Isotopic composition of strontium in the Valle de Tena (Spanish Central Pyrenees) fluorite deposits: relevance for the source of elements and genetic significance

The fluorite deposits of the Valle de Tena, Central Pyrenees, include stratabound (Portalet) and vein (Lanuza and Tebarray) deposits the formation of which are linked to a Namurian-Westfalian emersion episode and to post-Hercynian hydrothermal systems similar to those occurring elsewhere in Hercynian Europe. In this study, strontium isotopes were used to determine the source(s) of strontium, and by inference calcium, of the fluorite mineralizations, as well as the nature of the ore-forming fluids. Fluorite and calcite from each deposit have similar ⁸⁷Sr/⁸⁶Sr ratios (Portalet 0.7085–0.7108; Lanuza 0.7086–0.7104 and Tebarray 0.7086–0.7101). In all deposits, the Sr isotope composition of most of the Ca-minerals is more radiogenic than that of the host limestones. This indicates that the Ca-minerals contain a mixture of Sr derived locally from the host limestones and ⁸⁷ Sr-enriched Sr leached from silicate minerals in the siliciclastic portion of the basement sequence and in granites from the study area. Volcanic rocks are ruled out as a significant Sr source for the fluorite deposits. The observed trend in ⁸⁷Sr/⁸⁶Sr versus 1/Sr support a fluid-rock interaction model which satisfactorily reproduces the marked ⁸⁷Sr-enrichment in the fluorites and calcites from the deposits. Received: 19 February 1997 / Accepted: 22 July 1997     

Geochemical,and stable and radiogenic isotope records in Devonian and Early Carboniferous carbonates from Valle de Tena,central Pyrenees (Spain): evidence for their diagenetic environments

Mineralogical, textural and geochemical investigations were made to determine the post-depositional evolution of Devonian and Early Carboniferous carbonates from Valle de Tena. The carbonate association is made up of low-Mg calcite, which occurs as micrite, spar cements, neomorphic patches and spar filling veinlets. Non-stoichiometric dolomite and ankerite occur as cements (dolomite also as replacements) in the Middle Devonian, post-dating calcite types. All these phases pre-date tectonic stylolites, indicating compaction after stabilization of the carbonate minerals. Strontium concentrations indicate that Early Devonian and Early Carboniferous micrites initially precipitated as aragonite; Middle and Late Devonian micrites precipitated as high-Mg calcites. Both precursors were diagenetically stabilized to low-Mg calcites through interaction with meteoric waters in phreatic environments. Trace elements in dolomite and ankerite indicate precipitation from Sr-enriched meteoric water. All studied carbonates, except Middle Devonian limestones, precipitated in reducing environments, which favoured incorporation of Fe and Mn. Late calcite generations precipitated from more saline waters than micrites. Light ¹⁸O values in micrites suggest alteration mainly in meteoric-phreatic environments. The dolomites and ankerites precipitated from more ¹⁸O-depleted fluids than the calcites, suggesting a greater contribution from meteoric waters. Variations in ¹³C of micrites represent primary secular trends, according to published ¹³C variations. The ¹³C oscillations within each succession probably relate to sea-level oscillations. Strontium isotopes also point to a meteoric origin of diagenetic fluids. Model calculations suggest that O and Sr isotopes equilibrated between calcites and fluid at relatively low water/rock ratios, whereas C isotopic signatures are inherited from limestones.     

The Yenefrito Pb-Zn mine (Spanish Central Pyrenees): an example of superimposed metallogenetic events

Three types of base metal deposits occur in the Devonian of the Central Pyrenees accompanying and post-dating the Hercynian orogeny. Since spatial and temporal relationships between mineralization can be recognized in the Yenefrito area, they have been incorporated into a metallogenetic model. Sedex-like ore, composed of sphalerite with minor galena, pyrite, arsenopyrite and magnetite, is enclosed within a carbonate-siltstone succession containing volcanic sills. Crust-type mineralization is linked to an unconformity landscape and made up by quartz and minor sphalerite, pyrite and galena. Finally, vein deposit cross-cutting these deposit types, contains galena, sphalerite and pyrite. Sedex-like and crust-type deposits are linked to Hercynian extensional tectonics which favoured the development of an unstable depositional environment mainly controlled by synsedimentary faults, being sedex mineralizations developed prior to crust-type. Both mineralization types suffered diagenesis and deformation during the Hercynian. The vein-type was generated by extensional movements related to early Alpine rifting. Received: 18 June 1998 / Accepted: 30 June 1998     

