In the Late Neoarchaean, the lithosphere of the North China Craton (NCC) experienced a strong extensional event, which is of great significance for understanding the evolution of the continental crust in the Precambrian. In this study, a suite of mafic dykes from Shandong province in the northeastern NCC were investigated to determine the nature, timing and source of rift-related magma activities using zircon U–Pb data, whole-rock geochemistry and Nd–Hf isotopes. Zircon U–Pb dating of four dolerites by laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) yielded weighted mean 207Pb/206Pb ages in the range 2509 ± 6.1 to 2537 ± 6.2 Ma (2σ, 95 % confidence interval). The mafic dykes are classified as alkaline rocks based on their K2O + Na2O contents (6.78–7.21 wt %) and belong to the shoshonitic series according to their K2O contents (3.23–3.36 wt %). The dolerites show low concentrations of light rare earth elements ((La/Yb)N between 7.17 and 8.55), positive Eu anomalies (Eu/Eu* between 1.12 and 1.27), positive Ba, K, Pb, Sr, Eu, Dy and Lu anomalies, and depleted U, Nb, Pr, Ta, P, Nd and Ti anomalies. The dykes are characterized by low initial (87Sr/86Sr)i (∼0.6969), positive εNd(t) values (0.2–0.8) and εHf(t) values (0.5–8.6) and relatively old mean Nd and Hf model age (2.73 Ga). Collectively, the data suggest that the mafic dykes were derived from the partial melting (10–20 %) of an isotope-depleted garnet–lherzolite mantle source that was hybridized through interaction with subducted lower crustal material. The parental magmas of these dykes underwent a certain number of crustal contaminations during magma ascent. The mafic magmatism represented in the form of the dyke swarms is considered to be a response to widespread lithospheric extension which affected the NCC at c. 2.5 Ga during the Neoarchaean.

A reaction path model was constructed in a bid to simulate diagenesis in the Magnus Sandstone, an Upper Jurassic turbidite reservoir in the Northern North Sea, UKCS. The model, involving a flux of source rock-derived CO2 into an arkosic sandstone, successfully reproduced simultaneous dissolution of detrital K-feldspar and growth of authigenic quartz, ankerite and illite. Generation of CO2 occurred before and during the main phase of oil generation linking source rock maturation with patterns of diagenesis in arkosic sandstones and limiting this type of diagenesis to the earlier stages of oil charging. Independent corroborative evidence for the model is provided by formation water geochemical data, carbon isotope data from ankerite and produced gas phase CO2 and the presence of petroleum inclusions within the mineral cements. The model involves a closed system with respect to relatively insoluble species such as SiO2 and Al2O3 but is an open system with respect to CO2. There are up to seven possible rate-controlling steps including: influx of CO2, dissolution of K-feldspar, precipitation of quartz, ankerite and illite, diffusive transport of SiO2 and Al2O3 from the site of dissolution to the site of precipitation and possibly the rate of influx of Mg2+ and Ca2+. Given the large number of possible controls, and contrary to modern popular belief, the rate of quartz precipitation is thus not always rate limiting.

This research work deals with chlorite-vermiculite mixed-layer stability under hydrothermal and metamorphic conditions. We used as a case study a clayey flysch unit cropping out in an active geothermal area near to a Recent volcano (Mt. Amiata) in central Italy. The geothermal gradient is higher than the world average and temperatures over 100°C can occur at less than 1 km depth. The mineralogical data, obtained from X-Ray Power Diffraction (XRPD) analysis of clay samples from the same geologic unit, show that the primary anchimetamorphic mineral assemblage (illite, chlorite, illite-smectite mixed layers) is accompanied by secondary phases, such as chlorite-vermiculite mixed-layers and calcite. Reactive flow modelling was used to outline a realistic water-rock (W/R) interaction process able to generate the new minerals. In the numerical simulation, the pristine shale was made to react with a local thermal spring, at an estimated but realistic carbonate reservoir temperature. The simulation predicts that, at a temperature of 120°C, clinochlore dissolves and vermiculite crystallizes, a good proxy of the chlorite-vermiculite crystallization process. Under low water/rock conditions the proportions of the clay minerals (illite, chlorite, smectite and vermiculite) are comparable with the analytical results. The simulation also shows that temperatures higher than 120°C enhance the vermiculite formation. We conclude that the chlorite-vermiculite mixed-layers formed in the recent past due to the upflow of thermal water which permeated the flysch unit. This result indicates that the alteration of the clayey cap-rocks of geothermal reservoirs is enhanced by the interaction with geothermal fluids, and can be used as a prospecting tool.

This study characterizes the effects of fluid migration into a predominantly shale cover which seals the active geothermal system of Mt. Amiata (Tuscany, Italy). During Alpine orogenesis the shale unit was affected by regional metamorphism at the limit of the diagenesis-anchizone. Subsequently, the phyllosilicate clay minerals of the shales underwent significant alteration at diagenetic temperatures (175±25ºC as determined by the geochemical model) by the pervasive circulation of fluids activated by the geothermal field. The overall mineralogical assemblages indicate that the main transformations consisted mostly of destabilization of illite and formation of kaolinite together with large amounts of I-S mixed layers, with higher smectite content and decreased Reichweite I-S ordering (from R3 to R1) with respect to the original, unaltered phases. Application of computer modelling indicates that the circulation of CO2-rich geothermal fluids into the shale unit was responsible for the observed phyllosilicate clay mineral transformations.

