Darren R. Gröcke

Massive dissociation of gas hydrate during a Jurassic oceanic anoxic event

In the Jurassic period, the Early Toarcian oceanic anoxic event (about 183 million years ago) is associated with exceptionally high rates of organic-carbon burial, high palaeotemperatures and significant mass extinction. Heavy carbon-isotope compositions in rocks and fossils of this age have been linked to the global burial of organic carbon, which is isotopically light. In contrast, examples of light carbon-isotope values from marine organic matter of Early Toarcian age have been explained principally in terms of localized upwelling of bottom water enriched in 12C versus 13 C (refs 1,2,5,6). Here, however, we report carbon-isotope analyses of fossil wood which demonstrate that isotopically light carbon dominated all the upper oceanic, biospheric and atmospheric carbon reservoirs, and that this occurred despite the enhanced burial of organic carbon. We propose that—as has been suggested for the Late Palaeocene thermal maximum, some 55 million years ago—the observed patterns were produced by voluminous and extremely rapid release of methane from gas hydrate contained in marine continental-margin sediments.

Chemostratigraphy of the Jurassic System: applications, limitations and implications for palaeoceanography

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 (δ18O) 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.

Carbon-isotope composition of Lower Cretaceous fossil wood: Ocean-atmosphere chemistry and relation to sea-level change

The carbon-isotope composition of fossil wood fragments, collected through a biostratigraphically well-constructed Aptian (Lower Cretaceous) shallow-marine siliciclastic succession on the Isle of Wight, southern Britain, shows distinct variations with time. The results indicate that the stratigraphic signature of {delta}{sup 13}C{sub wood} through the Aptian was influenced primarily by fluctuations in the isotopic composition of CO{sub 2} in the global ocean-atmosphere system, as registered in marine carbonates elsewhere, and was not governed by local paleoenvironmental and/or paleoecological factors. Negative and positive excursions in {delta}{sup 13}C{sub wood} through the lower Aptian occur in phase with inferred transgressions and regressions, respectively -- a pattern that contrasts with that observed in many previous studies for different time intervals. The relationship between {delta}{sup 13}C variations and relative sea-level change is tentatively interpreted as a response to various climatic and eustatic factors, relating to rapid sea-floor spreading, thermal uplift of ocean floor, emplacement of plateaus, volcanic CO{sub 2} emissions, weathering, and sedimentary rate.

Nitrogen isotope evidence for water mass denitrification during the early Toarcian (Jurassic) oceanic anoxic event.

Bulk sedimentary nitrogen isotope (δ15Ntot) data have been generated from Lower Jurassic black, carbon-rich shales in the British Isles and northern Italy deposited during the early Toarcian oceanic anoxic event. A pronounced positive δ15Ntot excursion through the exaratum Subzone of the falciferum Zone (defined by characteristic ammonites in the British Isles) broadly correlates with a relative maximum in weight percent total organic carbon and, in some sections, with a negative δ13Corg excursion. Upwelling of a deoxygenated water mass that had undergone partial denitrification is the likely explanation for relative enrichment of δ15Ntot, and parallels may be drawn with Quaternary sediments of the Arabian Sea, Gulf of California, and northwest Mexican margin. The development of Early Toarcian suboxic water masses and consequent partial denitrification is attributed to increases in organic productivity. Approximately coincident phenomena include the following: a relative climatic optimum, realignment of major oceanic current systems, and a possible release of methane gas hydrates from continental margin sediments early in the history of the oceanic anoxic event.

Determination of the abundance and carbon isotope composition of elemental carbon in sediments

We report measurements of the susceptibility of a variety of elemental and organic carbon samples to oxidative degradation using both acid dichromate and basic peroxide reagents. Organic carbon is rapidly oxidized using either reagent, or both reagents sequentially. Elemental carbon exhibits a wide range of susceptibilities to oxidation related both to the degree to which the precursor plant material was carbonized during pyrolysis and to the surface area available for oxidation. Despite a range of susceptibilities, a component of oxidation-resistant elemental carbon has been identified which can be reproducibly separated from organic contaminants. The carbon isotope composition (δ13C value) of the precursor plant materials underwent a 0–1.6‰ decrease during the production of the elemental carbon by pyrolysis, while the subsequent oxidative degradation of the samples resulted in only small (generally < 0.5%o) changes in the δ13C value of the remaining elemental carbon. The results suggest that the technique can be used to obtain records of elemental carbon abundance in marine sediment cores, and thus a record of the intensity of biomass burning on adjacent continental land masses in the geologic past. In addition, the δ13C value of the elemental carbon can provide an indication of the type of vegetation being burnt.