Stable isotope composition of Hellenic bottled waters

Bottled waters are an increasingly significant product in the human diet. In this work, we present a dataset of stable isotope ratios for bottled waters sampled in Greece. A total of 25 domestic brands of bottled still waters, collected on the Greek market in 2009, were analysed for δ¹⁸O and δ²H. The measured stable isotope ratios range from − 9.9‰ to − 6.9‰ for δ¹⁸O and from − 67.50‰ to − 46.5‰ for δ²H. Comparison of bottled water isotope ratios with natural spring water isotope ratios demonstrates that on average the isotopic composition of bottled water tends to be similar to the composition of naturally available local water sources, showing that bottled water isotope ratios preserve information about the water sources from which they were derived and suggesting that in many cases bottled water should not be considered as an isotopically distinct component of the human diet. This investigation also helped to determine the natural origin of bottled water, and to indicate differences between the natural and production processes. The production process may influence the isotopic composition of waters. No such modification was observed for sampled waters in this study. The isotopic methods applied can be used for the authentication of bottled waters and for use in the regulatory monitoring of water products.     

Stable isotope constraints on the origin of the Cabo de Creus garnet-tourmaline pegmatites,Massif des Alberes,Eastern Pyrenees,Spain

Pegmatite dyke swarms are exposed within the easternmost Pyrenees at Cabo de Creus. These dykes were emplaced into high-grade metamorphosed sedimentary strata of Cambro-Ordovician age, but lack obvious field relationship to Hercynian intrusive rocks. Together with structural and geochemical data, equilibrium oxygen isotope fractionations at temperatures of ≈ 600°C, the lack of obvious subsolidus exchange, and the H- and O-isotopic signatures of water in equilibrium with pegmatite mica and quartz are interpreted to indicate a derivation from anatexis of a metapelitic source at shallow crustal levels.     

Stable isotope geochemistry and structural elements of the Sabina region (Central Apennines, Italy)

Various tectonic features are present in the Meso-Cenozoic basin units of the Sabina region (Central Apennines, Italy): Mio-Pliocene northeasterly verging thrusts are followed by Plio-Pleistocene, N-S oriented right-lateral strike-slip faults. Stable isotope geochemistry and examination of meso- and microstructures show that strain conditions differed through the course of tectonic history. Carbon and oxygen isotope analyses of the calate-filled extensional fractures, the sigmoidal veins present between stylolitic cleavage surfaces, and fault plane surfaces with differing motion, demonstrate those different geneses.
The "C/'" C of the older calcite-filling fractures (present both in the thrust and the strike-slip systems) suggests a deposition from shallow, fresh water circulation. Furthermore, the calcite fill of en echelon systems, that occur in the southernmost Plio-Pleistocene units, is clearly the result of a more recent, right-lateral strike-slip movement, connected with shallow water circulation within Mesozoic limestones.
The sigmoidal vein fills are derived from solid-state pressure solution processes which were the result of strike-slip movement. The deformation pattern related to the older thrust system is similar, but less intense; this also demonstrates general recrystallization processes in a closed system.
This suggests that the total shortening of the deformed sections is lower than that obtained on the basis of solution on stylolitic planes, because a sigruficant volume of dissolved carbonates remained in the system.
Stable isotope analysis also confirms that the deformational history of strongly cleaved rocks in the Sabina region took place in two phases and that extensional fractures formed before stylolithic planes, as suggested by structural and field observations.     

