An evaluation of the distributions of polychlorinated biphenyls and organic matter in coastal sediments

The objective of this thesis is to improve the understanding of what processes and mechanism affects the distribution of polychlorinated biphenyls (PCBs) and organic carbon in coastal sediments. Because of the strong association of hydrophobic organic contaminants (HOCs) such as PCBs with organic matter in the aquatic environment, these two entities are naturally linked. The coastal environment is the most complex and dynamic part of the ocean when it comes to both cycling of organic matter and HOCs. This environment is characterised by the largest fluxes and most diverse sources of both entities. A wide array of methods was used to study these processes throughout this thesis. In the field sites in the Stockholm archipelago of the Baltic proper, bottom sediments and settling particulate matter were retrieved using sediment coring devices and sediment traps from morphometrically and seismically well-characterized locations. In the laboratory, the samples have been analysed for PCBs, stable carbon isotope ratios, carbon-nitrogen atom ratios as well as standard sediment properties. From the fieldwork in the Stockholm Archipelago and the following laboratory work it was concluded that the inner Stockholm archipelago has a low (≈ 4%) trapping efficiency for freshwater-derived organic carbon. The corollary is a large potential for long-range waterborne transport of OC and OC-associated nutrients and hydrophobic organic pollutants from urban Stockholm to more pristine offshore Baltic Sea ecosystems. Theoretical work has been carried out using Geographical Information Systems (GIS) and statistical methods on a database of 4214 individual sediment samples, each with reported individual PCB congener concentrations. From this work it was concluded that the continental shelf sediments are key global inventories and ultimate sinks of PCBs. Depending on congener, 10-80% of the cumulative historical emissions to the environment are accounted for in continental shelf sediments. Further it was concluded that the many infamous and highly contaminated surface sediments of urban harbours and estuaries of contaminated rivers cannot be of importance as a secondary source to sustain the concentrations observed in remote sediments. Of the global shelf PCB inventory < 1% are in sediments near population centres while ≥ 90% is in remote areas (> 10 km from any dwellings). The remote sub-basin of the North Atlantic Ocean contains approximately half of the global shelf sediment inventory for most of the PCBs studied.

Sources and pathways of methane formed in oxidative environments

Methane is the most abundant reduced organic compound in the atmosphere. As the strongest known long-lived greenhouse gas after water vapour and carbon dioxide methane perturbs the radiation balance of Earth’s atmosphere. The abiotic formation of methane requires ultraviolet irradiation of organic matter or takes place in locations with high temperature and/or pressure, e.g. during biomass burning or serpentinisation of olivine, under hydrothermal conditions in the oceans deep or below tectonic plates. The biotic methane formation was traditionally thought to be formed only by methanogens under strictly anaerobic conditions, such as in wetland soils, rice paddies and agricultural waste. rnIn this dissertation several chemical pathways are described which lead to the formation of methane under aerobic and ambient conditions. Organic precursor compounds such as ascorbic acid and methionine were shown to release methane in a chemical system including ferrihydrite and hydrogen peroxide in aquatic solution. Moreover, it was shown by using stable carbon isotope labelling experiments that the thio-methyl group of methionine was the carbon precursor for the methane produced. Methionine, a compound that plays an important role in transmethylation processes in plants was also applied to living plants. Stable carbon isotope labelling experiments clearly verified that methionine acts as a precursor compound for the methane from plants. Further experiments in which the electron transport chain was inhibited suggest that the methane generation is located in the mitochondria of the plants. The abiotic formation of methane was shown for several soil samples. Important environmental parameter such as temperature, UV irradiation and moisture were identified to control methane formation. The organic content of the sample as well as water and hydrogen peroxide might also play a major role in the formation of methane from soils. Based on these results a novel scheme was developed that includes both biotic and chemical sources of methane in the pedosphere.rn

Calibration study of bivalve shells : implications for paleoenvironmental reconstruction

