The Cretaceous sediment-hosted copper deposits of San Marcos (Coahuila,Northeastern Mexico): An approach to ore-forming processes

In the San Marcos ranges of Cuatrociénegas, NE Mexico, several sediment-hosted copper deposits occur within the boundary between the Coahuila Block, a basement high mostly granitic in composition and Late Paleozoic to Triassic in age, and the Mesozoic Sabinas rift basin. This boundary is outlined by the regional-scale synsedimentary San Marcos Fault. At the basin scale, the copper mineralization occurs at the top of a ～1000 m thick red-bed succession (San Marcos Formation, Berrisian), a few meters below a conformable, transitional contact with micritic limestones (Cupido Formation, Hauterivian to Aptian). It consists of successive decimeter-thick roughly stratiform copper-rich horizons placed just above the red-beds, in a transitional unit of carbonaceous grey-beds grading to micritic limestones. The host rocks are fine- to medium-grained arkoses, with poorly sorted and subangular to subrounded grains. The detrital grains are cemented by quartz and minor calcite; besides, late iron oxide grain-coating cement occurs at the footwall unmineralized red-beds. The source area of the sediments, indicated by their modal composition, is an uplifted basement. The contents of SiO₂ (40.70–87.50 wt.%), Al₂O₃ (5.91–22.00 wt.%), K₂O (3.68–12.50 wt.%), Na₂O (0.03–2.03 wt.%) and CaO (0.09–3.78 wt.%) are within the ranges expected for arkoses. Major oxide ratios indicate that the sedimentary-tectonic setting was a passive margin.The outcropping copper mineralization essentially consists in a supergene assemblage of chrysocolla, malachite and azurite. All that remains of the primary mineralization are micron-sized chalcocite grains shielded by quartz cement. In addition, pyrite subhedral grains occur scattered throughout the copper-mineralized horizons. In these weathered orebodies copper contents range between 4.24 and 7.72 wt.%, silver between 5 and 92 ppm, and cobalt from 8 to 91 ppm. Microthermometric measurements of fluid inclusions in quartz and calcite crystals from footwall barren veinlets gave temperatures of homogenization between 98 °C and 165 °C, and ice-melting temperatures between ?42.5 °C and ?26.1 °C.The primary copper mineralization formed during the early diagenesis, contemporary with the active life of the Sabinas Basin. The mineralizing fluids were dense, near neutral, moderately oxidized brines that originally formed from seawater that, driven by gravity, infiltrated to the deepest parts of the basin and dissolved evaporites. As a result, they became hydrothermal fluids of moderate temperature capable of leaching high amounts of copper. The source of this metal could be mafic detrital grains and iron oxides of the underlying Jurassic and Lower Cretaceous red-beds. Copper precipitation took place when the brines passed through the redox boundary marked by the transition from red- to grey-beds. The upward movement of the brines was promoted by a high heat flow that allowed their convective circulation and their ascent along the synsedimentary San Marcos Fault.     

In-situ LA-ICPMS trace elements and U–Pb analysis of titanite from the Mesozoic Ruanjiawan W–Cu–Mo skarn deposit,Daye district,China

In this paper, we present U–Pb ages and trace element compositions of titanite from the Ruanjiawan W–Cu–Mo skarn deposit in the Daye district, eastern China to constrain the magmatic and hydrothermal history in this deposit and provide a better understanding of the U–Pb geochronology and trace element geochemistry of titanite that have been subjected to post-crystallization hydrothermal alteration. Titanite from the mineralized skarn, the ore-related quartz diorite stock, and a diabase dike intruding this stock were analyzed using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Titanite grains from the quartz diorite and diabase dike typically coexist with hydrothermal minerals such as epidote, sericite, chlorite, pyrite, and calcite, and display irregular or patchy zoning. These grains have low LREE/HREE and high Th/U and Lu/Hf ratios, coupled with negative Eu and positive Ce anomalies. The textural and compositional data indicate that titanite from the quartz diorite has been overprinted by hydrothermal fluids after being crystallized from magmas. Titanite grains from the mineralized skarn are texturally equilibrated with retrograde skarn minerals including actinolite, quartz, calcite, and epidote, demonstrating that these grains were formed directly from hydrothermal fluids responsible for the mineralization. Compared to the varieties from the quartz diorite stock and diabase dike, titanite grains from the mineralized skarn have much lower REE contents and LREE/HREE, Th/U, and Lu/Hf ratios. They have a weighted mean ²⁰⁶Pb/²³⁸U age of 142 ± 2 Ma (MSWD = 0.7, 2σ), in agreement with a zircon U–Pb age of 144 ± 1 Ma (MSWD = 0.3, 2σ) of the quartz diorite and thus interpreted as formation age of the Ruanjiawan W–Cu–Mo deposit. Titanite grains from the ore-related quartz diorite have a concordant U–Pb age of 132 ± 2 Ma (MSWD = 0.5, 2σ), which is 10–12 Ma younger than the zircon U–Pb age of the same sample and thus interpreted as the time of a hydrothermal overprint after their crystallization. This hydrothermal overprint was most likely related to the emplacement of the diabase dike that has a zircon U–Pb age of 133 ± 1 Ma and a titanite U–Pb age of 131 ± 2 Ma. The geochronological results thus reveal two hydrothermal events in the Ruanjiawan deposit: an early one forming the Wu–Cu–Mo ores related to the emplacement of the quartz diorite stock and a later one causing alteration of the quartz diorite and its titanite due to emplacement of diabase dike. It is suggested that titanite is much more susceptible to hydrothermal alteration than zircon. Results from this study also highlight the utilization of trace element compositions in discriminating titanite of magmatic and hydrothermal origins, facilitating a more reasonable interpretation of the titanite U–Pb ages.     

