黔北早寒武世缺氧事件：生物标志化合物及有机碳同位素特征

本文首次报道了黔北早寒武世黑色岩系的生物标志化合物，并结合有机碳同位素组成特征，探讨该时期所发生的重大地质事件。所有样品均检出了丰富的正构烷烃、类异戊二烯烃、萜类化合物以及甾类化舍物。在GC谱图上，正构烷烃显示明显的单峰型分布特征，碳数分布范围为nC14-nC31主峰碳为nC18、nC19或nC20，nC17／nC31为1．15～50．17，显示轻烃组分占绝对优势，OEP值为0．84～1．11，CPI值为0．92～1．16，接近平衡值1．0，无明显的奇偶碳数优势分布。Pr／Ph值为0．24～0．79，具有明显的植烷优势。萜烷化合物以C30藿烷占优势，其相对丰度三环萜烷〉五环三萜烷〉四环萜烷，并且检出少量的γ-蜡烷。规则甾烷C27-C28-C29呈“V”字型分布，∑（C27＋C28）〉∑C29，其比值为1．25～1．99，∑C27／∑C29为0．78～1．22，重排甾烷C27／规则甾烷C27值为0．21～0．47。4-甲基甾烷普遍存在，但丰度相对较低。在地层剖面上，有机碳含量（TOC（％））从0．05～7．91％，平均为2．52％；有机碳同位素组成（δ^13Corg）从-29．49‰～-34．41‰（PDB），发生负偏移，偏移量达到4．3‰，代表该期海平面处于上升阶段，底层水处于严重缺氧状态，底栖生物缺乏。本文根据生物标志化合物特征参数，结合有机碳同位素组成变化，详细分析了黔北早寒武世这套黑色岩系的有机质来源、成熟度、沉积环境以及古海洋意义，将为我国南方早寒武纪古地理重建、地质事件记录提供可靠依据。     

Stable isotope analysis of the Cenomanian–Turonian (Late Cretaceous) oceanic anoxic event in the Crimea

Carbon and oxygen isotope data from Cenomanian–Turonian sediments from the southwest of the Crimea are presented. The sediments consist of limestones, marls and organic-rich claystones, the latter with total organic carbon values up to 2.6 wt. %, representing Oceanic Anoxic Event 2. A shift to more negative δ¹⁸O values through the uppermost Cenomanian into the lowermost Turonian may be the result of warming; however, petrographic analysis shows that the samples have undergone a degree of diagenetic alteration. The carbon isotope data reveal a positive excursion from 2.7‰ to a peak of 4.3‰ at the Cenomanian/Turonian boundary; values then decrease in the early Turonian. This excursion is comparable to those of other Cenomanian–Turonian sections, such as those seen in the Anglo-Paris Basin, and is thought to be due to global changes in the oceanic carbon reservoir. On this curve are a number of negative δ¹³C excursions, just below the Cenomanian/Turonian boundary. It is suggested that these negative excursions are associated with the uptake of light carbon derived from the oxidation and deterioration of organic material during localised exposure of the sediments to oxic or meteoric diagenetic conditions, possibly during sea-level fluctuations.     

Carbon isotope records of the early Albian oceanic anoxic event (OAE) 1b from eastern Tethys (southern Tibet,China)

The early Albian Oceanic Anoxic Event (OAE), i.e., OAE1b, is well documented in western Tethys and in the primary North Atlantic Ocean, but has not yet been reported from eastern Tethys. In this paper, we present bulk carbon isotope data of hemipelagites to examine if it was recorded in eastern Tethys. Samples were taken from the upper Chuangdepu Member (nannofossil zone CC8) of the lower Gyabula (former Shadui) Formation at the Bangbu section, Qonggyai, southern Tibet of China. The δ¹³C values mainly range from −0.6‰ to 1.8‰ with a maximum of 1.87‰ and a minimum of −0.69‰. Three stages of carbon isotope evolution were distinguished with three boundaries. By the constraint of the stratigraphic sequence and nannofossil biostratigraphic zone CC8, the rapid δ¹³C change and correlation with western Tethys and Atlantic Ocean together suggest that these three boundaries of the carbon isotope evolution probably correspond to three subevents of the early Albian OAE1b, and the subevent levels of upper Kilian, Paquier, and Leenhardt are recorded in eastern Tethys (southern Tibet). The fact that the amount of δ¹³C shift is less by ∼1.5–2.0‰ in eastern Tethys than in western Tethys and Atlantic Ocean is interpreted as a result of possible cool sea surface (∼14–16 °C) of the southeastern Tethys (northern Indian passive margin of Greater India), which was probably located in a medium–high latitude during the Albian, leading to low primary productivity. The recognition of OAE-1b from Tethys Himalaya can improve our understanding of the Tethys and global paleoclimatic and paleoceanographic changes during the mid-Cretaceous.     

