Boron metasomatism and behaviour of rare earth elements during formation of tourmaline rocks in the eastern Arunta Inlier,central Australia

Tourmaline rocks of previously unclear genesis and spatially associated with W- (Cu)-bearing calc-silicate rocks occur in Palaeoproterozoic supracrustal and felsic intrusive rocks in the Bonya Hills in the eastern Arunta Inlier, central Australia. Tourmalinisation of metapelitic host rocks postdates the peak of regional low-pressure metamorphism (M₁/D₁, ~500 °C, ~0.2 GPa), and occurred synkinematically between the two main deformation events D₁ and D₂, coeval with emplacement of Late Strangways (~1.73 Ga) tourmaline-bearing leucogranites and pegmatites. Tourmaline is classified as schorl to dravite in tourmaline–quartz rocks and surrounding tourmaline-rich alteration zones, and as Fe-rich schorl to foitite in the leucogranites. Boron metasomatism resulted in systematic depletion of K, Li, Rb, Cs, Mn and enrichment of B, and in some samples of Na and Ca, in the tourmaline rocks compared to unaltered metasedimentary host rocks. Whole-rock REE concentrations and patterns of unaltered schist, tourmalinised schist and tourmaline–quartz veins—the latter were the zones of influx of the boron-rich hydrothermal fluid—are comparable to those of post-Archaean shales. Thus, the whole-rock REE patterns of these rocks are mostly controlled by the metapelitic precursor. In contrast, REE concentrations of leucogranitic rocks are low (10 times chondritic), and their flat REE patterns with pronounced negative Eu anomalies are typical for fractionated granitic melts coexisting with a fluid phase. REE patterns for tourmalines separated from metapelite-hosted tourmaline–quartz veins and tourmaline-bearing granites are very different from one another but each tourmaline pattern mirrors the REE distribution of its immediate host rock. Tourmalines occurring in tourmaline–quartz veins within tourmalinised metasediments have LREE-enriched (La_N/Yb_N=6.3–55), shale-like patterns with higher REE (54–108 ppm). In contrast, those formed in evolved leucogranites exhibit flat REE patterns (La_N/Yb_N=1.0–5.6) with pronounced negative Eu anomalies and are lower in REE (5.6–30 ppm). We therefore conclude that REE concentrations and patterns of tourmaline from the different tourmaline rocks studied are controlled by the host rock and not by the hydrothermal fluid causing boron metasomatism. From the similarity of the REE pattern of separated tourmaline with the host rock, we further conclude that incorporation of REEs in tourmaline is not intrinsically controlled (i.e. by crystal chemical factors). Tourmaline does not preferentially fractionate specific REEs or groups of REEs during crystallisation from evolved boron- and fluid-rich granitic melts or during alteration of clastic metasediments by boron-rich magmatic-hydrothermal fluids.Editorial responsibility: J. Hoefs     

Crystallization of the Little Three layered pegmatite-aplite dike, Ramona District, California

Subhorizontally layered pegmatite-aplite bodies are characterized by fine-grained, sodic to granitic aplite that is usually juxtaposed abruptly above by much coarser-grained, commonly graphic potassic pegmatite. Although well studied, there currently is little concensus as to how such dikes form. The Little Three dike near Ramona, California, is representative of such zoned bodies in this and other regions, and contains discontinuous miarolitic pockets near the base of the graphic pegmatite zone. Tourmaline, garnet, biotite, and muscovite show no changes in major- or minor-element compositions indicative of progressive magmatic fractionation until the immediate vicinity of the main miarolitic zone, where they record abrupt and extreme enrichments in Li, F, and Mn. There is no correlation of chemical changes in the dike with the appearance of small miarolitic vugs well below the main miarolitic zone, nor is there any indication that the aplite, graphic pegmatite, or miarolitic pockets represent separate magma injections. The chemistries of tourmaline, garnet, and micas, however, preclude conventional models of Rayleigh fractionation or traditional zone refining. Textural features and modeled cooling histories indicate that the dike cooled quickly and might have solidified partially or totally to glass before crystallization commenced. Geothermometry based on the compositions of coexisting plagioclase and homogeneous, nonperthitic K-feldspar indicates inward crystallization of the dike, from ∼400–435 °C at the margins to ∼350–390 °C within 20–30 cm of the pocket horizon, then a sharp decrease to 240–275 °C in the pockets where K-feldspar is perthitic. We interpret the feldspar geothermometry (except perhaps in the miarolitic cavities) to reflect the temperatures at crystallization fronts that advanced into the pegmatite, first from the foot wall and eventually joined by a similar front downward from the hanging wall. Crystallization down from the hanging wall may have commenced after ∼70–80% of the foot wall aplite had crystallized. The very abrupt increases of Li, Mn, and F in tourmaline and garnet near the miarolitic zone appear to be explained best by the process of constitutional zone refining, in which a fluxed crystallization front sweeps an incompatible element-enriched boundary layer through a solid or semi-solid. After these two highly fluxed boundary layers merged near the main miarolitic zone, compositional evolution could have proceeded by crystal-melt fractionation. Received: 24 March 1998 / Accepted: 10 March 1999     

