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1.
From considerations of relativeG-T surfaces inferred from publishedP-T data and the occurrence of replacement textures of Al2SiO5 polymorphs in rocks, the relative positions of curves representing the following equation in K+ —T — pH ispace on substituting Al2SiO5 different polymorphs are derived.3 Al2SiO5 + 3 SiO2 (quartz) + 2 K+ + 3 H2O 2 KAl2[AlSi3O10](OH)2 (muscovite)+ 2 H+. The curves are different because of the differentG-T values for the polymorphs which, in the field, is borne out by the observation that in a rock containing two or three Al2SiO5 polymorphs, in nearly all instances only one polymorph is replaced by white mica. Instances of textural relations showing the interpreted selective replacement of one Al2SiO5 polymorph by a white mica in the presence of one (or two) other Al2SiO5 polymorph(s) are cited both from the literature and various field examples. The selective replacement of kyanite if sillimanite and/or andalusite is/are present, and of andalusite if only sillimanite is present are interpreted to show that generally during the muscovitization reaction, the field of sillimanite in the above reaction (left hand side) at a particular pH (H+ concentration) and is larger in K+ —T space than that of andalusite which in turn is larger than that of kyanite. Theoretically it is shown that variations to this can exist but the field evidence suggests these only occur under rare geological conditions. Although this is not totally conclusive, the selectiveness of the replacement is interpreted to show that the fluid was buffered with respect to K+ and H+ on or near the curve of the polymorph showing the lowest stability field until that polymorph is totally consumed, after which the fluid composition moves to the next lowest curve for the remaining polymorph(s) present in the rock. The alteration of more than one polymorph by an apparently simultaneous process of alteration is rare and usually occurs at a low grade of metamorphism. This is interpreted to show that the buffering reaction could not keep pace with the influx of fluid and change the composition of this fluid (in most cases).  相似文献   

2.
Modern chemical sediments display a distinctive rare earth element + yttrium (REE + Y) pattern involving depleted LREE, positive La/La*SN, Eu/Eu*SN, and YSN anomalies (SN = shale normalised) that is related to precipitation from circumneutral to high pH waters with solution complexation of the REEs dominated by carbonate ions. This is often interpreted as reflecting precipitation from surface waters (usually marine). The oldest broadly accepted chemical sediments are c. 3,700 Ma amphibolite facies banded iron-formation (BIF) units in the Isua supracrustal belt, Greenland. Isua BIFs, including the BIF international reference material IF-G are generally considered to be seawater precipitates, and display these REE + Y patterns (Bolhar et al. in Earth Planet Sci Lett 222:43–60, 2004). Greenland Eoarchaean BIF metamorphosed up to granulite facies from several localities in the vicinity of Akilia (island), display REE + Y patterns identical to Isua BIF, consistent with an origin by chemical sedimentation from seawater and a paucity of clastic input. Furthermore, the much-debated magnetite-bearing siliceous unit of “earliest life” rocks (sample G91/26) from Akilia has the same REE + Y pattern. This suggests that sample G91/26 is also a chemical sediment, contrary to previous assertions (Bolhar et al. in Earth Planet Sci Lett 222:43–60, 2004), and including suggestions that the Akilia unit containing G91/26 consists entirely of silica-penetrated, metasomatised, mafic rock (Fedo and Whitehouse 2002a). Integration of our trace element data with those of Bolhar et al. (Earth Planet Sci Lett 222:43–60, 2004) demonstrates that Eoarchaean siliceous rocks in Greenland, with ages from 3.6 to 3.85 Ga, have diverse trace element signatures. There are now geographically-dispersed, widespread examples with Isua BIF-like REE + Y signatures, that are interpreted as chemically unaltered, albeit metamorphosed, chemical sediments. Other samples retain remnants of LREE depletion but are beginning to lose the distinct La, Eu and Y positive anomalies and are interpreted as metasomatised chemical sediments. Finally there are some siliceous samples with completely different trace element patterns that are interpreted as rocks of non-sedimentary origin, and include metasomatised mafic rocks. The positive La/La*SN, Eu/Eu*SN and YSN anomalies found in Isua BIFs and other Eoarchaean Greenland samples, such as G91/26 from Akilia, suggests that the processes of carbonate ion complexation controlling the REE − Y patterns were already established in the hydrosphere at the start of the sedimentary record 3,600–3,850 Ma ago. This is in accord with the presence of Eoarchaean siderite-bearing marbles of sedimentary origin, and suggests that CO2 may have been a significant greenhouse gas at that time.  相似文献   

