Geochemistry of coexisting hornblende and biotite from the Ambalavayal granite,Kerala

Major and trace element geochemistry of coexisting hornblendes and biotites from the Ambalavayal granite, northern Kerala, are presented. The hornblendes correspond to edenitic composition, whereas the biotites correspond to annite. The hornblendes typically show high Al₂O₃ contents (9·69–11·89%) comparable with those from anorogenic granites. The biotites are characteristically low Mg-type, similar to those reported from alkaline rocks. The distribution coefficients calculated for all the major and trace elements are presented and an evaluation of the nature of variation indicate near-chemical equilibrium conditions during the crystallization of the two minerals. The hornblende-biotite tie lines in the Fe³⁺?Fe²⁺?Mg compositional triangle, lie parallel to those of buffered biotites, indicating crystallization in an environment closed to oxygen and well above the Ni?NiO buffer. It is inferred that thefH₂O increased towards the residual stage andfO₂ values were high, in the range of 10^?15 bars.     

Mineralogy and geochemistry of biotites from Proterozoic granitoids of western Arunachal Himalaya: Evidence of bimodal granitogeny and tectonic affinity

Felsic magmatic rocks in Kameng corridor of western Arunachal Himalaya are represented by extensively exposed Palaeoproterozoic porphyritic muscovite-biotite granite (GGn) of the Bomdila Group and small stock-like Mesoproterozoic hornblende-biotite granite (HBG) of the Salari Group. Mineralogy and chemical composition of biotites from GGn and HBG have been utilized to understand the nature and tectonic environment of their parental felsic melts. Biotites in GGn (FeO^t/MgO=3.1–4.6) are Fe-biotites and have shown affinity with primary biotites co-precipitating with muscovite in a peraluminous (S-type) felsic melt of syn-collisional tectonic environment. Biotites in HBG (FeO^t/MgO=1.3–2.2) are transitional between Fe and Mg biotites evolved from Fayalite-Magnetite-Quartz (FMQ) to Nickel-Nickel Oxide (NNO) buffers and are related to primary biotites co-existing with amphibole and other ferromagnesian minerals in a calc-alkaline metaluminous (I-type) felsic melt mostly formed in a subduction setting. Both GGn and HBG biotites exhibit Mg⇌Fe substitution, which is more pronounced in HBG biotites. GGn biotites exhibit 2Al⇌3Fe²⁺ substitution as expected in peraluminous melt, whereas 3Mg⇌2Al substitution normally expected to operate in metaluminous melt is less pronounced in HBG biotites. GGn biotites are markedly enriched in siderophyllite, and depleted in phlogopite components as compared to HBG biotites, which point to diverse genetic conditions. HBG biotites indicate oxidizing environment of the felsic melt unlike the reducing nature of the porphyritic granite (GGn).     

Processes of regional metamorphism and ultrametamorphism and some problems of the geology of the deep-lying sections of folded zones

On the basis of 135 pairs of chemical analyses of coexisting hornblendes and biotites, we have established a relationship between the contents of Al^IV, Al^VI, Fe³⁺, Mg, Ti, Na, and K and the overall iron index in the hornblendes and the depth of granitoid formation. This relationship has been emphasized by the R-method of factor analysis. We have examined the strength and nature of the correlations between the elements in the hornblendes and have considered the types of Isomorphism in the amphiboles according to depth, from the viewpoint of crystal chemistry. A regular increase in the amounts of A^IV in hornblende from <0.8 to > 1.6 formula units; of (Al^VI + Fe³⁺ + Ti) from <0.5 to >1. 0 formula units; of (K + Na) from <0.35 to >0. 64 formula units; and of Group A from <0.24 to >0.51 formula units has been recorded from the near-surface granitoids to the ultra-abyssal types. Biotites In this respect display no adequately clear and reliable information.—Authors.     

