Geochemistry of metal-rich brines from central Mississippi Salt Dome basin, U.S.A.

Oil-field brines are the most favored ore-forming solutions for the sediment-hosted Mississippi Valley-type ore deposits. Detailed inorganic and organic chemical and isotope analyses of water and gas samples from six oil fields in central Mississippi, one of the very few areas with high metal brines, were conducted to study the inorganic and organic complexes responsible for the high concentrations of these metals. The samples were obtained from production zones consisting of sandstone and limestone that range in depth from 1900 to 4000 m (70–120°C) and in age from Late Cretaceous to Late Jurassic. Results show that the waters are dominantly bittern brines related to the Louann Salt. The brines have extremely high salinities that range from 160,000 to 320,000 mg/l total dissolved solids and are NaCaCl-type waters with very high concentrations of Ca (up to 48,000 mg/l) and other alkaline-earth metals, but with low concentrations of aliphatic acid anions. The concentrations of metals in many water samples are very high, reaching values of 70 mg/l for Pb, 245 mg/l for Zn, 465 mg/l for Fe and 210 mg/l for Mn. The samples with high metal contents have extremely low concentrations (<0.02 mg/l) of H₂S. Samples obtained from the Smackover Formation (limestone) have low metal contents that are more typical of oil-field waters, but have very high concentrations (up to 85 mg/l) of H₂S. Computations with the geochemical code SOLMINEQ.87 give the following results: (1) both Pb and Zn are present predominantly as aqueous chloride complexes (mainly as PbCl₄²⁻ and ZnCl₄²⁻, respectively); (2) the concentrations of metals complexed with short-chained aliphatic acid anions and reduced S species are minor; (3) organic acid anions are important in controlling the concentrations of metals because they affect the pH and buffer capacity of the waters at subsurface conditions; and (4) galena and sphalerite solubilities control the concentrations of Pb and Zn in these waters.     

Feldspar dissolution in the presence of organic acid anions under diagenetic conditions: an experimental study

Previous experiments to determine the aqueous solubility of lead-rich orthoclase in the presence of the ethanoic acid anion (acetate) at 150°C and 50 MPa have shown that the observed fluid compositions are essentially controlled by the presence of secondary mineral precipitates, which buffer dissolved species apart from lead. Data for lead suggest that dissolution increased with increasing fluid ethanoic acid anion content, but the ethanoic acid anion was unstable under the experimental conditions. Additional experiment have now been carried out using pure natural albite and ethanoic acid anion solutions at 150°C and 50 MPa, in which the ethanoic acid anion remains stable. The results for albite again demonstrate the influence on fluid composition of secondary mineral precipitates, but data for silica allow the rates of dissolution to be estimated. Values obtained for the dissolution rate constant increase from 1.8 × 10⁻⁷ to 5.3 × 10⁻⁷ s⁻¹ with increasing fluid ethanoic acid anion content (0.1–2.5 molal) and approximate to values for quartz and orthoclase dissolution rates for similar PT conditions, reflecting similarity in the mechanisms of dissolution of the minerals' three dimensional (alumino)silicate frameworks. However, these experiments provide no other evidence that the ethanoic acid anion enhances equilibrium solubilities of feldspars or quartz. In contrast to the results for the ethanoic acid anion, data for albite dissolution experiments in the presence of the ethanedioic acid anion (oxalate) at 150°C and 50 MPa show an inhibitionn of solubility (apart from aluminium), while data for the 2-hydroxy-1,2,3-propanetricarboxylic acid trivalent anion (citrate) show considerable enhancement of solubility for aluminium and silicon, and titanium derived from the reaction vessel. The 2-hydroxy-1,2,3-propanetricarboxylic acid trivalent anion is unstable, decaying according to first order kinetics (half life = 1.5 days). In their application to problems of diagenesis in the presence of organic acid anions, these results suggest that the ethanoic acid anion may influence feldspar dissolution by accelerating diagenetic reactions, while geologically short-lived species such as the 2-hydroxy-1,2,3-propanetricarboxylic acid trivalent anion and its decay products may dramatically enhance aluminosilicate solubility.     