The accretionary shells of bivalve mollusks can provide environmental information, such as water temperature, precipitation, freshwater fluxes, primary productivity and anthropogenic activities in the form of variable growth rates and variable geochemical properties, such as stable oxygen and carbon isotopes. However, paleoenvironmental reconstructions are constrained by uncertainties about isotopic equilibrium fractionation during shell formation, which is generally acknowledged as a reasonable assumption for bivalves, but it has been disputed in several species. Furthermore, the variation in shell growth rates is accepted to rely on multiple environmental variables, such as temperature, food availability and salinity, but can differ from species to species. Therefore, it is necessary to perform species-specific calibration studies for both isotope proxies and shell growth rates before they can be used with confidence for environmental interpretations of the past. Accordingly, the principal objective of this Ph.D research is to examine the reliability of selected bivalve species, the long-lived Eurhomalea exalbida (Dillwyn), the short-lived and fast growing species Paphia undulata (Born 1778), and the freshwater mussel Margaritifera falcata (Gould 1850), as paleoenvironmental proxy archives.rnThe first part is focused on δ18Oshell and shell growth history of live-collected E. exalbida from the Falkland Islands. The most remarkable finding, however, is that E. exalbida formed its shell with an offset of -0.48‰ to -1.91‰ from the expected oxygen isotopic equilibrium with the ambient water. If this remained unnoticed, paleotemperature estimates would overestimate actual water temperatures by 2.1-8.3°C. With increasing ontogenetic age, the discrepancy between measured and reconstructed temperatures increased exponentially, irrespective of the seasonally varying shell growth rates. This study clearly demonstrates that, when the disequilibrium fractionation effect is taken into account, E. exalbida can serve as a high-resolution paleoclimate archive for the southern South America. The species therefore provides quantifiable temperature estimates, which yields new insights into long-term paleoclimate dynamics for mid to high latitudes on the southern hemisphere.rnThe stable carbon isotope of biogenic carbonates is generally considered to be useful for reconstruction of seawater dissolved inorganic carbon. The δ13Cshell composition of E. exalbida was therefore, investigated in the second part of this study. This chapter focuses on inter-annual and intra-annual variations in δ13Cshell. Environmental records in δ13Cshell are found to be strongly obscured by changes in shell growth rates, even if removing the ontogenetic decreasing trend. This suggests that δ13Cshell in E. exalbida may not be useful as an environmental proxy, but a potential tool for ecological investigations. rnIn addition to long-lived bivalve species, short-lived species that secrete their shells extremely fast, can also be useful for environmental reconstructions, especially as a high-resolution recorder. Therefore, P. undulata from Daya Bay, South China Sea was utilized in Chapter 4 to evaluate and establish a potential proxy archive for past variations of the East Asian monsoon on shorter time-scales. The δ18Oshell can provide qualitative estimates of the amount of monsoonal rain and terrestrial runoff and the δ13Cshell likely reflect the relative amount of isotopically light terrestrial carbon that reaches the ocean during the summer monsoon season. Therefore, shells of P. undulata can provide serviceable proxy archives to reconstruct the frequency of exceptional summer monsoons in the past. The relative strength of monsoon-related precipitation and associated changes in ocean salinity and the δ13C ratios of the dissolved inorganic carbon signature (δ13CDIC) can be estimated from the δ18Oshell and δ13Cshell values as well as shell growth patterns. rnIn the final part, the freshwater pearl shell M. falcata from four rivers in British Columbia, Canada was preliminarily studied concerning the lifespans and the shell growth rates. Two groups separated by the Georgia Strait can be clearly distinguished. Specimens from the western group exhibit a shorter lifespan, while the eastern group live longer. Moreover, the average lifespan seems to decrease from south to north. The computed growth equations from the eastern and western groups differ as well. The western group exhibits a lower growth rate, while bivalves from the eastern group grow faster. The land use history seems to be responsible for the differences in lifespans of the specimens from the two groups. Differences in growth rate may be induced by differences in water temperature or nutrient input also related to the land use activities.

A sublimation technique for high-precision measurements of d13CO2 and mixing ratios of CO2 and N2O from air trapped in ice cores

In order to provide high precision stable carbon isotope ratios (δ13CO2 or δ13C of CO2) from small bubbly, partially and fully clathrated ice core samples we developed a new method based on sublimation coupled to gas chromatography-isotope ratio mass spectrometry (GC-IRMS). In a first step the trapped air is quantitatively released from ~30 g of ice and CO2 together with N2O are separated from the bulk air components and stored in a miniature glass tube. In an off-line step, the extracted sample is introduced into a helium carrier flow using a minimised tube cracker device. Prior to measurement, N2O and organic sample contaminants are gas chromatographically separated from CO2. Pulses of a CO2/N2O mixture are admitted to the tube cracker and follow the path of the sample through the system. This allows an identical treatment and comparison of sample and standard peaks. The ability of the method to reproduce δ13C from bubble and clathrate ice is verified on different ice cores. We achieve reproducibilities for bubble ice between 0.05 ‰ and 0.07 ‰ and for clathrate ice between 0.05 ‰ and 0.09 ‰ (dependent on the ice core used). A comparison of our data with measurements on bubble ice from the same ice core but using a mechanical extraction device shows no significant systematic offset. In addition to δ13C, the CO2 and N2O mixing ratios can be volumetrically derived with a precision of 2 ppmv and 8 ppbv, respectively.