3.
Zirconolite, allanite and hoegbomite are present as accessory phases in a metasomatically altered spinel-calcite-marble from the contact with the Bergell intrusives (Switzerland/Italy). Textural relationships indicate a step-wise alteration of spinel to 1) hoegbomite or corundum + magnetite, 2) margarite and 3) chlorite. Replacement of spinel by hoegbomite can be described by the substitution 1.94(Mg2+, Fe2+, Zn2+, Mn2+, Ca2+)Ti4+ +0.12(OH–) where Al3+ and Fe3+ are held constant. The average composition of the Bergell hoegbomites is given by the formula Fe 0.97 2+ Mg0.69Zn0.04Ti0.17Al3.94Fe 0.06 3+ O7.98(OH)0.02 and seems to be imposed by the composition of pre-existing spinel. During the first two steps of spinel alteration, calcite was replaced by anorthite+phlogopite, and the rare earth element(REE)-bearing minerals zirconolite, allanite and sphene were formed. Allanites have characteristic chondrite-normalized REE patterns with enrichment in the light REE. The zirconolite patterns show a marked increase in concentration from La to Ce, followed by an almost constant section. Sphene lacks detectable La, and its REE patterns vary from grain to grain. Contemporaneous formation of phlogopite, REE-bearing minerals and hoegbomite during replacement of the spinel-calcite-marble indicates that the metamorphic fluid introduced potassium along with REE and other high valence cations (Ti4+, Zr4+, U4+, Th4A3804265, Nb5A3804265, Y3A3804265) possibly as polynuclear complexes. The abundance of fluorine-bearing phlogopite and fluor-apatite as well as their close association with REE-bearing minerals and hoegbomite suggests F– and PO 4 3– as likely ligands for complexing of the above mentioned elements.  相似文献   

4.
The solid solution-aqueous solution system KCl-KBr-H2O is used as a model system to determine the mechanism of the replacement process of one crystalline phase by another. A single crystal of KBr was allowed to react with a saturated KCl solution enriched in 40K and the resulting new product phases were analyzed for changes in both anion and K isotope composition, using SEM, EDX, microprobe analysis, mass spectrometry and X-ray diffraction. The results show that the new product, K(Cl,Br), contains elements derived from both the original fluid and solid phases, indicating that both anions and K isotopes are exchanged during the replacement reaction. The interface between the advancing reaction front and the original parent crystal is sharp on a micron scale, showing no reaction profile that could indicate a solid state diffusion mechanism. Macroscopically the new phase is turbid due to the development of porosity that is consistent with a net volume deficit replacement reaction and this porosity may act as an indication that a replacement process has taken place. Single crystal X-ray diffraction patterns show the preservation of the crystallographic orientation during the replacement process. The replacement mechanism is interpreted as a result of a coupled process of dissolution and recrystallization occurring at the fluid-crystal interface.  相似文献   

5.
The intra-crystalline cation partitioning over T- and M-sites in a synthetic Mg(Fe,Al)2O4 spinel sample has been determined as a function of temperature by Rietveld structure refinements from powder diffraction data, combining in situ high-temperature neutron powder diffraction (NPD; POLARIS diffractometer, at ISIS, Rutherford Appleton Laboratory, UK), to determine the Mg and Al occupancy factors, with in situ high-temperature X-ray powder diffraction, to fix the Fe3+ distribution. The results obtained agree with a two-stage reaction, in which an initial exchange between Fe3+ and Mg, the former leaving and the latter entering tetrahedral sites, is successively followed by a rearrangement involving also Al. The measured cation distribution has then been compared and discussed with that calculated by the Maximum Configuration Entropy principle, for which only NPD patterns have been used. The cation partitioning has finally been interpreted in the light of the configuration model of O’Neill and Navrotsky.  相似文献   

