Carbonate microfacies and chemostratigraphy of a late Aptian–early Albian marine distal section from the primitive South Atlantic (SE Brazilian continental margin): Record of global ocean-climate changes?

Late Aptian–early Albian limestones from the eastern Brazilian continental margin record the early evolution of the South Atlantic Ocean. In Tethyan and North Atlantic domains, a planktic foraminiferal turnover and organic-rich deposits related to Oceanic Anoxic Event 1b (OAE 1b) point to major ocean-climate changes through this interval. Coeval organic-rich deposits of the South Atlantic Ocean have been interpreted as the product of restricted circulation rather than attributed to a global event. However, previous investigations of the early marine phase of South Atlantic lack data from more distal facies, making correlations to global events difficult. Here, we present C, O, and Sr isotopes, elemental geochemistry, TOC and pyrolysis data, as well as a microfacies analysis of an upper Aptian–lower Albian distal section from the Campos Basin (southeastern Brazil). Our focus is on the paleoenvironmental characterization of and the possible association between organic-rich deposits and major perturbations related to Aptian–Albian transition. Five microfacies associations (MA) were identified in the informal units I and III, which were deposited in the neritic region on a carbonate ramp. Organic-rich deposits were described in unit III, composed of planktic-dominated wackestones interbedded with black shales, in a distal dysoxic to anoxic environment. The carbonates ⁸⁷Sr/⁸⁶Sr ratios showed a drastic increase (0.7072–0.7074), interpreted as enhanced chemical weathering, supported by the increase of continental input to the top of section. This trend was accompanied by a long-term δ¹³C_carb negative excursion, which were assigned to the latest late Aptian–early Albian interval of the isotope reference curves, in accordance with the described occurrence of Colomiella recta. This scenario matches those proposed for the late Aptian–early Albian transition and OAE 1b set, as an enhanced greenhouse stage, pointing to the influence of the referred ocean-climate changes on the deposition of organic-rich deposits of the early South Atlantic Ocean. This investigation gives more evidences that these perturbations were a widespread event, as a product of broad-scale disturbances in the global carbon cycle which also controlled organic deposition and preservation on restricted settings.     

Carbon and oxygen-isotope stratigraphy of the Early Cretaceous carbonate platform of Pădurea Craiului (Apuseni Mountains,Romania): A chemostratigraphic correlation and paleoenvironmental tool

Stable C and O isotope records were obtained from carbonate rocks spanning the Hauterivian to Cenomanian interval collected in several sections from the carbonate platform of Pădurea Craiului (Apuseni Mountains, Romania). In the absence of some key biostratigraphic marker species, stable isotopes were applied as a tool for stratigraphic correlation and dating. The composite δ¹³C and δ¹⁸O curves for the Early Cretaceous shows variable conditions with large positive and negative excursions and provide information on past environmental changes. The Hauterivian and the Barremian limestones (Blid Formation) display lower δ¹³C values (−2.8‰ to +2.9‰) relative to the Aptian–Albian deposits (−2.6‰ to +5.4‰) (Ecleja, Valea Măgurii and Vârciorog Formations). The red detrital formation (Albian–Cenomanian) is characterized by a highly variable distribution of the δ¹³C values (−3.5‰ to +3.9‰). Based on the similarities between the C-isotope curve established in Pădurea Craiului and from other sections in the Tethyan and the Pacific regions, two major oceanic anoxic events characterized by δ¹³C positive excursions were clearly recognized. The first is the OAE1a event (Early Aptian) in the upper part of the Ecleja Formation and the Valea Măgurii Formation. The second is the OAE1b event (Late Aptian–Albian) in the upper part of the Vârciorog Formation and in the Subpiatră Member. The position of the Aptian/Albian boundary is estimated to be at the upper part of the Vârciorog Formation, immediately after the beginning of the δ¹³C positive excursion. The δ¹³C data show major negative excursions during the Barremian (Blid Formation), Early Aptian (Ecleja Formation), and Late Aptian (Vârciorog Formation). The O isotope variation pattern (−10.2‰ to −2.1‰) is consistent with progressively warming temperatures during the Early Barremian followed by a cooling period. A subsequent warming period culminated in the Early Aptian. A significant cooling phase corresponds to the Late Aptian and Early Albian and the climate cooled again during the Late Albian and into the Early Cenomanian stage. The data provide a better understanding of the Early Cretaceous sedimentation cycles in Pădurea Craiului and create a more reliable framework for regional correlations.     

