Weathering Processes in the Min Jiang: Major Elements, {}^{87}{\text{Sr/}}{}^{86}{\text{Sr}},\;\delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } ,\;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} }     

Junyeon Yoon  Youngsook Huh  Insung Lee  Seulgi Moon  Hyonjeong Noh  Jianhua Qin 《Aquatic Geochemistry》2008,14(2):147-170

We investigated the dissolved major elements, $ {}^{87}{\text{Sr/}}{}^{86}{\text{Sr}},\;\delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } ,\;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} } $ composition of the Min Jiang, a headwater tributary of the Chang Jiang (Yangtze River). A forward calculation method was applied to quantify the relative contribution to the dissolved load from rain, evaporite, carbonate, and silicate reservoirs. Input from carbonate weathering dominated the major element composition (58–93%) and that from silicate weathering ranged from 2 to 18% in unperturbed Min Jiang watersheds. Most samples were supersaturated with respect to calcite, and the CO₂ partial pressures were similar to or up to ～5 times higher than atmospheric levels. The Sr concentrations in our samples were low (1.3–2.5 μM) with isotopic composition ranging from 0.7108 to 0.7127, suggesting some contribution from felsic silicates. The Si/(Na^* + K) ratios ranged from 0.5 to 2.5, which indicate low to moderate silicate weathering intensity. The $ \delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } \;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} } $ for five select samples showed that the source of dissolved sulfate was combustion of locally consumed coal. The silicate weathering rates were 23–181 × 10³ mol/km²/year, and the CO₂ consumption rates were 31–246 × 10³ mol/km²/year, which are moderate on a global basis. Upon testing various climatic and geomorphic factors for correlation with the CO₂ consumption rate, the best correlation coefficients found were with water temperature (r ² = 0.284, p = 0.009), water discharge (r ² = 0.253, p = 0.014), and relief (r ² = 0.230, p = 0.019).  相似文献   

Stabilitätsbeziehungen zwischen Chlorit,Cordierit und Almandin bei der Metamorphose     

Dr. Achim Hirschberg  Helmut G. F. Winkler 《Contributions to Mineralogy and Petrology》1968,18(1):17-42

The stability relations between cordierite and almandite in rocks, having a composition of CaO poor argillaceous rocks, were experimentally investigated. The starting material consisted of a mixture of chlorite, muscovite, and quartz. Systems with widely varying Fe²⁺/Fe²⁺+Mg ratios were investigated by using two different chlorites, thuringite or ripidolite, in the starting mixture. Cordierite is formed according to the following reaction: $${\text{Chlorite + muscovite + quartz}} \rightleftharpoons {\text{cordierite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} + {\text{H}}_{\text{2}} {\text{O}}$$ . At low pressures this reaction characterizes the facies boundary between the albite-epidotehornfels facies and the hornblende-hornfels facies, at medium pressures the beginning of the cordierite-amphibolite facies. Experiments were carried out reversibly and gave the following equilibrium data: 505±10°C at 500 bars H₂O pressure, 513±10°C at 1000 bars H₂O pressure, 527±10°C at 2000 bars H₂O pressure, and 557±10°C at 4000 bars H₂O pressure. These equilibrium data are valid for the Fe-rich starting material, using thuringite as the chlorite, as well as for the Mg-rich starting mixture with ripidolite. At 6000 bars the equilibrium temperature for the Mg-rich mixture is 587±10°C. In the Fe-rich mixture almandite was formed instead of cordierite at 6000 bars. The following reaction was observed: $${\text{Thuringite + muscovite + quartz}} \rightleftharpoons {\text{almandite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + H}}_{\text{2}} {\text{O}}$$ . Experiments with the Fe-rich mixture, containing Fe²⁺/Fe²⁺+Mg in the ratio 8∶10, yielded three stability fields in a P,T-diagram (Fig.1):

1. Above 600°C/5.25 kb and 700°C/6.5 kb almandite+biotite+Al₂SiO₅ coexist stably, cordierite being unstable.
2. The field, in which almandite, biotite and Al₂SiO₅ are stable together with cordierite, is restricted by two curves, passing through the following points:
   1. 625°C/5.5 kb and 700°C/6.5 kb,
   2. 625°C/5.5 kb and 700°C/4.0 kb.
3. At conditions below curves 1 and 2b, cordierite, biotite, and Al₂SiO₅ are formed, but no garnet.

