Fluid migration at the basement/sediment interface along the margin of the Southeast basin (France): implications for Pb–Zn ore formation

This study investigates the isotopic composition (C, O, S and Sr) of carbonates, sulphates and sulphide cements in the rock matrix and fracture fillings in geological formations of the Southeast basin of France, using core samples collected during the Deep Geology of France programme (GPF Ardèche theme). The Southeast basin belongs to the Alpine Tethyan margin. It is one of the thickest sedimentary basins in Europe, reaching upwards of 9 km in certain locations. The main fluid transfer from the basin is related to the large Pb–Zn Mississippi Valley-type district along the southern margin of the Massif Central block. A synthesis of the tectonic, mineralogical and petrographic investigations on the GPF boreholes shows that a major fluid circulation event occurred across the Alpine margin of Tethys during the Early Jurassic (Hettangian–Bathonian). It produced a general cementation of the rock porosity through precipitation of dolomite, sulphate and barite. Fracture fillings yield isotopic signatures distinct from the matrix cements. Matrix cements have particular characteristics, i.e. δ³⁴S and δ¹³C that agree with a marine origin. The δ³⁴S values of Permo-Carboniferous to Triassic sulphides from fracture cements are interpreted as resulting from the thermo-chemical reduction of sulphates. Fracture sulphates in the same geological formations yield δ³⁴S values that define a relatively homogeneous end-member, whose composition is similar to sulphates in the Largentière Pb–Zn ore deposit. The source of S is attributed to the Permo-Carboniferous succession. The borehole fracture fillings are attributed to a major fluid circulation stage compatible with the Early Jurassic stage identified from the geological investigation of the boreholes. The formation of the Largentière deposit is considered as resulting from the mixing of this Early Jurassic fluid with continental hydrothermal fluids circulating in a basement horst, along its margin with the sedimentary basin. Other Pb–Zn deposits may also be related to fluid migration along the basement/sedimentary cover interface in the eastern and western parts of the Massif Central. This regional fluid circulation event may represent a geodynamic marker of the Jurassic extensional phase.     

Episodic mineralization of hydrothermal illite in the Soultz-sous-Forêts granite (Upper Rhine Graben, France)

Episodic and localized illite mineralization is documented in the hydrothermally altered Soultz-sous-Forêts granite (Upper Rhine Graben, France). Separated grain-size fractions of altered granite and argillite vein samples contain mixtures of 2M₁ and 1M trans-vacant illite varieties. The platy pseudohexagonal 2M₁ illite phases dominate the vein fillings, whereas the 1M illite occurs largely as a fibrous pore-filling variety, which is particularly abundant in the granite matrix. Multiple phases of fluid injections into the granite body have resulted in different illite assemblages, each sample containing a mixture of polytype generations formed during different crystal growth events. On the basis of mineralogical and K–Ar isotopic constraints, the ages of these vein-mineralizing events are determined by plotting the K–Ar values of the various grain-size fractions against polytype abundance and the fitted volume-weighted crystallite thickness distributions. The results suggest a Permian age for the formation of the studied argillite veins, characterized by successive injections of hydrothermal fluids. Secondary episodes of illite crystallization occurred during Jurassic and Cretaceous (or even younger times) in both the veins and the granite matrix. There are indications that the polytype structure and composition of illite were strongly influenced by variations in fluid chemistry and the degree of fluid–rock interaction as the granite was progressively sealed during post-Variscan, episodic hydrothermal activity.     

Geochemistry of highly saline fluids in siliciclastic sequences: genetic implications for post-Variscan fluid flow in the Moravosilesian Palaeozoic of the Czech Republic

