Exhumation of the Schistes Lustrés complex: in situ laser probe 40Ar/39Ar constraints and implications for the Western Alps

The Schistes Lustrés (SL) suture zone occupies a key position in the Alpine chain between the high‐pressure (HP) Brianconnais domain and the ultrahigh‐pressure (UHP) Dora Maira massif, and reached subduction depths ranging from c. 40–65 km (Cottian Alps). In order to constrain the timing of HP metamorphism and subsequent exhumation, several phengite generations were differentiated, on the basis of habit, texture, paragenesis and chemistry, as belonging to the first or second exhumation episode, respectively, D2 or D3, or to earlier stages of the tectono‐metamorphic evolution. Ten carefully selected samples showing D2, D3 (D2 + D3), or earlier (mostly peak temperature) phengite population(s) were subjected to laser probe ⁴⁰Ar/³⁹Ar analysis. The data support the results of the petrostructural study with two distinct age groups (crystallization ages) for D2 and D3 phengite, at 51–45 and 38–35 Ma, respectively. The data also reveal a coherent age cluster, at 62–55 Ma, for peak temperature phengite associated with chloritoid which were preserved in low strain domains. The age of the D3 event in the SL complex appears very similar to ages recently obtained for greenschist facies deformation on the border of most internal crystalline massifs. Exhumation rates of the order of 1–2 mm yr^?1 are obtained for the SL complex, which are compatible with velocities documented for accretionary wedge settings. Similarly, cooling velocities are only moderate (c.5 °C Myr^?1), which is at variance with recent estimates in the nearby UHP massifs.     

Stable-isotopes of groundwaters from the Albuquerque, New Mexico, basin: one decade later

In the spring of 1995, 24 samples were collected from a widely distributed system of municipal water wells in Albuquerque, N.M., and analyzed for hydrogen (δD) and oxygen (δ¹⁸O) isotopic compositions. δD values for 15 of these samples are largely similar to those reported by Yapp in 1985, but have locally become more negative by as much as 5 per mil (ö). δD–δ¹⁸O data define two endmembers that are well aligned along the familiar meteoric water line (MWL): (1) the eastern domain (mountain precipitation runoff), having δD>–86ö (similar to the criteria of Yapp) and δ¹⁸O>–12.1ö (this work); and (2) a central basin domain, which may be in part derived from water seepage from the Rio Grande, having δD<–95ö and δ¹⁸O<–13.2ö. Only a few wells across the basin have δD values near the "baseline" value of the Rio Grande, defined by Yapp as –92ö. The proximity of these wells to the Rio Grande is consistent with recharge by seepage from the river bed under baseline conditions. Extensive pumping in the eastern domain and West Mesa areas may be partly responsible for an apparent expansion of the central-basin regime of water more depleted in δD, much as a plume migrating in response to transient perturbations in original hydraulic gradients. Vertically stacked groundwater occurrences having limited interconnection are inferred from the significant differences in isotopic compositions of samples from two wells screened at multiple depths. The central and western parts of the basin are little influenced by contributions from the eastern domain. Some groundwaters from the western part of the basin plot below the MWL and clearly cannot be mixtures solely of the eastern domain and central basin endmembers. The origins of these western groundwaters and the most depleted central basin groundwaters are as yet unknown, but we speculate they may have received recharge under climatic conditions different from the present.     

Geochemistry of magmatic rocks and time constraints on deformational phases and shear zone slip in the Méiganga area,central Cameroon

