New triaromatic steroids distinguish Paleozoic from Mesozoic oil     

Silvana M. Barbanti  J. Michael MoldowanDavid S. Watt  E. Kolaczkowska 《Organic Geochemistry》2011,42(4):409-424

Certain biomarkers in petroleum provide information on of the geologic age of its source rock and these can also be used to track the evolution, radiation and relationships between taxa and as proxies for paleoenvironmental reconstruction. Triaromatic 23,24-dimethylcholesteroids (TA-DMC), which undoubtedly derive from 23,24-dimethylcholesterols in dinoflagellates, haptophytes and diatoms, provide a useful parameter to distinguish Paleozoic from Mesozoic and younger oil and rock extracts at higher specificity than previously proposed biomarkers. In this report, we present a study of the relative abundance of a novel series of TA-DMC in source rock extracts and crude oil from different global localities and ages. Based on their taxon specificity for important primary producers, such biogeochemicals also have implications for paleoenvironmental studies, including paleoclimate and global change, such as radiations following the Permian-Triassic boundary mass extinction.  相似文献   

Comparison of gas with liquid chromatography for the determination of benzenepolycarboxylic acids as molecular tracers of black carbon     

Maximilian P.W. Schneider  Rienk H. Smittenberg  Thorsten Dittmar  Michael W.I. Schmidt   《Organic Geochemistry》2011,42(3):275-282

Existing methods for black carbon (BC) quantification measure different parts of the BC continuum, which complicates the calculation of a global BC budget. Benzenepolycarboxylic acids (BPCA) are used as molecular markers to quantify and characterize BC in soils and sediments using gas chromatography for BPCA separation (GC-BPCA). Recently, this method was refined for BC analysis in seawater using high performance liquid chromatography (LC-BPCA), which omits the cleaning steps and derivatization necessary in GC analysis. As yet it is not clear whether the two analytical methods yield similar results. Here we apply both methods to a suite of laboratory produced charcoals derived from wood and grass. We found systematically lower total BPCA-C contents and larger analytical variability for all tested charcoals when using GC-BPCA compared to LC-BPCA, the latter giving 1.5 ± 0.3 times higher yields for the charcoal samples formed at 275-700 °C. At lower and higher pyrolysis temperatures the differences between the two analytical methods were larger. The main reason for the differences between the two methods is the loss of BPCA during sample preparation for GC analysis. We propose a correction factor of 1.5 to account for at least part of these losses. No qualitative biases, i.e. towards more or less functionalized BPCAs, were observed between the two methods. The relative contribution of mellitic acid C to total BPCA-C, a measure for the degree of condensation of BC, was the same in the two analytical techniques. Qualitative differences between wood and grass charcoals as detected by both methods were small.  相似文献   

Variation in n-alkane δD values from terrestrial plants at high latitude: Implications for paleoclimate reconstruction     

Hong Yang  Weiguo Liu  Qin Leng  Michael T. Hren  Mark Pagani 《Organic Geochemistry》2011,42(3):283-288

The molecular hydrogen isotope composition (δD) of leaf waxes from terrestrial plants is increasingly used to infer hydrological characteristics of ancient high latitude climates. Analysis of the hydrogen isotope composition of n-alkanes (δD_n-alkane) from a global dataset of individual plants growing at low and middle latitudes indicates that plant ecological life form is an important factor in determining the hydrogen isotope fractionation. However, environmental and biological controls of high latitudinal leaf wax δD values are poorly understood because of a lack of δD records from modern flora in these regions. We previously noticed smaller apparent hydrogen isotope fractionations between n-alkanes and environmental water (ε_alk-water) in deciduous trees growing at high latitudes (>59°N; Liu, W.-G., Yang, H., 2008. Multiple controls for the variability of hydrogen isotopic compositions in higher plant n-alkanes from modern ecosystems. Global Change Biology 14, 2166-2177.) To further examine these issues, we measured δD_n-alkane from a variety of plants that inhabit high latitude environments and added critically needed leaf wax δD data from grass and herbs to the existing global δD_n-alkane database. Inclusion of these new data with the existing global dataset (n = 408) confirms plant ecological life form as an important control for leaf wax δD variation for terrestrial plants living at high latitudes. Our results suggest that, while precipitation δD is captured in these high latitude plants, physiological characters such as leaf area, venation pattern and hydraulic system, that enhance transpiration rate during summer growth, may impart δD_n-alkane differences among plants with different ecological life forms.  相似文献   

