Fluid inclusions in diamonds from the Diavik mine, Canada and the evolution of diamond-forming fluids

The analysis of micro-inclusions in fibrous diamonds from the Diavik mine, Canada revealed the presence of high density fluids (HDFs) that span a continuous compositional range between carbonatitic and saline end-members. The carbonatitic end-member is rich in Na, Ca, Mg, Fe, Ba and carbonate; the saline one is rich in K, Cl and water. In molar proportions, the composition of the saline end-member is: K₃₈Na_7.7Ca_1.8Mg_1.6Fe_1.5Ba_1.9SiO_3.1Cl₄₆(CO₃)_5.5(H₂O)₅₆ and that of the carbonatitic end member is: K₁₅Na₂₁Ca_6.7Mg_8.1Fe_6.2Ba_5.7Si_4.8Ti_1.4Al_1.9O₁₇Cl₂₉(CO₃)₂₉(H₂O)₂₉. The micro-inclusions in one diamond span a narrow range between a silicic end-member (rich in Si, K and water) and a carbonatitic one (rich in Mg, Ca, Fe and carbonate). Its average composition is: K₂₆Na_5.5Ca_13.8Mg_8.3Fe_9.6Ba_0.9P_2.5Si₂₅Ti_1.6Al_3.8Cl_2.5O₈₁(CO₃)₂₉(H₂O)₇₈. Thus, the Diavik diamonds span most of the known compositional range for fluids trapped in diamonds. Based on these data and previous analyses of fluids trapped in diamonds, we discuss possible models for the evolution of diamond-forming fluids. The most plausible model is where carbonatitic-HDFs are parental to all the other compositions. They evolve by fractionation of divalentions- and alkali-carbonates and by immiscible separation into saline- and silicic-HDFs. Each phase continues to evolve separately, crystallizing carbonates, diamond, and accessory silicates, phosphates, halides and more of the immiscible phase. Other processes, like the mixing of evolved fluids with fresh parental carbonatitic fluids, or metasomatic interactions with the wallrock also play a role in the evolution of the HDFs. We also propose that the parental carbonatitic-HDF evolves through fractional crystallization of an alkali-rich, low degree melt that is similar to the high pressure parental melts of kimberlites or lamproites.     

Thermodynamic Analysis of Secondary Minerals Stability in Altered Carbonatites of the Oldoinyo Lengai Volcano,Northern Tanzania

Carbonatites from the Oldoinyo Lengai volcano, northern Tanzania, are unstable under normal atmospheric conditions. Owing to carbonatite interaction with water, the major minerals—gregoryite Na₂(CO₃), nyerereite Na₂Ca(CO₃)₂, and sylvite KCl—are dissolved and replaced with secondary low-temperature minerals: thermonatrite Na₂(CO₃) · H₂O, trona Na₃(CO₃)(HCO₃) · 2H₂O, nahcolite Na(HCO₃), pirssonite Na₂Ca(CO₃)₂ · 2H₂O, calcite Ca(CO₃), and shortite Na₂Ca₂(CO₃)₃. Thermodynamic calculations show that the formation of secondary minerals in Oldoinyo Lengai carbonatites are controlled by the pH of the pore solution, H₂O and CO₂ fugacity, and the ratio of Ca and Na activity in the Na₂O–CaO–CO₂–H₂O system.     

洛川黄土地层的再划分及其L9、L15古环境意义的新解释

洛川剖面的午城黄土是可以在野外进行细分的,洛川的午城黄土含有18层古土壤和18层黄土。其中,S₁₅～S₂₃的土壤组合与前人划分的WS1相当,L₂₄与WL₁相当,S_{24～S28与WS2相当,L29与WL2相当,S29～S32与WS3相当,L33与WL3相当。黄土高原的两个粉砂层L9和L15,虽然形成于第四纪的冷期,但并非代表了第四纪时期最为干冷的气候条件。笔者的解释是:其形成与这两个时期青藏高原及其周边山体的快速隆升导致的沙漠和黄土物源的快速增加有关。特别是1.1MaB.P.前后(L15)的隆起,使中国黄土记录对全球变化的响应显著增强,也正是在这次运动之后,中国黄土古气候记录可以与深海氧同位素很好对比,而此前的午城黄土与深海对比困难}     