6.
Over the range Ca/(Ca + Na) from zero to 0.75, scapolites vary linearly between Na4Al3Si9O24Cl and NaCa3Al5Si7O24CO3, by means of a coupled replacement of Na3Si2Cl by Ca3Al2CO3. Ca includes minor Sr, Na includes K, and CO3 may include substantial SO4. From Ca/(Ca + Na) = 0.75 to 1.00, variation is between NaCa3Al5Si7O24CO3 and Ca4Al6Si6O24CO3, by means of a coupled replacement of NaSi by CaAl, as in plagioclase. Anion substitution is complete at the 0.75 point. Recalculation of scapolite analyses on the basis of Al + Si atoms = 12.0, as suggested by computed unit cell contents, offers a reasonable basis for normalization of atomic proportions. On this basis, Ca + Sr + Na + K + Fe atoms total very close to 4.0. New limits on the minor element content of scapolite are proposed. In view of the inflection at 0.75, subdivision of the scapolites at Ca/(Ca + Na) ratios of 0.25, 0.5, and 0.75 seems more logical than the 0.2, 0.5, and 0.8 limits used hitherto for marialite, dipyre, mizzonite, and meionite.  相似文献   

7.
The Early to Middle Cambrian Red Heart Dolomite and lower Arthur Creek Formation of the southern portion of the Georgina Basin, Australia, is an entirely dolomitized succession of shallow-water evaporitic mudflat and deeper-water subtidal lithologies. Three types of dolomite have been identified and are interpreted as: (1) syndepositional dolomite; (2) regional replacement dolomite; and (3) void-filling dolomite (cement). Syndepositional dolomite, derived from saline pore fluids developed in a sabkha environment, is a minor dolomite type with very fine crystal mosaics and has a mottled, non-zoned cathodoluminescence. The widespread regional replacement dolomite ranges from fine- to medium-crystalline forming mainly planar-s and non-planar-a crystal mosaics, and displays blotchy, mottled, non-zoned cathodoluminescence. Void-filling dolomite commonly forms planar-s to planar-e, medium to very coarse crystal mosaics. Rare non-planar-c, very coarsely crystalline saddle dolomite also exists. Void-filling dolomite has a successively zoned cathodoluminescence pattern from non-, to brightly, to dully luminescent. Geochemically, the syndepositional dolomite has δ18O (PDB) values ranging between ? 5.3 and ? 8.6%o. Regional replacement dolomites exhibit a wide range of δ18O values from ? 3.3 to ? 10.9%o whereas void-filling dolomite has δ18O values ranging from ? 10.8 to ? 14.3%o. All three dolomite types have similar δ13C (PDB) values, in the range between +1.7 and ?1.7%o. Three initial dolomitization episodes are interpreted: (1) a sabkha stage, forming the syndepositional dolomite and dolomitizing the evaporitic mudflat lithologies; (2) a brine-reflux stage, replacing the subtidal lithologies; and (3) a burial stage, forming the void-filling dolomite type. Final dolomite stabilization occurred during burial, at elevated temperatures, in the presence of basinal fluids, resulting in progressive recrystallization and stabilization of the earlier-formed syndepositional and replacement dolomites. Both textural and geochemical evolution should be taken into account when studying the origin of dolomites, based on their present geochemical composition. Sulphates are represented by very fine-crystalline syndepositional anhydrite in association with the syndepositional dolomite, and coarse to very coarse anhydrite cement. Evaportic mudflat (sabkha) and burial environments are inferred for the origin of the former and the latter anhydrite types, respectively. Evaporite dissolution breccias, indicative of the former presence of evaporites, are common throughout the succession.  相似文献   