Trace element geochemistry by laser ablation ICP-MS of micas associated with Ta mineralization in the Tanco pegmatite,Manitoba, Canada

In the Tanco pegmatite, one of the world’s major Ta deposits, tantalum mineralization shows a complexity that reflects the complex petrogenesis of its host pegmatite. Micas are common in most of the pegmatite units and are intimately associated with the successive stages of Ta mineralization, from the wall zone to the central zones where micaceous replacement is pervasive. Different generations of micas, both primary and secondary, associated with Ta oxides, were selected for electron microprobe and laser ablation ICP-MS investigation. Their chemical trends are used to constrain the magmatic versus hydrothermal processes that played a role in their crystallization and their associated Ta mineralization. Micas range from dioctahedral muscovite to trioctahedral lepidolite through Al↔Li substitution. Unexpectedly, the most evolved compositions (low K/Rb ratios and high Li contents) occur in the wall zone; they are interpreted to reflect nonequilibrium crystallization from an undercooled melt, with or without boundary layer effects. In the central zones, the fine-grained mica–quartz assemblage hosts some coarser-grained Li-muscovite, which has the highest Ta contents (up to 400 ppm). These Li–F–a-rich micas are interpreted to originate from a magmatic metasomatic event, which was also at the origin of the MQM-style Ta mineralization at Tanco. However, the Li–Ta-poor, muscovite end-member compositions of fine-grained alteration micas suggest crystallization from an aqueous fluid, during a metasomatic (hydrothermal) event involving late pegmatitic fluids. The low Ta concentrations (around 50 ppm) of this fine-grained muscovite suggest that this fluid transported at least small amounts of Ta.     

The tetrad effect and geochemistry of apatite from the Altay Koktokay No. 3 pegmatite, Xinjiang, China: implications for pegmatite petrogenesis

In order to better constrain the evolution and petrogenesis of pegmatite, geochemical analysis was conducted on a suite of apatite crystals from the Altay Koktokay No. 3 pegmatite, Xinjiang, China and from the granitic and amphibolitic wall rocks. Apatite samples derived from pegmatite zones show convex tetrad effects in their REE patterns, extremely negative Eu anomalies and non-chondritic Y/Ho ratios. In contrast, chondritic Y/Ho ratios and convex tetrad effects are observed in the muscovite granite suggesting that different processes caused non-chondritic Y/Ho ratios and lanthanide tetrad effects. Based on the occurrence of convex tetrad effects in the host rocks and their associated minerals, we propose that the tetrad effects are likely produced from immiscible fluoride and silicate melts. This is in contrast to previous explanations of the tetrad effect; i.e. surface weathering, fractional crystallization and/or fluid-rock interaction. Additionally, we put forward that extreme negative Eu and non-chondritic Y/Ho in apatite are likely caused by the large amount of hydrothermal fluid exsolved from the pegmatite melts. Evolution of melt composition was found to be the primary cause of inter and intra-crystal major and trace element variations in apatite. Mn entering into apatite via substitution of Ca is supported by the positive correlation between CaO and MnO. Different evolution trends in apatite composition imply different crystallization environments between wall rocks and pegmatite zones. Based on the geochemistry of apatite samples, it is likely that there is a genetic relationship between the source of muscovite granite and the source of the pegmatite.     

