西藏错那洞电气石花岗岩中电气石化学组成、硼同位素特征及意义

为了对西藏错那洞电气石花岗岩源区进一步约束,利用显微镜、电子探针和激光剥蚀多接收等离子质谱仪,对错那洞电气石花岗岩中电气石的形态、成分及硼同位素组成进行了研究.结果表明,错那洞电气石花岗岩中的电气石为碱族黑/铁电气石,直接结晶自富硼熔体,与熔体之间未发生明显的硼同位素分馏.电气石δ11B值主要在-6.91‰^-9.17‰之间,与大陆地壳平均δ11B值(-10‰±3‰)相近,表明错那洞电气石花岗岩主要源自变质沉积岩的部分熔融.然而,与起源于变质沉积岩的花岗岩相比,样品的δ11B值明显偏高,而与前人报道的雅拉香波淡色花岗岩(源自石榴石角闪岩部分熔融)的δ11B值相似.因此,错那洞电气石花岗岩源区中,除了变质沉积岩外,可能还混入了少量石榴石角闪岩.     

Tourmaline breakdown in the migmatite zone of the Ryoke metamorphic belt,SW Japan

A sharp line delimitating the distribution of tourmaline (termed as a ‘tourmaline‐out isograd’) is defined in the migmatite zone of the Ryoke metamorphic belt, Japan. The trend of the tourmaline‐out isograd closely matches that of the isograds formed through the regional metamorphism, suggesting that it represents the breakdown front of tourmaline during regional metamorphism. This is confirmed by the presence of the reaction textures of tourmaline to sillimanite and cordierite near the tourmaline‐out isograd. The breakdown of tourmaline would release boron into associated melts or fluids and be an important factor in controlling the behaviour of boron in tourmaline‐bearing high‐temperature metamorphic rocks. Near the tourmaline‐out isograd, large tourmaline crystals occur in the centre of interboudin partitions containing leucosome. In the melanosome of the intervening matrix, reaction textures involving tourmaline are locally observed. These observations imply that tourmaline breakdown is related to a melting reaction and that the boron in the leucosome is derived from the breakdown of tourmaline in the melanosome during prograde metamorphism. Boron released by tourmaline breakdown lowers both the solidus temperature of the rock and the viscosity of any associated melt. Considering that the tourmaline‐out isograd lies close to the schist–migmatite boundary, these effects might have enhanced melt generation and segregation in the migmatite zone of the Ryoke belt. The evidence for the breakdown of tourmaline and the almost complete absence of any borosilicates throughout the migmatite zone suggest that boron was effectively removed from this region by the movement of melt and/or fluid. This implies that the tourmaline‐out isograd can reflect a significant amount of mass transfer in the anatectic zones.     

Tourmaline in a low grade clastic metasedimentary rock: an example of the petrogenetic potential of tourmaline

Detrital tourmaline grains and their associated tourmaline overgrowths provide a means to unravel the provenance and petrogenetic history of low grade clastic metasedimentary rocks. Evidence derives from tourmaline grains found in a lithic wacke metamorphosed to chlorite zone conditions. The detrital tourmaline cores are diagnostic indicators of the source rocks of the sediment whereas the overgrowths record both diagenetic and metamorphic reactions in the rock. Tourmaline grains consist of a detrital core surrounded by asymmetric overgrowths comprised of inner and outer rims. Abrupt chemical discontinuities between each of these zones implies that volume diffusion within tourmaline was minor under the conditions of formation. Compositions of the detrital cores vary widely, yet can be correlated with source rock types that are consistent with lithic fragments recognizable in the metawacke. At either the analogous or antilogous pole, inner rim compositions proximal to the detrital cores converge, despite the substrate tourmaline composition, indicating an approach to chemical equilibrium. However, significant dufferences in Al and X-site vacancies at the expense of Mg, Na and Ti between the analogous and antilogous poles of the inner rims demonstrate the presence of significant amounts of compositional polarity. Outer rim compositions at either pole also converge but compositional polarity between the analogous and antilogous poles persists. The presence of the inner and outer rims separated by a compositional discontinuity suggests punctuated evolution of the overgrowth. This implies that boron was sporadically available during diagenesis and metamorphism. Based on boron contents of minerals, this may correspond to a mechanism such as boron release due to polytypic change of illite or consumption of illite and/or muscovite. As such, tourmaline growth stages may serve as a monitor of chemical reactions in low grade metamorphic rocks.     

