The geochemical evolution of the Catalan potash subbasin, South Pyrenean foreland basin (Spain)

Over the last decade, our studies in ancient evaporitic basins have been based on a detailed study of a single borehole record. The detailed findings in medium- to large-sized evaporitic basins were shadowed with a relevant question: can interpretations from a representative evaporitic record in a single borehole be extended to the whole evaporitic basin? This paper addresses that question; the results obtained are compared with results from another distant point within the basin. The general methodology not only proves its reliability in interpreting the evolution of evaporitic basins from a single borehole but reveals its capability to obtain detailed palaeoenvironmental interpretations.

The chemical evolution of an Upper Eocene evaporitic sequence from the South Pyrenean foreland basin (Spain) has been investigated along the Súria-19 borehole record. Detailed petrographic and mineralogical study, X-ray microanalysis of frozen primary inclusions trapped in halite (Cryo-SEM-EDS), systematic isotopic analysis (δ³⁴S and δ¹⁸O in sulphates) and computer-based evaporation models have been integrated in a multi-proxy methodology. This study revealed that a variable amount of Ca excess is required throughout different parts of the marine Lower Halite Unit (LHU) for sylvite, instead of K–Mg sulphates, to form. This Ca excess is in turn different from that required for the western sector of the same evaporitic basin (Navarrese subbasin). Quick and variable changes in Ca-rich brines or equivalent dolomitization required are explained as internal processes within the basin rather than secular variations in seawater chemistry.

The general hydrological evolution of the Catalan subbasin is explained as a restricted subbasin with a first marine stage in which continental input (up to 50% of total input) had an important control on the geochemistry of the subbasin. A second stage was determined during potash precipitation, in which the subbasin was cut from any seawater input to end up in its last stage as a purely continental evaporitic basin. Coupling evaporation models and analytical results we have obtained the proportions of recycling and their sources, estimated to change from a 100% (total mass of sulphate) Eocene source to 20% Eocene and 80% Triassic (Keuper) towards the latest stage of potash precipitation. The results obtained have been compared with results from the Navarrese subbasin allowing an integrated interpretation of the hydrological evolution of the whole Upper Eocene South Pyrenean basin. Local geochemical variations within the Upper Eocene south Pyrenean basin are explained by the differences in paleogeographical setting of the Navarrese and Catalan subbasins.     

Geochemistry of evaporite-bearing series: A tentative guide for the identification of metaevaporites

Literature on metasedimentary rocks indicates that former evaporites have been assumed where brines are present as fluid inclusions or minerals such as scapolite, tourmaline and lazurite, which are considered as evidence of equilibria with brines. Very few works take into account the chemical composition of rocks, because chemical data on evaporite-bearing sedimentary series are scarce.This paper is a contribution to a geochemical approach: 172 analyses of major and trace elements are given on argillites, dolomitic marls and mixed sulphate rocks from some large evaporitic series, mainly from the Triassic of France, the Devonian of the Canning Basin and the Proterozoc of the Amadeus Basin in Australia. Compared with rocks from common platform series, these samples clearly exhibit specific chemical features: high Mg contents, high Mg/Ca ratios except for Ca-sulphate-rich rocks and relatively low iron contents caused by the widespread occurrence of Mg-rich clay minerals. Though sulphate-bearing rocks often show low Mg/Ca ratios, their chemical composition clearly indicates Mg-rich clay fractions. K content is high while Na is low, except in a few halite-bearing rocks. Argillites are characterized by high Li and F contents, and high Li/Mg and B/A1 ratios, while major amounts of Sr are recorded in sulphatebearing rocks.Application to metamorphic series is discussed with some illustrative examples. Though chemical changes during metamorphism are probably frequent in series of evaporitic origin, some relations between Al, Fe, Mg, Ca are often maintained. Under nearly isochemical conditions, the resulting metasediments exhibit abundant phlogopite through a large part of the metamorphic column, owing to high Mg, K and F contents. Such rocks are, for instance, well developed in the Zambian Copperbelt, Central Africa. Although further investigations are needed both on nonmetamorphic and metamorphic evaporite sequences, the efficiency of this approach for identifying an evaporitic origin is well established.     

