Chemistry of rainwater in the Massif Central (France): a strontium isotope and major element study

Atmospheric aerosols (sea salt, crustal dust, and biogenic aerosols) are the primary source of dissolved species in rainwater as well as one of the sources of dissolved species in river water. Chemical weathering studies require quantification of this atmospheric input. The crustal component of atmospheric input can have various origins, both distant and local. The proportions of the various inputs (marine, distant or local) are determined in this study.Strontium isotope ratios and Ca, Na, K, Mg, Al, Cl, SO₄, NO₃ and Sr concentrations were measured in rainwater samples collected in the Massif Central (France) over a period of one year. Each sample, collected automatically, represents a monthly series of rain events. Chemical composition of the rainwater samples varied considerably and the ⁸⁷Sr/⁸⁶Sr ratios ranged between 0.709198 and 0.713143.Using Na as an indicator of marine origin, and Al for the crustal input in rain samples, the proportion of marine and crustal elements was estimated from elemental ratios. A marine origin of 4 to 100% of Cl, of 0.6 to 20% of the SO₄, of <1 to 10% of Ca, <1 to 40% of K, 4 to 100% of Mg and 1 to 44% of Sr was determined.Strontium isotopes were used to characterize the crustal sources. The ⁸⁷Sr/⁸⁶Sr ratios of the crustal sources varied considerably from 0.7092 to 0.71625 and indicate the occurrence of multiple sources for the crustal component in the analysed rainwaters.     

NdSr isotope and REE geochemistry of alkali basalts from the Massif Central,France

Nd and Sr isotopic compositions as well as trace element concentrations have been determined on a suite of alkali basalts from the Massif Central, in France. Samples show a typical enrichment in incompatible elements. In particular, the REE patterns exhibit a strong fractionation characterized by a ($\text{La}\text{Yb}\text{)}{}_{\mathrm{<mtext>N</mtext>}}$ ratio of about 20. The Yb_N content is about 10 times chondrite. The $\text{143}\text{Nd}\text{144}\text{Nd}$ ratios exhibit a range from 0.512775 to 0.512989, values quite comparable to those from oceanic island basalts. The $\text{87}\text{Sr}\text{86}\text{Sr}$ ratios vary between 0.70338 and 0.70458 and are anti-correlated with the Nd isotopic ratio.The isotopic and the trace element (in particular REE) data have been used in order to quantitatively model the genesis of the alkali basalts. Among the several types of models tested here, the most likely one appears to be the model of mantle metasomatism. A semi-quantitative approach shows that the source of alkali basalts from the Massif Central was metasomatized prior to melting. In such a model, the basalts could be produced by rather high degrees of partial melting (such as 10 or 15%) of the metasomatically enriched mantle.     

Multi-isotopic (Li,B, Sr,Nd) approach for geothermal reservoir characterization in the Limagne Basin (Massif Central,France)

A multi-isotopic study of thermo-mineral waters from the Limagne Basin (French Massif Central) is reported. Lithium, B, Sr and Nd isotopic signatures in thermo-mineral waters and bedrocks were combined in order to determine the origin of these fluids from a reservoir point of view. Strontium and Nd isotopic systems showed that the thermo-mineral waters are mostly derived from a granitic reservoir type, with the exception of a few water samples having Sr and Nd isotopic signatures also reflecting a volcanic contribution (basalts). In a second step, Li and B isotopes were investigated, given that Li and B isotopic systematics are potentially affected by mass dependent fractionation during water/rock interaction and could provide some information on what takes place during this process. A great diversity of thermo-mineral waters within the Aigueperse area was clearly observed, which is directly related to the origin of these thermal waters in terms of reservoirs. These different geothermal reservoirs are characterized by different geological settings and intensity of water/rock interaction (i.e. depth and temperature).     