The Méiganga area is situated in the Adamawa–Yadé domain (AYD) of the Pan-African fold belt in Cameroon. The AYD is characterized by abundant plutonic rocks that intruded Palaeoproterozoic gneisses. It is cut by the transcurrent Central Cameroonian Shear Zone (CCSZ). The studied area is made up of metadiorite (MD), pyroxene-bearing granite (PGr) and biotite-muscovite granite (BMGr), hosted in a metasedimentary sequence of amphibole-biotite gneisses. The granitoids are metaluminous to slightly peraluminous, and mainly of I-type (ASI ≤ 1.1), representing a high-K calc-alkaline to shoshonitic suite. They were derived from crustal protoliths (BMGr), from rocks of mantle origin (MD, PGr), and/or from the remelting of metabasalt or metatonalite (MD, PGr). Four successive deformational phases (D1, D2, D3, and D4) are present in the Méiganga area. The S1 foliation is formed by tectonic transposition of the S0 primitive surface represented by contacts between the gneiss and intercalated amphibolites. The synmigmatitic D2 deformational phase is characterized by S2 banded schistosity, S2/C2 sinistral shear planes, and F2 folds with axes parallel to a L2 stretching lineation. Imprints of the D2 and subsequent deformational phases are similar in the metadiorite and host rocks, implying syn-D2 emplacement and crystallization of the metadiorite; therefore 614–619 Ma ²⁰⁷Pb/²⁰⁶Pb zircon evaporation ages obtained for this rock type date the syn-D2 magmagenesis. Similarly, the D3 phase of the PGr is 601 ± 1 Ma, dated by the ²⁰⁷Pb/²⁰⁶Pb evaporation method. D4 is a late-stage brittle deformational phase. Sinistral movement of the CCSZ is associated with D2, whereas its latest activity, characterized by dextral slip, cannot be older than emplacement of the 558 ± 2 Ma BMGr (²⁰⁷Pb/²⁰⁶Pb zircon evaporation age).     

Methodology to evaluate the renewal period of carbonate aquifers: a key tool for their management in arid and semiarid regions,with the example of Becerrero aquifer,Spain

A methodological procedure is proposed for determining the renewal period (RP), which expresses the ratio of total storage to recharge of carbonate aquifers, and it was applied to the overexploited moderate-size Becerrero carbonate aquifer (southern Spain). To this end, geological and subsurface data—time domain electromagnetic (TEM) soundings and borehole logs—were integrated to construct a three-dimensional (3D) geological model of the aquifer. The interconnected porosity was estimated by analyzing 73 rock samples. The resulting 3D geometrical model makes it possible to quantify the fractions of the aquifer having a confined or unconfined behaviour. Based on the total storage capacity (179?·?10⁶–514?·?10⁶ m³) and available aquifer recharge estimation (4.8?·?10⁶–6.4?·?10⁶ m³/year), an RP between 37 and 106 years is obtained. In view of the RP, an exploitation rate slightly lower than the average recharge of the system is recommended, so that the piezometric level will be stable but below the discharge head that is produced through the springs in natural conditions. The proposed methodology to obtain an aquifer RP and the management strategies designed accordingly are of broad interest, especially for carbonate aquifers, which are abundant in arid and semiarid regions.     

δC and δD identification of sources of lipid biomarkers in sediments of Lake Haruna (Japan)

Organic materials in lacustrine sediments are from multiple terrestrial and aquatic sources. In this study, carbon (δ¹³C) and hydrogen isotopic compositions (δD) of phytol, various sterols, and major n-fatty acids in sediments at Lake Haruna, Japan, were determined in their solvent-extractable (free) and saponification-released forms (bound). The δ¹³C-δD distributions of these lipid molecules in sediments are compared with those of terrestrial C3 and C4 plants, aquatic C3 plants, and plankton to evaluate their relative contributions. δ¹³C-δD of free phytol in sediments is very close to that of phytol in plankton samples, whereas δ¹³C-δD of bound phytol in sediments is on a mixing line between terrestrial C3 plant and plankton material. Unlike phytol, no significant δ¹³C-δD difference between free and bound forms was found in sterols and n-fatty acids. δ¹³C-δD values of algal sterols such as 24-methylcholesta-5,22-dien-3β-ol in sediments are close to those of plankton, whereas δ¹³C-δD of multiple-source sterols such as 24-ethylcholest-5-en-3β-ol and of major n-fatty acids such as n-hexadecanoic acid in sediments are between those of terrestrial C3 plants and plankton samples. Thus, δ¹³C-δD distributions clearly indicate the specific source contributions of biomarkers preserved in a lacustrine environment. Free phytol and algal sterols can be attributed to phytoplankton, and bound phytol, multiple source sterols, and major n-fatty acids are contributed by both terrestrial C3 plants and phytoplankton.     