Measurement of partition coefficients of phenol and cresols in gas-charged crude oil/water systems

An instrument has been constructed for monitoring the partition coefficients of phenol and cresols between crude oil and water under sub-surface conditions. The device has the capacity for introducing methane gas into crude oil, thereby allowing measurements under live oil (solution gas-containing) conditions. The partition coefficients of phenol and cresols have been measured in crude oil: water substrates under “live” oil and “dead” oil (without solution gas) conditions over a temperature range 25–150 °C. Over the range investigated it is seen that the introduction of gas (crude oil saturated at 100 bar with methane) into the system resulted in an approximate doubling of partition coefficients compared to the equivalent dead oil: brine systems. The partition coefficient data obtained using the device may be employed in a number of petroleum exploration and production activities such as the determination of residual oil saturation of a water-flooded petroleum reservoir. Partition coefficient measurements may help in predicting toxic organic solute loadings in oilfield discharge waters.     

Paleo-uplift and cooling rates from various orogenic belts of India, as revealed by radiometric ages

The significant discordance of the radiometric (Rb-Sr, Pb-U, K-Ar and fission track) ages from various orogenic cycles of the Dharwar, Satpura, Aravalli and Himalayan orogenic belts in India, coupled with their corresponding blocking temperatures for various radiometric clocks in whole rocks and minerals, has been used to evaluate the cooling and the uplift histories of the respective orogenic belts. The blocking temperatures used in the present study of various Rb-Sr (isotopic homogenization at 600°C, muscovite at 500°C and biotite at 300°C), Pb-U (monazite at 530°C), K-Ar (muscovite at 350°C and biotite at 300°C) and fission-track clock (zircon at 350°C, sphene at 300°C, garnet at 280°C, muscovite at 130°C, hornblende at 120°C and apatite at 100°C for the cooling rate l°C/Ma) have been found suitable to explain the differences in mineral ages by different radiometric techniques. The nature of the cooling curves drawn using the temperature versus age data for various orogenic cycles in India has also been discussed. The cooling and the uplift patterns determined for various orogenic cycles of India, suggest comparatively slow cooling (5.0–0.2°C/Ma) and uplift (180–2 m/Ma) for the Peninsular regions and rapid cooling (25.0–1.0° C/Ma) and fast uplift (800–30 m/Ma) during the Himalayan Orogenic Cycle (Upper Cretaceous—Tertiary) in the Extra-Peninsular region.     

Diagenetic history and porosity evolution of Upper Carboniferous sandstones from the Spring Valley #1 well, Maritimes Basin, Canada–implications for reservoir development

Eighty-two core samples were collected from the Spring Valley #1 well which penetrates the Upper Carboniferous strata in the Late Devonian–Early Permian Maritimes Basin. The strata consist of alternating sandstones and mudstones deposited in a continental environment. The objective of this study is to characterize the relationship of sandstone porosity with depth, and to investigate the diagenetic processes related to the porosity evolution. Porosity values estimated from point counting range from 0% to 27.8%, but are mostly between 5% and 20%. Except samples that are significantly cemented by calcite, porosity values clearly decrease with depth. Two phases of calcite cement were distinguished based on Cathodoluminescence, with the early phase being largely dissolved and preserved as minor relicts in the later phase. Feldspar dissolution was extensive and contributed significantly to the development of secondary porosity. Quartz cementation was widespread and increased with depth. Fluid inclusions recorded in calcite and quartz cements indicate that interstitial fluids in the upper part of the stratigraphic column were dominated by waters with salinity lower than that of seawater, the middle part was first dominated by low-salinity waters, then invaded by brines, and the lower part was dominated by brines. Homogenization temperatures of fluid inclusions generally increase with depth and suggest a paleogeothermal gradient of 25 °C/km, which is broadly consistent with that indicated by vitrinite reflectance data. An erosion of 1.1–2.4 (mean 1.75) km of strata is inferred to have taken place above the stratigraphic column. δ¹⁸O values of calcite cements (mainly from the late phase) decrease with depth, implying increasing temperatures of formation, as also suggested by fluid-inclusion data. δ¹³C values of calcite cements range from −13.4‰ to −5.7‰, suggesting that organic matter was an important carbon source for calcite cements. A comparison of the porosity data with a theoretical compaction curve indicates that the upper and middle parts of the stratigraphic column show higher-than-normal porosity values, which are related to significant calcite and feldspar dissolution. Meteoric incursion and carboxylic acids generated from organic maturation were probably responsible for the abundant dissolution events.     

