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1.
A novel series of 3-alkyl and 3-carboxyalkyl-5β(H)-steranes 7–10 along with a full homologous series of carboxyalkyl-sterane (C1 to C6) 4–6 with 3α(H)5α(H) configuration have been identified in marine-evaporitic oils from Fazenda Belém, Potiguar Basin (Brazil) on the basis of mass spectral interpretation. The synthesis of enantiomerically pure 3α-alkyl-5β(H)-cholestane and 3β-alkyl-5α(H)-cholestane standards and their coinjection with petroleum fractions confirmed the structural assignments.  相似文献   

2.
Series of α, β, ω and (ω-1) hydroxy fatty acids (FAOHs) were determined in several freshwater and brackish water lacustrine sediments in Japan. Analytical procedure used was digestion of the solvent-extracted sediment with HF/HCl followed by solvent and saponification extraction of the residue. Abundances of α/β and ω-FAOH determined by this procedure were 2–3 times higher than those obtained by single alkaline saponification and of the same order with those provided by HCl hydrolysis. Major portion of α/β-FAOH was obtained by solvent extraction of the acid-treated sediments, while subsequent alkaline saponification was needed for the majority of ω-FAOH to be recovered. Thus determined FAOHs comprised 33–61% (Av. = 42%) of the “bound” acid constituents in the lacustrine surface sediments. The α/β and ω-FAOH composition was principally the same among the samples examined, except for relative proportions of the iso to anteiso C15 and C17 ß(α)-FAOH, which showed significant variations in the ranges of 0.30–1.1 and 0.46–1.5, respectively. In the holomictic lakes, the ratios together with the same ratios of the “bound” branched monocarboxylic acids tended to decrease with increasing water depth of the lakes, suggesting that the ratios may indicate an extent of the early diagenetic alteration of the bacteria-derived lipids either in water column or in surface sediment.  相似文献   

3.
Lead sulfide (galena) of different purity and grain size was extruded through a round and rectangular die at temperatures between 773 and 923 K. Global and local lattice preferred orientations (here referred to as textures) were measured by neutron and electron back-scattering diffraction. Tension leads to a <100> <111> double fibre texture. Pure shear deformation yields texture components near the ideal face-centered cubic metal brass, copper, Goss and cube positions. The intensity of the components depends on the purity and/or grain size. The microstructure is partially recrystallized. Electron back-scattering diffraction indicates that in tension the <100> and in pure shear the Goss and cube components are associated with dynamic recrystallization. The deformation texture can be qualitatively explained by the full and relaxed constraints Taylor model using slip on {100}<110>, {110}<110> and {111}<110> systems. The texture formation in lead sulfide compares well with that observed for other ionic crystals with the NaCl-structure as well as for face-centered cubic metals with a high stacking fault energy.  相似文献   

4.
Pedogenic needle-fiber calcite was studied regarding its morphology, texture and stable isotope composition from the paleosol of the Quaternary Várhegy travertine (Budapest, Hungary). The needle-fiber calcite is composed of 40–200 μm long monocrystals. Smooth rods as well as serrated-edged crystals with calcite overgrowths were identified by SEM. Needles have several textural varieties: randomly distributed crystals in vugs and pores with calcite hypocoatings, bundles of subparallel crystals forming coatings around grains and alveolar structure with bridging needles in vugs.The morphological study of needle-fiber calcite suggests that needles are calcified fungal sheaths and produced by fungal biomineralization, a common process in recent and fossil soils and calcretes. The stable isotope composition of needle-fiber calcite (average: δ18O=-7.1‰ and δ13C=-7.3‰ vs. V-PDB) indicates significant incorporation of organically derived CO2 and probably biological influence on needle genesis. Dissolved host rock travertine and/or atmospheric CO2 could also contribute some carbon to the acicular calcite.  相似文献   

