Stable Isotope Stratigraphy

The data presented here comprise Ryazanian–Valanginian carbon isotope ratios analyzed from fossil wood and belemnites from the shallow marine Boyarka River succession in Siberia. Additional belemnite carbon isotope ratios from the Izhma River succession (also Ryazanian–Valanginian) in Russia are also presented. The wood-derived and belemnite-derived isotope ratios are considered to primarily reflct changes in the terrestrial and marine carbon isotope reservoirs respectively. The δ13Ccarb and δ13Cwood records reveal a distinct mid-Valanginian positive carbon isotope excursion, with the initiation occurring near the Boreal Russian michalskii–polyptychus zone boundary, which is broadly time-equivalent Tethyan campylotoxus–verrucosum boundary. The Ryazanian–Valanginian δ13Ccarb values fluctuate between c. –1 and +1.5‰ but reach a maximum of +4.1‰ in the Late Valanginian, whilst the δ13Cwood values fluctuate between c.–27 and –23.5‰ and reach a Late Valanginian maximum of –21.2‰. The excursion maximum in the Boreal Russian bidichotomus zones corresponds with the peak of the Tethyan marine carbonate excursion in the verrucosum–eperegrinus zones, the peak of a marine carbonate excursion recorded in the Argentinean atherstoni Zone and also with the peak of a terrestrial organic carbon isotope excursion in the Crimean trinodosum–ecallidiscus ammonite zones. The synchroneity of the positive carbon isotope event between the marine and terrestrial records and between the northern and southern hemispheres and Tethys, clearly indicates a strong coupling of the ocean-atmosphere system at this time and also confirms that this was a global event, which would have affected the total exchangeable carbon reservoir.

The Kačák Event in the Middle Devonian (Eifelian-Givetian (E-G) boundary) is a period of apparent global anoxia coincident with widespread deposition of black shale in hemipelagic, pelagic, and some neritic facies. Conodont biostratigraphy in the North American Appalachian Basin has proven to be problematic in precisely demarcating the E-G boundary. In this study, we show that the E-G boundary may be defined more accurately through isotope stratigraphy (δ13C) in conjunction with a conodont faunal change across this boundary, identified as the Kačák-otomari Event. The Canadian Hamilton Group outcropping in Hungry Hollow, Ontario, is a 22 m sedimentary succession spanning the Middle Devonian. Conodont biostratigraphy for this section makes it difficult to define the E-G boundary, but the otomari Event can be detected. High-resolution isotopic analysis of bulk sedimentary carbonate and organic matter for this succession records a significant negative δ13C excursion (δ13Ccarb = up to 2‰; δ13Corg = ~3.0‰) that is synchronous with total organic carbon (TOC) values up to 12.5%. We identify this negative δ13C excursion as a result of marine anoxia associated with the Kačák-otomari Event and suggest that the excursion is a global event driven by a source of isotopically light carbon, followed by a productivity event, similar to Mesozoic oceanic anoxic events. Such similarities between Devonian and Mesozoic oceanic anoxic events may become more evident with increased high-resolution isotopic and geochemical investigations of Devonian successions.