Tourmaline composition and boron isotopes record lateritic weathering during the Great Oxidation Event

Identifying evidence of oxidative weathering in the geological record is essential to trace the evolution of Earth's atmosphere oxygenation. Metamorphosed residues of lateritic weathering have been identified as two rock types in the 2.1‐Ga‐old Cercadinho Formation, Piracicaba Group, Quadrilátero Ferrífero of Minas Gerais. One is tourmaline–hematite–sillimanite–kyanite quartzite; the other is rutile–tourmaline–hematite–muscovite phyllite. Both rocks have abundant tourmaline with δ¹¹B values between about ?17‰ and ?13‰. The Cercadinho tourmaline is roughly parallel to the povondraite–“oxy‐dravite” join of meta‐evaporitic tourmaline, in its more aluminous segment, offset to higher contents of iron. These compositional and isotopic characteristics of the Cercadinho tourmaline indicate that continental evaporitic brines interacted with aluminium‐ and iron‐rich residues of lateritic weathering. The abundance of disseminated tourmaline, a mineral poorly reported from palaeosols worldwide, implies a boron‐rich brine overprint on the lateritic profile before the onset of metamorphism, reflecting a climatic change from humid to arid conditions in a continental setting. The recognition of lateritic weathering in the Cercadinho Formation contributes to the amount of evidence for increased levels of atmospheric oxygen between 2.22 and 2.06 Ga ago.     

Chemical compositions of tourmaline in the Yindongzi-Tongmugou Pb-Zn deposits,Qinling, China: Implications for hydrothermal ore-forming processes

A microprobe study has been carried out on the chemical composition of tourmaline from the Yindongzi and Tongmugou stratabound Pb-Zn ore deposits, eastern Qinling, China. Tourmaline was analysed from a variety of rock types representative of its various occurrences associated with the ore bodies. All the tourmalines studied here belong to the schorl-dravite series. Most are of hydrothermal origin with Mg > Fe and Na > Ca. Some detrital cores of tourmaline have been recognized from their geometry and chemistry, with Fe > Mg. The chemical trends from core to rim in zoned grains suggest a multi-stage model for the growth of tourmaline and genesis of the ore bodies. The first stage was represented by a more Mg-rich hydrothermal fluid in the submarine hydrothermal system, producing Mg-rich tourmalines by selective replacement of clay-rich sediments close to the sediment-water interface. The second stage was dominated by Fe-rich hydrothermal fluid and resulted in overgrowth of Fe-rich tourmaline rims. This stage also led to the nucleation and growth of new tourmaline crystals and was responsible for the formation of the main massive sulphide orebodies. Finally, a further period of hydrothermal activity or a metamorphic event led to the formation of an additional rim of Mg-rich tourmaline.     

Mineral chemistry of tourmaline from Mashak Pahar,South Purulia Shear Zone (SPSZ), eastern Indian Shield

The area of investigation at and around Mashak Pahar, Bankura district, West Bengal, India comprises a number of rock types namely: granite gneiss, migmatized quartz tourmaline gneiss, quartz pebble conglomerate, ferruginous quartzite, quartz tourmaline veins (as veins) and graphite schists. Interestingly, the study area lies in the region extending South Purulia Shear Zone (～Tamar–Porapahar Shear Zone) which marks the boundary between two contrasting tectonic blocks of eastern India, namely, the Chhotanagpur Gneissic Terrane (CGC) to the north and Singhbhum Group of rocks to the south. The rocks of the study area are poly-phasedly deformed by three phases of folding, namely, F₁, F₂ and F₃. All the tourmalines are classified to be of ‘Alkali Group’. Chemistry of tourmalines from migmatized quartz tourmaline gneiss and those from quartz tourmaline veins are in conformity with their relation to (earthquake induced) shear system evolution in this terrain. In general, the compositional evolution of tourmaline during prograde metamorphism (～400°–730°C) has been supported by both petrographic and chemical evidences. Assessment of mineral–chemical data of constituent tourmaline grains clearly suggests compositional variations across zonal boundaries within tourmaline that was controlled by changing metamorphic milieu in this terrane. Field and petrographic evidences clearly indicate activation of earlier and later shears in this region accompanied by infiltration of boron and formation of zoned tourmaline crystals.     