210Pb, 226Ra and 32Si in Pavin lake (Massif Central,France)

Measurements of cosmogenic ³²Si and the U-decay series' nuclides ²¹⁰Pb and ²²⁶Ra in waters and sediments of lake Pavin are reported. Both ²¹⁰Pb and ²²⁶Ra are enriched in the anoxic deep waters compared to the oxic surface waters, respectively by a factor of 4 and 10, whereas ³²Si is depleted by a factor of2. Redox conditions in the lake appear to have no marked effect on the ³²Si. Using a steady-state box model it is shown that the deep-water ³²Si concentration is controlled by the underground lacustrine springs. The residence times of ²¹⁰Pb, ³²Si and ²²⁶Ra are1,10 and80 a, respectively. In the case of ³²Si, where more data are available, the assessed inventory data from the overhead atmospheric fallout and that measured in the sediments agree very well as expected. The ²¹⁰Pb- and ³²Si-based deposition rates during the past100 a ranged from 0.8 to 1.9 mm a⁻¹, earlier these were a factor of3–5 faster. The geochemistry of ³²Si and ²¹⁰Pb in lake Pavin in many ways resembles that in the ocean, only the time scales of the processes involved are faster.     

Lead-isotope evidence for a Hercynian origin of the Salsigne gold deposit (Southern Massif Central,France)

The Salsigne gold deposit contains a complex association of sulphide layers, gold-rich disseminations, quartz-bearing veins and flat reefs, which are hosted by folded and slightly metamorphosed Paleozoic sediments on both sides of a major thrust zone. It is demonstrated that these various Au-As ore types have similar lead-isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.22–18.56), which are characteristic of Hercynian ore deposits in the southern Massif Central. The Lower Cambrian to Devonian host rocks and associated Pb-Zn-Ba occurrences display distinctly less radiogenic corrected isotopic signatures (²⁰⁶Pb/²⁰⁴Pb = 17.83–17.98), which are characteristic of Cambrian lead in the Montagne-Noire. Concerning the controversial origin of the Salsigne gold mineralization, these results disagree with the former syngenetic hypothesis and support a new model of Hercynian syntectonic gold concentration.This work was supported by BRGM'S scientific program: Le gisement de Salsigne: caractérisation du modèle et évaluation du potentiel aurifère du district     

Re-evaluation of lead isotopic data,southern Massif Central,France

Three independent Pb isotope homogenizing processes operating on large volumes of rock material during limited intervals in the Phanerozoic have been used to define a unique evolutionary curve for rock and ore lead isotopic compositions of the southern Massif Central, France. The model is

Petrological and geochemical relationships between pyroxene megacrysts and associated alkali-basalts from Massif Central (France)

Major, trace element, and REE analyses, as well as Sr isotopic ratios, have been obtained on twelve clinopyene megacrysts and phenocrysts and their alkali-basalt hosts from the French Massif Central. Equilibrium between crystals and host was examined based on petrographic and geochemical data.Two types of pyroxenes are recognized: the acmite-bearing clinopyroxenes, rich in incompatible elements and the salitic clinopyroxenes, poor in incompatible elements. ⁸⁷Sr/ ⁸⁶Sr isotopic data reveal no significant difference between clinopyroxenes and host lavas: they are in apparent isotopic equilibrium. The Sr isotopic ratios of the two types of pyroxenes are also quite similar. However pyroxene crystals from the first group are not in equilibrium with their host; they have crystallized at high-pressure from differentiated alkali-lavas and have been incorporated in a more primitive magma. Pyroxene crystals from the second group are in apparent equilibrium with their host lava; they have crystallized at various pressures. For the latter, distribution coefficients are proposed for compatible elements, trace elements and REE.     

Igneous scapolite-bearing associations in the Chaîne des Puys,Massif Central (France) and Atakor (Hoggar,Algeria)

A scapolite+amphibole+clinopyroxene+Fe-Ti oxide+apatite association has been found as megacrysts in tephra from the Enval-Volvic volcanic line, east of the Chaîne des Puys (Massif Central, France) and in the cinder cone of the Segueïka volcano (Atakor, Algeria). In both kinds, lavahosts are basanites. Although never seen together in a single xenolith, a study of their inclusions indicates close genetic relationship between all 5 phases. This association must be considered as a paragenesis that crystallized within a narrow PT range. Volcanological, petrological and geochemical data suggest that these megacrysts are high-pressure phenocrysts rather than mechanically desintegrated fragments derived from coarse rocks. The composition of the amphibole suggests a pressure between 5 and 15 kb; Fe-Ti oxides imply a temperature close to 1,100° C.Crystallization of sulfur-rich scapolite involves a high fSO₃, and therefore a high fO₂, remarkable for such relatively undifferenciated alkalic magmas. Coexisting Fe-Ti oxides indicate a fO₂ close to 10^–6 bar. Such conditions imply that H₂O was a major component of the gaseous phase. This high water content can be explained in terms of derivation from an hydrated upper mantle source. This is in agreement with other petrological evidences indicating that the basic magmas of the Massif Central crystallized under high fSO₃ conditions.     

