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1.
The enthalpy of drop-solution in molten 2PbO·B2O3 of synthetic and natural lawsonite, CaAl2(Si2O7)(OH)2·H2O, was measured by high-temperature oxide melt calorimetry. The enthalpy of formation determined for the synthetic material is (fHOxides=-168.7Dž.4 kJ mol-1, or (fH0298=-4,872.5dž.0 kJ mol-1. These values are in reasonable agreement with previously published data, although previous calorimetric work yielded slightly more exothermic data and optimisation methods resulted in slightly less exothermic values. The equilibrium conditions for the dehydration of lawsonite to zoisite, kyanite and quartz/coesite at pressures and temperatures up to 5 GPa and 850 °C were determined by piston cylinder experiments. These results, other recent phase equilibrium data, and new calorimetric and thermophysical data for lawsonite and zoisite, Ca2Al3(SiO4)(Si2O7)O(OH), were used to constrain a mathematical programming analysis of the thermodynamic data for these two minerals in the chemical system CaO-Al2O3-SiO2-H2O (CASH). The following data for lawsonite and zoisite were obtained: (fH0298 (lawsonite)=-4,865.68 kJ mol-1 , S0298 (lawsonite)=229.27 J K-1 mol-1 , (fH0298 (zoisite)=-6,888.99 kJ mol-1 , S0298 (zoisite)=297.71 J K-1 mol-1 . Additionally, a recalculation of the bulk modulus of lawsonite yielded K=120.7 GPa, which is in good agreement with recent experimental work.  相似文献   

2.
The Ashland pluton is a calc-alkaline plutonic complex thatintruded the western Paleozoic and Triassic belt of the KlamathMountains in late Middle Jurassic time. The pluton comprisesa series of compositionally distinct magma pulses. The oldestrocks are hornblende gabbro and two-pyroxene quartz gabbro withinitial 87Sr/86Sr = 0{dot}7044, 18O = 8{dot}7%, and REE patternswith chondrite normalized La/Lu = 7. These units were followedby a suite of tonalitic rocks (LaN/LuN = 7) and then by a suiteof K2O- and P2O5 rocks of quartz monzodioritic affinity (LaN/LuN= 13–21; LaN/SmN = 2{dot}4–3{dot}) The quartz monzodioriticrocks were then intruded by biotite granodiorite and granitewith lower REE abundances but more fractionated LREE(LaN/LuN= 13–19; LaN/SmN = 4{dot}3–6 and they, in turn,were host to dikes and bosses of hornblende diorite. The latestintrusive activity consisted of aplitic and granitic dikes.Combined phase equilibria and mineral composition data, indicateemplacement conditions of approximately Ptotal = 2{dot}3kb,PH2O between 1{dot}5 and 2{dot}2 kb, and fO2 between the nickel-nickeloxide and hematite-magnetite buffers. Successive pulses of magma display increasing SiO2 togetherwith increasing 18O and decreasing initial 87Sr/86Sr. The isotopicdata are consistent with either (1) combined fractional crystallizationof andesitic magma and concurrent assimilation of crustal materialcharacterized by low Sr1 and high (18O or, more probably, (2)a series of partial melting events in which sources were successivelyless radiogenic but richer in 18O Each intrusive stage displaysevidence for some degree of crystal accumulation and/or fractionalcrystallization but neither process adequately accounts fortheir compositional differences. Consequently, each stage appearsto represent a distinct partial melting or assimilation event. The P2O5-rich nature of the quartz monzodiorite suite suggestsaccumulation of apatite. However, the suite contains abundantmafic microgranitoid enclaves and most apatite in the suiteis acicular. These observations suggest that magma mixing affectedthe compositional variation of the quartz monzodiorite suite.Mass balance calculations are consistent with a simple mixingprocess in which P2O5-rich alkalic basalt magma (representedby the mafic microgranitoid enclaves) was combined with a crystal-poorfelsic magma (represented by the tonalite suite), yielding aquartz monzodioritic magma that then underwent differentiationby crystal fractionation and accumulation.  相似文献   

3.
MYSEN  BJORN 《Journal of Petrology》1992,33(2):347-375
The solubility mechanisms of H2O in peralkaline sodium aluminosilicatequenched melts (anhydrous NBO/T = 0.5) have been studied withRaman spectroscopy as a function of Al/(Al + Si) (0–0–3)and H2O content (0–7.5 wt.%). The coexisting structuralunits in the anhydrous quenched melts are TO2 (Q4), T2O5(Q3),and TO3 (Q2). In Al-free Na2Si4O9 (NS4) melt, H2O forms complexes with Na+(Na–OH bonds) and with Si4+ (Si–OH bonds). MolecularH2O is also detected. TO3 structural units are not detectedin this composition. In the H2O concentration range between0 and 4 wt.%, there is an approximately 20% increase in NBO/Tresulting from the increased abundance ratio, T2O5/TO2. Withfurther increments in water activity, the NBO/T of hydrous NS4melt is reduced. The depolymerization results from hydroxylationof the silica tetrahedra, whereas polymerization is due to formationof complexes with Na–OH bonding. In Al-bearing compositions on the Na2Si4O9–Na2(NaAl)4O9–join, there is evidence for Al–OH bonding in additionto Na–OH and Si–OH bonds. Among these complexes,the relative abundance of those with Si–OH bonds diminisheswith increasing Al/(A1 + Si), whereas complexes with Al–OHand Na–OH bonds become more important. Complexes withNa–OH bonds dominate for H2O4 wt.%, whereas complexeswith Al–OH dominate at higher water content. The threestructural units, TO3, T2O5, and TO2, were observed in bothanhydrous and hydrous peralkaline sodium aluminosilicate melts.Their abundance varies, however, with the H2O concentrationin the melts. The NBO/T decreases to a minimum (a 30–50%lowering of NBO/T relative to anhydrous materials) for low H2Ocontents (3–4 wt.% H2O), and increases as the H2O contentis increased further.  相似文献   