Ubiquitous post-Variscan dolomites occur in Zn–Pb–Cu veins at the Nízký Jeseník Mountains and the Upper Silesian Basin (Lower and Upper Carboniferous siliciclastics at the eastern part of the Bohemian Massif). Crush–leach, stable isotope (oxygen and carbon) and microthermometry analysis of the fluid inclusions in dolomites enable understanding the geochemistry, origin and possible migration pathways of the fluids. Homogenisation temperatures of fluid inclusions range between 66 and 148°C, with generally higher temperatures in the Nízký Jeseník Mountains area than in the Upper Silesian Basin. The highest homogenisation temperatures (up to 148°C) have been found near major regional faults and the lowest in a distant position or at higher stratigraphic levels. Highly saline (16.6–28.4 eq. wt% NaCl) H₂O–NaCl–CaCl₂ ± MgCl₂ fluids occur in inclusions. Na–Cl–Br systematics of trapped fluids and a calculated oxygen isotopic fluid composition between ?0.9 and +3.0‰ V-SMOW indicate that the fluid was derived from evaporated seawater. Stable isotopic modelling has been used to explain stable isotopic trends. Isotopic values (δ¹³C = ?6.0/+2.0‰ V-PDB, δ¹⁸O = +15.5/+22.5‰ V-SMOW of dolomites) resulted from fractionation and crystallisation within an open system at temperatures between 80 and 160°C. Rock-buffering explains the isotopic composition at low w/r ratios. Organic matter maturation caused the presence of isotopically light carbon in the fluids and fluid–rock interactions largely controlled the fluid chemistry (K, Li, Br and Na contents, K/Cl, I/Cl and Li/Cl molar ratios). The fluid chemistry reflects well the interaction between the fluid and underlying limestones as well as with clay- and organic-rich siliciclastics. No regional trends in temperature or fluid geochemistry favour a fluid migration model characterised by an important vertical upward migration along major faults. A permeable basement and fractured sedimentary sequence enhanced the general nature of the fluid system. Fluid characteristics are comparable with the main post-Variscan fluid flow systems in the Polish (Cracow-Silesian ore district) and German sedimentary basins.     

Permian tectonic evolution of the Mudanjiang Ocean: Evidence from zircon U-Pb-Hf isotopes and geochemistry of a N-S trending granitoid belt in the Jiamusi Massif,NE China

A combined study of LA-ICP-MS zircon U-Pb dating and geochemical analyses (major and trace elements, and Hf isotopic compositions) for five Permian granitic plutons (Mingyi, Tuoyaozi, Mengjiagang, Hengtoushan, and Qingbei plutons) from the Jiamusi Massif was carried out to determine their ages, petrogenesis, and tectonic evolution. The studied granitic plutons are composed of syengranites, monzogranites, and granodiorites, and they were emplaced in the Early-Middle Permian (278–263 Ma). These granitic plutons are mostly high-K calc-alkaline and weakly peraluminous, and show consistent correlations of different oxides versus SiO₂. They are all enriched in large ion lithophile elements (e.g., Rb, Th, K) and light rare earth elements, and depleted in high field strength elements (e.g., Nb, Ta, Ti) and heavy rare earth elements. And they have relatively homogeneous Hf isotopic compositions, with εHf(t) values varying from − 6.16 to + 2.95 and two-stage model ages ranging from 1681 to 1111 Ma. According to their emplacement ages, geochemical characteristics, and Hf isotopic compositions, we conclude that these granitoids might be originated from parental magmas with similar compositions but evolved different degrees of fractionation, and their magmas were derived from the partial melting of amphibolite-facies mafic lower crust. These data, combined with previous studies on contemporaneous magma-tectonic activities in the Jiamusi Massif and Songnen-Zhangguangcai Range Massif, indicate that two paralleled N-S trending Permian magmatic belts are distributed in these two massifs. The eastwards subduction of the Mudanjiang oceanic plate beneath the Jiamusi Massif induced crustal melting to produce the studied Permian N-S trending granitoids in the Jiamusi Massif. Furthermore, westwards subduction of the Mudanjiang oceanic plate beneath the Songnen-Zhangguangcai Range Massif gave rise to Permian magmatism along eastern margin of the Songnen-Zhangguangcai Range Massif. Taken together, we suggest that the Jiamusi Massif and Songnen-Zhangguangcai Range Massif were not collided before the Permian, and a double-side subduction model is favored for the tectonic evolution of the Mudanjiang Ocean during the Permian.     

Evolution of gas and aqueous fluid in low-permeability argillaceous rocks during uplift and exhumation of the central Swiss Alps