5.
The oxygen (δ18Oc) and carbon (δ13Cc) isotope compositions of the structural carbonate group (CO3) in apatites from lateritic profiles were investigated. The weathering profiles, located in southern Brazil and in western Senegal, are developed on three different types of apatite-rich parent rock: carbonatite, metamorphosed marine phosphorite and sedimentary marine phosphorite. The parent rock apatites are of magmatic, hydrothermal, metamorphic and sedimentary origins. The in situ formation of apatite of weathering origin in the profiles is well documented petrographically and geochemically.The overall range of measured δ18Oc and δ13Cc values of apatites of weathering origin (22 to 27 SMOW for δ18Oc and −15 to −10 PDB for δ13Cc) is much smaller than the range of measured and/or published isotope compositions of parent rock apatites (4–35 for δ18Oc and −11 to +1 for δ13Cc). In any profile, the apatites of weathering origin can exhibit lower, similar or higher δ18Oc values than parent rock apatites. In contrast, their δ13Cc values are systematically and significantly lower than those of the parent rock apatites. Apatites formed as a result of weathering in laterites can therefore be readily distinguished from apatites of other origin on the basis of their isotope composition.Assuming that apatite CO3 fractionates O in a way similar to calcite CO3, the structural carbonate group of the apatites of weathering origin appears to form in approximate isotopic equilibrium with the weathering solutions. The very low δ13Cc values exhibited by these apatites indicate that the dominant sources of dissolved CO2 in the soil water are organic. The isotope composition of structural carbonate in apatite of weathering origin in lateritic profiles may provide useful information for paleoenvironmental studies.  相似文献   

6.
Two homogeneous (humovitrain and xylain) and one heterogeneous (humoclarain) lithotype macerals, separated from a lignite, were subjected to mild reductive treatment by NaH. The extensive chromatographic separation of the decalin-soluble fraction revealed some structural peculiarities. A strong predominance of α-phyllocladane was characteristic for all macerals. Series of n-, iso-, and anteiso-alkanes, regular isoprenoids, alkylbenzenes and 1-methyl-4-n-alkylcyclohexanes were identified by mass spectrometry. An angiosperm source input was represented by friedelane, lupane and seco-hopane structures. Products of des-A and des-E-ring cleavages and C-10 demethylation were registered by mass spectrometry. The main difference was in the hopane distribution pattern. A strong prevalence of extended ββ-hopanes was found in the humoclarain sample. The mass spectral data revealed the existence of a basic difference in hopane precursors—diploptent or diplopterol for the homogeneous lithotypes and bacteriohopanetetrol for the heterogeneous lithotype.  相似文献   

7.
Different types of free water have been analysed for their deuterium and chemical composition in order to evaluate their source, mixing phenomena, and the underground dynamics. All types of ground water (mineral, geothermal and wellhead water) display δD values (− 82.6‰ to − 72.6‰) similar to surface waters from the studied area (− 77.1‰ to − 73.6‰). The global salt content varies from 1102 to 8707 mg/l for the groundwater, and from 46 to 392 mg/l for the surface water. From the co-variation between the δD values and the chemical composition of the waters, as well as from the seasonal variation of these two parameters, it is evident that the free water from Tuşnad Băi are meteoric in origin. The mineralization of the mineral water took place by means of an intense underground circulation, probably in the fault system developed within the Neogene magmatites.  相似文献   

8.
Oxygen isotope studies were carried out across units of a Neoproterozoic nappe system, south of São Francisco Craton. A temperature decrease toward the base of the system is found, consistent with a previously recognized inverted metamorphic pattern. The tectonic contact of the basal unit and the reworked southern São Francisco craton show a steep temperature gradient, suggesting that low temperature thrusting acted as the dominant tectonic process. The contrasts between the δ18O values of the Três Pontas-Varginha and Carmo da Cachoeira nappes and the differences among the samples and minerals are consistent with the preservation of sedimentary isotopic composition during metamorphism. The small differences in the δ18O values between the undeformed and the deformed calc-silicate samples (1.6‰) suggest that the δ18O value of mylonitization fluids was close to that which equilibrated with the metamorphic assemblage. The distinct δ18O values of metapelitic and calc-silicate samples and the great temperature difference from one type to the other indicate that no large-scale fluid interaction processes occurred during metamorphism. Oxygen isotopic estimations of both Três Pontas-Varginha undeformed rocks and Carmo da Cachoeira unaltered equivalents indicate δ18O values of up to 18‰. Comparison between these values and those from the ‘basement’ orthogneisses (8.3–8.5‰) indicates the latter are not sources for the metapelites.  相似文献   