Evidence of bottom-redox conditions during oceanic anoxic event 2 (OAE2) in Wadi Bazina,Northern Tunisia (Southern Tethyan margin)

Detailed chemostratigraphy across the Cenomanian-Turonian boundary in northern Tunisia points to several prevailing paleoceanographic conditions during the deposition of organic-rich beds of Bahloul Formation. The sedimentological study shows that there is no correlation between color and CaCO₃ content because both dark and light-colored intervals of Bahloul Formation are carbonate-rich. Stable isotope analysis displays a positive carbon isotope excursion characterized by four significant peaks (I to IV) which are ranging from 3.2 to 3.5‰. These peaks represent episodes of elevated rates of organic carbon burial during the C/T oceanic anoxic event (C/T boundary OAE2). The Cenomanian-Turonian boundary could be situated between the third isotopic peak and the filament event. The total organic carbon (TOC) measurements show values ranging from 0.28 to 6.19% with average value of 3.5%. This indicates that the Bahloul Formation shale is a very good oil source rock. The Hydrogen Index (HI) values range from 359 to 698 mg HC/g TOC. The T _max values range from 390 to 438 °C. Binary diagrams HI vs. T _max indicate a type II with values falling within the immature organic-matter range. The concentrations major elements reveal low values of Ti and K. The correlation between Al and Ti and K shows a significant correlation pointing to homogeneous provenance. Primary productivity indicators (Cu, Ba, and Ni) record its association with organic matter. Redox-sensitive elements such as U, V, and Mo and the high values of V/(V + Ni) ratio indicate a strongly reducing environment which led to the better preservation of the organic matter.     

Petrological, geochemical, and stable isotope constraints on the genesis of the Miocene igneous rocks of Chetaibi and Cap de Fer (NE Algeria)

Miocene igneous rocks (diorites, andesites, dacites, rhyolites and microgranites) of Chetaibi and Cap de Fer massif, NE Algeria, are high-K calc-alkaline to shoshonitic rocks. Fresh diorites have δ³⁴S and δ¹⁸O values ranging between −2.5‰ and +5.9‰, +6.5‰ and +6.7‰ respectively, indicating a mantle origin. The relatively low δ³⁴S values (−5.4‰ to −12.2‰) and high δ¹⁸O (+8.3‰ to +9.0‰) of altered diorites indicate the input of a crustal component to the initial magma. The microgranites’ I-type signature is indicated by the geochemical data and the δ³⁴S and δ¹⁸O values of −1.2‰ and −3.6‰, and +7.8‰ to +10.4‰ respectively. The andesites show a large variation of δ³⁴S, between −33.2‰ and +25.7‰. Massive andesites with δ³⁴S between +6.8‰ and +7.6‰ preserve a ³⁴S-enriched mantle signature. The δ³⁴S of the lava flows between +25.7‰ and +25.8‰ are attributed to open system magma degassing, whereas the low δ³⁴S of two andesitic dyke samples (−13.7‰ and −33.2‰) strongly suggest a crustal sulphur input. High δ¹⁸O (+9.2‰ to +15.7‰) of andesites indicate post-magmatic alteration (mainly silicification); the flyschs with δ¹⁸O between of +13.3‰ and +21.7‰ are most likely the contaminant. Quartz veins within the andesites gave a δ¹⁸O value of +23.0‰ while silica-filling vesicles yielded a value of +13.8‰. Initial Sr-isotope data are rather high for all the rocks (diorites: 0.707–0.708, andesites: 0.707–0.710, and microgranites and rhyolites: 0.717–0.719), and because geochemical and stable isotope data do not indicate a substantial amount of crustal assimilation, an extensive enrichment of the mantle source by subducted sediments is called for. A metasomatized-mantle source, characterized by high radiogenic Sr and relatively high δ¹⁸O, has also been indicated for the genesis of similar Tertiary igneous rocks in the Western Mediterranean basin, e.g. the Volcanic Province of southeasten Spain [Benito, R., Lopez-Ruiz, J., Cebria, J.M., Hertogen, J., Doblas M., Oyarzun, R., Demaiffe, D., 1999. Sr and O isotope constraints on source and crustal contamination in the high-K calc-alkaline and shoshonitic neogene volcanic rocks of SE Spain. Lithos 46, 773–802] and some plutons of northeastern Algeria [Ouabadi, A., 1994. Pétrologie, géochimie et origine des granitoïdes peralumineux à cordiérite (Cap Bougaroun, Béni-Touffout et Filfila), Algérie nord-orientale. Thèse de Doctorat, Université de Rennes I, France, 257p; Fourcade, S., Capdevila, R., Ouabadi, A., Martineau, F., 2001. The origin and geodynamic significance of the Alpine cordierite-bearing granitoids of northern Algeria. A combined petrological, mineralogical, geochemical and isotopic (O, H, Sr, Nd) study. Lithos 57, 187–216].     

