Fe-Mn Phosphate Research Articles

Lithium-, Phosphorus-, and Fluorine-Rich Intrusions and the Phosphate Sequence at Segura (Portugal): A Comparison with Other Hyper-Differentiated Magmas

Near the Segura pluton, hyper-differentiated magmas enriched in F, P, and Li migrated through shallowly dipping fractures, which were sub-perpendicular to the schistosity of the host Neoproterozoic to Lower Cambrian metasedimentary series, to form two swarms of low-plunging aplite–pegmatite dykes. The high enrichment factors for the fluxing elements (F, P, and Li) compared with peraluminous granites are of the order of 1.5 to 5 and are a consequence of the extraction of low-viscosity magma from the crystallising melt. With magmatic differentiation, increased P and Li activity yielded the crystallisation of the primary amblygonite–montebrasite series and Fe-Mn phosphates. The high activity of sodium during the formation of the albite–topaz assemblage in pegmatites led to the replacement of the primary phosphates by lacroixite. The influx of external, post-magmatic, and Ca-Sr-rich hydrothermal fluids replaced the initial Li-Na phosphates with phosphates of the goyazite–crandallite series and was followed by apatite formation. Dyke emplacement in metasediments took place nearby the main injection site of the muscovite granite, which plausibly occurred during a late major compression event.

Compositional Variations in Apatite and Petrogenetic Significance: Examples from Peraluminous Granites and Related Pegmatites and Hydrothermal Veins from the Central Iberian Zone (Spain and Portugal)

Apatite can be used as an archive of processes occurring during the evolution of granitic magmas and as a pegmatite exploration tool. With this aim, a detailed compositional study of apatite was performed on different Variscan granites, pegmatites and quartz veins from the Central Iberian Zone. Manganese in granitic apatite increases with increasing evolution degree. Such Mn increase would not be related to changes in the fO2 during evolution but rather to a higher proportion of Mn in residual melts, joined to an increase in SiO2 content and peraluminosity. In the case of pegmatitic apatite, the fO2 and the polymerization degree of the melts seem not to have influenced the Mn and Fe contents but the higher availability of these transition elements and/or the lack of minerals competing for them. The subrounded Fe-Mn phosphate nodules, where apatite often occurs in P-rich pegmatites and P-rich quartz dykes, probably crystallized from a P-rich melt exsolved from the pegmatitic melt and where Fe, Mn and Cl would partition. The low Mn and Fe contents in the apatite from the quartz veins may be attributed either to the low availability of these elements in the late hydrothermal fluids derived from the granitic and pegmatitic melts, or to a high fO2. The Rare Earth Elements, Sr and Y are the main trace elements of the studied apatites. The REE contents of apatite decrease with the evolution of their hosting rocks. The REE patterns show in general strong tetrad effects that are probably not related to the fluids’ activity in the system. On the contrary, the fluids likely drive the non-CHARAC behavior of apatite from the most evolved granitic and pegmatitic units. Low fO2 conditions seem to be related to strong Eu anomalies observed for most of the apatites associated with different granitic units, barren and P-rich pegmatites. The positive Eu anomalies in some apatites from leucogranites and Li-rich pegmatites could reflect their early character, prior to the crystallization of feldspars. The increase in the Sr content in apatite from Li-rich pegmatites and B-P±F-rich leucogranites could be related to problems in accommodating this element in the albite structure, favoring its incorporation into apatite. The triangular plots ΣREE-Sr-Y and U–Th–Pb of apatites, as well as the Eu anomaly versus the TE1,3 diagram, seem to be potentially good as petrogenetic indicators, mainly for pegmatites and, to a lesser extent, for granites from the CIZ.

Garnet as Indicator of Pegmatite Evolution: The Case Study of Pegmatites from the Oxford Pegmatite Field (Maine, USA)