Geochemical patterns of a sheared fluorite vein, Parzan, Spanish Central Pyrenees

The formation of Parzán fluorite-lead «extension-type» vein (Spanish Central Pyrenees) is related to the post-Hercynian hydrothermal activity widespread not only in the Pyrenees but in Western Europe as well. The lode was later strongly deformed during the Alpine orogeny with textural modifications and destruction of primary fluid inclusions. In order to determine if geochemical signatures of the vein were disturbed during Alpine deformation, post-ore fluid inclusions and quartz oxygen-isotopes have been addressed. Microthermometry and X-ray microanalysis of frozen inclusions confirm the Na-Ca-Cl character of post-ore fluid circulations and indicate that they were originally derived from a single source: Triassic connate waters. Oxygen isotope data on quartz formed during deformation along with trace element geochemistry suggest that the geochemical signatures of the vein (mainly REE and ⁸⁷Sr/⁸⁶Sr) were apparently not reset during deformation. The REE content of fluorites is very high (up to 0.12%); the chondrite normalized REE patterns display a continuous decrease from La to Lu. Sulphur isotope data for the Parzán vein is outside the typical “deep seated” range, suggesting dominantly crustal sources of sulphur for sulphides, while formation waters may be proposed for barite. Parzán fluorites have the most radiogenic Sr values of all the investigated fluorite deposits in Central Pyrenees. They scatter in the range of both the igneous rocks and the Cambrian-Ordovician and Triassic detrital sequences of the Parzán area. If REE contents and ⁸⁷Sr/⁸⁶Sr ratios reflect the primary stage of vein filling as suggested by the good correlation between both geochemical signatures, the linear array between ⁸⁷Sr/⁸⁶Sr and 1/ΣREE is suggestive of a mixing process. The δ³⁴S, δ¹⁸O and ⁸⁷Sr/⁸⁶Sr parameters in barite, which postdates the fluorite, also provide strong evidence that barite deposition is a result of fluid mixing. Such an interpretation is in line with present-day ideas for the genesis of many of the F-Ba-Pb-Zn vein deposits in the Hercynian belt of Iberia.     

Genesis and composition of endogenous borates in the skarns of the Eastern and Central Pyrenees

This paper addresses the genesis and composition of endogenous borates and other minerals from the magnesian-skarn aureoles at the contacts between dolomites and Hercynian granitoid intrusions of the Eastern and Central Pyrenees (Querigut and Costabonne peak massifs in France, and the Monchi deposit in Spain). It was shown that these occurrences and other magnesian skarns in the Sierra Morena Range, Spain, genetically belong to the periclase depth facies: zoned metasomatic aureoles of dolomites of primitive structure complicated by the development of periclase marble zones. The near-contact zones of the intrusions are represented by the granitoids of increasing basicity and alkalinity, which indicates the assimilation of host rocks by overheated granitic magmas. The postmagmatic stage was marked by the formation of magnesium and magnesium-iron borates of diverse composition in calciphyres and marbles, replacement of forsterite by humites in the calciphyres, and the development of silicates of decreasing Mg mole fraction after pyroxene skarns; the latter is accompanied by magnesium migration into the outer zones of the aureole. It was determined that the studied deposits of France contain boron minerals (kotoite, suanite, and pertsevite) previously unknown for this region in association with fluoborite and late szaibelyite. In skarns of Spain, the high-Fe borates are represented by monomineral aggregates of fine-prismatic parallel oriented crystals of vonsenite or its coarse-grained masses. It is conceivable that sulfide-bearing magnesian skarns and calciphyres of the studied deposits contain magnesium hydroxysulfides: tochilinite (after pyrrhotite) and valleriite (after chalcopyrite).     

Strata-bound As-Au mineralization in pre-Caradocian rocks from the Vall de Ribes,Eastern Pyrenees,Spain

In the lower part of a pre-Caradocian series associated with volcanics there are disseminations and lenses of arsenopyrite and pyrite with gold and Bi-Ag-Cu-Pb-Zn-W minerals. These ores are accompanied by veins and epigenetic masses of the same mineralogical composition. The disseminations are found in psammopelitic rhythmites and dolomites which also contain cmthick lenses. The epigenetic bodies, also enclosed in the rhythmites and dolomites, are interpreted as reconcentrations of preexisting disseminations and lenses caused by subsequent phases of deformation.     

