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1.
《Gondwana Research》2011,19(4):632-637
In South China, the Datangpo black shales (663 Ma–654.5 Ma) were deposited during the Cryognian interglacial time between the Sturtian and Marinoan glaciations. Multi-geochemical proxies, including different iron speciation and relevant ratios (FeHR/FeT, FeP/FeHR and FeT/Al ratios) and molybdenum concentrations, were used to reconstruct the paleo-depositional environment of this black shale horizon. The ratios of different iron species (FeHR/FeT > 0.38 and FeP/FeHR < 0.80) suggest an overall anoxic conditions (ferruginous) over the deposition of the black shales, although intermittent euxinic (FeHR/FeT > 0.38 and FeP/FeHR ≈ 0.80) and oxic (FeHR/FeT < 0.38) intervals could have occurred. Furthermore, FeT/Al ratios (FeT/Al ≤ 0.51) confirm that water column may not be persistent euxinia during the deposition of the Datangpo black shales. Meanwhile, molybdenum concentrations show a decreasing trend towards the top of the black shales, reconciling the gradual oxygenating trend during this period as stated above. Compared to δ34SPy values in the Mesoproterozoic deep ocean, more positive δ34SPy values of this study may result from a small size of sulfate reservoir. The small-size sulfate reservoir and concurrent enrichment of molybdenum indicate that the ocean chemistry in the Cryogenian Period is similar to that in the Archean Eon.  相似文献   

2.
Oxygenation of the Earth's atmosphere occurred in two major steps, near the beginning and near the end of the Proterozoic Eon (2500 to 542 Ma ago), but the details of this history are unclear. Chromium isotopes in iron-rich chemical sediments offer a potential to highlight fine-scale fluctuations in the oxygenation of the oceans and atmosphere and to add a further dimension in the use of redox-sensitive tracers to solve the question regarding fluctuations of atmospheric oxygen levels and their consequences for Earth's climate. We observe strong positive fractionations in Cr isotopes (δ53Cr up to + 5.0‰) in iron-rich cherts and banded iron formation horizons within the Arroyo del Soldado Group (Ediacaran; Uruguay) that can be explained by rapid, effective oxidation of Fe(II)-rich surface waters. These fluctuations are correlated with variations in ratios of highly reactive iron (FeHR) to total iron (Fetot) which indicate a predominance of anoxic water columns (FeHR/Fetot > 0.38) during the onset of oxidation pulses. We favor the scenario by which isotopically heavy Cr(VI) entered the basin after pulses of oxidative weathering on land and in which Fe(II) accumulated in the water column. Neodymium isotopes reveal that these oxygenation pulses were followed by increased influxes to the basin of continental crust-derived detrital components of Paleoproterozoic (Nd TDM model ages = 2.1–2.2 Ga) provenance typical of the Rio de la Plata Craton. The association of positive δ53Cr–ferruginous (FeHR/Fetot > 0.38) stratigraphic intervals with low-diversity acritarch assemblages dominated by Bavlinella faveolata strongly support models postulating a stratified, eutrophic Neoproterozoic ocean. Thus, even within a few million years of the Precambrian–Cambrian boundary, paleoceanographic conditions resembled more those of Paleoproterozoic oceans than Phanerozoic and present oceans. This highlights the sheer magnitude of ecological changes at the Precambrian–Cambrian transition, changes which ultimately led to the demise of the Precambrian world and the birth of the metazoan-dominated Phanerozoic.  相似文献   