Current chemostratigraphical studies of the Jurassic System primarily involve the use of one sedimentary component (marine organic carbon), one divalent transition metal substituted in carbonate (manganese), and two isotopic tracers: strontium-isotope ratios (87Sr/86Sr) and carbon-isotope ratios (δ13Ccarb and δ13Corg) in carbonate and in organic matter. Other parameters such as Mg/Ca and Sr/Ca ratios in calcite, oxygen-isotope ratios (ä18O) in carbonate, sulphur-isotope ratios (δ34S) in carbonate-hosted sulphate, nitrogen- isotope ratios (δ15Norg) in organic matter, osmium-isotope ratios (187Os/188Os) in black shales and neodymium-isotope ratios (143Nd/144Nd) in various mineral phases are also useful but at present give poor resolution because the database is incomplete or compromised by various factors. Stratigraphical patterns in total organic carbon (TOC) can be of either local or regional significance, depending on the lateral extent of the former nutrient-rich and productive water mass. Divalent manganese follows a similar pattern, being concentrated, most probably as a very early diagenetic phase, only in oxygen-depleted waters that typically underlie zones of elevated organic productivity. Shifts in Mg/Ca and Sr/Ca ratios on the time scale of ammonite subzones seem largely to reflect temperature changes. Strontium-isotope ratios from pristine skeletal calcite provide a global signal; δ13C values from carbonates with minimal diagenetic overprint potentially do the same, although small spatial differences in palaeo-water-mass composition may have been locally significant. Oxygen-isotope determinations on carbonate rocks and fossils generally yield values that are too scattered to be stratigraphically useful, because they reflect palaeotemperature, the evaporation–precipitation balance in sea water and the impact of any diagenesis involving an aqueous phase. Nitrogen-isotope ratios in organic matter reflect the chemistry of ancient water masses as affected by nitrate utilization and denitrification, and the stratigraphical pattern of this parameter is more likely to correlate only on a regional basis. Neodymium- isotope ratios in sea water are also water mass dependent and greatly affected by regional sources and oceanic current systems. Preliminary data on sulphur-isotope ratios in carbonates and osmium-isotope ratios in organic-rich shales, both potentially offering global correlation, indicate that these tracers may be valuable, although the records at present are not sufficiently well established to allow high-resolution regional correlation. In all cases, biostratigraphically well-dated reference sections, against which the relevant geochemical data have been calibrated, are required in the first instance. To date, studies on the stratigraphical distribution of organic carbon have been principally carried out in both northern (Boreal) and southern (Tethyan) Europe; carbon- isotope stratigraphy has been undertaken primarily, but not exclusively, on bulk pelagic sediments from the Alpine–Mediterranean or Tethyan domain; and strontium-isotope stratigraphy has been undertaken largely on calcitic skeletal material (belemnites and oysters) from northern and southern Europe. In many sections, including those containing ammonites, multi-parameter chemostratigraphy can give resolution that exceeds that attainable by classic biostratigraphical means. Strontium-isotope ratios in skeletal calcite are a particularly powerful tool for illustrating changes in sedimentary rate and revealing gaps in the stratigraphical record.

Our understanding of the ancient ocean-atmosphere system has focused on oceanic proxies. However, the study of terrestrial proxies is equally necessary to constrain our understanding of ancient climates and linkages between the terrestrial and oceanic carbon reservoirs. We have analyzed carbon isotope ratios from fossil plant material through the Valanginian and Lower Hauterivian from a shallow-marine, ammonite-constrained succession in the Crimean Peninsula of the southern Ukraine in order to determine if the Upper Valanginian positive carbon isotope excursion is expressed in the atmosphere. δ13Cplant values fluctuate around - 23‰ to - 22‰ for the Valanginian Hauterivian, except during the Upper Valanginian where δ13Cplant values record a positive excursion to ˜- 18‰. Based upon ammonite biostratigraphy from Crimea, and in conjunction with a composite Tethyan marine δ13Ccarb curve, several conclusions can be drawn: (1) the δ13Cplant record indicates that the atmospheric carbon reservoir was affected; (2) the defined ammonite correlations between Europe and Crimea are synchronous; and (3) a change in photosynthetic carbon isotope fractionation, caused by a decrease in atmospheric pCO2, occurred during the Upper Valanginian positive δ13C excursion. Our new data, combined with other paleoenvironmental and paleoclimatic information, indicate that the Upper Valanginian was a cool period (icehouse) and highlights that the Cretaceous period was interrupted by periods of cooling and was not an equable climate as previously thought.

Here we present initial 187Os/188Os (Osi) values integrated with δ13Corg for the first Paleozoic section — the Ordovician/Silurian boundary GSSP at Dob's Linn, Scotland. Our 187Os/188Os data tracks major changes in climate that occurred during the Late Ordovician (Hirnantian glaciation), which coincides with the second largest known mass extinction. During the complanatus and early anceps Biozones Osi values increase from 0.28–1.08. This provides evidence for a period of increased silicate weathering of radiogenic continental crust, likely from the Caledonian Orogen. This increase in weathering was likely the driving mechanism for the drawdown in atmospheric CO2 and global cooling that resulted in the onset of the Hirnantian Glaciation. A decrease to less radiogenic Osi occurs at the base Hirnantian extraordinarius Biozone and coincides with the trend to more positive δ13Corg values that mark the onset of the Hirnantian Glaciation. The trend in Osi during this interval is ascribed to Hirnantian ice cover and reduced chemical weathering rates cutting the supply of radiogenic material to the Iapetus Ocean. The reduction in silicate weathering enabled atmospheric CO2 to return back to greenhouse levels, causing rapid deglaciation during the mid persculptus Biozone. This period is marked by an abrupt increase in Osi values from 0.6 to 1.08 over 19 cm of stratigraphy and coincides with the deglacial limb of the δ13Corg profile. We interpret the Osi data to reflect the leaching of exposed radiogenic 187Os/188Os bearing glacial deposits and increased weathering of radiogenic 187Os/188Os silicate terrane during the deglaciation. Previous workers have identified the Hirnantian glaciation primarily through δ13C stratigraphy. However, our Os isotope data indicate that an initial mechanism (i.e. increased silicate weathering) was the driving mechanism behind the Hirnantian Glaciation and subsequent mass extinction. Thus, by coupling Osi and δ13Corg proxies we provide the most direct evidence for the initiation and cessation of the Hirnantian glaciation. Furthermore, this study demonstrates the first use of 187Os/188Os chemostratigraphy for the Paleozoic as a proxy for reconstructing the Earth's climate system, particularly palaeoceanography.