周口店东洞洞穴沉积物的地球化学特征及其环境指示意义

周口店地区的古环境变化研究多数研究集中在中更新世时期,而缺乏对早更新世时期环境变化的研究。这主要是由于缺少保存完好的早更新世沉积记录造成的。随着对20世纪80年代在周口地区发现的东洞剖面,发现这是一个保存完好的早更新世剖面,为研究早更新世时期的古环境变化特征提供了良好的研究材料。为了重建早更新世时期的古环境变化特征,利用XRF对东洞洞穴沉积物的主要元素（SiO₂,Al₂O₃,Fe₂O3和CaO）的化学组成进行了高分辨率分析,同时对沉积物中的FeO含量进行了测试。结果显示东洞剖面沉积物的主要化学组成为SiO₂,占41.6%～58.9%,其次是Al₂O₃和Fe₂O3,其含量的变化范围分别为13.69%～29.63%和5.00%～9.81%。Al₂O₃和Fe₂O3在剖面上与SiO₂含量成明显的镜像变化关系,显示出Al₂O₃和Fe₂O3对沉积物中SiO₂含量的稀释作用。另外,Fe₂O3与Al₂O₃在剖面上具有很好的相关性,表明Fe₂O3主要富集在富铝的矿物中。从元素含量在剖面的上分布看,东洞剖面的化学组成发生3次大的波动,主要表现为SiO₂和FeO含量增高,而Fe₂O3与Al₂O₃含量的减少。这3次波动分别出现在剖面的15.3～14.6m,11.0～9.9m和8.40～7.84m深度处。在3次化学组成的波动出现的同时,指示沉积物风化程度和温度变化的Si/Al（SiO₂/Al₂O₃）和FeO/Fe₂O3比值也发生了明显变化,比值增高,指示了3次大的干冷事件。另外,在剖面上部（10.00～7.84m,即第2次事件以后）SiO₂/Al₂O₃和FeO/Fe₂O3比值变高且波动频繁,表明自第2次干冷事件后沉积区的环境变得不稳定,逐渐向冷干气候转变。东洞剖面的地球化学记录（SiO₂/Al₂O₃和FeO/Fe₂O3）与泾川黄土剖面的粒度曲线具有较好的对比性,支持了东洞剖面记录的环境信息与黄土沉积记录的环境变化具有一致性。通过与泾川粒度曲线的对比发现,东洞剖面记录的3次干冷事件在时段上分别对应于黄土-古土壤序列中的L26,L15和L13。     

Effect of stress history on CPT and DMT results in sand

In order to investigate the effect of stress history on in-situ test results in granular sediments, a series of CPTs and DMTs are performed on Busan sand prepared in the calibration chamber. K_D is found to be the most sensitive to the stress history among CPT and DMT measurements. E_D and q_c are observed to be similarly affected by the stress history and, therefore, the E_D–q_c relation appears to be almost independent of the stress history. The K_D–D_R relation established without considering the stress history is likely to overestimate the relative density of OC sand. It is shown that the existence of the pre-stress of the granular sediment can be indirectly recognized by an estimation of the relative density larger than 100% when using the K_D–σ_v′–D_R relation suggested for NC sand. Although q_c/σ_v′–K_D/K₀ and E_D/σ_v′–K_D/K₀ relations are heavily influenced by the stress history, q_c/σ_m′–K_D/K₀ and E_D/σ_m′–K_D/K₀ relations are observed to be independent of the stress history. Based on these relations, charts to evaluate the K₀ value from q_c and/or DMT indices are developed for both NC and OC sands. The design chart based on E_D/σ_m′–K_D/K₀ and E_D/σ_v′–K_D/K₀ relations is expected to be practically useful as the usage of this chart requires only DMT indices. The developed design charts are applicable to Busan sand but different sets of equations and charts may be developed for other sands.     

