Mineralogy,petrology, and phase relations of glaucophane-lawsonite zone blueschists from the Tavşanli Region,Northwest Turkey

Glaucophane-lawsonite facies blueschists representing a metamorphosed sequence of basic igneous rocks, cherts and shales have been investigated northeast of the district of Tav?anli in Northwest Turkey. Sodic amphiboles are rich in magnesium reflecting the generally high oxidation states of the blueschists. Lawsonite has a very uniform composition with up to 2.5 wt.% Fe₂O₃. Sodic pyroxenes show an extensive range of compositions with all the end-members represented. Chlorites are uniform in their Al/(Al+Fe+Mg) ratio but show variable Fe/ (Fe+Mg) ratios. Garnets from metacherts are rich in spessartine (>50%) whereas those from metabasites are largely almandine. Pistacite rich epidote is found in metacherts coexisting with lawsonite. Phengites are distinctly higher in their Fe, Mg and Si contents than those from greenschist facies. Hematites with low TiO₂ are ubiquitous in metacherts. Fe²⁺/Mg partitioning between chlorite and sodic amphibole is strongly controlled by the calcium content of the sodic amphibole and ranges from 1.1 for low calcium substitution to 0.8 for higher calcium substitution. The Al/Fe³⁺ partition coefficient between sodic amphibole and sodic pyroxene is 2.1. A model system has been constructed involving projections from lawsonite, iron-oxide and quartz onto a tetrahedron with Na, Al, Fe²⁺ and Mg at its apices. Calcite is treated as an indifferent phase. The model system illustrates the incompatibility of the sodic pyroxene with chlorite in the glaucophanelawsonite facies; this assemblage is represented by sodic amphibole. Sodic amphibole compositions are plotted in terms of coexisting ferromagnesian minerals. Five major areas on the sodic amphibole compositional field are delineated, each associated with one of the following minerals: chlorite, stilpnomelane, talc, almandine, deerite.     

Occurrence, Mineral Chemistry, and Metamorphism of Precambrian Carbonate Rocks in a Portion of the Grenville Province

Marble occurs abundantly in a 31,000 km² segment of the southernGrenville Province of the Canadian Precambrian Shield, whereit is associated with quartzite, biotite-garnet gneiss, andamphibolite to form the Grenville Group. An 1800 km² area onthe western margin of this segment, north of the Ottawa river,displays a great variety of carbonate rocks, which may be dividedinto two groups: (I) major marble, with calcite, dolomite, graphite, phlogopite,Ca amphibole, Ca pyroxene, forsterite, humite group minerals, (II) minor marble, with pink calcite, phlogopite, Ca amphibole,Ca pyroxene, K feldspar, scapolite, sphene. Rocks of the first group are associated with plagioclase gneissand amphibolite, and are metamorphosed limestone, little affectedby metasomatism; rocks of the second group, which are less common,are associated with potassium feldspar gneiss and heterogeneousgranitic and syenitic rocks, and are inferred to be metasomaticrocks. Numerous mineral reactions have taken place in the carbonaterocks during metamorphism. The calcite-dolomite reaction, whichgoverns the Mg content of calcite, indicates a metamorphic temperatureof about 650 °C. Forsterite was possibly produced from low-Alamphibole, and forsterite + spinel from high-Al amphibole. Thecrystallization of some silicate minerals in the minor marbleunits, and the enrichment in the contained calcite in Fe andSr are attributed to metasomatic reactions. Metamorphic ion-exchangereactions involving carbonates produced the following distributioncoefficients: Sr in calcite/Sr in dolomite = 2.5 Mn in calcite/Mn in dolomite = 0.89 Fe in calcite/Fe in dolomite = 0.29 from which inferences may be drawn concerning the distributionof these elements between the Ca and Mg sites within dolomiteduring metamorphic crystallization. Ion-exchange reactions involvingsilicates produced the following distribution of Mn: humite group Ca pyroxene.Ca amphibole phlogopite where the numbers are distribution coefficients. An equilibriumdistribution of Fe between silicates and calcite in the minormarble was evidently not attained during metasomatic crystallization.Numerous retrograde reactions have taken place, including thealteration of pyroxene to amphibole, forsterite to serpentine,and the exsolution of dolomite from calcite. Forsterite in marble, and orthopyroxene in the associated gneissesand amphibolites crystallized sporadically in the Laurentianhighlands, but not in the lowlands of the Ottawa rift valley,where peak metamorphic temperatures may have been slightly lower.In the highlands, reactions to produce forsterite and orthopyroxenewere initiated in response to a local increase in temperature,local peculiarities in the chemical composition of amphibole,which produced these minerals, or a local decrease in the activityof CO₂ and H₂O in the grain-boundary phase.     