Carbon, oxygen, and sulfur isotope compositions of carbonate and sulfate rocks from the Famennian potassium-bearing subformation of the Pripyat trough

Peculiar features of evaporitic process at the stage of potassium accumulation are considered on the basis of carbon and oxygen isotope data on carbonate rocks and sulfur isotope data on anhydrite from the Famennian potassium-bearing subformation of the Starobin potassic salt deposit in the Pripyat trough. It was found that potassium accumulation was accompanied by the influx of continental waters and highly concentrated brines, while the formation of thick salt-free units was related to the replenishment of fresh seawater to the basin.     

The evaporitic celestite-barite deposits of Neuquen,Argentina

Celestite-barite occurrences of early Cretaceous age were studied in the Extra-Andean region of Neuquén, West central Argentina. The ores are located in a Subandean Mesozoic belt and show a conspicuous stratabound character related to evaporitic facies. The study of the geologic evolution of the sedimentary sequence allows prediction of the temporal and spatial setting of the evaporitic facies. Stratigraphy is the main geologic control for the celestite-barite ores and their areal distribution depends on the structure of the region. Based on the geometry and texture of the mineralization three types of ores have been recognized: 1) celestite beds syngenetic with the evaporitic facies; 2) epigenetic stratabound ores formed by "in situ" mobilization of celestite with stalactite growth and cavity infilling; 3) epigenetic vein-type ores formed by mobilized barium enriched solutions.Lithofacies and isotopic ⁸⁷Sr/⁸⁶Sr analyses together with the geological evidence confirm an evaporitic origin for the celestite beds.     

87Sr/86Sr composition of evaporitic carbonates and sulphates from Miocene sediment cores in the Mediterranean Sea (D.S.D.P., Leg 13)

The ⁸⁷Sr/⁸⁶Sr ratios of evaporitic carbonates and sulphates from Miocene sediment cored in the Mediterranean Sea show a depletion of ⁸⁷Sr when compared to the isotopic composition of the Miocene contemporaneous marine strontium: 0.70803 versus 0.70936. The arrival into the evaporitic environment of strontium brought by continental waters can explain this difference. The variation of the ⁸⁷Sr/⁸⁶Sr ratios is, nevertheless, noticeable only when the influence of the continental waters is already well marked. This is proved when one compares the results obtained with strontium, to the results of isotopic analysis made on oxygen, carbon, sulphur and hydrogen taken from the same samples.     

The origin of scapolite in the regionally metamorphosed rocks of Mary Kathleen,Queensland, Australia

Scapolite at Mary Kathleen (North-Western Queensland) occurs in calcareous and non-calcareous metapelites, acid and basic metavolcanics and metadolerites. Graphical treatment of the relationship between scapolite composition (Me%) and the host rock oxide ratios CaO/Na₂O and Al₂O₃/(CaO + Na₂O) reveals the following points:

1. The calcareous metapelites are also very sodic.
2. Scapolite in calcareous metapelites is more marialitic than that in low-calcium equivalents.
3. In graphs of Me% against CaO/Na₂O and Al₂O₃/(CaO + Na₂O) the metasediments and the metaigneous rocks show markedly different trends.

It is concluded that scapolite in the metasediments originated by isochemical metamorphism of shales and marls containing evaporitic halite. The local abundance of halite was the main control on the composition and distribution of the scapolite, but the relative abundance of CaO and Na₂O was a modifying factor. In the metaigneous rocks scapolite formed metasomatically during regional metamorphism by the introduction of volatile-rich fluids derived from the adjacent evaporitic sediments. The relative availability of CO₂ and Cl₂ again appears to have been the primary control on scapolite composition and may in turn have been controlled by bulk rock composition.     

