Evolution and organic geochemical significance of bicyclic sesquiterpanes in pyrolysis simulation experiments on immature organic-rich mudstone

Sesquiterpanes are ubiquitous components of crude oils and ancient sediments.Liquid saturated hydrocarbons from simulated pyrolysis experiments on immature organic-rich mudstone collected from the Lower Cretaceous Hesigewula Sag were analyzed by gas chromatography-mass spectrometry(GC-MS).C14 bicyclic sesquiterpanes,namely,8β(H)-drimane,8β(H)-homodrimane,and 8 a(H)-homodrimane were detected and identified on basis of their diagnostic fragment ions(m/z123,179,193,and 207),and previously published mass spectra data,and these bicyclic sesquiterpanes presented relatively regular characteristics in their thermal evolution.The ratios 8β(H)-drimane/8β(H)-homodrimane,8β(H)-homodrimane/8 a(H)-homodrimane,and 8β(H)-drimane/8 a(H)-homodrimane all show a clear upward trend with increasing temperature below the temperature turning point.Thus,all these ratios can be used as evolution indexes of source rocks in the immature-lowmaturity stage.However,the last two ratios may be more suitable than the first ratio as valid parameters for measuring the extent of thermal evolution of organic matter in the immature-low-maturity stage because their change amplitude with increasing temperature is more obvious.

Source diagnostic and weathering indicators of oil spills utilizing bicyclic sesquiterpanes

Bicyclic Sesquiterpanes （BSs） are ubiquitous components of crude oils and ancient sediments. BSs in crude oils and diesel oil were identified and characterized, the effects of moderate weathering on BS distributions were discussed, and a methodology using diagnostic indices of BSs was developed for oil correlation and dif- ferentiation. The results showed that crude oils and oil products had different abundances and distributions of BSs and, consequently, resulted in different diagnostic ratios. The selected diagnostic ratio indices of BSs, such as BS4/BS5 （ratio of 4,4,8,9,9-pentamethyl-decahydronaphthalene to 8/3 （H）-drimane）, BS6/BS5 （ratio of 4,4,9,9,10-pentamethyl-decahydronaphthalene to 8/3 （H）-drimane）, BS8/BS9 （ratio of the second peak to the third peak of C16 sequiterpane）, and BS8/BSIO （ratio of C16 sequiterpane to 8fl （H）-homodrimane）, still maintained better stabilities （%RSD 〈 5%） after weathering for 30 d. The longer weathering process （150 d） had some effect on such ratios （5% 〈 %RSD 〈 10%）. The facts of the uniqueness, abundance in petroleum, and chemical stability of BSs enable them to be suitable as an effective diagnostic means for identifying spilled oil with moderate weathering, particularly for lighter refined product samples that are difficult to identify by current techniques.

Novel C15 sesquiterpanes and their origin in different crude oils from the Pearl River Mouth Basin of China

In the saturate fractions of crude oils from the Zhu1 and Zhu2 depressions of the Pearl River Mouth Basin,two novel C_(15) sesquiterpanes have been detected except for drimanes and rearranged drimanes.By comparison with spectra and retention times in previous studies,they have been identified as 2,2,4α,7,8-pentamethyl-trans-decalin and 2,2,4α,7,8-pentamethyl-cis-decalin,respectively,which are related to the D/Eringsof18α(H)-and18β(H)-oleanane.ResultsshowthatthenovelC15sesquiterpanesarerelativelyabundantincondensateoilsthathavehighPr/PhratiosandarerichinterrigenoustriterpanessuchasoleananeandbicadinanesfromtheZhu2depression,butevidentlylowinlacustrineoilsthathavelowPr/Phratiosandarerichin4-methylsteranesfromtheZhu1depression.ThissuggeststhatthenovelC15sesquiterpanescouldberelatedtoterrigenousorganicmatterinoriginandcanhelpdistinguishtheoriginandsourceofcrudeoilsinthestudyarea.Inaddition,thereexistcompletelydifferentcorrelationsbetweentherelativeabundancesofdifferentC15sesquiterpanesthathavedifferentsourcesandthePr/Phratio,whichindicatesredoxconditionsinthecrudeoils.Forexample,thenovelC15sesquiterpanesandcadinanethatindicateterrigenousinputarepositivelycorrelatedwiththePr/Phratio,butdrimanesandrearrangeddrimaneshavingmicrobialoriginarenegativelycorrelatedwiththePr/Phratio.ThisimpliesthattheformationofthenovelC15sesquiterpanesrequiresrelativelyoxicconditions.ThenovelC15sesquiterpanesaremuchmoreabundantincarbonaceousmudstone(Pr/Ph=7.39)thanindarkmudstone(Pr/Ph=2.19)fromtheEnpingformation,althoughtheirorganicmatterishumic.However,theyarenotcommoninsapropeliclacustrinesourcerocks(Pr/Ph=2.29)fromtheWenchangFormation.Thissuggeststhatterrigenousorganicmatterisonlyasufficientcondition,butanoxicenvironmentduringdepositionanddiagenesismaybeaprerequisitefortheformationofnovelC15sesquiterpanes.

BIOMARKERS INDICATING SEDIMENTARY PALEOENVIRONMENTS

Samples involved in this paper are 35 pieces of crude oils and 43 pieces of source rocks, from which a series of biomarkers, capable of indicating paleoecology and paleoenvironment. This will provide a scientific basis for tracing back to sedimenta-y paleoenvironment and paleoecology.