The removal of dissolved trace metals during neutralization of acid mine drainage has usually been described and modelled as a progressive, pH-dependent sorption onto standard ferric or aluminous adsorbent. In the absence of adsorbent mineral surfaces, trace metals tend to form amorphous to low-crystallinity compounds which are often difficult to characterize. Here, we study the behaviour of the more soluble metals (Cu2+, Zn2+, Mn2+, Co2+, Ni2+, Cd2+) in the absence of ferric and aluminous adsorbent by neutralization experiments with waters from two acidic pit lakes. The objectives of our study were to identify the mineral products formed by trace-metal precipitation and the pH ranges at which these metals are removed from the solutions. Both geochemical modelling and detailed mineralogical and chemical analyses (XRD, SEM, TEM, XRF, ICP-AES) were undertaken to characterize the products. The schwertmannite and hydrobasaluminite colloids formed in the initial neutralization stages were removed from the waters at pH 3.5 and 5.1, respectively. These two minerals had previously adsorbed the Cr3+ and Pb2+ initially present in the solutions. The Cu precipitates were amorphous to X-rays, though chemical and modelling data suggest that Cu probably precipitated as a precursor of brochantite (Cu4(SO4)(OH)6·2H2O) at pH >6.0, together with minor quantities of other Cu hydroxysulfates (langite, antlerite) and Cu(OH)2. At higher pH, other divalent metals (Zn2+, Mn2+) precipitated as silicates, carbonates and/or (possibly) minor oxides and (oxy)hydroxides. The high concentration of aqueous SiO2 in the solutions allowed Zn to precipitate as willemite (Zn2SiO4) at pH >7.0. Similarly, the presence of inorganic carbon (originally as CO2 (aq.)) greatly influenced the nature of the corresponding precipitate of Mn. This metal was initially present as Mn2+ and experienced a partly oxidative precipitation forming, in combination with Mg2+, the hydroxyl carbonate desautelsite (Mg6Mn2(CO3)(OH)16·4H2O) at pH 9.0–10.0. The formation of Mn3+/Mn4+ oxides and hydroxides (hausmannite, manganite, birnessite) could not be demonstrated, although geochemical calculations support their subordinate formation. Other metallic cations such as Co2+, Ni2+ and Cd2+ did not form discrete mineral phases but were totally removed by sorption onto and/or incorporation into the cited Zn and Mn compounds. The discrepancies between theoretical and demonstrated mineralogy and the significance of these minerals for future pit-lake remediation initiatives are discussed.

A sharp negative δ13C excursion coincides with the end-Triassic mass extinction. This is followed by a protracted interval of 13C enrichment. These isotopic events occurred simultaneously with the emplacement of the Central Atlantic Magmatic Province (CAMP). Here we use a carbon cycle box model to explore the effects of episodic carbon release – constrained by recently developed high-resolution chronology – on atmospheric pCO2, ocean chemistry and the δ13C of the ocean–atmosphere carbon pool. Our results are consistent with previous modelling efforts in suggesting that the sharp negative δ13C excursion and acidification event associated with the extinction are best explained by the rapid release (<20 ka) of highly 13C-depleted carbon (−70‰). However, our model also indicates that the likely short duration of the excursion requires organic carbon burial to have closely followed carbon injection. The age within the Hettangian of the large positive δ13C excursion which follows is currently uncertain. If early Hettangian in age, then our modelling indicates that the interval of 13C enrichment was closely associated with the volcanic CO2 pulses and pCO2 peaks. If late Hettangian in age, then the 13C enrichment must have lagged the carbon input substantially (by hundreds of thousands of years) and was associated with CO2 drawdown and over-cooling. Our modelling highlights the need for improved age constraints on Hettangian stratigraphic sections in order to test between two distinct and contrasting possibilities: continuing carbon cycle instability due to recurrent perturbations from CAMP activity or a delayed recovery arising from internal biosphere dynamics.

Ring complex granites of the Peruvian Batholith are tabular bodies with flat roofs emplaced by cauldron subsidence. Marginal precursory ring dykes extend upwards above roof level and a typical intrusion is “H”-shaped in cross-section. Advance of magma by repeated subsidence would give a ladder-shaped profile for such intrusions above the brittle-ductile transition. Close relationships exist between intrusion geometry, emplacement process and petrogenetic evolution. Initially a granodioritic magma chamber lay beneath the present erosion level, trapping a rising mass of dioritic magma. Expansion of granodioritic liquid resulted in the injection of microgranite and tuffisite cone sheets accompanied by roof uplift within a ring fault. Next, during subsidence within the ring fault, liquids from deeper levels in the underlying chamber rose by stoping along the outer margin of the fault to form a ring dyke. Prior to intrusion, this liquid was vertically zoned from rhyodacite downwards to diorite and these liquids became partially mixed during emplacement. Finally, granodioritic magma rose to the present level by subsidence of a roof slab bounded by the ring fault. The precursory ring structures preserve evidence of significant but transient events in the underlying chamber. Liquid differentiation may be significant in the evolution of many large plutons.