Application of portable X-ray fluorescence analyses to metabasalt stratigraphy,Plutonic Gold Mine,Western Australia     

Michael F. Gazley  Julie K. Vry  Ettienne du Plessis  Monica R. Handler 《Journal of Geochemical Exploration》2011

Stratigraphy, structure and host-rock chemistry are dominant controls on the location of Au in Archaean greenstone-hosted Au deposits, but the stratigraphy in such deposits is seldom obvious due to the monotonous nature of the host rocks or pervasive alteration associated with Au mineralisation. Portable, hand-held, X-ray fluorescence (pXRF) spectrometry provides a method to rapidly collect large amounts of whole-rock geochemical data that can yield new insights into both stratigraphy and Au localisation. Here we present results of pXRF analyses of samples from a representative section through Au-mineralised amphibolite-facies metabasaltic rocks at Plutonic Gold Mine, Western Australia. These data illustrate a geochemical stratigraphy in which individual lava flows can be identified on the basis of element concentrations. The most evolved basalts are at the structural base of the succession, and the least evolved at the top of the sequence, confirming previous geochemical interpretations and textural evidence that the sequence is overturned, and demonstrating for the first time that the presented section does not involve significant structural repetition. In conjunction with Au assay data, the pXRF data reveal that Au commonly occurs along basalt flow boundaries. The elemental concentration data clearly demonstrates for the first time the stratigraphic control on Au mineralisation that is not readily apparent at the macroscopic level. The methods described in this paper are readily applied, and have the potential to enhance the understanding of otherwise unclear stratigraphy and its control on mineralisation in many different types of deposits worldwide.  相似文献   

Numerical modeling and experiments of coarsening foam     

Hyunsun Do  Michael Brady  Demetri P. Telionis  Pavlos P. Vlachos  Roe-Hoan Yoon 《International Journal of Mineral Processing》2011,98(1-2):66-73

Numerical and experimental results of drying and wetting foam are presented. Foam can be wetted by wash water delivered on its top boundary, or drained by allowing the liquid to move downward in response to gravity. These processes are governed by nonlinear equations that in special cases accept exact solutions. Here we develop a numerical model that satisfies realistic boundary conditions. Numerical results are presented in conjunction with experiments conducted with coarsening foam. In addition, calculations were carried out modeling the wetting and draining of coarsened foam. From the simulations and experiments, coarsening bubbles were found responsible for accelerating drainage, or vice versa.  相似文献   

Geology,mineral chemistry and tourmaline B isotopes of the Córrego Bom Sucesso area,southern Serra do Espinhaço,Minas Gerais,Brazil: Implications for Au–Pd–Pt exploration in quartzitic terrain     

Alexandre Raphael Cabral  Bernd Lehmann  Miguel Tupinambá  Michael Wiedenbeck  Michael Brauns 《Journal of Geochemical Exploration》2011

The Palaeo-Mesoproterozoic metasiliciclastic rocks of the southern Serra do Espinhaço, Minas Gerais, Brazil, are host to historically important alluvial deposits of diamonds and gold. Detrital gold grains often comprise Au–Pd–Pt intermetallic compounds, with low Ag contents, which contain inclusions of tourmaline and titaniferous hematite (up to ~ 6 wt.% TiO₂). The latter minerals connect the alluvial mineralisation to the rutile–hematite–quartz veins and tourmalinisation observed in the quartzitic country rocks of the alluvial gravel. The quartzite (Sopa-Brumadinho Formation of lacustrine to fan-deltaic origin) is affected by pervasive B metasomatism with F-bearing tourmaline replacing the recrystallised quartz fabric. The tourmaline belongs to the alkali group, with Mg/(Mg + Fe) and X/(X + Na) ratios in the ranges from 0.5 to 0.7 and 0.18 to 0.29, respectively, where X represents vacancies in the X site. Boron-isotopic values of tourmaline vary from ~ 1 to − 10.4‰ δ¹¹B. The B-isotope range, in conjunction with the Na–Mg-rich tourmaline composition, and the widespread occurrence of tourmalinite in the Sopa-Brumadinho Formation suggest a derivation from non-marine evaporitic brines. Brines are capable of transporting otherwise immobile Ti and explain, under oxidising conditions, the fractionation of Ag from Pd to precipitate palladiferous gold with extremely high Pd/Ag ratios. Zirconium-in-rutile and Ti-in-quartz temperatures for a variety of hematite-rich veins suggest episodic vein emplacement over a temperature range from around 500 °C to ~ 350 °C. Cross-cutting relationships and episodic vein emplacement indicate a late-Brasiliano age.  相似文献   

