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.     

Stratigraphic framework and calcareous nannofossil productivity of the Essaouira-Agadir Basin (Morocco) during the Aptian–Early Albian: Comparison with the north-Tethyan margin

In the southern Tethyan margin, the Essaouira-Agadir Basin (EAB), south of Morocco, exhibits well-exposed and fossiliferous sections of Aptian–Albian age. Biostratigraphy by ammonoids and sedimentological analysis have been realized for five sections located along an E-W transect in the EAB. The studied successions were dated from the latest Early Aptian to the Early Albian and are characterized by five major sedimentary discontinuities defining at least four main sedimentary sequences. The Late Aptian–Early Albian succession can be considered a gently westward-dipping ramp, marked by a deepening upward evolution. A quantitative study of calcareous nannofossils and calcium carbonate content has been performed on three of these sections. At this time, the EAB was located in the tropical-equatorial hot arid belt. The decrease in both calcium carbonate content and Nannoconus abundances at the Aptian–Albian transition could be the result of cooler climatic conditions recognized in the EAB, and/or of the associated increasing terrigenous input and nutrients, which hindered carbonate production. In the EAB, the nannofossil productivity is higher below the deposition of dark levels, which are coeval with the Niveau Paquier, recognized as the expression in southern France of the OAE 1b (Early Albian). During the Early Albian, the EAB was characterized by nannofossil fluxes two times lower than the upwelling-influenced Mazagan Plateau (southern Tethyan margin) and eight times lower than the Vocontian Basin (northern Tethyan margin). These results show that, with respect to the northern Tethyan margin, trophic conditions in sea surface waters of the pelagic realm of the southern Tethyan margin were lower. Comparable results obtained by Heldt et al. in the neritic realm of the southern Tethyan margin have been ascribed to more arid climatic conditions.     

Early Cretaceous (late Berriasian to early Aptian) palaeoceanographic change along the northwestern Tethyan margin (Vocontian Trough,southeastern France): δ13C, δ18O and Sr-isotope belemnite and whole-rock records

Stable carbon, oxygen, and strontium isotope records were obtained from uppermost Hauterivian to lowermost Aptian belemnite rostra, which were collected in well-dated sections from the Vocontian Trough (southeastern France). This data set complements previously published belemnite-isotope records from the uppermost Berriasian-Hauterivian interval from the same basin. The belemnite carbon and oxygen isotope record is compared to the carbonate bulk-rock isotope record from the same sections, and from additional Italian sections. With regards to their long-term trends, both belemnite and whole-rock δ¹⁸O records are well correlated, except for the uppermost Hauterivian-lower Barremian interval, within which they deviate. This discrepancy is interpreted to be linked to the latest Hauterivian Faraoni oceanic anoxic event and its early Barremian aftermath. The Faraoni level is characterized by enhanced sea-water stratification, probably induced by the onset of a warmer and more humid climate along the northern Tethyan margin. The early Barremian was characterized by stronger vertical sea-water mixing reflected by a decrease in density contrast between sea-surface and deeper waters. The belemnite oxygen isotope record shows a more stable evolution with smaller fluctuations than its bulk-rock counterpart, which indicates that deeper water masses were not as much subjected to density fluctuations as sea-surface water. The comparison of belemnite and bulk-rock carbon isotope records allows observing the impact of regional influence exerted by platform carbonate ooze shedding on the carbon cycle. Discrepancies in the two records are observed during time of photozoan carbonate platform growth. The strontium isotopic record shows a gradual increase from the uppermost Berriasian to the uppermost lower Barremian followed by a rapid decrease until the uppermost Barremian and a renewed small increase within the lowermost Aptian. The major inflection point in the uppermost lower Barremian appears to predate the onset in the formation of the Ontong-Java volcanic plateau.     