Isotopic Composition of Oxygen and Carbon and Formation Temperature of Accessory Minerals from Evaporitic Sediments in the Pripyat Trough

The isotopic composition of oxygen and carbon was studied in accessory carbonates and quartz separated from salts in Upper Devonian halogenous formations of the Pripyat Trough (Belorus). It is established that isotopic characteristics vary in a wide range. Values of ¹⁸O vary in the following range (SMOW): from 18.2 to 29.2 in calcites, from 15.7 to 32.5 in dolomites, and from 17.4 to 27.2 in quartz. Values of ¹³C range from –13.4 to 1.4 in calcites and from –11.1 to 1.7 in dolomites (PDB). Results obtained indicate highly variable isotope-geochemical conditions of sedimentation and early diagenesis during the formation of evaporitic sediments. Accessory minerals were repeatedly formed in a wide temperature range and probably at various stages of the lithogenesis.     

The influence of peripheral sabkhas on the geochemistry and sedimentology of a Tunisian lagoon: Bahiret el Biban

Bahiret el Biban is a restricted lagoon in an arid climate. The general geological setting is briefly analysed, especially with respect to the relations between the water body and its evaporitic bordering areas, i.e. supratidal sabkhas. The geochemical behaviour of the lagoon waters has been studied over a 2-year period following floodings. In spite of some exchange with the open sea, there is a general tendency towards increasing salinity, calcium sulphate impoverishment and a consequent increase of the Mg/Ca ratio. Thus, unless large floodings occur, the basin waters undergo an evaporitic evolution. Sedimentation and early diagenesis are controlled largely by this geochemical pattern, but also by exchange with the open sea and by the water depth. Organic matter derived from the sea is deposited on entering this highly saline basin and locally produces sediments which could eventually become source rocks. Bahiret el Biban is a possible model which may be of considerable interest in the reconstruction of the early stages of the evolution of evaporitic basins.     

Geological framework of the Brazilian continental margin

Based on distinctive stratigraphic and/or structural characteristics, the Brazilian continental margin can be divided into two main provinces:

1. The southeastern-eastern province, extending from the Pelotas to the Recife-João Pessoa Basin, presents a tensional tectonic style of Late Jurassic-Early Cretaceous age, paralleling the structural alignements of the Precambrian basement, except in the north-eastern segment where the Mesozoic faults of the Recife-João Pessoa Basin cut across the east-west basement directions. The basin-fill, Upper Jurassic through Recent, consists, where complete, of three stratigraphic sequences, each of a distinct depositional environment: (a) a lower clastic non-marine sequence; (b) a middle evaporitic sequence, and (c) an upper clastic paralic and open marine sequence.
2. The northern province, extending from the Potiguar Basin to the Amazon Submarine Basin, displays both tensional and compressional tectonic styles of Upper Jurassic (?) to Upper Cretaceous age either paralleling or cutting transversally the basement alignments. The stratigraphic column differs from the southeastern-eastern province in lacking the Lower Cretaceous evaporitic rocks.

The integration of the stratigraphie and structural data allows one to determine in the eastern Brazilian marginal basins the main evolutionary stages of a typical pull-apart continental margin: a continental pre-rift and rift stage, an evaporitic proto-ocean stage, and a normal marine open ocean stage. In the northern province it is possible to infer a continental rift-valley-stage, a transform stage and an open continental-margin stage. The relationship between the rift-valley and the transform stages is yet not clear.     

Evolution of photoautotrophy and early atmospheric oxygen levels

Current photochemical models suggest that oxygen levels in the prebiological atmosphere were extremely low, most probably remaining in the range 10⁻⁸–10⁻¹⁴ PAL (present atmospheric level). It is, therefore, reasonable to assume that only life processes were able to overwhelm these minor O₂-pressures, with free oxygen resulting from the reduction of carbon dioxide to the carbohydrate level during photoautotrophic carbon fixation using water as an electron donor (

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). It is by now well established that reduced (organic) carbon is a common constituent of sedimentary rocks from the very start of the geological record 3.8 Ga ago. Both direct assays and inferences derived from a carbon isotope mass balance suggest that the C_org-content of Archaean sediments was not basically different from that of geologically younger rocks. This poses the problem of the existence 3.5 Ga ago of an oxidation equivalent of such a formidable ancient C_org-reservoir which, depending on the model adopted for the growth of the sedimentary mass through time, might have amounted to between 20 and 100% of the present one. Low atmospheric oxygen pressures in the Early Precambrian that are inferred from retarded oxidation reactions, notably in the ancient continental weathering cycle, are likely, therefore, to indicate extremely rapid processes of oxygen consumption in other parts of the system (e.g., hydrosphere) rather than the general absence of photosynthetic oxidation equivalents during this time.     