The origin of fluids involved in the formation of gold-bearing skarns of the Andorra granite (Central Pyrenees,Spain): Sulphur isotope data

Summary Arsenopyrite-gold mineralization in the lower Paleozoic series of the eastern Pyrenees is of two types: disseminated in Hercynian metasediments, and veins cross-cutting the main foliation. In the central Pyrenees, gold-bearing arsenopyrite mineralizations have recently been discovered in skarns along the SW contact of the Andorra granite. The ore minerals are similar to those of the veins, with gold also being associated with arsenopyrite, bismuth and sulphides.The late Hercynian Andorra granite intruded Paleozoic metasediments of pre-Caradocian to Carboniferous age. Six types of skarns have developed at or close to the contact between the granite and Devonian limestones. Only three of these, the hedenbergite, pyrrhotite and arsenopyrite skarns, are sulphide-bearing. Gold grades in these skarns range from less than 0.8 g/t in pyrrhotite skarns to 7 g/t in arsenopyrite skarns.The ³⁴S of arsenopyrite from disseminated and vein mineralizations show values from 11 to 15, indicating a sulphur source of crustal origin. Vein sulphides are considered to have formed after a metamorphic remobilization of the sulphide rich disseminations in the Paleozoic series. Sulphur isotopic composition of skarn sulphides is variable: pyrrhotite from pyrrhotite skarns has a ³⁴S +, suggesting a sulphur of magmatic origin. Their gold grades are very low (>0.8 g/t). The heavier values of arsenopyrite from arsenopyrite skarns (³⁴S + 10) and of galena and sphalerite from hedenbergite skarns (³⁴S + 7) correlate with the higher gold grades (7 and 5 g/t, respectively). This is interpreted to reflect a contribution of wall-rock sulphur-rich fluids generated from the thermal metamorphism of arsenopyrite-bearing wall-rock metasediments (³⁴S + 12%o) during skarn formation or by assimilation of country rock by the granitic intrusion during its emplacement. The economic importance of these skarns appears to be related to the amount of crustal fluid involved in skarn formation.

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Lagerstättenbildende Fluide in den goldführenden Skarnen des Andorra-Granites, Zentralpyrenäen, Spanien: Schwefelisotopen-Daten

Zusammenfassung Arsenkies-Goldmineralisation in altpaläozoischen Serien der ostlichen Pyrenäen tritt in zwei Typen auf: Disseminiert in Hercynischen Metasedimenten, und in Gängen, die die Haupt-Foliation durchschlagen. In den Zentralpyrenäen wurden goldführende Arsenkies-Mineralisationen vor kurzem in Skarnen längs des SW-Kontaktes des Andorra-Granites entdeckt. Die Erzminerale sind ähnlich denen in den Gängen, wobei Gold mit Arsenkies, Wismut und Sulfiden assoziiert ist. Der spät-hercynische Andorra-Granit intrudierte paläozoische Metasedimente von Prä-Caradoc bis Karbon-Alter. Im Kontaktbereich Granit/Devonische Kalke kommen sechs Typen von Skarnen vor. Nur drei davon führen Sulflde, nämlich die Hedenbergit-, Magnetkies- und Arsenkiesskarne. Goldgehalte in diesen Skarnen schwanken von weniger als 0,8 g/t in Magnetkiesskarnen bis zu 7 g/t in Arsenkiesskarnen. Das ö34 S von Arsenopyrit in disseminierten und Gang-Mineralisationen schwankt von 11-15%o, und dies weist auf eine Schwefelquelle in der Kruste hin. Gangsulflde haben sich auch nach einer metamorphen Remobilisierung der Sulfid-reichen Disseminationen in den paläozoischen Serien gebildet. Die Schwefelisotopenzusammensetzung der Skarnsulfide schwankt: Magnetkies aus Magnetkiesskarnen hat ö34 S Werte von +4%o, dies weist auf magmatischen Ursprung hin. Ihre Goldgehalte sind sehr niedrig (<0,8 0,8 g/t). Die schwereren Isotopen von Arsenkies in Arsenkies-Skarnen ( ³⁴S+ 10%o) und von Bleiglanz und Zinkblende aus den Hedenbergit-Skarnen ( ³⁴S+ 7%o) lassen sich mit höheren Goldgehalten (7 und 5 g/t) korrelieren. Dies wird Fluiden zugeschrieben, die reich an Schwefel aus den Nebengesteinen sind und durch die thermale Metamorphose der Arsenkies-führenden Metasedimente (S + 12%o) während der Skarnbildung, oder durch Assimilation von Nebengestein durch den Granit wahrend seiner Platznahme entstanden sind. Die wirtschaftliche Bedeutung dieser Skarne scheint in einer direkten Beziehung zur Menge krustaler Fluide zu stehen.