Flory-Huggins' formulation,its validity and implications in retrieval of equilibrium temperature of binary and ternary systems at higher pressures,using liquid silicate data and 1 bar liquidus temperature

For a pure phase at equilibrium with a polycomponent melt, two sets of expressions can be derived; one expressing its activity as a function of enthalpy, entropy, heat capacity and temperature, and the other by coupling a Flory-Huggins' polymerisation model with the van Laar heat of mixing term. Interaction parameters for binary and ternary systems have been computed at 1 bar by equating these two expressions. Assuming the interaction parameter to be independent of temperature, equilibrium temperatures at higher pressures can be calculated by an iterative procedure. Such retrieval calculations were carried out in simple eutectic, volatile-free systems like CaAl₂Si₂O₈-CaMgSi₂O₆, Mg₂SiO₄-TiO₂, MgSiO₃-TiO₂, Mg₂SiO₄-CaMgSi₂O₆, NaAlSi₃O₈-SiO₂ and CaAl₂Si₂O₈-CaMgSi₂O₆-Mg₂SiO₄. The close agreement between the theoretically retrieved and the experimentally determined equilibrium temperatures testifies to the validity of the model at higher pressures. The successful application of the model to simple eutectic, binary and ternary systems involving vastly dissimilar phases without imposing added constraints implies that it can be possibly extended to hitherto unknown systems provided the thermodynamic parameters of the phases involved are known.     

Environmental risk assessment of some potentially toxic elements in El-Tabbin region (Cairo, Egypt)

As much as 24 soil samples and 6 stream sediments from the River Nile were studied in El-Tabbin region (Great Cairo, Egypt). Twelve chemicals, potentially toxic elements posing potential environmental risk, were the object of concern in this study. Mean contents of analysed elements (in mg kg^?1) in soils and the River Nile stream sediments were the following: As_s 3.6/As_ss 1.5, Cd_s 0.33/Cd_ss 0.12, Cr_s 87.7/Cr_ss 141.5, Cu_s 40.3/Cu_ss 43.8, Hg_s 0.03/Hg_ss 0.13, Pb_s 33.3/Pb_ss 20.2, Zn_s 150/Zn_ss 109, Se_s 0.24/Se_ss 0.05, Ni_s 37.2/Ni_ss 48, Sb_s 1.25/Sb_ss 1, Ba_s 892/Ba_ss 431, V_s 103.3/V_ss 167.8. Furthermore, geochemical background values were derived for soil and stream sediment samples. The values are as follows (in mg kg^?1): As_s 1.33/As_ss 1, Cd_s 0.48/Cd_ss 0.05, Cr_s 54.7/Cr_ss 106.5, Cu_s 23.8/Cu_ss 23, Hg_s 0.025/Hg_ss 0.095, Pb_s 15.3/Pb_ss 13.5, Zn_s 70/Zn_ss 55, Se_s 0.13/Se_ss 0.05, Ni_s 19.5/Ni_ss 32.5, Sb_s 1/Sb_ss 1, Ba_s 266/Ba_ss 275, V_s 50.7/V_ss 119. More than two-thirds of soil and sediment samples exceeded established (based on literature data) risk limit values for non-polluted environment. Based on environmental risk assessment for potentially toxic elements in soils and sediments in more than 45% of total area disturbed environment (I _ER = 1–3) was documented and more than 13% of territory was characterised with highly disturbed environment (I _ER > 3).     

Chemical composition of spinel from Uralian-Alaskan-type Mafic–Ultramafic complexes and its petrogenetic significance

Uralian-Alaskan-type mafic–ultramafic complexes are recognized as a distinct class of intrusions regarding lithologic assemblage, mineral chemistry and petrogenetic setting. In the present study, we discuss new data on the distribution of major elements in minerals of the spinel group in rocks from Uralian-Alaskan-type complexes in the Ural Mountains, Russia. Cr-rich spinel (Cr₂O₃ = 20–53 wt%) in dunite with interstitial clinopyroxene and in wehrlite cumulates indicate that it reacted with interstitial liquid resulting in the progressive substitution of Al₂O₂ and Cr₂O₃ by Fe₂O₃ and TiO₂. A distinct change in the spinel chemistry in dunite (Cr₂O₃ = 47–53 wt%), towards Al₂O₃- and Cr₂O₃-poor but Fe₂O₃-rich compositions monitors the onset of clinopyroxene fractionation in wehrlite (Cr₂O₃ = 15–35 wt%, Al₂O₃ = 1–8 wt%, Fe₂O₃ = 25–55 wt%). In more fractionated mafic rocks, the calculated initial composition of exsolved spinel traces the sustained crystallization of clinopyroxene by decreasing Cr₂O₃ and increasing FeO, Fe₂O₃ and fO₂. Finally, the initiation of feldspar crystallization buffers the Al₂O₃ content in most of the spinels in mafic rocks at very low Cr₂O₃ contents (<5 wt%). The fractionation path all along and the reaction with interstitial liquid are accompanied by increasing Fe₂O₃ contents in the spinel. This likely is caused by a significant increase in the oxygen fugacity, which suggests closed system fractionation processes. Spinel with Cr₂O₃ < 27 wt% is exsolved into a Fe₂O₃-rich and an Al₂O₃-rich phase forming a variety of textures. Remarkably, exsolved spinel in different lithologies from complexes 200 km apart follows one distinct solvus line defining a temperature of ca. 600°C. This indicates that the parental magmas were emplaced and eventually cooled at similar levels in the lithosphere, likely near the crust–mantle boundary. Eventually, these 600°C hot bodies were rapidly transported into colder regions of the upper crust during a regional tectonic event, probably during the major active phase of the Main Uralian Fault.     