4.
We have conducted experiments on dissolution of quartz, albite,orthoclase, and corundum into H2O-saturated haplogranite meltat 800°C and 200 MPa over a duration of 120–1488 hwith the aim of ascertaining the diffusive transport propertiesof granitic melts at crustal anatectic temperatures. Cylindersof anhydrous starting glass and a single mineral phase (quartzor feldspar) were juxtaposed along flat and polished surfacesinside gold or platinum capsules with 10 wt % added H2O. Concentrationprofiles in glass (quenched melt) perpendicular to the mineral–glassinterfaces and comparison with relevant phase diagrams suggestthat melts at the interface are saturated in the dissolvingphases after 384 h, and with longer durations the concentrationprofiles are controlled only by diffusion of components in themelt. The evolution of the concentration profiles with timeindicates that uncoupled diffusion in the melt takes place alongthe following four linearly independent directions in oxidecomposition space: SiO2, Na2O, and K2O axes (Si-, Na-, and K-eigenvectors,respectively), and a direction between the Al2O3, Na2O, andK2O axes (Al-eigenvector), such that the Al/Na molar ratio isequal to that of the bulk melt and the Al/(Na + K) molar ratiois equal to the equilibrium ASI (= mol. Al2O3/[Na2O + K2O])of the melt. Experiments in which a glass cylinder was sandwichedbetween two mineral cylinders—quartz and albite, quartzand K-feldspar, or albite and corundum—tested the validityof the inferred directions of uncoupled diffusion and exploredlong-range chemical communication in the melt via chemical potentialgradients. The application of available solutions to the diffusionequations for the experimental quartz and feldspar dissolutiondata provides diffusivities along the directions of the Si-eigenvectorand Al-eigenvector of (2·0–2·8) x 10–15m2/s and (0·6–2·4) x 10–14 m2/s, respectively.Minimum diffusivities of alkalis [(3–9) x 10–11m2/s] are orders of magnitude greater than the tetrahedral componentsof the melt. The information provided here determines the rateat which crustal anatexis can occur when sufficient heat issupplied and diffusion is the only mass transport (mixing) processin the melt. The calculated diffusivities imply that a quartzo-feldspathicsource rock with initial grain size of 2–3 mm undergoinghydrostatic, H2O-saturated melting at 800°C (infinite heatsupply) could produce 20–30 vol. % of homogeneous meltin less than 1–10 years. Slower diffusion in H2O-undersaturatedmelts will increase this time frame. KEY WORDS: chemical diffusion; haplogranite; mineral dissolution experiments; crustal anatexis  相似文献   

5.
Major and trace element, Sr–Nd–Pb isotope and mineralchemical data are presented for newly discovered ultrapotassiclavas in the Tangra Yumco–Xuruco graben in southern Tibet.The ultrapotassic lavas are characterized by high MgO, K2O andTiO2, low Al2O3 and Na2O contents, and also have high molarK2O/Al2O3, molar (K2O + Na2O)/Al2O3 and K2O/Na2O ratios. Theirhigh abundances of incompatible trace elements such as largeion lithophile elements (LILE) and light rare earth elements(LREE) reach the extreme levels typical of lamproites. The lamproitesshow highly radiogenic 87Sr/86Sr (0· 7166–0·7363) and unradiogenic 143Nd/144Nd (0· 511796–0·511962), low 206Pb/204Pb (18· 459–18· 931),and elevated radiogenic 207Pb/204Pb (15· 6732–15·841) and 208Pb/204Pb (39· 557–40· 058) ratios.On the basis of their geochemical and isotopic systematics,the lamproites in south Tibet have a distinct magma source thatcan be differentiated from the sources of potassic lavas inthe east Lhasa and Qiangtang blocks. Their high Nb/Ta ratios(17· 10–19· 84), extremely high Th/U ratios(5· 70–13· 74) and distinctive isotope compositionsare compatible with a veined mantle source consisting of partialmelts of subducted Tethyan oceanic sediments and sub-continentallithospheric depleted mantle. Identification of the lamproitesand the delineation of their mantle source provide new evidencerelevant for models of the uplift and extension of the Tibetanplateau following the Indo-Asia collision. Metasomatism by partialmelts from isotopically evolved, old sediment subducted on theyoung Tethyan slab is an alternative explanation for PrecambrianNd and Pb model ages. In this model, differences in isotopiccomposition along-strike are attributed to differences in thetype of sediment being subducted, thus obviating the need formultiple metasomatic events over hundreds of million years.The distribution of lamproites, restricted within a north–south-trendinggraben, indicates that the initiation of east–west extensionin south Tibet started at 25 Ma. KEY WORDS: lamproites; subducted oceanic sediment; Tibetan active continental collision belt  相似文献   

6.
Within the Zitácuaro–Valle de Bravo (ZVB) regionof the central Mexican Volcanic Belt (MVB), three lava serieshave erupted during the Quaternary: (1) high-K2O basaltic andesitesand andesites; (2) medium-K2O basaltic andesites, andesitesand dacites; (3) high-TiO2 basalts and basaltic andesites. Thedominant feature of the first two groups is the lack of plagioclaseaccompanying the various ferromagnesian phenocrysts (olivine,orthopyroxene, augite, and hornblende) in all but the dacites.This absence of plagioclase in the phenocryst assemblages ofthe high-K2O and medium-K2O intermediate lavas is significantbecause it indicates high water contents during the stage ofphenocryst equilibration. In contrast, the high-TiO2 group ischaracterized by phenocrysts of plagioclase and olivine. Thespatial distribution of these three lava series is systematic.The southern section of the ZVB transect, 280–330 km fromthe Middle America Trench (MAT), is characterized by high-K2Omelts that are relatively enriched in fluid-mobile elementsand have the highest 87Sr/86Sr ratios. Medium-K2O basaltic andesiteand andesite lavas are present throughout the transect, butthose closest to the MAT are MgO-rich (3·5–9·4wt %) and have phenocryst assemblages indicative of high magmaticwater contents (3·5–6·5 wt % water) andrelatively low temperatures (950–1000°C). In markedcontrast, the northern section of the ZVB transect (380–480km from the MAT) has high-TiO2, high field strength element(HFSE)-enriched magmas that have comparatively dry (< 1·5wt % magmatic water) and hot (1100–1200°C) phenocrystequilibration conditions. The central section of the ZVB transect(330–380 km from the MAT) is a transition zone and producesmoderately light rare earth element (LREE) and large ion lithophileelement (LILE)-enriched, medium-K2O lavas with phenocryst assemblagesindicative of intermediate (1·5–3·5 wt %)water contents and temperatures. The high-K2O series compositionsare the most enriched in LILE and LREE, with a narrow rangeof radiogenic 87Sr/86Sr from 0·704245 to 0·704507,143Nd/144Nd values ranging from 0·512857 to 0·512927(Nd = 4·27–5·63), and 208Pb/204Pb valuesfrom 38·248 to 38·442, 207Pb/204Pb values from15·563 to 15·585, and 206Pb/204Pb values from18·598 to 18·688. The medium-K2O series compositionsare only moderately enriched in the LILE and LREE, with a broaderrange of 87Sr/86Sr, but similar 143Nd/144Nd and 208Pb/204Pbvalues to those of the high-K2O series. In contrast, the high-TiO2series compositions have little enrichment in LILE or LREE andinstead are enriched in the HFSE and heavy rare earth elements(HREE). The high-TiO2 lavas are isotopically distinct in theirlower and narrower range of 143Nd/144Nd. The isotopic variationsare believed to reflect the upper mantle magma source regionsas the low content of phenocrysts in most lavas precludes significantupper crustal assimilation or magma mixing, other than thatrepresented by the presence of quartz xenocrysts (< 2 vol.%) with rhyolitic glass inclusions, which are found in manyof these lavas. The systematic spatial variation in compositionof the three lava series is a reflection of the underlying subduction-modifiedmantle and its evolution. KEY WORDS: central Mexico; geochemistry; isotopes; Quaternary volcanism; hydrous lavas  相似文献   