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This paper was presented at the IGCP 291 Project Symposium Metamorphic Fluids und Mineral Deposits, ETH Zürich, March 21–23, 1991.     

Anthropic effects on hydrochemical characteristics of the Valle de Toluca aquifer (central Mexico)

The Valle de Toluca aquifer, located in the Highlands of Mexico, is subject to intensive exploitation to meet the water demand in the valley, as well as for part of Mexico City. This intensive exploitation has produced a decline in groundwater level, land subsidence problems and a decrease in river and spring flows. This study is aimed at determining the extent to which the intensive groundwater abstraction is able to affect and modify the chemical characteristics of the water, using statistical techniques and historical data on the main physico-chemical parameters. Some changes in the chemical characteristics have been verified; initial water abstractions were mainly derived from a local flow zone (rainwater recharge and lateral flows from other aquifers), but currently the chemical characteristics are those of a regional flow zone, revealed by waters of sodium bicarbonate type. An increase in nitrate content has also occurred, although only occasionally is the limit for potable water (50 mg NO₃^- L^-1) exceeded.

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Resumen El acuífero del Valle de Toluca, localizado en el Altiplano Mexicano, se encuentra sometido a una intensa explotación para cubrir las necesidades de agua en el propio valle, así como parte de las de Ciudad de México. Los altos niveles de explotación han provocado el descenso del nivel piezométrico, problemas de subsidencia, disminución de caudales en ríos y desecación de manantiales. Este estudio pretender determinar en qué grado esta intensiva extracción del agua subterránea es capaz de afectar y modificar el quimismo del agua. Para ello se han empleado técnicas estadísticas y datos históricos de los principales parámetros físico-químicos. Se ha podido comprobar que existen algunos cambios en el quimismo, ya que, inicialmente, el agua extraída del acuífero estaba ligada en gran medida a un flujo local (recarga por agua de lluvia y por alimentación lateral desde otros acuíferos) mientras que ahora el quimismo es característico de un flujo regional, puesto de manifiesto por aguas de tipo bicarbonatado sódico. Adicionalmente, también se ha producido un aumento del contenido de nitratos, aunque sólo de forma ocasional se sobrepasa el límite para agua potable (50 mg NO₃^– L^–1).

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Résumé Laquifère Valle de Toluca, localisé dans les Hautes Terres du Mexique, est sujet à lexploitation intensive pour combler la demande importante en eau dans la vallée et dans une partie de Mexico. Cette exploitation intensive a causé une baisse importante des niveaux piézométriques, des problèmes daffaissement et de baisse de débits des sources et des rivières. Cette étude a pour objectif de déterminé la limite jusquà laquelle lexploitation intensive pourra affecté et modifié les caractéristiques chimiques de leau, en utilisant des techniques statistiques et des données historiques des principaux paramètres physico-chimiques. Certains changements des caractéristiques chimiques ont été vérifiés ; les premières eaux captées ont été compensées par dautres zones dalimentation (recharge par les eaux de pluie et écoulements latéraux venant dautres aquifères), mais couramment les caractéristiques chimiques sont bien ceux de la zone découlement régional, à faciès sodi bicarbonaté. Une augmentation des concentrations en nitrate est également mis en valeur, néanmoins la limite de potabilité (50 mg/l) est rarement dépassée.

