Abstract-Anew route for the formation of gammacerane from tetmhymanol is proposed; in addition to dehydration and hydrogenation, sulphurisation and early C-S cleavage are shown to be important in the pathway of formation, especially in marine sediments. Evidence is twofold. First, relatively large amounts of the gammacerane skeleton are sequestered in S-rich macromolecular aggregates formed by natural sulphurisation of functionalised lipids.
Abstract. The present paper is the result of a workshop sponsored by the DFG Research Center/Cluster of Excellence MARUM "The Ocean in the Earth System", the International Graduate College EUROPROX, and the Alfred Wegener Institute for Polar and Marine Research. The workshop brought together specialists on organic matter degradation and on proxy-based environmental reconstruction. The paper deals with the main theme of the workshop, understanding the impact of selective degradation/preservation of organic matter (OM) in marine sediments on the interpretation of the fossil record. Special attention is paid to (A) the influence of the molecular composition of OM in relation to the biological and physical depositional environment, including new methods for determining complex organic biomolecules, (B) the impact of selective OM preservation on the interpretation of proxies for marine palaeoceanographic and palaeoclimatic reconstruction, and (C) past marine productivity and selective preservation in sediments.It appears that most of the factors influencing OM preservation have been identified, but many of the mechanisms by which they operate are partly, or even fragmentarily, underCorrespondence to: G. J. M. Versteegh (versteegh@uni-bremen.de) stood. Some factors have not even been taken carefully into consideration. This incomplete understanding of OM breakdown hampers proper assessment of the present and past carbon cycle as well as the interpretation of OM based proxies and proxies affected by OM breakdown.To arrive at better proxy-based reconstructions "deformation functions" are needed, taking into account the transport and diagenesis-related molecular and atomic modifications following proxy formation.Some emerging proxies for OM degradation may shed light on such deformation functions. The use of palynomorph concentrations and selective changes in assemblage composition as models for production and preservation of OM may correct for bias due to selective degradation. Such quantitative assessment of OM degradation may lead to more accurate reconstruction of past productivity and bottom water oxygenation.Given the cost and effort associated with programs to recover sediment cores for paleoclimatological studies, as well as with generating proxy records, it would seem wise to develop a detailed sedimentological and diagenetic context for interpretation of these records. With respect to the latter, parallel acquisition of data that inform on the fidelity of the proxy signatures and reveal potential diagenetic biases would be of clear value.
Objective To determine risk factors for the occurrence of third degree perineal tears during vaginal delivery.Design A population-based observational study. Population All 284,783 vaginal deliveries in 1994 and 1995 recorded in the Dutch National Obstetric Database were included in the study. Methods Third degree perineal rupture was de®ned as any rupture involving the anal sphincter muscles. Logistic regression analysis was used to assess risk factors.Main outcome measures An overall rate of third degree perineal ruptures of 1.94% was found. High fetal birthweight, long duration of the second stage of delivery and primiparity were associated with an elevated risk of anal sphincter damage. Mediolateral episiotomy appeared to protect strongly against damage to the anal sphincter complex during delivery (OR: 0.21, 95% CI: 0.20±0.23). All types of assisted vaginal delivery were associated with third degree perineal ruptures, with forceps delivery (OR: 3.33, 95%-CI: 2.97±3.74) carrying the largest risk of all assisted vaginal deliveries. Use of forceps combined with other types of assisted vaginal delivery appeared to increase the risk even further. Conclusions Mediolateral episiotomy protects strongly against the occurrence of third degree perineal ruptures and may thus serve as a primary method of prevention of faecal incontinence. Forceps delivery is a stronger risk factor for third degree perineal tears than vacuum extraction. If the obstetric situation permits use of either instrument, the vacuum extractor should be the instrument of choice with respect to the prevention of faecal incontinence.
Abstract--A wide range of novel diagenetic and catagenetic products of the diaromatic carotenoid isorenieratene, a pigment of the photosynthetic green sulphur bacteria Chlorobiaceae, has been identified in a number of sedimentary rocks ranging from Ordovician to Miocene. Compound identification is based on NMR, mass spectrometry, the presence of atropisomers, and stable carbon isotopes. Atropisomers contain an axially chiral centre which, in combination with other chiral centres, results in two or more diastereomers that can be separated on a normal GC column. Chlorobiaceae use the reverse TCA cycle to fix carbon, so that their biomass is enriched in 13C. High ~3C contents of isorenieratene derivatives therefore support their inferred origins.Isorenieratene derivatives include C4o, C33, and C32, diaryl isoprenoids and short-chain aryl isoprenoids with additional aromatic and/or S-containing rings. C33 and C32 compounds are diagenetic products of C33 and C32 "carotenoids" formed from isorenieratene during early diagenesis through expulsion of toluene and m-xylene, respectively. Cyclisation of the polyene acyclic isoprenoid chain can proceed via an intramolecular Diels-Alder reaction, followed by aromatisation of the newly formed ring. Sulphurisation is also an important process during early diagenesis, competing with expulsion and cyclisation. Sulphur-bound isorenieratane is released during progressive diagenesis, due to cleavage of relatively weak S-S and C-S bonds. Cleavage of C-C bonds during aromatisation of newly formed rings and during catagenesis yields short-chain compounds. The inherent presence of a conjugated double bond system in carotenoids implies that similar diagenetic and catagenetic reactions can occur with all carotenoids.Chlorobiaceae live at or below the oxic/anoxic boundary layer and require both light and H2S. The presence of isorenieratene or its diagenetic and catagenetic products in ancient sedimentary rocks and crude oils is therefore an excellent indication for photic zone anoxia in the depositional environment. Diagenetic and catagenetic products of isorenieratene are expected to find applications in reconstruction of palaeoenvironments and in oil-oil and oil-source rock correlation studies. Their presence in several petroleum source rocks suggests that anoxia is an important environmental parameter for the preservation of organic matter.
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