Chemical and boron isotopic composition of tourmaline from the Gonghe Triassic intermediate -acid intrusive rocks,Qinghai and its implications for evolution of the magmatic-hydrothermal system.SCIEI北大核心CSCD

青海共和盆地干热岩经历的热历史过程、热源是了解干热岩地热藏形成亟待解决的难题,不同时期、不同类型的脉体可为其经历的热过程、热源提供证据。经调查发现,盆地东北当家寺岩体及井下干热岩中电气石脉体与该区后期断裂产状相近,是否代表后期热事件需要确定。本研究选择对GR1井、DR3井中酸性侵入岩岩芯和当家寺露头岩体中发现的电气石脉体开展了岩相学、锆石年代学、电子探针、LA-MC-ICPMS原位微量元素及B同位素分析,以约束电气石脉体的成因和源区。结果表明,GR1、DR3井岩芯及当家寺岩体含有电气石脉体的岩性分别是碱长花岗岩、高镁闪长岩及二长花岗岩;其中露头区花岗岩体中电气石脉的宽度约20cm,产状直立,其围岩的形成时代为239~241Ma。背散射及显微图像特征揭示,GR1井和DR3井下中酸性侵入岩及当家寺岩体中电气石为碱族的黑电气石和镁电气石,具有远近不同的多个流体来源。δ^(11)B分布在-11.50‰~-11.93‰,与大陆地壳平均的同位素组成δ^(11)B值(-10‰±3‰)相近。结合区域地质资料,认为在晚三叠世时期,该区域整体处于碰撞期或后碰撞期,陆壳加厚发生部分熔融形成S型花岗岩(~220Ma),其中含硼的热液流体侵位于早期具有俯冲背景的I型花岗岩(~240Ma)中形成电气石脉。     

Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).     

桦甸夹皮沟层状电气石岩特征及其地质找矿意义

描述了层状电气石岩的物理特征、岩性组合特征,分析了其化学成分,作了理论研究,确定了该层状电气石岩为火山喷气—沉积变质成因,形成于海底火山喷气—沉积构造环境中,其原岩是一套富硼镁的泥铁质—硅质岩石。它的发现对在该地区找矿具有重要指导意义。     

熔融制样-X射线荧光光谱法测定电气石中12种主次量元素

电气石是一类含硼的铝硅酸盐矿物,化学成分复杂、化学稳定性强,不易湿法分解,B_2O_3含量较高,导致其主次量元素的同时测定存在一定困难。本文采用熔融法制样,建立了X射线荧光光谱法测定电气石Na_2O、MgO、Al_2O_3、SiO_2、P_2O_5、K_2O、CaO、TiO_2、V_2O_5、Cr_2O_3、MnO、TFe_2O_3等主次量元素的分析方法。样品与四硼酸锂-偏硼酸锂-氟化锂(质量比为4.5∶1∶0.4)混合熔剂的稀释比例为1∶10,消除了粒度效应和矿物效应;在缺少电气石标准物质的情况下,选择土壤、水系沉积物及多种类型的地质标准物质绘制校准曲线,利用含量与电气石类似的标准物质验证准确度,测定结果的相对标准偏差小于4.2%。采用所建方法测定四种不同类型电气石实际样品,测定值与经典化学法基本吻合。本方法解决了电气石不易湿法分解和硼的干扰问题,测定结果准确可靠,与其他方法相比操作简便,分析周期短。     

辽东裂谷带硫化物矿床内电气石系列矿物学与找矿关系

本文通过辽东裂谷硫化物矿床中不同产状电气石的研究，提示了不同环境内形成电气石矿物的标型、光性、成分、同位素组成、红外光谱与Ｘ衍射特征方面存在一定差异。不同物化条件下形成的电气石其演化系列表现在由近矿围岩到硫化物矿层电气石由富镁由富铁－镁过渡从层状矿体到热液改造矿体电气石由铁镁向富钙－镁过渡。研究表明，电气石的形成与元古代早期底火山喷发作用后引起的富硼热泉活动有关。     

The nature and provenance of Golestan loess deposits in northeast Iran

Mineralogical, textural, geochemical, and weathering characteristics of loess deposits in Golestan province of Iran suggest that they are mostly derived from felsic igneous rocks and are related to Quaternary palaeoclimate. Whole‐rock analyses indicate heavy minerals such as zircon, tourmaline and phyllosillicate minerals (e.g. muscovite, chlorite, illite) exert a significant control on the chemical composition. The loess samples display uniform chemical composition, indicative of similar alteration history. Chemical index of alteration suggests a weak to moderate degree of weathering in a felsic source area. Scanning electron micrographs of quartz grains reveal abundant silt‐sized quartz particles, a result of glacial grinding during the Late Pleistocene in Central Asia. Subsequently, these silt particles were transported from Central Asia to their depositional site by wind and paraglacial processes. Local topography of northeast Iran (Alborz Mountains) acted as a major barrier, entrapping the airborne particles on the plains of Golestan province. Copyright © 2012 John Wiley & Sons, Ltd.     