3.
The in situ electrical conductivity of hydrous garnet samples (Py20Alm76Grs4–Py73Alm14Grs13) was determined at pressures of 1.0–4.0 GPa and temperatures of 873–1273 K in the YJ-3000t apparatus using a Solartron-1260 impedance/gain-phase analyzer for various chemical compositions and oxygen fugacities. The oxygen fugacity was controlled by five solid-state oxygen buffers (Fe2O3 + Fe3O4, Ni + NiO, Fe + Fe3O4, Fe + FeO, and Mo + MoO2). Experimental results indicate that within a frequency range from 10−2 to 106 Hz, electrical conductivity is strongly dependent on signal frequency. Electrical conductivity shows an Arrhenius increase with temperature. At 2.0 GPa, the electrical conductivity of anhydrous garnet single crystals with various chemical compositions (Py20Alm76Grs4, Py30Alm67Grs3, Py56Alm43Grs1, and Py73Alm14Grs13) decreases with increasing pyrope component (Py). With increasing oxygen fugacity, the electrical conductivity of dry Py73Alm14Grs13 garnet single crystal shows an increase, whereas that of a hydrous sample with 465 ppm water shows a decrease, both following a power law (exponents of 0.061 and −0.071, respectively). With increasing pressure, the electrical conductivity of this hydrous garnet increases, along with the pre-exponential factors, and the activation energy and activation volume of hydrous samples are 0.7731 ± 0.0041 eV and −1.4 ± 0.15 cm3/mol, respectively. The results show that small hopping polarons ( \textFe\textMg · ) \left( {{\text{Fe}}_{\text{Mg}}^{ \cdot } } \right) and protons ( \textH · {\text{H}}^{ \cdot } ) are the dominant conduction mechanisms for dry and wet garnet single crystals, respectively. Based on these results and the effective medium theory, we established the electrical conductivity of an eclogite model with different mineral contents at high temperatures and high pressures, thereby providing constraints on the inversion of field magnetotelluric sounding results in future studies.  相似文献   

4.
Marine black shales of the Lower Cambrian Niutitang Formation in southern China host Mo–Ni–platinum group elements (PGE) mineralization confined to a phosphate- and pyrite-rich stratiform body (max. 20-cm thick). The H/C atomic ratio, carbon isotopic composition, FTIR spectra of bulk organic matter, and spectra of extractable part of organic matter indicate similar sources and thermal evolution of organic matter in barren and mineralized black shales.The morphology and relative abundance of organic particles in barren and mineralized shales are different. In barren black shales, organic particles comprise only elongated bodies and laminae 2–10 μm across or elongated larger bodies (> 10 μm) with Rmax = 2.96–5.21% (Type I particles). Mineralized black shales contain Type I particles in rock matrix (90–95 vol%), small veinlets or irregular organic accumulations (Type II particles, 1–5 vol%) that display weak to well developed mosaic texture and a variable reflectance (Rmax = 3.55–8.65%), and small (< 1 to 5 μm) rounded or irregular Type III organic particles (1–4 vol%) distributed within phosphate nodules and sulphide rip-up clasts. Type III particles show similar reflectance as particles of Type I in rock matrix. Type I particles are interpreted as remnants of in situ bacterially reworked organic matter of cyanobacteria/algal type, Type II as solidified products or oil-derived material (migrabitumen), and Type III particles as remnants of original organic matter in phosphatized or sulphidized algal/microbial oncolite-like bodies. Equivalent vitrinite reflectances of Type I and III particles in barren and mineralized rocks are similar and correspond to semi-anthracite and anthracite. Micro-Raman spectra of organic particles in rocks display a wide belt in the area of 1600 cm− 1 (G belt) and approximately the same belt in the area of 1350 cm− 1 (D belt). The ratio of integrated areas of the two belts correlate with Rmax values.The Mo–Ni–PGE mineralized body is interpreted as to represent a remnant of phosphate- and sulphide-rich subaquatic hardground supplied with organic material derived from plankton and benthic communities as well as with algal/microbial oncolite-like bodies that originated in wave-agitated, shallow-water, nearshore environment.  相似文献   

5.
A reversal of the conventional carbon isotope relationship, “terrestrial-lighter-than-marine” organic matter, has been documented for two Pennsylvanian (Desmoinesian) cyclothemic sequence cores from the Midcontinent craton of the central United States. “Deep” water organic-rich phosphatic black shales contain a significant proportion of algal-derived marine organic matter (as indicated by organic petrography, Rock-Eval hydrogen index and ratios) and display the lightest δ13C-values (max −27.80‰ for kerogen) while shallower water, more oxic facies (e.g. fossiliferous shales and limestones) contain dominantly terrestrial organic matter and have heavier δ13Ckerogen-values (to −22.87‰ for a stratigraphically adjacent coal). δ13C-values for extract fractions were relatively homogeneous for the organic-rich black shales with the lightest fraction (often the aromatics) being only 1‰, or less, more negative than the kerogen. Differences between extract fractions and kerogens were much greater for oxic facies and coals (e.g. saturates nearly 5‰ lighter than the kerogen).A proposed depositional model for the black shales calls upon a large influx of nutrients and humic detritus to the marine environment from the laterally adjacent, extremely widespread Pennsylvanian (peat) swamps which were rapidly submerged by transgression of the epicontinental seas. In this setting marine organisms drew upon a CO2-reservoir which was in a state of disequilibrium with the atmosphere, being affected by isotopically light “recycled-CO2” derived from the decomposition of peaty material in the water column and possibly from the anoxic diagenesis of organic matter in the sediments.  相似文献   