Polystage deformation of the Gaoligong metamorphic zone: Structures, 40Ar/39Ar mica ages,and tectonic implications

The Gaoligong metamorphic zone is located southeast of the Eastern Himalayan Syntaxis in western Yunnan, China. The zone is characterized by four stages of deformation (D1–D4). D1 structures record early compressive deformation during the Indosinian orogeny, which formed tight to isoclinal F1 folds of bedding with a penetrative S1 foliation developed parallel to fold axial planes. Mid-crustal horizontal shearing during D2 resulted in overprinting of D1 structures. D1 and D2 structures are associated with granulite facies metamorphism. D3 doming resulted in late crustal thickening and the development of a regional NW–SE trending F3 antiform. Synchronous with or slightly subsequent to D3 deformation, the zone experienced D4 ductile strike-slip shearing, resulting in its exhumation to shallow crustal levels and retrograde metamorphism. Granitic D4 mylonites predominantly yield ⁴⁰Ar/³⁹Ar mica ages of 15–16 Ma, indicating that D4 dextral strike-slip shearing occurred in the Miocene. Weakly deformed leucogranite and protomylonite yield ⁴⁰Ar/³⁹Ar ages of 10–11 Ma, suggesting that ductile strike-slip shearing continued to the Late Miocene. The new ⁴⁰Ar/³⁹Ar data indicate that escape-related deformation along the Gaoligong strike-slip shear zone occurred in the Miocene. In association with recent geophysical studies, and on the basis of the structural, crystal preferred orientation (CPO), and geochronological data presented in this paper, we suggest that the Gaoligong metamorphic zone formed in response to intracontinental transpression in the southeast of Tibet, characterized as intense deformation and metamorphism at middle–upper crustal levels.     

天津地热资源评价与综合研究

以4 000 m以浅的主要热储层为研究对象,通过总结天津地热资源特征及勘查现状,利用热储法结合水均衡法和数值耦合优化管理模型计算天津市主要热储层30 a热流体可采资源量及可采热量。结果表明: 到2045年底,热储法结合水均衡法计算的热流体可采资源量和可采热量分别为27.012×10¹⁸ m³和47.0×10¹⁶ J; 数值耦合优化管理模型计算的热流体可采资源量和可采热量分别为26.6×10¹⁸ m³和49.74×10¹⁶ J; 2种方法计算结果基本一致。该计算结果可为天津市地热资源合理开发及科学管理提供依据。     

Isovolumetric geochemical investigation of a buried granite saprolite near Columbia,SC, U.S.A.

Saprolites are residual soils which preserve the textures of their parent rocks and thus have evolved by an isovolumetric process of weathering (MILLOT, 1970, The Geology of Clays, Springer). Using bulk density, saprolite elemental analyses can be converted to units of g cm^?3. Furthermore, an empirical reaction progress diagram can be constructed for a suite of saprolite samples by plotting element concentrations (in g cm^?3) against bulk density (B.D.). Our data for a granite saprolite show that Al₂O₃ and SiO₂ decrease in a linear fashion from B.D. 2.1g cm^?3 to 1.5g cm^?3 but that K₂O follows a curvilinear trend such that it decreases from 75% of its fresh rock value at B.D. 1.6 g cm^?3 to nearly zero at B.D. 1.5 g cm^?3. The only hypothetical reaction paths that are compatible with these B.D. vs A1₂O₃, SiO₂ and K₂O constraints are those in which orthoclase alters to kaolinite through an intermediate potassium phase similar to KAl₃Si₃O₁₀(OH)₂ or KAl₂Si₂O₆(OH)₃ (hypothetical K-kaolinite). Normative mineral calculations, X-ray diffraction data and structural H₂O data are employed to test this conclusion.     