gamma-tocopherol traps mutagenic electrophiles such as NO(X) and complements alpha-tocopherol: physiological implications

Peroxynitrite, a powerful mutagenic oxidant and nitrating species, is formed by the near diffusion-limited reaction of .NO and O2.- during activation of phagocytes. Chronic inflammation induced by phagocytes is a major contributor to cancer and other degenerative diseases. We examined how gamma-tocopherol (gammaT), the principal form of vitamin E in the United States diet, and alpha-tocopherol (alphaT), the major form in supplements, protect against peroxynitrite-induced lipid oxidation. Lipid hydroperoxide formation in liposomes (but not isolated low-density lipoprotein) exposed to peroxynitrite or the .NO and O2.- generator SIN-1 (3-morpholinosydnonimine) was inhibited more effectively by gammaT than alphaT. More importantly, nitration of gammaT at the nucleophilic 5-position, which proceeded in both liposomes and human low density lipoprotein at yields of approximately 50% and approximately 75%, respectively, was not affected by the presence of alphaT. These results suggest that despite alphaT's action as an antioxidant gammaT is required to effectively remove the peroxynitrite-derived nitrating species. We postulate that gammaT acts in vivo as a trap for membrane-soluble electrophilic nitrogen oxides and other electrophilic mutagens, forming stable carbon-centered adducts through the nucleophilic 5-position, which is blocked in alphaT. Because large doses of dietary alphaT displace gammaT in plasma and other tissues, the current wisdom of vitamin E supplementation with primarily alphaT should be reconsidered.

Origin and evolution of reactive and noble gases dissolved in matrix pore water

Reactive and noble gases dissolved in matrix pore water of low permeable crystalline bedrock were successfully extracted and characterized for the fist time based on drillcore samples from the Olkiluoto investigation site (SW Finland). Interaction between matrix pore water and fracture groundwater occurs predominately by diffusion. Changes in the chemical and isotopic composition of gases dissolved in fracture groundwater are transmitted and preserved in the pore water. Absolute concentrations, their ratios and the stable carbon isotope signature of hydrocarbon gases dissolved in pore water give valuable indications about the evolution of these gases in the nearby-flowing fracture groundwaters. Inert noble gases dissolved in matrix pore water and their isotopes combined with their in-situ production and accumulation rates deliver information about the residence time of pore water.

Taxon-specific δ13C analysis of chitinous invertebrate remains in sediments from Strandsjön, Sweden

Taxon-specific stable carbon isotope (δ13C) analysis of chitinous remains of invertebrates can provide valuable information about the carbon sources used by invertebrates living in specific habitats of lake ecosystems (for example, sediments, water column, or aquatic vegetation). This is complementary to δ13C of sedimentary organic matter (SOM), which provides an integrated signal of organic matter produced in a lake and its catchment, and of diagenetic processes within sediments. In a sediment record from Strandsjön (Sweden) covering the past circa 140 years, we analyzed SOM geochemistry (δ13C, C:Natomic, organic carbon content) and δ13C of chitinous invertebrate remains in order to examine whether taxon-specific δ13C records could be developed for different invertebrate groups and whether these analyses provide insights into past changes of organic carbon sources for lacustrine invertebrates available in benthic and planktonic compartments of the lake. Invertebrate taxa included benthic chironomids (Chironomus, Chironomini excluding Chironomus, Tanytarsini, and Tanypodinae), filter-feeders on suspended particulate organic matter (Daphnia, Plumatella and Cristatella mucedo), and Rhabdocoela. δ13C of chironomid remains indicated periodic availability of 13C-depleted carbon sources in the benthic environment of the lake as δ13C values of the different chironomid taxa fluctuated simultaneously between -34.7 and -30.5‰ (VPDB). Daphnia and Bryozoa showed parallel changes in their δ13C values which did not coincide with variations in δ13C of chironomids, though, and a 2-3‰ decrease since circa AD 1960. The decrease in δ13C of Daphnia and Bryozoa could indicate a decrease in phytoplankton δ13C as a result of lower lake productivity, which is in accordance with historical information about the lake that suggests a shift to less eutrophic conditions after AD 1960. In contrast, Rhabdocoela cocoons were characterized by relatively high δ13C values (-30.4 to -28.2‰) that did not show a strong temporal trend, which could be related to the predatory feeding mode and wide prey spectrum of this organism group. The taxon-specific δ13C analyses of invertebrate remains indicated that different carbon sources were available for the benthic chironomid larvae than for the filter-feeding Daphnia and bryozoans. Our results therefore demonstrate that taxon-specific analysis of δ13C of organic invertebrate remains can provide complementary information to measurements on bulk SOM and that δ13C of invertebrate remains may allow the reconstruction of past changes in carbon sources and their δ13C in different habitats of lake ecosystems.