Syntectonic crustal melting and high-grade metamorphism in a transpressional regime, Variscan Massif Central, France

Hot collisional orogens are characterized by abundant syn-kinematic granitic magmatism that profoundly affects their tectono-thermal evolutions. Voluminous granitic magmas, emplaced between 360 and 270 Ma, played a visibly important role in the evolution of the Variscan Orogen. In the Limousin region (western Massif Central, France), syntectonic granite plutons are spatially associated with major strike–slip shear zones that merge to the northwest with the South Armorican Shear Zone. This region allowed us to assess the role of magmatism in a hot transpressional orogen. Microstructural data and U/Pb zircon and monazite ages from a mylonitic leucogranite indicate synkinematic emplacement in a dextral transpressional shear zone at 313 ± 4 Ma. Leucogranites are coeval with cordierite-bearing migmatitic gneisses and vertical lenses of leucosome in strike–slip shear zones. We interpret U/Pb monazite ages of 315 ± 4 Ma for the gneisses and 316 ± 2 Ma for the leucosomes as the minimum age of high-grade metamorphism and migmatization respectively. These data suggest a spatial and temporal relationship between transpression, crustal melting, rapid exhumation and magma ascent, and cooling of high-grade metamorphic rocks.Some granites emplaced in the strike–slip shear zone are bounded at their roof by low dip normal faults that strike N–S, perpendicular to the E–W trend of the belt. The abundant crustal magmatism provided a low-viscosity zone that enhanced Variscan orogenic collapse during continued transpression, inducing the development of normal faults in the transpression zone and thrust faults at the front of the collapsed orogen.     

REE geochemistry of eclogites and associated rocks from Sauviat-sur-Vige, Massif Central, France

Representative samples of metagabbros, eclogites and a garnet peridotite from the Massif de Sauviat-sur-Vige (West Massif Central) have been analyzed for major and trace elements (including REE). The LREE enriched patterns are distinct from those of modern MORB but resemble those of continental or ocean island tholeiites. An intraplate tectoning setting is thus inferred. Geochemical modeling using REE and major element contents suggests that all the rock types might be related genetically by fractional crystallization, and, in some instances, by mixing of cumulates and differentiated liquid as in the case of the garnet peridotite. P, T estimates from microprobe analyses of coexisting garnet-clinopyroxene pairs yield about 820°C, and P > 15 kb for the eclogite facies metamorphism.     

Reduced sulfur and iron species in anoxic water column of meromictic crater Lake Pavin (Massif Central, France)

The vertical distribution of reduced sulfur species (RSS including H₂S/HS⁻, S⁰, electroactive FeS) and dissolved Fe(II) was studied in the anoxic water column of meromictic Lake Pavin. Sulfide concentrations were determined by two different analytical techniques, i.e. spectophotometry (methylene blue technique) and voltammetry (HMDE electrode). Total sulfide concentrations determined with methylene blue method (∑H₂S_MBRS) were in the range from 0.6 µM to 16.7 µM and were substantially higher than total reduced sulfur species (RSS_V) concentrations determined by voltammetry, which ranged from 0.1 to 5.6 μM. The observed difference in the sulfide concentrations between the two methods can be assigned to the presence of FeS colloidal species.Dissolved Fe was high (> 1000 µM), whereas dissolved Mn was only 25 µM, in the anoxic water column. This indicates that Fe is the dominant metal involved in sulfur redox cycling and precipitation. Consequently, in the anoxic deep layer of Lake Pavin, “free” sulfide, H₂S/HS⁻, was low; and about 80% of total sulfide detected was in the electroactive FeS colloidal form. IAP calculations showed that the Lake Pavin water column is saturated with respect to FeS_am phase. The upper part of monimolimnion layer is characterized by higher concentrations of S(0) (up to 3.4 µM) in comparison to the bottom of the lake. This behavior is probably influenced by sulfide oxidation with Fe(III) oxyhydroxide species.     