Upper Albian OAE 1d event in the Chihuahua Trough,New Mexico,U.S.A.

Oceanic anoxic events are clues to ocean processes and are correlation datums. In North America only OAE 1a and 2 are well documented. Based on a low-resolution sampling program, a multi-proxy geochemical approach constrained by a biostratigraphic framework was utilized to identify OAE 1d in the upper part of the upper Albian Mesilla Valley Formation near El Paso, Texas. Chronostratigraphic and biostratigraphic evidence indicate that the OAE 1d event in the Mesilla Valley section is located in the lower part of the upper Albian–Cenomanian Ovoidinium verrucosum zone, which correlates with the uppermost Albian Parathalmanninella appenninica and Stoliczkaia dispar zones. The chronostratigraphic age of the geochemical event in the Mesilla Valley Formation is uppermost Albian (97.39–97.30 Ma).The classic geochemical signatures for OAEs are enriched total organic carbon (TOC) concentrations and coupled positive δ¹³C excursions. OAE 1d at this location records TOC values ranging from 0.25 to 0.69 wt.% throughout the Mesilla Valley Formation, where TOC increases during the OAE (21.0–40.0 m) to more than 0.40 wt.%. Interestingly, the organic matter in the Mesilla Valley is dominantly type III, which indicates a pervasive terrigenous source. Although marine organic matter is abundant from the base into the middle of the proposed OAE interval, it is progressively replaced by terrestrial material above the OAE section during progradation. The δ¹³C_organic values record a positive δ¹³C shift of +1.6‰ from −26.41 to −24.80‰ across the stratigraphic interval from 21.0 to 40.0 m, which correlates with OAE 1d.Mn and Fe geochemistry suggest the depositional conditions of the Mesilla Valley Formation were dominated by anoxic and possibly Fe-rich bottom waters, specifically during the time period associated with the OAE 1d event. This interpretation is supported by the presence of Fe enrichment recorded by Fe_Total/Al and Fe_{Highly Reactive}/Fe_T with the lack of Fe_pyrite/Fe_{Highly Reactive} associated with Mn depletion.     

An integrated study of upper Campanian-lower Maastrichtian carbon isotopes and calcareous plankton biostratigraphy of the Kurdistan Region,northeastern Iraq

New carbon (δ¹³C) isotope records calibrated by planktonic bioevents provide general support for a late Campanian age assignment of the Shiranish Formation (Fm.) and its boundaries in the Dokan section (NE Iraq). The Shiranish Fm. is characterised at the base by a mid-Campanian unconformity as can be interpreted by absences of nannofossil zones CC20-21. The Shiranish Fm. then spans nannofossil biozones CC22-CC23a (UC15d-e^TP to UC16a^TP). Results obtained on carbon isotopes suggest that diagenesis affected and compromised a few carbonate samples in the uppermost 50 m of the section. However, once these samples are discarded, pristine trends suggest that the top of the section records a negative carbon isotope excursion that is interpreted as CMBa-c events that straddle the Campanian–Maastrichtian boundary. This interpretation is supported by the lowermost occurrence of planktic foraminifers Rugoglobigerina scotti and Contusotruncana contusa some 30 m above the base of the negative excursion and 10 m below a positive excursion identified as the Maastrichtian M1+ event. Discrepancies in the stratigraphic range of several planktic foraminifer bioevents are highlighted and advocate for the need of many more integrated records of planktic foraminifer and nannofossil biostratigraphy alongside carbon isotope stratigraphy in the eastern Tethys in order to improve regional and global schemes.     