Variations in temperature and extent of Atlantic Water in the northern North Atlantic during the Holocene

We compare six high-resolution Holocene, sediment cores along a S–N transect on the Norwegian–Svalbard continental margin from ca 60°N to 77.4°N, northern North Atlantic. Planktonic foraminifera in the cores were investigated to show the changes in upper surface and subsurface water mass distribution and properties, including summer sea-surface temperatures (SST). The cores are located below the axis of the Norwegian Current and the West Spitsbergen Current, which today transport warm Atlantic Water to the Arctic. Sediment accumulation rates are generally high at all the core sites, allowing for a temporal resolution of 10–10² years. SST is reconstructed using different types of transfer functions, resulting in very similar SST trends, with deviations of no more than ±1.0/1.5 °C. A transfer function based on the maximum likelihood statistical approach is found to be most relevant. The reconstruction documents an abrupt change in planktonic foraminiferal faunal composition and an associated warming at the Younger Dryas–Preboreal transition. The earliest part of the Holocene was characterized by large temperature variability, including the Preboreal Oscillations and the 8.2 k event. In general, the early Holocene was characterized by SSTs similar to those of today in the south and warmer than today in the north, and a smaller S–N temperature gradient (0.23 °C/°N) compared to the present temperature gradient (0.46 °C/°N). The southern proxy records (60–69°N) were more strongly influenced by slightly cooler subsurface water probably due to the seasonality of the orbital forcing and increased stratification due to freshening. The northern records (72–77.4°N) display a millennial-scale change associated with reduced insolation and a gradual weakening of the North Atlantic thermohaline circulation (THC). The observed northwards amplification of the early Holocene warming is comparable to the pattern of recent global warming and future climate modelling, which predicts greater warming at higher latitudes. The overall trend during mid and late Holocene was a cooling in the north, stable or weak warming in the south, and a maximum S–N SST gradient of ca 0.7 °C/°N at 5000 cal. years BP. Superimposed on this trend were several abrupt temperature shifts. Four of these shifts, dated to 9000–8000, 5500–3000 and 1000 and 400 cal. years BP, appear to be global, as they correlate with periods of global climate change. In general, there is a good correlation between the northern North Atlantic temperature records and climate records from Norway and Svalbard.     

Study on the kinetics of iron oxide leaching by oxalic acid

The presence of iron oxides in clay or silica raw materials is detrimental to the manufacturing of high quality ceramics. Although iron has been traditionally removed by physical mineral processing, acid washing has been tested as it is more effective, especially for extremely low iron (of less than 0.1% w/w). However, inorganic acids such as sulphuric or hydrochloric acids easily contaminate the clay products with SO₄²⁻ and Cl⁻, and therefore should be avoided as much as possible. On the other hand, if oxalic acid is used, any acid left behind will be destroyed during the firing of the ceramic products. The characteristics of dissolution of iron oxides were therefore investigated in this study.The dissolution of iron oxides in oxalic acid was found to be very slow at temperatures within the range 25–60 °C, but its rate increases rapidly above 90 °C. The dissolution rate also increases with increasing oxalate concentration at the constant pH values set within the optimum range of pH2.5–3.0. At this optimum pH, the dissolution of fine pure hematite (Fe₂O₃) (105–140 μm) follows a diffusion-controlled shrinking core model. The rate expression expressed as 1 − (2 / 3)x − (1 − x)^2 / 3 where x is a fraction of iron dissolution was found to be proportional to [oxalate]^1.5.The addition of magnetite to the leach liquor at 10% w/w hematite was found to enhance the dissolution rate dramatically. Such addition of magnetite allows coarser hematite in the range 0.5–1.4 mm to be leached at a reasonable rate.     