During the Early Toarcian there was a significant disruption in the short-term active carbon reservoir as revealed by carbon-isotope records, which show a broad positive shift that is interrupted by a large 5–7‰ negative excursion (δ13Corg). Carbon-isotope excursion co-occurs with the deposition of organic-rich shales in many areas. This perturbation in carbon isotopes is thought to be indicative of severe climate change and marine anoxia. The two leading hypotheses as to the cause of this event invoke either global or regional controls. Here we present carbon-isotope data from Haida Gwaii, British Columbia, Canada showing a significant perturbation within a temporally constrained Early Toarcian succession that was deposited in the northeastern paleo-Pacific Ocean. These data reinforce the concept that the short-term active carbon reservoir was affected globally, and assist with the correlation of ammonite zonal schemes between western North America and Europe. The δ13Corg data show a broad positive shift that is interrupted by a sharp and pronounced negative excursion of 7‰ (8.5‰ in δ13Cwood) in the Early Toarcian Kanense Zone. This negative excursion also coincides with increasing total organic carbon (TOC) from ~0.4% to ~1.2%. These data suggest that the Early Toarcian carbon-isotope perturbation was indeed global and imprinted itself on all active global reservoirs of the exchangeable carbon cycle (deep marine, shallow marine, atmospheric).

Oceanic anoxic events were time intervals in the Mesozoic characterized by widespread distribution of marine organic matter-rich sediments (black shales) and significant perturbations in the global carbon cycle. These perturbations are globally recorded in sediments as carbon isotope excursions irrespective of lithology and depositional environment. During the early Toarcian, black shales were deposited on the epi- and pericontinental shelves of Pangaea, and these sedimentary rocks are associated with a pronounced (ca. 7 ‰) negative (organic) carbon isotope excursion (CIE) which is thought to be the result of a major perturbation in the global carbon cycle. For this reason, the lower Toarcian is thought to represent an oceanic anoxic event (the T-OAE). If the T-OAE was indeed a global event, an isotopic expression of this event should be found beyond the epi- and pericontinental Pangaean localities. To address this issue, the carbon isotope composition of organic matter (δ13Corg of lower Toarcian organic matter-rich cherts from Japan, deposited in the open Panthalassa Ocean, was analysed. The results show the presence of a major (>6 ‰) negative excursion in δ13Corg that, based on radiolarian biostratigraphy, is a correlative of the lower Toarcian negative CIE known from Pangaean epi- and pericontinental strata. A smaller negative excursion in δ13Corg (ca. 2 ‰) is recognized lower in the studied succession. This excursion may, within the current biostratigraphic resolution, represent the excursion recorded in European epicontinental successions close to the Pliensbachian/Toarcian boundary. These results from the open ocean realm suggest, in conjunction with other previously published datasets, that these Early Jurassic carbon cycle perturbations affected the active global reservoirs of the exchangeable carbon cycle (deep marine, shallow marine, atmospheric).

Our understanding of the ancient ocean-atmosphere system has focused on oceanic proxies. However, the study of terrestrial proxies is equally necessary to constrain our understanding of ancient climates and linkages between the terrestrial and oceanic carbon reservoirs. We have analyzed carbon–isotope ratios from fossil plant material through the Valanginian and Lower Hauterivian from a shallow-marine, ammonite-constrained succession in the Crimean Peninsula of the southern Ukraine in order to determine if the Upper Valanginian positive carbon–isotope excursion is expressed in the atmosphere. δ13Cplant values fluctuate around –23‰ to –22‰ for the Valanginian–Hauterivian, except during the Upper Valanginian where δ13Cplant values record a positive excursion to ~–18‰. Based upon ammonite biostratigraphy from Crimea, and in conjunction with a composite Tethyan marine δ13Ccarb curve, several conclusions can be drawn: (1) the δ13Cplant record indicates that the atmospheric carbon reservoir was affected; (2) the defined ammonite correlations between Europe and Crimea are synchronous; and (3) a change in photosynthetic carbon–isotope fractionation, caused by a decrease in atmospheric pCO2, occurred during the Upper Valanginian positive δ13C excursion. Our new data, combined with other paleoenvironmental and paleoclimatic information, indicate that the Upper Valanginian was a cool period (icehouse) and highlights that the Cretaceous period was interrupted by periods of cooling and was not an equable climate as previously thought.