赣杭构造带灵山花岗岩体黑云母的矿物化学特征及其对岩石成因的指示意义

灵山花岗岩体在平面上为一环状分布的侵入体,中心为角闪石黑云母花岗岩,外围为黑云母花岗岩。在角闪石黑云母花岗岩中分布有大量的暗色镁铁质微粒包体。黑云母是大多数中酸性火成岩中比较重要的一种镁铁质矿物,它能很好地反映寄主岩浆的属性和成岩时的物理、化学条件,因此,本文对这两种花岗岩及镁铁质微粒包体中的黑云母开展了系统的岩相学观察和电子探针化学组成研究,探讨灵山岩体的物质来源、成岩条件和岩浆的混合作用过程。研究结果表明两种花岗岩体的黑云母具有不同化学成分,而暗色镁铁质微粒包体中黑云母的化学成分则变化较大。三种黑云母均在低氧逸度条件下晶出。两种花岗岩中的黑云母均富Fe贫Mg,属于铁质黑云母,含铁系数[(Fe~(3+)+Fe~(2+))/(Fe~(3+)+Fe~(2+)+Mg~(2+))]分别为0.65~0.70,0.72~0.78,FeOT/MgO均接近7.04。MF值[2×Mg/(Fe~(2+)+Mg+Mn)]分别为0.64~0.76和0.48~0.60,指示两种花岗岩的物质来源都是以壳源为主。镁铁质微粒包体中黑云母的MF值变化范围比较大,为0.63~1.06,为铁质黑云母到镁质黑云母,暗示包体岩浆经历过不同程度的岩浆混合作用。镁铁质微粒包体中部分黑云母与角闪石黑云母花岗岩中黑云母的结晶条件相似,而部分则有明显差异,推测是由于基性的镁铁质包体岩浆注入到酸性的花岗岩浆是一个连续多阶段的过程。     

40Ar/39Ar and Rb-Sr geochronology of the Qingyang batholith,Anhui Province,China

The geochronology and genesis of the Qingyang batholith were investigated using⁴⁰Ar/³⁹Ar and Rb-Sr isotopic techniques. The Qingyang is a composite batholith consisting of two major rock types granodiorite and granite in the Yangtze fold belt.⁴⁰Ar/³⁹Ar spectra for biotite and amphibole separates are internally concordant. The concordance of the minerals and spectra indicate no thermal disturbance of the ages, and rapid cooling of the rocks. The granodiorite has an age of 137.6±1.4 m.y. and the granite 122.7±1.2 m.y. Whole-rock Rb-Sr analysis yields ages consistent with the⁴⁰Ar/³⁹Ar dates. Thus, the Qingyang batholith was formed in two major stages in the late Jurassic and early Cretaceous. The batholith is not Triassic as was previously proposed. Special⁴⁰Ar/³⁹Ar analysis of two granodiorite samples has precisely documented a 1.0 m.y. apparent age difference between these samples. Several factors could account for this difference, but different emplacement times seem most convincible. The granodiorite and granite show little variation in initial⁸⁷Sr/⁸⁶Sr ratio (about 0.7085). The high initial Sr ratios suggest that the magmas were formed by anatexis of older crustal materials.     

Distribution and geochemical features of Hercynian-Indosinian granitoids in southeastern China

The tectonic patterns of the Hercynian-Indosinian cycle in southeastern China can be divided into two types. The first type is the Hercynian-Indosinian eugeosynclinal system, which is situated on the outer side of the Caledonian uplift belts. The second type is the Hercynian-Indosinian fault depression zone or superimposed basin system, which is developed on the basement formed by the Caledonian orogenic movement. There are two genetically different series of granitoids corresponding to two tectonic settings in the Hercynian-Indosinian tectonic regime of southeastern China. Among the transformation-series batholiths one of the largest in the Qinzhou Gulf geosyncline is known as the Darongshan granite (NE-extending) with an outcrop area of about 7000 km². The age of emplacement determined by whole-rock Rb-Sr isochron method ranges from 223 to 263 m.y., corresponding to late Permian, with higher Sr inital ratios (0.7179–0.7274). The granite is chemically rich in K₂O but poor in Na₂O with the atomic Na/K ratio<1.0 and the mole ratio Al₂O₃/(Na₂O + K₂O + CaO) > 1.0. K-feldsparg are usually predominated by medium to maximum microclines with a higher degree of Al-Si ordering characterized by the concentration of Al in T₁ sites of the feldspars (t₁ (o) = 0.57–0.99). Biotites are often rich in Fe but poor in Mg, belonging to Fe-biotite or siderophyllite, with a lower MF value (Mg/(Mg + Fe⁺³ +Fe²⁺ +Mn)), normally <0.4, and a lower Fe₃₊/Fe²⁺ ratio of 0.03-0.02 in their octahedron layers. This fact indicates that the oxidation degree of iron is relatively low in the transformation-series granites as compared with the syntexis-series granitoids. Granitic batholiths of the syntexis series distributed along the fault belts in the Hercynian depressions are usually more mafic, meta-aluminous granodiorites and smaller in size than those of the transformation series, with an outcrop area of 1–200 km₂. The Taiping granodiorite, for instance, is situated on the southern side of the Lower Yangtze River depression. It was emplaced 223 m.y. ago as dated by whole-rock Rb-Sr isochron method, with an initial Sr ratio of 0.706. Petrochemically, it is characterized by Na/K > 1.0 (1.31), mole Al₂O₃/(Na₂O + K₂O + CaO) < 1.0(0.95) and high Fe₂O₃/(Fe₂O₃ + FeO)(0.47), evidently differing from the transformation-series granites. K-feldspars are predominated by orthoclase with a lower degree of Si-Al ordering (t₁ (o) = t₁(m) = 0.30). Biotites are commonly rich in Mg in their octahedron layers (MF = 0.42–0.50) with higher Fe³⁺/Fe²⁺ ratios (0.36-0.51), indicating their formation under higher oxygen fugacity conditions. All this goes to prove that the syntexis-series granitoids were probably derived from mafic igneous or metamorphic source rocks in the lower crust.     