Formation and abundance of doubly-substituted methane isotopologues (CH3D) in natural gas systems

Formation of the Carbon-13 (¹³C) and deuterium (D) doubly-substituted methane isotopologues (¹³CH₃D) in natural gases is studied utilizing both first-principle quantum mechanism molecular calculation and direct FTIR laboratorial measurements of specifically synthesized high isotope concentration methane gas. For ¹³CH₃D, the symmetrically breathing mode A₀ emerges as IR-detectable attributed to the molecular symmetry lowering to C_3v from T_d of the non-isotopic methane (CH₄), along with a large vibrational frequency shift from ∼3000 to ∼2250 cm⁻¹. Our studies also indicate that the concentration of ¹³CH₃D is dependent on the environmental temperature through isotope exchanges among methane isotopologues; and the Gibbs’ Free Energy difference due to Quantum Mechanics Zero-Point vibrational motions has the major contribution to this temperature dependency. Potential geologic applications of the ¹³CH₃D measurement to natural gas exploration and assessments are also discussed. In order to detect the ¹³CH₃D concentration change of each 50 °C in the natural gas system, a 10⁻⁹ resolution is desirable. Such a measurement could provide important add-on information to distinguish natural gas origin and distribution.     

Weathering geochronology by (U-Th)/He dating of goethite

Nine samples of supergene goethite (FeOOH) from Brazil and Australia were selected to test the suitability of this mineral for (U-Th)/He dating. Measured He ages ranged from 61 to 8 Ma and were reproducible to better than a few percent despite very large variations in [U] and [Th]. In all samples with internal stratigraphy or independent age constraints, the He ages corroborated the expected relationships. These data demonstrate that internally consistent He ages can be obtained on goethite, but do not prove quantitative ⁴He retention. To assess possible diffusive He loss, stepped-heating experiments were performed on two goethite samples that were subjected to proton irradiation to produce a homogeneous distribution of spallogenic ³He. The ³He release pattern indicates the presence of at least two diffusion domains, one with high helium retentivity and the other with very low retentivity at Earth surface conditions. The low retentivity domain, which accounts for ∼ 5% of ³He, contains no natural ⁴He and may represent poorly crystalline or intergranular material which has lost all radiogenic ⁴He by diffusion in nature. Diffusive loss of ³He from the high retentivity domain is independent of the macroscopic dimensions of the analyzed polycrystalline aggregate, so probably represents diffusion from individual micrometer-size goethite crystals. The ⁴He/³He evolution during the incremental heating experiments shows that the high retentivity domain has retained 90%-95% of its radiogenic helium. This degree of retentivity is in excellent agreement with that independently predicted from the helium diffusion coefficients extrapolated to Earth surface temperature and held for the appropriate duration. Considering both the high and low retentivity domains, these data indicate that one of the samples retained 90% of its radiogenic ⁴He over 47.5 Ma and the other retained 86% over 12.3 Ma. Thus while diffusive-loss corrections to supergene goethite He ages are required, these initial results indicate that the corrections are not extremely large and can be rigorously quantified using the proton-irradiation ⁴He/³He method.     

Coexisting hornblendes and biotites from Precambrian gneisses of the south coast of Western Australia