Organic material from the Noordhoek area on the western margin of the Cape Peninsula, South Africa, was obtained from a ~ 50 m-long drill-core dominated by fluvio-lacustrine siliciclastic sediments. The aim of this study is to constrain fluctuations in climate and the decline of tropical vegetation elements along the southwestern coast and the Cape Peninsula of South Africa, during the Late Cenozoic phase, when the Benguela upwelling system was established. The approach was to combine palynological, biogeochemical (tetraether lipids) and stable isotope (C, N) studies of the organic-bearing record from the Noordhoek area on the western margin of the Cape Peninsula. Bulk C and N isotope data of sediment organic matter, point to a predominantly C3 higher plant source vegetation. Mean annual air temperature (MAT) from the analyses of tetraether lipids (MBT′–CBT index) was compared with palynomorphs from partly unpublished data of a previously drilled core adjacent to the study site. The palynomorphs are of subtropical affinities, and suggest that an open riparian forest would have existed in the early to middle Miocene of the southwestern coast of South Africa. Together these data sources allow vegetation and climate reconstructions of subtropical conditions during the early to middle Miocene, which comprised fluctuating open riparian forest and swamp vegetation. Temperatures rose in the middle Miocene and were higher than those of the present day.

Stable isotope ratios of whole rock carbonates and faunas from three low latitude Upper Ordovician sections demonstrate a coherent pattern of shifting subtropical and tropical water masses and associated climate belts. We suggest that tropical water beneath the Inter-tropical Convergence Zone (δ18O = − 10‰ to − 15‰) was isotopically light reflecting high sea-surface temperatures (SST) and reduced sea-surface salinity (SSS). Subtropical water in both the northern and southern hemispheres is characterised by δ18O values from −4 to −6‰. Our interpretation is consistent with the published results from physical–chemical modeling of Ordovician seawater composition and climate models. Deriving absolute temperature and salinity values from Ordovician δ18Ocarb data is problematic as they could reflect SST, SSS, ice volume and potentially a variable diagenetic overprint, and currently no independent constraints exist for any of these variables. The ITCZ was positioned at ~−10°N of the Equator during the early Katian consistent with the likely position of the region of peak sea-surface temperature (SST). During the late Katian Boda Event the ITCZ moved across the Equator to ~−10°S. By analogy with the Pliocene this resulted in a symmetrical distribution of sea- surface currents about the Equator. This led to a net increase in heat flow towards the poles and lower latitudinal temperature gradients, potentially explaining the migration of warm water faunas to higher southern latitudes during the Boda Event. During the Hirnantian the ITCZ shifted north of the Equator, resulting in a reduced poleward heat transport. ITCZ position has been proposed as a likely forcing mechanism of Neogene glaciation and the evidence from the Ordovician suggests a discrete palaeo-ITCZ whose position was controlled by solar insolation and latitudinal temperature gradients linked to ice volume changes and Hadley Cell dynamics. We hypothesize that the position of the ITCZ was sensitive to the growing Hirnantian ice sheet during the Late Ordovician. We propose that latitudinal movement of the ITCZ during the Late Ordovician resulted in a major atmosphere–ocean circulation re-organization. Higher pCO2 estimates for the Ordovician caused more extreme changes in this circulation that were the likely primary cause of biotic mass extinction. If the monsoon is considered an off-equator ITCZ then we provide direct evidence of an Ordovician monsoonal climate.

... cooling ages to uplift and erosion controlled by late orogenic collapse and not to contractional deformation'' (Hartz and Andre-sen, 1995 ... Strachan, RA, 1994, Evidence in North-East Greenland for Late Siluri-an–Early Devonian regional extension during the Caledonian orogeny ...

Organic material from the Noordhoek area on the western margin of the Cape Peninsula, South Africa, was obtained from a ~ 50 m-long drill-core dominated by fluvio-lacustrine siliciclastic sediments. The aim of this study is to constrain fluctuations in climate and the decline of tropical vegetation elements along the southwestern coast and the Cape Peninsula of South Africa, during the Late Cenozoic phase, when the Benguela upwelling system was established. The approach was to combine palynological, biogeochemical (tetraether lipids) and stable isotope (C, N) studies of the organic-bearing record from the Noordhoek area on the western margin of the Cape Peninsula. Bulk C and N isotope data of sediment organic matter, point to a predominantly C 3 higher plant source vegetation. Mean annual air temperature (MAT) from the analyses of tetraether lipids (MBT′–CBT index) was compared with palynomorphs from partly unpublished data of a previously drilled core adjacent to the study site. Th...