Coexisting hornblendes and biotites from Precambrian gneisses of the south coast of Western Australia

The compositions of coexisting hornblendes and biotites from amphibolite and granulite facies gneisses from the south coast of Western Australia were controlled by host rock composition, paragenesis, metamophic grade, pressure, and oxygen fugacity. The Mg/(Mg + Fe²⁺) and Mn/Fe²⁺ ratios in both minerals and possibly the Al^vi contents of the hornblendes are related to host rock compositions. Metamorphic grade appears to influence, perhaps only indirectly, the Ti, Mn, and Fe³⁺ contents of both minerals and possibly the hornblende Ca content. The higher Ti and lower Mn contents of the granulite facies hornblendes and biotites are attributed to their coexistence with pyroxenes, whereas their lower Fe³⁺/(Fe²⁺ + Fe³⁺) ratios are probably due to lower oxygen fugacity in the granulite facies environment. Grade-related colour variations in both minerals were controlled by their Ti/Fe²⁺ and Fe³⁺/(Fe²⁺ + Fe³⁺ ratios. The relatively low Al^vi contents of the hornblendes suggest low- to moderate-pressure metamorphism.Variations in element distribution coefficients are related to variations in mineral compositions rather than metamorphic grade. Thus K_{D(Al^iv ?Si)} is related to the Al^iv andedenite alkali contents of the hornblendes, K_{D(Fe²⁺ ?Mg)} to the distributions of Al^iv ?Si and Al^vi + Ti + Fe³⁺, K_D(Mn) to the Mn contents of both minerals, and K_D(Al^vi) to the Al^vi contents of the biotites.     

The crystal chemistry and mössbauer study of schorlomite

Six schorlomite samples with TiO₂ contents varying between 9.70 and 15.34 weight percent were studied by means of Mössbauer spectroscopy and chemical analysis. The measured Mössbauer spectra have complex shapes. The spectra of these samples were fitted with six doublets, which can be assigned to ^VIIIFe²⁺, ^VIFe²⁺, ^VIFe³⁺, ^IVFe³⁺ and two electron delocalizations, ^IVFe³⁺ ? ^VIIIFe²⁺ and ^IVFe³⁺ ? ^VIFe²⁺, respectively. The assignment of iron absorption doublets and their Mössbauer parameters are discussed in terms of the single crystal structure data of one of the samples studied in this work. Cation distributions are also given. The occupancies of cations at the tetrahedral (Z) site are Fe³⁺>Al³⁺, Ti⁴⁺, and the relative enrichments at Z site are always Fe³⁺>Ti⁴⁺. Most of the six samples contain Ti³⁺. Ti³⁺/ΣTi ratios range from 1.43 percent to 6.40 percent. Fe²⁺/ΣFe ratios vary from 8.84 percent to 11.31 percent. Four types of substitution must be considered for Ti entering the garnet structure.     

Activity-composition relationship in Tschermak's substituted Fe biotites at 700°C, 2 kbar