U–Pb detrital zircon geochronology and its implications: The early Late Triassic Yanchang Formation,south Ordos Basin,China

U–Pb detrital zircon geochronology has been used to identify provenance and document sediment delivery systems during the deposition of the early Late Triassic Yanchang Formation in the south Ordos Basin. Two outcrop samples of the Yanchang Formation were collected from the southern and southwestern basin margin respectively. U–Pb detrital zircon geochronology of 158 single grains (out of 258 analyzed grains) shows that there are six distinct age populations, 250–300 Ma, 320–380 Ma, 380–420 Ma, 420–500 Ma, 1.7–2.1 Ga, and 2.3–2.6 Ga. The majority of grains with the two oldest age populations are interpreted as recycled from previous sediments. Multiple sources match the Paleozoic age populations of 380–420 and 420–500 Ma, including the Qilian–Qaidam terranes and the North Qilian orogenic belt to the west, and the Qinling orogenic belt to the south. However, the fact that both samples do not have the Neoproterozoic age populations, which are ubiquitous in these above source areas, suggests that the Late Triassic Yanchang Formation in the south Ordos Basin was not derived from the Qilian–Qaidam terranes, the North Qilian orogenic belt, and the Qinling orogenic belt. Very similar age distribution between the Proterozoic to Paleozoic sedimentary rocks and the early Late Triassic Yanchang Formation in the south Ordos Basin suggests that it was most likely recycled from previous sedimentary rocks from the North China block instead of sediments directly from two basin marginal deformation belts.     

Trace metal speciation in sea and pore water of the Gotland Deep,Baltic Sea, 1994

Studies on the speciation (particulate, colloidal, anionic and cationic forms) of trace metals (Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Zn) in the water column and in pore waters of the Gotland Deep following the 1993/94 salt-water inflows showed dramatic changes in the total “dissolved” metal concentrations and in the ratios between different metal species in the freshly re-oxygenated waters below 125 m. Changes in concentrations were greatest for those metals for which the solubility differs with the redox state (Fe, Mn, Co) but were also noted for those metals which form insoluble sulphides (Cd, Pb, Cu, Zn) and/or stable complexes with natural ligands (Cu). Pore water data from segmented surface muds (0–200 mm) indicated that significant redox and related metal speciation changes took place in the surface sediments only a few weeks after the inflow of the oxygenated sea water into the Gotland Deep.     

Interaction of diamond mine waste and surface water in the Canadian Arctic

Factors controlling the chemical composition of water interacting with finely-crushed kimberlite have been investigated by sampling pore waters from processed kimberlite fines stored in a containment facility. Discharge water from the diamond recovery plant and surface water from the containment facility, which acts as plant intake water, were also sampled. All waters sampled are pH-neutral, enriched in SO₄, Mg, Ca, and K, and low in Fe. Pore-water samples, representing the most concentrated waters, are characterized by the highest SO₄ (up to 4080 mg l⁻¹), Mg (up to 870 mg l⁻¹), and Ca (up to 473 mg l⁻¹). The water discharged from the processing plant has higher concentrations of all major dissolved constituents than the intake water. The dominant minerals present in the processed fines and the kimberlite ore are serpentine and olivine, with small amounts of Ca sulphate and Fe sulphide restricted to mud xenoclasts. Reaction and inverse modeling suggest that much of the water-rock interaction takes place within the plant and involves the dissolution of chrysotile and Ca sulphate, and precipitation of silica and Mg carbonate. Evapoconcentration also appears to be a significant process affecting pore water composition in the containment facility. The reaction proposed to be occurring during ore processing involves the dissolution of CO_2(g) and may represent an opportunity to sequester atmospheric CO₂ through mineral carbonation.     