As–(Ag) sulphide veins in the Spanish Central System: further evidence for a hydrothermal event of Permian age

The Spanish Central System (SCS) has been subjected to repeated deformation and fluid flow events which have produced both sulphide-bearing and barren vein systems. Although several hydrothermal episodes took place between 300 and 100 Ma, fluid circulation during the Permian was especially important, giving rise to a range of different types of deposits. This study presents a multidisciplinary approach leading to the characterisation of the chemistry and age of the hydrothermal fluids that produced the As–(Ag) mineralised stockwork of Mónica mine (Bustaviejo, Madrid). Fluid inclusion data indicate the presence of two different fluids. An initial ore stage (I) formed from a low- to moderate salinity (3–8 wt.% eq. NaCl) H₂O–NaCl–CO₂–CH₄ fluid, at minimum trapping temperature of 350±15 °C and 0.3 kbar. A second H₂O–NaCl fluid is found in three types of fluid inclusions: a high temperature and low salinity type (340±20 °C; 0.8–3.1 wt.% eq. NaCl) also associated to ore stage I, a moderate temperature and very low salinity type (160–255 °C; 0–1.5 wt.% eq. NaCl) represented in ore stage III, and a very low temperature and hypersaline type (60–70 °C; 30–35 wt.% NaCl), unrelated to the mineralising stages and clearly postdating the previous types. ⁴⁰Ar–³⁹Ar dating on muscovite from the early As–Fe stage (I) has provided an age of 286±4 Ma, synchronous with the late emplacement phases of La Cabrera plutonic massif (288±5 Ma) and with other Permian hydrothermal events like Sn–W skarns and W–(Sn) sulphide veins. δ¹⁸O of water in equilibrium with stage I quartz (5.3–7.7‰), δD of water in equilibrium with coexisting muscovite (−16.0‰ to −2.0‰), and sulphide δ³⁴S (1.5–3.6‰) values are compatible with waters that leached metamorphic rocks. The dominant mechanism of the As–(Ag) deposition was mixing and dilution processes between aqueous–carbonic and aqueous fluids for stage I (As–Fe), and nearly isobaric cooling processes for stages II (Zn–Cu–Sn) and III (Pb–Ag). The origin and hydrothermal evolution of As–(Ag) veins is comparable to other hydrothermal Permian events in the Spanish Central System.     

Poly-orogenic multi-stage metamorphic evolution inferred via P–T pseudosections: An example from Aspromonte Massif basement rocks (Southern Calabria, Italy)

The metamorphic evolution of a key sector of the western Mediterranean internal Alpine orogenic belt (southern Calabrian Peloritani Orogen) is identified and described by means of P–T pseudosections calculated for selected metapelite specimens, showing evidence of multi-stage metamorphism.Attention focused on the two lowermost basement nappes of the Aspromonte Massif (southern Calabria), which were differently affected by poly-orogenic multi-stage evolution. After a complete Variscan orogenic cycle, the upper unit (Aspromonte Peloritani Unit) was involved in a late-Alpine shearing event. In contrast, the several underlying metapelite slices, here grouped together as Lower Metapelite Group, show exclusive evidence of a complete Alpine orogenic cycle.In order to obtain reliable P–T constraints, an integrated approach was employed, based on: a) garnet isopleth thermobarometry; and b) theoretical predictions of the P–T stability fields of representative equilibrium assemblages. This approach, which takes into account the role of the local equilibrium volumes in controlling textural developments, yielded reliable information about P–T conditions from early to peak metamorphic stages, as well as estimates of the retrograde trajectory in the pseudosection P–T space.According to inferred detailed P–T paths, the evolution of the Aspromonte Peloritani Unit is characterised by a multi-stage Variscan cycle, subdivided into an early crustal thickening stage with P–T conditions ranging from 0.56 ± 0.05 GPa at 570 ± 10 °C to 0.63–0.93 GPa at 650–710 °C (peak conditions) and evolving to a later crustal thinning episode in lower P–T conditions (0.25 GPa at 540 °C), as documented by the retrograde trajectory.Conversely, the prograde evolution of the rocks of the Lower Metapelite Group shows evidence of a HP-LT early Alpine multi-stage cycle, with P–T evolving from 0.75–0.90 GPa at 510–530 °C towards peak conditions, with pressure increasing northwards from 1.12 ± 0.02 GPa to 1.24 ± 0.02 GPa, and temperatures of 540–570 °C.A late-Alpine mylonitic overprint affected the rocks of both the Aspromonte Peloritani Unit and the Lower Metapelite Group. This overprint was characterised by an initial retrograde decompression trajectory (0.75 ± 0.05 GPa at 570–600 °C), followed by a joint cooling history, ranging from 0.38 ± 0.14 at temperature from 450 to 520 °C.These inferred results were then used: a) to interpret the Lower Metapelite Group as a single crystalline basement unit exclusively affected by a complete Alpine orogenic cycle, according to the very similar features of P–T paths, comparable petrography and analogous structural characteristics; b) as a tool for more reliable correlations between the Aspromonte Massif, the other Calabrian terranes and the north African Orogenic Complexes. They may therefore consider a contribution to the geodynamic modelling of the western Mediterranean.     