     

Early Pragian conodont‐based correlations between the Barrandian area and the Spanish Central Pyrenees

Occurrences and distribution of extremely scarce eognathodontids do not facilitate reliable correlation across the European regions. The correlation of the traditional early Pragian of the Prague Synform (a part of the classical Barrandian area) and the Spanish Central Pyrenees (section Segre 1) is based on conodont taxa of the Icriodus steinachensis and the Pelekysgnathus serratus stocks. This correlation has the potential to be extended to other peri‐Gondwanan regions where this scarcity of eognathodontid faunas exists as well. Application of the morphotype subdivision in I. steinachensis enables approximation of the beginning of the Pragian in the Pyrenees. It is based on the entry of I. steinachensis beta morphotype; it enters together with early eognathodontid taxa in the Barrandian sections. These correlations show that routine application of certain zonal concepts can lead to misleading conclusions. Copyright © 2007 John Wiley & Sons, Ltd.     

Stable isotope studies of the origins of mineralization at Mount Isa. I.

Further support for the view that mineralization at Mount Isa comprises two separate events is provided by ³⁴S/³²S measurement. Isotopic exchange between sulphides in lead-zinc-silver ores appears to have been promoted locally during metamorphism, whereas isotopic disequilibrium persists in the copper ores. These isotopic data are explained by a model in which sedimentary deposition of lead, zinc and silver was succeeded by the post-metamorphic emplacement of copper. Past biological activity is inferred from the occurrence of low concentrations of organic carbon with ¹³C values ranging from –21 to –26 PDB. Carbonate contents, expressed as carbon, vary from <0.1% to 10.9%. The ¹³C and ¹⁸O values for the carbonates are relatively constant at –4.4±1.1 and –17.6±1.1 PDB respectively. These values are interpreted as reflecting isotopic changes induced in original marine carbonates by isotopic exchange during lower greenschist metamorphism.     

南昌市PM2.5中稳定碳同位素组成特征

近几年,PM2.5浓度上升导致灰霾事件频繁发生,已经引起了广泛的关注。碳组分是PM2.5中的重要组分,被认为是灰霾形成和转化的重要因素,因此,研究PM2.5中含碳组分的来源及其化学过程具有重要的意义。本研究于2016年12月至2017年8月期间在南昌地区共采集105个PM2.5样品,分析了PM2.5样品中总碳(TC)浓度及其碳同位素(δ^13C)。结果表明,采样期间TC的年平均浓度为(12.1±2.1)μg/m^3,总体上呈现冬季高、夏季低的变化趋势,可能是受不同季节气象因素和来源变化的影响。δ^13C的年平均值为(?26.1±0.2)‰,总体上呈现冬季高、春季低的变化趋势,可能是受不同来源的影响。利用贝叶斯模型计算南昌地区PM2.5中TC主要来源于C3植物燃烧和机动车尾气,年源贡献分别为49.3%和28.7%;其次是煤燃烧和C4植物燃烧,年源贡献分别为17.7%和4.2%。春季δ^13C值偏低是由于C3植物燃烧贡献相对较高,而冬季δ^13C值偏高则是煤燃烧贡献增加。     

Genesis of the three concentrically-zoned granitoid Plutons of Cauterets-Panticosa (French and Spanish Western Pyrenees)

The petrogenesis of the Hercynian plutons of Cauterets-Panticosa was deduced from detailed cartographic, petrographic, chemical (> 300 analyses) and mineralogical evidence. The three adjacent calc-alkaline plutons were derived from a siliceous continental magma modified to varying degrees by hybridization with a mafic mantle-derived magma. The mafic inclusions are evidence for the mafic parent magma. Each of the three plutons is made up of several more or less concentrically disposed granitoid units. This concentric zonation is either recurrent (West Cauterets Pluton), or normal (Panticosa Pluton), or both normal and recurrent (East Cauterets Pluton). The combination of several processes (hybridization, differentiation, multiple intrusion, subterranean collapse) was responsible for the genesis of the three plutons.