The reaction-displacement technique was applied to the end-member reaction annite = sanidine + magnetite + H₂ in order to determine the activity of the annite component (a _Ann) in iron biotites with variable degrees of the Tschermak's substitution (^[6]Fe + ^[4]Si = ^[6]Al + ^[4]Al). Based on the simplified relation a _Ann = f _{H 2}/foH₂ (foH₂ = hydrogen fugacity of the end-member reaction at P, T), two types of experiments were performed at 700°C / 2 kbar: Type I used Fe-Al biotites of known starting composition together with sanidine + magnetite + H₂O. This assemblage was exposed to various f _{H 2} conditions (f _{H 2} < foH₂) produced in the pressure vessel either by using different ratios of water/oil as pressure medium (f _{H 2} in this case was measured by the hydrogen sensor technique), or by the Ni′NiO buffer. The composition of the Fe-Al biotites changed through incorporation or release of the annite component in response to the externally imposed f _{H 2}. By using opposite biotite starting compositions, the equilibrium composition as a function of f _H2 was bracketed. For type II, f _{H 2} in equilibrium with a specific combination of fine-grained Fe-Al biotite (+ sanidine + magnetite + H₂O) was measured internally by application of the hydrogen sensor technique. Both type I and type II experiments yield consistent results demonstrating that a fine-grained assemblage of Fe-Al biotite (+ sanidine + magnetite + H₂O) is able to act as a sliding-scale buffer. The final chemical composition of the Fe-Al biotite after the experiments was determined by electron microprobe and Mössbauer spectroscopy. The ^[4]Al and ^[6]Al in the biotites are coupled according to the Tschermak's substitution. In the tetrahedral sheet 0.1 Al-atoms per formula unit are present in excess to the amount required to balance ^[6]Al, and all Fe-Al biotites contain 8–10% Fe³⁺. Therefore, they are not members of the pure annite - siderophyllite join, but have an almost constant amount (15 Mol%) of two additional Fe³⁺-bearing components (ferri-siderophyllite and a vacancy end-member). The volume - composition relationship obtained does not indicate excess molar volumes of mixing for the annite (Ann) - siderophyllite (Sid) binary. The data are consistent with a molar volume of annite of 15.46 ± 0.02 Jbar^–1 and of 15.06 ± 0.02 Jbar^–1 for siderophyllite. The experimentally determined activity - composition relation shows that biotites on the join annite - siderophyllite deviate negatively from ideality. A symmetric interaction parameter W_AnnSid is sufficient to represent the data within error. This was constrained as: W _AnnSid = –29 ± 4 kJmol^–1. This is in contradiction to empirical interaction parameters derived from natural assemblages for this binary that predict positive deviation from ideality. Reasons for this discrepancy are discussed.     

Fe-rich Li-bearing magnesionigerite-6N6S from Xianghualing tin-polymetallic orefield, Hunan Province, P.R. China

The Fe-rich Li-bearing magnesionigerite-6N6S occurs in the Xianghualing tin-polymetallic ore field, Linwu County, Hunan Province, Peoples Republic of China. It was found near the outer contact zone of the Laizhiling granite body and in the Middle-Upper Devonian carbonate rocks of Qiziqiao Formation. The mineral formed during the skarn stage. Its empirical formula is Sn_1.81Li_0.67(Fe_1.43Zn_1.19 Mn_0.41)_Σ3.03(Al_14.89Mg_1.46 Ti_0.11Si_0.01)_Σ16.47O₃₀(OH)₂. The structure for magnesionigerite-6N6S was solved and refined in space group R-3?m, with a?=?5.7144(8), c?=?55.446(11) Å, V?=?1568.0(4) ų, to R1?=?0.0528. Based on the structural refinement of single crystal diffraction data the formula of magnesionigerite-6N6S is Sn_1.80Li_0.97(Fe_1.89Zn_0.91) _Σ2.80 (Al_14.60Mg_1.63 Ti_0.20)_Σ16.43O₃₀(OH)₂ with Z?=?3. Fe-rich Li-bearing magnesionigerite-6N6S contains 0.74 wt.% Li₂O. The idealized charge-balanced composition of magnesionigerite-6N6S may be expressed by bivalent and trivalent cations: (Mg²⁺)₄(Al³⁺)₁₈O₃₀(OH)₂. The simplified general formula for the 6N6S polysomes in the nigerite and högbomite groups can be given as A _x B_18-x O₃₀(OH)₂, x?=?~4, where A?=?Mg²⁺, Fe²⁺, Zn²⁺; B?=?Al³⁺, Sn⁴⁺, Ti⁴⁺, Li⁺, □.     

湘南宝山矿床花岗闪长斑岩中黑云母的矿物学特征及其指示意义

湖南宝山矿床处于坪宝矿带的北端,是湘南地区最大的铜多金属矿床。为了进一步探讨矿区内花岗质岩石的形成条件及成矿潜力,文章在详细的野外地质和岩相学观察的基础上,对与成矿密切相关的花岗闪长斑岩中的黑云母进行了详细的矿物化学分析。电子探针分析结果表明:宝山花岗闪长斑岩中的黑云母为铁质黑云母和镁质黑云母,其中,Ti介于0.18~0.30,且Mg/(Mg+Fe2+)值介于0.42~0.58,属于典型的岩浆成因黑云母;黑云母的氧化系数为0.16~0.26,w(Mg O)为8.17%~11.72%,平均9.3%,MF值范围为0.38~0.50,指示其岩体属于壳幔混源型的I型花岗岩;岩体中以黑云母的全铝含量计算的结晶压力为97~174 MPa,相应的结晶深度为3.67~6.57 km,平均深度为5.12 km。其log f(O2)变化范围为-14.5~-12.8,表明黑云母是在较高氧逸度条件下结晶形成的,有利于铜矿的形成。     