Mayenite-supergroup minerals from burned dump of the Chelyabinsk Coal Basin

Three minerals of the mayenite supergroup have been found in fluorellestadite-bearing metacarbonate rock (former fragment of petrified wood of ankeritic composition) from the dump at the Baturinskaya-Vostochnaya-1-2 mine. These are eltyubyuite Ca₁₂Fe1°Si₄O3₂Cl6, its fluorine analog Ca₁₂Fe₁₀³⁺Si₄O₃₀F₁₀, and chlormayenite-wadalite Ca₁₂(Al,Fe)₁₄O₃₂Cl₂-Ca₁₂(Al,Fe)₁₀Si₄O₃₂Cl₂. The first two phases occur in the reaction mantle around hematite, magnesioferrite, and Ca-ferrite aggregates (“calciohexaferrite” CaFe₁₂O₁₉, “grandiferrite” CaFe₄O₇, and “dorrite phase” Ca₂(Fe₅^3 +Mn0^0.5Mg_0.5)(Si_0.5Fe_5.5³⁺)O₂₀) and, rarely, as individuals in grained aggregates of fluorellestadite-cuspidine (± lar- nite ± rusinovite Ca₁₀(Si₂O₇)₃Cl₂). Assemblages of zoned chlormayenite-wadalite crystals are found in grained aggregates of fluorellestadite- cuspidine, which lack Ca-ferrite. Also, harmunite CaFe₂O₄, chlorellestadite, fluorapatite, anhydrite, rondorfite CasMg(SiO₄)₄Cl₂, fluorine analog of rondorfite CasMg(SiO₄)₄F₂, “Mg-cuspidine” Ca_3.5(Mg,Fe)_0.5(Si₂O₇)F₂, fluorite, barioferrite BaFe₁₂O₁9, zhangpeishanite BaFCl, and other rare phases are identified in this rock. Data on the chemical composition and Raman spectroscopy of the mayenite-supergroup minerals are given. The genesis of metacarbonate rock is considered in detail: “oxidizing calcination” of Ca-Fe-carbonates with the formation of hematite and lime; reaction between hematite and lime with the formation of different Ca-ferrites; formation of larnite as a result of reaction between SiO₂ and lime or CaCO₃; and reactionary impact of hot Cl-F-S-bearing gases on early assemblages. Eltyubyuite and its fluorine analog crystallized at the stages of gas impact. It is presumed that the maximum temperature during the formation of rock reached 1200–1230 °C. © 2015, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.     

Cervandonite-(Ce) in ores of the Berezitovoe deposit: Second finding in the world

The supposedly second finding of rare arsenosilicate cervandonite-(Ce) in the world is characterized. The mineral was recognized in the ore-bearing metasomatic rocks of the Berezitovoe gold-base metal deposit (Upper Priamurye, Russian Far East) in association with quartz, biotite, muscovite, orthoclase, garnet (almandine-spessartine), tourmaline, basic plagioclase, and sulfides. The cervandonite is represented by optically homogeneous and heterogeneous aggregates with visible crystals from 10 fum to 0.1–0.3 mm in size. Based on the microprobe analysis, the average chemical composition of the homogeneous cervandonite-(Ce) aggregates is as follows (wt %): Ce₂O₃ - 13.00, La₂O₃ - 5.70, Nd₂O₃ - 5.20, Pr₂O₃ - 1.41, Y₂O₃ - 0.77, Sm₂O₃ - 0.77, Eu₂O₃ - 0.23, Gd₂O₃ - 0.54, Dy₂O₃ - 0.31, ThO₂ - 1.12, UO₂ - 0.30, TiO₂ - 12.86, Al₂O₃ - 9.24, Fe₂O₃ - 8.93, FeO - 2.68, CaO - 0.14, SiO₂ - 19.98, As₂O₃ - 16.19. The comparative study of the cervandonite-(Ce) from the Berezitovoe deposit and the analogous minerals from the Alpine mica gneiss of Mt. Pizzo Cervandone (Central Alps) showed that the former mineral can be assigned to a new variety of cervandonite-(Ce) in terms of its compositional features. This variety is characterized by an ordered stoichiometric composition corresponding to the simpler theoretical formula (Ce,Nd,La)(Fe³⁺, Fe²⁺, Ti⁴⁺, Al)₃ (Si₂As³⁺)₃O₁₂.     