Lower Jurassic (Hettangian–Pliensbachian) microfossil biostratigraphy of the Ballinlea-1 well,Rathlin Basin,Northern Ireland,United Kingdom

The thickest section of Early Jurassic strata known from onshore Ireland (total Jurassic thickness 566 m) is reported from the Ballinlea-1 well (Rathlin Basin) situated on the north coast of Northern Ireland. A biostratigraphical and palaeoenvironmental assessment is presented for this section largely based on calcareous benthic microfossils (foraminifera and ostracods). The Early Jurassic Waterloo Mudstone Formation (Lias Group) of Northern Ireland has previously received little micropalaeontological attention, therefore this work provides an opportunity to enhance palaeogeographic and palaeoenvironmental understanding for the Early Jurassic of the province, and this paper illustrates the key microfossil taxa of this age from Ireland for the first time. The records, based on ditch-cuttings samples, demonstrate a stratigraphical range from Hettangian to Early Pliensbachian, consistent with other wells and boreholes in this basin. The assemblage compositions are comparable to those elsewhere in the European boreal Atlantic realm. Hettangian to earliest Sinemurian microfossil assemblages are generally of low diversity and are numerically dominated by metacopid ostracods with occasional influxes of foraminifera. Gradually, foraminiferal abundance (often dominated by species of the Lagenida) come to exceed those of the ostracods in the Early Sinemurian reaching their greatest diversity in the Late Sinemurian. The sediments are considered to represent an inner to mid-shelf environment throughout while the record thickness for this region indicates ongoing syn-sedimentary fault movement along the basin margins within this period.     

Petrology,geochemistry and zircon U–Pb dating of Band-e-Hezarchah metabasites (NE Iran): An evidence for back-arc magmatism along the northern active margin of Gondwana

The Band-e-Hezarchah granitoids (BHG) is located in the northern margin of the central Iran, where the very old continental crust of Iran is found. The BHG mainly include granodiorite, granite and leucogranite. Small meta-gabbroic stocks and dykes are associated with BHG. U–Pb zircon dating of the BHG granites and metabasites yield ²³⁸U/²⁰⁶Pb crystallization ages of ca. 553.6 and 533.5 Ma respectively (Ediacaran–early Cambrian). The metabasites have calc-alkaline signature and their magmas seem to have originated from a mantle wedge above a subduction zone. These rocks are thought to be formed in a continental back-arc setting, related to the oblique subduction of Proto-Tethys oceanic lithosphere beneath the northern margin of Gondwanan supercontinent during Ediacaran–Cambrian time. The initial ⁸⁷Sr/⁸⁶Sr ratios and ɛNd (t) values for metabasites are change from 0.705 to 0.706 and −3.5 to −3.6 respectively. Sr–Nd isotope composition of metabasites indicates that these rocks were derived from a subcontinental lithospheric mantle source. The BHG and associated metabasites are coeval with other similar aged metagranites and gneisses from Iranian basements exposed in central Iran, Sanandaj-Sirjan and Alborz zones. These rocks were formed due to continental arc magmatism of Neoproterozoic–early Cambrian, bordering the northern active margin of Gondwana.     

Relative sea-level change, climate, and sequence boundaries: insights from the Kimmeridgian to Berriasian platform carbonates of Mount Salève (E France)