Current chemostratigraphical studies of the Jurassic System primarily involve the use of one sedimentary component (marine organic carbon), one divalent transition metal substituted in carbonate (manganese), and two isotopic tracers: strontium-isotope ratios ( 87 Sr/ 86 Sr) ...

87Sr/86Sr data of belemnites are presented from a Middle Jurassic–Early Cretaceous succession from the Falkland Plateau (Deep Sea Drilling Project Sites 511 and 330) that was deposited in a periodically anoxic, semi-enclosed shallow water basin. Diagenetically screened strontium-isotope values of 0.706789 rise to 0.707044 before increasing sharply to 0.707428 in the uppermost part of the sampled succession. Comparison with published strontium calibration curves suggests that the oldest samples were Callovian to Oxfordian in age, whilst the remainder of the Jurassic part of the succession consisted of Kimmeridgian and Early Tithonian age sediments. The nannofossil, dinoflagellate and molluscan assemblages provide comparable age determinations. The strontium-isotope analysis of the youngest belemnites points to a Hauterivian–Barremian age,whilst age interpretations based upon the fauna provide a wide age range from the Barremian to early Albian. Strontium-isotope stratigraphy of this succession hence offers increased age resolution providing data regarding the timing of episodes of bottom water anoxia which have been recorded throughout the South Atlantic Basin. Well-preserved belemnite specimens display an oxygen-isotope range between +0.08 and –2.22‰ (PDB, Peedee belemnite international standard) and a carbon-isotope range from +2.35 to –1.33‰ (PDB). δ13C values become increasingly negative through the Late Jurassic–Early Cretaceous and in concert with the 87Sr/86Sr data reveal a trend that could be accounted for by increasing levels of weathering and erosion. The oxygen-isotope data if interpreted in terms of palaeotemperature are consistent with warm palaeotemperatures in the Kimmeridgian and slightly cooler temperatures for the Tithonian and Early Cretaceous parts of the succession. The proposed relative Kimmeridgian warmth (based upon strontium-isotope age assignments) is thus in good agreement with other published palaeotemperature records.

Carbon isotope ratios in higher-plant organic matter (δ13Cplant) have been shown in several studies to be closely related to the carbon isotope composition of the ocean–atmosphere carbon reservoir, and, in particular, the isotopic composition of CO2. These studies have primarily been focused on geological intervals in which major perturbations occur in the oceanic carbon reservoir, as documented in organic carbon and carbonates phases (e.g. Permian–Triassic and Triassic–Jurassic boundary, Early Toarcian, Early Aptian, Cenomanian–Turonian boundary, Palaeocene–Eocene Thermal Maximum (PETM)). All of these events, excluding the Cenomanian–Turonian boundary, record negative carbon isotope excursions, and many authors have postulated that the cause of such excursions is the massive release of continental-margin marine gas-hydrate reservoirs (clathrates). Methane has a very negative carbon isotope composition (δ13C, ca.−60‰) in comparison with higher-plant and marine organic matter, and carbonate. The residence time of methane in the ocean–atmosphere reservoir is short (ca.10yr) and is rapidly oxidized to CO2, causing the isotopic composition of CO2 to become more negative from its assumed back- ground value (δ13C, ca.−7‰). However, to date, only the Early Toarcian, Early Aptian and PETM are well-constrained chronometric sequences that could attribute clathrate release as a viable cause to create such rapid negative δ13C excursions. Notwithstanding this, the isotopic analysis of higher-plant organic matter (e.g. charcoal, wood, leaves, pollen) has the ability to (i) record the isotopic composition of palaeoatmospheric CO2 in the geological record, (ii) correlate marine and non-marine stratigraphic successions, and (iii) confirm that oceanic carbon perturbations are not purely oceanographic in their extent and affect the entire ocean–atmosphere system. A case study from the Isle of Wight, UK, indicates that the carbon isotope composition of palaeoatmospheric CO2 during the Mid-Cretaceous had a background value of −3‰, but fluctuated rapidly to more positive (ca.+0.5‰) and negative values (ca.−10‰) during carbon cycle perturbations (e.g. carbon burial events, carbon- ate platform drowning, large igneous province formation). Hence, fluctuations in the carbon isotope composition of palaeoatmospheric CO2 would compromise our use of palaeo-CO2 proxies that are dependent on constant carbon isotope ratios of CO2.