9.
Total extracts of sediment cores from five different stations in the North Sea and Wadden Sea were analysed for their biomarker composition. Only sediments of the Skagerrak contained significant amounts of marine biomarkers (mainly alkenones), other sites contained predominantly terrestrial biomarkers. Bioturbation in the Skagerrak is, however, far too high to determine sea surface temperature (SST) changes within short time intervals. These results indicate that biomarkers contained in these sediments are not useful to reconstruct climate fluctuations during the upper Holocene. High amounts of α-, β- and ω-hydroxy fatty acids as well as small amounts of α, β-dihydroxy fatty acids were released from the insoluble organic material of the sediments from the Wadden Sea station, indicating a significant input of the eelgrass Zostera marina. This was confirmed by microscopic observations. This is the first time the α,β-dihydroxy fatty acids have been found in a sediment core and they have proven to be potential biomarkers for these seagrass species.  相似文献   

10.
Lignin substructure model compounds having a β-O-4 linkage were synthesized. These were guaiacylglycerol-β-guaiacyl ether (GGE) and guaiacylglycerol-β-syringyl ether (GSE) which model guaiacyl and syringyl units respectively. Closed system microscale pyrolysis of GGE and GSE was carried out at 300 °C both in the presence and absence of water vapour. The laboratory degradation of GSE occurred predominantly by breaking the Cβ–O bond of the β-O-4 linkage to form the ring B fragment of the model compound. This was followed by demethylation of the aromatic methoxyl groups. Char formation was another significant process during pyrolysis. There are structural features of the char formed during the heating of GGE which indicate incorporation of the remaining fragment of the model compound (ring A coupled with the propyl segment of the aryl ether linkage).  相似文献   

11.
A high-resolution calcite oxygen stable isotopic (δ18O) record, covering the past 4000 years, was obtained from Kaite Cave, northern Spain. The record has a mean δ18O value of -6.25‰ VPDB and a range of 2‰. Spectral analysis of the δ18O data shows significant periodicities of 2400–1900, 600, 150, 27, and 22 years. The amplitudes during these periods range from 0.2‰ to 2‰. Factors controlling the isotopic ratio in the speleothem were evaluated. The calcite is most likely precipitated under equilibrium conditions, with the cave calcite δ18O interpreted as a proxy of oxygen isotopic composition in local rainwater. Other factors such as temperature or fractionation in the karst system prior to calcite precipitation are considered of negligible or of minor importance. Mechanisms affecting rainfall isotopic composition were also investigated on different time scales. Precipitation amount is the primary factor controlling the high-frequency δ18O oscillations. Other climate parameters, such as changes of storm tracks may have significant contributions on centennial and millennial time scales.  相似文献   

12.
This study presents a structural analysis based on hundreds of striated small faults (fault-slip data) in the Amman area east of the Dead Sea Transform System. Stress inversion of the fault-slip data was performed using an improved Right-Dihedral method, followed by rotational optimization (TENSOR Program, Delvaux, 1993). Fault-slip data (totaling 212) include fault planes, striations and sense of movements, are obtained from the Turonian Wadi As Sir Formation, distributed mainly along the southern side of the Amman – Hallabat structure in Jordan the study area. Results show that σ1 (SHmax) and σ3 (SHmin) are generally sub-horizontal and σ2 is sub-vertical in 8 of 11 paleostress tensors, which are belonging to a major strike-slip system with σ1 swinging around N to NW direction. The other three stress tensors show σ2 (SHmax), σ1 vertical and σ3 is NE oriented. This situation explained as permutation of stress axes σ1 and σ2 that occur during tectonic events and partitioned strike slip deformation. NW compressional stresses affected the area and produced the major Amman – Hallabat strike-slip fault and its related structures, e.g., NW trending normal faults and NE trending folds in the study area.The new paleostress results related with the active major stress field of the region the Dead Sea Stress Field (DSS) during the Miocene to Recent.  相似文献   