Fluid chemistry and the hydraulic regime in a marl formation of the Swiss Alps were studied by a number of techniques. Fluid inclusions record the conditions of maximum burial and regional low-temperature metamorphism, whereas fluid samples and hydraulic tests derived from deep boreholes reflect present-day, near-surface conditions. The characterization of the different types of fluids places constraints on the geochemical and hydraulic evolution of low-permeability argillaceous rocks during uplift and exhumation.Fluid inclusions were studied by microthermometry and sampled directly by decrepitation techniques. They contain a two-phase system consisting of an aqueous fluid and a coexisting CH₄-rich gas (T=190–250°C, P_lith≈2500 bar). Bulk and isotopic compositions of aqueous fluid inclusions are consistent with a mixture of connate seawater and water derived from the dehydration of clay minerals. Methane was generated in situ by thermal cracking of kerogen. Textural evidence and stable isotopic signatures of carbonates in veins and in the rock matrix indicate local buffering of fluid compositions and very low water/rock ratios. Free fluids residing in the present-day fracture and matrix porosity consist of CH₄-saturated Na–Cl groundwater with minute amounts of free CH₄ gas which occurs in druses. Their chemical and isotopic compositions are very similar to those of the fluid inclusions, suggesting a common origin. Post-metamorphic admixtures of externally derived waters cannot be identified, and it is suggested that present-day Na–Cl groundwaters that occur in the central parts of the marl have resided in the formation since the time of metamorphism some 20 Ma b.p. The only major change in the fluid composition has been the outgassing of CH₄ from the formation, most probably by diffusion.The hydraulic regime during metamorphism was characterized by localized fluid underpressures in open veins because widely scattered, sub-hydrostatic pressures were often identified in fluid inclusions. The central part of the argillaceous rock body, approximately coinciding with the region where Na–Cl groundwaters occur, has sub-hydrostatic pressures today, as indicated by hydraulic tests in deep boreholes.Both the closed-system behavior derived from the chemical and isotopic characteristics of the fluids and the (recurrent or continuous) existence of hydraulic underpressures suggest very low permeabilities of argillaceous rocks during metamorphism and throughout subsequent uplift and exhumation. All fluids present in the central parts of the formation are either connate or produced in situ. Even though major events of brittle faulting and unloading due to uplift occurred since the peak of metamorphism, fluid flow through the formation has been negligible.     

On the origin of saline fluids in the KTB (continental deep drilling project of Germany)

Highly saline fluids were encountered during the German Continental Deep Drilling Project (KTB) from depths ranging between 2 and 3 km to about 9 km. The most reliable data were obtained from samples extracted during a long-term pumping test in the 4000-m deep KTB pilot hole. Some 460 m³ CaNaCl brines with about 68 g l⁻¹ total dissolved solids (TDS) and some 270 m³ associated gases, mainly N₂ and CH₄ were pumped to the surface from the main fracture system situated near the bottom of the pilot hole. Geochemical and isotopic data support the hydraulic tests which suggest the presence of an open and large fluid reservoir at depth. The pumped fluids from this main fracture system were released from a deep reservoir situated at more than 5500 m depth which is hydraulically connected with the 9101 m deep KTB main hole, drilled some 250 m to the northeast of the pilot hole.While Ca and Sr contents of the extracted brines may be the result of water-rock interaction, Cl is most likely of external origin. The Cl is hypothesized to derive from geotectonic processes rather than to descending infiltration of paleo-seawater (evaporitic brines). The sampled fluids have probably migrated from a deeper reservoir to their present position since the Cretaceous-Tertiary period due to tectonic activity. However, several isotopic studies have identified an admixture of descending paleowaters down to more than 4000 m depth. The high ³⁶ClCl ratio of the fluids sampled during the long-term pumping test point to a host rock highly enriched in UTh, unlike the sampled KTB country rocks. The fluid reservoir is believed to be in contact with the Falkenberg granite massif situated about 2 km to the E of the KTB holes capable of supplying sufficient neutron flux for considerable subsurface production of 36C1. The NaCl(K, SO₄) precursor fluids of the CaNaCI brines were produced in the course of extensive tectonic processes since the Late Caledonian within the Bohemian Massif.     

Insights to magmatic-hydrothermal processes in the Manus back-arc basin as recorded by anhydrite

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REE_N patterns measured in anhydrite from mid-ocean ridge deposits. The REE_N patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. ⁸⁷Sr/⁸⁶Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate δ³⁴S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate δ³⁴S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO₂ degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.     

Origin of the Okrouhlá Radouň episyenite-hosted uranium deposit,Bohemian Massif,Czech Republic: fluid inclusion and stable isotope constraints

The Okrouhlá Radouň shear zone hosted uranium deposit is developed along the contact of Variscan granites and high-grade metasedimentary rocks of the Moldanubian Zone of the Bohemian Massif. The pre-ore pervasive alteration of wall rocks is characterized by chloritization of mafic minerals, followed by albitization of feldspars and dissolution of quartz giving rise to episyenites. The subsequent fluid circulation led to precipitation of disseminated uraninite and coffinite, and later on, post-ore quartz and carbonate mineralization containing base metal sulfides. The fluid inclusion and stable isotope data suggest low homogenization temperatures (～50–140 °C during pre-ore albitization and post-ore carbonatization, up to 230 °C during pre-ore chloritization), variable fluid salinities (0–25 wt.% NaCl eq.), low fluid δ¹⁸O values (?10 to +2 ‰ V-SMOW), low fluid δ¹³C values (?9 to ?15 ‰ V-PDB), and highly variable ionic composition of the aqueous fluids (especially Na/Ca, Br/Cl, I/Cl, SO₄/Cl, NO₃/Cl ratios). The available data suggest participation of three fluid endmembers of primarily surficial origin during alteration and mineralization at the deposit: (1) local meteoric water, (2) Na–Ca–Cl basinal brines or shield brines, (3) SO₄–NO₃–Cl–(H)CO₃ playa-like fluids. Pre-ore albitization was caused by circulation of alkaline, oxidized, and Na-rich playa fluids, whereas basinal/shield brines and meteoric water were more important during the post-ore stage of alteration.     