The compositions of coexisting hornblendes and biotites from amphibolite and granulite facies gneisses from the south coast of Western Australia were controlled by host rock composition, paragenesis, metamophic grade, pressure, and oxygen fugacity. The Mg/(Mg + Fe²⁺) and Mn/Fe²⁺ ratios in both minerals and possibly the Al^vi contents of the hornblendes are related to host rock compositions. Metamorphic grade appears to influence, perhaps only indirectly, the Ti, Mn, and Fe³⁺ contents of both minerals and possibly the hornblende Ca content. The higher Ti and lower Mn contents of the granulite facies hornblendes and biotites are attributed to their coexistence with pyroxenes, whereas their lower Fe³⁺/(Fe²⁺ + Fe³⁺) ratios are probably due to lower oxygen fugacity in the granulite facies environment. Grade-related colour variations in both minerals were controlled by their Ti/Fe²⁺ and Fe³⁺/(Fe²⁺ + Fe³⁺ ratios. The relatively low Al^vi contents of the hornblendes suggest low- to moderate-pressure metamorphism.Variations in element distribution coefficients are related to variations in mineral compositions rather than metamorphic grade. Thus K_{D(Al^iv ?Si)} is related to the Al^iv andedenite alkali contents of the hornblendes, K_{D(Fe²⁺ ?Mg)} to the distributions of Al^iv ?Si and Al^vi + Ti + Fe³⁺, K_D(Mn) to the Mn contents of both minerals, and K_D(Al^vi) to the Al^vi contents of the biotites.     

Metamorphic inheritance of Rheic passive margin evolution and its early‐Variscan overprint in the Teplá‐Barrandian Unit,Bohemian Massif

Rift‐related regional metamorphism of passive margins is usually difficult to observe on the surface, mainly due to its strong metamorphic overprint during the subsequent orogenic processes that cause its exposure. However, recognition of such a pre‐orogenic evolution is achievable by careful characterization of the polyphase tectono‐metamorphic record of the orogenic upper plate. A multidisciplinary approach, involving metamorphic petrology, P–T modelling, structural geology and in situ U‐Pb monazite geochronology using laser‐ablation split‐stream inductively coupled plasma mass spectrometry, was applied to unravel the polyphase tectono‐metamorphic record of metapelites at the western margin of the Teplá‐Barrandian domain in the Bohemian Massif. The study resulted in discovery of three tectono‐metamorphic events. The oldest event M1 is LP–HT regional metamorphism with a geothermal gradient between 30 and 50 °C km^?1, peak temperatures up to 650 °C and of Cambro‐Ordovician age (c. 485 Ma). The M1 event was followed by M2‐D2, which is characterized by a Barrovian sequence of minerals from biotite to kyanite and a geothermal gradient of 20–25 °C km^?1. D2‐M2 is associated with a vertical fabric S2 and was dated as Devonian (c. 375 Ma). Finally, the vertical fabric S2 was overprinted by a D3‐M3 event that formed sillimanite to chlorite bearing gently inclined fabric S3 also of Devonian age. The high geothermal gradient of the M1 event can be explained as the result of an extensional, rift‐related tectonic setting. In addition, restoration of the deep architecture and polarity of the extended domain before the Devonian history – together with the supracrustal sedimentary and magmatic record – lead us to propose a model for formation of an Ordovician passive continental margin. The subsequent Devonian evolution is interpreted as horizontal shortening of the passive margin at the beginning of Variscan convergence, followed by detachment‐accommodated exhumation of lower‐crustal rocks. Both Devonian shortening and detachment occurred in the upper plate of a Devonian subduction zone. The tectonic evolution presented in this article modifies previous models of the tectonic history of the western margin of the Teplá‐Barrandian domain, and also put constraints on the evolution of the southern margin of the Rheic ocean from the passive margin formation to the early phases of Variscan orogeny.     

Nested gridding and streamline-based simulation for fast reservoir performance prediction

Detailed reservoir models routinely contain 10⁶–10⁸ grid blocks. These models often cannot be used directly in a reservoir simulation because of the time and memory required for solving the pressure grid on the fine grid. We propose a nested gridding technique that efficiently obtains an approximate solution for the pressure field. The domain is divided into a series of coarse blocks, each containing several fine cells. Effective mobilities are computed for each coarse grid block and the pressure is then found on the coarse scale. The pressure field within each coarse block is computed using flux boundary conditions obtained from the coarse pressure solution. Streamline-based simulation is used to move saturations forward in time. We test the method for a series of example waterflood problems and demonstrate that the method can give accurate estimates of oil production for large 3D models significantly faster than direct simulation using streamlines on the fine grid, making the method overall approximately up to 1,000 times faster than direct conventional simulation.     