8.
 Mantle xenoliths hosted by the Historic Volcan de San Antonio, La Palma, Canary Islands, fall into two main group. Group I consists of spinel harzburgites, rare spinel lherzolites and spinel dunites, whereas group II comprises spinel wehrlites, amphibole wehrlites, and amphibole clinopyroxenites. We here present data on group I xenoliths, including veined harzburgites and dunites which provide an excellent basis for detailed studies of metasomatic processes. The spinel harzburgite and lherzolite xenoliths have modal ol−opx−cpx ratios and mineral and whole rock major element chemistry similar to those found in Lanzarote and Hierro, and are interpreted as highly refractory, old oceanic lithospheric mantle. Spinel dunites are interpreted as old oceanic peridotite which has been relatively enriched in olivine and clinopyroxene (and highly incompatible elements) through reactions with basaltic Canarian magmas, with relatively high melt/peridotite ratio. Group I xenoliths from La Palma differ from the Hierro and Lanzarote ones by a frequent presence of minor amounts of phlogopite (and amphibole). Metasomatic processes are also reflected in a marked enrichment of strongly incompatible relative to moderately incompatible trace elements, and in a tendency for Fe−Ti enrichment along grain boundaries in some samples. The veins in the veined xenoliths show a gradual change in phase assemblage and composition of each phase, from Fe−Ti-rich amphibole+augite+Fe−Ti-oxides+apatite+basaltic glass, to Ti-poor phlogopite+Cr-diopside±chromite+ Si−Na−K-rich glass+fluid. Complex reaction zones between veins and peridotite include formation of clinopyroxene±olivine+glass at the expense of orthopyroxene in harzburgite, and clinopyroxene+spinel±amphibole±glass at the expense of olivine in dunite. The dramatic change in glass composition from the broadest to the narrowest veins includes increasing SiO2 from 44 to 67 wt%, decreasing TiO2/Al2O3 ratio from >0.24 to about 0.02, and increasing K2O and Na2O from 1.8 to >7.0 wt% and 3.8 to 6.7 wt%, respectively. The petrographic observations supported by petrographic mixing calculations indicate that the most silicic melts in the veined xenoliths formed as the result of reaction between infiltrating basaltic melt and peridotite wall-rock. The highly silicic, alkaline melt may represent an important metasomatic agent. Pervasive metasomatism by highly silicic melts (and possibly fluids unmixed from these) may account for the enriched trace element patterns and frequent presence of phlogopite in the upper mantle under La Palma. Received: 15 January 1996 / Accepted 30 May 1996  相似文献   

9.
Metamorphic and magmatic garnets are known to fractionate REE, with generally HREE-enriched patterns, and high Lu/Hf and Sm/Nd ratios, making them very useful as geochemical tracers and in geochronological studies. However, these garnets are typically Al-rich (pyrope, almandine, spessartine, and grossular) and little is known about garnets with a more andraditic (Fe3+) composition, as frequently found in skarn systems. This paper presents LA-ICP-MS data for garnets from the Crown Jewel Au-skarn deposit (USA), discusses the factors controlling incorporation of REE into garnets, and strengthens the potential of garnet REE geochemistry as a tool to help understand the evolution of metasomatic fluids.Garnets from the Crown Jewel deposit range from Adr30Grs70 to almost pure andradite (Adr>99). Fe-rich garnets (Adr>90) are isotropic, whereas Al-rich garnets deviate from cubic symmetry and are anisotropic, often showing sectorial dodecahedral twinning. All garnets are extremely LILE-depleted, Ta, Hf, and Th and reveal a positive correlation of ΣREE3+ with Al content. The Al-rich garnets are relatively enriched in Y, Zr, and Sc and show “typical” HREE-enriched and LREE-depleted patterns with small Eu anomalies. Fe-rich garnets (Adr>90) have much lower ΣREE and exhibit LREE-enriched and HREE-depleted patterns, with a strong positive Eu anomaly. Incorporation of REE into garnet is in part controlled by its crystal chemistry, with REE3+ following a coupled, YAG-type substitution mechanism , whereas Eu2+ substitutes for X2+ cations. Thermodynamic data (e.g., Hmixing) in grossular-andradite mixtures suggest preferential incorporation of HREE in grossular and LREE in more andraditic compositions.Variations in textural and optical features and in garnet geochemistry are largely controlled by external factors, such as fluid composition, W/R ratios, mineral growth kinetics, and metasomatism dynamics, suggesting an overall system that shifts dynamically between internally and externally buffered fluid chemistry driven by fracturing. Al-rich garnets formed by diffusive metasomatism, at low W/R ratios, from host-rock buffered metasomatic fluids. Fe-rich garnets grow rapidly by advective metasomatism, at higher W/R ratios, from magmatic-derived fluids, consistent with an increase in porosity by fracturing.  相似文献   