Fractionation of major elements between coexisting H2O-saturated silicate melt and silicate-saturated aqueous fluids in aluminosilicate systems at 1-2 GPa

From experimental data in the systems Na₂O-Al₂O₃-SiO₂-H₂O, K₂O-Al₂O₃-SiO₂-H₂O at 1100°C, and CaO-Al₂O₃-SiO₂-H₂O at 1200°C in the 1-2 GPa pressure range, the solution behavior of the individual oxides in coexisting H₂O-saturated silicate melts and silicate-saturated aqueous fluids appears to be incongruent. Recalculated on an anhydrous basis, in the CaO-Al₂O₃-SiO₂-H₂O system, CaO^fluid/CaO^melt < 1, whereas in the Na₂O-Al₂O₃-SiO₂-H₂O and K₂O-Al₂O₃-SiO₂-H₂O systems, K₂O^fluid/K₂O^melt and Na₂O^fluid/Na₂O^melt both are greater than 1. The aqueous fluids are depleted in alumina relative to silicate melt.In the Na₂O-Al₂O₃-SiO₂-H₂O, K₂O-Al₂O₃-SiO₂-H₂O, and CaO-Al₂O₃-SiO₂-H₂O systems, fluid/melt partition coefficients for the individual oxides range between ∼0.005 and 0.35 depending on oxide, bulk composition and pressure. The alkali partition coefficients are about an order of magnitude higher than that of CaO. Alumina and silica partition coefficient values in the CaO-Al₂O₃-SiO₂-H₂O system are 10-20% of the values for the same oxides in the Na₂O-Al₂O₃-SiO₂-H₂O and K₂O-Al₂O₃-SiO₂-H₂O systems.Positive correlations among individual partition coefficients and oxide concentrations in the aqueous fluids are consistent with complexing in the fluid that involves silicate polymers associated with alkalis and alkaline earths and aluminosilicate complexes where alkalis and alkaline earths may serve to charge-balance Al³⁺, which is, perhaps, in tetrahedral coordination. Alkali aluminosilicate complexes in aqueous fluid appear more stable than Ca-aluminosilicate complexes.     

Jinshanjiangite and bafertisite from the Gremyakha-Vyrmes Alkaline Complex,Kola Peninsula

Jinshanjiangite (acicular crystals up to 2 mm in length) and bafertisite (lamellar crystals up to 3 × 4 mm in size) have been found in alkali granite pegmatite of the Gremyakha-Vyrmes Complex, Kola Peninsula. Albite, microcline, quartz, arfvedsonite, zircon, and apatite are associated minerals. The dimensions of a monoclinic unit cell of jinshanjiangite and bafertisite are: a = 10.72(2), b=13.80(2), c = 20.94(6) Å, β = 97.0(5)° and a = 10.654(6), b = 13.724(6), c = 10.863(8) Å, β = 94.47(8)°, respectively. The typical compositions (electron microprobe data) of jinshanjiangite and bafertisite are: (Na_0.57Ca_0.44)_Σ1.01(Ba_0.57K_0.44)_Σ1.01 (Fe_3.53Mn_0.30Mg_0.04Zn_0.01)_Σ3.88(Ti_1.97Nb_0.06Zr_0.01)_Σ2.04(Si_3.97Al_0.03O₁₄)O_2.00(OH_2.25F_0.73O_0.02)_Σ3.00 and (Ba_1.98Na_0.04K_0.03)_Σ2.05(Fe_3.43Mn_0.37Mg_0.03)_Σ3.83(Ti_2.02Nb_0.03)_Σ2.05 (Si_3.92Al_0.08O₁₄)(O_1.84OH_0.16)_Σ2.00(OH_2.39F_1.61)_Σ3.00, respectively. The minerals studied are the Fe-richest members of the bafertisite structural family.     

