Occurrence and Chemical Compositions of Amphiboles in Altered Dioritic Rocks of Laiwu Skarn‐Type Iron Deposit in West Shandong Area,China

The Laiwu Fe deposit is the largest skarn‐type deposit in West Shandong in China, with an estimated reserve of 290 Mt of iron ore. Here, we investigate the occurrence and chemical composition of amphiboles in altered dioritic rocks of this deposit. Three generations of amphibole group minerals were identified in these rocks. The first type (Type 1) is a hornblende with a generally euhedral crystal shape, 150–500 μm in size, and dominantly occurs in the host monzonite. The second type (Type 2) of hornblende occurs as fine grains (<100 μm) or concentric rims, less than 50 μm in thickness, around the Type 1 hornblende. The third type (Type 3) of amphibole is anhedral actinolite occurring along the boundary or the cracks of the Type 1 or 2 hornblende grains. The Type 1 hornblende has higher FeO (12.5–15.6 wt.%) and lower MgO contents (11.2–14.6 wt.%) than the Type 2 hornblende, which has an FeO content ranging from 8.8 to 10.5 wt.% and MgO content ranging from 14.2 to 17.1 wt.%. The Type 3 actinolite shows the lowest FeO (4.6–6.4 wt.%) and highest MgO (19.8–21.2 wt.%) contents. We infer that the Type 2 hornblende formed from Fe‐rich hydrothermal fluids released during rapid upwelling of the crystallizing magma. The fluids were relatively reduced and enriched in Fe. The Type 3 actinolite formed by coupled dissolution and reprecipitation, and its formation is one of the features denoting Fe‐enrichment events. Our study of these types of amphibole provides insights into the ore formation process.     

滇西双江县勐库地区退变质榴辉岩中闪石类矿物的成因研究

勐库地区新近发现的退变质榴辉岩中晚期退变质作用形成的闪石类矿物十分丰富,其携带了大量晚期退变质过程中的岩石成因信息。本文通过系统的矿物学研究,鉴定出了3期10种闪石类矿物,其中以镁钙闪石、镁角闪石、铁镁钙闪石、铁韭闪石、透闪石、阳起石等钙质闪石类为主,有少量冻蓝闪石、蓝透闪石等钠-钙闪石类。研究发现,随着退变质过程中时间的推移,角闪石的形成环境逐渐由还原环境向弱氧化环境、氧化环境演变。根据角闪石电子探针成分测试结果计算了相应的温度、压力条件。结合岩相学的资料,将退变质过程分为3期:(1)第1期早阶段为近等温降压过程(p=0.56~0.75 GPa,t=642~709℃),主要形成铁韭闪石、铁镁钙闪石、镁钙闪石;晚阶段为等温降压过程(p=0.39~0.56 GPa,t=619~642℃),主要形成镁钙闪石及少量镁绿钙闪石、铁韭闪石;(2)第2期为降温降压过程(p=0.23~0.42 GPa,t=460~610℃),主要形成镁角闪石、冻蓝闪石及铁角闪石;(3)第3期为近等温降压过程(p=0.09~0.31 GPa,t=350~420℃),主要形成透闪石、阳起石、蓝透闪石等。闪石类的成分变化反映了退变质榴辉岩从地壳底部的角闪石榴辉岩-高压麻粒岩相温压环境向中上地壳角闪岩相、绿片岩相温压环境的渐次退变质作用过程。这与昌宁-孟连构造带上印支期的碰撞造山作用、燕山期的区域性地壳伸展、喜马拉雅期的陆内造山运动具有较好的对应关系。     

A thermodynamic model for Ca–Na clinoamphiboles in Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–O for petrological calculations