Coexisting Amphiboles from Blueschist Facies Metamorphic Rocks

Four pairs of associated calcic and sodic amphiboles from blueschistfacies metamorphic rocks were analyzed with the electron microprobeand studied by single-crystal X-ray diffraction techniques.Except for ranges in the ratios Mg/(Mg+Fe) and Fe³⁺/(Fe³⁺+Al+Ti),the sodic amphiboles are similar in chemical composition. Theamount of calcium in the M(4)-site ranges only from 0·18to 0·21 ion per formula unit. The calcic amphiboles,in addition to a range in Mg/(Mg+Fe), vary in Na/(Na+Ca) ratio(0·29–0·48). Three of the calcic amphibolescontain less than 1·5 calcium ions per formula unit,indicating a significant solid solution of sodic amphibole componentsin the calcic amphibole phase. The a and b unit-cell parametersof the calcic amphiboles decrease with increased content ofthe sodic component.     

Micas from the Khaluta carbonatite deposit,western Transbaikal region

The Khaluta carbonatite deposit located in the western Transbaikal region was formed during the Late Mesozoic rifting in the southern framework of the Siberian Craton. Carbonatite is associated with shonkinite and syenite and is accompanied by fenitization. The composition of mica in more than 160 samples of country rocks, carbonatites, silicate rocks, and fenites was studied. The Fe³⁺ and Fe²⁺ contents, as well as oxygen isotopic composition, were determined. The Mg and Fe contents increase, whereas the Ti and Al contents decrease in micas when passing from silicate rocks and fenites to carbonatites. Micas from carbonatites are depleted in Al, enriched in Fe³⁺, and distinguished by high Si and F contents. According to our calculations, in some cases Al replaces Si in the tetrahedral site instead of replacement of Fe³⁺ as is characteristic of tetraferriphlogopite. Formally, the mica from carbonatites falls within the tetraferriphlogopite field, but typical inverse pleochroism is not always observable. The δ¹⁸O values of micas from carbonatite, shonkinite, syenite, and fenite are similar to those of mantle-derived silicate minerals. The δ¹⁸O values in the minerals coexisting with phlogopite testify to their isotopic equilibrium and make it possible to calculate the crystallization temperature of carbonatite.     

Compositions and phase relations of calcic amphiboles in epidote- and clinopyroxene-bearing rocks of the amphibolite and lower granulite facies,central Massachusetts,USA

Calcic amphiboles coexisting with epidotegroup minerals (zoisite, clinozoisite, epidote) and/or clinopyroxene±plagioclase±quartz±garnet occur in amphibolites and calc-silicate rocks that underwent amphibolite to lower granulite-facies metamorphism in the Acadian metamorphic high of central Massachusetts, USA. Across the region, peak metamorphic conditions range from about 580° C and 6.2 kbar to 730° C and 6.3 kbar. The coexistence of most Ca-amphiboles with Fe³⁺-rich epidote-group minerals suggests the presence of Fe³⁺ in most of these amphiboles. An empirical Fe³⁺ estimation for the microprobe analyses is based on two constraints: the Na?Ca content of the M4 sites of Ca-saturated, gravimetrically analyzed hornblendes gives the relation: Ca(M4) ^c =-1.479 Na(M4) ^c +2 (c=corrected). The second constraint is the stoichiometric equation Ca(M4)+Na(M4)+FM=15, where FM is the sum of all cations exclusive of Ca, Na, and K. Solving the two equations simultaneously gives: 20.185=0.479 Ca(M4)+1.479 ΣFM. Starting with the uncorrected values of Ca(M4) ^u and ΣFM(M4) ^u (u = uncorrected) of the all ferrous formula, the normalization factor NF for calculating the corrected cations of the ferric formulas is: 20.185/(0.478 Ca(M4) ^u +1.479 ΣFM ^u ). From the deficient oxygen the Fe³⁺ content which is equal to 2(23-ΣOX) can be calculated. Determinations of Fe³⁺ contents of four hornblende separates by Mössbauer spectroscopy are in agreement with the calculated values. The Ca-amphiboles show systematic changes in composition with increasing grade of metamorphism within the amphibolite and lower granulite-facies zones: increasing edenite and tschermakite substitution, increasing Ti content, and increasing Fe²⁺/(Fe²⁺+Mg) ratio. In addition, the coexisting clinopyroxenes are also characterized by an increase in Fe²⁺/(Fe²⁺+Mg) ratio. In quartz-free rocks with coexisting Ca-amphibole and plagioclase there is an increase in the ratio X _Ab/X _Ed, where X _Ab=Na/(Na+Ca) in plagioclase and X _Ed=Na in the amphibole A-site. These chemical changes in mineral composition together with the disappearance of epidote at the transition to granulite-facies metamorphic conditions are attributed to the continuous reaction: albite+epidote+Fe-Mg hornblende→Fe?Mg clinopyroxene+anorthite+(NaAlSi_-1)^Hbl+H₂O.     