Tourmaline from the rare-element Pinilla pegmatite, (Central Iberian Zone, Zamora, Spain): chemical variation and implications for pegmatitic evolution

Summary Tourmaline is an ubiquitous constituent in the Pinilla de Fermoselle rare-element pegmatite (Zamora, Spain), as well as in barren pegmatitic and quartz–tourmaline veins inside the associated leucogranite. The rare-element pegmatite shows internal zoning, evolving from a barren facies, in the lower border zone, in contact with the leucogranite, to a Li-rich facies in the upper border zone, close to the host-rocks.Tourmalines from the veins within the leucogranite have highest Mg contents, and belong to the schorl–dravite series. The tourmalines from the rare-element pegmatite mostly belong to the schorl–elbaite series, with chemical compositions within the range of the end-members, whereas the tourmalines associated with the most evolved zone in the pegmatite belong to the elbaite–rossmanite series. The broad compositional range shown by the tourmalines correlates quite well with the pegmatite zoning. The most plausible substitution mechanism for the chemical evolution of tourmalines during crystallization seems to be Mg_–1Fe²⁺₁, [X]_–1^YAl_–1^XNa_–1^YFe²⁺₁, for the foitite–schorl series; ^YFe²⁺_–3^YAl_1.5^YLi_1.5, for the schorl–elbaite vector; ^XNa_–1^YLi_–0.5[X]₁^YAl_0.5, for the elbaite–rossmanite series; and, (OH)₁F₁ for all the tourmalines except the pink elbaites. This chemical variation in tourmaline is consistent with a crystal fractionation model for the evolution of the Pinilla pegmatite.     

Sc- and REE-bearing ixiolite and associated minerals from the Sosedka pegmatite vein in the Malkhan pegmatite field, central Transbaikal region

Composition and localization of REE mineralization in miarolitic pegmatites and its role in the pegmatite formation were studied at the Malkhan gem deposit (jewel-quality tourmaline, morganite, danburite, and hambergite) in the central Transbaikal region. The chemical composition of Ti-, Ta-, Nb- and REE-bearing minerals, their relationships with rock-forming and accessory minerals indicate that two geochemically specialized stages of pegmatite formation are distinguished. The early stage gave rise to the crystallization of quartz-feldspar aggregates including K-feldspar block zone with Sc and REE mineralization. The rare-metal (Li, Cs, F, B, Be) albite-lepidolite-cleavelandite complex with pockets of gem mineralization was formed at the late stage.     

Petrology and Li-Be-B geochemistry of muscovite-biotite granite and associated pegmatite near Yellowknife,Canada

Prosperous granite (Rb-Sr 2520±25 Ma) occurs as several plutons (1–380 km² outcrop area) in a thick succession of metamorphosed greywacke-mudstone of the Yellowknife Supergroup. The average mineral content of the Sparrow pluton (in vol.%) is quartz (32), plagioclase (31), K-feldspar (24), muscovite (9), biotite (3), and apatite (<1). Average trace-element concentrations (in ppm) are Li (140), Be (4), B (28), Zn (47), Rb (250), Sr (76), Zr (75) and Ba (360). The central portion of the pluton is slightly richer in K, Sr, and Ba than the margin. Li is concentrated in mica (Li in biotite/Li in muscovite=4.7), and Be and B in muscovite and plagioclase. Countless pegmatite dikes occur in the Sparrow pluton and in schist-hornfels to the east; the outer limit is marked by the cordierite isograd, 9 km from the granite contact. Dikes vary greatly in size (1 km to a few cm in length), in mineral content (quartz, albite, K-feldspar, muscovite, tourmaline, beryl, spodumene), in major element composition (especially the NaK ratio), and in trace-element content (Li 18–5000 ppm, Be 5–260 ppm, B 20–150 ppm). Compared with Prosperous granite, the pegmatite bodies are richer in P and Rb, and poorer in Ti, Fe, Mg, Zr, and Ba. Dikes rich in tourmaline, beryl, and spodumene occur in overlapping zones situated progressively farther from the centre of the Sparrow pluton. The composition of tourmaline is related to host rock; the highest concentrations of Fe and Zn occur in crystals from pegmetite and the highest concentrations of Mg and V occur in crystals from tourmalinized schist, while those from granite and quartz veins occupy on intermediate position. Complex compositional zoning is present in some tourmaline crystals in pegmatite. Estimates of temperature (500°–600° C) and pressure (2–4 kb) of granite emplacement, based on the distribution of andalusite and sillimanite in the contact rocks, suggest that the final stage of granite emplacement occurred at sub-solidus conditions. A vaportransport model is proposed to explain the widespread distribution of the pegmatite dikes and their extreme compositional variability. Some of the pegmatite constituents, including Li, Be, and B, were possibly derived from Yellowknife graywacke and mudstone.     