First evidence for the Cenomanian–Turonian oceanic anoxic event (OAE2, ‘Bonarelli’ event) from the Ionian Zone,western continental Greece

Integrated biostratigraphic (planktonic foraminifera, calcareous nannofossils), chemostratigraphic (bulk C and O isotopes) and compound-specific organic geochemical studies of a mid-Cretaceous pelagic carbonate—black shale succession of the Ionian Zone (western Greece), provide the first evidence for the Cenomanian–Turonian oceanic anoxic event (OAE2, ‘Bonarelli’ event) in mainland Greece. The event is manifested by the occurrence of a relatively thin (35 cm), yet exceptionally organic carbon-rich (44.5 wt% TOC), carbonate-free black shale, near the Cenomanian–Turonian boundary within the Vigla limestone formation (Berriasian–Turonian). Compared to the ‘Bonarelli’ black-shale interval from the type locality of OAE2 in Marche–Umbria, Italy, this black shale exhibits greatly reduced stratigraphic thickness, coupled with a considerable relative enrichment in TOC. Isotopically, enriched δ¹³C values for both bulk organic matter (−22.2‰) and specific organic compounds are up to 5‰ higher than those of underlying organic-rich strata of the Aptian-lower Albian Vigla Shale member, and thus compare very well with similar values of Cenomanian–Turonian black shale occurrences elsewhere. The relative predominance of bacterial hopanoids in the saturated, apolar lipid fraction of the OAE2 black shale of the Ionian Zone supports recent findings suggesting the abundance of N₂-fixing cyanobacteria in Cretaceous oceans during the Cenomanian–Turonian and early Aptian oceanic anoxic events.     

The response of two Tethyan carbonate platforms to the early Toarcian (Jurassic) oceanic anoxic event: environmental change and differential subsidence

Chemostratigraphic analyses (⁸⁷Sr/⁸⁶Sr, δ¹³C_carb) of limestones from two Jurassic platform‐carbonate sequences in Italy (Trento and Campania–Lucania Platforms) illustrate previously established trends found in pelagic sediments and skeletal carbonates from biostratigraphically well‐calibrated sections elsewhere in Europe. Chemostratigraphic correlations between the platform‐carbonate successions and appropriate intervals from well‐dated reference sections allow the application of high‐resolution stratigraphy to these shallow‐water peritidal carbonates and, furthermore, elucidate the facies response to the Early Toarcian Oceanic Anoxic Event (OAE). Lower Jurassic (Toarcian) levels of the western Trento Platform (Southern Alps, Northern Italy) contain spiculitic cherts that appear where rising carbon‐isotope values characterize the onset of the OAE: a palaeoceanographic phenomenon interpreted as driven by increased nutrient levels in near‐surface waters. There is a facies change to more clay‐rich facies at the level of the abrupt negative carbon‐isotope excursion, also characteristic of the OAE, higher in the section. The Campania–Lucania Platform (Southern Apennines, Southern Italy) records a change to more clay‐rich facies where carbon‐isotope values begin to rise at the beginning of the OAE but the negative excursion, higher in the section, occurs within oolitic facies. Although, in both examples, the Early Toarcian OAE can be recognized by a change to more clay‐rich lithologies, this facies development is diachronous and in neither case did the platform drown. Although the Trento Platform, in the south‐west sector studied here, was adversely affected by the OAE, it did not drown definitively until Late Aalenian time; the Campania–Lucania Platform persisted throughout the Jurassic and Cretaceous. Differential subsidence rates, which can be calculated using comparative chemostratigraphy, are identified as a crucial factor in the divergent behaviour of these two carbonate platforms: relatively fast in the case of the Trento Platform; relatively slow in the case of the Campania–Lucania Platform. It is proposed that where water depths remained as shallow as a few metres during the OAE (Campania–Lucania Platform), dissolved oxygen levels remained high, nutrient levels relatively low and conditions for carbonate secretion and precipitation remained relatively favourable, whereas more poorly ventilated and/or more nutrient‐rich waters (Trento Platform) adversely influenced platform growth where depths were in the tens of metres range. The stage was thus set for drowning on the more rapidly subsiding western margin of the Trento Plateau and a pulse of oolite deposition post‐dating the OAE was insufficient to revitalize the carbonate factory.     