The Mid-Cenomanian Event in shallow marine environments: Influence on carbonate producers and depositional sequences (northern Aquitaine Basin,France)

The Mid-Cenomanian Event was a positive carbon-isotope (δ¹³C) excursion recorded in hemipelagic basins of the western Tethyan Sea, North to Tropical Atlantic Ocean, and Japan. It is thought of as a prelude to the Oceanic Anoxic Event 2. However, the Mid-Cenomanian Event has never been studied in detail in shallow marine platform deposits and it is not known how it relates to carbonate production and stratigraphic geometry. To better understand how this carbon cycle disruption influenced the neritic biological communities in shallow carbonates during the Cenomanian, a facies, geochemical, diagenetic, and sequence stratigraphic study of the northern Aquitaine platform has been conducted. Seventy-six δ¹³C and δ¹⁸O measurements have been made on micrite, rudists, and diagenetic cements. Fifteen sedimentary facies have been arranged into four depositional environments. Three third-order sequences (C_B, C_C, C_D) are defined from late early Cenomanian to early late Cenomanian and are well correlated with eustatic cycles in European basins. Two peaks of the Mid-Cenomanian Event (MCE1a, +1.2‰, and MCE1b, +1.7‰) have been identified for the first time in shallow marine carbonates. Analysis of diagenetic blocky calcite cements suggests that diagenesis did not affect the δ¹³C of micrite, which can be discussed in terms of the initial signal. The Mid-Cenomanian Event was synchronous with a turnover in neritic carbonate producers marking a transition from photozoan to heterozoan facies. This facies change resulted from the establishment of mesotrophic to eutrophic conditions at the early/mid-Cenomanian transition, reflecting a clear connection between the Mid-Cenomanian Event and neritic biological communities. Depositional geometry and carbonate production varied with δ¹³C during the Mid-Cenomanian Event on the Aquitaine platform. When δ¹³C values were between 2.5‰ and 3‰, the geometry was a flat platform with a high carbonate sedimentation rate leading to the formation of sandbars and rudist bioherms (Accommodation/Sedimentation ratio less than 1, A/S < 1). When the δ¹³C value exceeded 3‰, a carbonate demise occurred and clays and marls were deposited in the lower offshore environment (A/S >> 1). The general carbonate demise affecting the northern Aquitaine platform during the mid-Cenomanian can be explained by both a eustatic sea-level rise and the establishment of eutrophic conditions. The coincidence of the Mid-Cenomanian Event with both (1) the occurrence of mesotrophic to eutrophic conditions marked by carbonate producer turnover from photozoan to heterozoan facies and (2) the transgressive cycles, suggests that eustatic sea-level rise leading to high trophic conditions could explain this positive δ¹³C excursion in the Atlantic and western Tethyan domain. During the mid-Cenomanian, carbon cycle perturbations largely controlled the neritic biological communities on shallow carbonate platforms in a part of the western Tethyan domain.     

Cenomanian–Turonian carbon isotope stratigraphy of the Western Canadian Sedimentary Basin

The Cenomanian–Turonian boundary was characterized by distinctive positive carbon isotope excursions that were related to the formation of widespread oceanic anoxia. High-resolution geochemical proxies (TOC, CaCO₃, δ¹³C_org, and δ¹³C_carb) obtained from bulk rock, planktic foraminifers, and inoceramids from four marine marlstone-dominated stratigraphic sections in the Western Canada Sedimentary Basin (WCSB) were used to establish a regional carbon isotope stratigraphic framework and to investigate paleoenvironmental variability in four different depositional settings. Compared to background δ¹³C_org, (<−27‰) and δ¹³C_carb (<2‰) values which were correlative to stable isotope excursions during Oceanic Anoxic Event (OAE) II worldwide, the δ¹³C_org (>24‰), and δ¹³C_carb (>4‰) derived from inoceramid prisms in the studied sections within WCSB, were elevated during the Late Cenomanian–Early Turonian. During this interval, TOC and CaCO₃ values which increased sporadically to >40% and 7%, respectively, were not consistent enough to be used for stratigraphic correlations. Based on the δ¹³C_org excursions, two bentonite beds were regionally correlated across this portion of the Western Interior Seaway (WIS). The eruption associated with the “Red” bentonite occurred approximately coeval with the maximum δ¹³C_org-excursion during OAE II in the Neocardioceras juddii Zone, whereas the “Blue” bentonite coincides with the termination of OAE II in the latest Watinoceras devonense zone. During the Late Cenomanian–Early Turonian in the WCSB, benthic foraminifers were sparse or totally absent, indicating the existence of fully anoxic bottom-water conditions. Planktic foraminifera were common in the well-oxygenated surface waters. A benthic oxic zone characterized by several agglutinated species occurs in the eastern part of the WSCB at the beginning of OAE II in the Sciponoceras gracile zone. The termination of the OAE II in the WCSB coincides with the first occurrence of small ammonites (Subprionocyclus sp.) in the western part of the basin.     