新疆大红柳滩伟晶岩型锂矿床中磷铁锂矿地球化学特征及其对伟晶岩演化的指示意义

新疆大红柳滩伟晶岩型锂矿床近年来找矿取得了新进展。我们在该地区典型锂矿脉(90-1号)首次鉴定出磷铁锂矿,其在伟晶岩中呈树枝状、团簇状集合体分布岩脉的边缘带和中部。边缘带尤为富集磷铁锂矿,含量可达10%～15%。本文系统地开展了磷铁锂矿的岩相学和矿物学研究。利用电子探针和激光剥蚀等离子质谱测定了脉体边缘带和中间粗粒锂辉石-白云母-石英带磷铁锂矿的主微量元素含量。结果表明,磷铁锂矿除含有主要元素P、Fe、Mn及Li外,还含有较高的Mg、Ca和Zn,几乎不含高场强元素、稀土元素。综合电子探针和LA-ICP-MS分析结果,认为伟晶岩脉中部分磷铁锂矿已被氧化,成分向铁磷锂锰矿过渡。从脉体的边缘带往中间带,磷铁锂矿中Mg和Zn平均含量下降,而Mn/(Mn+Fe)比值由0.388升至0.409,显示逐渐富Mn特点,与前人关于花岗伟晶岩熔体演化过程中Fe-Mn的分离趋势一致,也与该伟晶岩脉中铌钽铁矿早期演化阶段Mn/(Mn+Fe)比值变化趋势相同;磷铁锂矿被晚期氟磷灰石部分交代,反映伟晶岩演化至热液阶段F、Ca活度增加。表明该矿物可以很好的记录伟晶岩岩浆及热液阶段的演化。     

喜马拉雅东段库曲岩体锂、铍和铌钽稀有金属矿物研究及指示意义

稀有金属矿物记录了花岗伟晶岩成岩成矿的重要信息。喜马拉雅是全球著名的淡色花岗岩带,库曲岩体位于喜马拉雅东段的特提斯喜马拉雅岩系中。本文调查了库曲岩体的二云母花岗岩、白云母花岗岩、电气石花岗岩和花岗伟晶岩,其中,花岗伟晶岩涉及花岗岩的伟晶岩相和独立伟晶岩脉。库曲岩体产出的稀有金属矿物包括锂辉石、锂绿泥石、绿柱石、铌铁矿-钽铁矿、钇铀钽烧绿石和细晶石,它们主要赋存于似文象伟晶岩、石英-钠长石-白云母伟晶岩、块体长石-钠质细晶岩、块体长石-电气石钠质细晶岩、锂辉石-块体长石-细晶岩、白云母花岗岩的伟晶岩相以及电气石花岗岩内。显微镜观察、电子探针和LA-ICP-MS测试结果显示锂辉石具有四种产状,包括粗粒锂辉石自形-半自形晶、细粒锂辉石-石英镶嵌晶、中细粒锂辉石-钾长石-钠长石-云母镶嵌晶以及发育锂绿泥石的粗粒锂辉石,揭示了其形成时复杂的熔流体动荡结晶环境。绿柱石背散射电子图像（BSE）下呈均一结构和不均一结构（蚀变边、不规则分带和补丁分带）,元素替代机制包括通道-八面体替代、通道-四面体替代以及通道中碱金属阳离子间的置换。铌铁矿族矿物包括原生、蚀变边和不规则分带结构,部分被钇铀钽烧绿石和细晶石交代。与原生铌铁矿相比,蚀变边和不规则分带铌铁矿族矿物总体上富钽贫锰,显示了结晶分异、过冷却引起的过饱和以及流体作用。根据稀有金属矿物揭示的成因信息,独立伟晶岩脉（似文象伟晶岩）、白云母花岗岩的伟晶岩相和电气石花岗岩在岩浆分异程度、经历的演化过程、以及流体活动方面存在差异,很可能是不同期次岩浆活动的产物。库曲岩体绿柱石的Rb和Zn含量、以及铌铁矿族矿物的Sc₂O₃、SiO₂和PbO含量,与已有指示标志存在相关性,作为潜在指示标志仍需开展更多的研究工作。综合含锂辉石伟晶岩的产出、岩浆分异演化程度、多期花岗质岩浆活动、复杂的流体作用以及所属锂丰度高值区等因素,库曲岩体是喜马拉雅东段找锂的有利地段。     