Magma mixing and gold mineralization in the Maevatanana gold deposit,Madagascar

The Maevatanana gold deposit in Madagascar is hosted by Archean metamorphic rocks in quartz–sulfide veins that are structurally controlled by NNW–SSE trending shear zones. Fluid inclusion data show that the trapping conditions in quartz range from 0.87 to 2.58 kbar at temperatures of 269–362 °C. Laser Raman spectroscopy confirms that these inclusions consist of CO₂, SO₂, and H₂O. The δ³⁴S values of the pyrites range from 1.7‰ to 3.6‰, with an average of 2.25‰, supporting a magmatic origin. Noble gases (He, Ne, Ar, Ke, Xe) are chemically inert, thus will not be involved in chemical reactions during geological processes. Also due to the low concentration of He in the atmosphere and the low solubility of He in aqueous fluids, the atmosphere-derived He is unlikely to significantly affect He abundances and isotopic ratios of crustal fluids, ensures that He production should have the typical crust ³He/⁴He ratios. The ³He/⁴He ratios of fluid inclusions in pyrite from the deposit range from 0.06 to 0.12 Ra, while the ⁴⁰Ar/³⁶Ar ratios range from 6631 to 11441. We infer that the ore-forming fluids could have been exsolved from a granitic magma. The oxygen and hydrogen isotope compositions of the ore-forming fluids (1.5‰ ≤ δ¹⁸O_H2O ≤ 7.8‰; –72‰ ≤ δD ≤ –117‰) indicate they were derived from a granitic magma. Four pyrite samples from the gold deposit yield a precise Re–Os isochron age of 534 ± 13 Ma. Given that the post-collisional granites in northern and central Madagascar were derived by melting of sub-continental lithospheric mantle and formed between 537 and 522 Ma, we can state that the gold metallogenesis was coeval with the crystallization age of these parental magmas. These data could be accounted for the formation of the Maevatanana gold deposit. First, the shear zones hosting the deposit formed around 2.5 Ga, when the Madagascan micro-continental blocks collided with other continental blocks, triggering large-scale tectono-magmatic activity and forming NNW–SSE trending shear zones. The gold mineralization at Maevatanana is coeval with the crystallization age of the Cambrian post-collisional A-type granitoid plutons in northern and central Madagascar, implying that this deposit is associated with extensional collapse of the East African Orogen. This extension in turn induced asthenospheric upwelling, melting of sub-continental lithospheric mantle. These magmas underplated the lower crust, generating voluminous granitic magmas by partial melting of the lower crust. The mixing magma during tectono-thermal reactivation of the East African Orogen produced large volumes of volatiles that extracted gold from the granitic magma and produced Au–S complexes (e.g., Au(HSO₃)²⁻). The shear zones, which were then placed under extensional collapse of the East African Orogen in the Cambrian, formed favorable pathways for the magmatic ore-forming fluids. These fluids then precipitated gold-sulfides that form the Maevatanana gold deposit.     

Zircon U–Pb and molybdenite Re–Os dating of the Chalukou porphyry Mo deposit in the northern Great Xing’an Range,China and its geological significance

The newly discovered Chalukou giant porphyry Mo deposit, located in the northern Great Xing’an Range, is the biggest Mo deposit in northeast China. The Chalukou Mo deposit occurs in an intermediate-acid complex and Jurassic volcano-sedimentary rocks, of which granite porphyry, quartz porphyry, and fine-grained granite are closely associated with Mo mineralization. However, the ages of the igneous rocks and Mo mineralization are poorly constrained. In this paper, we report precise in situ LA-ICP-MS zircon U–Pb dates for the monzogranite, granite porphyry, quartz porphyry, fine grained granite, rhyolite porphyry, diorite porphyry, and andesite porphyry in the Chalukou deposit, corresponding with ages of 162 ± 2 Ma, 149 ± 5 Ma, 148 ± 2 Ma, 148 ± 1 Ma, 137 ± 3 Ma, 133 ± 2 Ma, and 132 ± 2 Ma, respectively. Analyses of six molybdenite samples yielded a Re–Os isochron age of 148 ± 1 Ma. These data indicate that the sequence of the magmatic activity in the Chalukou deposit ranges from Jurassic volcano-sedimentary rocks and monzogranite, through late Jurassic granite porphyry, quartz porphyry, and fine-grained granite, to early Cretaceous rhyolite porphyry, diorite porphyry, and andesite porphyry. The Chalukou porphyry Mo deposit was formed in the late Jurassic, and occurred in a transitional tectonic setting from compression to extension caused by subduction of the Paleo-Pacific oceanic plate.     