7.
Experiments were conducted to determine the solubilities ofH2O and CO2 and the nature of their mixing behavior in basalticliquid at pressures and temperature relevant to seqfloor eruption.Mid-ocean ridge basaltic (MORB) liquid was equilibrated at 1200°Cwith pure H2O at pressures of 176–717 bar and H2O—CO2vapor at pressures up to 980 bar. Concentrations and speciationof H2O and CO2 dissolved in the quenched glasses were measuredusing IR spectroscopy. Molar absorptivities for the 4500 cm–1band of hydroxyl groups and the 5200 and 1630 cm–1 bandsof molecular water are 0•67±0•03, 0•62±0•07,and 25±3 l/mol-cm, respectively. These and previouslydetermined molar absorptivities for a range of silicate meltcompositions correlate positively and linearly with the concentrationof tetrahedral cations (Si+Al). The speciation of water in glass quenched from vapor-saturatedbasaltic melt is similar to that determined by Silver &Stolper (Journal of Petrology 30, 667–709, 1989) in albiticglass and can be fitted by their regular ternary solution modelusing the coefficients for albitic glasses. Concentrations ofmolecular water measured in the quenched basaltic glasses areproportional to f H2O in all samples regardless of the compositionof the vapor, demonstrating that the activity of molecular waterin basaltic melts follows Henry's law at these pressures. Abest fit to our data and existing higher-pressure water solubilitydata (Khitarov et al., Geochemistry 5, 479–492, 1959;Hamilton et al., Journal of Petrology 5, 21–39, 1964),assuming Henrian behavior for molecular water and that the dependenceof molecular water content on total water content can be describedby the regular solution model, gives estimates for the Vo, mH2Oof 12±1 cm3/mol and for the 1-bar water solubility of0•11 wt%. Concentrations of CO2 dissolved as carbonate in the melt forpure CO2-saturated and mixed H2O-CO2-saturated experiments area simple function of fCO2 These results suggest Henrian behaviorfor the activity of carbonate in basaltic melt and do not supportthe widely held view that water significantly enhances the solutionof carbon dioxide in basaltic melts. Using a Vo, mr of 23 cm3/mol(Pan et al., Geochimica et Cosmochimica Acta 55, 1587–1595,1991), the solubility of carbonate in the melt at 1 bar and1200°C is 0•5 p.p.m. Our revised determination of CO2solubility is 20% higher than that reported by Stolper &Holloway (Earth and Planetary Science Letters 87, 397–408,1988). KEY WORDS: mid-ocean ridge basalts; water and carbon dioxide solubility; experimental petrology  相似文献   

8.
Kornerupine and associated minerals in 31 samples of high-graderocks relatively rich in Al and Mg were analysed by wet chemistry,ion microprobe mass analyser, electron microprobe and X-raypowder diffraction. For 11 samples of kornerupine and threesamples of biotite (F only) analysed by both wet chemical andion microprobe methods, the best agreement was obtained forB2O3, whereas the ion microprobe Li2O values were systematicallysomewhat higher than the wet chemical values. The wet chemicalmethods give Li2O=0–0?19 wt.%; BeO=0–0?032 wt.%;B2O3=0–4?01 wt.%; and F=0?07–0?77 wt.% in kornerupine,whereas ion microprobe analyses on other kornerupines give valuesup to 0?35 wt.% Li2O, O066 wt.% BeO, and 4?72 wt.% B2O3. Thesum B+Al+Fe3++Cr is close to 6?9 atoms per 22 (O, OH, F) or21?5 (O) in kornerupine. In general, Li/Fe ratios decrease as follows: kornerupine ?sapphirinebiotite> Crd (Na<0?03 per 18 oxygens)>tourmaline, garnet,orthopyroxene. However, for cordierite with Na>004, Li/Fedecreases as follows: cordierite>kornerupine. Sapphirineand sillimanite are the only associated minerals to incorporatesignificant boron (0?1–0?85 wt.% B2O3) and then only whenthe single site for B in kornerupine is approaching capacity.Sillimanite B2O3 contents increase regularly with kornerupineF. Fractionation of fluorine increases as follows: kornerupine<biotite<tourmaline,and Kkrn-BtD=(F/OH)Krn/(F/(OH)Bt (assuming ideal anion composition)increases with biotite Ti. Kornerupine B2O3 content is a measureof B2O3 activity in associated metamorphic fluid, whereas sillimaniteB2O3 content increases with temperature, exceeding 0?4 wt.%whenT=900?C at very low water activities. New data on 11 kornerupines and literature data indicate thatthe unit cell parameters a, c, and V decrease with increasingB content and b, c, and V increase with increasing Fe3+ content.In Fe3+-poor kornerupines, b increases with Mg and with (Mg+ Fe2+) but the effect of Mg on b via the substitution VIMg+IVSi=VIAl+IVAloverwhelms the effect of Fe2+=Mg substitution.  相似文献   