The present study analyses the stratal architecture of the Late Jurassic (Kimmeridgian) to Early Cretaceous (Berriasian) sedimentary succession of Mount Salève (E France), and four Berriasian stratigraphic intervals containing four sequence-boundary zones reflecting lowering trends of the relative sea-level evolution. Massive Kimmeridgian limestones characterized by the presence of colonial corals appear to be stacked in an aggrading pattern. These non-bedded thick deposits, which are interpreted to have formed in balance between relative sea-level rise and carbonate accumulation, suggest a keep-up transgressive system. Above, well-bedded Tithonian-to-Berriasian peritidal carbonates reflect a general loss of accommodation. These strata are interpreted as a highstand normal-regressive unit. During the early phase of this major normal regression, the vertical repetition of upper intertidal/lower supratidal lithofacies indicates an aggrading depositional system. This is in agreement with an early stage of a highstand phase of relative sea level. The Berriasian sequence-boundary zones investigated (up to 4 m thick) developed under different climatic conditions and correspond to higher-frequency, forced- and normal-regressive stages of relative sea-level changes. According to the classical sequence-stratigraphic principles, these sequence-boundary zones comprise more than one candidate surface for a sequence boundary. Three sequence-boundary zones studied in Early Berriasian rocks lack coarse siliciclastic grains, contain a calcrete crust, as well as marly levels with higher abundances of illite with respect to kaolinite, and exhibit fossilized algal-microbial laminites with desiccation polygons. These sedimentary features are consistent with more arid conditions. A sequence-boundary zone interpreted for the Late Berriasian corresponds to a coal horizon. The strata above and below this coal contain abundant quartz and marly intervals with a higher kaolinite content when compared to the illite content. Accordingly, this Late Berriasian sequence-boundary zone was formed under a more humid climate. The major transgressive–regressive cycle of relative sea level identified and the climate change from more arid to more humid conditions recognized during the Late Berriasian have been reported also from other European basins. Therefore, the Kimmeridgian to Berriasian carbonate succession of Mount Salève reflects major oceanographic and climatic changes affecting the northern margin of the Alpine Tethys ocean and thus constitutes a reliable comparative example for the analysis of other coeval sedimentary records. In addition, the stratigraphic intervals including sequence-boundary zones characterized in this study constitute potential outcrop analogues for sequence-boundary reflectors mapped on seismic profiles of subsurface peritidal carbonate successions. The detailed sedimentological analyses provided here highlight that on occasions the classical principles of sequence stratigraphy developed on seismic data are difficult to apply in outcrop. A sequence-boundary reflector when seen in outcrop may present successive subaerial exposure surfaces, which formed due to high-frequency sea-level changes that were superimposed on the longer-term trend of relative sea-level fall.     

The Vendian passive continental margin in the southern Siberian Craton: geochemical and isotopic (Sr,Sm–Nd) evidence and U–Pb dating of detrital zircons by the LA-ICP-MS method

Geochemical and isotopic (Sm–Nd and Sr) studies of deposits of the Baikal and Oselok Groups in the southern Siberian Craton and LA-ICP-MS U–Pb dating of detrital zircons show that they accumulated in passive continental-margin settings in the Vendian. The time limits of sedimentation were assessed on the basis of Sr chemostratigraphy of carbonate deposits of the Baikal Group and LA-ICP-MS U–Pb dating of detrital zircons in first-cycle terrigenous deposits of the Oselok Group. The main provenances for rocks of these groups were constant. These were rocks of the cover and basement of the Siberian Craton. Tuffite horizons in upper portions of the groups are the only sign of Late Vendian activation of this block, which is reflected in changes of geochemical indices of terrigenous rocks and their younger Sm–Nd model ages.     

Palaeogeography of Neogene red bed sequences along the Aksa-Ata River in the Parkent–Nurekata intermontane basin (Tien Shan Mountains,Uzbekistan): With special reference to the magnetic susceptibility of siliciclastic rocks

Siliciclastic red beds formed by stream action in the Parkent–Nurekata intermontane basin of the Tien Shan Mountains, E Uzbekistan. The sedimentary rocks were cross-sectioned in the field and subject to heavy mineral, clay mineral and thin section analyses in the laboratory. In addition to these conventional methods, a survey into the variation of the magnetic susceptibility was conducted. During the Paleogene, calcareous rocks (unit A) developed in a subtidal through supratidal environment of deposition. Subsequently, tectonic disturbances tilted the Paleogene carbonate rocks and triggered the formation of an unconformity during the Oligocene. The Miocene to Pliocene red beds have the hallmarks of a delta-like wedge actively prograding over near-shore marine deposits. Two progradational stages (units B and C) were substituted for by a more regressive event (unit D). During deposition and burial the siliciclastics were percolated by strongly alkaline pore fluids under semi-arid climatic conditions. The joint action of rapid uplift in the hinterland and the afore-mentioned hydrological processes were instrumental for heavy minerals such as epidote and staurolite to survive and some peculiar phyllosilicates such as smectite and palygorskite to precipitate. Debris from metamorphic and igneous rocks were delivered from the rising hinterland. The petrographic and magnetic records of red beds are a mirror image of the unroofing of a magmatic edifice in the provenance area between 11 and 3 Ma.     