P–T–t conditions of high-grade metamorphic rocks of the Garzon Massif, Andean basement, SE Colombia

The metamorphic evolution of the Garzón Massif, Colombia, is established on the basis of the textural, goethermobarometric, and geochronological relationships of the metamorphic minerals. The geothermobarometric data define a clockwise, nearly isothermal decompression path (ITD) for rocks from Las Margaritas migmatites, constrained by four P–T areas: 780–826 °C and 6.3–8.0 kbar, 760–820 °C and 8.0–8.8 kbar, 680–755 °C and 6.6–9.0 kbar, and 630 °C and 4 kbar. For the a garnet-bearing charnockitic gneiss from the Vergel granulites, the path is counterclockwise, constrained by geothermobarometric data of 5.3–6.2 kbar and 700–780 °C and 6.2–7.2 kbar and 685–740 °C. The clockwise ITD path represents a loop followed by the orogen during the transitional granulite–amphibolite metamorphic conditions, probably associated with a subduction process followed by a collisional tectonic event. This subduction framework produced continental crust thickening between 1148 and 1034 Ma and later collision with another continental block approximately 1000 Ma ago. The orogenic exhumation occurred with moderate uplift rate. The counterclockwise trajectory and two metamorphic events suggest a vertical displacement between the Vergel granulites and Las Margaritas migmatites units, because there is no isotopic difference that indicates the existence of different terranes. The data confirm that the metamorphic evolution for this domain was more dynamic than previously believed and includes: (1) metamorphic processes with the generation of new crust with a possible mixture of old material and (2) metamorphic recycling of continental crust. These geological processes characterize a complex Mesoproterozoic orogenic event that shares certain features with the Grenvillian basement rocks participating in the formation of Rodinia.     

Mechanisms of sulfur introduction chemically controlled: δS imprint

Organic sulfur in marine sediment is ³⁴S enriched relative to the co-existing pyrite. This phenomenon is still enigmatic. Timing of the sulfur incorporation, immobilization and different sulfur species involved are part of the explanations. The reduced sulfur species incorporation into organic matter (OM) is generally assumed to have negligible δ³⁴S fractionation. This assumption has never been confirmed by laboratory experimental data. The present study measures the δ³⁴S changes resulting from reduced sulfur species (sulfides and polysulfide anions) incorporation into organic model compounds in an aquatic and low temperature (25 °C) system that simulates diagenetic marine environment. In addition, we also investigate the δ³⁴S fractionation and the isotope chemical mixing in the formation of polysulfide anions produced from elemental sulfur and sulfide anions. The results showed total isotope mixing between the two species in the formation of polysulfides. Acidification of the polysulfides solution caused δ³⁴S fractionation between the released elemental sulfur and H₂S. The incorporation of polysulfides and sulfides into carbonyl groups, caused ³⁴S enrichment relative to the starting polysulfides and sulfide of 4–5‰. The ³⁴S enrichment of the sulfurized carbonyl groups showed a minimal effect by temperature (0–70 °C) and is not affected by salinity, polysulfides composition, reaction time or solubility in water. The incorporation of polysulfides and sulfides into brominated organic compounds was negligibly ³⁴S enriched. The chemical mechanisms controlling the polysulfides incorporation into OM depend mostly on the functional groups and determine the ³⁴S enrichment of the sulfurized OM. The results presented in this study can explain part of the difference between pyrite δ³⁴S and sulfurized OM δ³⁴S in natural marine sediments.     