A calibration is presented for an activity–composition model for amphiboles in the system Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O–O (NCFMASHO), formulated in terms of an independent set of six end‐members: tremolite, tschermakite, pargasite, glaucophane, ferroactinolite and ferritschermakite. The model uses mixing‐on‐sites for the ideal‐mixing activities, and for the activity coefficients, a macroscopic multicomponent van Laar model. This formulation involves 15 pairwise interaction energies and six asymmetry parameters. Calibration of the model is based on the geometrical constraints imposed by the size and shape of amphibole solvi inherent in a data set of 71 coexisting amphibole pairs from rocks, formed over 400–600 °C and 2–18 kbar. The model parameters are calibrated by combining these geometric constraints with qualitative consideration of parameter relationships, given that the data are insufficient to allow all the model parameters to be determined from a regression of the data. Use of coexisting amphiboles means that amphibole activity–composition relationships are calibrated independently of the thermodynamic properties of the end‐members. For practical applications, in geothermobarometry and the calculation of phase diagrams, the amphibole activity–composition relationships are placed in the context of the stability of other minerals by evaluating the properties of the end‐members in the independent set that are in internally consistent data sets. This has been performed using an extended natural data set for hornblende–garnet–plagioclase–quartz, giving the small adjustments necessary to the enthalpies of formation of tschermakite, pargasite and glaucophane for working with the Holland and Powell data set.     

中国蓝片岩中闪石族矿物的研究

本文对中国篮片岩中间石族矿物进行了综合研究,可将它们分为三个亚族:碱性问石亚族;钠钙闪石亚族;钙质闪石亚族。碱性闪石亚族再按Fe 、Mg、Al的比值,后二者按Si的含量划分为矿物种。编制了闪石成分分类图。碱性闪石的光学性质、红外吸收光谱和x射线衍射数据,与其它两个亚族有明显差异,但各亚族内特征基本相似。利用多色性和延性特征鉴别碱性问石各矿物种较为准确,并发现青铝闪石的多色性公式应为Ng-紫色、Nm-深蓝色、Np-浅黄色,与前人描述不一致。     

东南沿海长乐—南澳变质带的某些角闪石研究

本文论述了长乐—南澳变质带中,各岩相带的角闪石。通过穆斯堡尔谱探讨了角闪石的阳离子占位,测定了氧同位素的分馏特征和温度,以及Al、Fe~(2+)、Mg,Mn、Ti量的变化规律,共生矿物对的平衡条件的系统研究,获得了不同相带的特征数值。据此,将该变质带划分成三个岩相带:C带——高温带,600—900℃;M带——中温带,450—550℃;Ⅰ带——低温带,170—300℃,压力4—6k bar。     

A Mössbauer and FTIR study of synthetic amphiboles along the magnesioriebeckite – ferri-clinoholmquistite join

A series of amphiboles along the magnesioriebeckite—Na₂Mg₃Fe³⁺ ₂Si₈O₂₂(OH)₂– ferri-clinoholmquistite—Li₂Mg₃Fe³⁺ ₂Si₈O₂₂(OH)2 - join, defined by the ^BLi^B Na_–1 exchange vector, were hydrothermally synthesized at 700°C, 0.4 GPa, NNO + 1 redox conditions. Powder XRD and SEM-EDAX showed a very high (> 90%) amphibole yield for all samples. X-ray patterns were indexed in the C2/m space group; refined cell-parameters show a linear decrease of a and as a function of chemistry. IR spectra in the OH-stretching region show four main and rather sharp bands; these are assigned to Mg and Fe²⁺ at M(1,3), and indicate that the obtained amphiboles depart from the nominal octahedral composition (^M1,3Mg₃). The IR spectra also show that there is an increasing filling-up of the A-site for increasing Na in the system (increasing solid-solution toward, arfvedsonite). Mössbauer spectra show four well-defined quadrupole doublets which are assigned to Fe³⁺ at M2 and to Fe²⁺ at M1, M3 and M4, respectively. The Fe³⁺/Fe²⁺ content derived from fitted peak areas show variable Fe³⁺ concentration along the series. Mössbauer spectra also show a distinct alteration of ⁵⁷Fe hyperfine parameters with changing Na–Li at M4. The most evident variation is observed for the quadrupole splitting of Fe³⁺ at M2, which increases by 50% from ferri-clinoholmquistite to magnesio-riebeckite; this suggest that the M2 octahedron in ferri-clinoholmquistite is much closer to the ideal geometry than the M2 octahedron in magnesio-riebeckite. Mössbauer spectra show also a well-defined increase in the Fe²⁺ quadrupole splitting of the M1 and M3 octahedra, which is attributed to the Na–Li distribution at the B-sites.     