Controls on the geochemistry of rare earth elements along a groundwater flow path in the Carrizo Sand aquifer,Texas, USA

Groundwater samples were collected along a groundwater flow path in the Carrizo Sand aquifer in south Texas, USA. Field measurements that included pH, specific conductivity, temperature, dissolved oxygen (DO), oxidation–reduction potentials (Eh in mV), alkalinity, iron speciation, and H₂S concentrations were also conducted on site. The geochemistry (i.e., concentrations, shale-normalized patterns, and speciation) of dissolved rare element elements (REEs) in the Carrizo groundwaters are described as a function of distance along a flow path. Eh and other redox indicators (i.e., DO, Fe speciation, H₂S, U, and Re) indicate that redox conditions change along the flow path in the Carrizo Sand aquifer. Within the region of the aquifer proximal to the recharge zone, groundwaters exhibit both highly oxidizing and localized mildly reducing conditions. However, from roughly 10 km to the discharge zone, groundwaters are reducing and exhibit a progressive decrease in redox conditions. Dissolved REE geochemical behavior exhibits regular variations along the groundwater flow path in the Carrizo Sand aquifer. The changes in REE concentrations, shale-normalized patterns, and speciation indicate that REEs are not conservative tracers. With flow down-gradient, redox conditions, pH and solution composite, and adsorption modify groundwater REE concentrations, fractionation patterns, and speciation.     

The behavior of trace elements during the chemical evolution of the H2O-, B-, and F-rich granite–pegmatite–hydrothermal system at Ehrenfriedersdorf, Germany: a SXRF study of melt and fluid inclusions

Detailed melt and fluid inclusion studies in quartz hosts from the Variscan Ehrenfriedersdorf complex revealed that ongoing fractional crystallization of the highly evolved H₂O-, B-, and F-rich granite magma produced a pegmatite melt, which started to separate into two immiscible phases at about 720°C, 100 MPa. With cooling and further chemical evolution, the immiscibilty field expanded. Two conjugate melts, a peraluminous one and a peralkaline one, coexisted down to temperatures of about 490°C. Additionally, high-salinity brine exsolved throughout the pegmatitic stage, along with low-density vapor. Towards lower temperatures, a hydrothermal system gradually developed. Boiling processes occurred between 450 and 400°C, increasing the salinities of hydrothermal fluids at this stage. Below, the late hydrothermal stage is dominated by low-salinity fluids. Using a combination of synchrotron radiation-induced X-ray fluorescence analysis and Raman spectroscopy, the concentration of trace elements (Mn, Fe, Zn, As, Sb, Rb, Cs, Sr, Zr, Nb, Ta, Ag, Sn, Ta, W, rare earth elements (REE), and Cu) was determined in 52 melt and 8 fluid inclusions that are representative of distinct stages from 720°C down to 380°C. Homogenization temperatures and water contents of both melt and fluid inclusions are used to estimate trapping temperatures, thus revealing the evolutionary stage during the process. Trace elements are partitioned in different proportions between the two pegmatite melts, high-salinity brines and exsolving vapors. Concentrations are strongly shifted by co ncomitant crystallization and precipitation of ore-forming minerals. For example, pegmatite melts at the initial stage (700°C) have about 1,600 ppm of Sn. Concentrations in both melts decrease towards lower temperatures due to the crystallization of cassiterite between 650 and 550°C. Tin is preferentially fractionated into the peralkaline melt by a factor of 2–3. While the last pegmatite melts are low in Sn (64 ppm at 500°C), early hydrothermal fluids become again enriched with about 800 ppm of Sn at the boiling stage. A sudden drop in late hydrothermal fluids (23 ppm of Sn at 370°C) results from precipitation of another cassiterite generation between 400 and 370°C. Zinc concentrations in peraluminous melts are low (some tens of parts per million) and are not correlated with temperature. In coexisting peralkaline melts and high-T brines, they are higher by a factor of 2–3. Zinc continuously increases in hydrothermal fluids (3,000 ppm at 400°C), where the precipitation of sphalerite starts. The main removal of Zn from the fluid system occurs at lower temperatures. Similarly, melt and fluid inclusion concentrations of many other trace elements directly reflect the crystallization and precipitation history of minerals at distinctive temperatures or temperature windows.     