Enrichment of redox-sensitive trace metals (U,V, Mo,As) associated with the late Hauterivian Faraoni oceanic anoxic event

The Faraoni Level is a short-lived oxygen-deficient event that took place during the latest Hauterivian. In order to improve our understanding of the palaeoenvironmental conditions that occurred during this event, we have analysed the contents of several redox-sensitive trace elements (U, V, Mo, As, Co, Cd, Cu, Zn, Ni, Pb, Cr) from bulk limestone samples of late Hauterivian–early Barremian age from three reference sections. U, V, Mo and As show consistent and significant enrichments during the Faraoni event whereas the other redox-sensitive trace elements analysed here are not systematically enriched. In order to explain this discrepant behaviour, we propose that the Faraoni Level was deposited during a period of anoxic conditions near the sediment–water interface. The distinctive peaks in U, V, Mo and As contents are traceable throughout the three studied sections and represent a good correlation tool which helps to identify the Faraoni Level and its equivalents in the western Tethyan realm and outside of the Tethys. For example, a peak in U contents in upper Hauterivian sediments of the northwestern Pacific realm (ODP leg 185, site 1149) may well be an expression of the Faraoni event in this particular basin.     

The wider context of the Lower Jurassic Toarcian oceanic anoxic event in Yorkshire coastal outcrops,UK

The Toarcian Oceanic Anoxic Event (T-OAE, ～183 Ma) was characterized by enhanced carbon burial, a prominent negative carbon-isotope excursion (CIE) in marine carbonate and organic matter, and numerous geochemical anomalies. A precursor excursion has also been documented at the Pliensbachian/Toarcian boundary, but its possible causes are less constrained. The T-OAE is intensively studied in the Cleveland Basin, Yorkshire, UK, whose sedimentary deposits have been litho-, bio- and chemostratigraphically characterised. Here, we present new elemental data produced by hand-held X-ray fluorescence analysis to test the expression of redox-sensitive trace metals and detrital elements across the upper Pliensbachian to mid-Toarcian of the Cleveland Basin. Detrital elemental concentrations (Al, Si, Ti, Zr) are used as proxies for siliciclastic grain content and thus, sea-level change, which match previous sequence stratigraphic interpretations from the Cleveland Basin. The timescale of the event is debated, though our new elemental proxies of relative sea level change show evidence for a cyclicity of 350 cm that may be indicative of ～405 kyr eccentricity cycles in Yorkshire. Trends in total organic carbon and redox-sensitive elements (S, Fe, Mo, As) confirm scenarios of widespread ocean deoxygenation across the T-OAE. The correlation of comparable trends in Mo across the T-OAE in Yorkshire and the Paris Basin suggests a similar oceanic drawdown of this element accompanying widespread anoxia in the two basins. Data from Yorkshire point to a transgressive trend at the time of the Mo drawdown, which contradicts the “basin restriction” model for the euxinic conditions that characterise the CIE interval.     

Geochemistry,fluid inclusion and stable isotope constraints (C and O) of the Sivrikaya Fe-skarn mineralization (Rize,NE Turkey)

The Sivrikaya Fe-skarn mineralization is hosted by dolomitic limestone layers of Late Cretaceous volcano-sedimentary unit, comprised of andesite, basalt and their pyroclastites, including, sandstone, shale and dolomitic limestone layers. Intrusion of the Late Cretaceous–Eocene İkizdere Granitoid in the volcano–sedimentary unit resulted in skarn mineralization along the granitoid–dolomitic limestone contact. The ore is associated with exoskarns, and mineralization is characterized by early anhydrous garnet and pyroxene with late hydrous minerals, such as epidote, tremolite, actinolite and chlorite. The ore minerals are mainly magnetite and hematite, with minor amounts of pyrite and chalcopyrite. The composition of garnet and pyroxene in the exoskarn is Adr_{79.45−99.03}Grs_0−17.9Prs_0.97−2.65 and Di_69.1−77.1Hd_22.2−29.8Jhn_0.6−1.4, respectively, and abundances of magnetite in the ore suggest that the Fe-skarn mineralization formed under relatively oxidized conditions.Homogenization temperatures (T_h) of all fluid inclusions and calculated salinity content are in the range of 166 °C–462 °C and 0.35–14.3 wt% NaCl equ., respectively. Well-defined positive correlation between Th and salinity values indicates that meteoric water was involved in the hydrothermal solutions. Eutectic temperatures (Te) between −40.8 °C and −53.6 °C correspond to the presence of CaCl₂ in the early stage of fluid inclusions. On the other hand, the Te temperatures of later-stage fluid inclusions, in the range of −38 °C and −21.2 °C, correspond to the presence of MgCl₂, FeCl₂, KCl and NaCl type salt combinations. None of the fluid inclusions were found to contain separated gas phases in microscopy observations. However, a limited amount of dissolved CH₄ was identified in the early stage, high temperature fluid inclusions using Raman spectroscopic studies.Δ¹⁸O values in both dolomitic limestone (10.8–12.5‰) and skarn calcite (7.6–9.8‰) were highly depleted compared to the typical δ¹⁸O values of marine limestones. Decreases in δ¹⁸O values are accepted as an indication of dilution by meteoric water because retrograde brecciation of garnet, magnetite and breccia filling epidote and quartz in volcanic host rocks are an indication of increasing permeability, allowing infiltration of meteoric water. Highly depleted δ¹³C isotopes (up to −6.5‰) of dolomitic limestone, indicate that organic matter in carbonates had an effect on the decreasing isotopic ratios. The presence of CH₄ and CH₂ in fluid inclusions can be explained by the thermal degradation of these organic materials.     