Origin and migration of palaeofluids in the Upper Visean of the Campine Basin, northern Belgium

Upper Visean limestones in the Campine Basin of northern Belgium are intensively fractured. The largest and most common fractures are cemented by non-ferroan, dull brown-orange luminescent blocky calcite. First melting temperatures of fluid inclusions in these calcites are around -57°C, suggesting that precipitation of the cements occurred from NaCl-CaCl₂-MgCl₂ fluids. The final melting temperatures (T_m^ice) are between -5 and -33°C. The broad range in the T_m^ice data can be explained by the mixing of high salinity fluids with meteoric waters, but other hypotheses may also be valid. Homogenization temperatures from blocky calcite cements in the shelf limestones are interpreted to have formed between 45 and 75°C. In carbonates which were deposited close to and at the shelf margin, precipitation temperatures were possibly in the range 70-85°C and 72-93°C, respectively. On the shelf, the calcites have a δ¹⁸O around -9.3‰ PDB and they are interpreted to have grown in a fluid with a δ¹⁸O between −3.5 and +1.0‰ SMOW. At the shelf margin, blocky calcites (δ¹⁸O∼ - 13.5‰ PDB) could have precipitated from a fluid with a δ¹⁸O betweenn -4.0 and -1.1‰ SMOW. The highest oxygen isotopic compositions are comparable to those of Late Carboniferous marine fluids (δ¹⁸O= - 1‰ SMOW). The lowest values are more positive than a previously reported composition for Carboniferous meteoric waters (δ¹⁸O= -7‰ SMOW). Precipitation is likely to have occurred in marine-derived fluids, which mixed with meteoric waters sourced from near the Brabant Massif. Fluids with a similar negative oxygen isotopic composition and high salinity are actually present in Palaeozoic formations. The higher temperature range in the limestones near the shelf margin is explained by the upward migration of fluids from the ‘basinal’ area along fractures and faults into the shelf.     

Incipient metamorphism and deformation in the Variscides of SW Dyfed, Wales: first steps towards isotopic equilibrium

Incipient metamorphism accompanying thrusting, folding and cleavage development has been investigated in a varied sequence of Palaeozoic sediments near the Variscan front in SW Dyfed, Wales. The aim was to evaluate a critical stage in the progression from heterogeneous sediment, whose detrital phases are neither in equilibrium with one another, nor with pore fluids, through indurated sedimentary rock to metamorphic rock comprising newly formed crystals that equilibrated with one another as they grew. Quartz veins are widely developed in the area, especially in the more psammitic lithologies, while finer grained rocks became cleaved during tectonic deformation. Mineralogical constraints and fluid inclusion measurements suggest maximum temperatures around 200-310d? C (slightly higher in the Marloes-Musselwick Thrust Sheet than in other parts of the structural succession) at depths of the order of 6-13 km. Quartz veins yield distinctly heavier oxygen isotopic compositions than detrital quartz grains in the adjacent wall rocks, although care must be taken in interpreting the data because slivers of detrital grains may become incorporated into veins, while matrix detrital grains may incorporate veinlets or rims of newly formed quartz. It is concluded that vein quartz grew in isotopic equilibrium with a fluid phase whose isotopic composition was primarily controlled by exchange with phyllosilicates, not detrital quartz grains. Vein and matrix quartzes from the Marloes-Musselwick Thrust Sheet are distinctly lighter (δ¹⁸O_veins=+14 to +18% and δ¹⁸O_matrix=+11 to +14%) than those from other thrust sheets (δ¹⁸O =+17 to +20% and +14 to +17%, respectively). We conclude that vein quartz and phyllosilicate grains in cleavage domains probably attained equilibrium with a locally buffered pore fluid at the peak of metamorphism, but many relict grains of different chemical and isotopic composition remained elsewhere in the rock. Local fluid migration along veins and through cleavage lamellae facilitated the attainment of equilibrium, but there is little evidence for large-scale infiltration of externally derived fluids. With further metamorphism the quartz in these rocks would attain an isotopic composition intermediate between that of the heavy vein material and light detritus which coexist here.     