9.
We have performed time series experiments for periods rangingfrom 3 min to 44 h on the interaction of granite melt and partiallymolten basalt at 920C and 10 kbar, in the presence of 5 wt.%water. With time, the assemblage of the basalt domain changesfrom predominantly amphibole+plagioclase to clinopyroxene+garnet;the melt fraction increases from {small tilde}2•5 to 40%;and between the two domains, the melt compositions progressivelyequilibrate. Initially in each run, melts of the basalt domainhave uniform plateau concentrations for SiO2, Al2O3, CaO, MgO,and FeO because the activities of these components are regulatedby the mineral assemblage, but at advanced stages of reaction,no such control is evident. We have derived analytical expressionsto describe and simulate the diffusion profiles. The concentrationprofiles for SiO2, Al2O3, CaO, and Na2O in the granite, emanatingfrom the basalt–granite interface, have been used to estimateeffective diffusivities. The values from the shorter runs arecompared with those of the experiment of longest duration forwhich we assumed finite couples in our calculations. In thediffusion calculations for K2O the difference in melt fractionbetween the two domains is accounted for. The resulting values(in cm2/s) are: DNa2O=6 10–7, DK2O=3 10–7, DMgO=9 10–8, DCaO=(4–6) 10–8, and DSiO2 and DAl2O3=(3–0•6) 10–8. They are in reasonable agreement with values fromother studies. On the basis of our experiments we calculatethat mafic enclaves of magmatic origin should equilibrate toa large degree with their host magma in slowly cooling non-convectinggranitic plutons. Enclaves approaching complete re-equilibrationretain distinctly higher modal amounts of mafic minerals. Theydo not compositionally resemble binary magma mixtures, but aremore like host magma with accumulated crystals. We show thatthe modal differences between enclave and host are indicativeof the temperature of homogenization and that, in principle,this temperature can be deduced from equilibrium phase diagrams. * Present address: Mineralogisch-Petrologisches Institut, Universitt Gttingen, Goldschmidtstrasse 1, 3400 Gttingen, Germany  相似文献   

10.
A new method has been suggested for evaluating the overall basicityof minerals and rocks by using ionization reactions involvingone proton: (sum of cations) + H2O = mineral + H+, (sum of cations) + H2O = (sum of normative minerals of a rock)+ H+. The basicity indicators are expressed as standard free energychanges of these reactions (). At standard water pressure (logPH2O = 0) and chemical activity of the metal ions ( log Mn+= 0), the relationship between and alkalinity of solutions(pH) becomes: = –2.303 RTlog H+ = 2.303 RT pH. The overall basicities of rock-forming oxides, minerals andmajor rocks were calculated from the thermodynamic data on ionsin water solutions and solid compounds.  相似文献   

11.
Calorimetric and experimental data on AlF-bearing titanite are presented that yield thermodynamic properties of CaAlFSiO4, as well as activity-composition relations of binary titanite CaTiOSiO4-CaAlFSiO4. The heat capacity of synthetic CaAlFSiO4 was measured with differential scanning calorimetry between 170 and 850 K: CP=689.96-0.38647T+2911300T-2-8356.1T-0.5+0.00016179T2 Based on low-temperature heat capacity calculations with lattice vibrational theory (Debye model), the calorimetric entropy of CaAlFSiO4 can be expected to lie between 104.7 and 118.1 J mol-1 K-1. The temperature of the P21/a to A2/a phase change was determined calorimetrically for a titanite with XAl=0.09 (Ttransition=390 K). The decrease of the transition temperature at a rate of about 11 K per mol% CaAlFSiO4 is in good agreement with previous TEM investigations. The displacement of the reaction anorthite + fluorite = CaAlFSiO4 in the presence of CaTiOSiO4 was studied with high P-T experiments. Titanite behaves as a non-ideal, symmetrical solid-solution. The thermodynamic properties of CaAlFSiO4 consistent with a multi-site mixing model are: % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfKttLearuavTnhis1MBaeXatLxBI9gBam % XvP5wqSXMqHnxAJn0BKvguHDwzZbqegm0B1jxALjhiov2Daebbnrfi % fHhDYfgasaacH8srps0lbbf9q8WrFfeuY-Hhbbf9v8qqaqFr0xc9pk % 0xbba9q8WqFfea0-yr0RYxir-Jbba9q8aq0-yq-He9q8qqQ8frFve9 % Fve9Ff0dmeaabaqaciaacaGaaeqabaWaaeaaeaaakeaafaqaaiWaca % aabaGaeeyrauKaeeOBa4MaeeiDaqNaeeiAaGMaeeyyaeMaeeiBaWMa % eeiCaaNaeeyEaKNaeeiiaaIaee4Ba8MaeeOzayMaeeiiaaIaeeOzay % Maee4Ba8MaeeOCaiNaeeyBa0MaeeyyaeMaeeiDaqNaeeyAaKMaee4B % a8MaeeOBa4MaeeiiaaIaeeikaGIaeeyzauMaeeiBaWMaeeyzauMaee % yBa0MaeeyzauMaeeOBa4MaeeiDaqNaee4CamNaeeykaKIaeeiiaaIa % emizaq2aaSbaaSqaaiabdAgaMbqabaGccqWGibasdaahaaWcbeqaai % abicdaWaaaaOqaaiabg2da9iabgkHiTiabikdaYiabiEda3iabisda % 0iabicdaWiabc6caUiabiIda4iabgglaXkabiodaZiabc6caUiabic % daWiabbccaGiabbUgaRjabbQeakjabb2gaTjabb+gaVjabbYgaSnaa % CaaaleqabaGaeyOeI0IaeGymaedaaaGcbaGaee4uamLaeeiDaqNaee % yyaeMaeeOBa4MaeeizaqMaeeyyaeMaeeOCaiNaeeizaqMaeeiiaaIa % ee4CamNaeeiDaqNaeeyyaeMaeeiDaqNaeeyzauMaeeiiaaIaeeyzau % MaeeOBa4MaeeiDaqNaeeOCaiNaee4Ba8MaeeiCaaNaeeyEaKNaeeii % aaIaee4uam1aaWbaaSqabeaacqqGWaamaaaakeaacqqG9aqpcqqGXa % qmcqqGWaamcqqG0aancqqGUaGlcqqG5aqocqGHXcqScqqGXaqmcqqG % UaGlcqqGXaqmcqqGGaaicqqGkbGscqqGTbqBcqqGVbWBcqqGSbaBda % ahaaWcbeqaaiabgkHiTiabigdaXaaakiabbUealnaaCaaaleqabaGa % eyOeI0IaeGymaedaaaGcbaGaeeyta0KaeeyyaeMaeeOCaiNaee4zaC % MaeeyDauNaeeiBaWMaeeyzauMaee4CamNaeeiiaaIaeeiCaaNaeeyy % aeMaeeOCaiNaeeyyaeMaeeyBa0MaeeyzauMaeeiDaqNaeeyzauMaee % OCaiNaeeiiaaYaamWaaeaacqWGxbWvdaWgaaWcbaGaemisaG0aaWba % aWqabeaacqGHsislaaaaleqaaOGaeeivaqLaem4vaC1aaSbaaSqaai % abdohaZbqabaaakiaawUfacaGLDbaaaeaacqGH9aqpcqaIXaqmcqaI % ZaWmcqGGUaGlcqaI2aGncqGHXcqScqaIWaamcqGGUaGlcqaI0aanca % aMe8UaeeOsaOKaeeyBa0Maee4Ba8MaeeiBaW2aaWbaaSqabeaacqGH % sislcqaIXaqmaaaaaaaa!E403!
Enthalpy of formation (elements) df H0
amp; = - 2740.8 ±3.0kJmol - 1
Standard state entropy S0
amp; = 104.9 ±1.1 Jmol - 1 K - 1
WV) was determined from the excess volume of mixing based on XRD measurements (214ᆦ J mol-1 kbar-1), as well as refined from the piston-cylinder experimental results (198뀺 J mol-1 kbar-1), demonstrating consistency between crystal structure data and thermodynamic properties. The stability of AlF-bearing titanite Ca(Ti,Al)(O,F)SiO4 was investigated by thermodynamic modelling in the system Ca-Al-Si-Ti-O-F-H-C and subsystems. The petrogenetic grids are in good agreement with natural mineral assemblages, in that very Al-rich titanite (XAl>0.65ǂ.15) is generally absent because it is either unstable with respect to other phases, or its stability field lies outside the P-T conditions realised on Earth. The grids explain both the predominant occurrence of natural Al-rich titanite at high metamorphic grade such as eclogite facies conditions, as well as its scarcity in blueschist facies rocks. Wide spacing of the Al-isopleths for titanite of many high-grade assemblages prevents their use as geobarometers or thermometers. The instability of end-member CaAlFSiO4 with respect to other phases in most assemblages modelled here is consistent with the hypothesis that the presence of structural stresses in the crystal lattice of CaAlFSiO4 influences its thermodynamic stability. The titanite structure is not well suited to accommodate Al and F instead of Ti and O, causing the relatively high Gibbs free energy of CaAlFSiO4, manifested in its standard state properties. Thus, the increasing amount of CaAlFSiO4 along the binary join is the reason why titanite with XAl>0.65ǂ.15 becomes unstable in most petrogenetic grids presented here. The compositional limit of natural titanite (XAlƸ.54) probably reflects the point beyond which the less stable end member begins to dominate the solid-solution, affecting both crystal structure and thermodynamic stability.  相似文献   

