We present new, detailed carbon-isotope records for bulk carbonate, total organic carbon (TOC) and phytane from three key sections spanning the Cenomanian-Turonian boundary interval (Eastbourne, England; Gubbio, Italy; Tarfaya, Morocco), with the purpose of establishing a common chemostratigraphic framework for Oceanic Anoxic Event (OAE) 2. Isotope curves from all localities are characterized by a positive carbon-isotope excursion of c. 4‰ for TOC and phytane and c. 2.5‰ for carbonate, although diagenetic overprinting appears to have obliterated the primary carbonate carbon-isotope signal in at least part of the Tarfaya section. Stratigraphically, peak ä 13 C values for all components are followed by intervals of high, near-constant ä 13 C in the form of an isotopic plateau. Recognition of an unambiguous return to background ä 13 C values above the plateau is, however, contentious in all sections, hence no firm chemostratigraphic marker for the end-point of the positive isotopic excursion can be established. The stratigraphically consistent first appearance of the calcareous nannofossil Quadrum gartneri at or near the Cenomanian-Turonian boundary as established by ammonite stratigraphy, in conjunction with the end of the ä 13 C maximum characteristic of the isotopic plateau, provides a potentially powerful tool for delimiting the stratigraphic extent and duration of OAE 2. This Oceanic Anoxic Event is demonstrated to be largely, if not wholly, confined to the latest part of the Cenomanian stage.
The TEX86 is a recently proposed paleothermometer through which ancient seawater temperatures of up to 120 My ago can be reconstructed. It is based on the relative distribution of glycerol dibiphytanyl glycerol tetraethers as measured by high-performance liquid chromatography/atmospheric pressure chemical ionization-mass spectrometry (HPLC/APCI-MS). The aim of this study was to examine and improve several analytical aspects in the determination of this important proxy in environmental matrices. Comparison of TEX86 analysis using single ion mode (SIM) and mass scanning (m/z 950 to 1450) detection, respectively, revealed that SIM is up to 2 orders of magnitude more sensitive and that the TEX86 can be determined with a reproducibility of +/-0.004 or +/-0.3 degrees C using this method. Comparison of TEX86 values obtained with two different HPLC/APCI-MS set-ups revealed no significant differences. In addition, analysis of TEX86 of extracts obtained by Soxhlet, ultrasonic, and accelerated high-pressure extraction techniques also showed no significant differences between the methods. Our results suggest that TEX86 analysis by HPLC/APCI-MS is robust and can be determined with analytical errors comparable to those of other temperature proxies.
[1] We reconstruct the latest Paleocene and early Eocene ($57-50 Ma) environmental trends in the Arctic Ocean and focus on the Paleocene-Eocene thermal maximum (PETM) ($55 Ma), using strata recovered from the Lomonosov Ridge by the Integrated Ocean Drilling Program Expedition 302. The Lomonosov Ridge was still partially subaerial during the latest Paleocene and earliest Eocene and gradually subsided during the early Eocene. Organic dinoflagellate cyst (dinocyst) assemblages point to brackish and productive surface waters throughout the latest Paleocene and early Eocene. Dinocyst assemblages are cosmopolitan during this time interval, suggesting warm conditions, which is corroborated by TEX 86 0 -reconstructed temperatures of 15°-18°C. Inorganic geochemistry generally reflects reducing conditions within the sediment and euxinic conditions during the upper lower Eocene. Spectral analysis reveals that the cyclicity, recorded in X-ray fluorescence scanning Fe data from close to Eocene thermal maximum 2 ($53 Ma, presence confirmed by dinocyst stratigraphy), is related to precession. Within the lower part of the PETM, proxy records indicate enhanced weathering, runoff, anoxia, and productivity along with sea level rise. On the basis of total organic carbon content and variations in sediment accumulation rates, excess organic carbon burial in the Arctic Ocean appears to have contributed significantly to the sequestration of injected carbon during the PETM.
Ammonia-oxidizing archaea (AOA) and anaerobic ammonia-oxidizing (anammox) bacteria have emerged as significant factors in the marine nitrogen cycle and are responsible for the oxidation of ammonium to nitrite and dinitrogen gas, respectively. Potential for an interaction between these groups exists; however, their distributions are rarely determined in tandem. Here we have examined the vertical distribution of AOA and anammox bacteria through the Arabian Sea oxygen minimum zone (OMZ), one of the most intense and vertically exaggerated OMZs in the global ocean, using a unique combination of intact polar lipid (IPL) and gene-based analyses, at both DNA and RNA levels. To screen for AOA-specific IPLs, we developed a high-performance liquid chromatography/mass spectrometry/mass spectrometry method targeting hexose-phosphohexose (HPH) crenarchaeol, a common IPL of cultivated AOA. HPH-crenarchaeol showed highest abundances in the upper OMZ transition zone at oxygen concentrations of ca. 5 lM, coincident with peaks in both thaumarchaeotal 16S rDNA and amoA gene abundances and gene expression. In contrast, concentrations of anammox-specific IPLs peaked within the core of the OMZ at 600 m, where oxygen reached the lowest concentrations, and coincided with peak anammox 16S rDNA and the hydrazine oxidoreductase (hzo) gene abundances and their expression. Taken together, the data reveal a unique depth distribution of abundant AOA and anammox bacteria and the segregation of their respective niches by 4400 m, suggesting no direct coupling of their metabolisms at the time and site of sampling in the Arabian Sea OMZ.
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