Distribution of Mg and Fe in cummingtonite-hornblende and cummingtonite-actinolite pairs from metamorphic assemblages

The atomic fractions Mg/(Mg + Fe) and the Mg-Fe distribution coefficient $$K_{{\text{D}}{\text{.Mg - Fe}}}^{{\text{Ca - am - Cum}}} \left( { = \tfrac{{[{\text{Mg/Fe]}}_{{\text{Ca - am}}} }}{{{\text{[Mg/Fe]}}_{{\text{Cum}}} }}} \right)$$ are calculated for 31 metamorphic cummingtonite-hornblende pairs. Data on 21 pairs are taken from the litterature, and new electron microprobe analyses and structural formulae are presented of nine pairs from Tydal, Sör-Tröndelag, Norway, and of one pair from Cooma, N.S.W., Australia (cf. Kisch, 1969). The electron microprobe methods used are described, particularly the use of mineral standards, and the variation of the mass absorption in substitution series. The hornblendes from the Tydal pairs are markedly pargasitic in composition, and contain minor proportions of the cummingtonite “molecule”. The Mg-Fe distributions in the cummingtonite-hornblende pairs — as plotted on a [Mg/(Mg + Fe)]_Ca-am vs. [Mg/(Mg + Fe)]_Cum diagram (Fig. 3) — differ significantly from the Mg-Fe distribution curve for cummingtonite-actinolite pairs from Quebec (Mueller, 1961). Whereas the actinolites have markedly higher Mg/Fe ratios than the co-existing cummingtonites (K _D.Mg-Fe ^Ca-am-Cum ≈ 1.5–2.0), the cummingtonite-hornblende pairs diverge towards lower values from the distribution coefficient. In most of the metamorphic cummingtonite-hornblende pairs — including the nine pairs from Tydal — the Mg/Fe ratio of the hornblende is lower than in the co-existing cummingtonite, i.e K _D.Mg-Fe ^Ca-am-Cum <1. A relation appears to exist between the Mg-Fe distribution and the Al content of the calcic amphibole phase. This is believed to be due to the non-random distribution of Al^Y among the octahedral lattice sites: in hornblende Al^VI enters the M ₁+M₃ positions, in which Mg is preferred over Fe, rather than M ₂, in which Fe is preferred (Ghose, 1965). Since the cummingtonites remain Al-poor, the over-all Mg/Fe ratio in the hornblende is reduced relative to the co-existing cummingtonite as a result. The variations of the Mg-Fe distribution in the cummingtonite-hornblende pairs can also be related directly to the presence and composition of the plagioclase and other Al-rich phases in the metamorphic mineral assemblage. In any range of Mg/Fe ratios, the cummingtonite-hornblende pairs associated with oligoclase have lower distribution coefficients (0.61–0.81; 12 pairs) than those associated with calcic plagioclase or plagioclase-free assemblages (0.97 to 1.89; 6 pairs); the pairs associated with andesine have intermediate Mg-Fe distributions (0.74–1.15; 6 pairs).     