12.
Mineral assemblages in pegmatite samples from Kolsva, Swedenand Marikov, Czechoslovakia show that chrysoberyl is alwaysaccompanied by quartz, and is a breakdown product of primarypegmatitic beryl. Textures and the mineral-forming process forthe Kolsva pegmatite are explained by the reactions beryl +K-feldspar + H+ = chrysoberyl + quartz + SiO2, aq + K+ + H2Oor alternatively beryl —K—feldspar + H2O = chrysoberyl+ quartz + melt. Mineral assemblages from mica-rich parts ofthe pegmatite include sillimanite—K—feldspar, muscovite—K—feldspar—sillimanite,and annite—magnetite—spinel—sillimanite—garnet.Details about the composition and the textural relationshipsof these minerals are given; they indicate a post-pegmatiticmetamorphic event at P—T conditions near to the anatecticregime. The samples from Marikov show textures, which are explainedby the reactions beryl + albite + H+ = chrysoberyl + quartz+ Na+ + H2O or alternatively beryl + albite + H2O = chrysoberyl+ quartz + melt. Breakdown of muscovite produces sillimaniteaccording to the reactions beryl + albite + muscovite + H+ =chrysoberyl + quartz + sillimanite + Na+ + K+ + H2O or alternativelyberyl + albite + muscovite + H2O = chrysoberyl + quartz + sillimanite+ melt. Similar reaction textures and mineral assemblages were foundin other chrysoberyl-bearing pegmatites (Maroankora, Madagascar;Helsinki, Finland; Haddam, Greenfield, Greenwood, U.S.A.). Hydrothermal experiments located the reaction beryl + alkalifeldspar + H2O = chrysoberyl + phenakite + melt at P—Tconditions between the K—feldspar—quartz—H2Osolidus and the K—feldspar—albite—quartz-H2Osolidus. It is concluded that the formation of Al-rich minerals likechrysoberyl and sillimanite in pegmatites is due to a post-pegmatiticevent at high P—T conditions. The question as to whichof the alternative set of reactions is more likely, the ionicequilibria or the anatectic chrysoberyl formation, must be leftopen. The previous hypothesis of a desilification of a pegmatitewhich intruded into SiO2-poor country rocks, or of the assimilationof Al2O3-rich country rocks, cannot explain the mineral assemblagesof the two pegmatites.  相似文献   