Statistical chemistry of calcic amphiboles

Principal components analysis is used to study the chemistry of 639 calcic amphiboles. Eigenvectors representing multiple partial correlation coefficients give various sets of substitutional relationships. The relative significance of each set can be noted by the percent variation of the data it represents. The highest percent variation (36%) is associated with the substitutions $$Si + Mg \rightleftharpoons Al^{IV} + Al^{VI} + Ti + Fe^{3 + } + Fe^{2 + } + Na + K$$ . Other expected substitutions among the ions such as Al^IV + Na ? Si, the positive correlation between Al^IV and Al^VI etc. are shown statistically. The substitution of Al in T ₁ and T ₂ positions imposes an ordering in the M ₁, M ₂ and M ₃ sites. Variability of OH in the amphiboles is found to be significant. There is no definite correlation between OH and Fe³⁺ but OH and Ti are positively correlated. Under certain conditions and provided the concentration of Al^IV does not change significantly, Fe and Mg may be assumed to mix ideally in the amphibole solid solution.     

IIb trioctahedral chlorite from the Barberton greenstone belt: crystal structure and rock composition constraints with implications to geothermometry

IIb trioctahedral chlorite in the Barberton greenstone belt (BGB) metavolcanic rocks was formed during pervasive greenschist metamorphism. The chem‐ical composition of the chlorite is highly variable, with the Fe/(Fe+Mg) ratio ranging from 0.12 to 0.8 among 53 samples. The chemical variation of the chlorite results from the chemical diversity of the host rock, especially the MgO content of the rock, but major details of the variation pattern of the chlorite are due to the crystal structure of the chlorite. All major cation abundances in the chlorite are strongly correlated with each other. Sil‐icon increases with Mg and decreases with Fe, while Al^IV and Al^VI decrease with Mg and increase with Fe²⁺. A complex exchange vector explains over 90% of the chlorite compositional variation: Mg₄SiFe²⁺ ₋₃Al^VI ₋₁ Al^IV ₋₁, which has 3 parts Fe-Mg substitution coupled with one part tschermakite substitution. This ratio is required to maintain the charge and site balances and the dimensional fit between the tetrahedral and octahedral sheets. The subtle change in Al substitution in chlorite implies that Al^VI is preferentially ordered in the M(4) site, and about 84% of the Al^VI present is in the M(4) sites when they are nearly filled with Al^VI. Based on 47 analyzed chlorite-bearing rock samples, chlorite (Chl) composition is strongly correlated with the MgO content of the host rock. Calculated correlation coefficients are +0.91 for SiO_2Chl-MgO_Rock, −0.87 for Al₂O_3Chl-MgO_Rock, +0.89 for MgO_Chl-MgO_Rock, and −0.85 for FeO_Chl-MgO_Rock. Only weak correlations have been found between chlorite oxides and other oxides of rock (between same oxides in chlorite and rock: SiO₂−0.67, Al₂O₃ + 0.59, FeO −0.41). However, MgO_Chl is saturated at about 36 wt% in rocks that have MgO above 22 wt%.The MgO_Chl is about 5 wt% when the host rock approaches 0 wt% of MgO. This implies that Mg substituting into the chlorite is approximately limited to 1.5–9.2 Mg atoms per formula unit and 1.0–3.2 Al^IV. Chlorite geothermometers can not be applied to all BGB samples. However, the empirical chlorite geothermometer based on Al^IV of chlorite may be applicable to chlorites formed under metamorphic conditions because it can predict the chemical composition of the chlorite from basaltic and dacitic samples in this study. An estimated temperature of about 320°C for the greenschist metamorphism of the greenstone belt through this geothermometer is consistent with that obtained by other geothermometers. Received: 22 January 1996 / Accepted: 15 August 1996     