An appreciable MnO-content in the system lowers the pressures needed for the formation of almandite garnet, but the quantitative influence of the spessartite-component on the formation of almandite could not yet be determined. the Mg-rich system with Fe²⁺/Fe²⁺+Mg=0.4 garnet did not form at pressures up to 7 kb in the temperature range investigated. Experiments at unspecified higher pressures (in a simple squeezer-type apparatus) yielded the reaction: $${\text{Ripidolite + muscovite + quartz}} \rightleftharpoons {\text{almandite + biotite + Al}}_{\text{2}} {\text{SiO}}_{\text{5}} {\text{ + H}}_{\text{2}} {\text{O}}$$ . Further experiments are needed to determine the equilibrium data. The occurence of garnet in metamorphic rocks is discussed in the light of the experimental results.  相似文献   

Partition of Ni between olivine and sulfide: the effect of temperature,f_{{\text{O}}_{\text{2}} } and f_{{\text{S}}_{\text{2}} }     

M. E. Fleet  N. D. MacRae 《Contributions to Mineralogy and Petrology》1987,95(3):336-342

The experimental distribution coefficient for Ni/ Fe exchange between olivine and monosulfide (K_D3) is 35.6±1.1 at 1385° C, \(f_{{\text{O}}_{\text{2}} } = 10^{ - 8.87} ,f_{{\text{S}}_{\text{2}} } = 10^{ - 1.02} \) , and olivine of composition Fo96 to Fo92. These are the physicochemical conditions appropriate to hypothesized sulfur-saturated komatiite magma. The present experiments equilibrated natural olivine grains with sulfide-oxide liquid in the presence of a (Mg, Fe)-alumino-silicate melt. By a variety of different experimental procedures, K _D3 is shown to be essentially constant at about 30 to 35 in the temperature range 900 to 1400° C, for olivine of composition Fo97 to FoO, monosulfide composition with up to 70 mol. % NiS, and a wide range of \(f_{{\text{O}}_{\text{2}} } \) and \(f_{{\text{S}}_{\text{2}} } \) .  相似文献   

P,T, f_{{\text{CO}}_{\text{2}} } and f_{{\text{H}}_{\text{2}} {\text{O}}} during metamorphism of calcareous sediments in the Waterville-Vassalboro area,south-central Maine     

J. M. Ferry 《Contributions to Mineralogy and Petrology》1976,57(2):119-143

In a regional metamorphic terrain where six isograds have been mapped based on mineral reactions that are observed in metacarbonate rocks, the P-T conditions and fugacities of CO₂ and H₂O during metamorphism were quantified by calculations involving actual mineral compositions and experimental data. Pressure during metamorphism was near 3,500 bars. Metamorphic temperatures ranged from 380° C (biotite-chlorite isograd) to 520° C (diopside isograd). \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{CO}}_{\text{2}} }\) / \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) in general is higher in metacarbonate rocks below the zoisite isograd than in those above the zoisite isograd. Calculated \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) are consistent with carbonate rocks above the zoisite isograd having equilibrated during metamorphism with a bulk supercritical fluid in which \(P_{{\text{CO}}_{\text{2}} }\) + \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) = P _total. Calculations indicate that below the zoisite isograd, however, \(P_{{\text{CO}}_{\text{2}} }\) + \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) was less than P_total, and that this condition is not due to the presence of significant amounts of species other than CO₂ and H₂O in the system C-O-H-S. Calculated \(P_{{\text{CO}}_{\text{2}} }\) /( \(P_{{\text{CO}}_{\text{2}} }\) + \(P_{{\text{H}}_{\text{2}} {\text{O}}}\) ) is low (0.06–0.32) above the zoisite isograd. The differences in conditions above and below the zoisite isograd may indicate that the formation of zoisite records the introduction of a bulk supercritical H₂O-rich fluid into the metacarbonates. The results of the study indicate that \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) are constant on a thin section scale, but that gradients in \(f_{{\text{CO}}_{\text{2}} }\) and \(f_{{\text{H}}_{\text{2}} {\text{O}}}\) existed during metamorphism on both outcrop and regional scales.  相似文献   

The stability and phase relations of iron chlorite below 8.5 kb P_{{\text{H}}_{\text{2}} {\text{O}}}     