Pumpellyites and coexisting minerals in different low-grade metamorphic facies of Liguria, Italy

Pumpellyite from four-phase assemblages (pumpellyite + epidote + prehnite + chlorite; pumpellyite + epidote + actinolite + chlorite; pumpellyite + epidote + Na-amphibole + chlorite, together with common excess phases), considered to be low variance in a CaO-(MgO + FeO)-Al₂O₃-Fe₂O₃ (+Na₂O + SiO₂+ H₂O) system, have been examined in areas which underwent metamorphism in the prehnite-pumpellyite, pumpellyite-actinolite and low-temperature blueschist facies respectively. The analysed mineral assemblages are compared for nearly constant (basaltic) chemical composition at varying metamorphic grade and for varying chemical composition (basic, intermediate, acidic) at constant metamorphic conditions (low-temperature blueschist facies). In the studied mineral assemblages, coexisting phases approached near chemical equilibrium. At constant (basaltic) bulk rock composition the MgO content of pumpellyite increases, and the X_Fe3+ of both pumpellyite and epidote decreases with increasing metamorphic grade, the Fe³⁺ being preferentially concentrated in epidote. Both pumpellyite and epidote compositions vary with the bulk rock composition at isofacial conditions; pumpellyite becomes progressively enriched in Fe and depleted in Mg from basic to intermediate and acidic bulk rock compositions. The compositional comparison of pumpellyites from high-variance (1–3 phases) assemblages in various bulk rock compositions (basic, intermediate, acidic rocks, greywackes, gabbros) shows that the compositional fields of both pumpellyite and epidote are wide and variable, broadly overlapping the compositional effects observed at varying metamorphic grade in low-variance assemblages. The intrinsic stability of both Fe- and Al-rich pumpellyites extends across the complete range of the considered metamorphic conditions. Element partitioning between coexisting phases is the main control on the mineral composition at different P-T conditions.     

Synthetic ANaB(Na x Li1 − x Mg1)CMg5Si8O22(OH)2 (with x = 0.6, 0.2 and 0) P21/m amphiboles at high pressure: a synchrotron infrared study

The high-pressure behavior of three synthetic amphiboles crystallized with space group P2₁/m at room conditions in the system Li₂O–Na₂O–MgO–SiO₂–H₂O has been studied by in situ synchrotron infrared absorption spectroscopy. The amphiboles have compositions ^ANa ^B(Na _x Li_1 − x Mg₁) ^CMg₅ Si₈ O₂₂(OH)₂ with x = 0.6, 0.2 and 0.0, respectively. The high-P experiments up to 32 GPa were carried out on the U2A beamline at Brookhaven National Laboratory (NY, USA) using a diamond anvil cell under non-hydrostatic or quasi-hydrostatic conditions. The two most intense absorption bands in the OH-stretching infrared spectra can be assigned to two non-equivalent O–H dipoles in the P2₁/m structure, bonded to the same local environment ^M1M3Mg₃–OH–^ANa, and pointing toward two differently kinked tetrahedral rings. In all samples these bands progressively merge to give a unique symmetrical absorption with increasing pressure, suggesting a change in symmetry from P2₁/m to C2/m. The pressure at which the transition occurs appears to be linearly correlated to the aggregate B-site dimension. The infrared spectra collected for amphibole ^B(Na_0.2Li_0.8Mg₁) in the frequency range 50 to 1,400 cm⁻¹ also show a series of changes with increasing pressure. The data reported here support the inference of Iezzi et al. (Am Miner 91:479–482, 2006a) regarding a new high-pressure amphibole polymorph.     