Geochemical constraints for the origin of thermal waters from western Turkey

The combined chemical composition, B and Sr isotopes, and the basic geologic setting of geothermal systems from the Menderes Massif in western Turkey have been investigated to evaluate the origin of the dissolved constituents and mechanisms of water–rock interaction. Four types of thermal water are present: (1) a Na–Cl of marine origin; (2) a Na–HCO₃ type with high CO₂ content that is associated with metamorphic rocks of the Menderes Massif; (3) a Na–SO₄ type that is also associated with metamorphic rocks of the Menderes Massif with H₂S addition; and (4) a Ca–Mg–HCO₃–SO₄ type that results from interactions with carbonate rocks at shallow depths. The Na–Cl waters are further subdivided based on Br/Cl ratios. Water from the Cumalı Seferihisar and Bodrum Karaada systems are deep circulated seawater (Br/Cl=sea water) whereas water from Çanakkale–Tuzla (Br/Cl<sea water) are from dissolution of Messinian evaporites. Good correlations between different dissolved salts and temperature indicate that the chemical composition of the thermal waters from non-marine geothermal systems is controlled by: (1) temperature dependent water–rock interactions; (2) intensification of reactions due to high dissolved CO₂ and possibly HCl gasses; and (3) mixing with overlying cold groundwater. All of the thermal water is enriched in B. The B isotopic composition (δ¹¹B=2.3‰ to 18.7‰; n=6) can indicate either leaching of B from the rocks, or B(OH)₃ degassing flux from deep sources. The large ranges in B concentrations in different rock types as well as in thermal waters from different systems suggest the water-rock mechanism. ⁸⁷Sr/⁸⁶Sr ratios of the thermal water are used to differentiate between solutes that have interacted with metamorphic rocks (⁸⁷Sr/⁸⁶Sr ratio as high as 0.719479) and carbonate rocks (low ⁸⁷Sr/⁸⁶Sr ratio of 0.707864).     

The temporal evolution of fluid flow through the Tahiti barrier reef traced by Sr isotopes and pore water chemistry

The internal fluid circulation of the Tahiti barrier reef has been studied with Sr isotopes and pore water chemistry. The study is based on 15 sample series recovered over 2 years from a 150-m deep core drilled through the entire barrier reef down to the volcanic basement.Temperature data suggest that the interstitial fluids originate from seawater that penetrated the volcanic basement to at least 200 m depth on the ocean-sided slope below the barrier reef. Subsequently, the fluids migrated upward driven by buoyancy through the entire reef.Chemical evolution of the interstitial fluids is mainly controlled by basalt–seawater interaction and by admixture of seawater from the open ocean during upward migration. These processes are monitored with ⁸⁷Sr/⁸⁶Sr isotope ratios, H₄SiO₄ concentrations and alkalinity to give a picture of the evolution of interstitial fluid flow over 2 years. The results indicate that the internal circulation patterns change through time. The modifications concern mainly the residence time of the fluids within the volcanics and the intensity and localization of lateral seawater admixture within the karstified Pleistocene reef.     

Tectonic affinity of the Khanka Massif in the easternmost Central Asian Orogenic Belt: evidence from detrital zircon geochronology of Permian sedimentary rocks

ABSTRACT

The tectonic affiliation of the Khanka Massif, in the easternmost section of the Central Asian Orogenic Belt (CAOB), is still a matter of debate. Here, we provide new constraints on the provenance and timing of deposition of Permian strata in the western margin of the Khanka Massif. The results, which include U–Pb dating of detrital zircon grains using laser ablation–inductively coupled plasma–mass spectrometry (LA-ICP-MS), provide evidence regarding the tectonic position of the Khanka Massif and its role in the late Palaeozoic evolution of the eastern CAOB. Detrital zircon grains from a sublitharenite (Pingyangzhen Formation), a litharenite (Liangzichuan Formation), and a metamorphic siltstone (Qinglongcun Group) yielded multiple age populations ranging from Neoproterozoic (~914 Ma) to Permian (~272 Ma). Combined with age constraints from overlying/late-stage igneous rocks and other magmatism of the Khanka Massif, we conclude that the dated strata were deposited during the early–middle Permian and were sourced from the Khanka Massif. A comparison between the detrital zircon age populations and the history of magmatic activity in the neighbouring areas suggests that the Khanka Massif was tectonically linked to the Songnen–Zhangguangcai Range Massif. Based on tectonic discrimination diagrams, we conclude that the western margin of the Khanka Massif was positioned in a convergent-boundary basin during the early–middle Permian. Strike-slip faulting along the Dunhua–Mishan Fault, in response to ridge subduction of the Paleo-Asian Ocean Plate, resulted in a north-eastward movement of the Khanka Massif. The occurrence of Precambrian detrital zircon grains (with ages of 1900–1700 and 900–700 Ma) implies the presence of an ancient basement within the Khanka Massif.     