Minor changes in surface-water fertility across the oceanic anoxic event 1d (latest Albian,SE France) evidenced by calcareous nannofossils

The latest Albian sediments deposited in the Vocontian basin in south-eastern France record the oceanic anoxic event (OAE) 1d, locally named the Breistroffer interval. They are represented by argillaceous marls and marls, containing organic matter (total organic carbon varying from 0.8 to 1%). Changes in calcareous nannofossil abundance and assemblage composition as well as macrofauna abundance, ichnofossil assemblage, and bioturbation intensity were analysed in order to evaluate the main palaeoenvironmental factors controlling the deposition of the OAE 1d sediments in this area. The pelagic carbonate production is limited and the carbonate fraction is predominantly of nektonic/benthic, and of allochthonous origin from carbonate platforms. The enrichment in organic carbon within the Breistroffer interval is weak and not associated with high surface-water productivity. The organic matter is mainly terrigenous. Its record is due to (1) a good preservation under dysoxic conditions within the sediments, and (2) a weak input of allochthonous carbonates. Eustatic fluctuations strongly influenced the variations of nannofossil and macrofauna abundances. Distinctive patterns in nannofossil assemblages and macrofauna abundances within the Breistroffer interval are also recognized, reflecting changes from mesotrophic to more oligotrophic conditions which are probably controlled by climate.     

Deep‐water anoxia over the Frasnian–Famennian boundary (La Serre,France): a tectonically induced oceanic anoxic event?

The Frasnian–Famennian (F‐F) transition is well exposed in the basinal setting of La Serre (Montagne Noire, France), where oxygen‐deficient conditions prevailed in bottom environments. In this paper, we study the F‐F transition using inorganic geochemistry (notably, major elements, redox‐sensitive and/or sulphide‐forming trace metals, and productivity proxies). The results are compared with published data concerning the La Serre section, other F‐F sections and other geological formations also deposited in basinal settings. The very high enrichment in redox and productivity tracers indicates that anoxic conditions prevailed across the F‐F boundary, and that surface productivity was intense. Such deep‐water restricted conditions coupled with high productivity occurred in various places in Late Devonian oceans. Recycling alone cannot account for the intense nutrient supply and therefore the most probable source was via land runoff. We discuss the Eovariscan episode of uplift that stimulated rock weathering, and hence long‐term nutrient supply to the seas.     

The November 26 and 27, 1927 devastating flood event (NW Algeria): characterization and reconstruction using historical data

The historical records show that the Northwestern Algeria has experienced more than 130 floods, which were sometimes catastrophic. They caused more than 1000 deaths and significant damage. In this work, we try to reconstruct the most devastating and deadly historical flood that occurred on November 26 and 27, 1927. This event is interesting to discuss disaster scenario because of its extent and impacts and the availability of data. For this purpose, we used historical press reports, scientific papers, and archival reports. This work allowed the reconstruction of the hydroclimatic situation during the flood and the regional scale impacts. It presents also the catastrophic flooding of the Ain Sefra river at Mostaganem and that of El Hammam river, as well as the Fergoug dam breaking at Mohammadia. The main factor triggering these floods was the heavy rainfall. Other factors have increased the damage such as the occupation of high-risk areas and the human failure. This event caused 430 killed persons, more than 1200 disaster victims, and around one billion francs losses. These effects evidence the high vulnerability of the Northwestern Algeria to the occurrence of floods. For that, if a similar event occurs in the future, it can be extremely negative.     