6.
Metasomatic oxidation of upper mantle periodotite   总被引：1，自引：0，他引：1  
Examination of Fe3+ in metasomatized spinel peridotite xenoliths reveals new information about metasomatic redox processes. Composite xenoliths from Dish Hill, California possess remnants of magmatic dikes which were the sources of the silicate fluids responsible for metasomatism of the peridotite part of the same xenoliths. Mössbauer spectra of mineral separates taken at several distances from the dike remnants provide data on Fe3+ contents of minerals in the metasomatized peridotite. Clinopyroxenes contain 33% of total iron (FeT) as Fe3+ (Fe3+/FeT=0.33); orthopyroxenes contain 0.06–0.09 Fe3+/FeT; spinels contain 0.30–0.40 Fe3+/FeT; olivines contain 0.01–0.06 Fe3+/FeT; and metasomatic amphibole in the peridotite contains 0.85–0.90 Fe3+/FeT. In each mineral, Fe3+ and Fe2+ cations per formula unit (p.f.u.) decrease with distance from the dike, but the Fe3+/FeT ratios of each mineral do not vary. Clinopyroxene, spinel, and olivine Fe3+/FeT ratios are significantly higher than in unmetasomatized spinel peridotites. Metasomatic changes in Fe3+/FeT ratios in each mineral are controlled by the oxygen fugacity of the system, but the mechanism by which each phase accommodates this ratio is affected by crystal chemistry, kinetics, rock mode, fluid composition, fluid/rock ratio, and fluid-mineral partition coefficients. Ratio increases in pyroxene and spinel occur by exchange reactions involving diffusion of Fe3+ into existing mineral grains rather than by oxidation of existing Fe2+ in peridotite mineral grains. The very high Fe3+/FeT ratio in the metasomatic amphibole may be a function of the high Fe3+/FeT of the metasomatic fluid, crystal chemical limitations on the amount of Fe3+ that could be accommodated by the pyroxene, spinel, and olivine of the peridotite, and the ability of the amphibole structure to accommodate large amounts of 3 + valence cations. In the samples studied, metasomatic amphibole accounts for half of the bulk-rock Fe2O3. This suggests that patent metasomatism may produce a greater change in the redox state of mantle peridotite than cryptic metasomatism. Comparison of the metasomatized samples with unmetasomatized peridotites reveals that both Fe2+ and Fe3+ cations p.f.u. were increased during metasomatism and 50% or more of iron added was Fe3+. With increasing distance from the dike, the ratio of added Fe3+ to added Fe2+ increases. The high Fe3+/FeT of amphibole and phlogopite in the dikes and in the peridotite, and the high ratios of added Fe3+/added Fe2+ in pyroxenes and spinel suggest that the Fe3+/FeT ratio of the metasomatic silicate fluid was high. As the fluid perolated through and reacted with the peridotite, Fe3+ and C–O–H volatile species were concentrated in the fluid, increasing the fluid Fe3+/FeT.  相似文献   

7.
The Upper Permian Xuanwei Formation widely occurs in western Guizhou, unconformably overlying the Emeishan basalts, and mainly consists of black shales. It is ∼170 m thick at Cuyudong Village, Weining County, West Guizhou, China, where the samples of black shale and sandy shale were collected and analyzed. The shales mainly contain SiO2, 18.9%–44.1%, Al2O3, 14.8%–52.8%, Fe2O3, 1.0%–41.2%, LOI, 3.2%–21.1%, TiO2, 1.0%–6.7%, and MgO, 0.2%–2.5%. The contents of all other major elements are lower than 1.0%. It is shown that the black shales have higher contents of Fe2O3 and LOI than normal shales. The siderites occurred in the black shales with higher contents of Fe2O3, which may be attributed to hydrothermal activities on seafloor. All analyzed shale samples have extremely high Ga, 47.8×10−6–109.9×10−6 (70.5×10−6 on average), higher than the industrial mining standard of Ga Resource Industry Standard. The total contents of rare-earth elements (REE) of 9 black shale samples vary from 213×10−6 to 1460×10−6, suggesting that these black shales are enriched in REE. The shale-normalized REE patterns display both positive and negative Ce anomalies (Ce/Ce* from 0.5 to 1.7), revealing that the Xuanwei shales were precipitated under oxic and anoxic conditions. The Rb-Sr chronological diagram of 6 shale samples in the Xuanwei Formation shows an age of 255±12 Ma. Strontium isotopic ratios (87Sr/86Sr)t0 range from 0.70635 to 0.70711, suggesting that these Xuanwei black shales might be derived from chemical weathering of the Emeishan basalts.  相似文献   