Phase relations of pyroxene and amphibole in greenstone,blueschist and eclogite of the Franciscan Complex,California

The phase relations of pyroxenes, amphiboles and associated minerals in metamorphic rocks of the Franciscan Complex can be graphically depicted on a ternary diagram which has at its apices the metamorphic clinopyroxene end members, viz NaAl-NaFe³⁺-Ca(Fe²⁺, Mg). Phases are plotted by projection from a constant subassemblage of minerals. This analysis allows interpretation of the effects of pressure, temperature, bulk rock composition and fluid composition on stability of minerals within the Franciscan.Pyroxenes in meta-igneous rocks and metagraywackes have a limited compositional range and fall into two groups: the omphacites, with 50±5% diopside +hedenbergite component; and the jadeitic pyroxenes with 10±5% diopside+hedenbergite. Pyroxenes intermediate between these two groups are unstable relative to assemblages containing Na-amphibole+other minerals.Coexisting pyroxenes and amphiboles in eclogites and associated coarse blueschists comprise equilibrium assemblages, and the proportion of pyroxene to amphibole is a function of rock composition. Eclogites are stable at higher temperature than regionally developed fine-grained greenstones and blueschists in the Franciscan, and at higher pressure than amphibolites. X _H2O ^fluid is not an important factor in the stability of Franciscan eclogite relative to amphibolite.     

Mechanism of pyroxene and amphibole weathering—I. Experimental studies of iron-free minerals

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 a_H⁺ 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.     

Amphibolitization of metagabbros in the Scottish Highlands

Abstract Compositions of actinolite, hornblende and cummingtonite, together with pyroxene and plagioclase, are studied in basic intrusions in the Dalradian of north-east Scotland, and the Glen Scaddle complex in the West Moine. Amphibolitization is due to influx of water from the country rocks. Pyroxene compositions are found to have adjusted to the regional metamorphic environment. Owing to the difficulty of diffusion of Al and Si, calcic amphiboles are zoned and commonly contain quartz blebs. Discontinuities in zoning give rise to actinolite-hornblende pairs. Compared with north-east Scotland, disequilibrium is less strong in the Glen Scaddle area: in the latter, plagioclase compositions have been greatly changed, Na partition between hornblende and plagioclase is close to equilibrium, the maximum Al content of hornblende is lower and zoning patterns are more consistent. The Fe/Mg ratio in calcic amphiboles varies with Al content, while approaching equilibrium partition with other minerals. Both zoning patterns and Fe/Mg partition with cummingtonite suggest that Fe/Mg of the calcic amphiboles increases more strongly with increasing (Al^vi+Fe³⁺) than can be explained simply by substitution of Al,Fe³⁺ for Mg on M2. Model reactions for amphibole formation are constructed. Cummingtonite formed at lower chemical potential of CaO than actinolite: Ca was exchanged for Mg,Fe between orthopyroxene-derived and clinopyroxene-derived local systems. Both cummingtonite and actinolite were formed because of kinetic constraints, as intermediate reaction products: actinolite-hornblende pairs represent disequilibrium. This work suggests that many occurrences of actinolite with hornblende, where the minerals are zoned, may also be due to diffusion kinetics.     

Chromium mineralization in the Khibiny alkaline massif (Kola Peninsula,Russia)

This paper presents new data on chromium mineralization in a fenitized xenolith in Mt. Kaskasnyunchorr in the Khibiny alkaline massif (Kola Peninsula, Russia) and summarizes data on Cr mineralogy in the Khibiny Mountains. Protolith silicates that contained Cr³⁺ admixture are believed to be the source of this element in the fenite. Cr-bearing (maximum Cr₂O₃ concentrations, wt %, are in parentheses) aegirine (5.8), crichtonite-group minerals (2.1), muscovite (1.3), zirconolite (1.1), titanite (1.0), fluorine-magnesioarfvedsonite (0.8), biotite (0.8), ilmenite (0.6), and aenigmatite (0.6) occur in the fenite. The late-stage spinellides of the FeTi-chromite-CrTi-magnetite series, which are very poor in Mg and Al and which formed after Crrich aegirine and ilmenite, are the richest in Cr (up to 42% Ct₂O₃). Cr concentrations grew with time during the fenitization process. Unlike minerals in the Khibiny ultramafic rocks where Cr is associated with Mg, Al (it is isomorphic with Cr), and with Ca, chromium in the fenites is associated with Fe, Ti, and V (with which Cr³⁺ is isomorphic) and with Na in silicate minerals. Cr³⁺ Mobility of Cr³⁺ and the unique character of chromium mineralization in the examined fenites were caused by high alkalinity of the fluid.     