Carbon-isotope records of the Early Jurassic (Toarcian) oceanic anoxic event from the Valdorbia (Umbria–Marche Apennines) and Monte Mangart (Julian Alps) sections: palaeoceanographic and stratigraphic implications

The Toarcian oceanic anoxic event ( ca 183 Ma) coincides with a global perturbation marked by enhanced organic carbon burial and a general decrease in calcium carbonate production, probably triggered by changes in the composition of marine plankton and elevated carbon dioxide levels in the atmosphere. This study is based on high-resolution sampling of two stratigraphic successions, located in Valdorbia (Umbria–Marche Apennines) and Monte Mangart (Julian Alps), Italy, which represent expressions of the Toarcian oceanic anoxic event in deep-water pelagic sediments. These successions are characterized by the occurrence of black shales showing relatively low total organic carbon concentrations (compared with coeval strata in Northern Europe), generally < 2%, and low hydrogen indices. On this basis, they are similar to other Toarcian black shales described from the Tethyan region. The positive and negative carbon-isotope records from the two localities permit a high-resolution correlation such that ammonite biostratigraphy information from Valdorbia can be transferred to those parts of the Monte Mangart section that lack these fossils. Spectral analyses of δ¹³C_org values and of CaCO₃ percentages from the sedimentary records of both the Valdorbia and Monte Mangart sections reveal a strong cyclic pattern, best interpreted as an eccentricity signal which hence implies a duration of ca 500 kyr for the negative carbon-isotope excursion. Based on the carbon-isotope curves obtained, the high-resolution correlation between the Italian successions and a section in Yorkshire (Northern Europe) confirms the supposition that the apparent mismatch between the dating of the Toarcian oceanic anoxic event in the Boreal and Tethyan realms is an artefact of biostratigraphy.     

Latitudinally different responses of Tethyan shoal‐water carbonate systems to the Early Aptian oceanic anoxic event (OAE 1a)

Ocean‐wide anoxic events represent intensively investigated anomalies in the global carbon cycle. Most previous research has focussed on hemipelagic and pelagic settings and on the relationship between black‐shale deposition and carbon‐isotope excursions. The study of ocean‐wide anoxic events and coeval shallow‐water settings is now increasingly seen as an interesting complementary approach, but one that is not without problems. Whereas platform drowning characterizes the Early Aptian of the northern Tethyan margin, Lithocodium–Bacinella‐rich facies and ongoing shoal‐water sedimentation at the southern Tethyan margin (Oman) bears important information on potential causes of carbon‐cycle perturbations. The present paper seeks to test the supra‐regional relevance of the Oman data by investigating coeval central Tethyan limestones. Three Lower Aptian shoal‐water sections in Istria (Croatia), deposited on the isolated Adriatic Carbonate Platform, are investigated applying chemostratigraphy (carbon and strontium) and detailed sedimentological analysis. The focus is on peritidal to lagoonal facies characterized by mass occurrences of Lithocodium–Bacinella, an enigmatic microencruster community. Lithocodium–Bacinella facies occurs predominantly in layers ranging from one to several centimetres in stratigraphic thickness, with several layers merging to metre‐thick packages. Growth fabrics within the layers include oncoidal morphotypes, lumps, interconnected patches and columns, layers and rare nodular to massive bindstone facies. These growth patterns show a remarkable regional extent and consistency over study sites distributed several kilometres apart. This widespread distribution suggests that specific Lithocodium–Bacinella morphotypes might serve as regional stratigraphic markers. The high‐resolution carbon‐isotope chemostratigraphy presented here is based on pristine rudist shells and matrix micrite samples and calibrated against strontium‐isotope data obtained from screened rudist low‐Mg calcite. The chemostratigraphic data are consistent with existing biostratigraphic data and place the studied strata at the onset of Early Aptian oceanic anoxic event 1a. Moreover, results indicate the near‐coeval nature of Lithocodium–Bacinella bloom facies in Istria and Oman. The outcomes of this study point to latitudinally different responses of Tethyan shoal‐water carbonate systems (platform drowning versus Lithocodium–Bacinella blooms) to the ocean‐wide anoxic event 1a.     