Crystal structures of the Rb- and Sr-exchanged forms of ivanyukite-Na-T

The Rb- and Sr-exchanged forms of ivanyukite have been obtained and structurally characterized. The chemical formulas derived from the electron microprobe data are as follows: the Rb-exchanged form (Na_0.10K_0.07Ca_0.15Sr_0.05Rb_1.81Ba_0.02)_{Σ = 2.20}[(Ti_3.65Nb_0.19Fe_0.05Mn_0.01)_{Σ = 3.90}O_2.07/(OH)_1.93(Si_2.98Al_0.02)_{Σ = 3.00} O₁₂] · 3.61H₂O; the Sr-exchanged form (K_0.03Sr_0.81Ca_0.04Ba_0.07)_{Σ = 0.95}[(Ti_3.74Nb_0.19Fe_0.03)_{Σ = 3.96}] [O_1.83/(OH)_2.17](Si_2.99Al_0.01)_{Σ = 3.00}O₁₂) · 7H₂O. The structures of the Rb- and Sr-exchanged forms of ivanyukite have been solved and refined using the least squares method. The structures are based on a mixed three-dimensional octahedral-tetrahedral framework of the pharmacosiderite type with channels occupied by Rb⁺ and Sr²⁺ cations and water molecules. The Rb⁺ cations in the Rb-exchanged form are 12-coordinated, whereas the Sr²⁺ cations in the Sr-exchanged form are 9- or 7-coordinated. The statistical investigation of the geometric parameters of the pharmacosiderite-type titanosilicates showed that symmetry changes are associated with the interactions of extraframework cations with the O atom of the Ti₄(O,OH)₄ clusters of the titanosilicate framework. The relationship between the unit-cell parameters in titanosilicates of the pharmacosiderite type and the structural geometric parameters of the titanosilicate framework has been proved by the use of multiple regression equations.     

Experiments on liquid immiscibility in silicate melts with H2O, P, S, F and Cl: implications for natural magmas

Isobaric (200 MPa) experiments have been performed to investigate the effects of H₂O alone or in combination with P, S, F or Cl on liquid-phase separation in melts in the systems Fe₂SiO₄–Fe₃O₄–KAlSi₂O₆–SiO₂, Fe₃O₄–KAlSi₂O₆–SiO₂ and Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ with or without plagioclase (An₅₀). Experiments were heated in a rapid-quench internally heated pressure vessel at 1,075, 1,150 or 1,200 °C for 2 h. Experimental fO₂ was maintained at QFM, NNO or MH oxygen buffers. H₂O alone or in combination with P, S or F increases the temperature and composition range of two-liquid fields at fO₂ = NNO and MH buffers. P, S, F and Cl partition preferentially into the Fe-rich immiscible liquid. Two-liquid partition coefficients for Fe, Si, P and S correlate well with the degree of polymerization of the SiO₂-rich liquid and plot on similar but distinct power-law curves compared with equivalent anhydrous or basaltic melts. The addition of 2 wt% S to the system Fe₃O₄–Fe₂O₃–KAlSi₂O₆–SiO₂ stabilizes three immiscible melts with Fe-, FeS- and Si-rich compositions. H₂O-induced suppression of liquidus temperatures in the experimental systems, considered with the effects of pressure on the temperature and composition ranges of two-liquid fields in silicate melts, suggests that liquid-phase separation may be stable in some H₂O-rich silicate magmas at pressures in excess of 200 MPa.     

A microscopic study of synthetic PbS-Rich homologues nPbS-mBi2S3

The PbS-Bi₂S₃ join was studied up to 25 mole percent Bi₂S₃ by electron microscopy and diffraction. It was found that Bi₂S₃ can be incorporated into the PbS matrix by tropochemical twinning, forming isolated {113}_PbS microtwins, or after clustering of these defects, lamellar twinned regions. Only two known mineral members of the homologous series (lillianite Pb₃Bi₂S₆ and heyrowskyite Pb₆Bi₂S₉) were found to be stable in this part of the PbS-Bi₂S₃ join, while irregularly spaced twin bands within these two structures were observed where deviations in the PbS/Bi₂S₃ ratio from 6/1 and 3/1, respectively, took place. No ordered intergrowth members were found between heyrowskyite and lillianite. The difference between the PbS-Bi₂S₃ join and the analogous MnS-Y₂S₃ one was attributed to the lone pair of nonbonded electrons from the Bi³⁺ ions, which tends to concentrate these ions in the vicinity of the twin planes.     