Variable water column structure of the South Atlantic on glacial–interglacial time scales

The structure of the glacial ocean was significantly different to that of the present day with intermediate to mid-depth waters being notably more δ¹³C enriched than deep waters. This contrast was especially pronounced in the South Atlantic suggesting the development of a sharp chemical divide, or ‘chemocline’, at around 2500 m water depth between upper and lower layers, with implications for deep-ocean carbon storage [Hodell et al., 2003. Pleistocene vertical carbon isotope and carbonate gradients in the South Atlantic sector of the Southern Ocean. Geochemistry, Geophysics, Geosystems, 4(1): doi: 1004 10.1029/2002GC000367.]. We evaluate existing benthic foraminiferal δ¹³C, Cd/Ca and derived carbon isotope air–sea exchange signature (δ¹³C_as) data sets for the Atlantic during the Last Glacial Maximum (LGM), and Marine Isotope Stages (MIS) 6 and 8 in order to examine the regional extent of the chemocline in the South Atlantic. Benthic δ¹³C data north of the approximate latitude of the LGM Subantarctic Front (LGM-SAF, 43°S) linearly decrease with water depth, indicative of mixing between upper ‘well’ and lower ‘poorly’ ventilated water masses, with little evidence of the sharp chemical divide. Conversely, benthic δ¹³C data south of the LGM-SAF below 2500 m water depth are uniformly around ?0.8‰. The apparent δ¹³C gradient across the LGM-SAF suggests enhanced mid-depth ventilation north of the SAF and reduced ventilation to the south. From this pattern we conclude that the regional chemocline in the South Atlantic constituted a dominantly meridional, rather than a vertical gradient, and was developed during at least the past three glacial periods. Benthic Cd/Ca data indicate that the gradient was not nutrient related, although further data from the South Atlantic are needed for a better assessment of this suggestion. The combined benthic δ¹³C and Cd/Ca data indicate the source of well-ventilated upper waters in the South Atlantic changed from Northern Component Water (NCW) during early glacial phases to Upper Southern Component Water (USCW) during mid-to-late glacial phases when the Southern Ocean may have become isolated. USCW maintained a positive δ¹³C and δ¹³C_as signature simulating a North Atlantic origin that has been implicated in previous studies. The data demonstrate that secular imprints on δ¹³C must be taken into consideration when assessing the implications of the vertical δ¹³C gradient. This data also supports a variable water column architecture and modes of water mass formation as primary means to draw down atmospheric CO₂ and storage in the abyssal ocean by involving processes occurring on either side of the SAF in the glacial Southern Ocean.     

A new sediment core from the Bedoulian (Lower Aptian) stratotype at Roquefort-La Bédoule,SE France

New drill cores from the Lower Aptian historical stratotype at Roquefort-La Bédoule (SE France) provide continuous high-resolution geochemical and isotope records which closely track the onset of OAE 1a in a subtropical intra-shelf basin (South Provençal Basin). The drilling operation recovered a total of 180 m of undisturbed sediments in three holes. The lowermost 67 m correspond to the Bedoulian (core LB1) and are here analyzed in high-resolution using geochemical proxies (stable carbon isotopes, stable oxygen isotopes, and carbonate content) and foraminiferal biostratigraphy. Pervasive bioturbation through core LB1 suggests mostly oxygenated bottom water conditions with transient dysoxic episodes, as shown by higher pyrite and glauconite concentrations within the marlstones. Unprecedented resolution over the negative δ¹³C excursion preceding OAE 1a (segment C3) reveals a characteristic double trough extending over ∼5.5 m in core LB1. This long-lasting negative excursion was possibly linked to multiple pulses of enhanced CO₂ release to the atmosphere. Estimated sedimentation rates of 1.6–2 cm/kyr indicate that the negative δ¹³C excursion lasted >200 kyr, while the main positive carbon isotope shift (segment C4) had a duration of >300 kyr. Fluctuations in δ¹⁸O suggest transient episodes of climate warming and cooling at the northern margin of the Tethys or even on a more global scale prior to the onset of OAE 1a.     

