Deep reaching fluid flow in the North East German Basin: origin and processes of groundwater salinisation

Major element chemistry, rare-earth element distribution, and H and O isotopes are conjointly used to study the sources of salinisation and interaquifer flow of saline groundwater in the North East German Basin. Chemical analyses from hydrocarbon exploration campaigns showed evidence of the existence of two different groups of brines: halite and halite Ca–Cl brines. Residual brines and leachates are identified by Br^?/Cl^? ratios. Most of the brines are dissolution brines of Permian evaporites. New analyses show that the pattern of rare-earth elements and yttrium (REY) are closely linked to H and O isotope distribution. Thermal brines from deep wells and artesian wells indicate isotopically evaporated brines, which chemically interacted with their aquifer environment. Isotopes and rare-earth element patterns prove that cross flow exists, especially in the post-Rupelian aquifer. However, even at depths exceeding 2,000 m, interaquifer flow takes place. The rare-earth element pattern and H and O isotopes identify locally ascending brines. A large-scale lateral groundwater flow has to be assumed because all pre-Rupelian aquifer systems to a depth of at least 500 m are isotopically characterised by Recent or Pleistocene recharge conditions.     

The geochemical characteristics of aqueous rare-earth elements in shallow karst groundwater in Guiyang City,China

Fifty-seven shallow groundwater samples were collected from Guiyang karst basin, China, to analyze the aqueous rare-earth elements in low-water seasons and it is shown that the total amount of rare-earth elements (ΣREE) in karst groundwater is exceedingly low compared with that in carbonate rocks or weathering crusts of carbonate rocks, and ranges from 0.01 to 0.43, from 0.03 to 0.27, from 0.03 to 0.19 and from 0.05 to 1.38 μg·L-1 for dolomite, dolomitic & limestone, limestone and clastic rock aquifer, respectively. Both distributions and contents of rare-earth elements (REE) in karst groundwater reflect the lithology of host rocks or weathering crusts of carbonate rocks through which groundwater flows. The chondrite-normalized patterns show a non-flat profile with higher enrichment of slightly light rare-earth elements (LREE) than heavy rare-earth elements (HREE), prominent fractionation between LREE and HREE, negative Ce anomalies and negative or positive Eu anomalies. There is more obvious fractionation between LREE and HREE in groundwater than that in carbonate rocks and their weathering crusts due to high contents of HCO3? and PH in groundwater. In shallow karst groundwater, REE(CO3)n2n-3 (n=1 and 2) is the main inorganic species of REE. But for a clastic rock aquifer, both REESO4+ and REECO3+ are the main inorganic species of REE. Species of REE in groundwater is closely associated with the hydrochemical type of groundwater which is predominated by the lithology of host rocks, groundwater-rock interaction and weathering-pedogenesis of carbonate rocks.     

华南地区晚二叠世煤的稀土元素特征

在华南地区贵州六盘水、江西乐平和湖北黄石矿区以及重庆钟梁山和磨心坡煤矿晚二叠世煤的稀土元素电感耦合等离子质谱分析数据的基础上,系统研究了华南地区煤的稀土元素的质量分数分布特征、赋存特征、配分模式及其地质控制因素.煤的稀土元素质量分数与灰分质量分数呈正相关关系,部分煤样品由于有富稀土元素的重矿物组合的存在而出现稀土元素的异常高值.同一矿区晚二叠世煤的稀土元素配分模式具有一定的相似性,而不同地区晚二叠世煤的稀土元素配分模式则差异较大.煤的沉积环境、煤中无机矿物的组成以及海水的影响是控制煤的稀土元素质量分数及其配分模式的主要地质因素.     

姑婆山花岗岩主岩体的稀土元素赋存状态研究

稀土元素在姑婆山花岗岩主岩体过渡相中,主要以稀土矿物和类质同象两种形式存在,并以稀土矿物形式为主,其中稀土元素含量占全岩含量的64％以上。轻稀土元素主要赋存于褐帘石和独居石中,重稀土元素主要赋存于褐钇铌矿等矿物中。岩石中至少有65％以上的稀土元素赋存于抗风化能力小的矿物中,为花岗岩风化壳离子吸附型稀土矿床提供了物质来源。     

Geochemistry and petrogenesis of Late Ladinian OIB-like basalts from Tabai, Yunnan Province, China