赣北大湖塘钨矿成岩成矿物质来源的矿物学和同位素示踪研究

赣北大湖塘超大型钨矿位于九岭钨多金属矿集区东部。本文对大湖塘钨矿石门寺矿段矿物学特征进行了系统的研究,结合同位素示踪分析了成岩成矿物质来源。岩相学研究表明,石门寺矿段蚀变以黑云母化、云英岩化及碱交代(钾长石化、钠长石化)作用为主。黑云母化的过程中释放了一定量的挥发分,云英岩化和碱交代作用除萃取部分的成矿物质外,使岩体中的Ca2+大量活化迁移。晋宁晚期黑云母花岗闪长岩与燕山中期似斑状花岗岩、花岗斑岩矿物成分研究表明:(1)斜长石普遍富钠,似伟晶岩壳主晶为钾长石,客晶为钠长石;(2)黑云母具有富铁贫镁的特点,黑云母花岗闪长岩及似斑状花岗岩中的黑云母均为铁质黑云母,花岗斑岩中黑云母为铁叶云母。黑云母成分指示大湖塘石门寺矿段花岗岩类均为过铝质S型花岗岩,成岩物质均为壳源。石英氢、氧同位素及黑钨矿氧同位素研究表明成矿流体为岩浆水。黄铜矿、辉钼矿硫同位素表明成矿流体中硫来自于岩浆。结合前人研究成果,本文认为富钨的双桥山群浅变质岩在燕山中期发生了部分熔融,产生了高分异的富含钨元素及挥发分的岩浆,岩浆分异演化过程中形成的含矿热液使侵入体自身及围岩发生大规模的蚀变作用,进而在燕山中期侵入岩的内外接触带形成了大湖塘超大型钨多金属矿床。     

Corrensite and mixed-layer chlorite/corrensite in metabasalt from northern Taiwan: TEM/AEM,EMPA, XRD,and optical studies

Many chloritic minerals in low-grade metamorphic or hydrothermally altered mafic rocks exhibit abnormal optical properties, expand slightly upon glycolation (expandable chlorite) and/or have excess Al^VI relative to Al^IV, as well as significant Ca, K and Na contents. Chloritic minerals with these properties fill vesicles and interstitial void space in low-grade metabasalt from northern Taiwan and have been studied with a combination of TEM/AEM, EMPA, XRD, and optical microscopy. The chloritic minerals include corrensite, which is an ordered 1:1 mixed-layer chlorite/smectite, and expandable chlorite, which is shown to be a mixed-layer chlorite/corrensite. Corrensite and some mixed-layer chlorite/corrensite occur as rims of vesicles and other cavities, while later-formed mixed-layer chlorite/corrensite occupies the vesicle cores. The TEM observations show that the mixed-layer chlorite/corrensite has ca. 20%, and the corrensite has ca. 50% expandable smectite-like layers, consistent with XRD observations and with their abnormal optical properties. The AEM analyses show that high Si and Ca contents, high Al^VI/Al^IV and low Fe^VI/(Fe+Mg)^VI ratios of chlorites are correlated with interstratification of corrensite (or smectite-like) layers in chlorite. The AEM analyses obtained from 200–500 Å thick packets of nearly pure corrensite or chlorite layers always show that corrensite has low Al^IV/Si^IV and low Fe^VI/(Fe+Mg)^VI, while chlorite has high Al^IV/Si^IV and high Fe^VI/(Fe+Mg)^VI. This implies that the trioctahedral smectite-like component of corrensite has significantly lower Al^IV/Si^IV and Fe^VI/(Fe+Mg)^VI. The ratios of Fe^VI/(Fe+Mg)^VI and Al^IV/Si^IV thus decrease in the order chlorite, corrensite, smectite. The proportions of corrensite (or smectite-like) layers relative to chlorite layers in low-grade rocks are inferred to be controlled principally by Fe/Mg ratio in the fluid or the bulk rock and by temperature. Compositional variations of chlorites in low-grade rocks, which appear to correlate with temperature or metamorphic grade, more likely reflect variable proportions of mixed-layered components. The assemblages of trioctahedral phyllosilicates tend to occur as intergrown discrete phases, such as chlorite-corrensite, corrensite-smectite, or chlorite-corrensite-smectite. A model for the corrensite crystal structure suggests that corrensite should be treated as a unique phase rather than as a 1:1 ordered mixed-layer chlorite/smectite.     