Upper Campanian-Maastrichtian nannofossil biostratigraphy and high-resolution carbon-isotope stratigraphy of the Danish Basin: Towards a standard δC curve for the Boreal Realm

High-resolution carbon isotope stratigraphy of the upper Campanian-Maastrichtian is recorded in the Boreal Realm from a total of 1968 bulk chalk samples of the Stevns-1 core, eastern Denmark. Isotopic trends are calibrated by calcareous nannofossil bio-events and are correlated with a lower-resolution δ¹³C profile from Rørdal, northwestern Denmark. A quantitative approach is used to test the reliability of Upper Cretaceous nannofossil bio-events and provides accurate biohorizons for the correlation of δ¹³C profiles. The Campanian-Maastrichtian boundary (CMB) is identified through the correlation of dinoflagellate biostratigraphy and δ¹³C stratigraphy between Stevns-1 and the Global boundary Standard Stratotype-section and Point at Tercis les Bains (SW France), allowing the identification of new chemical and biostratigraphic markers that provide a precise placement of the stage boundary on a regional scale. The boundary interval corresponds to the third phase of a stepwise 0.8‰ negative δ¹³C excursion, lies in calcareous nannofossil subzone UC16d^BP, and encompasses the last occurrence of nannofossil Tranolithus stemmerikii and first occurrence of nannofossil Prediscosphaera mgayae. Fifteen δ¹³C events are defined and correlated to sixteen reliable nannofossil biohorizons, thus providing a well-calibrated standard high-resolution δ¹³C curve for the Boreal Realm.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

Carbon isotope stratigraphy using carbonate cements in the Triassic Sherwood Sandstone Group: Corrib Field,west of Ireland

Carbon stable isotopes from carbonate minerals (mainly dolomite) from six wells from the Lower Triassic Sherwood Sandstones of the Corrib Gas Field, Slyne Basin, west of Ireland, allow stratigraphic correlation. The results also provide information on palaeoenvironmental change during the deposition of these continental redbed sedimentary rocks. The Triassic reservoir rocks have been buried to > 4000 m and heated to > 165 °C and now contain methane-rich gas. Although the oxygen isotopic signal has been at least partially reset during burial and heating, a primary carbon isotopic signal appears to have survived diagenesis. The carbon isotope ratio varies from − 3.2‰ to + 2.1‰. All six wells show similar stratigraphic changes when all the carbon isotope data are plotted relative to a major playa horizon. δ¹³C increases from about − 3‰ at the base of the Sherwood to about + 2‰ 170 m above the base. δ¹³C then decreases to about − 2‰ for the next 70 m and remains steady for the following 50 m. The top 20 m of the Sherwood contains carbonate with a δ¹³C values decreasing to about − 3‰. The occurrence of a stratigraphically-correlatable carbon isotope pattern implies that the primary evolution signal has been preserved. The change in δ¹³C correlates with indicators of aridity and biological stress such that the highest δ¹³C values are in sedimentary rocks deposited in a playa lake (arid times); these rocks contain the greatest quantity of dolomite cement. Conversely, the lowest δ¹³C values correspond to sedimentary rocks deposited from well-developed rivers (relatively humid times) from the lowest quantity of dolomite cement. The same carbon isotope evolution has been found in another well in the Slyne basin and in Belgium, suggesting that the palaeoenvironmental isotope signal in the Triassic sedimentary rocks of the Corrib Field may have a regional significance.     

Carbon and oxygen isotope compositions of Lower-Middle Ordovician carbonate rocks in the northwestern Russian platform

Carbon and oxygen isotope compositions of Lower-Middle Ordovician carbonate rocks in the northwestern Russian Platform (eastern Ladoga Klint, Lynna River, and Babino quarry sections) are considered. In the studied section interval, average δ¹³C and δ¹⁸O values are 0 ± 0.5 and ?5 ± 0.5‰ (V-PDB), respectively. Two closely-spaced negative carbon isotope excursions with the amplitude of 2‰ are established near the Lower-Middle Ordovician boundary (between the Floian and Dapingian stages). The lower part of the Darriwilian Stage is marked by the gradual decrease in δ¹³C values to 1‰. Excursions of δ¹³C do not correlate with δ¹⁸O variations and can be considered as primary. The carbon isotope event defined at the Lower-Middle Ordovician boundary is traceable at the interregional level and represents a promising stratigraphic reference level. It may likely be explained by decrease in the relative rate of organic matter burial due to sea level fall and expansion of well-aerated shallow-water basins with a low primary production of phytoplankton.     