The Mesoproterozoic Abra polymetallic sedimentary rock-hosted mineral deposit,Edmund Basin,Western Australia

Abra is a blind, sedimentary rock-hosted polymetallic Fe–Pb–Zn–Ba–Cu ± Au ± Ag ± Bi ± W deposit, discovered in 1981, located within the easterly trending Jillawarra rift sub-basin of the Mesoproterozoic Edmund Basin, Capricorn Orogen, Western Australia. The Edmund Basin contains a 4–10 km thick succession of siltstone, sandstone, dolomitic siltstone, and stromatolitic dolomite. The age of the Edmund Group is between 1.66 and 1.46 Ga. The Abra polymetallic deposit is hosted in siltstone, dolostone, sandstone and conglomerate of the Irregully and Kiangi Creek Formations, but the mineralised zones do not extend above an erosion surface marking the change from fluvial to marine facies in the lower part of the Kiangi Creek Formation. The Abra deposit is characterised by a funnel-shaped brecciated zone, interpreted as a feeder pipe, overlain by stratiform–stratabound mineralisation. The stratiform–stratabound mineralisation includes a Red Zone and an underlying Black Zone. The Red Zone is characterised by banded jaspilite, hematite, galena, pyrite, quartz, barite, and siderite. The jaspilite and hematite cause the predominant red colouration. The Black Zone consists of veins and rhythmically banded sulphides, laminated and/or brecciated hematite, magnetite, Fe-rich carbonate and scheelite. In both zones, laminations and bands of sulphide minerals, Fe oxides, barite and quartz commonly exhibit colloform textures. The feeder pipe (Stringer Zone) merges with Black Zone and consists of a stockwork of Fe-carbonate-quartz, barite, pyrite, magnetite and chalcopyrite, exhibiting fluidised and/or jigsaw textures.The Abra mineral system is characterised by several overprinting phases of hydrothermal activity, from several stages of brecciation and fluidisation, barite and sulphide veining to barren low-temperature chalcedonic (epithermal regime) veining. Hydrothermal alteration minerals include multi-stage quartz, chlorite, prehnite, Fe-rich carbonate and albite. Albite (Na metasomatism) is an early alteration phase, whereas Fe-rich carbonate is a late phase. Fluid inclusion studies indicate that the ore fluids had temperatures ranging from 162 to 250 °C, with salinities ranging from 5.8 to about 20 wt.% NaCl. In the course of our studies, microthermometric and Raman microprobe analyses were performed on fluid inclusions in carbonate, quartz and barite grains. Fluid inclusions in quartz show homogenisation temperatures ranging from 150 to 170 °C with calculated salinities of between 3.7 and 13.8 wt.% NaCl.The sulphur isotopic system shows δ³⁴S values ranging from 19.4 to 26.6‰ for sulphides and from 37.4 to 41.9‰ for barite (Vogt and Stumpfl, 1987, Austen, 2007). Sulphur isotope thermometry between sulphides and sulphide–barite pairs yields values ranging from 219 to 336 °C (Austen, 2007).Galena samples were analysed for Pb isotope ratios, which have been compared with previous Pb isotopic data. The new Pb isotope systematics show model ages of 1650–1628 Ma, consistent with the formation of the host Edmund Basin.Re–Os dating of euhedral pyrite from the Black Zone yielded an age of ~ 1255 Ma. This age corresponds to the 1320–1170 Ma Mutherbukin tectonic event in the Gascoyne Complex. This event is manifested primarily along a WNW-trending structural corridor of amphibolite facies rocks, about 250 km to the northwest of the Abra area. It is possible that the Re–Os age represents a younger re-activation event of an earlier SEDEX style system with a possible age range of 1640–1590 Ma.A genetic model for Abra is proposed based on the above data. The model involves two end-members ore-forming stages: the first is the formation of the SEDEX style mineral systems, followed by a second multi-phase stage during which there was repeated re-working of the mineral system, guided by seismic activity along major regional faults.     

Bonanza-grade accumulations of gold tellurides in the Early Cretaceous Sandaowanzi deposit,northeast China