Corundum- and kyanite-bearing anatexites from the Precambrian of tanzania

In the Precambrian near Morogoro (East Tanzania) there are anatectic gneisses which are composed of two different domains: (1) Medium grained gneiss with the assemblage (+ rutile + baddeleyite): albite (ab₉₅an₀₃or₀₂) + muscovite + phlogopite_ss + corundum, and albite (ab₈₈an₀₉or₀₃ + kyanite or sillimanite + phlogopite_ss. (2) Coarse grained nests of corundum and antiperthite with minor albite, muscovite, phlogopite, rutile, baddeleyite, and tourmaline. The bulk composition of the antiperthite id ab₇₅an₀₂or₂₃, the composition of the Na-phase ab₉₅an₀₃or₀₂, that of the K-phase ab₁₃an₀₀or₈₇. Phase relationship of the rock can be modelled in the Na-rich, Si-undersaturated part of the KNASH system. P-T conditions are close to the intersection of the melting curve muscovite_ss + H₂O = corundum + liquid with the kyanite-sillimanite transition, i.e. 7.7 kb/695°C assuming a_H2O = 1.     

Synthesis and stability of micas in the system K2O-MgO-SiO2-H2O and their relations to phlogopite

A series of alumina-free micas was synthesized hydrothermally in the potassium-poor portion of the system K₂O-MgO-SiO₂-H₂O. One end member of this series has the composition KMg_2.5[Si₄O₁₀](OH)₂, which, because of its octahedral occupancy, is intermediate between the dioctahedral and trioctahedral micas.From this end member a series of mica solid solutions extends towards more Mg-rich compositions. Single phase micas were obtained along the substitution line 2Mg for Si which appears to involve incorporation of part of the Mg in tetrahedral sites. It leads to a theoretical end member with a structural formula KMg₃[Si_3.5Mg_0.5O₁₀](OH)₂. Solid solutions containing up to 75 mole % of this theoretical end member could be synthesized. The observed densities, water contents, and a one-dimensional Fourier synthesis are consistent with the assumed substitution.At 1 kb fluid pressure and 620° C the Si-rich end member KMg_2.5[Si₄O₁₀](OH)₂ decomposes to a more Mg-rich mica, the roedderite phase K₂Mg₅Si₁₂O₃₀, liquid, and H₂O-rich vapor. With increasing Mg-content the thermal stability of the mica solid solutions increases up to 860°C at a composition of about K₂O·6.2MgO·7.4SiO₂·2H₂O, i.e. KMg_2.8[Si_3.7Mg_0.3O₁₀](OH)₂. This mica disintegrates directly into forsterite + liquid + H₂O-rich vapor. The mica phase richest in Mg with a composition of about K₂O·6.5MgO·7.25SiO₂·2H₂O, i.e. KMg_2.875 [Si_3.625Mg_0.375O₁₀](OH)₂, breaks down at 765° C into forsterite, a more Si-rich mica, liquid, and H₂O-rich vapor.This binary series of alumina-free micas forms a complete series of ternary solid solutions with normal phlogopite, KMg₃[Si₃AlO₁₀](OH)₂. Analyses of some natural phlogopites showing Si in excess of 3.0 (up to 3.18) per formula unit can be explained through this ternary miscibility range.     

Rare metal mineralization of calcite carbonatites from the Cape Verde Archipelago

Rare metal mineralization of oceanic carbonatites was studied for the first time by the example of calcite carbonatite from Fogo Island in the Cape Verde Archipelago. The following evolutionary sequence of rare metal minerals was established: zirconolite-Th-calciobetafite-betafite + Th-pyrochlore-thorite + Ti-Zr-Nb silicates + zircon.Schematic reactions were proposed for zirconolite transformation to secondary phases: (Ca,Th,U)Zr(Ti,Nb)₂O₇ (zirconolite) + SiO₂ + Ca(F,OH)₂ → ZrSiO₄ (zircon) + (Ca,Th,U)₂(Ti,Nb)₂O₆(OH,F) (Th-calciobetafite) and (Ca,Th,U)₂(Ti,Nb)₂O₆(OH,F) + Na₂Si₂O₅ → ThSiO₄ (thorite) + (Ca,Na,Th)₂(Nb,Ti)₂O₆(OH,F) (Th-pyrochlore), where SiO₂, Ca(F,OH)₂, and Na₂Si₂O₅ are the components of melt-solution coexisting with the carbonatite.It was shown that the distribution and behavior of rare and radioactive elements in oceanic carbonatites show the same tendencies as in continental carbonatites. The contents and distribution of Ti, Ta, and Th in zirconolites and pyrochlores from oceanic and continental carbonatites are different: the minerals of oceanic carbonatites are enriched in Ti and Th and strongly depleted in Ta.     