Major and trace elements analysis has been carried out on the Late Ladinian Tabai basalts from Yunnan Province with the aim of studying their petrogenesis. Their SiO2 contents range from 43.63 wt.% to 48.23 wt.%. The basalts belong to the weakly alkaline(average total alkalis Na2 O+K2O=3.59 wt.%), high-Ti(3.21 wt.% to 4.32 wt.%) magma series. The basalts are characterized by OIB-like trace elements patterns, which are enriched in large ion lithosphile elements(LILE) including Rb and Ba, and display negative K, Zr and Hf anomalies as shown on the spider diagrams. The Tabai basalts display light rare-earth elements(LREE) enrichment and are depleted in heavy rare-earth elements(HREE) on the REE pattern. Those dates indicate that the parental magma of the Tabai basalts was derived from low-degree(1%–5%) partial melting of garnet peridotite. The magma underwent olivine fractional crystallization and minor crustal contamination during their ascent. The Tabai basalts were related to a relaxation event which had triggered the Emeishan fossil plume head re-melting in the Middle Triassic.     

华南地区晚二叠和晚三叠世煤中稀土元素特征研究

在华南地区贵州六盘水、江西乐平、露庆和湖北黄石矿区晚二叠和晚三叠世煤层的稀土元素ICP—MS分析数据的基础上，系统研究了研究区煤中稀土元素的含萤分布特征、赋存特征、配分模式以及地质控制因素。含量分布表明晚二叠世稀土元素含量总体高于晚三叠世；煤中稀土元素与灰分成正相关关系，部分煤样品由于有富稀土元素的重矿物组合的存在而出现稀土元素的异常高值；同一矿区、同一时代煤中稀土元素的配分模式具有一定的相似性，而不同地区同一时代和同一地区不同时代煤中稀土元素的配分模式具有较大差异；煤的沉积环境，煤中无机矿物组成以及海水的影响是控制煤中稀土元素含量和配分模式的主要地质因素。     

Rb-Sr age of the Sivamalai alkaline complex,Tamil Nadu

The Sivamalai alkaline complex comprises ferro-, pyroxene-hornblende- and nepheline-syenites. Field relations show that the nepheline syenites followed the emplacement of non-feldspathoidal syenites. Mineralogical data on the syenite suite have been reviewed. The Sivamalai alkaline rocks are not strongly enriched in rare-earth elements like most miaskites. Rb-Sr isotopic analyses of a suite of six samples from the various members of the complex define an isochron corresponding to an age of 623 ±21 Ma (2σ) and initial Sr ratio of 0.70376 ±14 (2σ). This is consistent with a model of fractional crystallization of a parent magma derived from an upper mantle source with apparently no isotopic evidence for more than one magma source for the complex. The Sivamalai alkaline complex represents a Pan-African alkaline magmatic event in the southern granulite terrane of Peninsular India.     

应用电子探针-扫描电镜研究陕西华阳川铀稀有多金属矿床稀土矿物特征

陕西华阳川铀稀有多金属矿床伴生大量的稀土资源,其矿石类型独特、组分复杂,系统的稀土矿物学工作将揭示矿石主要稀土矿物类型、稀土元素赋存状态,进而对矿床开发中稀土元素综合利用及选冶技术提供重要参考。本文在岩相学基础上,利用电子探针、扫描电镜对陕西华阳川铀稀有多金属矿床矿石中的稀土独立矿物与含稀土矿物进行系统研究,在矿石中发现了褐帘石（La₂O₃ 6.49%～7.61%,Ce₂O₃ 11.50%～14.00%）、磷铈镧矿（La₂O₃ 16.30%～21.21%,Ce₂O₃ 32.06%～39.18%）、磷钇矿（La₂O₃ 2.29%～3.58%,Ce₂O₃ 1.89%～2.37%,Y₂O₃ 39.77%～42.80%）、氟碳铈镧矿（La₂O₃ 12.86%～14.20%,Ce₂O₃ 36.67%～39.90%）、褐钇铌矿（La₂O₃ 1.19%～2.11%,Ce₂O₃ 1.29%～2.30%,Y₂O₃ 22.67%～25.88%）等5种稀土独立矿物;同时发现磷灰石、贝塔石、榍石等矿物中稀土元素含量较高。研究表明,该矿床稀土元素以独立矿物（褐帘石、磷铈镧矿、磷钇矿、氟碳铈镧矿、褐钇铌矿）与类质同象（磷灰石、贝塔石、榍石等矿物）两种形式存在,稀土资源以La、Ce轻稀土元素为主,并富含重稀土元素Y。     