8.
The Happo-O’ne peridotite complex is situated in the northeastern part of the Hida Marginal Tectonic Zone, central Japan, characterized by the high-P/T Renge metamorphism, and is considered as a serpentinite mélange of Paleozoic age. Peridotitic rocks, being massive or foliated, have been subjected to hydration and metamorphism. Their protoliths are mostly lherzolites to harzburgites with subordinate dunites. We found a characteristic mineral assemblage, olivine + orthopyroxene + tremolite + chlorite + chromian spinel, being stable at low-T, from 650 to 750°C, and high-P, from 16 to 20 kbar, tremolite–chlorite peridotites of the tremolite zone. Olivines are Fo88–Fo91, and orthopyroxenes (Mg# = 0.91) show low and homogenous distributions of Al2O3 (up to 0.25 wt%), Cr2O3 (up to 0.25 wt%), CaO (up to 0.36 wt%) and TiO2 (up to 0.06 wt%) due to the low equilibration temperature. Chromian spinels, which are euhedral and enclosed mainly in the orthopyroxenes, have high TiO2, 3.1 wt% (up to 5.7 wt%) on average, and high Cr# [=Cr/(Cr + Al) atomic ratio], 0.95 on average but low Fe3+ [=Fe3+/(Cr + Al + Fe3+) atomic ratio, <0.3]. The bulk-rock chemistry shows that the Happo-O’ne metaperidotites with this peculiar spinel are low in TiO2 (0.01–0.02 wt%), indicating no addition of TiO2 from the outside source during the metamorphism; the high TiO2 of the peculiar spinel has been accomplished by Ti release from Ti-bearing high-T pyroxenes during the formation of low-T, low-Ti silicates (<0.1 wt% TiO2) during cooling. Some dunites are intact from hydration: their olivine is Fo92 and spinel shows high Cr#, 0.72. The Happo-O’ne metaperidotites (tremolite–chlorite peridotites), being in the corner of the mantle wedge, are representative of a hydrous low-T, high-P mantle peridotite facies transitional from a higher T anhydrous peridotite facies (spinel peridotites) formed by in situ retrograde metamorphism influenced by fluids from the subducting slab. They have suffered from low-T (<600°C) retrogressive metamorphism to form antigorite and diopside during exhumation of the Renge metamorphic belt.  相似文献   

9.
Nitrogen geochemistry of Upper Carboniferous shales from the Central European Basin (CEB) was investigated by elemental analysis, stable isotope mass spectrometry and non-isothermal pyrolysis. Total N-contents of Namurian shales from four deep wells (4400–7000 m) in NE Germany ranged between 520 and 2680 ppm. Up to 90% of this nitrogen occurs as ammonium in minerals with δ15N values between + 1‰ and + 3.5‰. Low nitrogen contents (down to 460 ppm) and high δ15N values (up to + 5.6‰) in one well in the basin centre suggest a large-scale release of nitrogen associated with isotopic fractionation. Pyrolytic liberation of N2 from pelagic Namurian A shales of NW and NE Germany occurred at significantly lower temperatures than from paralic Namurian B shales and terrestrial Westphalian samples. On-line isotope analysis of N2 liberated between 400 and 1200 °C indicates the presence of precursor pools with different thermal stability and nitrogen isotopic composition.  相似文献   

10.
The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al2O3 and TiO2, SiO2, K2O, and Na2O, and strong negative correlations between Al2O3 and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K2O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ13C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO3? from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter.  相似文献   