Quartz fabric transition in a cooling syntectonic granite (Hermitage Massif,France)

The Hermitage Granite, situated in the northwest Massif Central (France) is a syntectonic Hercynian leucogranite emplaced along an active transcurrent shear zone. During emplacement and cooling, the progressive deformation is marked by the development of a primary homogeneous foliation gradually affected by ductile shear bands (C-S mylonites). Increase in strain heterogeneity during cooling corresponds to a change of dominant deformation mechanism of the quartz phase from grain growth and migration recrystallization to intracrystalline 〈a〉 slip and rotation recrystallization. Migration recrystallization is characterized by preferred orientations of c axes close to the principal extension direction. We discuss relevant deformation mechanisms and rheological implications for syntectonic plutons. In particular, we argue that the transitions between homogeneous and heterogeneous accumulation of strain cannot generally be correlated with transition between magmatic and solid-state flow.     

Unearthing deep-time biodiversity changes: The Palaeogene mammalian metacommunity of the Quercy and Limagne area (Massif Central,France)

The long-term changes of the mammalian diversity of the Quercy and Limagne area (Massif Central, France) is quantitatively investigated through a ∼16-Myr time span running from the late Middle Eocene (∼38 Myr) to the Early Miocene (∼22 Myr). Within the specific context of ecosystem response to extreme climatic events, the goal of such a deep-time approach to local community and regional metacommunity evolution is to give time-scaled reference series with which extant changes can be objectively compared. The results indicate that local and regional ecological integration levels show very distinct evolutionary dynamics, involving at least partially independent sets of controlling parameters; those driving the metacommunity still remain largely to be better understood. Clearly, the analyzed data set constitutes a rather unique deep-time key into several major current macroecological debates.     

Rare earth element transport and fractionation in small streams of a mixed basaltic–granitic catchment basin (Massif Central, France)

We present dissolved load (< 0.45 μm) rare earth element (REE) patterns of small streams from a catchment basin in the Massif Central in order to characterize the individual fractionation stages for the dissolved REE from the source to the catchment outlet. The upper part of the catchment is located on a basalt plateau, followed downstream by deep and narrow valleys with granitic and orthogneissic bedrock. Stream water has basalt-like REE patterns on the basaltic plateau close to the source, followed by a continuous depletion in light REE (La-Sm, LREE) downstream. Strontium and neodymium isotope ratios of stream water demonstrate that the dissolved REE are essentially of basaltic origin, even in the lower, granitic and gneissic part of the catchment. Mixing with gneiss or granite derived REE thus cannot explain the observed evolution of the REE patterns. There seems also to be no link with the calculated speciation of the dissolved REE. In contrast, a correlation between saturation indexes for hematite and La/Yb ratios suggests that REE fractionation is mainly controlled by precipitation of Fe-oxide particles that preferentially remove LREE from solution.     

Muscovite recrystallization and saddle-shaped Ar/Ar age spectra: example from the Blond granite (Massif Central, France)

Muscovites from the Blond granite (West French Massif Central) were dated by the ⁴⁰Ar/³⁹Ar single-grain method. The ⁴⁰Ar/³⁹Ar ages obtained vary from 305.5 ± 0.3 Ma to 311.3 ± 0.5 Ma, and most of the age spectra are slightly saddle-shaped. The analyzed muscovites show phengitic recrystallization under optical microscope observations, SEM images, and electron microprobe chemical analyses. It is proposed that the saddle-shaped age spectra result from a partial recrystallization, which produced three different isotopic reservoirs in the analyzed white mica single grains: domains of early muscovite, domains of neocrystallized muscovite formed by phengitic and Al-Fe substitutions, and “low-activation energy sites.”     