The Sandaowanzi epithermal gold deposit (0.5 Moz or ca. 14 tons), located at the northern edge of the Great Xing'an range, NE China, is unique in that nearly all the gold (> 95%) is contained in gold tellurides mostly in bonanza grade ore shoots (the highest grade being up to 20,000 g/t). The bonanza ores are hosted in the central parts of large-scale (> 3 m wide, 200 m long) quartz veins which crosscut Early Cretaceous andesitic trachyte and trachytic andesite, and are, in turn, crosscut by diabase dykes of similar age. There are two ore types: low-grade disseminated ores and high-grade vein ores. In the former, very fine grains of Ag-rich tellurides (mainly hessite and petzite) coexist with sulfides (pyrite, sphalerite, galena and chalcopyrite), occurring as disseminated grains or sometimes as grain aggregates. In the high-grade vein ores, coarse-grained Au–(Ag)–tellurides (calaverite, sylvanite, krennerite, and petzite) form a major part of quartz–telluride veins. Chalcopyrite forms separate monomineralic veins emplaced within the quartz–telluride veins. Spectacular textures among coarse-grained (up to 3 cm in diameter) tellurides, and micron-scale bamboo shoot-like grains are observed. Two- and three-phase telluride symplectites are common in the vein ores.Fluid inclusion studies suggest that the mineralizing fluids are a mixture of magmatic and meteoric fluids, that homogenized in the temperature range of 260–280 °C. Sulfur isotope compositions of pyrite and chalcopyrite (δ³⁴S − 1.64 to 1.91‰) support the origin of fluids from a deep source. It is suggested that faulting, temperature changes and variation in fS₂ and fTe₂ were major factors contributing to the two main types of mineralization and the differences between them. Early rapid cooling and subsequent slow cooling of the later fluids along fault and fracture zones were instrumental in formation of the two superposed ore types. Open-space filling and crack-sealing along fractures predominates over replacement during telluride mineralization. The Sandaowanzi deposit is a unique bonanza-grade accumulation of gold tellurides genetically related to subalkaline magmatism, which was genetically associated with Early Cretaceous regional extension.     

Colloidal and truly dissolved metal(oid) fractionation in sediment pore waters using tangential flow filtration

The partitioning of trace metal(oid)s between colloidal and “truly” dissolved fractions in sediment pore waters is often overlooked due to the analytical challenge; indeed, only small volumes are available and filtration membranes are rapidly clogged. Moreover, metal(oid)s are subject to co-precipitate with Fe. In this study, tangential flow filtration (TFF) was assessed for the fractionation of Fe, Mn, Cu, As, Co, Ni, Zn and Cd in sediment pore waters with a 5 kDa cut-off size membrane. Five natural sediments were collected and used for different tests. Results on blank samples showed that this technique was appropriate for Fe, Mn, Co, Zn, As and Cd. Although the applied concentration factors (CF) were low (<7.4) due to the small available volume of pore waters (50 mL), it was shown that colloidal concentrations obtained from the TFF procedure were similar whatever the applied concentration factor. The mass balance approach showed satisfying results (100 ± 25%) for Mn, Co, Zn and As. Mass balances were higher than 130% and highly variable for Cd, Ni and Cu. For Fe, mass balance was reproducible but low (71 ± 10%), probably due to sorption of positively charged Fe oxides on the membrane. Applying this method to five contrasting metal(oid)-contaminated sediments, it was shown that Mn, As, Co and Fe were mainly present in the “truly” dissolved phase (<5 kDa). This technique is a necessary step to assess sediment toxicity and bioavailability of metal(oid)s and could be of great interest for emergent pollutants such as nanometals.     

Uplift-denudation history of the Qinling orogen: Constrained from the detrital-zircon U–Pb geochronology

This paper presents a great number of detrital zircon U–Pb ages from the Middle Triassic to the Middle Jurassic sediments in the Jiyuan basin, southern North China. The results represent age spectra from 2.9 Ga to 216 Ma, with five peaks at 2.5 Ga, 1.9 Ga, 840 Ma, 440 Ma, and 270 Ma and two grains of ∼220 Ma. The ages of 2.5 Ga and 1.9 Ga are mainly derived from the Precambrian basement of the North China Block, whereas the others are typical characteristics of the Qinling orogenic belt. An important observation is that the Qinling-sourced detrital zircons become older as the strata get younger. Samples from the Middle Triassic to early Late Triassic strata are characterized by the age peak at 270 Ma, whereas the Late Late Triassic to Early Middle Jurassic samples are dominated by age peaks at 840 Ma and 440 Ma and minor grains within 800–650 Ma. Two grains of ∼220 Ma are preserved in the Late Middle Jurassic sample, which may be contributed by the Carnian deep plutons. These signatures indicate that the unroofing pattern of the Qinling orogenic belt developed by the denudation of materials from young covers to old basements and the Carnian deep plutons. Integrated with the data reported from the Hefei Basin, it is well-established that the intensity of unroofing increased from the Qinling to the Dabie orogen in the Early Jurassic, and the denudation timing of the ultra-high pressure (UHP) and high pressure (HP) rocks or Carnian plutons changed successively from the Early Jurassic in the Dabie to the Late Middle Jurassic in the Qinling orogen.     