Chemical composition and species attribution of tourmalines from a rare-metal pegmatite vein with scapolite, Sangilen Upland, Tuva

A detailed study of the chemical composition and substitutions in calcium tourmalines from a scapolite-bearing rare-metal pegmatite vein from the Sol’bel’der River basin has shown that their species attribution is determined by occupancy of octahedral site Y. The composition of the yellow tourmaline most abundant in the central part of the pegmatite bodyis rather constant and characterized by the ideal formula Ca(Mg₂Li)Al₆(Si₆O₁₈)(BO₃)₃(OH)₃F. Variations in the chemical composition of zonal tourmaline crystals from the contact part of the pegmatite are controlled by abrupt change in the chemical medium during their formation. The yellow cores of these crystals are close in composition to tourmaline from the central part of the pegmatite vein. The Mg content abruptly decreases toward the crystal margin: Mg²⁺ → Fe²⁺, 2Mg²⁺ → Li⁺ + Al³⁺, and Mg²⁺ + OH → Al³⁺ + O²⁻. The composition of dark green marginal zones in tourmaline is characterized by the ideal formula Ca(Al_1.5Li_1.5)Al₆(Si₆O₁₈)(BO₃)₃ (OH₂O)(F). The results indicate specific formation conditions of pegmatite. The crystallochemical formulas of the studied tourmalines allow us to regard them as new mineral species in the tourmaline group.     

Controls of fluid chemistry and complexation on rare-earth element contents of anhydrite from the Pacmanus subseafloor hydrothermal system,Manus Basin,Papua New Guinea

Ocean Drilling Program (ODP) leg 193 successfully drilled four deep holes (126 to 386 m) into basement underlying the active dacite-hosted Pacmanus hydrothermal field in the eastern Manus Basin. Anhydrite is abundant in the drill core material, filling veins and vesicles, cementing breccias, and occasionally replacing igneous material. We report rare-earth element (REE) contents of anhydrite from a site of diffuse venting (Site 1188) which show extreme variability, in terms of both absolute concentrations (e.g., 0.08–28.3 ppm Nd) and pattern shape (La_N/Sm_N=0.08–3.78, Sm_N/Yb_N=0.48–23.1, Eu/Eu*=0.59–6.1). The range of REE patterns in anhydrite includes enrichments in the middle and heavy REEs and variable Eu anomalies. The patterns differ markedly from those of anhydrite recovered during ODP Leg 158 from the TAG hydrothermal system at the Mid-Atlantic Ridge which display uniform LREE-enriched patterns with positive Eu anomalies, very similar to TAG vent fluid patterns. As the system is active, the host-rock composition is uniform, and the anhydrite veins appear to relate to the same hydrothermal stage, we can rule out predominant host-rock and transport control. Instead, we propose that the variation in REE content reflects waxing and waning input of magmatic volatiles (HF, SO₂) and variable complexation of REEs in the fluids. REE speciation calculations suggest that increased fluoride and possibly sulfate concentrations at Pacmanus may affect REE complexation in fluids, whereas at TAG only chloride and hydroxide complexes play a significant role. The majority of the anhydrites do not show positive Eu anomalies, suggesting that the fluids were more oxidizing than in typical mid-ocean ridge hydrothermal systems. We use other hydrothermal fluids from the Manus Basin (Vienna Woods and Desmos), which bracket the Pacmanus fluids in terms of acidity and ligand concentrations, to examine the dependence of REE complexation on fluid composition. Geochemical modeling reveals that under the prevailing conditions at Pacmanus (pH~3.5, T=250–300 °C), Eu oxidation state and the relative importance of fluoride versus chloride complexing are very sensitive to small variations in oxygen fugacity, temperature, and pH. Patterns with extreme mid-REE enrichment may reflect speciation effects (free-ion abundance) coupled with crystal chemical control. We conclude that the great variability in REE concentrations and pattern shape is likely due to variable fluid composition and REE complexation in the fluids. Editorial handling: L. Meinert     

Changes in tourmaline composition during magmatic and hydrothermal processes leading to tin-ore deposition: The Cornubian Batholith,SW England