20 My of nitrogen fixation during deposition of mid-Cretaceous black shales on the Demerara Rise,equatorial Atlantic Ocean

Thick sequences of dark colored, organic carbon rich, finely laminated Santonian–Cenomanian claystones and homogeneous Albian siltstones were recovered from Ocean Drilling Program Sites 1257, 1258 and 1260 on the Demerara Rise in the western equatorial Atlantic Ocean. Total organic carbon (TOC) concentrations vary from 2 to over 20 wt% in the sequences of “black shales” that were deposited over a period of ～20 million years. Similarly long periods of elevated marine productivity implied by the high TOC concentrations are uncommon in the geological record and must have required unusual paleoceanographic conditions. The importance of nitrogen fixing bacteria to sustaining the amplified export production of organic matter is indicated by δ¹⁵N values that remain between ?4‰ and 0‰, a range that is notably less positive than the average of +5‰ for modern ocean sediments. Although containing mostly marine organic matter, the black shales have TOC/TN molar ratios between 20 and 40 that mimic those of land plant organic matter. The anomalously large TOC/TN ratios suggest selective organic matter degradation, probably associated with low oxygen conditions in the water column, that favored preservation of nitrogen poor forms of organic matter relative to nitrogen rich components. Deposition of black shales on the Demerara Rise was likely a consequence of the mid-Cretaceous warm and wet greenhouse climate that strengthened thermohaline stratification of this part of the Atlantic Ocean, which in turn encouraged bacterial nitrogen fixation, enhanced primary production, magnified organic matter export, and ultimately established anoxic conditions at the seafloor that improved preservation of organic matter for much of the 20 My period represented by these thick sequences.     

Early Jurassic climatic trends in the south-Tethyan margin

The Early Jurassic period was characterized by extreme environmental changes, as reflected by major global carbon isotope anomalies and abrupt changes in oxygen isotope and elemental records of marine organisms. Available data suggest an overall warm Early Jurassic climate interrupted by periods of severe cooling, with a climatic optimum during the early Toarcian. Available geochemical studies, however, have mainly focused on the northern margin of the Tethys Ocean, so that the palaeogeographic extent of these environmental perturbations, latitudinal palaeotemperature gradients and climate belt boundaries remain poorly constrained. Here we report the first stable isotope records of brachiopod shells (δ¹³C and δ¹⁸O values) from the Upper Sinemurian-Middle Toarcian interval in the southern margin of the Tethys Ocean (northwest Algeria). These data were used to better constrain the palaeoenvironmental evolution of the North Gondwana margin during the Early Jurassic, which likely played an important role on supra-regional climate. The diagenetic history of the analysed brachiopod shells was monitored using scanning electron microscopy, and elemental (manganese and strontium) compositions. The brachiopod δ¹³C and δ¹⁸O data show very similar trends as those reported for various Tethyan regions, and record negative carbon and oxygen isotope excursions near the Sinemurian–Pliensbachian and Pliensbachian–Toarcian transitions and during the Toarcian oceanic anoxic event (T-OAE). Despite these similarities, the carbon and oxygen isotope records are systematically offset towards more positive δ¹³C values (average +0.5‰) and more negative δ¹⁸O values (−1.0‰) compared to those obtained from sites of higher palaeolatitudes in the northern Tethyan margin. These offsets suggest a spatial heterogeneity in the stable isotope composition of dissolved inorganic carbon in the Early Jurassic Ocean and a marked latitudinal temperature gradient between the southern and northern margins of the Tethys.     