Dilatant plasticity in high-strain experiments on calcite–muscovite aggregates

Torsion experiments were performed on synthetic aggregates of calcite with a 50% volume of muscovite. The tests were performed at 627–727 °C with a confining pressure of 300 MPa at constant shear strain rates of 3 × 10^?5–3 × 10^?4 s^?1 on cylindrical samples with the starting foliation parallel and perpendicular to the cylinder axis. Both the foliation parallel and the foliation perpendicular experiments show similar stress–strain patterns, with an initial hardening stage followed by significant strain weakening (>60%) before a catastrophic rupture. Microstructural analysis shows that in low-strain experiments calcite grains are intensely twinned while muscovite grains appear slightly bent and kinked. Higher strains promote a segregation of the two phases with calcite forming thin layers of fine, dynamically recrystallized grains, which act as localized shear bands, while muscovite grains keep their original size and rotate assuming a strong shape preferred orientation. This strain localization of the calcite from an initially homogeneous rock produced catastrophic failure at moderate bulk shear strains (γ ～ 3). Localization of the strain first involved ductile deformation to produce a new calcite layering with fine dynamically recrystallized grains along which cavities nucleated. The orientation and kinematics of the cavities are comparable to R1 Riedel structures. All experiments on calcite–muscovite mixtures resulted in heterogeneous strain. In these torsion experiments chemical changes and crystallization of new phases (anorthite and kalsilite) are observed at 627 °C. Whereas, samples hot pressed or deformed in compression at 670 °C did not show such reactions or any localization. The effect of stress-field geometry and pore pressure upon mineral reactions is discussed. It is concluded that deformation-induced heterogeneous phase distributions caused local strength differences initiating strain localization in the calcite–muscovite mixtures, eventually leading to plastic failure.     

Genesis of Cenozoic basalts in Central Asia and northern Mongolia (from helium isotope and petrochemical data)

Isotopic compositions of He (27 samples) and Ar (7 samples) as well as major and trace elements have been determined in Cenozoic effusive rocks and hosted olivine and pyroxene phenocrysts from northern and central Mongolia. The R = ³He/⁴He values are within (0.1–13)⋅10⁻⁶. Abnormally high R value, 13⋅10⁻⁶, atypical of Cenozoic basaltic-volcanism areas in Mongolia, has been first revealed at one of the sites of the Hangayn upland. In composition the rocks under study correspond to tephrites, trachybasalts, and subalkalic andesite-basalts. Analysis of their REE patterns and spidergrams shows that the elements participating in the formation of basalt fields of the Hangayn upland were supplied from the enriched mantle (EM1). These patterns are similar to the OIB ones; (La/Yb)_n = 9–53. The R values in the olivine phenocrysts are higher as compared with the pyroxene phenocrysts and the bulk rock compositions of the same samples. Based on the elemental composition of the rocks, their contents of radiogenic ⁴He and ³He were calculated. The rate of ³He formation is 5.65⋅10⁻² at/(g⋅year). The calculated and measured R values in the rock samples point to the presence of trapped mantle helium.     

Chemical effects of sulfur dioxide co-injection with carbon dioxide on the reservoir and caprock mineralogy and permeability in depleted gas fields

The most suitable candidates for subsurface storage of CO₂ are depleted gas fields. Their ability to retain CO₂ can however be influenced by the effect which impurities in the CO₂ stream (e.g. H₂S and SO₂) have on the mineralogy of reservoir and seal. In order to investigate the effects of SO₂ we carried out laboratory experiments on reservoir and cap rock core samples from gas fields in the northeast of the Netherlands. The rock samples were contained in reactor vessels for 30 days in contact with CO₂ and 100 ppm SO₂ under in-situ conditions (300 bar, 100 °C). The vessels also contained brine with the same composition as in the actual reservoir. Furthermore equilibrium modeling was carried out using PHREEQC software in order to model the experiments on caprock samples.After the experiments the permeability of the reservoir samples had increased by a factor of 1.2–2.2 as a result of dissolution of primary reservoir minerals. Analysis of the associated brine samples before and after the experiments showed that concentrations of K, Si and Al had increased, indicative of silicate mineral dissolution.In the caprock samples, composed of carbonate and anhydrite minerals, permeability changed by a factor of 0.79–23. The increase in permeability is proportional to the amount of carbonate in the caprock. With higher carbonate content in comparison with anhydrite the permeability increase is higher due to the additional carbonate dissolution. This dependency of permeability variations was verified by the modeling study. Hence, caprock with a higher anhydrite content in comparison with carbonate minerals has a lower risk of leakage after co-injection of 100 ppmv SO₂ with CO₂.     