10.
Eclogite-facies rocks within the Bergen Arcs, western Norway, have formed from granulites along shear zones and fluid pathways. Garnets that were inherited from granulite facies protoliths show different types of replacement patterns due to an incomplete eclogitisation process including concentric rim zoning, zoning along vein fillings and inclusion trails, and zoning bands without inclusions. The interfacial part between the granulitic core and the eclogitic rim of garnet as well as the microstructure of other relevant minerals (omphacite, plagioclase) has been analysed using analytical transmission electron microscopy (ATEM). In garnet, the interface is characterised by gradual changes in composition from Xalm=0.31, Xpyr=0.50 to Xalm=0.54, and Xpyr=0.25 within ≈20 μm and exhibits no distinct change in microstructure. Granulitic plagioclase shows exsolution lamellae of the Bøggild intergrowth. In omphacite, anti-phase domains (APDs) which potentially record the temperature of cation ordering after mineral growth have been observed and their size suggest eclogitisation at 600–700 °C. The electron backscatter diffraction (EBSD) analysis revealed that the lattice orientation of the granulitic feldspar is basically unrelated to tectonic axes whereas newly formed eclogitic minerals omphacite and kyanite show a crystallographic relation to the foliation. In garnet, no change in the basic crystallographic orientation between the eclogitic and granulitic garnet composition was confirmed. However, misorientation analysis suggests a cellular microstructure not more than 1° misorientation in the core of the garnets, which is missing in the eclogitic rim indicating textural equilibration of the latter. The heterogeneous replacement patterns are characteristic for dissolution and re-precipitation reactions in an open system limited to fluid availability. The appearance of the compositional profile in garnet is interpreted as a diffusional re-equilibration step after the time-limited, fluid-mediated eclogitisation event that apparently obscured the initially sharp interface within the further retrograde metamorphic history.  相似文献   

11.
Corona textures around kyanite, involving for example zoned plagioclase separating kyanite from the matrix, reflect the instability of kyanite with the matrix on changing P–T conditions, commonly related to decompression. The chemical potential gradients set up between the kyanite and the matrix as a consequence of slow Al diffusion drive corona development, with the zoning of the plagioclase reflecting the gradients. Calculated mineral equilibria are used to account for corona textures involving plagioclase ± garnet around kyanite, and replacement of kyanite by plagioclase + spinel symplectite, in quartz + plagioclase + K‐feldspar + garnet + kyanite granulite facies gneiss from the Blanský les massif in the Bohemian massif, Czech Republic. In the garnet‐bearing coronas, a commonly discontinuous garnet layer lies between the kyanite and the continuous plagioclase layer in the corona, with both the garnet and the plagioclase appearing mainly to replace matrix rather than kyanite. The garnet layer commonly extends around kyanite from original matrix garnet adjacent to the kyanite. Where garnet is missing in the corona, the kyanite itself may be replaced by a spinel–plagioclase corona. In a local equilibrium model, the mineral and mineral compositional spatial relationships are shown to correspond to paths in μ(Na2O)–μ(CaO)–μ(K2O)–μ(FeO)–μ(MgO)–μ(SiO2) in the model chemical system, Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2 (NCKFMAS). The discontinuous nature of the garnet layer in coronas is accounted for by the effect of the adjacent original garnet on the chemical potential relationships. The replacement of kyanite by spinel + plagioclase appears to be metastable with respect to replacement by corundum + plagioclase, possibly reflecting the difficulty of nucleating corundum.  相似文献   

12.
Some of the factors that affect the preferred positions of cations in ionic-solid solutions were investigated utilizing vibrational spectroscopy. Solid solutions of the sulfate and chromate ions codoped with La3+ and Ca2+ in a KBr host lattice were examined as a function of the polyvalent-cation concentration. The cation—anion pairing process was found to be random for Ca2+ whereas the formation of La3+SO42? ion-pairs with a C2v bonding geometry is highly preferential to any type of La3+CrO42? ion-pair formation. The relative populations of ion-pair site configurations are discussed in terms of an energy—entropy competition which can be applied to the partition of trace elements during magmatic processes.  相似文献   