The origin of high δ<Superscript>18</Superscript>O zircons: marbles,megacrysts, and metamorphism     

Aaron J. Cavosie  John W. Valley  Noriko T. Kita  Michael J. Spicuzza  Takayuki Ushikubo  Simon A. Wilde 《Contributions to Mineralogy and Petrology》2011,162(5):961-974

The oxygen isotope ratios (δ¹⁸O) of most igneous zircons range from 5 to 8‰, with 99% of published values from 1345 rocks below 10‰. Metamorphic zircons from quartzite, metapelite, metabasite, and eclogite record δ¹⁸O values from 5 to 17‰, with 99% below 15‰. However, zircons with anomalously high δ¹⁸O, up to 23‰, have been reported in detrital suites; source rocks for these unusual zircons have not been identified. We report data for zircons from Sri Lanka and Myanmar that constrain a metamorphic petrogenesis for anomalously high δ¹⁸O in zircon. A suite of 28 large detrital zircon megacrysts from Mogok (Myanmar) analyzed by laser fluorination yields δ¹⁸O from 9.4 to 25.5‰. The U–Pb standard, CZ3, a large detrital zircon megacryst from Sri Lanka, yields δ¹⁸O = 15.4 ± 0.1‰ (2 SE) by ion microprobe. A euhedral unzoned zircon in a thin section of Sri Lanka granulite facies calcite marble yields δ¹⁸O = 19.4‰ by ion microprobe and confirms a metamorphic petrogenesis of zircon in marble. Small oxygen isotope fractionations between zircon and most minerals require a high δ¹⁸O source for the high δ¹⁸O zircons. Predicted equilibrium values of Δ¹⁸O(calcite-zircon) = 2–3‰ from 800 to 600°C show that metamorphic zircon crystallizing in a high δ¹⁸O marble will have high δ¹⁸O. The high δ¹⁸O zircons (>15‰) from both Sri Lanka and Mogok overlap the values of primary marine carbonates, and marbles are known detrital gemstone sources in both localities. The high δ¹⁸O zircons are thus metamorphic; the 15–25‰ zircon values are consistent with a marble origin in a rock-dominated system (i.e., low fluid_(external)/rock); the lower δ¹⁸O zircon values (9–15‰) are consistent with an origin in an external fluid-dominated system, such as skarn derived from marble, although many non-metasomatized marbles also fall in this range of δ¹⁸O. High δ¹⁸O (>15‰) and the absence of zoning can thus be used as a tracer to identify a marble source for high δ¹⁸O detrital zircons; this recognition can aid provenance studies in complex metamorphic terranes where age determinations alone may not allow discrimination of coeval source rocks. Metamorphic zircon megacrysts have not been reported previously and appear to be associated with high-grade marble. Identification of high δ¹⁸O zircons can also aid geochronology studies that seek to date high-grade metamorphic events due to the ability to distinguish metamorphic from detrital zircons in marble.  相似文献   

Effect of leaf litter degradation and seasonality on D/H isotope ratios of n-alkane biomarkers     

Michael Zech  Nikolai Pedentchouk  Katharina Leiber  Slobodan B. Markovi? 《Geochimica et cosmochimica acta》2011,75(17):4917-4928