Osumilite and a spinel + quartz association in garnet–sillimanite gneiss from Rundvågshetta,Lützow-Holm Complex,East Antarctica

This is the first report of osumilite occurring as fine isolated inclusions within garnet porphyroblasts, as observed in garnet–sillimanite gneiss from Rundvågshetta, Lützow-Holm Complex, East Antarctica. The osumilite is characterized by high Si content (10.60 and 10.95 atoms based on 30 oxygens per formula unit), low Al content (2.99 and 3.82), a high content of M site-occupying cations (2.51 and 3.03), and high X_Mg values (about 0.81). We also report a spinel + quartz association found as inclusions within garnet porphyroblasts. Spinel grains, which are in direct contact with quartz and are spatially associated with sillimanite, show extremely high Zn contents (X_Zn^Spl = 0.33 ? 0.46) and high X_Mg values (0.45–0.54). The garnet is rimmed by sillimanite, K-feldspar, plagioclase, and quartz. Biotite and cordierite are found only as inclusions within garnet porphyroblasts, where biotite coexists with spinel–quartz or with rutile. Porphyroblastic garnet contains rutile needles and has low X_Mg values (about 0.36). The sillimanite contains a high Fe content (about 1.2 wt.% Fe₂O₃).The occurrence of osumilite and spinel + quartz indicates a clockwise pressure–temperature path of ultrahigh-temperature metamorphism, involving the following events: (1) the Rundvågshetta granulites suffered prograde metamorphism within the kyanite and sapphirine + quartz fields; (2) subsequent retrograde metamorphism, involving near-isothermal decompression, occurred in the orthopyroxene + sillimanite + quartz field; (3) the granulites passed through the garnet + cordierite + sillimanite + quartz field during decreasing temperature; (4) the granulites entered the osumilite stability field at around 8 kbar and 950 °C; and (5) the granulites retain a final record of retrograde metamorphism within the biotite + sillimanite + K-feldspar and quartz field at 6.1 kbar and about 830 °C.     

Cretaceous to Cenozoic evolution of the northern Lhasa Terrane and the Early Paleogene development of peneplains at Nam Co,Tibetan Plateau

Highly elevated and well-preserved peneplains are characteristic geomorphic features of the Tibetan plateau in the northern Lhasa Terrane, north–northwest of Nam Co. The peneplains were carved in granitoids and in their metasedimentary host formations. We use multi-method geochronology (zircon U–Pb and [U–Th]/He dating and apatite fission track and [U–Th]/He dating) to constrain the post-emplacement thermal history of the granitoids and the timing and rate of final exhumation of the peneplain areas. LA-ICP-MS U–Pb geochronology of zircons yields two narrow age groups for the intrusions at around 118 Ma and 85 Ma, and a third group records Paleocene volcanic activity (63–58 Ma) in the Nam Co area. The low-temperature thermochronometers indicate common age groups for the entire Nam Co area: zircon (U–Th)/He ages cluster around 75 Ma, apatite fission track ages around 60 Ma and apatite (U–Th)/He ages around 50 Ma. Modelling of the thermochronological data indicates that exhumation of the basement blocks took place in latest Cretaceous to earliest Paleogene time. By Middle Eocene time the relief was already flat, documented by a thin alluvial sediment sequence covering a part of the planated area. The present-day horst and graben structure of the peneplains is a Late Cenozoic feature triggered by E–W extension of the Tibetan Plateau. The new thermochronological data precisely bracket the age of the planation to Early Eocene, i.e. between ca. 55 and 45 Ma. The erosional base level can be deduced from the presence of Early Cretaceous zircon grains in Eocene strata of Bengal Basin. The sediment generated during exhumation of the Nam Co area was transported by an Early Cenozoic river system into the ocean, suggesting that planation occurred at low elevation.     

The Variscan Tamlalt–Menhouhou gold deposit,Eastern High-Atlas,Morocco

The Tamlalt–Menhouhou gold deposit belongs to the Neoproterozoic–Palaeozoic Tamlalt inlier located in the Eastern High-Atlas (Morocco). It occurs in altered Upper Neoproterozoic bimodal volcanic and volcano-sedimentary units outcropping in the Tamlalt–Menhouhou area. Gold mineralization has been identified in quartz veins related to shear-zones associated with a strong quartz-phyllic-argillic alteration. Visible free gold is related to goethite–malachite–barite boxworks in quartz veins. The other alteration minerals accompanying gold mineralization are mainly carbonates, chlorite, hematite, albite and pyrite whose relative proportion defines three alteration types. ⁴⁰Ar/³⁹Ar geochronology performed on phengite grains from phyllic alteration and the auriferous quartz veins, yields plateau ages ranging from 300 ± 5 Ma to 284 ± 12 Ma with a weighted mean age of 293 ± 7 Ma. This identifies a Late Variscan age for the Tamlalt–Menhouhou “shear zones-related” gold deposit and emphasizes the consequences of the Variscan orogeny for gold mineralization in the High-Atlas and Anti-Atlas Neoproterozoic inliers.     