Paleoecological reconstruction of a lower Pleistocene large mammal community using biogeochemical (δ13C, δ15N, δ18O, Sr:Zn) and ecomorphological approaches

Abstract Ecomorphological and biogeochemical (trace element, and carbon, nitrogen, and oxygen isotope ratios) analyses have been used for determining the dietary niches and habitat preferences of large mammals from lower Pleistocene deposits at Venta Micena (Guadix-Baza Basin, Spain). The combination of these two approaches takes advantage of the strengths and overcome the weakness of both approaches. The range of δ13Ccollagen values for ungulate species indicates that C3 plants were dominant in the diet of these mammals. δ13Ccollagen values vary among ungulates: perissodactyls have the lowest values and bovids the highest ones, with cervids showing intermediate values. The hypsodonty index measured in lower molar teeth and the relative length of the lower premolar tooth row indicate that the horse, Equus altidens, was a grazing species, whereas the rhino, Stephanorhinus etruscus, was a mixed feeder in open habitats. The similar δ13Ccollagen values shown in both perissodactyls does not reflect differences in feeding behavior with other ungulates, but rather a lower isotope enrichment factor in these monogastric herbivores than in ruminants, owing to their lower metabolic efficiency. The cervids Eucladoceros giulii and Dama sp. show low hypsodonty values, indicating that they were mixed feeders or browsers from forested habitats, an ecomorphologically based conclusion corroborated in the former by its low δ15Ncollagen content (canopy effect). Bovid species (Bovini aff. Leptobos, Soergelia minor, and Hemitragus albus) presumably inhabited open environments, according to their comparatively high hypsodonty and δ15Ncollagen values. Carnivore species (Homotherium latidens, Megantereon whitei, Pachycrocuta brevirostris, Canis falconeri, and Canis etruscus) exhibit higher δ15Ncollagen values than ungulates. These results record the isotopic enrichment expected with an increase in trophic level and are also supported by low bone Sr:Zn ratios. The elevated δ15Ncollagen value for a sample of Mammuthus meridionalis, which came from an individual with unfused epiphyses, confirms that it was a suckling animal. The δ15Ncollagen value of the scimitar-cat H. latidens is well above that obtained for the young individual of Mammuthus, which indicates that juvenile elephants were an important part of its diet. The hippo, Hippopotamus antiquus, yielded unexpectedly high δ15Ncollagen values, which suggest feeding on aquatic, non-N2-fixing plants. The high δ18Ohydroxyl values of bovids Hemitragus and Soergelia and of cervid Dama indicate that these ungulates obtained most of their water requirements from the vegetation. The megaherbivores and Eucladoceros exhibit the lowest δ18Ohydroxyl values, which suggest increased water dependence for them. Paleosynecological analysis was based on the relative abundance of species of large mammals from different ecological categories, determined by feeding behavior and locomotion types. The comparison of the frequencies of such categories in Venta Micena with those found in modern African communities indicates that the composition of the paleocommunity closely resembles those of savannas with tall grass and shrubs. The net above-ground primary productivity estimated for the on-crop biomass of the mammalian species preserved in the fossil assemblage also yields a figure congruent with that expected for an open environment.

The carbon isotope composition of ancient CO2 based on higher-plant organic matter.

Carbon isotope ratios in higher-plant organic matter (δCplant) 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 continentalmargin 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. 10 yr) and is rapidly oxidized to CO2, causing the isotopic composition of CO2 to become more negative from its assumed background 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, carbonate 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.