Newania carbonatites, Western India: example of mantle derived magnesium carbonatites

The key mineralogical features of the Newania carbonatites, that illustrate their derivation from primary mantle melts (Gruau et al. Terra Nova, Abstract Suppl 1:336, 1995; Viladkar Petrology 6(3):272–283, 1998; Basu and Murty Abstracts of Goldschmidt Conference A40, 2006), are the presence of magnesite, graphite and Cr-rich magnetite. Magnesite is an early crystallizing phase. Cr-rich magnetite and graphite coexist with carbonatite minerals and precipitated from carbonate magma. Graphite, as well as gaseous CO₂ and carbonate minerals such as dolomite and magnesite, can be stable in peridotite mantle. Coexistence of these minerals is controlled by fO ₂ and PT-conditions. Mineral geothermometers for the Newania carbonatite give temperatures from 463 to 950°C. The parental source for Newania carbonatites was characterized by a relatively high log (fHF/fH₂O) level which increased during the crystallization history of Newania. The estimated oxygen fugacity (for ilmenite–magnetite pairs) varies from ?1.5 to +3.5 (log-bar unit deviation from FMQ buffer), which is supported by the presence of Fe-columbite, and the composition of phlogopite, amphibole and pyroxene that have an elevated concentration of Fe³⁺. However, the oxygen fugacity range represented by co-existing early-crystallized graphite and magnesite is below that of the FMQ buffer and lies on the CCO buffer.     

川西冕宁-德昌稀土矿带霓长岩的地球化学特征及地质意义

霓长岩化作用是指碳酸岩(或碱性岩)流体对围岩的交代蚀变,它是碳酸岩型稀土(REE)矿床常见的蚀变类型,其所形成的岩石即为霓长岩。对霓长岩的深入研究可以鉴别碳酸岩体的存在,厘定碳酸岩岩浆(或流体)的地球化学性质及源区特征,这对于找寻碳酸岩相关的矿产资源(尤其是REE)以及剖析矿床成因机制有着重要的地质意义。川西冕宁-德昌稀土矿带是中国最重要的轻稀土矿带之一,包括牦牛坪超大型、大陆槽大型、木落寨和里庄中小型REE矿床以及一系列矿点。REE矿化与碳酸岩-碱性岩杂岩体密切相关,受一系列新生代走滑断裂的控制。该矿带广泛发育霓长岩化蚀变带,尤以大陆槽及里庄矿床为显著。岩相学分析表明,大陆槽和里庄霓长岩中的矿物多呈他形粒状结构,主要由长石、黑云母、霓辉石以及少量副矿物组成;主微量元素分析表明,霓长岩的碱质(K_2O+Na_2O)、MgO、Fe_2O_3T含量较高,且富集REE、Sr、Ba等微量元素;电子探针分析表明,霓长岩中的霓辉石Fe OT含量较高,长石Na_2O及K_2O含量较高,Ca O含量极低。An-Ab-Or三角图解显示长石主要为透长石和钠长石,属碱性长石系列;黑云母的地球化学成分图解表明云母的成因类型为交代型且具有相对富镁、贫铁等特征,属镁质黑云母。霓长岩化作用的交代流体含有较高的CO_2组分,且富含碱质、Mg、Fe及REE、Sr、Ba等元素。对比霓长岩与原岩的主微量元素发现:相比于正长岩原岩,在主量元素中,霓长岩的Fe、Mg、Ca等元素含量增加,Si、Al等元素含量降低;微量元素中,霓长岩的REE及Sr、Ba等元素显著增加。这意味着交代流体含有的Fe_2O_3T、MgO、CaO等组分在霓长岩化过程中被带进了围岩,而SiO_2和Al_2O_3等从围岩中被逐出。大陆槽及里庄矿区发育的角砾岩指示了矿区曾经历过频繁的角砾岩化事件,这提高了霓长岩作用的强度,并且为矿脉的穿插及REE矿物的沉淀提供了空间。在霓长岩化过程中,流体-围岩的组分交换反复发生,这削弱了REE络合物的稳定性,伴随多期次的热液活动及构造事件,最终完成REE活化→迁移→沉淀的过程。     

Thermodynamics of multicomponent pyroxenes: III. Calibration of Fe2+(Mg)-1, TiAl2(MgSi2)-1, TiFe 2 3+ (MgSi2)-1, AlFe3+(MgSi)-1, NaAl(CaMg)-1, Al2(MgSi)-1 and Ca(Mg)-1 exchange reactions between pyroxenes and silicate melts