Regional record of a global oceanic anoxic event: OAE1a on the Apulia Platform margin, Gargano Promontory, southern Italy

The Gargano Promontory of southern Italy, located on the eastern margin of the Apulia Platform, represents a peculiar Tethyan area where the transition between carbonate platform and adjacent basins is exposed on land. The Aptian stratigraphic record, represented in shallow-water, slope and deep-water deposits, provides a good opportunity to investigate the regional response to the worldwide documented climatic, biotic and palaeoceanographic changes related to Oceanic Anoxic Event 1a (OAE1a). A synthesis of data previously published (Ischitella and Coppitella sections), together with original data (Val Carbonara and Coppa della Guardia sections), from four stratigraphic sections from different depositional settings (proximal to distal) is provided, using an integrated, high-resolution micropalaeontological (planktonic foraminifera and calcareous nannofossils) and, for one section, geochemical (stable carbon and oxygen isotopes) approach. Organic matter preservation is confined to the more distal areas and consists of two thin intervals of black shales in the Aptian portion of the Marne a Fucoidi Formation. Biostratigraphic data assign the older black shale (5 cm thick) to the Selli Level equivalent (OAE1a, Lower Aptian); this carbon-rich interval is immediately followed by another black shale (7–10 cm thick) of early Late Aptian age.OAE1a is generally interpreted as a high-productivity event during a warming interval, followed by a cooling trend. In the Gargano Promontory, although the oxygen isotope curve indicates the above-mentioned climatic evolution, the micropalaeontological data do not support high fertility of the surface water, whereas micropalaeontological and geochemical data for the younger black shale do record high productivity (radiolarian increase in overall abundance, low nannofossil and foraminiferal species richness, increase in abudance of nannofossil fertility indices) associated with a cooling trend. The carbon and oxygen isotope record is in line with evidence from the curves documented elsewhere, whereas, among the biotic events, only the “nannoconid crisis” preceding OAE1a is revealed to be globally correlable.Environmental models for the two episodes of organic matter preservation are proposed, taking into account both global and local controlling factors.     

Geochemistry and isotope (Sr, Nd, O) study of Al–Mg granulites from the In Ouzzal Archaean block (Hoggar, Algeria)

The In Ouzzal Al–Mg granulites are found within sedimentary units deposited after 2.7 Ga, the whole association being metamorphosed under extreme temperature conditions (c. 1000 °C) at 2 Ga. The Al–Mg granulites are interlayered with other metasediments, including metapelites, quartzites and magnetite-bearing quartzites, forsterite-spinel marbles, and a few meta-igneous rocks (mainly pyroxenites). They do not occur at a specific position in the sedimentary suite, and they do not reflect any particular structural control. The major and trace element compositions of Al–Mg granulites (especially the high Cr, Ni, Co contents) show that their peculiar ‘refractory’ chemistry is more compatible with premetamorphic sedimentary characteristics rather than with metasomatic, metamorphic or partial melting processes. Sedimentary admixtures of a common mature detrital component coming from the weathering of the local acidic igneous crustal protoliths (normal pelitic component) with an extremely immature component derived from reworking of basic/ultrabasic lithologies (Al–Mg–Cr–Co–Ni–rich chloritic component) is consistent with the geochemistry of such rocks. As in other instances, the quartz-garnet oxygen isotopic thermometer here records an apparent temperature close to the peak metamorphism (c. 1000 °C). Although the persistence of pre-existing δ¹⁸O variations on a small scale during the metamorphism does not support a major pervasive fluid flow during metamorphism, it does not rule out the presence of syn- to post-metamorphic CO₂. The low δ¹⁸O (c.+ 5 to + 6‰) of the most typical Al–Mg granulites indicate that the ‘chloritic component’ in these rocks was derived from hydrothermally altered mafic/ultramafic protoliths rather than dominantly from palaeosols. It is suggested that the presence of such Al–Mg–Cr–Co–Ni–rich sediments is indirect evidence for the presence of greenstone belts in the local crust of the In Ouzzal at 2.6–2.7 Ga.     

Oxygen and hydrogen isotope study of high-pressure metagabbros and metabasalts (Cyclades, Greece): implications for the subduction of oceanic crust