Diachronous Palaeoproterozoic deformation and metamorphism in the Committee Bay belt,Rae Province,Nunavut: insights from 40Ar–39Ar cooling ages and thermal modelling

Regional‐scale ⁴⁰Ar–³⁹Ar data presented in this paper reveal significant across‐strike and along‐strike age differences in the Committee Bay belt (CBb), Rae Province, Nunavut, Canada, that complement variations in observed monazite ages. ⁴⁰Ar–³⁹Ar hornblende ages are c. 1795, 1775, and 1750 Ma in the western, eastern and central parts of the Prince Albert Group (PAG) domain respectively. The migmatite domain and Walker Lake intrusive complex are characterized by c. 1750–1730 ⁴⁰Ar–³⁹Ar hornblende ages without significant along‐strike variation. The ⁴⁰Ar–³⁹Ar data provide important constraints on the cooling history and on thermal modelling that elucidates the controls on diachroneity and metamorphic patterns within the belt. In the western CBb, prograde monazite growth occurred 26 ± 10 Myr earlier in the migmatite domain (1864 ± 9 Ma; peak P–T = 5 kbar?700 °C) than in the PAG domain (1838 ± 5 Ma; peak P–T = 5 kbar?580 °C). Calculations indicate that this earlier monazite growth results from tectonic thickening of higher heat productivity Archean lithologies in the migmatite domain, which undergoes more rapid prograde heating than the less radiogenetic and lower grade rocks of the PAG domain. Granite generation via biotite dehydration melting at 800 °C and 20 km depth is predicted to occur c. 1835 Ma, in agreement with geochronological constraints. The tectonic burial of crustal domains with contrasting radiogenic properties also explains the general congruence of lower to upper amphibolite facies metamorphic zones generated during the two main orogenic cycles (i.e. M₂–D₁ and M₃–D₂). The modelled timing of prograde monazite growth in the migmatite domain suggests that D₂ tectonic thickening began at 1872 ± 9 Ma, some 8 ± 3 Myr before monzazite growth, coeval with the inferred time of collision of the Meta Incognita terrane with the southern Rae Province. Along‐strike diachroneity, reflected in 25 Myr younger monazite and ⁴⁰Ar–³⁹Ar hornblende ages in the eastern relative to the western PAG domain, cannot be accounted for by heat productivity contrasts along the belt. Instead the younger deformation and metamorphism in the eastern CBb was driven by its proximity to the eastern promontory of the Superior Province which collided with the Rae Province at c. 1820 Ma. The ⁴⁰Ar–³⁹Ar data presented here support the interpretation that the youngest monazite in the CBb crystallized at c. 1790 Ma in the central CBb when this part of the belt was downfolded into a gentle synformal structure while the western part of the belt cooled through ⁴⁰Ar–³⁹Ar hornblende closure. The results of this study illustrate the important influence of contrasting rock properties on the thermal evolution of orogenic belts and on the temporal record of this evolution.     

The crustal structure of the Eastern Alps from a combination of 3D gravity modelling and isostatic investigations

The transition between European and Adriatic crust is an important feature related to the plate collision that formed the European Alps. The diversity of seismic and geological information allows the construction of two alternative 3D density models, which both match the observed gravity field. Different seismic experiments suggest a thickness for the Adriatic crust between 30 and 40 km. The thick crust model requires an unusually dense lower crust (>3050 kg/m³) to reproduce the observed Bouguer anomaly. To evaluate the two alternative models, the isostatic implications of the geometry and density distribution within both 3D models are investigated, using local (Airy) and regional (Vening Meinesz) isostasy.Airy isostatic investigations show that the Eastern Alps are not isostatically compensated and the residuals correlate strongly with exposed geological formations. Subsequently, subsurface loading is an important factor controlling isostatic processes. The different geometry and densities in the two 3D models imply different loading at the crust–mantle boundary. The subsurface loads calculated from the 3D density models were used to estimate regional isostasy by a convolution method. In general, small rigidity values (D<10×10²¹ Nm) are determined for the Eastern Alpine lithosphere. In the model with a 40-km-thick Adriatic crust, high flexural rigidities are inferred for the Adriatic plate (>100×10²¹ Nm), but these values are unusual for an active orogenic region. The results point to the interfingering of European and Adriatic crust that results in the squeezing of European crust between Adriatic crust and mantle with additional contamination by mantle material.     