13.
The Maastrichtian–Danian limestones of the Yacoraite Formation (northwestern Argentina) show carbon and oxygen isotopic values consistent with shallow marine conditions. The members of the formation respond to different sedimentary environments and are characterised by distinctive stable isotopes and geochemistry. The basal Amblayo Member is composed of high-energy dolomitic limestones and limestones with positive isotopic values (+2‰ δ13C, +2‰ δ18O). The top of the member reveals an isotopic shift of δ13C (−5‰) and δ18O (−10‰), probably related to a descent in the sea level. The sandy Güemes Member has isotopically negative (−2‰ δ13C, −1‰ δ18O) limestones, principally controlled by water mixing, decreased organic productivity, and compositional changes in the carbonates. The isotopically lighter limestones are calcitic, with a greater terrigenous contribution and different geochemical composition (high Si–Mn–Fe–Na, low Ca–Mg–Sr). These isotopic and lithological changes relate to the Cretaceous–Palaeogene transition. The Alemanía Member, composed of dolomitic limestones and pelites, represents a return to marine conditions and shows a gradual increase in isotopic values, reaching values similar to those of the Amblayo Member. The Juramento Member, composed of stromatolite limestones, shows isotopic variations that can be correlated with the two well-defined, shallowing-upward sequences of the member.  相似文献   

14.
Si stable isotopes in the Earth's surface: A review   总被引：2，自引：0，他引：2  
Silicon (Si) is the second most abundant element on Earth after oxygen. Only few studies have attempted to use stable isotopes of Si as proxies for understanding the Si cycle and its variations in the past. By using three different methods (IRMS, MC–ICP–MS and SIMS), the overall measurements show that the isotopic composition (δ30Si) of terrestrial samples ranges from − 5.7‰ to + 3.4‰. Dissolved Si in rivers and seawater is 30Si-enriched (− 0.8‰ < δ30Si < + 3.4‰) compared to Si in endogeneous rocks (− 1.1‰ < δ30Si < + 0.7‰). This global enrichment is counterbalanced by the Si-bearing phases (biogenic silica, clays, quartz) where Si is, in average, 30Si-depleted (− 5.7‰ < δ30Si < + 2.6‰). These values are the result of fractionation which have been measured or estimated from − 0.3‰ to − 3.8‰. The fractionation is modeled by two types of approaches: the Rayleigh distillation model (closed system) and the steady-state model (open system). These models have been used in the most recent studies to explain the observed δ30Si variations in continental environments and in the sub-Antarctic Ocean.  相似文献   

15.
The major steranes of the non-asphaltene fraction of Nigerian tar sand bitumen (maltene) are the c27-c29 diasteranes [13β(H),17α(H); 20R + S] and C28-C29 regular steranes [14β (H),17β (H); 20S]. The reducing metal reaction products of the corresponding asphaltenes (maltene-I) contain mainly C27-C29 regular steranes with the 14β(H),17β(H); 20R + S and 14α(H),17α(H); 20R + S configurations as well as the corresponding diasteranes having the 13β(H),17α(H); 20R + S configuration. These sterane distributions suggest that maltene-I corresponds to an unaltered oil whilst the maltene is equivalent to the product of severe biodegradation of maltene-I. This is consistent with maltene-I being the remnant of “original oil” trapped within the asphaltene matrix and protected from the effect of in-reservior biodégradation.Degradation of Nigerian asphaltenes by refluxing with ferric chloride-acetic anhydride or methanolic potassium hydroxide also releases soluble reaction products having the characteristics of unaltered oil such as the presence of n-alkanes having an unbiased distribution. These methods appear to be milder and more suitable than reducing metal reactions for releasing hydrocarbons occluded by asphaltenes.  相似文献   