R. S. James  A. C. Turnock  J. J. Fawcett 《Contributions to Mineralogy and Petrology》1976,56(1):1-25

Iron chlorites with compositions intermediate between the two end-members daphnite (Fe₅Al₂Si₃O₁₀(OH)₈) and pseudothuringite (Fe₄Al₄Si₂O₁₀(OH)₈) were synthesized from mixtures of reagent chemicals. The polymorph with a 7 Å basal spacing initially crystallized from these mixtures at 300 °C and 2 kb after two weeks. Conversion to a 14 Å chlorite required a further 6 weeks at 550 °C. Shorter conversion times were required at higher water pressures. The products contained up to 20% impurities.The maximum equilibrium decomposition temperature for iron chlorite, approximately 550 °C at 2kb, is at an between assemblages (1) and (2) listed below. Synthetic iron chlorite will break down by various reactions with variable P, T, and fugacity of oxygen. For the composition FeAlSi = 523, the sequence of high temperature breakdown products with increasing traversing the magnetite field for P _total = =2kb is: (1) corierite+ fayalite+hercynite; (2) cordierite+fay alite+magnetite; (3) cordierite+magnetite+quartz; (4) magnetite+mullite+quartz. Almandine should replace cordierite in assemblages (1) and (2) but it did not nucleate. The significance of the relationship between iron cordierite and almandine in this system is discussed.At water pressures from 4 to 8.5 kb and at the nickel-bunsite buffer, iron chlorite+quartz break down to iron gedrite+magnetite with temperature 550 to 640 °C along the curve. At temperatures 50 °C greater and along a parallel curve, almandine replaces iron gedrite. For on this buffer curve, almandine is unstable below approximately 4 kb for temperatures to approximately 750 °C.  相似文献   

Effect of temperature,pressure and iron content on the electrical conductivity of orthopyroxene     

Baohua?ZhangEmail authorView author&#;s OrcID profile  Takashi?Yoshino 《Contributions to Mineralogy and Petrology》2016,171(12):102

  相似文献   

Water diffusion in Mount Changbai peralkaline rhyolitic melt     

Haoyue Wang  Zhengjiu Xu  Harald Behrens  Youxue Zhang 《Contributions to Mineralogy and Petrology》2009,158(4):471-484

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The crystal chemistry of lithium and Fe3+ in synthetic orthopyroxene     

Fernando Cámara  Gianluca Iezzi  Massimo Tiepolo  Roberta Oberti 《Physics and Chemistry of Minerals》2006,33(7):475-483

Lithian ferrian enstatite with Li₂O = 1.39 wt% and Fe₂O₃ 7.54 wt% was synthesised in the (MgO–Li₂O–FeO–SiO₂–H₂O) system at P = 0.3 GPa, T = 1,000°C, fO₂ = +2 Pbca, and a = 18.2113(7), b = 8.8172(3), c = 5.2050(2) Å, V = 835.79(9) Å³. The composition of the orthopyroxene was determined combining EMP, LA-ICP-MS and single-crystal XRD analysis, yielding the unit formula ^M2(Mg_0.59Fe _0.21 ²⁺ Li_0.20) ^M1(Mg_0.74Fe _0.20 ³⁺ Fe _0.06 ²⁺ ) Si₂O₆. Structure refinements done on crystals obtained from synthesis runs with variable Mg-content show that the orthopyroxene is virtually constant in composition and hence in structure, whereas coexisting clinopyroxenes occurring both as individual grains or thin rims around the orthopyroxene crystals have variable amounts of Li, Fe³⁺ and Mg contents. Structure refinement shows that Li is ordered at the M2 site and Fe³⁺ is ordered at the M1 site of the orthopyroxene, whereas Mg (and Fe²⁺) distributes over both octahedral sites. The main geometrical variations observed for Li-rich samples are actually due to the presence of Fe³⁺, which affects significantly the geometry of the M1 site; changes in the geometry of the M2 site due to the lower coordination of Li are likely to affect both the degree and the kinetics of the non-convergent Fe²⁺-Mg ordering process in octahedral sites.  相似文献   

Das P{\text{ - }}T{\text{ - }}X_{{\text{CO}}_{\text{2}} } Stabilitätsfeld von Lawsonit     

Karl -Heinz Nitsch 《Contributions to Mineralogy and Petrology》1972,34(2):116-134

At pressures which are expected in the earth's crust, the high temperature border of the lawsonite stability field is marked by reaction lawsonite = zoisite + kyanite/andalusite + pyrophyllite + H₂O. (1a) The equilibrium data of reaction (1a) have been experimentally determined, and the equilibrium curve is characterized by the following P, T-data: 4 kb; 360±20° C; 5 kb; 375 ±20° C; 7kb;410±20° C. In the P, T diagram the equilibrium curve of reaction lawsonite + quartz = zoisite + pyrophyllite + H₂O (6) is very close to the curve of reaction (1a); the distance is smaller than the error stated for curve (1a), i.e. below ±20° C. The stability fields of lawsonite and anorthite + H₂O are not adjacent fields in the P, T diagram. This means that no stable reaction of lawsonite to anorthite + H₂O can exist. Thus, the CaAl-silicate formed by the decomposition of lawsonite is always zoisite. Further, as shown by experimental determination of reaction calcite + pyrophyllite + H₂O = lawsonite + quartz + CO₂, (7) lawsonite can coexist with a gas phase only if the CO₂ content of the gas phase does not exceed 3±2 Mol-%. This means, for metamorphism of lawsonite glaucophane rocks, that the fluid phase that was present during metamorphism has been quite rich in H₂O. Ernst (1971, in press) who applied a different, indirect investigation method when studying the composition of the fluid-attending Franciscan and Sanbagawa metamorphism has come to the result that during metamorphism of lawsonite-glaucophane rocks the fluid phase did not contain more than 1–3 Mol-% of CO₂.  相似文献   