An attempt to separate Q from the Allende meteorite by physical methods

In order to characterize the planetary noble gas carrier Q, we separated a Q-rich floating fraction from the Allende meteorite into ten fractions by a combination of colloidal and density separations. All five noble gases in the separated fractions were analyzed by pyrolysis in 600 and 1600°C temperature steps. Half of Q in the floating fraction is concentrated in the fraction C1-8D with the density of 1.65 ± 0.04 g/cm³. All the separated fractions show similar isotopic ratios except for ⁴⁰Ar/³⁶Ar ratios. C1-8D has the lowest ³⁸Ar/³⁶Ar and ⁴⁰Ar/³⁶Ar ratios (0.18784 ± 0.00020 and 4.36 ± 0.15, respectively) in the 1600°C fraction, confirming that the fraction is enriched in Q. Most grains in C1-8D are carbonaceous with small amounts of F and O. These results imply either that the density of Q is 1.65 ± 0.04 g/cm³ or that Q preferentially sticks to matter of that density. All the separates have similar Q to diamond ratios, indicating that Q and diamond are closely associated.     

Comparison of microbial gases from the Middle America Trench and Scripps Submarine Canyon: implications for the origin of natural gas

Chemical and isotopic compositions have been measured on 62 microbial gases from Tertiary hemipelagic sediments in the Middle America Trench off Guatemala and from decaying kelp and surf grass currently accumulating in Scripps Submarine Canyon off southern California. Gases from the Middle America Trench have been generated primarily by the reduction of carbon dioxide; methane δ¹³C varies from −84‰ to −39‰, methane δD varies from −208‰ to −145‰, and carbon dioxide δ¹³ C varies from −27‰ to +28‰. Gases from Scripps Submarine Canyon have been generated primarily by acetate dissimilation; methane δ¹³ C varies from −63‰ to −43‰, methane δD varies from −331‰ to −280‰, and carbon dioxide δ¹³C varies from −17‰ to +3‰.Methane δ¹³C values as heavy as −40‰ appear to be uncommon for gases produced by carbon dioxide reduction and, in the Middle America Trench, are associated with unusually positive carbon dioxide δ¹³C values. However, based on the 25‰ intramolecular fractionation between acetate car☐yl carbon and methyl carbon estimated from the Scripps Submarine Canyon data, methane produced by acetate dissimilation may commonly have heavy δ¹³C values. The δD of methane derived from acetate is more negative than natural methanes from other origins. Microbial methane δD values appear to be controlled primarily by interstitial water δD and by the relative proportions of methane derived from carbon dioxide and acetate.The chemical and isotopic compositions of microbial gas and thermogenic gas overlap, making it difficult to determine the origins of many commercial natural gases from methane δ¹³C and C₂₊ hydrocarbon concentrations alone. Measurements of methane δD and carbon dioxide δ¹³C can provide useful additional information, and together with ethane δ¹³C data, help identify gases with mixed microbial and thermogenic origins.     