During the last decade, compound-specific hydrogen isotope analysis of plant leaf-wax and sedimentary n-alkyl lipids has become a promising tool for paleohydrological reconstructions. However, with the exception of several previous studies, there is a lack of knowledge regarding possible effects of early diagenesis on the δD values of n-alkanes. We therefore investigated the n-alkane patterns and δD values of long-chain n-alkanes from three different C3 higher plant species (Acer pseudoplatanus L., Fagus sylvatica L. and Sorbus aucuparia L.) that have been degraded in a field leaf litterbag experiment for 27 months.We found that after an initial increase of long-chain n-alkane masses (up to ∼50%), decomposition took place with mean turnover times of 11.7 months. Intermittently, the masses of mid-chain n-alkanes increased significantly during periods of highest total mass losses. Furthermore, initially high odd-over-even predominances (OEP) declined and long-chain n-alkane ratios like n-C₃₁/C₂₇ and n-C₃₁/C₂₉ started to converge to the value of 1. While bulk leaf litter became systematically D-enriched especially during summer seasons (by ∼8‰ on average over 27 months), the δD values of long-chain n-alkanes reveal no systematic overall shifts, but seasonal variations of up to 25‰ (Fagus, n-C₂₇, average ∼13‰).Although a partly contribution by leaf-wax n-alkanes by throughfall cannot be excluded, these findings suggest that a microbial n-alkane pool sensitive to seasonal variations of soil water δD rapidly builds up. We propose a conceptual model based on an isotope mass balance calculation that accounts for the decomposition of plant-derived n-alkanes and the build-up of microbial n-alkanes. Model results are in good agreement with measured n-alkane δD results. Since microbial ‘contamination’ is not necessarily discernible from n-alkane concentration patterns alone, care may have to be taken not to over-interpret δD values of sedimentary n-alkanes. Furthermore, since leaf-water is generally D-enriched compared to soil and lake waters, soil and water microbial n-alkane pools may help explain why soil and sediment n-alkanes are D-depleted compared to leaves.  相似文献   

Solubility and near-equilibrium dissolution rates of quartz in dilute NaCl solutions at 398-473 K under alkaline conditions     

Michael C. Davis  Jörgen Rosenqvist  Susan L. Brantley 《Geochimica et cosmochimica acta》2011,75(2):401-415

The dissolution-precipitation of quartz controls porosity and permeability in many lithologies and may be the best studied mineral-water reaction. However, the rate of quartz-water reaction is relatively well characterized far from equilibrium but relatively unexplored near equilibrium. We present kinetic data for quartz as equilibrium is approached from undersaturation and more limited data on the approach from supersaturated conditions in 0.1 molal NaCl + NaOH + NaSiO(OH)₃ solutions with pH 8.2-9.7 at 398, 423, 448, and 473 K. We employed a potentiometric technique that allows precise determination of solution speciation within 2 kJ mol⁻¹ of equilibrium without the need for to perturb the system through physical sampling and chemical analysis. Slightly higher equilibrium solubilities between 423 and 473 K were found than reported in recent compilations. Apparent activation energies of 29 and 37 kJ mol⁻¹ are inferred for rates of dissolution at two surface sites with different values of connectedness: dissolution at Q¹ or Q² silicon sites, respectively. The dissolution mechanism varies with ΔG such that reactions at both sites control dissolution up until a critical free energy value above which only reactions at Q¹ sites are important. When our near-equilibrium dissolution rates are extrapolated far from equilibrium, they agree within propagated uncertainty at 398 K with a recently published model by Bickmore et al. (2008). However, our extrapolated rates become progressively slower than model predictions with increasing temperature. Furthermore, we see no dependence of the postulated Q¹ reaction rate on pH, and a poorly-constrained pH dependence of the postulated Q² rate. Our slow extrapolated rates are presumably related to the increasing contribution of dissolution at Q³ sites far from equilibrium. The use of the potentiometric technique for rate measurement will yield both rate data and insights into the mechanisms of dissolution over a range of chemical affinity. Such measurements are needed to model the evolution of many natural systems quantitatively.  相似文献   

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France   总被引：2，自引：0，他引：2  

Farid Juillot  Delphine Jouvin  Philipe Telouk  Philippe Ildefonse  Steve Sutton  Gordon E. Brown Jr. 《Geochimica et cosmochimica acta》2011,75(9):2295-2308

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.  相似文献