16.
The thermodynamic stability of selected alkylated, dealkylated and rearranged 17α- and 17β-hopane isomers in the C27, C28, C29, C30 and C31 families were calculated using molecular mechanics (MM2) methods and, where possible, calculated equilibrium ratios of certain isomers were compared with observed ratios of isomers in thermally mature crude oil samples. Those calculated and observed ratios having similar values include: (1) the relative distributions among 17β(H)/17α(H) and 21β(H)/21α(H)-hopanes including the absence of the 17β(H),21β(H)- and 17α(H),21α(H)-hopanes; (2) the 22R/22S ratios in 30-methyl-17α-hopane and 30-methyl-17β-moretane; (3) the relative distributions among 17α(H)/17β(H)- and 21α(H)/21β(H)-28,30-bisnorhopanes and among 25,28,30-trisnorhopanes, including the relatively greater stability of 17β(H) isomers in contrast to the regular hopane series; and (4) the ratios of 28(18−17S)abeo hopanes with respect to their unrearranged counterparts including the C27 compounds, Ts/Tm.  相似文献   

17.
Here the authors present results of an isotope study on precipitation collected during a 2-a period from a rain-gauge network consisting of 6 stations located at different elevations in the Hyblean Mountains (HM) region, in south-eastern Sicily. The slope of the local meteoric water line (δD = 6.50 δ18O + 9.87) obtained for the region suggests that precipitation is affected by evaporation during rainfall events. The main variations in rainwater isotope composition are due to seasonal effects and elevation. An average 2H excess value of +21.2‰ was found for precipitation events less affected by evaporation (i.e. when the rainfall was >65 mm/month). The spatial distribution of O isotope composition of precipitation shows a negative gradient from east and south to the inner areas. The depositional rate of Cl, used as a tracer of the origin of air masses, is highest at the coastal rain-gauges (SR and MRG stations) and lowest on the northern flank of the HM region (SC station). Based on these findings, a model is proposed for the origin of precipitation in the HM region, which assumes that a Mediterranean-derived component is the main source of moisture in the studied area. D/H and 18O/16O ratios of inferred meteoric recharge waters were also compared with the isotope composition of waters collected from the main local springs and wells. The best linear fit of the δ18O vs δD relationship for Hyblean groundwater is δD = 4.85 δ18O–2.01. The enrichment of heavy isotopes in Hyblean groundwater is probably due to evaporation occurring after precipitation events or to a recharging contribution from surface waters (lakes or rivers) enriched in heavy isotopes.  相似文献   

18.
The igneous complex of Neukirchen–Kdyn is located in the southwestern part of the Teplá–Barrandian unit (TBU) in the Bohemian Massif. The TBU forms the most extensive surface exposure of Cadomian basement in central Europe. Cambrian plutons show significant changes in composition, emplacement depth, isotopic cooling ages, and tectonometamorphic overprint from NE to SW. In the NE, the V epadly granodiorite and the Smr ovice diorite intruded at shallow crustal levels (<ca. 7 km depth) as was indicated by geobarometric data. K–Ar age data yield 547±7 and 549±7 for hornblende and 495±6 Ma for biotite of the Smr ovice diorite, suggesting that this pluton has remained at shallow crustal levels (T<ca. 350 °C) since its Cambrian emplacement. A similar history is indicated for the V epadly granodiorite and the Stod granite. In the SW, intermediate to mafic plutons of the Neukirchen–Kdyn massif (V eruby and Neukirchen gabbro, Hoher–Bogen metagabbro), which yield Cambrian ages, either intruded or were metamorphosed at considerably deeper structural levels (>20 km). The Teufelsberg ( ert v kámen) diorite, on the other hand, forms an unusual intrusion dated at 359±2 Ma (concordant U–Pb zircon age). K–Ar dating of biotite of the Teufelsberg diorite yields 342±4 Ma. These ages, together with published cooling ages of hornblende and mica in adjacent plutons, are compatible with widespread medium to high-grade metamorphism and strong deformation fabrics, suggesting a strong Variscan impact under elevated temperatures at deeper structural levels. The plutons of the Neukirchen area are cut by the steeply NE dipping Hoher–Bogen shear zone (HBSZ), which forms the boundary with the adjacent Moldanubian unit. The HBSZ is characterized by top-to-the-NE normal movements, which were particularly active during the Lower Carboniferous. A geodynamic model is presented that explains the lateral gradients in Cambrian pluton composition and emplacement depth by differential uplift and exhumation, the latter being probably related to long-lasting movements along the HBSZ as a consequence of Lower Carboniferous orogenic collapse.  相似文献   