Isotope (δ13C and δ18O) compositions of dolomites from the Permian evaporitic sequences of the Eastern Russian Plate: Evidence from the Syukeevo gypsum deposit

Carbon and oxygen isotope compositions has been studied in dolomites of the Syukeevo gypsum deposit located in the Eastern Russian Plate. Values of δ¹³C in the dolomites vary from 0.3 to 6.6 ‰; δ¹⁸O, from 28.0 to 36.6‰. It is shown that the dolomites were formed in the epicontinental evaporitic basin in different paleoecological settings. This led to the formation of diverse lithological types of dolomites with peculiar isotope-geochemical features.     

The structure of Jebel El Mourra,Tunisia: a diapiric structure causing a positive gravity anomaly

Detailed gravity data integrated with geological data and mining well data are analysed to constrain the shape of the Triassic evaporitic body at Jebel El Mourra (northern Tunisian Atlas) and the mechanism of its emplacement at the surface. The gravity data analysis included the construction of a gravity anomaly maps, and synthetic and forward 2.5D gravity models. The complete Bouguer and residual gravity anomaly maps indicate a positive amplitude gravity anomaly over the Triassic evaporitic outcrops and prominent NE–SW‐trending features associated with the boundary of the Triassic rocks and surrounded layers. A NW–SE‐trending gravity model that crosses the Triassic evaporitic outcrop at Jebel El Mourra shows that the positive gravity anomaly can be explained by a deep‐rooted salt diapir. Conventional models of salt dome formation suggest that they produce negative gravity anomalies; however, this study shows that this model is not universal. The studied area is an example of a diapir expressed by positive gravity anomaly and this result is supported by synthetic gravity models at different stages of salt piercing.     

The Albert Formation of New Brunswick: a paleozoic lacustrine model

Recent work on the Lower Carboniferous Albert Formation of New Brunswick, Canada, has confirmed it to be mainly limnitic (lacustrine) in origin. Within its smallsized basin (ca. 4,000 sq. km.) over 1,300 m of sediment were deposited. These greyish beds are stratigraphically bounded below, above, and toward the south by terrestrial, mainly redbed, formations. Abundant organic varves in a dolomitic marlstone are present, and in places contain articulated fish skeletons. Elsewhere, symmetrical ripple-marks predominate, testifying to gentle water-current movements. The crossopterygianLatvius sp. dates basal beds, in part at least, as Upper Devonian. Ostracodes from an upper member —Euestheria sp., cf.E. lirella; Hilboldtina sp.,Carbonita sp., cf.C. subula — are from the Carboniferous. It is concluded that the Albert Formation was deposited in a tropical or sub-tropical environment, probably in an east-trending rift valley or fault-block basin, over a period of several hundred thousand years, and terminating with evaporitic deposits, at least a part of which were non-marine in origin.     

The geological setting of tourmalinite at Rum Jungle,N.T., Australia — genetic and economic implications

Tourmalinite is a common rock type associated with Proterozoic strata-bound mineral deposits. Although common, it is often difficult to recognise in the field, leading to misidentification. It occurs as a conformable banded quartz-tourmaline lithological unit comprising at least 15% and as much as 50% of the rock. At Rum Jungle, tourmalinite occurs within the oldest sediments (arenites and magnesites) as distinct lenses, as facies equivalents of quartz-magnetite units and mafic schists (tuffs?) and distal equivalents of polymetallic sulfides. Distinct layering, slump folding, rip-up clasts and the association with diagenetic pyrite suggest a sedimentary environment. Enechelon fracturing of the fine-grained, light green tourmaline crystals spectacularly supports pre-deformation formation. The crystals are optically and chemically zoned parallel to the c axis, with irregular growth lamellae width — which supports a pre-regional metamorphic origin. Analyses show the tourmaline to be the Mg-rich variety “dravite”. Most tourmalinites are interpreted as subaqueous marine deposits. It is more likely that they form in lacustrine, shallow water, evaporitic environments, particularly continental rifts. Suitable B-bearing fluids can be generated by hotspring activity and mobilized by CO₂-rich fluids. Association with chemical sediments suggests tourmalinites also have a chemical sediment precursor. Ample evidence at Rum Jungle supports the notion of a continental rift environment, which was the site of deposition of fluvial arenites and alkaline, evaporitic lake sediments. Localised hot-spring activity contributed B-bearing fluids which precipitated chemical sediments according to the pertaining pH, temperature etc. Diagenetic alteration produced the tourmalinite now present. These tourmalinites are comparable to those of similar age elsewhere e.g. Sullivan, Broken Hill. They can be genetically modelled upon Recent borate concentrations, all of which occur in continental rift environments.     

Cordierite-anthophyllite rocks from north-west Queensland, Australia: metamorphosed magnesian pelites

Abstract Cordierite-anthophyllite rocks and related cordierite-rich, talc-rich and chlorite-rich rocks occur in the Rosebud Syncline, north-west Queensland, Australia, as part of a Proterozoic metasedimentary sequence. Field relations and rock compositions attest the sedimentary origin of these rather unusual metamorphic rocks. Their chemical composition is comparable to that of unmetamorphosed, alkali- and Ca-poor pelites, which are associated with some evaporite deposits. Other occurrences of cordierite-anthophyllite rocks have commonly been interpreted as metamorphosed chloritic alteration products derived from mafic or felsic volcanics. A comparative chemical study, using analyses of cordierite-anthophyllite rocks from such alteration zones and analyses of unmetamorphosed magnesian pelites, demonstrates the general chemical similarity between these two rock groups of entirely different origin. However, distinct differences in major element relations help to distinguish these two genetic groups. Particularly useful are Al₂O₃–FeO–MgO plots, in which evaporitic pelites occupy the Fe-poor side. The highly magnesian metamorphic rocks from the Rosebud Syncline fall entirely into the compositional field of evaporitic clays and shales. Furthermore, analyses of relatively immobile trace elements give supporting evidence for the sedimentary origin of these cordierite-anthophyllite rocks. The correlation with trace element ranges of clays and shales is very good. However, the correlation with trace element ranges of mafic and felsic volcanics is poor, and major discrepancies occur with Cr, Ni, Co, Nb, Sc, Th and Ti. Thus, the magnesian metamorphics of the Rosebud Syncline appear to be derived from evaporitic clays rich in magnesian clay minerals, such as palygorskite, sepiolite, chlorite or corrensite. The complete metamorphic rock assemblage of interlayered calcareous, aluminous and magnesian rocks is interpreted as a metamorphosed carbonate-evaporite-pelite sequence.     

Stratigraphic framework of the thrust geometry and structural inversion in the southeastern Pyrenees : La Garrotxa area

Abstract

The structure of la Garrotxa area within the Cadi unit (south-eastern Pyrenees) consists of a set of duplexes at different scales which repeat the different carbonatic litho-units of the Lower and Middle Eocene. These duplexes are folded by antiformal stacks structures with basement rocks in their cores. The north boundary of these antiformal stacks represents an inversion of pre-existent extensional faults which formed half-graben geometries. The basement rocks involved in the structure represent short-cuts formed in the footwall of the extensional faults. All thrusts of La Garrotxa area branch with the upper Garrotxa thrust. The more complex structure of La Garrotxa area than the adjacent areas within the Cadí unit, is due to the initial complex synsedimentary geometry of the sedimentary pile.

The Cadi unit overlies the Serrat unit with a hangingwall ramp geometry. This unit was deduced from the Serrat-1 well, drilled in 1987. The Serrat unit is made up of a Middle Eocene evaporitic sequence, with alternating shales and anhydrites and a 100 meters thick salt layer close to the top. The total thickness of this evaporitic Beuda sequence is 1 000 meters. The Beuda sequence clearly controlled the thrust geometry of the younger thrusts.     