青海尕林格矽卡岩铁矿富Cl角闪石矿物地球化学特征与其成矿意义

本文通过研究青海尕林格矽卡岩型铁矿床内成矿阶段富Cl角闪石的矿物学特征,来反演岩浆-流体-矿物三者间的演化关系。尕林格富Cl角闪石应属于镁绿钙闪石亚族,化学成分特征显示:0.3Mg/(Mg+Fe2+)0.69,Si6.25apfu,0.681%Cl3.161%。XCl与XMg显示具有很好的负相关性,而XK和X2+Fe则与XCl显示具有正相关性。这些阴阳离子间的线性关系与角闪石的晶体结构特征密切相关。对于Cl-交代OH-进入角闪石分子结构可以用经验公式表示为ln(XCl/XOH)amp=ln(fCl/fOH)fluid+A·[4]Al·Fe2+/RT+B/RT,其中A和B为常数。因此,当所有富Cl角闪石的成分与流体在同一温度和相对不变fCl/fOH下平衡时,则角闪石中的ln(XCl/XOH)对其成分[4]Al·Fe2+投影应为线性关系,这一特点可理解为阳离子成分对Cl的加入的影响随流体成分的改变而改变。尕林格富Cl角闪石环带成分从核部到边部具有XCl先降低后升高的特点,这与OH-比Cl-更易交代进入分子结构有关。当角闪石和与之平衡的流体进入相对封闭环境时,随着角闪石的结晶,流体中Cl的含量逐渐增加导致角闪石环带边缘XCl明显比核部高。晶体和液体间的微量元素分异不仅受到晶体结构的控制,而且流体中的挥发分也是控制微量元素分异的主要因素。富Cl角闪石中Cl的含量对REE的分异同样也有影响,REE元素的分配系数随着流体中Cl含量的降低而升高。通常认为硅酸质岩浆早期结晶分异出来的高温高盐度流体是重要的载矿流体,因其含有大量的Cl-并且pH值较低,有利于Fe的Cl络合物进行长期迁移。当流体遇到偏碱性的碳酸盐地层导致流体pH值升高,或与天水混合形成低温低盐度流体时,Fe的Cl络合物就会发生解离沉淀。而此时流体中fOH升高,从而导致OH-交代进入早期矽卡岩矿物中形成角闪石等退化蚀变矿物。     

金川岩浆铜镍（铂）硫化物矿床中两类橄榄石的发现及其成矿意义

金川铜镍硫化物矿床是世界第三大岩浆型铜镍硫化物矿床,其成因机制一直备受争议。主要成矿模型有以下两种:(1)岩浆通道堆积模型;(2)深部熔离-多次贯入模型。目前,二者均不能较好解释矿区中存在的各种地质现象。本文重点研究矿区橄榄石的特征,借此来探讨"硫化物矿浆"的迁移方式与侵位能力。本次研究在金川矿床中发现了两类橄榄石:LREE亏损型(Ⅰ型)与LREE富集型(Ⅱ型)。其中,Ⅰ型橄榄石为岩浆正常结晶的原始颗粒,常见复杂的成分环带,由原生橄榄石与晶间硅酸盐熔体/不混溶硫化物熔体发生物质交换所形成,继承了玄武质岩浆稀土含量低的特征,广泛分布于各类超基性岩石与矿石中;Ⅱ型橄榄石常见包裹斜方辉石的反序列包含关系,以稀土含量高(～2个数量级)且相对富Mg而显著区别于前者,为辉石堆晶颗粒经流体触发不一致熔融后再结晶形成的橄榄石,多见于硫化物矿石中。金川矿床硫化物矿石中广泛发育的原生富Cl含水矿物(金云母、角闪石、磷灰石)与Ⅰ型橄榄石边部活动性元素含量的剧增,暗示金川矿体形成过程受富Cl流体影响显著。实验岩石学与动力学模拟的新研究进展表明流体的加入可有效推动高密度硫化物的迁移,流体的加入可能是金川硫化物矿浆上侵运移的主要机制。结合硫化物Cu/Ni西高东低的空间演化规律,橄榄石Fo值西高东低的空间变化趋势与晶体粒度西细东粗的分布特征可以推测,金川铜镍硫化物矿床岩浆通道的前进方向为自西向东。