On the origin of saline fluids in the KTB (Continental Deep Drilling Project of Germany)

Highly saline fluids were encountered during the German Continental Deep Drilling Project (KTB) from depths ranging between 2 and 3 km to about 9 km. The most reliable data were obtained from samples extracted during a long-term pumping test in the 4000-m deep KTB pilot hole. Some 460 m³ Ca–Na–Cl brines with about 68 g l⁻¹ total dissolved solids (TDS) and some 270 m³ associated gases, mainly N₂ and CH₄ were pumped to the surface from the main fracture system situated near the bottom of the pilot hole. Geochemical and isotopic data support the hydraulic tests which suggest the presence of an open and large fluid reservoir at depth. The pumped fluids from this main fracture system were released from a deep reservoir situated at more than 5500 m depth which is hydraulically connected with the 9101 m deep KTB main hole, drilled some 250 m to the northeast of the pilot hole.While Ca and Sr contents of the extracted brines may be the result of water–rock interaction, Cl is most likely of external origin. The Cl is hypothesized to derive from geotectonic processes rather than to descending infiltration of paleo-seawater (evaporitic brines). The sampled fluids have probably migrated from a deeper reservoir to their present position since the Cretaceous–Tertiary period due to tectonic activity. However, several isotopic studies have identified an admixture of descending paleowaters down to more than 4000 m depth. The high ³⁶Cl/Cl ratio of the fluids sampled during the long-term pumping test point to a host rock highly enriched in U–Th, unlike the sampled KTB country rocks. The fluid reservoir is believed to be in contact with the Falkenberg granite massif situated about 2 km to the E of the KTB holes, capable of supplying sufficient neutron flux for considerable subsurface production of ³⁶Cl. The Na–Cl–(K-, SO₄) precursor fluids of the Ca–Na–Cl brines were produced in the course of extensive tectonic processes since the Late Caledonian within the Bohemian Massif.     

Evolution of mass-transfer during progressive oblique under-thrusting of the Variscan foreland: eastern Bohemian Massif

Abstract

Four ductile shear zones were sampled in the autochthonous Thaya basement and the Upper Bíte? nappe (Moravian unit) at the Eastern margin of the Bohemian massif. In both studied units, the tectono-metamorphic evolution and the chemical mass transfer are different. Two deformational events are recognised: the first deformation stage under amphibolite facies conditions is overprinted by a second event under greenschist facies conditions.

The first deformation affected the western margin of the Thaya basement and the whole Bíte? nappe: microstructures are characterised by dynamic recrystallisation of feldspars and quartz, and occurrence of myrmekites and grain-boundary migration of quartz. None or weak chemical mass transfer is related to this medium to high temperature deformation. This deformation corresponds to the thrusting of Moldanubdian units on the Brunovistulian units (Moravian nappes and autochthonous Thaya basement).

The second deformation generated shear zones in the until then preserved Thaya basement and reactivated both shear zones of the western margin of the Thaya basement and those of the Bíte? nappe. This deformation is retrograde and mainly associated with chemical mass transfer: a decrease of CaO, FeO, FeO/Fe₂O₃ and an increase of MgO, K₂O and H₂O. These chemical changes are related to greenschist metamorphic reactions leading to the destabilisation of feldspars and the crystallisation of white micas and Ca-silicates. The large chemical mass transfer is associated with the circulation of a large volume of fluids. A model of progressive fluid circulation correlated with Variscan prograde and retrograde metamorphism during the collision of Moldanubian and Brunovistulian units is proposed.     