11.
A revised regular solution-type thermodynamic model for twelve-component silicate liquids in the system SiO2-TiO2-Al2O3-Fe2O3-Cr2O3-FeO-MgO-CaO-Na2O-K2O-P2O5-H2O is calibrated. The model is referenced to previously published standard state thermodynamic properties and is derived from a set of internally consistent thermodynamic models for solid solutions of the igneous rock forming minerals, including: (Mg,Fe2+,Ca)-olivines, (Na,Mg,Fe2+,Ca)M2 (Mg,Fe2+, Ti, Fe3+, Al)M1 (Fe3+, Al,Si)2 TETO6-pyroxenes, (Na,Ca,K)-feldspars, (Mg,Fe2+) (Fe3+, Al, Cr)2O4-(Mg,Fe2+)2 TiO4 spinels and (Fe2+, Mg, Mn2+)TiO3-Fe2O3 rhombohedral oxides. The calibration utilizes over 2,500 experimentally determined compositions of silicate liquids coexisting at known temperatures, pressures and oxygen fugacities with apatite ±feldspar ±leucite ±olivine ±pyroxene ±quartz ±rhombohedral oxides ±spinel ±whitlockite ±water. The model is applicable to natural magmatic compositions (both hydrous and anhydrous), ranging from potash ankaratrites to rhyolites, over the temperature (T) range 900°–1700°C and pressures (P) up to 4 GPa. The model is implemented as a software package (MELTS) which may be used to simulate igneous processes such as (1) equilibrium or fractional crystallization, (2) isothermal, isenthalpic or isochoric assimilation, and (3) degassing of volatiles. Phase equilibria are predicted using the MELTS package by specifying bulk composition of the system and either (1) T and P, (2) enthalpy (H) and P, (3) entropy (S) and P, or (4) T and volume (V). Phase relations in systems open to oxygen are determined by directly specifying the f o 2 or the T-P-f o 2 (or equivalently H-P-f o 2, S-P-f o 2, T-V-f o 2) evolution path. Calculations are performed by constrained minimization of the appropriate thermodynamic potential. Compositions and proportions of solids and liquids in the equilibrium assemblage are computed.  相似文献   

12.
The effects of low-temperature on the crystal structure of a natural epidote [Ca1.925Fe0.745Al2.265Ti0.004Si3.037O12(OH), a = 8.8924(7), b = 5.6214(3), c = 10.1547(6)? and β = 115.396(8)° at room conditions, Sp. Gr. P21 /m] have been investigated with a series of structure refinements down to 100 K on the basis of X-ray single-crystal diffraction data. The reflection conditions confirm that the space group is maintained within the T-range investigated. Structural refinements at all temperatures show the presence of Fe3+ at the octahedral M(3) site only [%Fe(M3) = 70.6(4)% at 295 K]. Only one independent proton site was located and two possible H-bonds occur, with O(10) as donor and O(4) and O(2) as acceptors. The H-bonding scheme is maintained down to 100 K and is supported by single crystal room-T polarised FTIR data. FTIR Spectra over the region 4,000–2,500 cm−1 are dominated by the presence of a strongly pleochroic absorption feature which can be assigned to protonation of O(10)–O(4). Previously unobserved splitting of this absorption features is consistent with a NNN influence due to the presence of Al and Fe3+ on the nearby M(3) site. An additional relatively minor absorption feature in FTIR spectra can be tentatively assigned to protonation of O(10)–O(2). Low-T does not affect significantly the tetrahedral and octahedral bond distances and angles, even when distances are corrected for “rigid body motions”. A more significant effect is observed for the bond distances of the distorted Ca(1)- and Ca(2)-polyhedra, especially when corrected for “non-correlated motion”. The main low-T effect is observed on the vibrational regime of the atomic sites, and in particular for the two Ca-sites. A significant reduction of the magnitude of the thermal displacement ellipsoids, with a variation of U eq (defined as one-third of the trace of the orthogonalised U ij tensor) by ~40% is observed for the Ca-sites between 295 and 100 K. Within the same T-range, the U eq of the octahedral and oxygen sites decrease similarly by ~35%, whereas those of the tetrahedral cations by ~22%.  相似文献   