13.
In a series of timed experiments, monazite inclusions are induced to form in the Durango fluorapatite using 1 and 2 N HCl and H2SO4 solutions at temperatures of 300, 600, and 900°C and pressures of 500 and 1,000 MPa. The monazite inclusions form only in reacted areas, i.e. depleted in (Y+REE)+Si+Na+S+Cl. In the HCl experiments, the reaction front between the reacted and unreacted regions is sharp, whereas in the H2SO4 experiments it ranges from sharp to diffuse. In the 1 N HCl experiments, Ostwald ripening of the monazite inclusions took place both as a function of increased reaction time as well as increased temperature and pressure. Monazite growth was more sluggish in the H2SO4 experiments. Transmission electron microscopic (TEM) investigation of foils cut across the reaction boundary in a fluorapatite from the 1 N HCl experiment (600°C and 500 MPa) indicate that the reacted region along the reaction front is characterized by numerous, sub-parallel, 10–20 nm diameter nano-channels. TEM investigation of foils cut from a reacted region in a fluorapatite from the 1 N H2SO4 experiment at 900°C and 1,000 MPa indicates a pervasive nano-porosity, with the monazite inclusions being in direct contact with the surrounding fluorapatite. For either set of experiments, reacted areas in the fluorapatite are interpreted as replacement reactions, which proceed via a moving interface or reaction front associated with what is essentially a simultaneous dissolution–reprecipitation process. The formation of a micro- and nano-porosity in the metasomatised regions of the fluorapatite allows fluids to permeate the reacted areas. This permits rapid mass transfer in the form of fluid-aided diffusion of cations to and from the growing monazite inclusions. Nano-channels and nano-pores also serve as sites for nucleation and the subsequent growth of the monazite inclusions.  相似文献   

14.
The chemical analysis of 19 water wells in Ferdows area, Northeastern Iran, has been evaluated to determine the hydrogeochemical processes and ion concentration background in the region. In the study area, the order of cation and anion abundance is Na+ > Ca2+ > Mg2+ > K+ and Cl? > SO 4 ?2  > HCO3 ? > NO3 ?, respectively, and the dominating hydrochemical types are Na–Cl. Most metal concentrations in water depend on the mineral solubility, and pH, Eh, and salinity of the solution. Their ΣREE concentrations showed excellent correlations with parameters such as TDS and pH. North American Shale Composite (NASC)-normalized REE patterns are enriched in the HREEs relative to the LREEs for all groundwaters. They all have positive Eu anomalies (Eu/Eu* = 0.752–3.934) and slightly negative Ce anomalies (Ce/Ce* = 0.019–1.057). Reduction–oxidation, complexation, desorption, and re-adsorption alter groundwater REE concentrations and fractionation patterns. The positive Eu anomalies in groundwaters are probably due to preferential mobilization of Eu2+ relative to the trivalent REEs in the reducing condition.  相似文献   

15.
系统的微量元素和Sm-Nd同位素分析表明,川西地区早震旦世苏雄组双峰式火山岩中的大多数玄武岩具有高的正εNd(T)值(+5～+6)、大离子亲石元素和LREE富集,与现代典型的洋岛玄武岩和大陆溢流玄武岩省中的碱性玄武岩有非常相似的地球化学和同位素组成特征。酸性火山岩的εNd(T)值较低(+1.1～+2.6),地球化学特征总体上与A2-型花岗岩相似,它们是受地壳混染的OIB型玄武质岩浆在地壳中部的一个“双扩散”岩浆房通过结晶分异形成的。苏雄组双峰式火山岩形成于典型的大陆裂谷环境,非常类似于现代与地幔柱活动有关的高火山活动型裂谷火山岩,扬子块体西缘 800Ma前的裂谷作用和火山活动应是约825Ma前的华南地幔柱活动引发的结果。  相似文献   