The nature and origin of brecdation and mineralization at the White Crystal ore deposit,Ardlethan tin mine,New South Wales

The White Crystal ore zone consists of an ovoid mass of fine grained quartz‐tourmaline topaz rock containing disseminated cassiterite together with prominent vughs of quartz and/or tourmaline, cassiterite, and sulphides. Toward the margins of the ore zone the decreasing intensity of alteration illustrates formation via a process of brecciation, infill, and alteration. The rectangular slab‐like fragments are commonly aligned and their plunge indicates a dip towards a common epicentre. The tourmalinized ore zone is surrounded by successive zones of sericitization and argillization. The brecciation is of large scale tensional origin which is suggestive of collapse. Beneath the ore zone mineralization/alteration continues at subeconomic grades and limited data suggests an intrusive hydrothermal style of brecciation. The entire system is a form of breccia pipe and has yielded some 1.5 Mt of ore at around 0.64% Sn.     

凤城地区硫铁矿床中热水沉积电气石岩的发现及其找矿意义

电气石岩是辽东裂谷盆地内元古宙硫铁矿床中重要容矿岩石,呈纹层状发育在硫铁矿床下部或矿层内。受裂谷内同生断裂控制呈线状断续延伸。为一种以富含硅、硼、镁为特征的富硼化学沉积岩。其中电气石属镁-铁系列,在不同成矿环境图解中,均分布在海底喷气热水沉积成因范围内,其氢氧同位素组成与世界典型海底喷气块状硫化物矿床内电气石一致。本区电气石岩稀土元素以总量低,具有明显 Ce 亏损与 Eu 正异常为特征,其成因主要与海底火山喷发后而引起热泉沿同生断裂活动有关,经成岩-变质作用后形成电气石岩与硫铁矿床。在硫化物矿床分布区内,二者关系密切,找矿标志意义重要,依据这一标志在老矿山外围找到了可采矿体。     

彩色电气石致色离子的化学状态研究

为探究不同颜色电气石中致色元素的化学状态及其化学环境,利用X射线光电子能谱方法对绿色调（墨绿色、蓝绿色、淡绿色）和粉红色调电气石样品进行分析。结果表明,绿色调和粉红色调电气石样品中均含有少量的过渡金属离子,如Fe,Mn,Ti,Cr,且不含Li和Be。不同颜色的电气石晶体中过渡金属阳离子的化学状态相同,且分别为Fe3＋,Mn4＋,Ti4＋,Cr3＋,但其与阴离子配位的环境有所差别。绿色调电气石样品中虽然Fe的质量分数有较大的差别,但均有部分Fe元素与F结合,即占据晶体结构中的Y位;粉红色电气石样品中,Fe离子没有与F形成配位,仅占据结构中的Z位。相反,在粉红色电气石样品中,Mn主要与F结合配位的方式存在,占据结构中的Y位,而绿色调电气石样品中大部分的Mn与O配位成键,只有少部分的Mn与F结合配位。由于Fe3＋,Mn4＋离子对之间电荷转移的可能性不大,故电气石的颜色可能主要由于d—d电子跃迁和氧与金属离子（O2--M）间电荷转移吸收引起,尤其是由于化学环境的差异（包括配位阴离子种类、杂质缺陷、结构畸变等）所引起。     

电气石的化学特征与相关矿床的关系

电气石是一种含挥发分的硅酸盐矿物，作为副矿物的电气石与其他矿物共生，且含量较少，但在电气石岩中可达60％以上，以前很少被人们重视。近10年来，随着对一些大型锡、钨等矿床的勘探和研究，发现电气石与这些矿床有着密切的关系。分析对比电气石成分中w(FeO)/w(FeO MgO)的比值，把国内几个有关矿床与国外一些典型矿床作比较，再借鉴前人对典型矿床中的电气石进行硼同位素的研究结果，找出不同特征电气石与不同矿床之间的关系。     