Mingling of Immiscible Dolomite Carbonatite and Trachyte in Tuffs from the Massif Central, France

A pyroclastic tuff from the Velay volcanic province in the FrenchMassif Central contains blocks up to 30 cm long of local basementrocks, lava clasts, coarse-grained cumulates and pyroclasticfragments, with more or less diffuse boundaries with the hosttuff, which probably represent more consolidated parts of thetuff. All of the pyroclastics examined and approximately 10%of the cumulate xenoliths contain carbonates in variable amounts,textures and mineralogy. In some of the tuff samples, dolomiteoccurs in large amounts (up to 57%), principally as immiscibleglobules in trachytic melt (now glass), and represents the firstoccurrence of carbonatite reported from the Massif Central.The other carbonates, magnesiosiderite in the mafic cumulatesor occasionally in some tuffs, and calcite in the felsic cumulates,are always associated with a silicate glass of trachytic composition.Coexisting feldspars and carbonates in the various types ofsample are approximately in Sr isotopic equilibrium with aninitial ratio of about 0·7042. C- and O-isotopic compositionsof the carbonates covary and cover a very wide range of compositionfrom -2·9 to 3·9     

A mantle-derived bimodal suite in the Hercynian Belt: Nd isotope and trace element evidence for a subduction-related rift origin of the Late Devonian Brévenne metavolcanics, Massif Central (France)

In the Brévenne Series (NE Massif Central), a low-grade bimodal association of metabasalts and metarhyolites is exposed, together with intrusive trondhjemite bodies. Zircon U-Pb dating constrains their magmatic emplacement at 366 ± 5 Ma and 358 ± 1 Ma, respectively. The metabasalts are characterized by a distinct enrichment in incompatible elements (e.g. Th and LREE) and positive ɛNd_i (from +5 to +8). Combined isotope and trace element systematics rule out crustal contamination of mafic melts as a suitable cause of the LILE (large ion lithophile element)-enrichment. Rather, a mixing process between a component similar to mid ocean ridge basalts and an enriched end-member with ɛNd_i > +5 is suggested. An enriched-mantle source of ocean island basalt affinity is precluded by the relative depletion of high field strength elements, especially Nb which shows negative anomalies in chondrite-normalized patterns. On the contrary, a subduction-related origin for the LILE enrichment would be more consistent. It may be inferred that arc-like melts [enriched in Th and LREE (light rare earth elements) and depleted in Nb, with ɛNd_i > +5] were produced through partial melting of a depleted-mantle source, to which a small amount of crustally derived component had been added. The metarhyolites are enriched in LILE, and have a close genetic relationship with the metabasalts, as evidenced by their high ɛNd_i (from +4.7 to +6.8). Although the chemical evidence remains ambiguous, it is suggested that fractional crystallization, accompanied by subordinate assimilation, is the petrogenetic process most consistent with the data. The trondhjemites are isotopically distinct from the metarhyolites. Their ɛNd_i values (from −1.0 to +2.2) reflect an important contribution of continental crust to their genesis, and disprove their inferred cogenetism with the felsic volcanics. A review of modern environments in which such bimodal suites are exposed, shows that settings involving incipient rifting of a volcanic arc fringing a continental margin, or built upon young, thin continental crust might provide suitable analogues. Geodynamic reconstructions are complicated by subsequent tectonic events which disrupted the initial patterns, and by Mesozoic-Cenozoic sedimentary cover. However, this subduction-related magmatism enlarges the growing body of evidence for southward subduction processes until the Late Devonian during the evolution of the northern flank of the European Variscides. As a general implication, it is suggested that the combined use of the Sm-Nd system with incompatible elements relatively resistant during alteration and low-grade metamorphism (REE, Th, Zr, Nb) may provide diagnostic criteria for recognizing the tectonic setting of bimodal metaigneous suites in ancient orogenic belts. Received: 21 April 1997 / Accepted: 30 June 1997     

Pollen analytical biostratigraphy of the last five climatic cycles from a long continental sequence from the Velay region (Massif Central,France)