Crystal chemistry of Fe3+-bearing (Mg,Fe)SiO3 perovskite: a single-crystal X-ray diffraction study     

Ryosuke Sinmyo  Elena Bykova  Catherine McCammon  Ilya Kupenko  Vasily Potapkin  Leonid Dubrovinsky 《Physics and Chemistry of Minerals》2014,41(6):409-417

Magnesium silicate perovskite is the predominant phase in the Earth’s lower mantle, and it is well known that incorporation of iron has a strong effect on its crystal structure and physical properties. To constrain the crystal chemistry of (Mg, Fe)SiO₃ perovskite more accurately, we synthesized single crystals of Mg_0.946(17)Fe_0.056(12)Si_0.997(16)O₃ perovskite at 26 GPa and 2,073 K using a multianvil press and investigated its crystal structure, oxidation state and iron-site occupancy using single-crystal X-ray diffraction and energy-domain Synchrotron Mössbauer Source spectroscopy. Single-crystal refinements indicate that all iron (Fe²⁺ and Fe³⁺) substitutes on the A-site only, where \( {\text{Fe}}^{ 3+ } /\Upsigma {\text{Fe}}\sim 20\,\% \) based on Mössbauer spectroscopy. Charge balance likely occurs through a small number of cation vacancies on either the A- or the B-site. The octahedral tilt angle (Φ) calculated for our sample from the refined atomic coordinates is 20.3°, which is 2° higher than the value calculated from the unit-cell parameters (a = 4.7877 Å, b = 4.9480 Å, c = 6.915 Å) which assumes undistorted octahedra. A compilation of all available single-crystal data (atomic coordinates) for (Mg, Fe)(Si, Al)O₃ perovskite from the literature shows a smooth increase of Φ with composition that is independent of the nature of cation substitution (e.g., \( {\text{Mg}}^{ 2+ } - {\text{Fe}}^{ 2+ } \) or \( {\text{Mg}}^{ 2+ } {\text{Si}}^{ 4+ } - {\text{Fe}}^{ 3+ } {\text{Al}}^{ 3+ } \) substitution mechanism), contrary to previous observations based on unit-cell parameter calculations.  相似文献   

Fe<Superscript>3+</Superscript> reduction during biotite melting in graphitic metapelites: another origin of CO<Subscript>2</Subscript> in granulites     

Bernardo?CesareEmail author  Sandro?Meli  Luca?Nodari  Umberto?Russo 《Contributions to Mineralogy and Petrology》2005,149(2):129-140

The Fe³⁺/Fe_tot of all Fe-bearing minerals has been analysed by Mössbauer spectroscopy in a suite of biotite-rich to biotite-free graphitic metapelite xenoliths, proxies of an amphibolite-granulite transition through progressive biotite melting. Biotite contains 9 to 16% Fe³⁺/Fe_tot, whereas garnet, cordierite and ilmenite are virtually Fe³⁺ -free (0–1% Fe³⁺/Fe_tot) in all samples, regardless of biotite presence. Under relatively reducing conditions (graphite-bearing assemblages), biotite is the only carrier of Fe³⁺ during high-temperature metamorphism; therefore, its disappearance by melting represents an important event of iron reduction during granulite formation, because haplogranitic melts usually incorporate small amounts of ferric iron. Iron reduction is accompanied by the oxidation of carbon and the production of CO₂, according to the redox reaction: Depending on the nature of the peritectic Fe-Mg mineral produced (garnet, cordierite, orthopyroxene), the CO₂ can either be present as a free fluid component, or be completely stored within melt and cordierite. The oxidation of graphite by iron reduction can account for the in situ generation of CO₂, implying a consequential rather than causal role of CO₂ in some granulites and migmatites. This genetic model is relevant to graphitic rocks more generally and may explain why CO₂ is present in some granulites although it is not required for their formation.  相似文献   

The upper thermal stability of clinochlore,Mg5Al[AlSi3O10](OH)8, at 10–35 kb P_{{\text{H}}_{\text{2}} {\text{O}}}     

Hubert Staudigel  Werner Schreyer 《Contributions to Mineralogy and Petrology》1977,61(2):187-198