13.
The bulk (post-eruptive) wt% FeO concentration in each of 11 phenocryst-poor (<5%) andesite and dacite (60–69 wt% SiO2) lavas from different monogenetic vents in the Mexican arc has been measured by titration, in duplicate. The results match, within analytical error, the wt% FeO content of the magmas during phenocryst growth (pre-euptive), which were calculated on the basis of oxygen fugacity and temperature results from Fe–Ti two-oxide oxygen barometry. The average deviation between the pre- and post-eruptive FeO concentrations is ±0.15 wt%. Application of the plagioclase-liquid hygrometer shows that at the time of phenocryst growth, these 11 magmas contained from ~3–8 wt% H2O, which was extensively degassed upon eruption. There is no evidence that degassing of ≤8 wt% H2O changed the oxidation state of these magmas. Calculations of pre-eruptive and post-eruptive oxygen fugacity values relative to the Ni-NiO buffer (in terms of log10 units) for the 11 samples span a similar range; pre-eruptive ∆NNO = −0.9 to +0.7 and post-eruptive ∆NNO = −0.4 to +0.8. The data further show that extensive groundmass (closed-system) crystallization had no affect on bulk Fe3+/Fe2+ ratios. Finally, there is no systematic variation in the range of pre-eruptive Fe3+/FeT values of the samples as a function of SiO2 concentration (i.e., differentiation). Therefore, the results of this study indicate that the elevated Fe3+/FeT ratios of arc andesites and dacites, compared with magmas erupted in other tectonic settings, cannot be attributed to the effects of (1) degassing of H2O, (2) closed-system crystallization, and/or (3) differentiation effects, but instead must be inherited from their parental source rocks (i.e., mantle-derived arc basalts).  相似文献   

14.
Ilvaite, Ca(Fe2+,Fe3+)Fe2+Si2O8(OH) shows two magnetic phase transitions, which have been studied by Mössbauer spectroscopy within the temperature range 120–4 K. The continued charge localization between Fe2+ and Fe3+ ions in octahedral A-sites causes the Fe2+-Fe3+ interaction to be ferromagnetic, although the overall magnetic order is antiferromagnetic. The thermal evolution of the hyperfine fields at the Fe2+ (A) and Fe3+ (A) sites indicates B hf: 328 and 523 kOe respectively at 0 K and T N1= 116K. The corresponding values for Fe2+ (B) site are: B hf 186 kOe and T N2=36K. An additional hyperfine field exists at the Fe2+(B) site within the temperature range 116–36K due to short-range order induced by the spin ordering in A sites. The considerable difference between the two magnetic transition temperatures is due to spin frustration, because the Fe2+ (B) site occurs on a corner common between two triangles with respect to two sets of Fe2+ (A) and Fe3+ (A) sites with opposite spin directions.  相似文献   

15.
Albian pelagic successions of the Nebeur area in northwestern Tunisia consist of radiolarian-bearing and organic-rich black shale beds, which represent the lower part of the Fahdene Formation. The carbonate content of the organic-rich beds ranges between 40 and 48%. Total organic carbon (TOC) analyses via Rock Eval pyrolysis yielded values ranging between 0.7 and 2.8% and a mixed marine/terrestrial origin. Tmax values vary between 424 and 450 °C, indicative of submature to mature organic matter. High resolution planktic foraminiferal and radiolarian biostratigraphy suggest that the black shales beds span the mid- to late Albian, confined to the middle part of the Ticinella primula zone, upper Biticinella breggiensis zone and lower appeninica + buxtorfi zone. Episodes of organic-rich deposition in the “Tunisian Trough” are interpreted as being the sedimentary record of the global oceanic anoxic events OAE1b, c, and d respectively. Age-diagnostic radiolarian assemblages recovered from late Albian organic-rich black shales lie within the UA13–UA14 boundary biochronozones. The abundance of radiolarian and calcispheres (i.e. pithonella) within the black shales suggests high productivity periods and eutrophic conditions probably triggered by upwelling currents.  相似文献   