兴蒙造山带南缘东段和龙地区Ⅰ型花岗岩锆石U-Pb定年、地球化学特征及其地质意义

本文对兴蒙造山带南缘东段和龙地区八家子岩体和勇新岩体进行了岩相学、地球化学、LA-ICP-MS U-Pb定年和Sr-Nd同位素研究,以便制约该区的区域构造演化。锆石测年结果显示,八家子石英闪长岩结晶年龄为257.8±0.9Ma,形成于晚二叠世早期,勇新二长花岗岩的结晶年龄为243.2±1.1Ma和238.5±2.8Ma,形成于中三叠世。八家子石英闪长岩为钠质钙碱系列、偏铝质的Ⅰ型花岗岩类,富集轻稀土(LREEs)和大离子亲石元素(LILEs,Cs、Ba、K和Sr),亏损重稀土(HREEs)和高场强元素(HFSEs,Nb、Ta和P),结合Sr-Nd同位素特征显示其为壳源成因,形成于俯冲环境下,是玄武质下地壳部分熔融的产物。勇新二长花岗岩富硅、铝和钾,为高钾钙碱性系列、偏铝质-弱过铝质的Ⅰ型花岗岩,富集轻稀土(LREEs)及大离子亲石元素(LILEs,Cs、K、Sr),亏损重稀土(HREEs)和高场强元素(HFSEs,Nb、Ta、P和Ti),结合Sr-Nd同位素特征显示其为壳源成因,形成于同碰撞环境下,是玄武质下地壳部分熔融的产物。花岗岩的侵位反映了研究区晚二叠世早期古亚洲洋板块俯冲于华北克拉通之下,中三叠世华北克拉通与兴凯地块碰撞拼合,说明古亚洲洋应闭合于晚二叠世末期-早三叠世期间。     

华北板块北缘东段二叠纪的构造属性:来自火山岩锆石U-Pb年代学与地球化学的制约

本文对华北板块北缘东段大河深组、关门咀子组火山岩进行了锆石LA-ICP-MSU-Pb定年和岩石地球化学研究以便制约该区的区域构造演化。大河深组和关门咀子组火山岩中的锆石均呈自形-半自形晶,具有清晰的岩浆振荡生长环带和条痕状吸收(玄武安山岩)的特点,其Th/U比值高达0.31～1.56,表明其岩浆成因。测年结果表明,桦甸大河深组流纹岩形成于早二叠世(279±3Ma～293±2Ma),珲春和图们关门咀子组玄武安山岩和玄武岩分别形成于早二叠世(275±7Ma)和晚二叠世(250±5Ma)。大河深组火山岩SiO2含量介于64.9%～75.4%,Mg#值介于0.21～0.57,属于中钾-高钾钙碱性系列,明显富集轻稀土元素(LREEs)和大离子亲石元素(LILEs)、亏损高场强元素(HFSEs,如Nb、Ta、Ti)以及P元素,类似活动大陆边缘火山岩;其锆石的εHf(t)值为+0.9～+10.37,Hf同位素二阶段模式年龄值为785～1240Ma,表明它们均起源于中-新元古代新增生玄武质下地壳的部分熔融。珲春早二叠世关门咀子组属于中钾钙碱性系列;贫硅(53.4%～53.7%)和HFSEs,富铝(16.4%～16.8%)和LILEs,具有较低的稀土元素总量,以及较平坦的稀土配分型式,显示出岛弧火山岩的地球化学属性;该组火山岩的原始岩浆应起源于受俯冲板片脱水熔融交代的亏损地幔楔。图们晚二叠世关门咀子组玄武岩SiO2含量为48.7%～49.6%,Mg#值高达0.64～0.72,相对富集LREEs和LILEs,亏损HREEs和HFSEs,具有火山弧玄武岩的地球化学属性,同时其εNd(t)=+6.01,暗示其原始岩浆起源于亏损的岩石圈地幔。综上所述,我们认为早二叠世至晚二叠世期间,华北板块北缘东段(吉林中部地区)和兴凯地块西南缘均处于古亚洲洋的俯冲作用下。     

Rare earth elements,neodymium and strontium isotopic systematics in mineral waters: evidence from the Massif Central,France

Rare Earth Elements (REEs), and Sr and Nd isotope distributions, have been studied in mineralized waters from the Massif Central (France). The CO₂-rich springs are characterized by a neutral pH (6–7) associated with total dissolved solids (TDS) from 1 to 7 g l⁻¹. The waters result from the mixing of very mineralized water pools, thought to have equilibrated at a temperature of around 200°C with superficial waters. These two mineral water pools evidenced by Sr isotopes and dissolved REEs could reflect 2 different stages of water–rock interaction and an equilibrium with different mineral assemblages.The concentrations of individual dissolved REEs and total dissolved REEs (ΣREE), in the mineral waters examined, vary over several orders of magnitude but are not dependent on the main parameters of the waters (TDS, T°C, pH, Total Organic C). The dissolved REE concentrations presented as upper continental crust normalized patterns show HREE enrichment in most of the samples. The time evolution of REE patterns does not show significant fluctuations except in 1 borehole, located in the Limagne d’Allier area, which was sampled on 16 occasions over an 18 month period. Ten samples are HREE-enriched, whereas 6 samples show flat patterns.The aqueous speciation of REEs shows that CO²⁻₃ complexes dominate (>80%) over the free metal, F⁻, SO²⁻₄ and HCO⁻₃ complexes. The detailed speciation demonstrates that the fractionation of REEs (i.e. the HREE enrichment) in CO₂-rich and pH neutral fluids is due essentially to the predominance of the CO²⁻₃ complexes.The Sr isotopic composition of the mineral waters in the Massif Central shows different mixing processes; in the Cézallier area at least 3 end-member water types exist. The most dilute end-member is likely to originate as poorly mineralized waters with minimal groundwater circulation. Two other mineralized end-members are identified, although the link between the geographical location of spring outflow and the mixing proportion between the 2 end-members is not systematic. The range in ϵ_Nd(0) for mineralized waters in the Massif Central correlates well with that of the known parent rocks except for 4 springs. One way to explain the ϵ_Nd(0) in these instances is a contribution from drainage of volcanic rocks. The isotopic systematics help to constrain the hydrogeological models for this area.     