Effects of Fe and Al incorporations on the bridgmanite–postperovskite coexistence domain

The postperovskite phase transition of Fe and Al-bearing MgSiO₃ bridgmanite, the most aboundant mineral in the Earth's lower mantle, is believed to be a key to understanding seismological observations in the D″ layer, e.g., the discontinuous changes in seismic wave velocities. Experimentally reported phase transition boundaries of Fe and Al-bearing bridgmanite are currently largely controversial and generally suggest wide two-phase coexistence domains. Theoretical simulations ignoring temperature effects cannot evaluate correctly two-phase coexistence domains under high-temperature. We show high-pressure and high-temperature phase transition boundaries for various compositions with geophysically relevant impurities of Fe²⁺SiO₃, Fe³⁺Fe³⁺O₃, Fe³⁺Al³⁺O₃, and Al³⁺Al³⁺O₃ derived from the ab initio finite-temperature free energies calculated combining the internally consistent LSDA + U method and a lattice dynamics approach. We found that at ～ 2500 K, incorporations accompanied by Fe³⁺ expand the two-phase coexistence domains distinctly, implying that D″ seismic discontinuities likely arise from the phase transition of Fe²⁺-bearing bridgmanite.     

Helium isotope compositions in sedimentary basins in China

The abundance and isotopic composition of He have been determined for a variety of natural gases (oil-field gases) in sedimentary basins in the continent of China. The³He/⁴He and⁴He/²⁰Ne ratios range from 0.004 to 4.99 Ra (where Ra denotes atmospheric³He/⁴He ratio = 1.4 × 10⁻⁶), and from 100-39,000, respectively. Helium in the gas sample is composed of mantle-derived He and crustal radiogenic He.The high³He/⁴He ratios were observed in the sedimentary basins which underwent Cenozoic extension in the eastern domain, such as the Songliao, Liaohe, North China, Subei, Sanshui and South China Sea basins. The basins where mantle-derived He is recognized are characterized by the presence of surface and subsurface volcanic rocks, high terrestrial heat flow, deep faults and thinned crust. On the other hand, regions which underwent pre-Tertiary extension such as the Jungar, Tarim, Tuba, Caidam and Yumen basins in the NW and tectonic loading such as the Ordos and Sichuan basins in the central domain are marked by almost pure radiogenic⁴He of crustal origin and thus by an apparent absence of mantle-derived He, which coincides with complete lack of Cenozoic volcanics, low terrestrial heat flow and thickened crust. Such a³He/⁴He distribution pattern clearly indicates that tectonic environment control the distribution of He isotopes in the continent of China.     

Oxidation Experiment of Natural Megacrystal Clinopyroxene: Implications for Assignment of Mössbauer Spectra

The Mössbauer spectra of natural megacrystal clinopyroxene are usually fitted by 4 sets of symmetric doublets, A‐A', B‐B', C‐C' and D‐D', respectively, in terms of increasing Qs value in literature. But the assignments of those doublets are quite different, except the D‐D' doublet assigned to Fe³⁺at the lattice site M***1 in previous papers. Particularly, the assignment and interpretation of the C‐C' doublet are diverse. The oxidation experiments of natural megacrystal clinopyroxene collected from the Hannuoba basalt, North China, were performed under controlled conditions of temperature at 1000°C and oxygen fugacity of FMQ buffer in 1, 2, ***3 and 5 days respectively. The oxidized samples were then measured by X‐ray diffraction spectrometry and Mössbauer spectrometry. The oxidation of clinopyroxene is characterized by Fe²⁺ → Fe³⁺at M1 under the subsolidus conditions, which is consistent with the increase of the area of the D‐D' doublet when the heating time increases. Accordingly, the area of the A‐A' and B‐B' doublets decreases with the increasing heating time. However, the area of C‐C' keeps almost constant. Therefore, the 4 sets of doublets can be assigned correctly as follows: A‐A' doublet to Fe⁺²at M1, B‐B' Fe²⁺at M1, C‐C' Fe²⁺at M2, and D‐D' Fe³⁺at M1. The M1 site splitting is due to the NNN (Next Nearest Neighbour) effect of the M2 site. The amount of Fe³⁺at the tetrohedral site of megacrystal clinopyroxene is negligible according to this study.