Description: Analysis of sediments deposited at different latitudes around the world during the Palaeocene-Eocene Thermal Maximum (PETM; ~56 Ma) have revealed a globally profound warming phase, regionally varying from 5-8 °C. Such records from Europe have not yet been obtained. We studied the variations in sea surface and continental mean annual air temperatures (SST and MAT, respectively) and the distribution patterns and stable carbon isotopes of higher plant derived n-alkanes in two proximal PETM sections (Fur and Store Bælt, Denmark) from the epicontinental North Sea Basin. A negative carbon isotope excursion (CIE) of 4-7 per mil was recorded in land plant derived n-alkanes, similar to what has been observed for other PETM sections. However, differences observed between the two proximal sites suggest that local factors, such as regional vegetation and precipitation patterns, also influenced the CIE. The presence of S-bound isorenieratene derivatives at the onset of the PETM and increased organic carbon contents points to a rapid shift in depositional environment; from well oxygenated to anoxic and sulfidic. These euxinic conditions are comparable with those during the PETM in the Arctic Ocean. SSTs inferred from TEX86 show relatively low temperatures followed by an increase of ~7 °C across the PETM. At the Fur section, a remarkably similar temperature record was obtained for MAT using the MBT'/CBT proxy. However, the MAT record of the Store Bælt section did not reveal this warming.

Description: The Paleocene-Eocene Thermal Maximum (PETM; ~56 Ma) and Eocene Thermal Maximum 2 (ETM2; ~53 Ma) are geological short (〈200,000 years) episodes of extreme global warming and environmental change. Both the PETM and ETM2 are associated with the injection of 13C-depleted carbon into the ocean-atmosphere system as revealed through a globally recognized carbon isotope excursion (CIE) and massive dissolution of deep sea carbonate. However, the magnitude of these CIEs vary with the type of fossil matter, i.e. multiple carbonate phases, bulk organic matter, and terrestrial and marine biomarker lipids, making it difficult to constrain the actual CIE in atmospheric and oceanic carbon pools. Here we analyzed the stable carbon isotopic composition (d13C) of glycerol dibiphytanyl glycerol tetraether lipids (GDGTs) derived from marine Thaumarchaeota in sediments deposited during the PETM in the North Sea Basin and ETM2 in the Arctic Ocean. The d13C values of these lipids are potentially directly recording variations in d13C dissolved inorganic carbon (DIC) and can thus provide a record of marine d13C DIC across both these Eocene carbon cycle perturbations. Reconstructed pre-CIE d13CDIC values are slightly lower (0.5-1 per mil) than modern day values, possibly because Thaumarchaeotal lipids are not only derived from surface waters but also from 13C-depleted subsurface waters. Their values decrease by ~3.6 (±0.3) per mil and ~ 2.5 (±0.7) per mil during the PETM and ETM2, respectively. The CIE in crenarchaeol for ETM2 is higher than that in marine calcite from other locations, possibly because of the admixture of deep water 13C-depleted CO2 generated by the euxinic conditions that developed occasionally during ETM2. However, the reconstructed PETM CIE lies close to the CIE inferred from marine calcite, suggesting that the d13C record of crenarchaeol may document changes in marine DIC during the PETM in the North Sea Basin. The d13C of thaumarchaeotal lipids may thus be a novel tool to reconstruct the d13C of DIC in sediments that are devoid of carbonates, but relatively rich in organic matter, such as shallow marine coastal settings

Description: Petrography of recrystallised ikaite from Ocean Drilling Program material has been presented previously from Nankai Trough and Congo (ex-Zaire) deep-sea fan. This paper expands on the Nankai Trough ikaite observations, drawing on evidence from Laptev Sea, South Georgia, Okhotsk Sea, and coastal lagoon Point Barrow. However, even though many ikaite and glendonite sites occur at high latitudes, it cannot be that ikaite forms exclusively in polar environments, as demonstrated by the occurrences in the low latitude low temperature deep sea sediments offshore Gulf of Guinea (Angola Congo) and mid-latitude deep-sea trenches offshore Japan. Recrystallised ikaite occurs as mm large, zoned calcite crystals in all samples, along with secondary phases of calcite. Our data set is unique in that the origin, storage, and recrystallisation process of natural formed ikaite is recorded in detail and confirms that glendonite petrographic characteristics are a consequence of the structure and chemistry of recrystallising ikaite and not the physical or geochemical environment. The transformation of man-made ikaite to calcite as recorded in laboratory studies, is a process very similar to the one we have observed for natural ikaite. Most significant is that there is variation in the order of the calcite types within a single sample, leading to the conclusion that the variation is a consequence of impurities and geochemical variability in the ikaite, not the external environment. Morphological observations reveal similarities in ikaite and glendonite, this and the similarity in internal textures in glendonite and recrystallised ikaite confirms that glendonite may be used as an indicator of past presence of ikaite.

Description: Marine sedimentary ikaite is the parent mineral to glendonite, stellate pseudomorphs found throughout the geological record which are most usually composed of calcite. Ikaite is known to be metastable at earth surface temperatures and pressures, readily breaking down to more stable carbonate polymorphs when exposed to warm (ambient) conditions. Yet the process of transformation of ikaite to calcite is not well understood, and there is an ongoing debate as to the palaeoclimatic significance of glendonites in the geological record. This study uses a combination of techniques to examine the breakdown of ikaite to calcite, outside of the ikaite growth medium, and to assess the palaeoclimatic and palaeoenvironmental significance of stable and clumped isotope compositions of ikaite-derived calcite. Powder X-ray diffraction shows that ikaite undergoes a quasi- solid-state transformation to calcite during heating of samples in air, yet when ikaite transforms under a high temperature differential, minor dissolution-recrystallisation may also occur with the ikaite structural waters. No significant isotopic equilibration to transformation temperature is observed in the resulting calcite. Therefore, in cases of transformation of ikaite in air, clumped and stable isotope thermometry can be used to reconstruct ikaite growth temperatures. In the case of ancient glendonites, where transformation of the ikaite occurred in contact with the interstitial waters of the host sediments over unknown timescales, it is uncertain whether the reconstructed clumped isotope temperatures reflect ikaite crystallisation or its transformation temperatures. Yet clumped and stable isotope thermometry may still be used conservatively to estimate an upper limit for bottom water temperatures. Furthermore, stable isotope along with element/Ca ratios shed light on the chemical environment of ikaite growth. Our data indicate that a range of (bio)geochemical processes may act to promote ikaite formation at different marine sedimentary sites, including bacterial sulphate reduction and anaerobic oxidation of methane. The colours of the ikaites, from light brown to dark brown, indicate a high organic matter content, favouring high rates of bacterial sulphate reduction as the main driver of ikaite precipitation. Highest Mg/Ca ratios are found in the most unstable ikaites, indicating that Mg acts to destabilise ikaite structure.