Multiple tree-ring proxies (earlywood width, latewood width and δ13C) from pedunculate oak (Quercus robur L.), Hungary

The aim of this study was to analyse the effects of climatic factors (i.e. monthly mean temperature and total precipitation) on radial growth (earlywood width, latewood width, and total ringwidth) and on latewood stable carbon isotope composition in a pedunculate oak (Quercus robur L) stand in northeastern Hungary. Earlywood widths showed the weakest common variance and lack of statistically significant relationship to monthly precipitation and temperature. Latewood width showed the strongest common chronological signal. Correlation analysis with the monthly climate series pointed out the strongest positive/negative correlation with June precipitation for latewood width/stable carbon isotope ratio. These parameters shared the strongest climatic response also for seasonal scale since the highest correlation coefficients, 0.49 and -0.62 for latewood width and stable carbon isotope ratio, respectively, were obtained for both with a 10-month precipitation total (from previous November to current August of the growing season). A combined parameter, derived as difference between latewood width and stable carbon isotope indices showed improved statistical relationship compared to the hydroclimatic calibration target both for local and regional spatial scales. Spatial correlation analysis indicated that the hydroclimatic signal encoded in these moisture sensitive tree-ring parameters from Bakta Forest is expected to be representative for the northeastern Carpathians and for the large part of the Great Hungarian Plain. In addition, the hydroclimatic signal of latewood width chronology was compared to three independent records. Results showed that neither the strength nor the rank of the similarity of the local hydroclimate signals were stable throughout the past two centuries. Future palaeo(hydro)climatological efforts targeting the Carpathian(-Balkan) region are recommended to track carefully the spatial domains for which a given, local, proxy-derived hydroclimate reconstruction might provide useful information.

Social stratigraphy in Late Iron Age Switzerland: Analysis of human remains from Münsingen

The Iron Age cemetery of Münsingen in Switzerland with 220 abundantly equipped burials marked a milestone for Iron Age research. The horizontal spread throughout the time of its occupancy laid the foundation for the chronology system of the Late Iron Age. Today, skulls of 77 individuals and some postcranial bones are still preserved and were investigated anthropologically. Collagen was analysed via stable isotope mass spectrometry (carbon, nitrogen, and sulphur). Additionally, some bones showed pathologies or lesions which were examined via imaging and histological methods. The aim of the study was to obtain biological-anthropological information about the Iron Age population. There are significant differences between males and females in δ13C and δ15N values. This points to a gender restriction in the access to animal protein with males having more access to meat and dairy products. Differences in δ15N values were also observed for different age classes. δ34S values indicate a terrestrial-based diet with no significant intake of marine or freshwater fish. Seven adults with enriched δ34S values might have immigrated to Münsingen, four of which were found in the oldest part of the cemetery. Furthermore, possible changes of the vegetation are indicated by the more positive stable carbon ratios in the later phases. The results lead to the suggestion that especially males buried with weapons might have played a special role in the Iron Age society. Also, skull trepanations in two males suggest that surgical treatment of injuries caused by weapons may have been performed.