TITAN2D simulations of pyroclastic flows at Cerro Machín Volcano,Colombia: Hazard implications

Cerro Machín is a dacitic tuff ring located in the central part of the Colombian Andes. It lies at the southern end of the Cerro Bravo–Cerro Machín volcanic belt. This volcano has experienced at least six major explosive eruptions during the last 5000 years. These eruptions have generated pyroclastic flows associated with Plinian activity that have traveled up to 8 km from the crater, and pyroclastic flows associated with Vulcanian activity with shorter runouts of 5 km from the source. Today, some 21,000 people live within a 8 km radius of Cerro Machín. The volcano is active with fumaroles and has shown increasing seismic activity since 2004, and therefore represents a potentially increasing threat to the local population. To evaluate the possible effects of future eruptions that may generate pyroclastic density currents controlled by granular flow dynamics we performed flow simulations with the TITAN2D code. These simulations were run in all directions around the volcano, using the input parameters of the largest eruption reported. The results show that an eruption of 0.3 km³ of pyroclastic flows from a collapsing Plinian column would travel up to 9 km from the vent, emplacing a deposit thicker than 60 m within the Toche River valley. Deposits >45 m thick can be expected in the valleys of San Juan, Santa Marta, and Azufral creeks, while 30 m thick deposits could accumulate within the drainages of the Tochecito, Bermellón, and Coello Rivers. A minimum area of 56 km² could be affected directly by this kind of eruption. In comparison, Vulcanian column-collapse pyroclastic flows of 0.1 km³ would travel up to 6 km from the vent depositing >45 m thick debris inside the Toche River valley and more than 30 m inside the valleys of San Juan, Santa Marta, and Azufral creeks. The minimum area that could be affected directly by this kind of eruption is 33 km². The distribution and thickness of the deposits obtained by these simulations are consistent with the hazard map presented by INGEOMINAS (Geological Survey of Colombia) in 2002. The composite map of the simulated flow deposits suggests that after major explosive events such as these, the generation of lahars is probable.     

Petrogenesis of Dongguashan skarn-porphyry Cu-Au deposit related intrusion in the Tongling district,eastern China: Geochronological,mineralogical, geochemical and Hf isotopic evidence

The Dongguashan skarn-porphyry Cu-Au deposit, located in the Tongling district of the Middle-Lower Yangtze River Valley metallogenic belt (MLYB), consists of skarn ore bodies in the upper part and porphyry ore bodies in the lower part, both of which are hosted in quartz diorite and quartz monzodiorite. Zircon U-Pb age and geochemical studies show that the quartz diorite of the Dongguashan intrusion formed at 140.3 ± 2.0 Ma (MSWD = 0.19) and belongs to the high potassium calc-alkaline series. It is enriched in large ion lithophile elements (LILE) and light rare earth elements (LREE), depleted in high field-strength elements (HFSE) and heavy rare earth elements (HREE), and has a slightly negative Eu anomaly. ¹⁷⁶Hf/¹⁷⁷Hf values of the rims of zircons show a variable range (0.282087–0.282391), corresponding with calculated ε_Hf(t) values of − 10.72 to − 21.46. Plagioclases in the quartz diorite have unbalanced structure characterized by bright andesine and labradorite (An = 37.0–65.5) cores with higher contents of Fe and Sr and are corroded by dark oligoclase (An = 13.8–27.6) rim. Major elements, trace elements, Hf isotope, and the composition of plagioclases indicate that the parental magma of the Dongguashan intrusion was produced by the mixing of underplating mafic magma and felsic magma formed by remelting of Paleoproterozoic and Neoarchean crustal rocks, Neoproterozoic crust may also provide some material to the felsic magma. Mafic magma played a key role and made the parental magma rich in water, sulfur, metals (Cu, Au) and gave it a high oxygen fugacity. During its magmatic evolution, the parental magma underwent fractional crystallization of hornblende, apatite, sphene and other mafic minerals. Some quartz diorite and quartz monzodiorite samples that show adakitic signatures, may result from injection of mafic magma. Some inherited zircons of the quartz diorite in the Dongguashan intrusion gave ages of 2.40–2.50 Ga, 1.95–2.05 Ga and 0.74–0.81 Ga, coming from ultramafic, mafic and andesitic igneous rocks, and this indicates that there may have been three periods (2.4, 2.0, and 0.8 Ga) of magmatic activity in the Tongling district.     

Carbonate dissolution in Mesozoic sand- and claystones as a response to CO2 exposure at 70 °C and 20 MPa

The response to CO₂ exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO₂ injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO₂ injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO₂ and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO₂; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO₂, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions.