This study is a multi-proxy analysis of a 30-m section of a Barremian-Aptian succession of interbedded, grayish black (N2) and black (N1) limestones from a quarry of the Sierra de Prada. Index taxa include planktic foraminifera Globigerinelloides blowi and Hedbergella sigali, which combined with δ13C data from Cresmina and Gorgo a Cerbara sections indicate a late Barremian to early Aptian age. The rocks are organic-rich with 0.67 - 3.10 wt% total organic carbon (TOC). A marlstone interval (~1m) at 2.24 m has a low bioturbation index (1), TOC ~6.66 wt%, framboidal pyrite, and enrichment spikes of major, biolimiting, and redox-sensitive trace elements (Al, Si, Ti, P, Fe, and Mo, Cr, Cu, V, Th), indicating an anoxic episode. Biomarker analyses show a predominance of n-alkanes (≤nC20) at this level, suggesting an in situ origin of organic matter from phytoplankton. Pr/Phy ratios below 2 imply that organic matter did not reach overmaturity.

El treball descrit en aquesta tesi té com a objectiu l'estudi de la matèria orgànica soluble de conques geològiques reductores amb un elevat contingut en sofre. Els estudis previs de geoquímica orgànica endegats en conques reductores posen de manifest que els biomarcadors sofrats són de gran importància per a la descripció dels paleoambients, donat que reflecteixen els biocompostos funcionalitzats, que, d'altra forma s'haurien alterat. Per aquest estudi s'han seleccionat quatre conques sedimentàries que destaquen de forma significativa per la seva anoxicitat, així com, per haver experimentat una important sulfato- reducció. Les conques escollides són: Orce, Ribesalbes, Mequinensa i Organyà.La conca d'Orce és d'origen lacustre i de tipus endorreica, data del Plio-Plistocè (1-5 milions d'anys) i es localitza al nord de la província de Granada. El seu interès rau en el descobriment d'importants jaciments paleontològics amb restes antropogèniques.La conca de Ribesalbes també és lacustre i endorreica, pertany al Miocè mitjà (Serraval·là, de 12 a 13 milions d'anys) i es situa a l'oest de la província de Castelló. A principis d'aquest segle s'hi van explotar les pissarres bituminoses mitjançant tècniques de piròlisi.La conca de Mequinensa igualment és d'origen lacustre i de caràcter endorreica, pertany a l'Oligocè superior (Catià, al voltant dels 30 milions d'anys) i es localitza al sud del Sistema dels Monegros, a la província de Lleida. La importància d'aquesta conca es deu a l'explotació de lignits molt rics en sofre.La conca d'Organyà és d'origen marí i data del Cretaci inferior (més de 100 milions d'anys). Es situa a la província de Lleida, a la comarca de l'Alt Urgell. Els materials que formen aquesta conca constitueixen una roca mare de petroli.Els objectius d'aquest treball són:1. L'anàlisi dels biomarcadors per a la determinació de l'origen de les aportacions de la matèria orgànica que reberen les conques estudiades, caracteritzant-ne les contribucions més significatives.2. La descripció de les condicions paleoambientals que donaren lloc a aquests dipòsits sedimentaris.3. L'avaluació de la maduresa de la matèria orgànica.La tesi comença amb una introducció on es descriu la singularitat de cada conca, es continua amb les descripcions geològiques i petrogràfiques, tot localitzant les mostres estudiades a la columna estratigràfica. Després, es mostra l'anàlisi elemental de la matèria orgànica, per prosseguir amb la descripció dels biomarcadors apolars i polars: en primer lloc es descriuen els compostos acíclics, lineals i ramificats, tot començant pels compostos hidrocarbonats, després els oxigenats i finalment els sofrats; en segon lloc, els biomarcadors cíclics, començant pels diterpenoides i continuant amb els triterpenoides, amb especial rellevància dels esteroides i els hopanoides, i finalment, els oleanoides, ursanoides i lupanoides. Cal destacar la identificació de més d'una vintena de nous biomarcadors identificats per primera vegada en aquesta tesi. La descripció de les conques finalitza amb les conclusions sobre els aports de la matèria orgànica, l'ambient deposicional i la maduresa. / The aim of this thesis is the study and characterization of the soluble organic matter in sulphur rich geological basins. The previous studies carried out on reducing sedimentary basins show the significant presence of organic geochemical biomarkers with sulphur, which are very relevant for the description of the paleo-environment conditions of the sedimentation, since they reflect the presence of biological compounds very well preserved.For this study four sedimentary basins of Spain have been selected due to their anoxicity and also for having suffered an important sulphate-reduction process. The selected basins are: Orce, Ribesalbes, Mequinensa and Organyà.The basin of Orce is of lacustrine origin, it belongs to the Plio-Pleistocene period (1 to 5 million years) and it is located to the north of the province of Granada. Its interest comes from the fact that there are important palaeontology deposits with anthropogenic rests.The basin of Ribesalbes also is also of type lacustrine and belongs to the Miocene period (Serravalià, 12 to 13 million years). It is located to the west of the province of Castellon. At the beginning of XX century the bituminises shales were extracted in order to obtain oil with techniques of pyrolisis.The basin of Mequinensa is also of lacustrine origin and belongs to the upper Oligocene period (Catià from around 30 million years) and is located to the south System of the Monegros, in the province of Lleida. The importance of this basin is due to the high sulphur content of the lignite that is formed in this place.The basin of Organyà is of marine origin and dates from the lower Cretaceous (more than 100 million years). It is located in the province of Lleida, in the region of the Alt Urgell. The materials that form this basin constitute a oil source rock.The items of this work are:1. The analysis of biomarkers for the determination of the origin of the contribution of the matter organic.2. The description of the paleoenvironmetal conditions that gave rise to these sedimentations deposits.3. The evaluation of the maturity of the organic matter.The thesis is divided into nine chapters: The study begins with a general geological description to go on with the analysis of the paleoconditions of the environmental deposition that favour the preservation of the organic matter. Subsequently, after that, there is an accurate geochemical description of each basin. The results of this work show that the Orce basin is characterized by type I querogen and, the Ribesalbes basin is of type I-S kerogen, the Organyà basin is of type II-S and the Mequinensa basin is of type III-S querogen. The study ends with the conclusions on the contributions of the organic matter, the depositional environment and the maturity. In the case of the Organyà basin only non polar fractions have been studied, due to the little presence of polar compounds, attributed to the high maturity of the organic matter. Finally, there is also a compilation of biomarkers identified for the first time in this thesis, indicating in its case if their biological precursors.

The hallmark of oceanic anoxic event 1a (OAE1a) (early Aptian ~125 Ma) corresponds to worldwide deposition of black shales with total organic carbon (TOC) content > 2% and a d13C positive excursion up to ~5‰. OAE1a has been related to large igneous province volcanism and dissociation of methane hydrates during the Lower Cretaceous. However, the occurrence of atypical, coeval and diachronous organic-rich deposits associated with OAE1a, which are also characterized by positive spikes of the d13C in epicontinental to restricted marine environments of the Tethys Ocean, indicates localized responses decoupled from complex global forcing factors. The present research is a high-resolution, multiproxy approach to assess the paleoenvironmental conditions that led to enhanced carbon sequestration from the late Barremian to the middle Aptian in a restricted, Tethyan marginal basin prior to and during OAE1a. I studied the lower 240 m of the El Pui section, Organyà Basin, Spanish Pyrenees. The basin developed as the result of extensional tectonism linked to the opening of the Atlantic Ocean. At the field scale the section consists of a sequence of alternating beds of cm – m-scale, medium-gray to grayish-black limestones and marlstones with TOC up to ~4%. The results indicate that the lowest 85 m of the section, from latest Barremian –earliest Aptian, characterize a deepening phase of the basin concomitant with sustained riverine flux and intensified primary productivity. These changes induced a shift in the sedimentation pattern and decreased the oxygen levels in the water column through organic matter respiration and limited ventilation of the basin. The upper 155 m comprising the earliest – late-early Aptian document the occurrence of OAE1a and its associated geochemical signatures (TOC up to 3% and a positive shift in d13C of ~5‰). However, a low enrichment of redox-sensitive trace elements indicates that the basin did not achieve anoxic conditions. The results also suggest that a shallower-phase of the basin, coeval with platform progradation, may have increased ventilation of the basin at the same time that heightened sedimentation rates and additional input of organic matter from terrestrial sources increased the burial and preservation rate of TOC in the sediment.