Almandine-spessartine garnets, from the Oxford County pegmatites and the Palermo No. 1 pegmatite, record significant compositional variations according to the degree of evolution of their hosting rock. Garnets from the most fractionated pegmatites (Mt. Mica, Berry-Havey, and Emmons) show the highest Mn, Nb, Ta, Zr, and Hf values, followed by those from the intermediate grade pegmatites (Palermo No. 1) and, finally, garnets from the barren pegmatites show the lowest values (Perham and Stop-35). Iron, Ca, and Mg contents follow an inverse order, with the highest contents in the latter pegmatites. Major element zoning shows increasing Mn values from core to rim in most garnet samples, while trace element zoning is not systematic except for some crystals which show a core to rim depletion for most of these elements. Chondrite normalized HREE (Heavy Rare Earth Elements) spectra show positive slopes for garnets from barren pegmatites, both positive and negative slopes for those associated with the intermediate pegmatite, and negative or flat slopes in garnets from the highly fractionated pegmatites. Ion exchange mechanisms, including Fe2+−1Mn2+1, (Fe2+, Mn2+)−1Si−1Li1P1; and, (Y, Ho3+)2(vac)1(Fe2+, Mn2+)−3, could explain most of the compositional variations observed in these garnets. These compositional variations are the reflection of the composition of the pegmatitic magma (barren pegmatites originate from a more ferromagnesian magma than fractionated pegmatites); and of the coexisting mineral phases competing with garnets to host certain chemical elements, such as biotite, schorl, plagioclase, apatite, Fe-Mn phosphates, Nb-Ta oxides, zircon, xenotime, and monazite.

Determining the origin of inclusions in garnet: Challenges and new diagnostic criteria

ABSTRACT Permian metapegmatite garnets from the Koralpe region (Eastern Alps, Austria) contain abundant submicrometer- to micrometer-sized inclusions of rutile, corundum, Fe-Mn phosphate, ilmenite, xenotime, zircon, and apatite. Variations in inclusion abundance, phase assemblage, habit, and size define sector and concentric zones in the garnets, tracing low-indexed garnet facets. Zoning resulted from a process occurring at the garnet-melt interface, homogeneous along each facet, but sensitive to its crystallographic plane. Furthermore, inclusion and host lattices interacted, generating host-inclusion crystallographic orientation relationships (CORs). These phenomena exclude inclusion formation via overgrowth of pre-existing phases, infiltration of fluids/melts, or dissolution-reprecipitation. Magmatic garnet rims contain rutile needles up to 100 μm long, showing an interface-dependent shape-preferred orientation (SPO) that cannot be explained by exsolution models. Furthermore, the COR distribution for needles is unique, and implies large 3D lattice mismatches. These phenomena suggest that needles originated via oriented heterogeneous nucleation at the garnet interface and subsequent simultaneous growth of both phases. The origin of equant inclusions in core domains is less clear. With some assumptions, integrated compositions remain compatible with closed system exsolution or open system precipitation (OSP) involving divalent cation loss. Still, the oriented interface nucleation hypothesis seems to better explain the fact that the frequency of rutile-garnet CORs varies strongly not only between cores and rims but also between garnet core domains. Inclusion formation by oriented interface nucleation and simultaneous growth can explain many observations commonly attributed to exsolution, making distinguishing between these two mechanisms a challenge. We suggest interface-dependence of SPOs and COR frequencies as criteria for identifying inclusion formation via oriented nucleation at an interface and subsequent simultaneous growth.

Phosphate mineral associations from the Tres Arroyos aplite-pegmatites (Badajoz, Spain): Petrography, mineral chemistry, and petrogenetic implications

ABSTRACTIn the Tres Arroyos granite-pegmatite system (Badajoz, Spain) a zoned aplite-pegmatite field occurs, with poorly evolved, intermediate, and Li-rich dikes intruded into metasediments, close to the contact with the Nisa-Alburquerque granitic batholith. A large variety of Fe-Mn phosphate minerals occur in the poorly evolved aplite-pegmatites; Al-phosphates occur mainly in the intermediate and Li-rich dikes. The Fe/(Fe + Mn) ratio of the Fe-Mn phosphates is the highest reported for aplite-pegmatite fields in the Central Iberian Zone, suggesting a low degree of fractionation for the poorly evolved aplite-pegmatites that host these minerals. In contrast, the high F contents observed in crystals of the amblygonite–montebrasite series from the intermediate and Li-rich aplite-pegmatites indicates a higher fractionation degree for these dikes. The relatively common occurrence of phosphate minerals in the three types of aplite-pegmatites from Tres Arroyos attests to a significant availability of P in the pegmatitic melt. In this granite pegmatite system, P first started behaving as a compatible element, thus favoring the crystallization of discrete phosphates, during the crystallization of the poorly evolved aplite-pegmatites. In more fractionated melts, where Fe-Mn-(Mg) contents were extremely depleted, P was still available, allowing the crystallization of the Al-phosphates, mainly of the amblygonite–montebrasite series, in the more evolved intermediate and Li-rich aplite-pegmatites. Subsolidus replacement of the early phosphate phases, such as those of the amblygonite–montebrasite series, by lacroixite, together with the presence of late Ca- and Sr-bearing phosphates such as jahnsite-(CaMnFe), whiteite-(CaFeMg), mitridatite, and goyazite, attest to a high activity of metasomatic fluids in the Tres Arroyos granite-pegmatite system. Consequently, variations in the phosphate mineral associations and in their chemical compositions reflect well the fractional crystallization processes suffered by the pegmatitic melts from the poorly evolved up to the Li-rich dikes, as well as the subsolidus history of the Tres Arroyos system.