Clinochlore, which is, within the limits of error, the thermally most stable member of the Mg-chlorites, breaks down at = P _tot to the assemblage enstatite+forsterite+spinel+H₂O along a univariant curve located at 11 kb, 838 ° C; 15kb, 862 ° C; and 18 kb, 880 ° C (±1 kb ±10 ° C). At water pressures above that of an invariant point at 20.3 kb and 894 ° C involving the phases clinochlore, enstatite, forsterite, spinel, pyrope, and hydrous vapor, clinochlore disintegrates to pyrope+forsterite+spinel+H₂O. The resulting univariant curve has a steep, negative dP/dT slope of –930 bar/ °C at least up to 35 kb.Thus, given the proper chemical environment, Mg-chlorites have the potential of appearing as stable phases within the earth's upper mantle to maximum depths between about 60 and 100 km depending on the prevailing undisturbed geotherm, and to still greater depths in subduction zones. However, unequivocal criteria for mantle derived Mg-chlorites are difficult to find in ultrabasic rocks.  相似文献   

Dehydration experiments on natural omphacites: qualitative and quantitative characterization by various spectroscopic methods   总被引：1，自引：0，他引：1  

M. Koch-Müller  I. Abs-Wurmbach  D. Rhede  V. Kahlenberg  S. Matsyuk 《Physics and Chemistry of Minerals》2007,34(9):663-678

A series of natural omphacites from a wide range of P, T occurrences were investigated by electron microprobe (EMP), infrared (IR)-, Mössbauer (MS)- and optical spectroscopy in the UV/VIS spectral range (UV/VIS), secondary ion mass spectrometry (SIMS) and single crystal structure refinement by X-ray diffraction (XRD) to study the influence of hydrogen loss on valence state and site occupancies of iron. In accordance with literature data we found Fe²⁺ at M1 as well as at M2, and in a first approach assigned Fe³⁺ to M1, as indicated by MS and XRD results. Hydrogen content of three of our omphacite samples were measured by SIMS. In combination with IR spectroscopy we determined an absorption coefficient: ε _i,tot = 65,000 ± 3,000 lmol_H2O ^?1 cm^?2. Using this new ε _i,tot value, we obtained water concentrations ranging from 60 to 700 ppm H₂O (by weight). Hydrogen loss was simulated by stepwise heating the most water rich samples in air up to 800°C. After heat treatment the samples were analyzed again by IR, MS, UV/VIS, and XRD. Depending on the type of the OH defect, the grade of dehydration with increasing temperature is significantly different. In samples relatively poor in Fe³⁺ (<0.1 Fe³⁺ pfu), hydrogen associated with vacancies at M2 (OH bands around 3,450 cm^?1) starts to leave the structure at about 550°C and is completely gone at 780°C. Hydrogen associated with Al³⁺ at the tetrahedral site (OH bands around 3,525 cm^?1, Koch-Müller et al., Am Mineral, 89:921–931, 2004) remains completely unaffected by heat treatment up to 700°C. But all hydrogen vanished at about 775°C. However, this is different for a more Fe³⁺-rich sample (0.2 Fe³⁺ pfu). Its IR spectrum is characterized by a very intense OH band at 3,515 cm^?1 plus shoulder at 3,450 cm^?1. We assign this intense high-energy band to vibrations of an OH dipole associated with Fe³⁺ at M1 and a vacancy either at M1 or M2. OH release during heating is positively correlated with decrease in Fe²⁺ and combined with increase in Fe³⁺. That dehydration is correlated with oxidation of Fe²⁺ is indirectly confirmed by annealing of one sample in a gas mixing furnace at 700°C under reducing conditions keeping almost constant OH^? content and giving no indication of Fe²⁺-oxidation. Obtained data indicate that in samples with a relatively high concentration of Fe²⁺ at M2 and low-water concentrations, i.e., at a ratio of Fe^{2+ M2}/H > 10 dehydration occurs by iron oxidation of Fe²⁺ exclusively at the M2 site following the reaction: \( {\left[ {{\text{Fe}}^{{{\text{2 + [ M2]}}}}{\text{OH}}^{ - } } \right]} = {\left[ {{\text{Fe}}^{{{\text{3 + [ M2]}}}} {\text{O}}^{{{\text{2}} - }} } \right]} + {\text{1/2}}\;{\text{H}}_{{\text{2}}} \uparrow . \) In samples having relatively low concentration of Fe²⁺ at M2 but high-water concentrations, i.e., ratio of Fe^{2+ M2}/H < 5.0 dehydration occurs through oxidation of Fe²⁺ at M1.  相似文献   

Continental ca 1.7 – 1.69 Ga Fe-rich metatholeiites in the Curnamona Province,Australia: a record of melting of a heterogeneous,subduction-modified lithospheric mantle     