Chemical compositions of tourmaline in the vein-type tungsten deposits of the kaneuchi mine,Japan

Chemical compositions of tourmaline from the vein-type tungsten deposits of the Kaneuchi mine in Japan are obtained with an electron probe microanalyzer. Tourmaline occurring at this mine belongs to the dravite-schorl series. Magnesium contents are high compared with tourmaline from granitic zones. This suggests that ore-forming solutions are not formed directly from magmatic fluid and reacted with sedimentary rocks. Compositions of tourmaline in quartz veins are similar to those in host rocks, and the bulk compositions of host rocks do not indicate magnesium metasomatic reactions. It can therefore be concluded that water/rock interactions occurred at a deeper level which remains unexplored.     

The effects of surface weathering on the geochemical analysis of archaeological lithic samples using non‐destructive polarized energy dispersive XRF

The purpose of this paper is to show the effects of lithic artifact surface weathering on whole rock non‐destructive polarized energy dispersive X‐ray fluorescence (P‐ED‐XRF) major and trace element determinations. Chemical results for a weathered and subsequently mechanically ground subset of New Hampshire Ossipee archaeological flakes, cataloged as hornfels, show that both groups of elements are variably affected by weathering. A graphic approach is developed and proposed to highlight the role and importance of immobile elements. A case is made and an analytical method is proposed for the routine use of P‐ED‐XRF spectrometers to determine the chemical makeup of lithic artifacts and therefore provide a data set compatible with existing geochemical databases and literature. The use of specific variation diagrams is adopted to portray the weathering trend. Internationally approved geochemical rock type diagrams are used to correct the rock type previously assigned to Ossipee artifacts and in turn narrow down potential quarry sources. © 2011 Wiley Periodicals, Inc.     

The geological setting of tourmalinite at Rum Jungle,N.T., Australia — genetic and economic implications

Tourmalinite is a common rock type associated with Proterozoic strata-bound mineral deposits. Although common, it is often difficult to recognise in the field, leading to misidentification. It occurs as a conformable banded quartz-tourmaline lithological unit comprising at least 15% and as much as 50% of the rock. At Rum Jungle, tourmalinite occurs within the oldest sediments (arenites and magnesites) as distinct lenses, as facies equivalents of quartz-magnetite units and mafic schists (tuffs?) and distal equivalents of polymetallic sulfides. Distinct layering, slump folding, rip-up clasts and the association with diagenetic pyrite suggest a sedimentary environment. Enechelon fracturing of the fine-grained, light green tourmaline crystals spectacularly supports pre-deformation formation. The crystals are optically and chemically zoned parallel to the c axis, with irregular growth lamellae width — which supports a pre-regional metamorphic origin. Analyses show the tourmaline to be the Mg-rich variety “dravite”. Most tourmalinites are interpreted as subaqueous marine deposits. It is more likely that they form in lacustrine, shallow water, evaporitic environments, particularly continental rifts. Suitable B-bearing fluids can be generated by hotspring activity and mobilized by CO₂-rich fluids. Association with chemical sediments suggests tourmalinites also have a chemical sediment precursor. Ample evidence at Rum Jungle supports the notion of a continental rift environment, which was the site of deposition of fluvial arenites and alkaline, evaporitic lake sediments. Localised hot-spring activity contributed B-bearing fluids which precipitated chemical sediments according to the pertaining pH, temperature etc. Diagenetic alteration produced the tourmalinite now present. These tourmalinites are comparable to those of similar age elsewhere e.g. Sullivan, Broken Hill. They can be genetically modelled upon Recent borate concentrations, all of which occur in continental rift environments.     

Magmatic Nature of Mineralizing Fluids in the Solnechnoye Sn Deposit (Russia) Deduced from Isotopic (H,O) Compositions of Tourmaline

In this paper, we present new isotopic (H, O) data of fluids in tourmalines from the large Sn deposit at Solnechnoye (Far East Russia). These data indicate that the deposit formed by fluid‐rock interactions in a hydrothermal system where the mineralizing fluid was mainly magmatic and to a lesser extent meteoric. This is in agreement with a magmatic fluid model. Our interpretation of the new isotopic data is consistent with earlier findings of the studies on fluid‐rock interactions that magmatic fluids form larger Sn deposits than exogenic fluids. We propose that isotopic (H, O) data of fluids in tourmaline, rather than those in quartz, muscovite, or chlorite, support robust interpretation on the nature of mineralizing fluids associated with Sn deposits.