Mössbauer and ELNES spectroscopy of (Mg,Fe)(Si,Al)O3 perovskite: a highly oxidised component of the lower mantle

(Mg,Fe)(Si,Al)O₃ perovskite samples with varying Fe and Al concentration were synthesised at high pressure and temperature at varying conditions of oxygen fugacity using a multianvil press, and were characterised using ex?situ X-ray diffraction, electron microprobe, Mössbauer spectroscopy and analytical transmission electron microscopy. The Fe³⁺/ΣFe ratio was determined from Mössbauer spectra recorded at 293 and 80?K, and shows a nearly linear dependence of Fe³⁺/ΣFe with Al composition of (Mg,Fe)(Si,Al)O₃ perovskite. The Fe³⁺/ΣFe values were obtained for selected samples of (Mg,Fe)(Si,Al)O₃ perovskite using electron energy-loss near-edge structure (ELNES) spectroscopy, and are in excellent agreement with Mössbauer data, demonstrating that Fe³⁺/ΣFe can be determined with a spatial resolution on the order of nm. Oxygen concentrations were determined by combining bulk chemical data with Fe³⁺/ΣFe data determined by Mössbauer spectroscopy, and show a significant concentration of oxygen vacancies in (Mg,Fe)(Si,Al)O₃ perovskite.     

Mineralogy and geochemistry of granitoids from Kinnaur region,Himachal Higher Himalaya,India: Implication on the nature of felsic magmatism in the collision tectonics

Felsic magmatism in the southern part of Himachal Higher Himalaya is constituted by Neoproterozoic granite gneiss (GGn), Early Palaeozoic granitoids (EPG) and Tertiary tourmaline-bearing leucogranite (TLg). Magnetic susceptibility values (<3 ×10^?3 SI), molar Al₂ O ₃/(CaO + Na₂ O + K ₂O) (≥1.1), mineral assemblage (bt–ms–pl–kf–qtz ± tur ± ap), and the presence of normative corundum relate these granitoids to peraluminous S-type, ilmenite series (reduced type) granites formed in a syncollisional tectonic setting. Plagioclase from GGn (An₁₀–An₃₁) and EPG (An₁₅–An₃₃) represents oligoclase to andesine and TLg (An₂–An₁₅) represents albite to oligoclase, whereas compositional ranges of K-feldspar are more-or-less similar (Or₈₈ to Or₉₅ in GGn, Or₈₆ to Or₉₇ in EPG and Or₈₇ to Or₉₄ in TLg). Biotites in GGn (Mg/Mg + Fe^t= 0.34–0.45), EPG (Mg/Mg + Fe^t= 0.27–0.47), and TLg (Mg/Mg + Fe^t= 0.25–0.30) are ferribiotites enriched in siderophyllite, which stabilised between FMQ and HM buffers and are characterised by dominant 3Fe\(\rightleftharpoons \)2Al, 3Mg\(\rightleftharpoons \)2Al substitutions typical of peraluminous (S-type), reducing felsic melts. Muscovite in GGn (Mg/Mg + Fe^t=0.58–0.66), EPG (Mg/Mg + Fe^t=0.31?0.59), and TLg (Mg/Mg + Fe^t=0.29–0.42) represent celadonite and paragonite solid solutions, and the tourmaline from EPG and TLg belongs to the schorl-elbaite series, which are characteristics of peraluminous, Li-poor, biotite-tourmaline granites. Geochemical features reveal that the GGn and EPG precursor melts were most likely derived from melting of biotite-rich metapelite and metagraywacke sources, whereas TLg melt appears to have formed from biotite-muscovite rich metapelite and metagraywacke sources. Major and trace elements modelling suggest that the GGn, EPG and TLg parental melts have experienced low degrees (～13, ～17 and ～13%, respectively) of kf–pl–bt fractionation, respectively, subsequent to partial melting. The GGn and EPG melts are the results of a pre-Himalayan, syn-collisional Pan-African felsic magmatic event, whereas the TLg is a magmatic product of Himalayan collision tectonics.     

Pseudosinhalite: discovery of the hydrous MgAl-borate as a new mineral in the Tayozhnoye, Siberia, skarn deposit

After its initial synthesis as the new compound Mg₂Al₃B₂O₉(OH) (Daniels et al. 1997) pseudosinhalite has now been discovered as a new mineral. It occurs, together with hydrotalcite, as a replacement product of sinhalite, MgAlBO₄, in an impure marble of the contact metasomatic iron boron deposit of Tayozhnoye in the Aldan Shield of Siberia. Its chemical composition determined by electron microprobe is (wt%): Al₂O₃ 46.88; MgO 25.12; FeO 1.99; B₂O₃ (calculated) 21.75; H₂O (calculated) 2.81 giving a total of 98.55 and leading to the empirical formula (Mg_2.00 Fe²⁺ _0.09)_Σ=2.09 Al_2.94 B₂O₉(OH). The small deviation from the ideal stoichiometry with (Mg?+?Fe²⁺):Al?≠?2:3 may be caused by either solid solution towards, or submicroscopic interlayering with lamellae of, the structurally similar mineral sinhalite. The underlying substitution involving also B and H would be (Mg?+?Fe)+?B=Al+2H. Pseudosinhalite is monoclinic, space group P2₁/c, with a=7.49(1), b=4.33(1), c=9.85(2) Å; β=110.7(1)°; V?=?299(1) ų; Z?=?2. Calculated density is 3.508?g/cm³. Pseudosinhalite is colourless with white streak and has a vitreous lustre. It is transparent; no fluorescence was detected. There is no cleavage and parting; fractures are concoidal. Optical constants could not be measured properly due to polysynthetic microtwinning, but α<1.72<γ. For synthetic pseudosinhalite α=1.691(1); β=1.713(1); γ=1.730(1); Δ=0.039; 2?V=80°. The temperature of pseudosinhalite formation was below about 400?°C at low pressures and with a hydrous, CO₂-bearing fluid participating in the reaction.     