Microwave assisted extraction and hydrolysis: An alternative to pyrolysis for the analysis of recalcitrant organic matter? Application to a forest soil (Landes de Gascogne,France)

A comparison was made between the composition of the recalcitrant organic matter (ROM) isolated from a sandy forest soil, as revealed with microwave assisted extractions and/or hydrolysis, and using common pyrolysis techniques. Successive microwave irradiation treatments were performed in H₂O, 0.1 and 1 M HCl and 0.1 and 1 M KOH. At each step the insoluble residue was examined via Curie point pyrolysis (CuPy) and Curie point thermally assisted hydrolysis and methylation (CuTHM). Sequential irradiation treatment resulted in ca. 35% degradation of the ROM. Compounds released on microwave irradiation in H₂O and in HCl were dominated by glucose, suggesting the occurrence of carbohydrate-containing molecular associations in the soil organic matter (SOM) which were not disrupted during acid hydrolysis and extraction as applied for the isolation of the ROM. The product distribution from the microwave irradiation in KOH showed an important contribution to the ROM from the higher plant polyesters cutin and suberin, and to a lesser extent from lignin. Different lignin-derived compounds were specifically released upon microwave acid or base hydrolysis. This suggested that two types of lignin monomers, ether- or ester-linked, occurred in the ROM. The changes in the composition of the CuPy pyrolysates of the residues from the different microwave hydrolyses are consistent with the near complete removal of carbohydrates by microwave HCl hydrolysis. The changes in the composition of the CuTHM pyrolysates of the residues from the different microwave acid and base hydrolyses are in agreement with a major release of cutin- and suberin-derived compounds upon microwave KOH hydrolysis. The CuPy and CuTHM pyrolysates of the final residue consist predominantly of lignin-derived compounds. The study emphasizes the potential of microwave assisted hydrolysis to give a better estimate of the actual contribution of cutin to ROM than pyrolysis. However, the technique appears to be unable to completely release the lignin-based constituent of the ROM. Microwave irradiation appears to provide great potential as a tool for extraction and chemical characterisation of complex OM and could be an attractive additional technique to pyrolysis.     

The crystal chemistry of lithium in the alluaudite structure: a study of the (Na1− x Li x )1.5Mn1.5Fe1.5(PO4)3 solid solution (x = 0 to 1)

Summary Phosphates of compositions (Na_1–xLi_x)_1.5Mn_1.5Fe_1.5(PO₄)₃ were synthesized by solid state reactions in air, and pure alluaudite-type compounds were obtained for x=0.00, 0.25, and 0.50. Rietveld refinements of X-ray powder diffraction data indicate the occurrence of Mn²⁺ in the M(1) site, and of Fe³⁺ and Mn²⁺ in the M(2) site. For x=0.25 and 0.50, A(1) is occupied by Li⁺ and Na⁺, whereas A(2) is occupied by Na⁺ and vacancies. A careful examination of the number of electrons occurring in the A sites of the alluaudite-type compounds (Na_1–xLi_x)MnFe₂(PO₄)₃ and (Na_1–xLi_x) CdIn₂(PO₄)₃ confirms that lithium occupies only the A(1) crystallographic site of the alluaudite structure.     