L. Rutherford  K. Barovich  M. Hand  J. Foden 《Australian Journal of Earth Sciences》2013,60(3):501-519

Mg-rich and Fe-rich metatholeiites intruded the Willyama Supergroup of the southern Australian Curnamona Province in the Late Palaeoproterozoic at ca 1700 Ma and 1685 Ma, respectively. Intrusion of the Fe-rich metatholeiites occurred during a period of punctuated extension in the Willyama basin. Major-element concentrations are variable (SiO₂ 45.4 – 56.5 wt%; Fe₂O₃? 8.5 – 20.7; TiO₂ 0.46 – 2.52 wt%; Mg# 70.5 – 29.1) and, in conjunction with trace-element data, support near-closed-system fractionation of a mantle-derived melt with little or no replenishment. Fractionation produced progressively Fe-rich derivative melts. Crystallising phases were dominated by clinopyroxene and olivine, whereas Fe – (Ti) oxide crystallisation was hindered. Primitive mantle-normalised immobile trace elements are characterised by variable Th, Nb, Sr, P and Ti anomalies. Chondrite-normalised rare-earth element patterns for the most primitive, Mg-rich samples from the western Broken Hill Domain have La_N/Sm_N < 1, whereas the most evolved Fe-rich samples from the Olary Domain have ratios of La_N/Sm_N > 1. Initial εNd values range between – 2.2 and + 2.7 for the majority of the samples, with the isotopic compositions showing no correlation with differentiation or assimilation. The combined geochemical and isotopic data suggest that the southern Curnamona Province metatholeiites were extracted from a depleted mantle in the western Broken Hill Domain, and a variably enriched, heterogeneous subcontinental lithospheric mantle in the Olary Domain. Magmatism most likely occurred in a backarc basin or intracontinental setting. It is speculated that the geochemically enriched mantle component was derived from subduction-related processes, probably related to pre-Willyama basin accretionary processes along the southern and eastern margins of the North Australian Craton.  相似文献   

The influence of Fe<Superscript>3+</Superscript> on garnet–orthopyroxene and garnet–olivine geothermometers     

Vladimir?MatjuschkinEmail author  Gerhard?P.?Brey  Heidi?E.?H?fer  Alan?B.?Woodland 《Contributions to Mineralogy and Petrology》2014,167(2):972

Applying Fe²⁺–Mg exchange geothermometers to natural samples may lead to incorrect temperature estimates if significant Fe³⁺ is present. In order to quantify this effect, high-pressure experiments were carried out in a belt apparatus in a natural system close to CFMAS at 5 GPa and 1,100–1,400 °C. The oxygen fugacity in the experiments was at or below the Re–ReO₂ buffer. This is at significantly more oxidized conditions than in previous experiments, and, as consequence, higher Fe³⁺/Fe²⁺ ratios were generated. The Fe³⁺ content of garnet in the experiments was quantified by electron microprobe using the flank method. Making the usual assumption that Fe_total = Fe²⁺, the two-pyroxene thermometer of Brey and Köhler (J Pet 31:1353–1378, 1990) reproduced the experimental temperature to ±35 °C and the garnet–clinopyroxene Fe²⁺–Mg exchange thermometer of Krogh (Contrib Miner Pet 99:44–48, 1988) overestimated the temperatures on average by only 25 °C. On the other hand, application of the garnet–olivine (O’Neill and Wood in Contrib Miner Pet 70:59–70, 1979) and garnet–orthopyroxene (Harley in Contrib Miner Pet 86:359–373, 1984) exchange geothermometers yielded an underestimation in calculated temperatures of >200 °C. However, making explicit accounting for Fe³⁺ in garnet (i.e. using only measured Fe²⁺) leads to a vast improvement in the agreement between calculated and experimental temperatures, generally to within ±70 °C for the garnet–orthopyroxene geothermometer as well as noticeable improvement of calculated temperatures for the garnet–olivine geothermometer. Our results demonstrate that the two-pyroxene and garnet–clinopyroxene thermometers are rather insensitive to the presence of Fe³⁺ whilst direct accounting of Fe³⁺ in garnet is essential when applying the garnet–olivine and garnet–orthopyroxene thermometers.  相似文献   

Theoretical calculation of equilibrium Mg isotope fractionation between silicate melt and its vapor     