Syn-sedimentary hydrothermal dolomites in a lacustrine rift basin: Petrographic and geochemical evidence from the lower Cretaceous Erlian Basin,Northern China

Dolomites occur extensively in the lower Cretaceous along syn-sedimentary fault zones of the Baiyinchagan Sag, westernmost Erlian Basin, within a predominantly fluvial–lacustrine sedimentary sequence. Four types of dolomite are identified, associated with hydrothermal minerals such as natrolite, analcime and Fe-bearing magnesite. The finely-crystalline dolomites consist of anhedral to subhedral crystals (2 to 10 μm), evenly commixed with terrigenous sediments that occur either as matrix-supporting grains (Fd1) or as massive argillaceous dolostone (Fd2). Medium-crystalline (Md) dolomites are composed of subhedral to euhedral crystals aggregates (50 to 250 μm) and occur in syn-sedimentary deformation laminae/bands. Coarse-crystalline (Cd) dolomites consist of non-planar crystals (mean size >1 mm), and occur as fracture infills cross-cutting the other dolomite types. The Fd1, Md and Cd dolomites have similar values of δ¹⁸O (−20·5 to −11·0‰ Vienna PeeDee Belemnite) and δ¹³C (+1·4 to +4·5‰ Vienna PeeDee Belemnite), but Fd2 dolomites are isotopically distinct (δ¹⁸O −8·5 to −2·3‰ Vienna PeeDee Belemnite; δ¹³C +1·4 to +8·6‰ Vienna PeeDee Belemnite). Samples define three groups which differ in light rare-earth elements versus high rare-earth elements enrichment/depletion and significance of Tb, Yb and Dy anomalies. Medium-crystalline dolomites have signatures that indicate formation from brines at very high temperature, with salinities of 11·8 to 23·2 eq. wt. % NaCl and T_h values of 167 to 283°C. The calculated temperatures of Fd1 and Cd dolomites extend to slightly lower values (141 to 282°C), while Fd2 dolomites are distinctly cooler (81 to 124°C). These results suggest that the dolomites formed from hydrothermal fluid during and/or penecontemporaneous with sediment deposition. Faults and fractures bounding the basin were important conduits through which high-temperature Mg-rich fluids discharged, driven by an abnormally high heat flux associated with local volcanism. It is thought that differing amounts of cooling and degassing of these hydrothermal fluids, and of mixing with lake waters, facilitated the precipitation of dolomite and associated minerals, and resulted in the petrographic and geochemical differences between the dolomites.     

白云鄂博的氟碳钡铈矿

氟碳钡铈矿(Cordylite)BaCe₂(CO₃)₃ F₂本世纪初首先发现于格陵兰纳尔萨尔苏克(Narssarssuk)的碱性正长伟晶岩脉中,与霓石、氟碳铈钙矿、柱星叶石和碳锶铈矿共生。1965年该矿物又发现于我国白云鄂博西矿区热液交代的元古代白云岩中。1975年,加拿大魁北克省圣赫莱山(Mont st. Hilaire,Quebec)的霞石正长岩中的伟晶岩脉中也发现了这一矿物,它与方沸石、霓石和钠闪石共生。     

Importance of Skewness and Kurtosis Statistical Tests for Outlier Detection and Elimination in Evaluation of Geochemical Reference Materials

A common characteristic of concentration data compilations for geochemical reference materials (GRM) is a skewed frequency distribution because of aberrant analytical data. Rejection of outlying results usually is required to obtain a better estimate of mean concentration values. The present work describes the application of an approach, based on skewness and kurtosis statistical tests, to establish reliable concentration values in study of rare-earth element compilations for GRM. Frequency histograms of initial concentrations for these elements differ significantly from a normal distribution, as deduced from their skewness and kurtosis coefficients. The statistical procedure shows that rejection of outliers yields normal distributions which can be used to provide mean concentrations with smaller standard deviations for a large number of cases, although for many elements our %RSD are similar (within 5%) to literature values. This procedure has been applied to derive new concentration data for rare-earth elements in 26 GRM, which are compared with earlier compilations to show that the statistical procedure proposed here provides mean values with greater quality value. Although most present mean concentrations are similar (within 5%) to those reported in previous literature, some of them are significantly different (with differences of up to 40%) in a few GRM.     

