Zusammenfassung
Spezifische geochemische Umwandlungsreaktionen von Steroidkohlenwasserstoffen wurden ausgewählt, um die molekulare Entwicklung des organischen Materials in Tiefseese-dimenten zu illustrieren. Die zunehmende Isomerisierung von (Δ5→Δ4)-Sterenen, (20R→20S)-Diasterenen, (20R→ 20S)-Spirosterenen und (14α→14β)-monoaromatischen Anthrasteroiden mit zunehmender Teufe wurde in Kernproben von zehn DSDP-Bohrlokationen untersucht. Regionen mit hohen geothermischen Gradienten werden solchen mit niedrigem geothermischem Wärmefluß gegenübergestellt. Die Bildung der Sterene und Anthrasteroide aus Vorläufern mit funktionellen Gruppen beginnt bereits in der Nähe der Sediment/Wasser-Grenze kurz nach der Ablagerung des organischen Materials. Wegen der hohen Reaktionsgeschwindigkeiten schon bei niedrigen Temperaturen sind diese Reaktionen innerhalb der für diese Studie zur Verfügung stehenden Probendichte unabhängig vom geothermischen Regime. Im Gegensatz dazu hängt die Bildung der Diasterene und der Spirosterene vom geothermischen Gradienten ab. Über den Einfluß der Versenkungstiefe bestimmt die Sedimentationsrate indirekt das Alter der Sedimente, in denen diese beiden Verbindungsklassen zuerst auftreten. Der Einfluß des geothermischen Gradienten auf die meisten der hier untersuchten Isomerisierungsreaktionen ist erheblich, und er ist am stärksten bei der Umwandlung der 14α(H)-B-Ring-monoaromatischen Anthrasteroide in die 14β(H)-Isomeren.
Abstract
Specific geochemical transformation reactions of steroid hydrocarbons have been chosen to illustrate the molecular evolution of organic matter in deep sea sediments. The progression of isomerisation of (Δ5→Δ4)-sterenes, (20R→ 20S)-diasterenes, (20R→20S)-spirosterenes, and (14α→14β) monoaromatic anthrasteroids with depth has been monitored in core samples from ten DSDP sites. Areas with high geothermal gradients are compared to those with low geothermal heat flow. The formation of regular sterenes and anthrasteroids from functionalized precursors starts close to the sediment/water interface soon after deposition of the organic matter. Due to the high reaction rates these low temperature reactions are independent of the geothermal regime within the limits of sample resolution of this study. In contrast to this, the depth of formation of diasterenes and spirosterenes is dependent on the geothermal gradient. Sedimentation rates indirectly determine, through the effect of the resulting burial depth, the age of the sediments in which these compounds first occur. There is a significant effect of the geothermal gradient on most of the isomerisation reactions studied, and it is most pronounced for the conversion of the 14α(H)-B ring monoaromatic anthrasteroids to the 14β(H) isomers.
Résumé
L'évolution de la matière organique dans les sédiments des grands fonds océaniques est illustrée à l'aide de certaines réactions bien définies de transformation géochimique des stéroïdes. Pour les réactions d'isomérisation du type (Δ5→Δ4)-stérènes, (20R→20S)-diastérènes, (20R→20S)-spirostérènes et (14α→14β)-anthrastéroïdes aromatiques, la progression en fonction de la profondeur a été étudiée dans une série d'échantillons carottés provenant de dix forages DSDP. Des régions à gradient géothermique élevé sont comparées à d'autres où le flux géothermique est plus faible. La formation des stérènes et anthrastéroïdes réguliers à partir de précurseurs à groupements fonctionnels appropriés débute à proximité de l'interface eau-sédiment peu de temps après le dépôt de la matière organique et progresse assez rapidement même à de basses températures; toutefois le nombre limité d'échantillons disponibles ne permet pas de déceler une influence nette de la situation géothermique. En revanche, la formation des diastérènes et des spirostérènes dépend du gradient géothermique. Puisque la profondeur d'enfouissement augmente avec la vitesse de sédimentation, celle-ci détermine indirectement l'âge des sédiments dans lesquels ces composés apparaissent pour la première fois. La plupart des réactions d'isomérisation étudiées sont sensiblement affectées par le gradient géothermique dont l'influence se manifeste particulièrement pour la transformation des 14α(H)-B cyclo-anthrastéroïdes monoaromatiques en leurs 14β(H)-analogues.
Краткое содержание
Для иллюстрации моле кулярного преобразо вания органического матер иала в глубоководных седиментах, выбрали ряд специфич ных геохимических ре акций преобразования стер оидных углеводородо в. На пробах кернов из 10-ти бу ровых скважин в рамка х DSDP исследовали процесс ы прогрессивной изом ериштдаа (Δ5 → Δ4)-стеренов, (20R → 20S)-диа стеренов, (20R → 20S)-спиростеренов и (14а → 14β)-моноароматически х антрастероидов с воз растающей глубиной и х захоронения. Сравнил и регион высокого геотермического градиента с таковым н изкого геотермическ ого теплового потока. Обр азование стеренов и антрастеренов, как предтеч с функцио нальными группами, на чинается уже в близи рубежа суш а/вода, вскоре после отложения органичес кого материала. Т.к. эти реакции протекают с большой с коростью даже при низ кой температуре, они, при и меющейся для данного исследования плотности распредел ения проб, не зависили от геотермического р ежима. Зато образован ие диастеренов и спиростеренов ясно проявило зависимост ь от геотермического г радиента. Влияние его на большенство процессов изомериза ции оказалось значит ельным, причем наиболее силь но оно проявилось при преобразовании 14α (H)-B-Ring-монoapoмaтичecких антрастероидов в их 14β (Н)-изомеры.
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Ten Haven, H.L., Rullkötter, J. & Welte, D.H. Steroid biological marker hydrocarbons as indicators of organic matter diagenesis in Deep Sea sediments: geochemical reactions and influence of different heat flow regimes. Geol Rundsch 78, 841–850 (1989). https://doi.org/10.1007/BF01829326
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DOI: https://doi.org/10.1007/BF01829326