Magnetic behavior of trioctahedral micas with different octahedral Fe ordering

This contribution is finalized at the discussion of the magnetic structure of two samples, belonging to phlogopite–annite [sample TK, chemical composition ^IV(Si_2.76Al_1.24) ^VI(Al_0.64Mg_0.72 $ {\text{Fe}}_{1.45}^{2 + } $ Mn_0.03Ti_0.15) (K_0.96Na_0.05) O_10.67 (OH)_1.31 Cl_0.02] and polylithionite–siderophyllite joints [sample PPB, chemical composition ^IV(Si_3.14Al_0.86)^VI(Al_0.75Mg_0.01 $ {\text{Fe}}_{1.03}^{2 + } $ $ {\text{Fe}}_{1.03}^{3 + } $ Mn_0.01Ti_0.01Li_1.09) (K_0.99Na_0.01) O_10.00 (OH)_0.65F_1.35]. Samples differ for Fe ordering in octahedral sites, Fe²⁺/(Fe²⁺?+?Fe³⁺) ratio, octahedral composition, defining a different environment around Fe cations, and layer symmetry. Spin-glass behavior was detected for both samples, as evidenced by the dependency of the temperature giving the peak in the susceptibility curve from the frequency of the applied alternating current magnetic field. The crystal chemical features are associated to the different temperature at which the maximum in magnetic susceptibility is observed: 6?K in TK, where Fe is disordered in all octahedral sites, and 8?K in PPB sample, showing a smaller and more regular coordination polyhedron for Fe, which is ordered in the trans-site and in one of the two cis-sites.     

Crystal chemical variations in Ba-rich biotites from gabbroic rocks of lower crust (Ivrea Zone,NW Italy)

Biotites from mafic rocks occurring at different stratigraphic levels of the Ivrea-Verbano Mafic Complex are studied. The rocks are gabbros and diorites. All the biotites are intermediate between phlogopite and annite [0.282 (up to 7.14 and 9.32 wt%, respectively) with respect to those of the diorites (up to 1.26 and 6.26 wt%, respectively). Systematic compositional variations support the substitution model 2 ^IV Si+( ^IV R²⁺)2 ^IV Al+ ^VI Ti (R²⁺=Fe+Mg+Mn) in gabbros and ^IV Si+ ^VI Al ^IV Al+ ^VI Ti in diorites. A predominance of disordered stacking sequences, coexisting with 1M, 2M ₁ and 3T polytypes was observed in all biotites. It was possible to carry out structural refinements only on three biotites-2M ₁ from diorites (R-values between 2.68 and 3.77) and one biotite-1M from gabbros (R-value=3.09). It was shown that: (1) the reduced thickness of the tetrahedral sheet in Ba-rich biotites supports the coupled substitution ^IV Si+ ^XII K ^IV Al+ ^XII Ba; (2) the interlayer site geometry is affected by the whole layer chemistry and does not reflect only local chemical variations; (3) in two samples of the 2M ₁ polytype, the M(1) octahedral site is larger and more distorted than the M(2) sites because of the preferential ordering of Fe²⁺ in the M(1) site, whereas one sample shows complete cation disorder in the octahedral sites. Biotite-1M shows that Fe²⁺ can also be located in the M(2) site. Some of the differences between the biotites of gabbros and diorites (e.g. Ba concentration and exchange vectors) may be linked to the host rock composition and to its crystallization process. Biotite occurs in trace amounts in gabbros and its crystallization is related to the interstitial melt which contributed to the adcumulus growth of the main rock forming phases and became highly enriched in K, Ba and Ti. Diorites are the result of equilibrium crystallization of a residual melt rich in incompatible elements, where biotite is a major constituent.