Oxygen and hydrogen stable isotope ratios of eclogite-facies metagabbros and metabasalts from the Cycladic archipelago (Greece) document the scale and timing of fluid–rock interaction in subducted oceanic crust. Close similarities are found between the isotopic compositions of the high-pressure rocks and their ocean-floor equivalents. High-pressure minerals in metagabbros have low δ¹⁸O values: garnet 2.6 to 5.9‰, glaucophane 4.3 to 7.1‰; omphacite 3.5 to 6.2‰. Precursor actinolite that was formed during the hydrothermal alteration of the oceanic crust by seawater analyses at 3.7 to 6.3‰. These compositions are in the range of the δ¹⁸O values of unaltered igneous oceanic crust and high-temperature hydrothermally altered oceanic crust. In contrast, high-pressure metabasalts are characterised by ¹⁸O-enriched isotopic compositions (garnet 9.2 to 11.5‰, glaucophane 10.6 to 12.5‰, omphacite 10.2 to 12.8‰), which are consistent with the precursor basalts having undergone low-temperature alteration by seawater. D/H ratios of glaucophane and actinolite are also consistent with alteration by seawater. Remarkably constant oxygen isotope fractionations, compatible with isotopic equilibrium, are observed among high-pressure minerals, with Δ_{glaucophane−garnet} = 1.37 ± 0.24‰ and Δ_{omphacite−garnet} = 0.72 ± 0.24‰. For the estimated metamorphic temperature of 500 °C, these fractionations yield coefficients in the equation Δ = A * 10⁶/T ² (in Kelvin) of A_{glaucophane−garnet} = 0.87 ± 0.15 and A_{omphacite−garnet} = 0.72 ± 0.24. A fractionation of Δ_{glaucophane–actinolite} = 0.94 ± 0.21‰ is measured in metagabbros, and indicates that isotopic equilibrium was established during the metamorphic reaction in which glaucophane formed at the expense of actinolite. The preservation of the isotopic compositions of gabbroic and basaltic oceanic crust and the equilibrium fractionations among minerals shows that high-pressure metamorphism occurred at low water/rock ratios. The isotopic equilibrium is only observed at hand-specimen scale, at an outcrop scale isotopic compositional differences occur among adjacent rocks. This heterogeneity reflects metre-scale compositional variations that developed during hydrothermal alteration by seawater and were subsequently inherited by the high-pressure metamorphic rocks. Received: 4 January 1999 / Accepted: 7 July 1999     

Organic matter provenance,palaeoproductivity and bottom water anoxia during the Cenomanian/Turonian oceanic anoxic event in the Newfoundland Basin (northern proto North Atlantic Ocean)

Free and sulfur-bound biomarkers in sediments deposited in the northern proto North Atlantic (Newfoundland Basin, ODP Site 1276) during the Cenomanian–Turonian oceanic anoxic event 2 (OAE-2) were studied. The δ¹³C records of phytane and lycopane confirmed the stratigraphic position of the positive carbon isotope excursion associated with OAE-2, previously reported for total organic carbon (TOC) and β,β-homohopane. Sediments before and after the OAE-2 interval were poor in organic matter (OM) and comprised numerous gravity flow deposits. The interval itself was composed of pelagic sediments with occasionally a much higher TOC content of up to 12.7%. The OAE-2 sediments were characterized by a low amount of terrestrial OM since the dominant biological sources of the biomarkers were aquatic in origin. High hopane, pentamethylicosane (PMI), and squalane abundances in the OM-rich sediments pointed to a relatively high input of prokaryotes, partly derived from cyanobacteria, as suggested by the occasional occurrence of 2-methylhopanes. PMI comprised both the regular and irregular isomer and changes in the δ¹³C of PMI are thought to reflect contributions from methanogenic and methanotrophic archea. The high relative concentration of lycopane indicated that bottom water conditions were anoxic during large parts of the OAE-2 interval. In one horizon, trace amounts of isorenieratane provided evidence for the occasional occurrence of photic zone anoxia. Taken together, the data imply that oceanic anoxia, and probably also high productivity, reached the northernmost part of the proto-North Atlantic during OAE-2, albeit that photic zone anoxia was much less common than in the southern proto-North Atlantic.     

Characteristics of stable isotope and hydrochemistry of the groundwater around Qinghai Lake, NE Qinghai-Tibet Plateau, China

The integrated use of isotopic and hydrochemical tracers is an effective approach for investigating complex hydrological processes of groundwater. The stable isotope composition and hydrochemistry of the groundwater around Qinghai Lake were investigated to study the sources and recharge areas. Most of the groundwater points lie close to the local meteoric water line, indicating that the ground waters were recharged primarily from precipitation in the basin, though it had undergone varying degrees of evaporation. The hydrochemical analysis showed that the groundwater was mainly freshwater and that the hydrochemical type was Ca–Mg–HCO₃; the results of the boomerang envelope model and solutes calculated indicated that the groundwater chemistry was mainly controlled by carbonate dissolution around Qinghai Lake. The recharge altitudes of groundwater were relatively low (at 3,400 m.a.s.l) on the northern shore of Qinghai Lake (locations G1 and G5), relatively high (above 3,900 m.a.s.l) on the southern shore (locations G3 and G4), and approximately 3,700 m.a.s.l on the western shore (location G2). Furthermore, groundwater samples from the fault zone (e.g., G3) would be recharged in part from fissure or inter-basin water. High salinity of groundwater on the western shore (location G2) was related with the evaporite dissolution, the groundwater is unsuitable for drinking, and the drinking water should be improved and enhanced in this area. Knowledge of our research can promote effective management of water resources in this cold and semiarid region and add new data to global groundwater database.