13.
Phase relations for the bulk compositions 3CaO·2FeOx·3SiO2+excessH2O and CaO·FeOx·2SiO2+excess H2O were determinedusing conventional hydrothermal techniques with solid phaseoxygen buffers to control fO2. Andradite, Ca3Fe3+2Si3O12, synthesized above 550 °C hasan average unit cell edge, ao, of 12.055±0.001 Å,and an index of refraction, n, of 1.887±0.003. Belowthis temperature, ao increases whereas n decreases, indicatingthe formation of a member of the andradite-hydroandradite solidsolution. At 2000 bars Pfluid andradite is stable above an fO2of 1015 bar at 800 °C and 10-32 bar at 400 °C. At lowerfO2 andradite+fluid gives way at successively lower temperaturesto the condensed assemblages magnetite+wollastonite, kirschsteinite(CaFe2+SiO4)+ wollastonite and kirschsteinite+xonotlite (Ca6Si6O17(OH)2). Synthetic hedenbergite, CaFe2+Si2O6, has average unit cell dimensionsof ao = 9.857± 0.004 Å, bo = 9.033±0.002Å, co = 5.254±0.002 Å and ß = 104.82°±0.03°,and refractive indices of n = 1.731±0.003 and n = 1.755±0.005.At 2000 bars Pfiuid, hedenbergite is stable below an fO2 of10-13 bar at 800 °C and 10-28 bar at 400 °C. Above thesefO2 values, hedenbergite+O2 breaks down to andradite+magnetite+quartz. The mineral pair andradite +hedenbergite thus limit the fO2range possible for their joint formation under equilibrium conditions. The hydration of wollastonite to xonotlite occurs at much lowertemperatures than previous experimental work indicated. A tentativehigh temperature limit for this reaction is set at 185°±15°C and 5000±25 bars and 210°±15 °Cand 2000±20 bars. Inasmuch as the growth of xonotlitefrom wollastonite + H2O was never accomplished, this high temperaturelimit does not represent an equilibrium univariant curve. Nine phases were encountered in the study of andradite and hedenbergite.They are andradite, hedenbergite, magnetite, wollastonite, kirschsteinite,xonotlite, quartz, ilvaite, and vapor (fluid). An invariantpoint analysis using the method of Schreinemakers shows thetopologic relations of the reactions involved. The resultinggrid can be used to interpret natural occurrences.  相似文献   

14.
Subsolidus phase relations have been determined in the systemsSiO2-Cr-0 and MgO-SiO2-Cr-O in equilibrium with metallic Cr,at 1100–1500C and 0–288 kbar. There are no ternaryphases in the SiO2-Cr-O system at these conditions, ie. onlythe assemblage eskolaite + Cr-metal + SiO2 is found. However,in the MgO-containing system, extensive substitution of Cr2+for Mg is observed in (Mg,Cr2+)2SiO4 olivine, (Mg,Cr2+)2Si2O6pyroxene, and (Mg,Cr2+)Cr3+204 spinel. Cr 3+ levels in olivineand pyroxene are below detection limits. The pyroxene is orthorhombicat monoclinic at higher . The structure of the spinels becomestetragonally distorted at is limited by the breakdown of olivine to pyroxene + spinel+ metal. This maximum amount increases strongly with increasingtemperature, reaching >0.2 at 1500C and 48 kbar. Increasing pressure reduces the maximum. Increasing temperature also increases the maximum amounts of Cr2+ which substitute intopyroxene and spinel, indicating that end-member Cr2Si206 andCr3O4 may become stable above 1650C if melting does not intervene.Powder X-ray diffraction analysis of selected runs has beenused to extract molar volumes of the Mg-Cr2+ solid solutionsas a function of composition, which may be extrapolated to predictmolar volumes for Cr2SiO4 (olivine), Cr2Si2O6 (ortho- and clino-pyroxene)and Cr2O4 (cubic spinel) of 477, 680 and 449 cm3, respectively.The experimental data have been fitted to a thermodynamic model,including free energies of formation for end member Cr2SiO4,Cr2Si2O6 and Cr3O4. This model is then used to predict the amountsof Cr2+ which can be expected in olivine in equilibrium withCr-bearing spinel as a function of T, P and fo2. This amountincreases strongly with temperature along standard T-fo2 buffercurves, and is sufficient to explain the observed high Cr contentsof olivine from komatiites and diamond inclusions at reasonableterrestrial fo, values. The lower fo2 of the lunar environmentresults in significant Cr2+ in olivine being stable to muchlower temperatures. The tendency for the oxidation state ofCr, and hence its geochemical properties, to change with temperaturerelative to other redox reactions makes it a potentially usefulmonitor of the temperatures of uppermantle processes, and isa significant factor in the differing styles of igneous differentiationin the Earth and Moon. Corresponding author  相似文献   

15.
Four natural peridotite nodules ranging from chemically depletedto Fe-rich, alkaline and calcic (SiO2 = 43.7–45.7 wt.per cent, A12O3 = 1.6O–8.21 wt. per cent, CaO = 0.70–8.12wt. per cent, alk = 0.10–0.90 wt. per cent and Mg/(Mg+Fe2+)= 0.94–0.85) have been investigated in the hypersolidusregion from 800? to 1250?C with variable activities of H2O,CO2, and H2. The vapor-saturated peridotite solidi are 50–200?Cbelow those previously published. The temperature of the beginningof melting of peridotite decreases markedly with decreasingMg/(Mg+SFe) of the starting material at constant CaO/Al2O3.Conversely, lowering CaO/Al2O3 reduces the temperature at constantMg/(Mg+Fe) of the starting material. Temperature differencesbetween the solidi up to 200?C are observed. All solidi displaya temperature minimum reflecting the appearance of garnet. Thisminimum shifts to lower pressure with decreasing Mg/(Mg + Fe)of the starting material. The temperature of the beginning ofmelting decreases isobarically as approximately a linear functionof the mol fraction of H2O in the vapor (XH2Ov). The data alsoshow that some CO2 may dissolve in silicate melts formed bypartial melting of peridotite. Amphibole (pargasitic hornblende) is a hypersolidus mineralin all compositions, although its P/T stability field dependson bulk rock chemistry. The upper pressure stability of amphiboleis marked by the appearance of garnet. The vapor-saturated (H2O) liquidus curve for one peridotiteis between 1250? and 1300?C between 10 and 30 kb. Olivine, spinel,and orthopyroxene are either liquidus phases or co-exist immediatelybelow the temperature of the peridotite liquidus. The data suggest considerable mineralogical heterogeneity inthe oceanic upper mantle because the oceanic geotherm passesthrough the P/T band covering the appearance of garnet in variousperidotites. The variable depth to the low-velocity zone is explained byvariable aHjo conditions in the upper mantle and possibly alsoby variations in the composition of the peridotite itself. Itis suggested that komatiite in Precambrian terrane could formby direct melting of hydrous peridotite. Such melting requiresabout 1250?C compared with 1600?C which is required for drymelting. The genesis of kimberlite can be related to partial meltingof peridotite under conditions of XH2Ov = 0.5–0.25 (XCO2v= 0.5–0.75). Such activities of H2O result in meltingat depths ranging between 125 and 175 km in the mantle. Thisrange is within the minimum depth generally accepted for theformation of kimberlite.  相似文献   