Geochemistry and stable isotopic composition of tufa waters and precipitates from the Interlake Region, Manitoba, Canada: Constraints on groundwater origin, calcitization, and tufa formation

New major, trace and isotopic geochemical results from a regional study of springs discharging from the major carbonate rock aquifer in the Interlake Region of Manitoba, Canada, are used to understand water–rock reactions, timing of recharge/discharge, tufa formation processes, and as baseline data. Spring waters are fresh with total dissolved solids (TDS) concentrations ranging from 150 to 880 mg/L. Waters discharging in the northern part of the study area have lower TDS, are dominantly Ca–Mg–HCO₃ waters with low SO₄ concentrations (<< 50 mg/L), and appear to have interacted primarily with Silurian carbonate lithologies. In contrast, waters in the southeastern part of the study area have higher TDS and have elevated SO₄ concentrations (up to 210 mg/L). Spring waters have elevated Mg/Ca_molar (1.23 ± 0.23), typically greater than congruent dissolution of dolomite. Ca and Mg concentrations and Mg/Ca_molar indicate that groundwater residence times were sufficient to allow equilibration with bedrock dolomite lithologies; elevated tritium in northern waters indicates a significant recharge component in the 1960's and 1970's. Tufa precipitates that have formed from many of the spring waters are low-Mg calcite (MgO = 1.70 to 5.80 wt.%). Sr concentrations are variable (57 to 657 ppm) and tufa Sr/Ca_molar ratios appear to be entirely controlled by spring water Sr/Ca_molar. Empirically determined Sr distribution coefficients (D_Sr = 0.389 ± 0.083) indicate rapid crystallization following CO₂ degassing, consistent with heavier δ¹³C_VPDB compared to spring waters. Sulfate concentrations are generally too low for calcitization (dedolomitization) reactions driven by anhydrite dissolution to be the dominant control on the elevated groundwater Mg/Ca_molar, implying either extensive sulfate reduction along the flow paths (however, δ¹³C_DIC suggests the elevated SO₄ is more consistent with Fe-sulfide oxidation), or that other processes are involved. Major ion ratios suggest that the waters in the southern part of the study area are more consistent with interaction with siliciclastic rocks than with anhydrite dissolution. We suggest that calcitization (dedolomitization) reactions driven by anhydrite dissolution may not dominate all carbonate aquifers and that mixing of waters in karst conduits combined with ion exchange reactions are important controls on water chemistry in these systems.     

Textures and phase relationships in ferrous granulites from Tidjenouine (Hoggar, Algeria): fayalite–ferrossilite–quartz secondary assemblage

Ferrous granulites in the area of Tidjénouine (Central Hoggar) exhibit a remarkable mineralogical composition characterized by the association orthoferrossilite–fayalite–quartz. These granulites are metamorphosed mafic igneous rocks showing the juxtaposition of different metamorphic parageneses. Peak paragenesis with garnet–clinopyroxene–amphibole–plagioclase–quartz reach to assemblage with orthopyroxene–plagioclase₂. Secondary orthopyroxene reacted with garnet to produce symplectites with fayalite + plagioclase + quartz. The latest stage corresponds to an orthopyroxene–fayalite–quartz–plagioclase assemblage. The metamorphic history of the ferrous granulites is inferred by combining the study of phase relations with the construction of a petrogenetic grid and pseudosection in the CFMASH and CFAS systems using the Thermocalc program of [J. Metamorph. Geol. 6 (1988) 173]. The evolution of paragenetic minerals indicates a metamorphic P–T path through the following conditions: 7.1 ± 1 kbar at 880 °C, 4.9 ± 1.6 kbar at 750 °C and 3–4 kbar at 700 °C, which is consistent with a clockwise P–T path recorded throughout the area.     

Hydrothermal evolution of the Sar-Cheshmeh porphyry Cu–Mo deposit, Iran: Evidence from fluid inclusions