Haiyang Luo  Huiming Bao  Yuhong Yang  Yun Liu 《中国地球化学学报》2018,37(5):655-662

Isotope fractionation during the evaporation of silicate melt and condensation of vapor has been widely used to explain various isotope signals observed in lunar soils, cosmic spherules, calcium–aluminum-rich inclusions, and bulk compositions of planetary materials. During evaporation and condensation, the equilibrium isotope fractionation factor (α) between high-temperature silicate melt and vapor is a fundamental parameter that can constrain the melt’s isotopic compositions. However, equilibrium α is difficult to calibrate experimentally. Here we used Mg as an example and calculated equilibrium Mg isotope fractionation in MgSiO₃ and Mg₂SiO₄ melt–vapor systems based on first-principles molecular dynamics and the high-temperature approximation of the Bigeleisen–Mayer equation. We found that, at 2500 K, δ²⁵Mg values in the MgSiO₃ and Mg₂SiO₄ melts were 0.141?±?0.004 and 0.143?±?0.003‰ more positive than in their respective vapors. The corresponding δ²⁶Mg values were 0.270?±?0.008 and 0.274?±?0.006‰ more positive than in vapors, respectively. The general \(\alpha - T\) equations describing the equilibrium Mg α in MgSiO₃ and Mg₂SiO₄ melt–vapor systems were: \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.264 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\) and \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.340 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\), respectively, where m is the mass of light isotope ²⁴Mg and m′ is the mass of the heavier isotope, ²⁵Mg or ²⁶Mg. These results offer a necessary parameter for mechanistic understanding of Mg isotope fractionation during evaporation and condensation that commonly occurs during the early stages of planetary formation and evolution.  相似文献   

Experimental investigation and application of the equilibrium rutile + orthopyroxene = quartz + ilmenite     

Jodie L. Hayob  Steven R. Bohlen  Eric J. Essene 《Contributions to Mineralogy and Petrology》1993,115(1):18-35

Equilibria in the Sirf (Silica-Ilmenite-Rutile-Ferrosilite) system: $${\text{SiO}}_{\text{2}} + ({\text{Mg,Fe}}){\text{TiO}}_{\text{3}} {\text{ + (Mg,Fe)SiO}}_{\text{3}} $$ have been calibrated in the range 800–1100° C and 12–26 kbar using a piston-cylinder apparatus to assess the potential of the equilibria for geobarometry in granulite facies assemblages that lack garnet. Thermodynamic calculations indicate that the two end-member equilibria involving quartz + geikielite = rutile + enstatite, and quartz + ilmenite = rutile + ferrosilite, are metastable. We therefore reversed equilibria over the compositional range Fs_40–70, using Ag₈₀Pd₂₀ capsules with \(f_{{\text{O}}_{\text{2}} } \) buffered at or near iron-wüstite. Ilmenite compositions coexisting with orthopyroxene are \(X_{{\text{MgTiO}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.06 to 0.15 and \(X_{{\text{Fe}}_{\text{2}} {\text{O}}_{\text{3}} }^{{\text{Ilm}}} \) of 0.00 to 0.01, corresponding toK _D values of 13.3, 10.2, 9.0 and 8.0 (±0.5) at 800, 900, 1000 and 1100° C, respectively, whereK _D =(XMg/XFe)^Opx/(XMg/XFe)^Ilm. Pressures have been calculated using equilibria in the Sirf system for granulites from the Grenville Province of Ontario and for granulite facies xenoliths from central Mexico. Pressures are consistent with other well-calibrated geobarometers for orthopyroxeneilmenite pairs from two Mexican samples in which oxide textures appear to represent equilibrium. Geologically unreasonable pressures are obtained, however, where oxide textures are complex. Application of data from this study on the equilibrium distribution of iron and magnesium between ilmenite and orthopyroxene suggests that some ilmenite in deep crustal xenoliths is not equilibrated with coexisting pyroxene, while assemblages from exposed granulite terranes have reequilibrated during retrogression. The Sirf equilibria are sensitive to small changes in composition and may be used for determination of activity/composition (a/X) relations of orthopyroxene if an ilmenite model is specified. A symmetric regular solution model has been used for orthopyroxene in conjunction with activity models for ilmenite available from the literature to calculatea/X relations in orthopyroxene of intermediate composition. Data from this study indicate that FeSiO₃?MgSiO₃ orthopyroxene exhibits small, positive deviations from ideality over the range 800–1100°C.  相似文献   

Clinoeulite (magnesian clinoferrosilite) in a eulysite of a metamorphosed iron formation in the vredefort structure,South Africa     