Biogenic processes in crystalline bedrock fractures indicated by carbon isotope signatures of secondary calcite

Variation in ¹³C/¹²C-isotope ratios of fracture filling calcite was analyzed in situ to investigate carbon sources and cycling in fractured bedrock. The study was conducted by separating sections of fracture fillings, and analyzing the ¹³C/¹²C-ratios with secondary ion mass spectrometry (SIMS). Specifically, the study was aimed at fillings where previously published sulfur isotope data indicated the occurrence of bacterial sulfate reduction. The results showed that the δ¹³C values of calcite were highly variable, ranging from −53.8‰ to +31.6‰ (VPDB). The analysis also showed high variations within single fillings of up to 39‰. The analyzed calcite fillings were mostly associated with two calcite groups, of which Group 3 represents possible Paleozoic fluid circulation, based on comparison with similar dated coatings within the Baltic Shield and the succeeding Group 1–2 fillings represent late-stage, low temperature mineralization and are possibly late Paleozoic to Quaternary in age. Both generations were associated with pyrite with δ³⁴S values indicative of bacterial sulfate reduction. The δ¹³C values of calcite, however, were indicative of geochemical environments which were distinct for these generations. The δ¹³C values of Group 3 calcite varied from −22.1‰ to +11‰, with a distinct peak at −16‰ to −12‰. Furthermore, there were no observable depth dependent trends in the δ¹³C values of Group 3 calcite. The δ¹³C values of Group 3 calcite were indicative of organic matter degradation and methanogenesis. In contrast to the Group 3 fillings, the δ¹³C values of Group 1–2 calcite were highly variable, ranging from −53.8‰ to +31.6‰ and they showed systematic variation with depth. The near surface environment of <30 m (bsl) was characterized by δ¹³C values indicative of degradation of surface derived organic matter, with δ¹³C values ranging from −30.3‰ to −5.5‰. The intermediate depth of 34–54 m showed evidence of localized methanotrophic activity seen as anomalously ¹³C depleted calcite, having δ¹³C values as low as −53.8‰. At depths of ∼60–400 m, positive δ¹³C values of up to +31.6‰ in late-stage calcite of Group 1–2 indicated methanogenesis. In comparison, high CH₄ concentrations in present day groundwaters are found at depths of >300 m. One sample at a depth of 111 m showed a transition from methanogenetic conditions (calcite bearing methanogenetic signature) to sulfate reducing (precipitation of pyrite on calcite surface), however, the timing of this transition is so far unclear. The results from this study gives indications of the complex nature of sulfur and carbon cycling in fractured crystalline environments and highlights the usefulness of in situ stable isotope analysis.     

The carbon isotopic response of algae, (cyano)bacteria, archaea and higher plants to the late Cenomanian perturbation of the global carbon cycle: Insights from biomarkers in black shales from the Cape Verde Basin (DSDP Site 367)

The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ¹³C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C₃₁ and C₃₂ hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ¹³C_TOC with the δ¹³C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ¹³C values of S-bound phytane and C₃₅ hopane were also used to estimate pCO₂ levels. Before the OAE burial event, pCO₂ levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO₂ levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO₂ levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO₂ levels.     

High-resolution stable carbon isotope monitoring indicates variable flow dynamic patterns in a deep saline aquifer at the Ketzin pilot site (Germany)

Stable isotopes of injected CO₂ act as useful tracers in carbon capture and storage (CCS) because the CO₂ itself is the carrier of the tracer signal and remains unaffected by sorption or partitioning effects. At the Ketzin pilot site (Germany), carbon stable isotope composition (δ¹³C) of injected CO₂ at the injection well was analyzed over a time period of 4 months. Occurring isotope variances resulted from the injection of CO₂ from two different sources (an oil refinery and a natural gas-reservoir). The two gases differed in their carbon isotope composition by more than 27‰. In order to find identifiable patterns of these variances in the reservoir, more than 250 CO₂-samples were collected and analyzed for their carbon isotope ratios at an observation well 100 m distant from the injection well. An isotope ratio mass spectrometer connected to a modified Thermo Gasbench system allowed quick and cost effective isotope analyses of a high number of CO₂ gas specimens. CO₂ gas from the oil refinery (δ¹³C = −30.9‰, source A) was most frequently injected and dominated the reservoir δ¹³C values at the injection site. Sporadic injection of the CO₂ from the natural gas-reservoir (δ¹³C = −3.5‰, source B) caused isotope shifts of up to +5‰ at the injection well. These variances provided a potential ideal tracer for CO₂ migration behavior. Based on these findings, tracer input signals that were injected during the last 2 years of injection could be reconstructed with the aid of an isotope mixing model and CO₂ delivery schedules. However, in contrast to the injection well, δ¹³C values at the observation well showed no variances and a constant value of −28.5‰ was measured at 600 m depth. This is in disagreement with signals that would be expected if the input signals from the injection would arrive at the observation well. The lack of isotope signals at the observation well suggests that parts of the reservoir are filled with CO₂ that is immobilized.     

