen.     

An Early Cretaceous carbonate replacement origin for the Xinqiao stratabound massive sulfide deposit,Middle-Lower Yangtze Metallogenic Belt,China

Stratabound massive sulfide deposits are widespread along the Middle-Lower Yangtze Metallogenic Belt (MLYMB) and serve as an important copper producer in China. Two contrasting genetic models have been proposed, interpreting the stratabound massive sulfide deposits as a Carboniferous SEDEX protore overprinted by Cretaceous magmatic-hydrothermal system or an Early Cretaceous carbonate replacement deposit. These two contrasting models have been applied to the Xinqiao stratabound Cu-Au sulfide deposit, which is dominated by massive sulfide ores hosted in marine carbonates of the Carboniferous Chuanshan and Huanglong Formations, with minor Cu-Au skarn ores localized in the contact zone between the Cretaceous diorite Jitou stock and the Carboniferous carbonate rocks. New SIMS zircon U-Pb dating suggests that the Jitou stock formed at 138.5 ± 1.1 Ma (2σ, MSWD = 0.6). Pyrite Re-Os dating yields an imprecise date of 142 ± 47 Ma (2σ, MSWD = 7.8). The geochronological data thus constrain the mineralization of the Xinqiao deposit at Early Cretaceous.Fluid inclusions in prograde skarn diopside have homogenization temperatures of 450–600 °C and calculated salinities of 13–58 wt.% NaCl equiv. Quartz from the stratabound ores and pyrite-quartz vein networks beneath the stratabound ores have homogenization temperatures of 290–360 and 200–300 °C, with calculated salinities of 5–12 and 2–10 wt.% NaCl equiv., respectively. Quartz from the skarn ores and veins beneath the stratabound ores have δ¹⁸O values of 12.32 ± 0.55 (2 SD, n = 22) and 15.57 ± 1.92‰ (2 SD, n = 60), respectively, corresponding to calculated δ¹⁸O values of 6.22 ± 1.59 (2σ) and 6.81 ± 2.76‰ (2σ) for the equilibrated ore-forming fluids. The fluid inclusion and oxygen isotope data thus support a magmatic-hydrothermal origin rather than a SEDEX system for the stratabound ores, with the hydrothermal fluids most likely being derived from the Jitou stock or associated concealed intrusion. Results from this study have broad implications for the genesis and exploration of other stratabound massive sulfide deposits along the MLYMB.     

Numerical analysis of pile response to open face tunnelling in stiff clay

Three-dimensional (3D) finite element analyses have been performed to study the behaviour of a single pile and 3 × 3 and 5 × 5 pile groups during open face tunnelling in stiff clay. Several governing factors, such as tunnelling-induced ground and pile settlement, axial pile force changes and shear transfer mechanism at the pile–soil interface, have been studied in detail. Tunnelling resulted in the development of pile head settlement larger than the free-field soil surface settlement. In addition, axial force distributions along the pile change substantially due to changes in the shear transfer between the pile and the soil next to the pile, which triggers tunnelling-induced tensile forces in the piles with tunnel advancement. It was found that the relative displacements and the normal stresses at the pile–soil interface drastically affected shear transfer. The extent of slip length along a pile increased as the tunnelling proceeded. The apparent allowable pile capacity was reduced by up to approximately 42% due to the development of tunnelling-induced pile head settlement. Shear stress on the pile was increased for most of the pile depth with tunnel advancement, which was associated with changes in soil stresses and ground deformation, and hence, the axial pile force was gradually reduced with tunnel advancement, indicating the development of tunnelling-induced tensile pile force. The maximum tunnelling-induced tensile force on the pile was approximately 0.33P_a, where P_a is the allowable pile capacity applied to the pile head prior to tunnel excavation. The range affected by tunnelling in the longitudinal direction may be identified as approximately −2D ∼ +(1.5–2.0D), where D is the tunnel diameter, from the pile centre (behind and ahead of the pile axis), in terms of pile settlement and axial pile force changes based on the analysis conditions assumed in the current study. Larger pile head settlements and smaller changes in axial pile forces were computed for piles that were part of groups. It has been found that the serviceability of piles experiencing adjacent tunnelling is more affected by pile settlement than by axial pile force changes, in particular for piles inside groups. The magnitude of the tunnelling-induced excess pore pressure was small and may not substantially affect pile behaviour.