Comments on “An approximation to short-term evolution and sediment transport pathways along the littoral of Cadiz Bay (SW Spain)” by Anfuso and et al. (Environ Geol 56:69–79)

Environmental Earth Sciences -     

Contribution of {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} and 13CTDIC Evaluation to the Identification of CO2 Sources in Volcanic Groundwater Systems: Influence of Hydrometeorological Conditions and Lava Flow Morphologies—Application to the Argnat Basin (Chaîne des Puys, Massif Central, France)

Mineralization of groundwater in volcanic aquifers is partly acquired through silicates weathering. This alteration depends on the dissolution of atmospheric, biogenic, or mantellic gaseous CO₂ whose contributions may depend on substratum geology, surface features, and lava flow hydrological functionings. Investigations of $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ¹³C_TDIC (total dissolved inorganic carbon) on various spatiotemporal scales in the unsaturated and saturated zones of volcanic flows of the Argnat basin (French Massif Central) have been carried out to identify the carbon sources in the system. Mantellic sources are related to faults promoting CO₂ uplift from the mantle to the saturated zone. The contribution of this source is counterbalanced by infiltration of water through the unsaturated zone, accompanied by dissolution of soil CO₂ or even atmospheric CO₂ during cold periods. Monitoring and modeling of δ¹³C_TDIC in the unsaturated zone shows that both $ {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} $ and δ¹³C_TDIC are controlled by air temperature which influences soil respiration and soil-atmosphere CO₂ exchanges. The internal geometry of volcanic lava flows controls water patterns from the unsaturated zone to saturated zone and thus may explain δ¹³C heterogeneity in the saturated zone at the basin scale.     

High-pressure phase relations in the system TiO2–ZrO2 to 12?GPa: stability of αPbO2-type srilankite solid solutions of (Ti1?x , Zr x )O2 (0?≤?x?≤?0.6)

Phase relations in the system TiO₂–ZrO₂ were examined in the pressure range of 3.5–12?GPa at 1,800?°C, using multianvil apparatus. At 1,800?°C, TiO₂ rutile transforms to αPbO₂ structure at 10?GPa, and the αPbO₂-type solid solution is stable in compositional range between TiO₂ and about (Ti_0.6, Zr_0.4)O₂ at 3.5–12?GPa. Combination of the present results with the published data at 0–3?GPa demonstrates that continuous solid solution with the αPbO₂-type structure is stable between TiO₂ and (Ti_1?x , Zr _x )O₂ (x?≈?0.6) at 0–12?GPa. This indicates that both the αPbO₂-type TiO₂ and srilankite Ti₂ZrO₆ with the same structure belong to the continuous solid solution system though the two phases have been regarded as different minerals. With increasing ZrO₂ content, lattice parameters of a- and c-axes of the αPbO₂-type solid solution increase, but b-axis is almost constant or slightly decreases. At higher pressure, the αPbO₂-type solid solution dissociates into two phases, αPbO₂-type phase and tetragonal zirconia. Srilankite with more TiO₂-rich composition than Ti₂ZrO₆ might be found in natural rocks derived from the deep upper mantle.     

Comment on: “Enriched mantle – Dupal signature in the genesis of the Jurassic Ferrar tholeiites from Prince Albert Mountains (Victoria Land, Antarctica)” by Antonini P. et al. (Contributions to Mineralogy and Petrology 136, 1–19; 1999)

18 O values, the magmas retain initial ⁸⁷Sr/⁸⁶Sr Compositions of greater than 0.709 (e.g. Hoefs et al. 1980). Consistent with this is the lack of a radiogenic Os isotope signature in these rocks (e.g. Molzahn et al. 1996) as would be expected with assimilation of continental crust. Comments here are not concerned with the AFC calculations employed to describe the variations within the suite of samples from the Prince Albert mountains studied by Antonini et al., but rather, the extrapolation of these to more primitive compositions. Antonini et al. have revived the possibility that the unusual chemical features of the least evolved low Ti continental flood basalts of the Ferrar Province reflect a crustal-level interplay between mantle-derived magmas and the continental crust. It is argued here that they have not demonstrated their claim. Received: 7 October 1999 / Accepted: 25 January 2000