A relationship between aerosol transport and compound-specific d13C land plant biomarker and pollen records

We examined near-surface, late Holocene deep-sea sediments at nine sites on a north-south transect from the Congo Fan (4°S) to the Cape Basin (30°S) along the Southwest African continental margin. Contents, distribution patterns and molecular stable carbon isotope signatures of long-chain n-alkanes (C27-C33) and n-alkanols (C22-C32) are indicators of land plant vegetation of different biosynthetic types, which can be correlated with concentrations and distributions of pollen taxa in the same sediments. Calculated clusters of wind trajectories and satellite Aerosol Index imagery afford information on the source areas for the lipids and pollen on land and their transport pathways to the ocean sites. This multidisciplinary approach on an almost continental scale provides clear evidence of latitudinal differences in lipid and pollen composition paralleling the major phytogeographic zonations on the adjacent continent. Dust and smoke aerosols are mainly derived from the western and central South African hinterland dominated by deserts, semi-deserts and savannah regions rich in C4 and CAM plants. The northern sites (Congo Fan area and northern Angola Basin), which get most of their terrestrial material from the Congo Basin and the Angolan highlands, may also receive some material from the Chad region. Very little aerosol from the African continent is transported to the most southerly sites in the Cape Basin. As can be expected from the present position of the phytogeographic zones, the carbon isotopic signatures of the n-alkanes and n-alkanols both become isotopically more enriched in 13C from north to south. The results of the study suggest that this combination of pollen data and compound-specific isotope geochemical proxies can be effectively applied in the reconstruction of past continental phytogeographic developments.

Isotope measurements from late Paleocene - early Eocene of 5 cores from Atlantic and Pacific Ocean

High-resolution stable carbon isotope records for upper Paleocene - lower Eocene sections at Ocean Drilling Program Sites 1051 and 690 and Deep Sea Drilling Project Sites 550 and 577 show numerous rapid (40 - 60 kyr duration) negative excursions of up to 1 per mill. We demonstrate that these transient decreases are the expected result of nonlinear insolation forcing of the carbon cycle in the context of a long carbon residence time. The transients occur at maxima in Earth's orbital eccentricity, which result in high-amplitude variations in insolation due to forcing by climatic precession. The construction of accurate orbital chronologies for geologic sections older than ~ 35 Ma relies on identifying a high-fidelity recorder of variations in Earth's orbital eccentricity. We use the carbon isotope records as such a recorder, establishing a robust orbitally tuned chronology for latest Paleocene-earliest Eocene events. Moreover, the transient decreases provide a means of precise correlation among the four sites that is independent of magnetostratigraphic and biostratigraphic data at the <10^5-year scale. While the eccentricity-controlled transient decreases bear some resemblance to the much larger-amplitude carbon isotope excursion (CIE) that marks the Paleocene/Eocene boundary, the latter event is found to occur near a minimum in the ~400-kyr eccentricity cycle. Thus the CIE occurred during a time of minimal variability in insolation, the dominant mechanism for forcing climate change on 104-year scales. We argue that this is inconsistent with mechanisms that rely on a threshold climate event to trigger the Paleocene/Eocene thermal maximum since any threshold would more likely be crossed during a period of high-amplitude climate variations.

Chemobiostratigraphy of the Cretaceous/Paleocene boundary at ODP Hole 120-750A

An integrated biostratigraphic and stable isotope investigation was conducted on a high-latitude sequence across the Cretaceous/Paleogene (K/P) boundary recovered in Hole 750A in the southern Indian Ocean. The sequence consists of nannofossil chalk and is discontinuous across the boundary; missing is an estimated 0.3-m.y. late Maestrichtian and early Danian interval. Nonetheless, because calcareous nannofossil Zones NP1 and NP2 are well-developed, micropaleontological studies of the sequence have yielded a detailed record of Danian high-latitude microplankton evolution. In addition, stable carbon isotope analyses of planktonic and benthic foraminifer and bulk samples provide a record of late Maestrichtian and early Danian surface- and deep-water carbon isotope variations. Together, the carbon isotope and carbonate accumulation records serve as an index of regional marine net productivity across the boundary. Earliest Danian nannoplankton assemblages consisted mainly of persistent genera that were generally rare or absent in the Upper Cretaceous at Hole 750A. However, by 0.5-0.6 m.y. after the boundary, newly evolving Danian taxa became dominant. The turnover in nannofossil assemblages was accompanied by significant changes in rates of net productivity as gauged by carbon isotope distributions and carbonate accumulation rates. During the period dominated by persistent taxa, net productivity was extremely low, as reflected by the absence of vertical delta13C gradients and reduced carbonate accumulation rates. Later in the Danian, as new species evolved and flourished, vertical delta13C gradients reappeared and carbonate accumulation rates increased, signaling partial recovery of net productivity in this region. The absolute timing and magnitude of late Maestrichtian and early Danian biotic and geochemical changes in the southern Indian Ocean were similar to those recorded in other pelagic K/P boundary sequences from low- and mid-latitude Atlantic and Pacific sites, indicating that these events were ubiquitous.