Strontium isotopic geochemistry of Tianqiao Pb-Zn deposit,Southwest China

Tianqiao carbonate-hosted Pb-Zn deposit, controlled by NW-trending F37 thrust fault and NW-trending Tianqiao anticline, is located in the eastern part of Sichuan-Yunnan-Guizhou （SYG） Pb-Zn metallogenic province, southwestern Yangtze Block, southwest China. Ore bodies in this deposit are hosted in the Devonian-Carboniferous carbonate rocks, and ore minerals include sphalerite, galena and pyrite, while the gangue minerals are dominated by calcite and dolomite. Using high-precision solid thermal ionization mass spectrometry （TIMS）, this paper reports the strontium isotopic compositions （0.7119 to 0.7167） of sulfide samples from the Tianqiao deposit in order to trace the origin of hydrothermal fluids. Compared with the country rocks, the calculated 87Sr/86Sr200 Ma values of sulfide range from 0.7118 to 0.7130, higher than those of the age-corrected Devonian to Permian sedimentary rocks （0.7073 to 0.7101） and the Middle Permian Emeishan flood basalts （0.7078 to 0.7039）, but lower than those of the age-corrected Proterozoic basement rocks （such as the Kunyang and Huili Groups, 87Sr/86Sr200 Ma=0.7243 to 0.7288）. This implies a mixed strontium source between the older basement rocks and the younger cover sequences. Together with geologic and previous isotopic evidences, we considered that the fluids＇ mixing is a possible mechanism for sulfide precipitation in the Tianqiao deposit.     

Palaeozoic to Early Jurassic history of the northwestern corner of Gondwana,and implications for the evolution of the Iapetus,Rheic and Pacific Oceans

The Palaeozoic to Mesozoic igneous and metamorphic basement rocks exposed in the Mérida Andes of Venezuela and the Santander Massif of Colombia are generally considered to define allochthonous terranes that accreted to the margin of Gondwana during the Ordovician and the Carboniferous. However, terrane sutures have not been identified and there are no published isotopic data that support the existence of separate crustal domains. A general paucity of geochronological data led to published tectonic reconstructions for the evolution of the northwestern corner of Gondwana that do not account for the magmatic and metamorphic histories of the basement rocks of the Mérida Andes and the Santander Massif. We present new zircon U–Pb (ICP-MS) data from 52 igneous and metamorphic rocks, which we combine with whole rock geochemical and Pb isotopic data to constrain the tectonic history of the Precambrian to Mesozoic basement of the Mérida Andes and the Santander Massif. These data show that the basement rocks of these massifs are autochthonous to Gondwana and share a similar tectono-magmatic history with the Gondwanan margin of Peru, Chile and Argentina, which evolved during the subduction of oceanic lithosphere of the Iapetus Ocean. The oldest Palaeozoic arc magmatism is recorded at ~ 500 Ma, and was followed shortly by Barrovian metamorphism. Peak metamorphic conditions at upper amphibolite facies are recorded by anatexis at ~ 477 Ma and the intrusion of synkinematic granitoids until ~ 472 Ma. Subsequent retrogression resulted from localised back-arc or intra-arc extension at ~ 453 Ma, when volcanic tuffs and interfingered sedimentary rocks were deposited over the amphibolite facies basement. Continental arc magmatism dwindled after ~ 430 Ma and terminated at ~ 415 Ma, coevally with most of the western margin of Gondwana. After Pangaea amalgamation in the Late Carboniferous to Early Permian, a magmatic arc developed on its western margin at ~ 294 Ma as a result of subduction of oceanic crust of the palaeo-Pacific ocean. Intermittent arc magmatism recorded between ~ 294 and ~ 225 Ma was followed by the onset of the Andean subduction cycle at ~ 213 Ma, in an extensional regime. Extension was accompanied by slab roll-back which led to the migration of the arc axis into the Central Cordillera of Colombia in the Early Jurassic.