ANNUAL RAINFALL AND NITROGEN-ISOTOPE CORRELATION IN MACROPOD COLLAGEN : APPLICATION AS A PALAEOPRECIPITATION INDICATOR

Abstract Collagen has been extracted and analysed for δ 15 N from modern kangaroos, macropods ( Macropus eugenii, M. antilopinus, M. fuliginosus, M. rufus, M. robustus ), in Western Australia and South Australia. Comparison of nitrogen-isotope ratios with annual rainfall for the respective areas produced a good negative correlation for macropods, but not for other marsupials. This may be related to metabolic adaptations in macropods to compete against water loss. Hence, the correlation between δ 15 N and annual rainfall may be species-specific. Nitrogen-isotope analyses on collagenic material extracted from fossil macropods ( Macropus spp.) have been determined from two Late Pleistocene deposits in South Australia. Corroboration with spore-pollen and sedimentological data confirm that δ 15 N of collagenic material can be used as a proxy for palaeoprecipitation levels in Australia. This has great potential for understanding palaeoclimatic changes, especially drought periods, in Australia during the Pleistocene.

Isotopic evidence for Late Jurassic^Early Cretaceous climate change

Abstract Strontium-, oxygen- and carbon-isotope ratios have been determined from Late Jurassic–Early Cretaceous belemnites from the Volga Basin, Russia, and Kawhia Harbour, New Zealand. 87Sr/86Sr ratios derived from well-preserved belemnites from the Volga Basin support a Middle Tithonian age derived from the analysis of the endemic ammonite fauna. The Kawhia Harbour section records a gradual rise in 87Sr/86Sr values and in comparison with the published 87Sr/86Sr curve suggests that the lower part of the section is latest Oxfordian in age, whilst the upper part of the section correlates well with the biostratigraphic correlation suggestion of an Early–Middle Tithonian age. Although the published strontium calibration curve shows a degree of scatter, our new data confirm the uniform rise in 87Sr/86Sr values from the Late Jurassic into the Early Cretaceous. Such an increase may result from either a decrease in mid-oceanic ridge spreading and/or an increase in weathering rates and flux of radiogenic strontium, although a eustatic drop in sea level and concurrent Western Cordillera uplift suggests that weathering may have been the controlling factor of Late Jurassic seawater strontium-isotope composition. Palaeotemperatures derived from the well-preserved belemnite δ18Ocarb values from the Volga Basin indicate that the Middle Volgian (Late Kimmeridgian) was warm (∼14–20°C), followed by a slight cooling and a subsequent gradual increase to the Jurassic–Cretaceous boundary. The δ18Ocarb values from New Zealand (located at a palaeolatitude of ∼80°S), if interpreted in terms of palaeotemperature, indicate a high degree of variability. Such variability may not be related to palaeotemperature, but to changes in oceanic chemistry resulting from the formation and dissolution of an ice-sheet and/or snow during the Oxfordian–Kimmeridgian. Carbon-isotope trends for the Late Jurassic show a fall in values from the Oxfordian with lowest values occurring in the Early–Middle Tithonian, before rising but without reaching values obtained in the Oxfordian. The overall low δ13Ccarb may be related to a global increase in continental weathering and/or upwelling of cooler oceanic water enriched in oxidised organic carbon (12C-enriched).

Recognizing the Albian-Cenomanian (OAE1d) sequence boundary using plant carbon isotopes : Dakota Formation, Western Interior Basin, USA.

Analysis of bulk sedimentary organic matter and charcoal from an Albian-Cenomanian fluvial-estuarine succession (Dakota Formation) at Rose Creek Pit (RCP), Nebraska, reveals a negative excursion of ∼3‰ in late Albian strata. Overlying Cenomanian strata have δ13C values of −24‰ to −23‰ that are similar to pre-excursion values. The absence of an intervening positive excursion (as exists in marine records of the Albian-Cenomanian boundary) likely results from a depositional hiatus. The corresponding positive δ13C event and proposed depositional hiatus are concordant with a regionally identified sequence boundary in the Dakota Formation (D2), as well as a major regressive phase throughout the globe at the Albian-Cenomanian boundary. Data from RCP confirm suggestions that some positive carbon-isotope excursions in the geologic record are coincident with regressive sea-level phases. We estimate using isotopic correlation that the D2 sequence boundary at RCP was on the order of 0.5 m.y. in duration. Therefore, interpretations of isotopic events and associated environmental phenomena, such as oceanic anoxic events, in the shallow-marine and terrestrial record may be influenced by stratigraphic incompleteness. Further investigation of terrestrial δ13C records may be useful in recognizing and constraining sea-level changes in the geologic record.