鄂尔多斯奥陶系碳酸盐岩碳氧同位素特征及其意义*

鄂尔多斯古生代海相地层沉积厚度巨大。鄂尔多斯奥陶系碳酸盐岩的碳氧同位素组成受后期成岩作用影响较小,基本保留了原始海洋的同位素组成： δ¹³C值分布于-7.30‰～2.26‰之间,均值-0.30‰;δ¹⁸O值分布于-13.14‰～-1.94‰之间,均值-6.38‰,碳氧同位素组成与全球基本一致。区域上,鄂尔多斯西缘具有相对较高的δ¹³C值,南缘次之,而东缘最低。纵向上,碳同位素组成逐渐增重,并在中晚奥陶世发生明显的正向偏移,δ¹³C均值由马家沟组的-0.36‰增加到平凉组的0.15‰,至背锅山组增加至0.68‰。碳同位素的区域分布差异表明鄂尔多斯西缘水体相对较深,南缘次之,东缘相对较浅,由早奥陶世至晚奥陶世水体逐渐加深,碳同位素组成反映的海平面变化趋势与沉积相演化一致。鄂尔多斯西南缘中晚奥陶世碳同位素组成的正向偏移,标志着较高的生产力和有机碳埋藏率,具有重要的石油地质学意义,西南缘的平凉组/乌拉力克组和背锅山组是下古生界最重要和有效的烃源岩层。     

Pleistocene geochemical stratigraphy of the borehole 1317E (IODP Expedition 307) in Porcupine Seabight,SW of Ireland: applications to palaeoceanography and palaeoclimate of the coral mound development

Stable isotopes and element compositions of the fine‐grained matrix were measured for IODP Expedition 307 Hole U1317E drilled from the summit of Challenger Mound in Porcupine Seabight, northeast Atlantic, to explore the palaeoceanographic and palaeoclimatic background to development of the deep‐water coral mound. The 155 m long mound section was divided into two units by an unconformity at 23.6 mbsf: Unit M1 (2.6–1.7 Ma) and Unit M2 (1.0–0.5 Ma). Results from 519 specimens show a difference in δ¹³C value between Unit M1 (?0.6‰ to ?5.0‰) and Unit M2 (?1.0‰ to 1.0‰), but such a distinct difference was not seen in δ¹⁸O values (1.0‰–2.5‰), CaCO₃ content (40–60 wt%), Sr/Ca ratio (2.0–8.0 mmol mol^?1), and Mg/Ca ratio (10.0–20.0 mmol mol^?1) through the mound. Positive δ¹⁸O and negative δ¹³C shifts at the mound base are consistent with the oceanographic changes in the northeast Atlantic at the beginning of the Quaternary. The positive δ¹³C regression in Unit M2 suggests a linkage to the mid Pleistocene intensified glaciation in the Northern Hemisphere. Warm Mediterranean Upper Core Water of Mediterranean Outflow Water, Eastern North Atlantic Water and cold Labrador Sea Water of North Atlantic Deep Water are key oceanographic features that cause spikes and shifts in stable isotope and element composition. However, the stable isotope values of the sediment matrix could not primarily record the glacial–interglacial eustatic/temperature change, but indirectly indicate current regimes of the intermediate oceanic layer where the coral mound grew. Similarly, elemental ratios and CaCO₃ content may not represent the productivity and temperature of surface sea water, respectively, but superpose the fractions from both surface and bottom water. It is concluded that palaeoceanographic change coupled to the Pleistocene glacial/interglacial cycles is a key control on the geochemical stratigraphy of the matrix sediments of the carbonate mound developed in Porcupine Seabight. Copyright © 2011 John Wiley & Sons, Ltd.