19.
Deep-water temperatures (DWTs) from the Western Mediterranean Sea are reconstructed for the last 50 ka based on the analysis of Mg/Ca ratios in benthic foraminifera from core MD95-2043 collected in the Alboran Sea. The exceptionally high sedimentation rates of this core and the robust chronology available allow discussion of the results in the context of the Dansgaard–Oeschger (D–O) rapid climatic variability. The applicability of Mg/Ca thermometry in the Western Mediterranean Deep-Water mass (WMDW) is first tested by the analysis of different benthic species in a collection of Mediterranean core tops. The results indicate the need of a readjustment of the existing Cibicidoides spp. calibrations in order to reconstruct present Western Mediterranean DWT values (12.7 °C). Different physiological effects in the Mg uptake between the C. pachydermus living in different regions could account for this offset in the Mediterranean samples. Consequently, the obtained DWT record still has many uncertainties in absolute terms but trends provide valuable information on past changes in WMDW conditions. The DWT record shows significant oscillations in relation to the D–O cycles, colder values occurred during the time of D–O stadials and warmer ones during D–O interstadials. Surprisingly, the coldest DWTs occurred during the time of Heinrich Event 4 (HE4) and not during the Last Glacial Maximum (LGM) when DWTs were mostly warm. These and other particular features of the DWT reconstruction mimic changes in the vegetation from the Eastern Mediterranean indicating the control of the Mediterranean climate on the DWT record. Paired analyses of Mg/Ca and δ18Occ (calcite δ18O) provide the opportunity to reconstruct deep-water δ18O (δ18Odw) and past salinities and hence changes in past WMDW density. Due to the large error associated with these calculations, they can only be discussed in terms of relative changes between different intervals. The results suggest the dominance of a heavier water end member during glacial times and a lighter one during the early Holocene in relation to the δ18Odw conditions present today. Densest WMDW were formed during most of Marine Isotopic Stage (MIS) 2 and during the D–O Stadials not associated with HEs, while lightest WMDW dominated during D–O Interstadials. The δ18Odw record shows a D–O variability pattern likely controlled by changes in the composition and intensity of the local run-off and also to changes in the δ18Ow signal of the Atlantic inflow. Changes in the residence time of the Mediterranean waters, governed by the global sea level, are also considered to exert an important role governing Mediterranean δ18Ow and salinity, particularly during MIS 2. Overall, our results are consistent with the formation of dense WMDW during D–O stadials and even denser during most of MIS 2.  相似文献   

20.
The Huize Pb–Zn deposit of Yunnan Province, China, is located in the center of the Sichuan–Yunnan–Guizhou Pb–Zn–Ag district. Four primary orebodies (orebody No. 1, No. 6, No. 8 and No. 10), with Pb + Zn reserves from 0.5 Mt to 1 Mt, have been found at depth in this deposit. This paper provides new data on the sulfur isotopic compositions of the four orebodies. The data show that the principal sulfide minerals (galena, sphalerite and pyrite) in the four orebodies are enriched in heavy sulfur, the δ34S values between 10.9‰ and 17.7‰ and where δ34Spyrite > δ34Ssphalerite > δ34Sgalena. The δ34S values of sulfide are close to that of the sulfates from the carbonate strata within the region. The similarity in sulfur isotope composition between sulfides and sulfates indicates the sulfur in the ore-forming fluids was likely derived by thermochemical sulfate reduction of sulfates contained within carbonate units.  相似文献   

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