In the volcanic region of Velay (Massif Central, France), lake sediment sequences derived from maar craters situated close to one another (Ribains, Praclaux and Lac du Bouchet) have been correlated on the basis of tephrostratigraphical analyses. This has enabled the construction of a sequence (2980 pollen spectra) that begins during the glaciation preceding the Holsteinian and ends in the present. This sequence covers the period from 450 ka, i.e. from the end of marine oxygen isotope stage 12, to the present time, and includes five climatic cycles. The study of a second core from the Praclaux site completed the long Velay sequence. The biostratigraphy of the whole sequence is described in detail and illustrated by a synthetic and simplified pollen diagram. Thirteen temperate forest episodes (interglacials or interstadials) and as many cold periods (glacials or stadials) are defined. Each temperate episode is characterised by particular forest development and vegetation dynamics, and all of them, with the exception of the Holocene, begin and end with a Pinus forest. The vegetation dynamics observed during the Holocene resemble more closely those recorded during the interstadials than during the interglacials. Copyright © 2000 John Wiley & Sons, Ltd.     

Early Ordovician continental break-up in Variscan Europe: Nd---Sr isotope and trace element evidence from bimodal igneous associations of the Southern Massif Central, France

The high-grade Marvejols Group and the low-grade Albigeois-Cévennes sedimentary sequence contain bimodal igneous rocks of Early Ordovician age which are representative of a widespread thermal event in the European Variscides. Comparison of their Nd---Sr isotope and trace-element characteristics provides additional evidence for their origin in an ensialic extensional setting. As an alternative to the back-arc model proposed by previous authors, we propose that these associations record a continental break-up episode unrelated to contemporaneous subduction. In this model, the widespread Early Paleozoic bimodal magmatism marks the birth of a Mid-European oceanic arm. We propose that the break-up was controlled by both transtensional processes and mantle-plume activity.

High grade associations, such as the Marvejols Group, and low-grade bimodal associations, such as the Albigeois-Cévennes, might be regarded as representing opposite rifted passive margins. The “northern”, Marvejols-type margin was involved in a Late Ordovician-Silurian subduction-like process, with HP-HT metamorphism. In contrast, the “southern” Albigeois/Cévennes margin remained largely unaffected, possibly as part of the overriding plate of the subduction zone.

“Pseudo-calc-alkaline” signatures unrelated to subduction processes may occur in magmatic rocks associated with continental break-up episodes. In this case, negative Nb anomalies are produced by the addition of crustal components enriched in Th and LREE relative to Nb. This inferred alternative origin of Nb anomalies has important bearing on the paleogeodynamic settings based on geochemical data.     

Brunovistulian terrane (Bohemian Massif, Central Europe) from late Proterozoic to late Paleozoic: a review

The Brunovistulian terrane represents a microcontinent of enigmatic Proterozoic provenance that was located at the southern margin of Baltica in the early Paleozoic. During the Variscan orogeny, it represented the lower plate at the southern margin of Laurussia, involved in the collision with the Armorican terrane assemblage. In this respect, it resembles the Avalonian terrane in the west and the Istanbul Zone in the east. There is a growing evidence about the presence of a Devonian back-arc at the margin of the Brunovistulian terrane. The early Variscan phase was characterized by the formation of Devonian extensional basins with the within-plate volcanic activity and formation of narrow segments of oceanic crust. The oldest Viséan flysch of the Rheic/Rhenohercynian remnant basin (Protivanov, Andelska Hora and Horní Benesov formations) forms the highest allochthonous units and contains, together with slices of Silurian Bohemian facies, clastic micas from early Paleozoic crystalline rocks that are presumably derived from terranes of Armorican affinity although provenance from an active Brunovistulian margin cannot be fully excluded either. The development of the Moravo–Silesian late Paleozoic basin was terminated by coal-bearing paralic and limnic sediments. The progressive Carboniferous stacking of nappes and their impingement on the Laurussian foreland led to crustal thickening and shortening and a number of distinct deformational and folding events. The postorogenic extension led to the formation of the terminal Carboniferous-early Permian Boskovice Graben located in the eastern part of the Brunovistulian terrane, in front of the crystalline nappes. The highest, allochthonous westernmost flysch units, locally with the basal slices of the Devonian and Silurian rocks thrusted over the Silesicum in the NW part of the Brunovistulian terrane, may share a similar tectonic position with the Giessen–Harz nappes. The Silesicum represents the outermost margin of the Brunovistulian terrane with many features in common with the Northern Phyllite Zone at the Avalonia–Armorica interface in Germany.