16.
The stability of pumpellyite + actinolite or riebeckite + epidote + hematite (with chlorite, albite, titanite, quartz and H2O in excess) mineral assemblages in LTMP metabasite rocks is strongly dependent on bulk composition. By using a thermodynamic approach (THERMOCALC), the importance of CaO and Fe2O3 bulk contents on the stability of these phases is illustrated using P–T and P–X phase diagrams. This approach allowed P–T conditions of ～4.0 kbar and ～260 °C to be calculated for the growth of pumpellyite + actinolite or riebeckite + epidote + hematite assemblages in rocks containing variable bulk CaO and Fe2O3 contents. These rocks form part of an accretionary wedge that developed along the east Australian margin during the Carboniferous–Triassic New England Orogen. P–T and P–X diagrams show that sodic amphibole, epidote and hematite will grow at these conditions in Fe2O3‐saturated (6.16 wt%) metabasic rocks, whereas actinolite and pumpellyite will be stable in CaO‐rich (10.30 wt%) rocks. With intermediate Fe2O3 (～3.50 wt%) and CaO (～8.30 wt%) contents, sodic amphibole, actinolite and epidote can coexist at these P–T conditions. For Fe2O3‐saturated rocks, compositional isopleths for sodic amphibole (Al3+ and Fe3+ on the M2 site), epidote (Fe3+/Fe3+ + Al3+) and chlorite (Fe2+/Fe2+ + Mg) were calculated to evaluate the efficiency of these cation exchanges as thermobarometers in LTMP metabasic rocks. Based on these calculations, it is shown that Al3+ in sodic amphibole and epidote is an excellent barometer in chlorite, albite, hematite, quartz and titanite buffered assemblages. The effectiveness of these barometers decreases with the breakdown of albite. In higher‐P stability fields where albite is absent, Fe2+‐Mg ratios in chlorite may be dependent on pressure. The Fe3+/Al and Fe2+/Mg ratios in epidote and chlorite are reliable thermometers in actinolite, epidote, chlorite, albite, quartz, hematite and titanite buffered assemblages.  相似文献   

17.
The chromites from the alpine type ultramafic intrusive of Sukinda, India, display a typical partly inverse spinel form and occur in two distinct zones: Brown Ore Zone (BOZ) and Grey Ore Zone (GOZ). The host ultramafites are mostly altered and are represented by the serpentinite, tremolite-talc(chlorite) schist, talc-serpentine schist and chlorite rock. The less altered variants are dunite, harzburgite and websterite. A dyke of orthopyroxenite runs through the main ultramafic body.The composition of olivine (Fo92), orthopyroxene (En92–89) and Al2O3 contents of the parental liquid (10.40–11.45%) determined from chromites, suggest that the parent melt is of boninitic affinity. The chemical plot of TiO2 content against cr# of chromites corroborates a boninitic parental melt. The Fe–Mg partitioning in olivine and chromite depicts the temperature for chromitites as 1200 °C. A compositional plot of mg# and cr# suggests crystallization at high pressure conditions, corresponding to the kimberlite xenolith field. From the P–T diagram of pyrolite melting and mineral assemblage, the pressure of crystallization is stipulated to be ≥1.2 GPa. The fO2 values estimated from Fe3+/Cr+Al+Fe3+ ratios range from 10−8.3 to 10−9.3 for the GOZ and 10−7.1 to 10−7.3 for the BOZ. The fO2 values together with the pressure range suggest crystallization at upper mantle conditions. The heterogeneity in chemical composition and fO2 conditions for the GOZ and BOZ could be linked to heterogeneity in the upper mantle.  相似文献   

18.
OH in zoned amphiboles of eclogite from the western Tianshan,NW-China   总被引：1，自引：0，他引：1  
Chemically-zoned amphibole porphyroblast grains in an eclogite (sample ws24-7) from the western Tianshan (NW-China) have been analyzed by electron microprobe (EMP), micro Fourier-transform infrared (micro-FTIR) and micro-Raman spectroscopy in the OH-stretching region. The EMP data reveal zoned amphibole compositions clustering around two predominant compositions: a glaucophane end-member ( B Na2 C M2+ 3 M3+ 2 T Si8(OH)2) in the cores, whereas the mantle to rim of the samples has an intermediate amphibole composition ( A 0.5 B Ca1.5Na0.5 C M 2+ 4.5 M 0.53+ T Si7.5Al0.5(OH)2) (A = Na and/or K; M 2+ = Mg and Fe2+; M 3+ = Fe3+ and/or Al) between winchite (and ferro-winchite) and katophorite (and Mg-katophorite). Furthermore, we observed complicated FTIR and Raman spectra with OH-stretching absorption bands varying systematically from core to rim. The FTIR/Raman spectra of the core amphibole show three lower-frequency components (at 3,633, 3,649–3,651 and 3,660–3,663 cm−1) which can be attributed to a local O(3)-H dipole surrounded by M(1) M(3)Mg3, M(1) M(3)Mg2Fe2+ and M(1) M(3) Fe2+ 3, respectively, an empty A site and T Si8 environments. On the other hand, bands at higher frequencies (3,672–3,673, 3,691–3,697 and 3,708 cm−1) are observable in the rims of the amphiboles, and they indicate the presence of an occupied A site. The FTIR and Raman data from the OH-stretching region allow us to calculate the site occupancy of the A, M(1)–M(3), T sites with confidence when combined with EPM data. By contrast M(2)- and M(4) site occupancies are more difficult to evaluate. We use these samples to highlight on the opportunities and limitations of FTIR OH-stretching spectroscopy applied to natural high pressure amphibole phases. The much more detailed cation site occupancy of the zoned amphibole from the western Tianshan have been obtained by comparing data from micro-chemical and FTIR and/or Raman in the OH-stretching data. We find the following characteristic substitutions Si(T-site) (Mg, Fe)[M(1)–M(3)-site] → Al(T-site) Al[M(1)–M(3)-site] (tschermakite), Ca(M4-site)□ (A-site) → Na(M4-site) Na + K(A-site) (richterite), and Ca(M4-site) (Mg, Fe) [M(1)–M(3)-site] → Na(M4-site) Al[M(1)–M(3)-site] (glaucophane) from the configurations observed during metamorphism.  相似文献   