16.
Blue Mountain is a central-type alkali ultrabasic-gabbro ringcomplex (lxl7middot;5 km) introducing Upper Jurassic sediments,Marlborough, New Zealand. The ultrabasic-gabbroic rocks containlenses of kaersutite pegmatite and sodic syenite pegmatite andare intruded by ring dykes of titanaugite-ilmenite gabbro andlamprophyre. The margin of the intrusion is defined by a ringdyke of alkali gabbro. The plutonic rocks are cut by a swarmof hornblendebiotite-rich lamprophyre dykes. Thermal metamorphismhas converted the sediments to a hornfels ranging in grade fromthe albite-epidote hornfels facies to the upper limit of thehornblende hornfels facies. The rocks are nepheline normative and consist of olivine (Fo82–74),endiopside (Ca45Mg48Fe7–Ca36Mg55Fe9), titanaugite (Ca40Mg50Fe10–Ca44Mg39Fe17),plagioclase (An73–18), and ilmenitetitaniferous magnetite,with various amounts of titaniferous hornblende and titanbiotite.There is a complete gradation between endiopside and titanaugitewith the coupled substitution Ry+2+Si;;(Ti+4+Fe+3+Al+3 and asympathetic increase in CaAl2SiO6 (0·2–10·2percent) and CaTiAl2O6 (2·1–8·1 per cent)with fractionation. Endiopside shows a small, progressive Mgenrichment along a trend subparallel to the CaMgSi2O6–Mg2Si2O6boundary, and titanaugite is enriched in Ca and Fe+2+Fe+3 withdifferentiation. Oscillatory zoning between endiopside and titanaugiteis common. Exsolved ilmenite needles occur in the most Fe-richtitanaugites. The amphiboles show the trend: titaniferous hornblende(1·0–57middot;7 per cent TiO2) kaersutite (6·4per cent TiO2) Fe-rich hastingsite (18·0–19·1per cent FeO as total Fe). Biotite is high in TiO2 (6·6–7·8per cent). Ilmenite and titaniferous magnetite (3·5–10·6per cent TiO2) are typically homogeneous grains; their compositioncan be expressed in terms of R+2RO3:R+2O:R2+3O4. The intrusion of igneous rocks was probably controlled by subterraneanring fracturing. Subsidence of the country rock within the ringfracture provided space for periodic injections of magma froma lower reservoir up the initial ring fracture to form the BlueMountain rocks at a higher level. Downward movement of the floorof the intrusion during crystallization caused inward slumpingof the cumulates which affected the textural, mineralogical,and chemical evolution of the rocks in different parts of theintrusion. The order of mineral fractionation is reflected by the chemicalvariation in the in situ ultrabasic-gabbroic rocks and the successiveintrusions of titanaugite-ilmenite gabbro and lamprophyre ringdykes, marginal alkali gabbro and lamprophyre dyke swarm. Aninitial decrease, then increase in SiO2; a steady decrease inMgO, CaO, Ni, and Cr: an initial increase, then decrease inFeO+Fe2O3, TiO2, MnO, and V; almost linear increase in A12O3and late stage increase in alkalis and P2O3, implies fractionationof olivine and endiopside, followed by titanaugite and Fe-Tioxides, followed by plagioclase, hornblende, biotite, and apatite.Reversals in the composition of cumulus olivine and endiopsideand Solidification Index, indicate that the ultrabasic-gabbroicsequence is composed of four main injections of magma. The ultrabasic rocks crystallized under conditions of high PH2Oand fairly high, constant  相似文献   

17.
Anomalous geogenic arsenic occurs in drinking water from the Goose River crystalline ground-watershed in mid-coastal Maine. Isotope investigations were useful in understanding release areas of arsenic into affected water wells. The isotope composition of sulfate associated with probable arsenian pyrite oxidation is described. Correlation of '18OSO4 enrichment [+4.57 to +7.46‰ Vienna Standard Mean Ocean Water (VSMOW)] is discussed with specific and recurring areas of elevated arsenic (10-52 µg l-1). Although arsenic concentrations were highly variable over 2 years per well, '18OSO4 values were always consistent and suggested a specific and consistent risk for elevated arsenic occurrences for each well. The '18O values in the water molecule (-12.07 to -8.81‰ VSMOW) and the '18OSO4 values may serve as prospective indicators of prominent zones of aeration at depth in discrete fracture zones. The '18O values in the water molecule and sulfate ion appear to indicate that more than 60% of O2 incorporated into the SO42- ion are from dissolved oxygen and belong to distinct fractured areas. These aeration zones or oxidation fronts, as outlined by oxygen isotopes, are sentinels for high arsenic risk in groundwater.  相似文献   

18.
Potassic volcanic rocks from the Wudalianchi, Erkeshan and Keluo(WEK) fields in NE China are located between the Mesozoic SongliaoBasin and the Palaeozoic Xing'am Mountains fold belt. Theserocks erupted during three main eruptive episodes-Miocene (9•6–7•0Ma), Pleistocene (0•56–0•13 Ma) and Recent (AD1719–1721)-and are subdivided into three types-olivineleucitite, leucite basanite and trachybasalt—on the basisof modal composition. In comparison with Cenozoic alkaline basaltsfrom East China that are similar to oceanic island basalts (OIBs),WEK volcanic rocks are lower in Al2O3, CaO, Fe2O3 and Sc, buthigher in K2O (3•5–7•1 wt %), K2O/Na2O (>1)and incompatible elements. High 87Sr/86Sr (0•7050–0•7056),low 143Nd/144Nd (0•51238–0•51250) and 206Pb/204Pb(17•06–16•61) ratios also distinguish them fromoceanic and Chinese basalts. Trace element and isotope dataindicate that a post-Archaean subcontinental lithospheric mantlesource similar to the postulated EM1 component (enriched mantlewith low l43Nd/144Nd and moderate high 87Sr/86Sr) must haveplayed a significant role in magma generation. The source rockis considered to be refractory phlogopite-bearing garnet peridotiteheterogeneously enriched in both large ion lithophile elementsand light rare earth elements by ancient metasomatism duringProterozoic times. This source may have mixed recently withOIB-like melts, but has not been modified by subduction of theKula-Pacific plate. Primitive WEK potassic magma was generatedby a low degree of partial melting, initiated by an extensionalphase beginning in the late Tertiary, at pressures of 20–45kbar and in the presence of mixed volatile components of H2O,CO2 and halogens. KEY WORDS: potassic volcanic rocks; NE China; geochemistry; montle sourc *Corresponding author. Present address: Centre for Petrology and Lithoipheric Studies, School of Earth Sciences, Macquarie University, NSW 2109, Australia  相似文献   