To investigate the potential of tourmaline as a geochemical monitor, a comprehensive dataset on major, minor and trace element concentrations as well as Fe³⁺/ΣFe ratios of tourmaline is presented. The dataset includes samples from five plutonic complexes related to diverse magmatic to hydrothermal stages of the Cornubian Batholith (SW England). Tourmaline composition found in barren and cassiterite-bearing samples include all three primary tourmaline groups and tourmaline species with the general endmembers schorl, dravite, elbaite, uvite, feruvite, foitite and Mg-foitite.Based on textures and compositions, it is possible to distinguish not only between late-magmatic and hydrothermal tourmaline, but also between several formation stages. Hence, tourmaline monitors late-magmatic processes and the partitioning of elements during exsolution of an aqueous phase. For example, in hydrothermal tourmaline Sn is strongly enriched, while Ti, Cr, V and Sc are depleted compared to late-magmatic tourmaline of the same sample. Several tourmaline generations that precipitated from magmatic fluids can be distinguished with differing major and minor elements and REE patterns depending on the composition of the melt from which they were expelled from. Strongly zoned tourmaline allows for unraveling the hydrothermal history of a distinct location including ore precipitation. The precipitation of SnO₂ in the study area was probably caused by mixing between acidic, reduced, Sn-bearing magmatic fluids and oxidized meteoric fluids, which is in agreement with London and Manning (1995) and Williamson et al. (2000). Hence, the ability of tourmaline composition to monitor changes in Sn concentration and redox conditions in hydrothermal fluids has potential as an exploration tool.     

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素“四分组效应”及其意义

新疆阿尔泰可可托海3号伟晶岩脉磷灰石矿物中稀土元素（REE）和其他微量元素的ICP－MS分析结果表明，Y／Ho,Zr/Hf和Nb/Ta明显偏离球粒陨石中对应的比值，并存在显著的REE“四分组效应”，REE“四分组效应”量化特征参数TE3，4主要与Y／Ho,Nb/Ta分异程度有关，与δEu负异常演化程度相一致，锰铝榴石也呈现REE“四分组效应”和Y／Ho,Nb/Ta显著分异，指示REE“四分组效应”是形成伟晶岩熔体的一个基本特征，并不是由富LREE矿物（如独居石）和富HREE矿物（如四榴子石）结晶引起的残余熔体REE含量的异常变化，其机制可能是富F，B和P的过铝质窝本与含水流体间相互作用，REE在流体相／熔体相的分配受温度，压力和流体相组成复合控制的综合结果。     

Trace element and Nd isotope analyses of apatite in granitoids and metamorphosed granitoids from the eastern Central Asian Orogenic Belt: Implications for petrogenesis and post-magmatic alteration

We present in situ trace element and Nd isotopic data of apatites from metamorphosed and metasomatized (i.e., altered) and unaltered granitoids in the Songnen and Jiamusi massifs in the eastern Central Asian Orogenic Belt, with the aim of fingerprinting granitoid petrogenesis, including both the magmatic and post-magmatic evolution processes. Apatites from altered granitoids (AG) and unaltered granitoids (UG) are characterized by distinct textures and geochemical compositions. Apatites from AG have irregular rim overgrowths and complex internal textures, along with low contents of rare earth elements (REEs), suggesting the re-precipitation of apatite during epidote crystallization and/or leaching of REEs from apatite by metasomatic fluids. ε_Nd(t) values of the these apatites are decoupled from zircon ε_Hf(t) values for most samples, which can be attributed to the higher mobility of Nd as compared to Sm in certain fluids. Apatites from UG are of igneous origin based on their homogeneous or concentric zoned textures and coupled Nd-Hf isotopic compositions. Trace element variations in igneous apatite are controlled primarily by the geochemical composition of the parental melt, fractional crystallization of other REE-bearing minerals, and changes in partition coefficients. Sr contents and Eu/Eu* values of apatites from UG correlate with whole-rock Sr and SiO₂ contents, highlighting the effects of plagioclase fractionation during magma evolution. Apatites from UG can be subdivided into four groups based on REE contents. Group 1 apatites have REE patterns similar to the host granitoids, but are slightly enriched in middle REEs, reflecting the influence of the parental melt composition and REE partitioning. Group 2 apatites exhibit strong light REE depletions, whereas Group 3 apatites are depleted in middle and heavy REEs, indicative of the crystallization of epidote-group minerals and hornblende before and/or during apatite crystallization, respectively. Group 4 apatites are depleted in heavy REEs, but enriched in Sr, which are features of adakites. Some unusual geochemical features of the apatites, including the REE patterns, Sr contents, Eu anomalies, and Nd isotopic compositions, indicate that inherited apatites are likely to retain the geochemical features of their parental magmas, and thus provide a record of small-scale crustal assimilation during magma evolution that is not evident from the whole-rock geochemistry.     