Phase relations in the systems Cu2S-PbS-Bi2S3 and Ag2S-PbS-Bi2S3 and their mineral assemblages

The phase diagrams of the systems Cu₂S-PbS-Bi₂S₃ and Ag₂S-PbS-Bi₂S₃ have been investigated in the present study. The paper is concerned with the complete solid solution between bismuthtite and aikinite above 300°C in the system Cu₂S-PbS-Bi₂S₃. The synthetic phases CuBi₃S₅ and Cu₃Bi₅S₉ have their solid solution ranges in the ternary system with 9 and 26 mole% PbS at maximum, respectively. A complete solid solution between PbS and AgBiS₂ divides the phase diagram of the system Ag₂S-PbS-Bi₂S₃ into two parts: Bi-rich and Ag-rich. All sulfosalt minerals and solid solutions, including pavonite ss, lillianite ss, heyovskyite and benjaminite are on the Bi-rich side. And divarant relations were found between pavonite ss -lillianite ss, benjaminite and bismuthtite as well as between lillianite ss -bismuthtite and galenobismutite. Synthetic experiments using LiCl-KCl flux technique show that when a minor amount of copper (less lwt.%) is added in, many of Ag-and Pb-bismuth sulfosalt minerals, for example, vikingite (Ag₅Pb₈Bi₁₃S₃₀), are synthesized successively, particularly at 400°C. So is heyrovskyite, which has a solid solution range with 3.7 mole% Cu₂S at maximum in the system Cu₂S-PbS-Bi₂S₃.     

A multi-analytical study of the crystal structure of unusual Ti–Zr–Cr-rich Andradite from the Maronia skarn, Rhodope massif, western Thrace, Greece

Unusual Ti–Cr–Zr-rich garnet crystals from high-temperature melilitic skarn of the Maronia area, western Thrace, Greece, were investigated by electron-microprobe analysis, powder and single-crystal X-ray diffraction, IR, Raman and Mössbauer spectroscopy. Chemical data showed that the garnets contain up to 8 wt.% TiO₂, 8 wt.% Cr₂O₃ and 4 wt.% ZrO₂, representing a solid solution of andradite (Ca₃Fe³⁺ ₂Si₃O₁₂ ≈46 mol%), uvarovite (Ca₃Cr₂Si₃O₁₂ ≈23 mol%), grossular (Ca₃Al₂Si₃O₁₂ ≈10 mol%), schorlomite (Ca₃Ti₂[Si,(Fe³⁺,Al³⁺)₂]O₁₂ ≈15 mol%), and kimzeyite (Ca₃Zr₂[Si,Al₂]₃O₁₂ ≈6 mol%). The Mössbauer analysis showed that the total Fe is ferric, preferentially located at the octahedral site and to a smaller extent at the tetrahedral site. Single-crystal XRD analysis, Raman and IR spectroscopy verified substitution of Si mainly by Al³⁺, Fe³⁺ and Ti⁴⁺. Cr³⁺ and Zr⁴⁺ are found at the octahedral site along with Fe³⁺, Al³⁺ and Ti⁴⁺. The measured H₂O content is 0.20 wt.%. The analytical data suggest that the structural formula of the Maronia garnet can be given as: (Ca_2.99Mg_0.03)_Σ=3.02(Fe³⁺ _0.67Cr_0.54Al_0.33Ti_0.29Zr_0.15)_Σ=1.98(Si_2.42Ti_0.24Fe_0.18Al_0.14)_Σ=2.98O₁₂OH_0.11. Ti-rich garnets are not common and their crystal chemistry is still under investigation. The present work presents new evidence that will enable the elucidation of the structural chemistry of Ti- and Cr-rich garnets.