The Sar-Cheshmeh porphyry Cu–Mo deposit is located in Southwestern Iran (65 km southwest of Kerman City) and is associated with a composite Miocene stock, ranging in composition from diorite through granodiorite to quartz-monzonite. Field observations and petrographic studies demonstrate that the emplacement of the Sar-Cheshmeh stock took place in several pulses, each with associated hydrothermal activity. Molybdenum was concentrated at a very early stage in the evolution of the hydrothermal system and copper was concentrated later. Four main vein Groups have been identified: (I) quartz+molybdenite+anhydrite±K-feldspar with minor pyrite, chalcopyrite and bornite; (II) quartz+chalcopyrite+pyrite±molybdenite±calcite; (III) quartz+pyrite+calcite±chalcopyrite±anhydrite (gypsum)±molybdenite; (IV) quartz±calcite±gypsum±pyrite±dolomite. Early hydrothermal alteration produced a potassic assemblage (orthoclase-biotite) in the central part of the stock, propylitic alteration occurred in the peripheral parts of the stock, contemporaneously with potassic alteration, and phyllic alteration occurred later, overprinting earlier alteration. The early hydrothermal fluids are represented by high temperature (350–520 °C), high salinity (up to 61 wt% NaCl equivalent) liquid-rich fluid inclusions, and high temperature (340–570 °C), low-salinity, vapor-rich inclusions. These fluids are interpreted to represent an orthomagmatic fluid, which cooled episodically; the brines are interpreted to have caused potassic alteration and deposition of Group I and II quartz veins containing molybdenite and chalcopyrite. Propylitic alteration is attributed to a liquid-rich, lower temperature (220–310 °C), Ca-rich, evolved meteoric fluid. Influx of meteoric water into the central part of the system and mixing with magmatic fluid produced albitization at depth and shallow phyllic alteration. This influx also caused the dissolution of early-formed copper sulphides and the remobilization of Cu into the sericitic zone, the main zone of the copper deposition in Sar-Cheshmeh, where it was redeposited in response to a decrease in temperature.     

Origins of high pH mineral waters from ultramafic rocks, Central Portugal

This paper reviews the geochemical, isotopic (²H, ¹⁸O, ¹³C, ³H and ¹⁴C) and numerical modelling approaches to evaluate possible geological sources of the high pH (11.5)/Na–Cl/Ca–OH mineral waters from the Cabeço de Vide region (Central-Portugal). Water–rock interaction studies have greatly contributed to a conceptual hydrogeological circulation model of the Cabeço de Vide mineral waters, which was corroborated by numerical modelling approaches. The local shallow groundwaters belong to the Mg–HCO₃ type, and are derived by interaction with the local serpentinized rocks. At depth, these type waters evolve into the high pH/Na–Cl/Ca–OH mineral waters of Cabeço de Vide spas, issuing from the intrusive contact between mafic/ultramafic rocks and an older carbonate sequence. The Cabeço de Vide mineral waters are supersaturated with respect to serpentine indicating that they may cause serpentinization. Magnesium silicate phases (brucite and serpentine) seem to control Mg concentrations in Cabeço de Vide mineral waters. Similar δ²H and δ¹⁸O suggest a common meteoric origin and that the Mg–HCO₃ type waters have evolved towards Cabeço de Vide mineral waters. The reaction path simulations show that the progressive evolution of the Ca–HCO₃ to Mg–HCO₃ waters can be attributed to the interaction of meteoric waters with serpentinites. The sequential dissolution at CO₂ (g) closed system conditions leads to the precipitation of calcite, magnesite, amorphous silica, chrysotile and brucite, indicating that the waters would be responsible for the serpentinization of fresh ultramafic rocks (dunites) present at depth. The apparent age of Cabeço de Vide mineral waters was determined as 2790 ± 40 a BP, on the basis of ¹⁴C and ¹³C values, which is in agreement with the ³H concentrations being below the detection limit.     

Heat flow, heat production and fission track data from the Hercynian basement around the Provençal Basin (Western Mediterranean)

In the complex structural framework of the Western Mediterranean. Hercynian areas are expected to be thermally preserved from the recent tectonic evolution. The thermal regime of these areas is studied using heat flow, heat production and fission track data. The surface heat flow is significantly higher in Corsica (76 ± 10 mW m⁻²) than in the Maures and Estérel (58 ± 2 mW m⁻²). Neither heat production nor erosion subsequent to the Alpine orogeny in Corsica can explain such a difference. It is suggested that a deep thermal source related to the asymmetric evolution of the Provençal basin could explain the higher heat flow in Corsica. A model of thermal structure based on the present day thermal regime of the Maures and Estérei is proposed for the stable Hercynian crust in this area. The mantle heat flow is 20–25 mW m⁻² and the temperature at Moho level is 375–500°C, depending on the thermal parameter distribution with depth.     