Genesis of yellow manganese-rich elbaite from the Canary mining area,Lundazi, Zambia

The most important source of yellow gem elbaite is the Canary mining area in the Lundazi District of eastern Zambia. The tourmaline has been mined since 1983 from both pegmatite and eluvial/alluvial deposits, in colors typically ranging from yellow-green to yellow to orange and brown; much of the orange-to-brown material is heated to attain a ‘golden’ or ‘canary’ yellow color. The elbaite is Mn-rich (up to 9.18 wt% MnO documented in the literature) and contains small amounts of Ti and little or no Fe. The distinctive composition of this tourmaline is probably the result of the early crystallization of abundant schorl from an unusual B-rich, Li-poor pegmatite melt, which depleted Fe while conserving Mn until the late-stage crystallization of gem pockets. The simple mineralogy of the pegmatite consists of feldspars, quartz, and tourmaline; the lack of micas, phosphates, or Li minerals, and the presence of very little garnet, allowed Mn to fractionate to high levels during pegmatite crystallization. The presence of abundant gem tourmaline in a Li-poor pegmatite is highly unusual.     

Geochemistry and origin of rare earth elements (REEs) in the Shengli River oil shale, northern Tibet, China

The Shengli River-Changshe Mountain oil shale zone, located in the North Qiangtang depression, northern Tibet plateau, represents a potentially large marine oil shale resource in China. Twenty-eight samples including oil shale, micritic limestone and marl were collected from the Shengli River area to determine the contents and distribution patterns of rare earth elements (REEs) in marine oil shale. Oil shale samples from the Shengli River area have high ash yield (61.86–67.48%) and TOC content (8.02–13.67%) with low total sulfur (S_t,d) content (0.76–1.39%) and intermediate shale oil content (3.60–16.30%). The total rare earth element (ΣREE) content in oil shale samples is notably depleted (46.79–67.90 μg/g), approximately one third of the mean value of the North American Shale Composite (NASC), and lower than that of world-wide black shales and Chinese coals, but higher than that of world-wide coals and micritic limestone samples (29.21 μg/g) from the Shengli River area. The oil shale samples from the Shengli River area exhibit shale-like Chondrite or NASC-normalized REE patterns similar to those of micritic limestone and marl samples from this area, indicating that REEs of these different lithological samples may have been derived from a similar terrigenous source.REE contents of oil shale samples are highly positive correlated with ash yield and show a positive correlation with Fe and a weakly positive correlation with organic sulfur, and the vertical variations of REEs mainly follow those of Si, Al, K and Ti. All these facts indicate that the REE contents in oil shale seams are mainly controlled by clay minerals and, to a lesser extent, by pyrite, as well as partly associated with oil shale organic constituents. Rare earth elements in the Shengli River oil shale have originated from two sources: a felsic volcanic rock source and a clastic or/and limestone source.     

辽西兴城地区首山南花岗伟晶岩地质特征及其地质意义

通过对辽西兴城地区首山南花岗伟晶岩进行岩相学、锆石LA-ICP-MS U-Pb年代学及岩石地球化学的研究,揭示其形成年代、与其围岩成因关系以及其形成环境。研究结果表明:花岗伟晶岩的形成时代为(2 486±8)Ma(NSWD=3.1)。锆石CL图像形态特征以及微量元素特征显示,伟晶岩锆石属于岩浆成因但受到热液改造。首山南伟晶岩同绥中花岗岩的黑云母二长花岗岩作对比,在主量元素、微量元素及稀土元素方面表现出与围岩极其相似的特征。伟晶岩样品表现出高硅(SiO_2=77.28%~77.9%)、富碱(K_2O+Na_2O=5.5%~5.69%)、过铝质(A/CNK=2.53~2.54)特征,在SiO_2-K_2O判别图解上属钾玄系列。稀土元素总量低(33.1×10~(-6)~41.01×10~(-6))。球粒陨石标准化配分模式显示出LREE相对富集,HREE相对亏损;(La/Yb)_N=16.33~32.41,平均值为24.37;δEu值为0.92~1.11,表现为无异常至轻微正异常。这些地化特征总和表明首山南伟晶岩是黑云母二长花岗岩高度演化的结果。结合前人Hf研究结果,认为伟晶岩及其母岩形成均与底板垫托作用有关。