16.
Simon et al. (2005) reported low Ti3+/Ti4+ values in Ti-rich pyroxenes in the Wark-Lovering rim (WL) of a Leoville CAI (144A) as compared to the interior of the inclusion. These electron microprobe analyses were interpreted as evidence that the growth of the WL rim is the manifestation of an evolution to a more oxidizing environment. Further work by Simon et al. (2007) used XANES analyses to argue for higher Ti3+ abundances and interpreted the data of Simon et al. (2005) as the result of X-ray contamination by neighboring phases, specifically spinel. Late-stage alteration was also included as a possible explanation.To investigate further the oxidation state of Ti in WL rims, we re-analyzed Leoville 144A to obtain a more complete data set of Ti3+/Ti4+ values in the Wark-Lovering rims. We conducted experiments on spinel-mixing to determine whether this was a plausible explanation for the observed paucity of Ti3+ in WL rims. While we found a wider range of Ti3+/Ti4+ in these WL rim data than in our original study, our new data show that the original conclusion that rims are lower in Ti3+/Ti4+ than interiors remains valid. We conclusively rule out spinel-mixing as an explanation for our data, and we see no clear inconsistency between our electron microprobe data and the XANES data. The WL rim of CAI Ef3 was also analyzed by EMPA and compared to the results of Leoville 144A.To predict compositional consequences of this hypothesis, we constructed a reaction space between Ti-rich pyroxene in the WL rim, perovskite, Mg(g), Ca(g), O2(g), and SiO(g). We find the oxidation of Ti3+, coupled with Ti loss via perovskite formation, explains many features of WL rim EMPA analyses. We maintain that the WL rim pyroxenes are compositionally distinct from those in the interior, and are evidence of a more oxidizing environment during WL rim formation.  相似文献   

17.
The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca2+, Mg2+, and Si(OH)4 and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M2 structural sites. Loss mainly from M2 sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca2+ and/or Mg2+ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on aH+ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.  相似文献   

18.
The Cretaceous Banhad?o alkaline complex in southeastern Brazil presents two potassic SiO2-undersaturated series. The high-Ca magmatic series consist of initially fractionated olivine (Fo92-91) + diopside (Wo48-43En49-35Ae0-7), as evidenced by the presence of xenocrysts and xenoliths. In that sequence, diopside (Wo47-38En46-37Ae0-8) + phlogopite + apatite + perovskite (Prv>92) crystallized to form the phlogopite melteigite and led to the Ca enrichment of the magma. Diopside (Wo47-41En32-24 Ae3-14) continued to crystallize as an early mafic mineral, followed by nepheline (Ne74.8-70.1Ks26.3-21.2Qz7.6-0.9) and leucite (Lc65-56) and subsequently by melanite and potassic feldspar (Or85-99Ab1-7) to form melanite ijolites, wollastonite-melanite urtites and melanite-nepheline syenites. Melanite-pseudoleucite-nepheline syenites are interpreted to be a leucite accumulation. Melanite nephelinite dykes are believed to represent some of the magmatic differentiation steps. The low-Ca magmatic series is representative of a typical fractionation of aegirine-augite (Wo36-29En25-4Ae39-18) + alkali feldspar (Or57-96Ab3-43) + nepheline (Ne76.5-69.0Ks19.9-14.4Qz15.1-7.7) + titanite from phonolite magma. The evolution of this series from potassic nepheline syenites to sodic sodalite syenites and sodalitolites is attributed to an extensive fractionation of potassic feldspar, which led to an increase of the NaCl activity in the melt during the final stages forming sodalite-rich rocks. Phonolite dykes followed a similar evolutionary process and also registered some crustal assimilation. The mesocratic nepheline syenites showed interactions with phlogopite melteigites, such as compatible trace element enrichments and the presence of diopside xenocrysts, which were interpreted to be due to a mixing/mingling process of phonolite and nephelinite magmas. The geochemical data show higher TiO2 and P2O5 contents and lower SiO2 contents for the high-Ca series and different LILE evolution trends and REE chondrite-normalized patterns as compared to the low-Ca series. The 87Sr/86Sr, 143Nd/144Nd, 206Pb/204Pb and 208Pb/204Pb initial ratios for the high-Ca series (0.70407–0.70526, 0.51242–0.51251, 17.782–19.266 and 38.051–39.521, respectively) were slightly different from those of the low-Ca series (0.70542–0.70583, 0.51232–0.51240, 17.758–17.772 and 38.021–38.061, respectively). For both series, a CO2-rich potassic metasomatized lithospheric mantle enriched the source with rutile-bearing phlogopite clinopyroxenite veins. Kamafugite-like parental magma is attributed to the high-Ca series with major contributions from the melting of the veins. Potassic nephelinite-like parental magma is assigned to the low-Ca series, where the metasomatized wall-rock played a more significant role in the melting process.  相似文献   