A cystoid with two left facets: the significance of Tetracystis in the evolution and classification of the Callocystitidae (Echinodermata,Glyptocystitoida)

Revision of some North American Silurian callocystitid cystoids shows that Tetracystis Schuchert has the first two brachioles to the left in ambulacra B and D (B D different pattern), whereas Troosticystis Paul and Lovenicystis Regéll have only the first brachiole to the left in all four ambulacra (B–E the same pattern). ‘Apiocystites’ elegans Hall is transferred to Tetracystis because it has the B D different pattern. Lovenicystis kopfi sp. nov. is characterized by four short ambulacra. Salirocystis gen. nov. has the B D different pattern and two hydropores. All callocystitids that lack ambulacrum A are assigned to a new subfamily, the Tetracystinae; those with five ambulacra are referred to informally as ‘lepadocystines’. The previously recognized subfamily Callocystitinae is reduced in rank to a tribe within the ‘lepadocystines’. Preliminary character analysis suggests that the loss of ambulacrum A was the most significant evolutionary event within the family Callocystitidae, but has been overlooked in taxonomy. Character analysis also shows that all ‘lepadocystines’ had the B D different pattern of primary brachioles, which is retained in four tetracystine genera, Lepocrinites Conrad, Sphaerocystites Hall, Tetracystis and Salirocystis. Since Salirocystis has the plesiomorphic B D different pattern plus the apomorphic double hydropore, one cannot define a monophyletic taxon characterized by the B–E the same pattern plus one characterized by a double hydropore. Both alternatives are equally parsimonious. Here a new monophyletic tribe Lipsanocystini is defined characterized by a double hydropore. The B–E the same pattern evolved independently twice. Among current characters the loss of ambulacrum A, development of the B–E the same pattern and development of two hydropores are the most significant evolutionary events. Number of periproct border plates, length and structure of ambulacra are less significant. Copyright © 2014 John Wiley & Sons, Ltd.     

辽宁宽甸、山东蓬莱幔源巨晶矿物中陨硫铁的研究

陨硫铁发现于山东、辽宁新生代碱性玄武岩所携带的幔源巨晶辉石等矿物中。两地的陨硫铁由于载体的巨晶辉石与碱性玄武岩之间曲混融程度不同,导致他们的稀土配分型式亦不同,即混融程度高,稀土配分型式复杂,混融程度低,则稀土配分型式与球粒陨石的配分型武相同。幔源陨硫铁以富镍为特征,并且是在特定的物理化学条件下生成的,即     

REE concentrations of garnet and omphacite in eclogites from the Dabie Mountain, central China

Distributions of the rare-earth elements (REE) in omphacite and garnet and REE behaviors during metamorphic processes were discussed. The REE concentrations of garnet and omphacite in six eclogite samples from the Dabie Mountain, central China, were measured by inductively coupled plasma-mass spectrometry (ICP-MS). The correlation of δEu ratios between garnet and omphacite indicated that chemical equilibrium of REE distribution between garnet and omphacite could be achieved during ultra-high pressure (UHP) metamorphism. Most of the partition coefficients (Kd=CiOmp/CiGrt) of light rare-earth elements (LREE) are higher than 1. However the partition coefficients of heavy rare-earth elements (HREE) are lower than 1. This indicated that the LREE inclined to occupy site M2 in omphacite, but the HREEs tended to occupy eightfold coordinated site in garnet during the eclogite formation. The REE geochemistry of the eclogites indicated that LREE could be partially lost during the prograde metamorphic process of protolith, but be introduced into the rocks during the symplectite formation. LREE are more active than HREE during the UHP metamorphism. The results are favorable to highlighting the REE behavior and evolution of UHP metamorphic rocks.     

中国东部新生代玄武岩稀土配分的分形结构因子与其它化学组成的相关性

本文提出了稀土配分分形结构因子概念和计算方法。利用这个新方法，计算了中国东部新生代玄武岩中稀土配分的分形结构因子。研究了这些因子与玄武岩主元素、稀土元素、分散元素和同位素之间的关系，并求出了其相关性参数。利用这些参数，求出了两个端元玄武岩的主元素和稀土元素含量；提出了五大莲池地区玄武岩可能与富钾交代地幔部分熔融作用有关，其它玄武岩的形成与软流圈地幔或岩石圈地幔部分熔融有关；玄武岩同位素的比值不仅受玄武岩浆地幔源区本身的特征制约，还可能受地幔岩部分熔融程度的制约。     

Effect of the <Emphasis Type="Italic">d</Emphasis> electrons on phase transitions in transition-metal sesquioxides