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Zusammenfassung Diese Publikation gibt eine Übersicht der kartographischen, petrographischen und chemisch-mineralogischen (> 300 Analysen) Arbeiten, die in den granitoïden Massiven von Cauterets-Panticosa unternommen wurden. Es handelt sich um drei kalkoalkaline Massive, die nebeneinanderliegen, und die während der variskischen Orogenese in einem metasedimentären, gefalteten, epizonalen Zusammenhang entstanden sind. Die Herkunft der Granitoïde von Cauterets-Panticosa wird auf Grund der Ergebnisse der vergleichenden chemisch-mineralogischen Arbeiten zwischen diesen Granitoïden mit ihren basischen Einschlüssen diskutiert. Diese Granitoïde stammen aus vier Grund-Magmen. Jedes dieser vier Magmen soll durch Hybridation mit einem erdmantel-basischen Magma eine mehr oder weniger stark veränderte Fraktion eines sialischen, sauren Magmas darstellen. Die Einschlüsse weisen auf das erdmantel-basische Magma hin. Der Ursprung all dieser Granitoïde läge gleichzeitig in der kontinentalen Kruste und im Mantel. Jeder dieser drei Massive von Cauterets-Panticosa besitzt eine zonale, konzentrische Struktur. Im westlichen Massiv von Cauterets ist diese Struktur rekurrent. Im Massiv von Panticosa ist sie normal und regelmäßig und komplex im östlichen Massiv von Cauterets. Die Beobachtungen im Gelände und die zahlreichen chemisch-mineralogischen Angaben geben Aufschluß über den Ursprung jeder dieser drei Strukturen ebenso wie über die Granitoïd-Einheiten, die sie zusammensetzen. Die Genese der drei Granitoïd-Einheiten des westlichen Massivs wird durch magmatische Hybridationsprozesse erklärt. Die rekurrente Struktur dieses Massivs ist hingegen an vielfache Injektionen und an ein intrakrustales Zusammenschmelzen älterer Granitoïde gebunden. Die magmatische Differentiation einer einzigen Intrusion — hauptsächlich in größerer Tiefe — vor und während der Platznahme, wäre für die Genese der vier granitoïden Haupteinheiten, und für die normale und gleichzeitige Struktur des Massivs von Panticosa verantwortlich. Die fünf granitoïden Haupteinheiten und die komplexe Struktur des östlichen Massivs würde aus einer Kombination der Prozesse, die im westlichen Massiv und im Massiv von Panticosa beobachtet wurden, hervorgehen.

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Résumé Cette note dresse le bilan pétrogénétique des travaux cartographiques, pétrographiques et chimico-minéralogiques (> 300 analyses) détaillés récemment effectués sur les granitoïdes et leurs enclaves des massifs de Cauterets-Panticosa. Il s'agit de trois massifs calcoalcalins, juxtaposés sur le terrain et d'âge hercynien. L'étude comparée des granitoïdes et de leurs enclaves «microgrenues basiques» montre que ces massifs dériveraient d'un magma continental acide plus ou moins modifié par hybridation avec un magma mantellique basique. Par ailleurs, chacun des trois massifs se compose de plusieurs unités granitoïdes disposées de façon concentrique. Cette structure concentrique est soit récurrente (massif occidental de Cauterets), soit normale et régulière (massif de Panticosa), soit, enfin, tout à la fois normale et récurrente (massif oriental de Cauterets). La combinaison de plusieurs processus (hybridation sélective ou globale, différenciation, intrusions multiples, effondrements souterrains) serait responsable de la genèse des ces trois massifs.

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Stable isotope geochemistry and diagenetic mineralization associated with the Tono sandstone-type uranium deposit in Japan