A thermodynamic model for the Gibbs free energy of igneous pyroxenes with the general formula [Na, Ca, Fe²⁺, Mg]^M2[Fe²⁺, Mg, Ti, Al, Fe³⁺]^M1[Al, Fe³⁺, Si]^TetSiO₆ is calibrated from experimentally determined compositions of coexisting pyroxene and silicate melt. The model is based upon the general formulation, and relies upon the calibration of the “quadrilateral” subsystem, previously published by the present authors. The calibration database of pyroxene-liquid equilibria spans a broad spectrum of temperature, pressure and oxygen fugacity conditions, ranging from 1000°–1600°C, 0.001–30 kbar and iron-wüstite to air. Chemical potentials of endmember pyroxene components as well as exchange potentials between pyroxenes and coexisting liquids are defined utilizing the present authors' thermodynamic melt model. Model parameters are extracted from these relations by regression analysis. The resulting model and derivative endmember properties are internally consistent with an existing standard state thermodynamic database. The success of the model and its applicability to igneous petrogenesis are demonstrated by comparing calculated and experimentally determined liquidus compositions, temperatures and symmetry states for pyroxenes crystallizing from a variety of silicate melts, ranging in composition from tholeiites and angrites through rhyolites to potash ankaratrites.     

Fractionation of chromium,nickel, cobalt and copper in a differentiated dolerite‐granophyre sequence at Red Hill,Tasmania

Fractionation of tholeiitic magma in the Red Hill intrusion produced a gradational series of rocks ranging from dolerite to granophyre (McDougall, 1962). Granophyres are enriched in Fe, Si and alkalies, and impoverished in Mg, Ca and Al. With fractionation the magma was depleted rapidly in Cr and Ni owing to their removal in early crystallizing pyroxene and iron oxides. Cobalt decreases gradually from chilled dolerite to silicic dolerite, followed by a significant maximum in the most Fe‐enriched rocks, and finally decreases markedly in the granophyres. Cobalt follows Fe²+ closely and shows no obvious relationship with Mg. Copper was progressively enriched in the magma during the main stages of fractionation until precipitation of sulphide occurred, which caused impoverishment of Cu in the final liquid. Copper also is present in the silicates, it substitutes for Na in the feldspars and Fe²+ in pyroxenes and iron oxides.     

Geochemical characteristics of tin-bearing magnetite-skarns

Geological and geochemical characteristics of tin-bearing magnetite-skarns are reviewed in this paper, together with the author’s opinion with respect to the mechanism of transport of tin in this environment. In addition to cassiterite, the most common form of occurrence of tin in nature, three other forms of occurrence are also of interest in tin-bearing magnetite-skarns: (1) tin present in the form of fine exsolution colloidal grains of cassiterite; (2) tin found as independent tin-bearing minerals, such as malayaite, stokesite, nordenskiöldine, Sn-paigeite, Sn-ludwigite and hulsite in a variety of skarns; (3) tin occurring in the lattice of some skarn minerals, such as garnet, pyroxene, spinel, amphibole, epidote, wollastonite and axinite in the manner of ionic replacement. When Mg²⁺ and Fe²⁺ bearing minerals, in some cases even Sulfides or other mineralizer-containing minerals, replace tin-bearing Fe³⁺ and Ti⁴⁺ skarn minerals during the late stage of skarn alteration, tin in the pre-existing silicates maybe extracted and remobilized, thus contributing to the formation of associated tin deposits.     

Biotite and garnet compositional variation and mineral equilibria in Grenville gneisses of the Otter Lake area, Quebec