We present a systematic density-functional study of phase relations in three 4d-transition-metal sesquioxides: Y₂O₃, Rh₂O₃, and In₂O₃. Y₂O₃ and In₂O₃ undergo pressure-induced transitions to phases with larger cation coordination number (from 6 to 7) at low pressures. However, this does not occur in Rh₂O₃ at least up to ~300 GPa. This cannot be explained by usual arguments based on ionic-radii ratios often used successfully to explain phase relations in simple-metal and rare-earth sesquioxides and sesquisulfides. Inspection of their electronic structures shows that, in Rh₂O₃, the electronic occupancy of 4d orbitals, 4d ⁶, plays a fundamental role in the extraordinary stability of the Rh₂O₃(II)-type phase with respect to coordination increase. We point out that d-orbital occupancy is a fundamental factor in explaining phase relations in transition-metal sesquioxides and sesquisulfides.     

冕宁稀土矿床稀土元素的赋存状态及其配分特征

冕宁稀土矿是我国西南地区的大型轻稀土矿床。它不仅含有丰富的轻稀土,而且铕、钇等中重稀土较国内外同类型矿床高。该矿的特点是工业稀土矿物组成简单,矿石易选、易冶。矿石中90％左右的REO呈稀土矿物产出,其中氟碳铈矿占稀土矿物总量的80％—97％。矿石和主要稀土矿物的REF配分均属Ce>La>Nd富LREE的强选择配分型。矿石中轻稀土配分值高达97.48％—98.81％。矿石中Eu、Y配分值较高,而氟碳铈矿反而比矿石低。矿石中的黑色风化土状物富含次生稀土,其Eu、Y配分值比矿石、氟碳铈矿都高。     

Mineral chemistry of Plio-Quaternary subvolcanic rocks,southwest Yazd Province,Iran

The NW–SE-trendingLate Cretaceous–Cenozoic Urumieh-Dokhtar Magmatic Arc (UDMA) in southwest Iran hosts numerous Plio-Quaternary subvolcanic porphyritic andesitic to rhyodacitic domes intruded into a variety of rock sequences. Bulk-rock geochemical data show that the calc-alkaline dacitic to rhyodacitic subvolcanic rocks share compositional affinities with high-silica adakites, including high ratios of Na₂O/K₂O >1, Sr/Y (most >70), and La/Yb (>35), high Al₂O₃ (>15 wt.%), low Yb (<1.8 ppm) and Y (<18 ppm) contents, no significant Eu anomalies, and flat to gently upward-sloping chondrite-normalized heavy rare-earth element (HREE) patterns. All analysed rocks are characterized by enrichment in large-ion lithophile elements (LILEs) and depletion in high field strength elements (HFSEs). They also display typical features of subduction-related calc-alkaline magmas. In chondrite-normalized rare-earth element patterns, the light rare-earth elements (LREEs) are enriched ((La/Sm) _N = 3.49–7.89) in comparison to those of the HREE ((Gd/Yb) _N = 1.52–2.38). Except for the G-Aliabad Dome, plagioclase crystals in the Shamsabad, Ostaj, Abdollah, and Bouragh Domes are mostly oligoclase to andesine (An_19–49). Amphibole and biotite are abundant ferromagnesian minerals in the subvolcanic rocks. Calcic amphiboles are dominantly magnesiohornblende, magnesiohastingsite, and tschermakite with Mg/(Mg + Fe_tot) ratios ranging from 0.58 to 0.78. In all the studied domes, amphiboles are typically ferric iron-rich, but that those the Shamsabad Dome have the highest Fe³⁺/(Fe³⁺ + Fe²⁺) ratios, between 0.69 and 0.98. Amphiboles from the Ostaj and Shamsabad Domes are relatively rich in F (0.39–1.01 wt.%) in comparison to the other studied domes. This phase commonly shows pargasitic and hastingsitic substitutions with a combination of tschermakitic and edenitic types.