Algal crusts, autochthonous and clastic gypsum in a cannibalistic evaporite basin: a case history from the Messinian of Northern Apennines

The Messinian Vena del Gesso Basin in the Northern Apennines is filled by very thick (up to 35 m) beds of coarse crystalline gypsum (selenite) associated with thinner carbonate and shaly (euxinic) intercalations. The conventional Usiglio model of salt fractionation does not apply to this evaporitic sequence for the following reasons: carbonate which underlies gypsum is not evaporitic but algal in origin; most gypsum did not precipitate from surface brines but at and below a sediment-water interface occupied by algal mats; a significant portion (10–80%) of gypsum beds is composed of redeposited selenite which was removed from the margins and transported toward the centre of the basin by slope-controlled currents and gravity flows (debris flows). We call this process cannibalistic because of its intraformational character (connected with evaporative fall of water level) and volumetric importance. A recurrent vertical pattern of six main facies (euxinic to gypsum fanglo-merates) is interpreted as a bathymetric, regressive cycle controlled by both sedi-mentological and tectonic-eustatic factors. The inferred environmental setting is a residual turbidite trough (Marnoso-arenacea) evolving abruptly toward lagoonal conditions and filled up to sea level by evaporitic and mechanical (mostly fluvial) processes. Repeated inundations of restricted-marine water started the depositional cycle thirteen or fourteen times.     

Polar constituents of organic matter rich marls from evaporitic series of the Mulhouse basin

A suite of marl samples from the evaporitic series of the Mulhouse basin (France; Lower Oligocene) was studied for its biomarker content, in particular its polar constituents. Novel series of 3-carboxyalkyl steranes and 15-oxo triaromatic ketones were identified by synthesis. The 3-carboxyalkyl steranes probably originate from highly polar precursors yet unreported in living organisms. Our data suggest that micro-algae could be the major source of these compounds which seem to be indicators of high algal input rather than characteristic of evaporitic environments. The 15-oxo triaromatic ketones could be oxidation products of triaromatic steroid hydrocarbons formed during diagenesis, although their formation during work-up procedure could not be excluded.     

Microanalysis of primary fluid inclusions in halite: constraints for an evaporitic sedimentation modeling. Application to the Mulhouse Basin (France)

The chemistry of the waters from which the evaporitic minerals crystallized in the lower part of the Salt IV unit of the Mulhouse Basin (France) has been investigated. The lithological and fluid inclusion data have been compared to the output data of the mass transfer program NEWEQUI which simulates the change in brine composition during its evaporation advancement. The results show that the evolution of the composition of the brine is compatible with the calculated sequence of evaporation of a parent water corresponding to a seawater modified by CaCl₂-rich hydrothermal water. In the studied sequence fluid inclusion data provide useful constraints for reconstructing the paleoenvironment controlling the evaporitic sedimentation. They also provide data on the water stratification in the basin and on its connectivity with the open sea, and important parameters controlling the productivity (possible sources for the nutrients) and the preservation of organic matter in the sediment.     

Filtering of the gravimetric anomalies to the study of the geological structures of Oued Zarga (Septentrional Tunisia): structural implications

Gravity data were analysed in the Northern Tunisian Atlas (case study of Oued Zarga area) to better understand the organization of its underlying structures. The gravity data analysis included the construction of a gravity anomaly maps and two and a half dimensional gravity model. The qualitative analysis of gravimetric maps served for the foundation of a new structural map of the study region that constitutes a new contribution of the gravimetry in this present work. In addition, the complete Bouguer and residual gravity anomaly maps indicate a negative gravity anomaly over the Triassic evaporitic outcrops of Jebel Guerouaou and prominent NE?CSW-trending features associated with the boundary of the Triassic rocks and surrounded layers. A NW?CSE-trending gravity model that crosses the Triassic evaporitic outcrop at Jebel Guerouaou can be explained by a deep-rooted salt diapir.