19.
Mount Galunggung is a historically active volcano in southwesternJava that has erupted four times in the last two centuries.During the most recent event, which occurred during a 9–monthinterval in 1982– 83, some 305 106 m3 of medium–K,calc–alkaline magma was erupted. This eruption was unusualbecause of its duration, the diversity of eruption dynamicsand products, and the range of lava compositions produced. Thecomposition of juvenile material changed gradually during thecourse of the eruption from initial plagioclase (An60–75)and two–pyrozene bearing andesites with 58% SiO2 to finalplagioclase (An85–90), diopside, and olivine (Fo85–90)bearing primitive magnesium basalts with 47% SiO2 Mineralogicaland compositional relationships indicate a magmatic evolutioninvolving differentitation of high–Mg parental melt. Theeruptive volumes of 35 106 m3 andesite, 120 106 m3 maficandesite, and 150 106 m3 basalt are consistent with the ideathat the 1982– 83 eruption progressively tapped and draineda magma chamber that had become chemically stratified throughextensive crystal fractionation. Separates of plagioclase and pyroxene have 18O( SMO W) rangesof + 5. 6 to + 6.0 and + 5.3 to + 5.6, respectively, with 18Oplag–pxvalues of + 0.4 to + 0.6o, indicating internal O–isotopeequiliburium at temperature of 1100–850 C. The magenesianbasalts have magmatic 18O/ 16O ratios similar to those of mid–oceanridge basalt, and the O–isotope ratios of compositionallyevolved derivative melts show no evidence for contaminationof the galunggung magmas by 18O–rich crust during differentiation.Andesites and transitional mafic and sites have a more variableO–isotope character, with laves and phenocrysts havingboth higher and lower 18O values than observed in the parentalmagnesium basalts. These features are interpreted to reflectintramagma chamber processes affecting the upper portions ofthe differentiating Galunggung magma body before the 1982–83eruption.  相似文献   

20.
Blue Mountain is a central-type alkali ultrabasic-gabbro ringcomplex (1?1?5 km) introducing Upper Jurassic sediments, Marlborough,New Zealand. The ultrabasic-gabbroic rocks contain lenses ofkaersutite pegmatite and sodic syenite pegmatite and are intrudedby ring dykes of titanaugite-ilmenite gabbro and lamprophyre.The margin of the intrusion is defined by a ring dyke of alkaligabbro. The plutonic rocks are cut by a swarm of hornblende-biotite-richlamprophyre dykes. Thermal metamorphism has converted the sedimentsto a hornfels ranging in grade from the albite-epidote hornfelsfacies to the upper limit of the hornblende hornfels facies. The rocks are nepheline normative and consist of olivine (Fo82-74),endiopside (Ca45Mg48Fe7-Ca36Mg55Fe9), titanaugite (Ca40Mg50Fe10-Ca44Mg39Fe17),plagioclase (An73-18), and ilmenitetitaniferous magnetite, withvarious amounts of titaniferous hornblende and titanbiotite.There is a complete gradation between end-iopside and titanaugitewith the coupled substitution Ry+z+Si(Ti+4+Fe+3)+Al+3 and asympathetic increase in CaAl2SiO6 (0?2-10?2 percent) and CaTiAl2O6(2?1-8?1 per cent) with fractionation. Endiopside shows a small,progressive Mg enrichment along a trend subparallel to the CaMgSi2O6-Mg2Si2O6boundary, and titanaugite is enriched in Ca and Fe+2+Fe+3 withdifferentiation. Oscillatory zoning between endiopside and titanaugiteis common. Exsolved ilmenite needles occur in the most Fe-richtitanaugites. The amphiboles show the trend: titaniferous hornblende(1?0–5?7 per cent TiO2)kaersutite (6?4 per cent TiO2)Fe-richhastingsite (18?0–19?1 per cent FeO as total Fe). Biotiteis high in TiO2 (6?6–7?8 per cent). Ilmenite and titaniferousmagnetite (3?5–10?6 per cent TiO2) are typically homogeneousgrains; their composition can be expressed in terms of R+2RO3:R+2O:R2+3O4. The intrusion of igneous rocks was probably controlled by subterraneanring fracturing. Subsidence of the country rock within the ringfracture provided space for periodic injections of magma froma lower reservoir up the initial ring fracture to form the BlueMountain rocks at a higher level. Downward movement of the floorof the intrusion during crystallization caused inward slumpingof the cumulates which affected the textural, mineralogical,and chemical evolution of the rocks in different parts of theintrusion. The order of mineral fractionation is reflected by the chemicalvariation in the in situ ultrabasic-gabbroic rocks and the successiveintrusions of titanaugite-ilmenite gabbro and lamprophyre ringdykes, marginal alkali gabbro and lamprophyre dyke swarm. Aninitial decrease, then increase in SiO2; a steady decrease inMgO, CaO, Ni, and Cr: an initial increase, then decrease inFeO+Fe2O3, TiO2, MnO, and V; almost linear increase in Al2O3and late stage increase in alkalis and P2O3, implies fractionationof olivine and endiopside, followed by titanaugite and Fe-Tioxides, followed by plagioclase, hornblende, biotite, and apatite.Reversals in the composition of cumulus olivine and endiopsideand Solidification Index, indicate that the ultrabasic-gabbroicsequence is composed of four main injections of magma. The ultrabasic rocks crystallized under conditions of high PH2Oand fairly high, constant PO2; PH2 and PO2 increased duringthe formation of the gabbroic rocks until fracturing of thechamber roof occurred. The abundance of euhedral amphibole inthe latter injection phases suggests that amphibole accumulatedfrom a hydrous SiO2 undersaturated magma when an increase inPO2, stabilized its crystallization. Plutonic complexes similar to Blue Mountain are found withinand beneath the volcanic piles of many oceanic islands, e.g.Canaries, Reunion, and Tahiti, and those intruding thick sedimentarysequences, as at Blue Mountain, e.g. the pipe-like intrusionsof the Monteregian Hills, Quebec.  相似文献   

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