Biomarker transformations as constraints for the depositional environment and for maximum temperatures during burial of Opalinus Clay and Posidonia Shale in northern Switzerland

Samples from two argillaceous formations (Opalinus Clay and Posidonia Shale) of near-identical maturity from northern Switzerland were subjected to a geochemical characterisation of organic matter and to confined-system pyrolysis experiments. Throughout the study area, the characteristics of organic matter are similar, indicating a spatially homogeneous sedimentary facies. Posidonia Shale contains marine organic matter deposited in a reducing environment, while a predominantly terrigenous source and a more oxidising environment of deposition was identified for Opalinus Clay. In the western and central parts of the study area, organic maturity is close to the onset of oil generation. In the easternmost part, a higher maturity has been reached due to a deeper burial below thick Tertiary Molasse deposits.Isothermal pyrolysis experiments were conducted at temperatures between 250 and 390 °C over 24 h. Bitumen yields increase along similar pathways for both Opalinus Clay and Posidonia Shale, but the maximum values are displaced by 10–20 °C. Data pertaining to maturity were determined from GC–MS analyses of saturated hydrocarbons, and specific attention was given to C₂₉-sterane and C₃₂-hopane isomerisation ratios. The evolution of these parameters with rising temperature is slightly different in the two formations, which is attributed to the contrasting organic facies. The pyrolysis data, together with literature data from natural basins, were used to calculate kinetic parameters for C₂₉-sterane and C₃₂-hopane, assuming a single-step isomerisation scheme according to the Arrhenius law. The resulting values based on pyrolysis data alone are very similar to those based on the combination of pyrolysis and natural data. Activation energies are similar in both formations, while the frequency factors are up to one order of magnitude higher for Posidonia Shale when compared to Opalinus Clay. For the Benken site, maximum temperature during Cretaceous burial was calculated on the basis of the kinetic data, using the TTI approach. The resulting temperatures of 75–80 °C are 5–10 °C below those derived in the literature from apatite fission-track analysis, vitrinite reflectance and basin modelling.     

Decompression reactions and P–T conditions in high-pressure granulites from Casares-Los Reales units of the Betic-Rif belt (S Spain and N Morocco)

High-pressure granulites are exposed in the Casares-Los Reales group (internal zones of Betic-Rif belt, S Spain–N Morocco) as part of the crustal envelope of Beni Bousera-Ronda Peridotites. They are mostly metapelitic but include intercalations of mafic composition. The metamorphic history is marked by the preservation of early high-pressure assemblages together with secondary low-pressure assemblages suggesting a state of textural and compositional disequilibrium. The P–T path constrained by geothermobarometry and reaction textures from mafic and pelitic lithotypes passes from 800 °C/15 kbar to 600 °C/5 kbar, to indicating a strong decompression related to cooling, followed by a near-isobaric cooling 430 °C and 4 kbar. Such P–T evolution of granulites is thought to reflect some sort of rapid tectonic collapse of crust previously thickened through collision.     

Reaction textures in Proterozoic calcsilicates from northern Guinea: a record of the fluid evolution

Proterozoic calcsilicate rocks in contact with the different types of granite from the granitic belt of northern Guinea show particular mineral assemblages, recording different steps of the tectono-metamorphic and magmatic evolution of the area. Petrological study provides evidence of a clockwise metamorphic P–T path with a metamorphic peak at temperature around 800 °C and pressure of 4–6 kb, corresponding to the emplacement of both generations of massive granite between 2115 and 2075 Ma. Retrograde metamorphism is characterized by decompression to 2–3 kb, associated with the emplacement of late small granite stocks and followed by cooling until 450–600 °C. Hydrothermal alteration involved by late fluid circulation is only weakly developed and limited to calcsilicate/granite contact (specially small stocks) and shear zones. Early fluids were essentially metamorphic and magmatic fluids, largely buffered by calcsilicate mineral assemblages, whereas surface-derived fluids were introduced at the end of the tectonic evolution via shear-zones.     

Dissolution kinetics of probertite in boric acid solution

Probertite (NaCaB₅O₉·5H₂O) and ulexite (NaCaB₅O₉·8H₂O) posses identical chemical formula except for their water content. In this study, the dissolution of probertite in boric acid solution was investigated as a function of temperature and time. As the boric acid concentration increased, the dissolution of probertite also increased. However, the boric acid concentrations above 5 wt.% at 60 °C and 80 °C did not significantly affect the dissolution of probertite. The stirring speed had almost no effect on the dissolution of probertite. The dissolution kinetics of probertite in boric acid solution was controlled by first order pseudo homogeneous reaction. The activation energies for different probertite particle sizes varied from 25.25 kJ/mol K to 28.25 kJ/mol K, indicating that particle size had minor effect on the dissolution of probertite.