The Tono sandstone-type uranium mine area, middle Honsyu, Japan is composed of Miocene lacustrine sedimentary rocks in the lower part (18–22 Ma) and marine facies in the upper part (15–16 Ma). Calcite and pyrite occur as dominant diagenetic alteration products in these Neogene sedimentary rocks. The characteristics of calcite and pyrite differ significantly between lacustrine and marine facies. Abundant pyrite, calcite, organic matter, and small amounts of marcasite or pyrrhotite occur in the lacustrine facies, whereas small amounts of calcite and framboidal pyrite, organic matter and no marcasite or pyrrhotite are found within the marine units. The δ¹³C values of calcite in the lacustrine deposits are low (−19 to −6‰ PDB) but those in marine formation are high (−11 to +3‰). This implies that the contribution of marine carbonate is larger in upper marine sedimentary rocks, and carbon in calcite in the lower lacustrine formation was derived both from oxidation of organic matter and from dissolved marine inorganic carbon. The δ³⁴S values of framboidal pyrite in the upper marine formation are low (−14 to −8‰ CDT), indicating a small extent of bacterial seawater sulfate reduction, whereas those of euhedral-subhedral pyrite in the lower lignite-bearing arkose sandstone are high (+10 to +43‰), implying a large extent of closed-system bacterial seawater sulfate reduction. The δ³⁴S and δ¹³C data which deviate from a negative correlation line toward higher δ¹³C values suggest methanogenic CO₂ production. During diagenesis of the lacustrine unit, large amounts of euhedral-subhedral pyrite were formed, facilitated by extensive bacterial reduction of seawater sulfate with concomitant oxidation of organic matter, and by hydrolysis reactions of organic matter, producing CH₄ and CO₂. Uranium minerals (coffinite and uraninite) were also formed at this stage by the reduction of U⁶⁺ to U⁴⁺. The conditions of diagenetic alteration within the lacustrine deposits and uranium mineralization is characterized by low Eh in which nearly equal concentrations of CH₄ and HCO₃ ⁻ existed and reduced sulfur species (H₂S, HS⁻) are predominant among aqueous sulfur species, whereas diagenetic alteration of the marine formations was characterized by a predominance of SO₄ ²⁻ among dissolved sulfur species. Modern groundwater in the lacustrine formation has a low Eh value (−335 mV). Estimated and measured low Eh values of modern and ancient interstitial waters in lacustrine environments indicate that a reducing environment in which U⁴⁺ is stable has been maintained since precipitation of uranium minerals. Received: 9 February 1996 / Accepted: 11 April 1997     

The Barranco de Arás flood of 7 August 1996 (Biescas, Central Pyrenees, Spain)

Geomorphic effects observed in the Barranco (creek) de Arás basin are used to characterize the flood. Sediment features allow to qualify the flood as essentially a water flow. Using the critical section method, the peak flood discharge is estimated to be between 400 and 600 m³ s⁻¹. Similar results were obtained using a paleohydraulic formula based on the size of the largest mobilized clasts. Using the rational method with available rainfall data, the discharge for a recurrence interval of 500 years is estimated to be between 150 and 200 m³ s⁻¹. These results agree with predictions obtained using curves of peak discharge versus basin area based on regional data. Several trenches dug on the fan showed that the size of boulders mobilized by the event is larger that those left by previous floods at the same place. When the estimated peak flood discharge is related to the basin area, values between 20 and 30 m³ s⁻¹ km⁻² are obtained, demonstrating that the Barranco de Arás flood was most unusual.     

Asynchroneity of maximum glacier advances in the central Spanish Pyrenees

The deglaciation history of the Escarra and Lana Mayor glaciers (Upper Gállego valley, central Spanish Pyrenees) had been reconstructed on the basis of detailed geomorphological studies of glacier deposits, sedimentological and palynological analyses of glacial lake sediments and an accelerator mass spectrometry (AMS) ¹⁴C chronology based on minimum ages from glacial lake deposits. The maximum extent of the Pyrenean glaciers during the last glaciation was before 30 000 yr BP and pre‐dated the maximum advances of the Scandinavian Ice Sheet and some Alpine glaciers. A later advance occurred during the coldest period (around 20 000 yr BP), synchronous with the maximum global ice extent, but in the Pyrenees it was less extensive than the previous one. Later, there were minor advances followed by a stage of debris‐covered glaciers and a phase of moraine formation near cirque backwalls. The deglaciation chronology of the Upper Gállego valley provides more examples of the general asynchroneity between mountain and continental glaciers. The asynchroneity of maximum advances may be explained by different regional responses to climatic forcing and by the southern latitude of the Pyrenees. Copyright © 2002 John Wiley & Sons, Ltd.     

Mineralisation from Vall de Ribes area (Eastern Pyrenees,Spain)

Vein mineralisation with no preferred orientation, cutting lower Palaeozoic rocks, and local replacement deposits in dolomite show a zoning in tungsten-bismuth, arsenic and antimony minerals away from the adjacent late-Hercynian Costabona granite. A local reversed zoning is related to higher temperatures indicated by fluid inclusion study. Many of the minerals have not previously been reported from this area.