19.
Abstract Declining temperatures during decay of a hydrothermal system, or during uplift and erosion, tend to result in veins involving progressive hydration reactions, e.g. veins with laumontite cutting prehnitepumpellyite facies rocks, and stilbite veins cutting laumontite veins. In contrast, examples are described of analcime replacement of heulandite along fractures in heulanditized vitric tuff, of replacement of analcime by albite along fractures in quartz-analcime rock, of joint-controlled replacement of heulandite in tuff by laumontite + quartz + (Na, K)-feldspars, of replacement of laumontite by prehnite + quartz along fractures in alumontitized vitric tuff, and of laumontitebearing feldspathic sandstones cut by vein assemblages of quartz and prehnite ° Calcite. The vein mineral assemblage, sometimes with pumpellyite and/or epidote in the prehnite-bearing veins, tends to spread as a zone of dehydration into the adjacent country rock. Except perhaps for albite replacement of analcime, and for laumontite replacement of heulandite, these open-system reactions involve cation activity ratios in the fluid. All involve dehydration. They are favoured by an increase in temperature, and except under certain situations where P-T equilibrium curves have negative slopes, are favoured by a fall in PH2O. Evidence indicates that in at least some cases the triggering mechanism was a drop in PH2O; this may be a widespread phenomenon associated with brittle fracture in the seismogenic upper crust. This may cause fluid pressure to drop from values approaching lithostatic to nearer hydrostatic, and equilibrium may be displaced to yield a less hydrous assemblage that appears as a dehydration vein and vein verge. The dehydration vein assemblage may be diagnostic of a higher grade mineral facies and adds to the mineral complexity attributable to varying permeabilities and fluid pressures in upper crustal strata. Mineral facies are likely to be more uniformly distributed in higher grade rocks from below the brittle-ductile transition zone. Reactions involving complex solid solutions are inappropriate as facies boundaries.  相似文献   

20.
The Neoarchean (ca. 2.75 Ga) Luanga Complex, located in the Carajás Mineral Province in Brazil, is a medium-size layered intrusion consisting, from base to top, of ultramafic cumulates (Ultramafic Zone), interlayered ultramafic and mafic cumulates (Transition Zone) and mafic cumulates (Mafic Zone). Chromitite layers in the Luanga Complex occur in the upper portion of interlayered harzburgite and orthopyroxenite of the Transition Zone and associated with the lowermost norites of the Mafic Zone. The stratigraphic interval that hosts chromitites (∼150 meters thick) consists of several cyclic units interpreted as the result of successive influxes of primitive parental magma. The compositions of chromite in chromitites from the Transition Zone (Lower Group Chromitites) have distinctively higher Cr# (100Cr/(Cr + Al + Fe3+)) compared with chromite in chromitites from the Mafic Zone (Upper Group Chromitites). Chromitites hosted by noritic rocks are preceded by a thin layer of harzburgite located 15–20 cm below each chromitite layer. Lower Cr# in chromitites hosted by noritic rocks are interpreted as the result of increased Al2O3 activity caused by new magma influxes. Electron microprobe analyses on line transverses through 35 chromite crystals indicate that they are rimmed and/or extensively zoned. The composition of chromite in chromitites changes abruptly in the outer rim, becoming enriched in Fe3+ and Fe2+ at the expense of Mg, Cr, Al, thus moving toward the magnetite apex on the spinel prism. This outer rim, characterized by higher reflectance, is probably related to the metamorphic replacement of the primary mineralogy of the Luanga Complex. Zoned chromite crystals indicate an extensive exchange between divalent (Mg, Fe2+) cations and minor to none exchange between trivalent cations (Cr3+, Al3+ and Fe3+). This Mg-Fe zoning is interpreted as the result of subsolidus exchange of Fe2+ and Mg between chromite and coexisting silicates during slow cooling of the intrusion. A remarkable feature of chromitites from Luanga Complex is the occurrence of abundant silicate inclusions within chromite crystals. These inclusions show an adjacent inner rim with higher Cr# and lower Mg# (100 Mg/(Mg + Fe2+)) and Al# (100Al/(Cr + Al + Fe3+)). This compositional shift is possibly due to crystallization from a progressively more fractionated liquid trapped in the chromite crystal. Significant modification of primary cumulus composition of chromite, as indicated in our study for the Luanga Complex, is likely to be common in non-massive chromitites and the rule for disseminated chromites in mafic intrusions.  相似文献   

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