19.
Ocean Drilling Program Leg 207 recovered thick sequences of Albian to Santonian organic-carbon-rich claystones at five drill-sites on the Demerara Rise in the western equatorial Atlantic Ocean. Dark-colored, finely laminated, Cenomanian–Santonian black shale sequences contain between 2% and 15% organic carbon and encompass Oceanic Anoxic Events 2 and 3. High Rock-Eval hydrogen indices signify that the bulk of the organic matter in these sequences is marine in origin. However, δ13Corg values lie mostly between −30‰ and −27‰, and TOC/TN ratios range from 15 to 42, which both mimic the source signatures of modern C3 land plants. The contradictions in organic matter source indicators provide important implications about the depositional conditions leading to the black shale accumulations. The low δ13Corg values, which are actually common in mid-Cretaceous marine organic matter, are consequences of the greenhouse climate prevailing at that time and an associated accelerated hydrologic cycle. The elevated C/N ratios, which are also typical of black shales, indicate depressed organic matter degradation associated with low-oxygen conditions in the water column that favored preservation of carbon-rich forms of marine organic matter over nitrogen-rich components. Underlying the laminated Cenomanian–Santonian sequences are homogeneous, dark-colored, lower to middle Albian siltstones that contain between 0.2% and 9% organic carbon. The organic matter in these rocks is mostly marine in origin, but it occasionally includes large proportions of land-derived material.  相似文献   

20.
Natural Fe2+, Fe3+-bearing spinel solid solutions from the spinel s.s.-hercynite and gahnite-hercynite series were analyzed and studied by electronic absorption spectroscopy in the spectral range 30000–3500 cm–1 in the temperature and pressure ranges 77 TK 600 and 10–4 PGPa 11.0. Two crystals were light-violet in color (type I) and six green or bluish-green (type II). The spectra of both types of spinels are dominated by an UV-absorption edge near 28000 to 24000 cm–1, depending on the iron contents, and a very intense band system in the NIR centered around 5000 cm–1, which is caused by spin-allowed dd-transition of tetrahedral Fe2+, derived from 5 E5 T2. The strong band is in all spinels studied, split into four sub-bands, which can only be observed in very thin platelets. Between the UV-edge and the high-energy wing of the NIR-band there occur a number of very weak bands in type I spinels while the green type II spinels show some of these with significantly enhanced intensity. The intensity of the very weak bands is nearly independent from temperature. Such bands are attributed to spin-forbidden electronic transitions of IVFe2+. Temperature and pressure dependence of the intensity enhanced bands of spinels type II indicate that they are caused by IVFe2+ and VIFe3+. They are attributed to spin-forbidden transitions 6A1g4A1g, 4Eg, 4T2g and 4T1g of VIFe3+, the two latter being strongly intensified by exchange-coupling interaction with adjacent IVFe2+. The pressure dependence of IVFe2+ dd-band system in the NIR caused by spin-allowed 5 E5 T2 transition noticeably differs from that of octahedral Fe2+, an effect which is attributed to a dynamic Jahn-Teller effect of IVFe2+ in the spinel structure.
Monika Koch-MüllerEmail: Phone: +49-331-288-1492/1402Fax: +49-331-288-1492/1402
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