Garnet-biotite gneisses, some of which contain sillimanite or hornblende, are widespread within the Otter Lake terrain, a portion of the Grenville Province of the Canadian Shield. The metamorphic grade is upper amphibolite to, locally, lower granulite facies. The atomic ratio Fe²⁺/(Fe²⁺+ Fe³⁺) in biotite ranges from 0.79 to 0.89 (ferrous iron determinations in 10 highly pure separates), with a mean of 0.86. Mg and Fe²⁺ atoms occupy 67–78% of the octahedral sites, the remainder are occupied by Fe³⁺, Ti, and Al, and some are vacant. Mg/(Mg + Fe²⁺), denoted X, in the analysed samples ranges from 0.32 to 0.65. Garnet contains 1–24% grossular, 1–12% spessartine and X ranges from 0.07 to 0.34. Compositional variation in biotite and garnet is examined in relation to three mineral equilibria: (I) biotite + sillimanite + quartz = garnet + K-feldspar + H₂O; (II) pyrope + annite = almandine + phlogopite; (III) anorthite = grossular + sillimanite + quartz. Measurements of X (biotite) and X (garnet) are used to construct an illustrative model for equilibrium (I) which relates the observed variation in X to a temperature range of 70°C or a range in H₂O activity of 0.6; the latter interpretation is preferred. In sillimanite-free gneisses, the distribution of Mg and Fe²⁺ between garnet (low in Ca and Mn) and biotite is adequately described by a distribution coefficient (KD) of 4.1 (equilibrium II). The observed increase in the distribution coefficient with increasing Ca in garnet is ln K_D= 1.3 + 2.5 × 10^?2 [Ca] where [Ca] = 100 Ca/(Mg + Fe²⁺+ Mn + Ca). The distribution coefficient is apparently unaffected by the presence of up to 12% spessartine in garnet. In several specimens of garnet-sillimanite-plagioclase gneiss, the Ca contents of garnet and of plagioclase increase in unison, as required by equilibrium (III). The mean pressure calculated from these data (n= 17) is 5.9 kbar, and the 95% confidence limits are ±0.5 kbar.     

Crystal chemistry, structure analyses and phase transition experiment on an omphacite from eclogitic metagabbro from Syros island, Greece

Summary Pyroxene samples, from the Greek island of Syros, taken from a blueschist-eclogite facies Mg-rich metagabbro, were investigated by chemical and XRD analyses and M?ssbauer spectroscopy. Single-crystal XRD and microprobe analysis showed that the natural sample is a typical omphacite of intermediate composition in the Ca–Na pyroxene solid solutions. The space group P2/n was confirmed and the cations Mg, Al and Ca, Na were found to be ordered in the M1 and M2 positions, respectively. M?ssbauer spectroscopy showed that there is both ferrous and ferric iron in the structure, with the ratio 1.38:1. The M2 sites are fully occupied by Ca and Na, thus the iron (Fe²⁺ and Fe³⁺) can substitute only for Mg and Al in the M1 sites. Partial disorder was attained by annealing the sample at 850 °C, 20 kbar for 7 days, as confirmed by decrease of intensity of reflections affected by the C-type extinction.     

Metasomatic oxidation of upper mantle periodotite

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

西垄玄武质岩石中的橄榄岩类包体、捕虏晶以及巨晶的矿物化学研究

浙江衢县西垄和金华龙游一带分布有许多第三纪的霞石玄武岩、玻基橄辉岩、橄辉玢岩和超基性火山角砾岩岩体和岩脉。它们富含橄榄岩类包体和来源于破碎的橄榄岩包体的各种捕虏晶(橄榄石、斜方辉石、透辉石和石榴石)。此外,还常含有富铝普通辉石、石榴石和钛铁矿巨晶。本文试图在大量的单矿物分析数据基础上,讨论橄榄岩类包体、捕虏晶以及巨晶的矿物化学及其形成条件。关于橄榄岩包体的主要元素和微量元素地球化学以及成因岩石学的研究,笔者已在另一篇论文中专门论述(从柏林和张儒瑗,1983),这里不再重复。     

An analytical electron microscopic study of a pyroxene-amphibole intergrowth

Samples of a garnet granulite from the mafic border units of the Lake Chatuge, Georgia alpine peridotite body were found to contain lamellar intergrowths of a pargastic amphibole in augite having the typical appearance of an exsolution feature. Single crystal X-ray diffraction, optical, electron microprobe and conventional and analytical electron microscopic studies have provided data limiting the compositions and structures of the coexisting phases. Individual lamellae of both materials are from 0.5 to 2.0 m in width with the lamellar interface parallel to {0 1 0}. The formulae of the minerals, as determined by a combination of electron microprobe and analytical electron microscopy, are (Na_0.1Ca_1.0Mg_0.6Fe³⁺ _0.3)(Si_1.8Al_0.2)O₆ for the pyroxene and Na_0.7Ca_1.9(Mg_2.1Fe²⁺ _1.4Fe³⁺ _0.5Ti_0.1Cr_0.1Al_0.8)(Si_5.9Al_2.1) O₂₂(OH)₂ for the amphibole. Several other studies have described intergrowths similar to those observed in this work, in general favoring exsolution as the formation mechanism for the intergrowths. In the Lake Chatuge samples however, replacement of pyroxene by amphibole is in part indicated by continuous gradation of amphibole lamellae into amphiboles rimming the clinopyroxenes.Contribution No. 368 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan