A major extinction of intermediate‐water (500–1000 m) benthic foraminiferal species coincided with a major decrease in δ13C (2.8‰) of terrestrial organic matter (n‐C29 alkane) and δ34S (20‰) of whole rock sulfide in a continuous siltstone sequence in the Tawanui Section (46°S paleolatitude) along the Akitio River, southeastern North Island, New Zealand, in the middle part of the uppermost Paleocene nannofossil zone (CP8). The benthic extinction (25% of species) occurred over ∼3 kyr at ∼55.5 Ma. Increases in kaolinite/illite and kaolinite/smectite ratios and in terrestrial organic carbon percentages started ∼3 kyr before the major benthic extinctions, lasted over ∼40 kyr, and probably reflect warmer climate and increased rainfall. The productivity of planktonic foraminifera and calcareous nannoplankton decreased ∼3 kyr prior to the major extinctions and recovered at the time of benthic extinctions. These events that started ∼3 kyr before the extinction can be best explained by warming, increased rainfall, reduced salinity of surface waters, and increased influence of warm saline deep water (WSDW). Benthic foraminiferal oxygen indices indicate a strong decrease in dissolved oxygen levels within the intermediate water from low oxic (1.5–3.0 mL/L O2) to suboxic (0.3–1.5 mL/L O2) conditions coinciding with the benthic extinctions. Increases in total organic carbon (TOC) and in the hydrocarbon‐generating potential of kerogen (measured as the hydrogen index (HI)) agree with the interpretation of decreased dissolved oxygen levels of the intermediate water. The lowest oxygen conditions lasted ∼40 kyr and coincided with a decrease in calcareous benthic foraminiferal productivity, highest TOC levels, and lowest δ13C of terrestrial organic carbon. Dominant formation of WSDW or sluggish intermediate‐water circulation caused by warming and high rainfall in high‐latitude areas most likely led to the ∼3‐kyr time lag between events on land and in surface waters preceeding the extinction and the development of dysaerobia in the sea, coinciding with the major benthic extinction and decrease in δ13C and δ34S in New Zealand. Global warming of deep and intermediate waters may have caused decomposition of methane hydrate in sediments, resulting in a strongly decreased δ13C of marine carbonates, promoting dysaerobia in the ocean, and warming global climate by increased methane concentrations in the atmosphere. Upwelling of WSDW, occurring soon after it became dominant in high‐latitude areas, is likely responsible for the recovery of normal salinity and the concomitant recovery of planktonic foraminifera and calcareous nannoplankton productivity in high‐latitude surface waters. Minor benthic foraminiferal extinctions (9% of species) occurred ∼40 kyr after the major extinctions, lasted ≤ ∼6 kyr, and coincided with the initiation of environmental recovery.
Abstract. Thirty-six different geochemical and foraminiferal analyses were conducted on samples collected at closely spaced intervals across the Cretaceous/Tertiary (K/T) boundary exposed at Caravaca, Spain. A rapid reduction in the gradient between 15•3C values in fme fraction carbonate and benthic foraminiferal calcite and a decrease in the abundance of phosphorus (a proxy for organic carbon) and calcium were recorded in sediments 0-0.5 cm above the K/T boundary. These trends imply that an abrupt mass mortality occurred among pelagic organisms, leading to a significant reduction in the flux of organic carbon to the seafloor. In addition, variations in sulfur isotope ratios, the hydrocarbon-generating potential of kerogen (measured as the hydrogen index), and foraminiferal indices of dissolved oxygen level all imply that a rapid decrease in dissolved oxygen was coincident with the 15•3C event. Evidence of the low oxygen event has also been recognized in
Elemental AnalysesElements can be divided into three groups on the basis of our analyses: group I elements concentrated in the fallout lamina: these include Fe, Ti, Zn, Ni, and V; group 2 elements showed higher contents in the foraminiferal P0 zone and include Li, Na, Mg, and Al; and group 3 elements showed low contents in the P0 zone and include P, Ca, Ba, Mn, Sr, and Y
Paraquat (PQ) and diquat (DQ) in human whole blood and urine were analyzed by high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS) with positive ion electrospray ionization (ESI). The compounds were extracted with Sep-Pak C18 cartridges from whole blood and urine samples containing ethyl paraquat as an internal standard. The separation of PQ and DQ was carried out using ion-pair chromatography with heptafluorobutyric acid in 20 mM ammonium acetate and acetonitrile gradient elution for successful coupling with MS. Both compounds formed base peaks due to [M-H]+ ions by HPLC/ESI-MS and the product ions produced from each [M-H]+ ion by HPLC/MS/MS. Selective reaction monitoring (SRM) showed much higher sensitivity for both body fluids. Therefore, a detailed procedure for the detection of compounds by SRM with HPLC/MS/MS was established and carefully validated. The recoveries of PQ and DQ were 80.8-95.4% for whole blood and 84.2-96.7% for urine. The calibration curves for PQ and DQ showed excellent linearity in the range of 25-400 ng ml(-1) of whole blood and urine. The detection limits were 10 ng ml(-1) for PQ and 5 ng ml(-1) for DQ in both body fluids. The intra- and inter-day precision for both compounds in whole blood and urine samples were not greater than 13.0%. The data obtained from the determination of PQ and DQ in rat blood after oral administration of the compounds are also presented.
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