Age determination and grwoth rates of stalagmites and stalactites from the Okshola cave, Fauske, northern Norway

The sensitivity of terrestrial environments to past changes in heat transport is expected to be manifested in Holocene climate proxy records on millennial to seasonal timescales. Stalagmite formation in the Okshola cave near Fauske (northern Norway) began at about 10.4 ka, soon after the valley was deglaciated. Past monitoring of the cave and surface has revealed stable modern conditions with uniform drip rates, relative humidity and temperature. Stable isotope records from two stalagmites provide time-series spanning from c. 10380 yr to AD 1997; a banded, multi-coloured stalagmite (Oks82) was formed between 10380 yr and 5050 yr, whereas a pristine, white stalagmite (FM3) covers the period from ~7500 yr to the present. The stable oxygen isotope (delta18Oc), stable carbon isotope (delta13Cc), and growth rate records are interpreted as showing i) a negative correlation between cave/surface temperature and delta18Oc, ii) a positive correlation between wetness and delta13Cc, and iii) a positive correlation between temperature and growth rate. Following this, the data from Okshola show that the Holocene was characterised by high-variability climate in the early part, low-variability climate in the middle part, and high-variability climate and shifts between two distinct modes in the late part. A total of nine Scandinavian stalagmite delta18Oc records of comparable dating precision are now available for parts or most of the Holocene. None of them show a clear Holocene thermal optimum, suggesting that they are influenced by annual mean temperature (cave temperature) rather than seasonal temperature. For the last 1000 years, delta18Oc values display a depletion-enrichment-depletion pattern commonly interpreted as reflecting the conventional view on climate development for the last millennium. Although the delta18Oc records show similar patterns and amplitudes of change, the main challenges for utilising high-latitude stalagmites as palaeoclimate archives are i) the accuracy of the age models, ii) the ambiguity of the proxy signals, and iii) calibration with monitoring data.

Cenomanian/Turonian sea surface temperatures of the equatorial Atlantic reconstructed from geochemical data

Oceanic anoxic event 2 (OAE-2) occurring during the Cenomanian/Turonian (C/T) transition is evident from a globally recognized positive stable carbon isotopic excursion and is thought to represent one of the most extreme carbon cycle perturbations of the last 100 Myr. However, the impact of this major perturbation on and interaction with global climate remains unclear. Here we report new high-resolution records of sea surface temperature (SST) based on TEX86 and d 18O of excellently preserved planktic foraminifera and stable organic carbon isotopes across the C/T transition from black shales located offshore Suriname/French Guiana (Demerara Rise, Ocean Drilling Program Leg 207 Site 1260) and offshore Senegal (Cape Verde Basin, Deep Sea Drilling Project Leg 41 Site 367). At Site 1260, where both SST proxy records can be determined, a good match between conservative SST estimates from TEX86 and d 18O is observed. We find that late Cenomanian SSTs in the equatorial Atlantic Ocean (33°C) were substantially warmer than today (27°-29°C) and that the onset of OAE-2 coincided with a rapid shift to an even warmer (35°-36°C) regime. Within the early stages of the OAE a marked (4°C) cooling to temperatures lower than pre-OAE conditions is observed. However, well before the termination of OAE-2 the warm regime was reestablished and persisted into the Turonian. Our findings corroborate the view that the C/T transition represents the onset of the interval of peak Cretaceous warmth. More importantly, they are consistent with the hypotheses that mid-Cretaceous warmth can be attributed to high levels of atmospheric carbon dioxide (CO2) and that major OAEs were capable of triggering global cooling through the negative feedback effect of organic carbon-burial-led CO2 sequestration. Evidently, however, the factors that gave rise to the observed shift to a warmer climate regime at the onset of OAE-2 were sufficiently powerful that they were only briefly counterbalanced by the high rates of carbon burial attained during even the most extreme interval of organic carbon burial in the last 100 Myr.