W. Schreyer  D. Stepto  K. Abraham  W. F. Müller 《Contributions to Mineralogy and Petrology》1978,65(4):351-361

A unique clinopyroxene (En₁₉Fs₇₈Wo₃), clinoeulite, space group P2₁/c, $${\text{(Fe}}_{{\text{1}}{\text{.48}}} {\text{Mg}}_{{\text{0}}{\text{.37}}} {\text{Mn}}_{{\text{0}}{\text{.08}}}^{{\text{2 + }}} {\text{Ca}}_{{\text{0}}{\text{.05}}} {\text{Al}}_{{\text{0}}{\text{.01}}} {\text{)}}_{{\text{1}}{\text{.99}}} {\text{ [Si}}_{{\text{2}}{\text{.01}}} {\text{O6],}}$$ contains sharp exsolution lamellae of ferroaugite (En₁₇Fs₄₃Wo₄₀) from which the former presence of a ferropigeonite near En₁₇Fs₇₀Wo₁₃ can be calculated. This two-pyroxene intergrowth is the main component of a eulysite containing also magnetite, olivine (Fo₉Fa₈₆Te₅), quartz, oligoclase-K feldspar inter-growth, and retrograde cummingtonite with about 76 % grunerite end member. The occurrence of this most unusual rock type in the center of the Vredefort structure is attributed to a period of high-temperature metamorphism (at least 800 °–850 °C) which was followed by hot deformation of the rock during the Vredefort event thus probably preventing the common formation of orthopyroxene through pigeonite exsolution and inversion upon cooling. After this tectonic deformation, the rock recrystallized within the low-temperature stability range of clinoeulite to yield fine annealing textures. Late-stage equilibria at temperatures well below 500 °C include the complete unmixing of a former high-temperature anorthoclase, a Mg/Fe redistribution in the clinoeulite and olivine and, with the introduction of water, the partial formation of cummingtonite through reaction of clinoeulite, olivine, and quartz. During weathering the olivine was transformed to a nearly opaque, anhydrous ferrisilicate which, except for the change of Fe²⁺ to Fe³⁺ and the oxygen introduction, largely retained its original chemistry.  相似文献   

Breakdown of hydrous ringwoodite to pyroxene and spinelloid at high P and T and oxidizing conditions     

M. Koch-Müller  D. Rhede  R. Schulz  R. Wirth 《Physics and Chemistry of Minerals》2009,36(6):329-341

To get deeper insight into the phase relations in the end-member system Fe₂SiO₄ and in the system (Fe, Mg)₂SiO₄ experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity. The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission electron microscopy. At fO₂ corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe₂SiO₄ + O₂ = 6 FeSiO₃ + 5 Fe_2.40Si_0.60O₄. Refinement of site occupancies in combination with stoichiometric Fe³⁺ calculations show that 32% of the total Fe is incorporated as Fe³⁺ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to accept higher Fe³⁺ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite with considerable Fe³⁺ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K _D independent on composition and a bulk composition of x _Fe = 0.44 this fractionation would stabilize spl with x _Fe = 0.72. Thus, spl could be a potential Fe³⁺ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.

M. Koch-MüllerEmail:

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Crystal-poor, multiply saturated rhyolites (obsidians) from the Cascade and Mexican arcs: evidence of degassing-induced crystallization of phenocrysts     

Laura E. Waters  Rebecca A. Lange 《Contributions to Mineralogy and Petrology》2013,166(3):731-754

A detailed petrological study is presented for six phenocryst-poor obsidian samples (73–75 wt% SiO₂) erupted as small volume, monogenetic domes in the Mexican and Cascade arcs. Despite low phenocryst (+microphenocryst) abundances (2–6 %), these rhyolites are each multiply saturated with five to eight mineral phases (plagioclase + orthopyroxene + titanomagnetite + ilmenite + apatite ± zircon ± hornblende ± clinopyroxene ± sanidine ± pyrrhotite). Plagioclase and orthopyroxene phenocrysts (identified using phase-equilibrium constraints) span ≤30 mol % An and ≤15 % Mg#, respectively. Eruptive temperatures (±1σ), on the basis of Fe–Ti two oxide thermometry, range from 779 (±25) to 940 (±18) °C. Oxygen fugacities (±1σ) range from ?0.4 to 1.4 (±0.1) log units relative to those along the Ni–NiO buffer. With temperature known, the plagioclase-liquid hygrometer was applied; maximum water concentrations calculated for the most calcic plagioclase phenocryst in each sample range from 2.6 to 6.5 wt%. This requires that the rhyolites were fluid-saturated at depths ≥2–7 km. It is proposed that the wide compositional range in plagioclase and orthopyroxene phenocrysts, despite their low abundance, can be attributed to changing melt water concentrations owing to degassing during magma ascent. Phase-equilibrium experiments from the literature show that higher dissolved water concentrations lead to more Fe-rich orthopyroxene, as well as more calcic plagioclase. Loss of dissolved water leads to a progressive increase in melt viscosity, and phenocrysts often display diffusion-limited growth textures (e.g., dendritic and vermiform), consistent with large undercoolings caused by degassing. A kinetic barrier to microlite crystallization occurred at viscosities from 4.5 to 5.0 log₁₀ Pa s for these rhyolites, presumably because the rate at which melt viscosity changed was high owing to rapid loss of dissolved water during magma ascent.  相似文献