Temperature-corrected Al-in-hornblende data show that amphibole phenocrysts from the Ostaj, Abdollah, and G-Aliabad Domes crystallized at pressures ranging from 2.14 to 3.42 kbar, 3.49 to 3.96 kbar, and 2.02 to 3.47 kbar, respectively. Temperatures of crystallization calculated with the amphibole–plagioclase thermometer for the Ostaj, Abdollah, and G-Aliabad subvolcanic domes range from 735°C to 826°C (mean = 786 ± 29), 778°C to 808°C (mean = 791 ± 13), and 866°C to 908°C (mean = 885 ± 12), respectively. In the annite–siderophyllite–phlogopite–eastonite quadrilateral, biotite from the G-Aliabad, Bouragh, and Ostaj Domes are characterized by relatively low total Al contents with variable Fe_tot/(Fe_tot + Mg) values from 0.26 to 0.43. All biotite analyses define a nearly straight line in the X _Mg versus Fe_tot plot, with r = –0.96 correlation coefficient. In comparison to other domes, the F content of biotite from the G-Aliabad Dome shows high concentrations in the range of 1.80–2.57 wt.% (mean = 2.20). Inferred pre-eruptive conditions based on the calcic amphibole thermobarometric calculations for the Shamsabad, Abdollah, and Ostaj Domes show that the calc-alkaline subvolcanic magma chamber, on average, was characterized by a water content of 6.10 wt.%, a relatively high oxygen fugacity of 10^–10.66 (ΔNNO + 1.28), a temperature of 896°C, and a pressure of 2.75 kbar.     

Coupled evolution of back-arc and island arc-like mafic crust in the late-Neoproterozoic Agardagh Tes-Chem ophiolite, Central Asia: evidence from trace element and Sr–Nd–Pb isotope data

. We report major-element, trace-element and isotopic data of volcanic rocks from the late-Neoproterozoic (570 Ma) Agardagh Tes-Chem ophiolite in Central Asia, south-west of Lake Baikal (50.5°N, 95°E). The majority of samples are high-alumina basalts and basaltic andesites having island-arc affinities. They were derived from an evolved parental magma (Mg#̾.60, Cr~180 ppm, Ni~95 ppm) by predominantly clinopyroxene fractionation. The parental magma developed from a primary mantle melt by fractionation of about 12% of an olivine+spinel assemblage. The island-arc rocks have high abundances of incompatible trace elements (light rare-earth element abundances up to 100 times chondritic, chondrite-normalised (La/Yb)_n=14.6-5.1) and negative Nb anomalies (Nb/La=0.37-0.62), but low Zr/Nb ratios (7-14). Initial )_Nd values are around +5.5, initial Pb isotopic compositions are ²⁰⁶Pb/²⁰⁴Pb=17.39-18.45, ²⁰⁷Pb/²⁰⁴Pb=15.49-15.61, ²⁰⁸Pb/²⁰⁴Pb=37.06-38.05. Enrichment of large-ion lithophile elements within this group is significant (Ba/La=11-130). Another group of samples consists of back-arc basin-related volcanic rocks. They are most likely derived from the same depleted mantle source as the island-arc rocks, but underwent higher degrees of melting (8-15%) and are not influenced by slab components. They have lower abundances of incompatible trace elements, flat rare-earth element patterns [(La/Yb)_n=0.6-2.4] and higher )_Nd values (+7.8 to +8.5). Negative Nb anomalies are absent (Nb/La=0.81-1.30), but Zr/Nb is high (21-48). At least three components are necessary to explain the geochemical evolution of the volcanic rocks: (1) an enriched (ocean island-like) component characterised by a high Nb concentration (up to 30 ppm), an absent negative Nb anomaly, a low Zr/Nb ratio (~6.5), a low )_Nd value (around 0), and radiogenic ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb; (2) a back-arc basin component similar to N-MORB with a flat rare-earth element pattern and a high )_Nd value (around +8.5); and (3) an island-arc component from a mantle source which was modified by the downgoing slab. Crystal fractionation superimposed on mixing and source contamination by subducted sediments is suitable to explain the observed geochemical data. The most likely geodynamic environment to produce these characteristics is a young, intra-oceanic island-arc system and an associated back-arc basin.     

Color centers,associated rare-earth ions and the origin of coloration in natural fluorites

Natural colored fluorites were studied by means of optical absorption and electron paramagnetic resonance (EPR). Complex centers involving rare-earth ions and/or oxygen give rise to the various colors observed. These include yttrium-associated F centers (blue), coexisting yttrium and cerium-associated F centers (yellowish-green), the (YO₂) center (rose) and the O ₃ ^? molecule ion (yellow). Divalent rare-earth ions also contribute to the colorations, as for instance Sm³⁺ (green fluorites), or they are at the origin of strong fluorescence observed (Eu²⁺). Strong irradiation of the crystals with ionizing radiation leads to coagulation of color centers, and to precipitation of metallic calcium colloids. There is probably no simple relation connecting the coloration and the growth process of the crystal. Thermal stability studies, however, have allowed to partially classify the colors as being of primary or secondary origin.