Mineralogical Characterization and Preliminary Beneficiation of the Zoro Lithium Project, Manitoba, Canada

The Zoro pegmatite project in east-central Manitoba occurs 20 km east of the historic mining town of Snow Lake. A composite sample (Master Comp) was prepared from three pegmatite zones within Zoro Dyke “D1” including the North, Central, and South Zones for mineralogical analysis and heavy liquid separation (HLS). The mineralogical examination was conducted on a subsample crushed to ca. P80 of 600 μm to determine the overall mineral assemblage, liberation of spodumene, and assess the potential recovery of spodumene by flotation. XRD and QEMSCAN results show that the sample consists of spodumene (10.5%), quartz (29.3%), plagioclase (29.0%), K-feldspars (21.3%), micas (5.1%), tourmaline (2.9%), and Fe-Mn-phosphates (0.1%). Spodumene is well liberated (88%), but also forms complex particles (7%), and middlings with quartz (4%). Liberation of spodumene increases from 81 in the + 600 μm to 95% in the − 106 μm size fraction. Liberation of quartz, feldspars, and micas account for 89%, 94%, and 83%, respectively. Electron probe micro-analyses and LA-ICP-MS showed that the average Li concentration is 3.7% in spodumene, 2196 ppm in micas, 1001 ppm in tourmaline, and 115 ppm in K-feldspars. Thus, spodumene accounts for 96%, micas 2%, Fe-Mn phosphates 1%, and both K-feldspars and tourmaline for < 1% of the total Li in the sample. The mineralogical data indicate the potential to recover spodumene by flotation with minimal Li losses due to other than spodumene carriers. Heavy liquid separation was conducted on the Master Comp which was crushed to − 6.4 mm, while the − 600 μm fraction was removed from this test. The coarse fraction − 6.4 mm/+ 600 μm was subjected to HLS tests with eight heavy liquid-specific gravity cut-points (2.65 to 3.10 g/cm3). HLS indicates that it is possible to produce a high-grade lithium concentrate (close to 6% Li2O) after the rejection of iron silicates with magnetic separation.

Paragenetic relationships, geochemistry and petrogenetic significance of primary Fe[sbnd]Mn phosphates from pegmatites: The case study of Cañada (Salamanca, Spain) and Palermo (New Hampshire, USA) pegmatites

Primary FeMn phosphates from four pegmatites (Cañada, Palermo#1, Palermo#2 and Palermo#11) typical of the beryl-columbite-phosphate subtype have been characterized texturally and geochemically. Most of the common FeMn phosphates (triphylite, sarcopside, ferrisicklerite, wagnerite and wolfeite) are extremely poor in trace elements, with the exception of Zn for all them, Li for sarcopside, and Nb and Ta for wagnerite and wolfeite. Calcium-bearing FeMn phosphates (graftonite and johnsomervilleite) are the richest in trace elements, with contents usually over the mean continental crust for Zn, Y, REE and Pb. Crystal-chemical constraints, combined with paragenetic relationships, geochemical and geological processes, are thought to control the content, distribution and behavior of trace elements in FeMn phosphates. Zinc contents in graftonite and triphylite increase with fractionation, whereas Y, Nb, Ba, REE, U and Pb contents in graftonite decrease. Crystallization of REE-bearing phases, such as xenotime-(Y), strongly affects the REE content of the FeMn phosphates. Recrystallization processes also seem to affect the trace element contents in phosphates. The earliest primary phosphate associations from Cañada and Palermo pegmatites (those containing graftonite), show Y/Ho and Zr/Hf ratios inside or close to the CHARAC (Charge-and-Radius-Controlled) field. This could indicate that such associations crystallized in a magmatic stage without a high H2O activity. Phosphates from the latest associations plot outside the CHARAC field, suggesting that fluid activity became important during the crystallization of these latest associations. Ti-in-biotite, garnet-biotite and triphylite-sarcopside geothermometers have yielded relatively high temperatures of crystallization, between 633 and 386 °C, for the earliest associations (presumably crystallized under magmatic conditions). In contrast, the latest associations, whose crystallization presumably proceeded with a higher H2O activity, are in the range of 281–360 °C.

Geochemistry of primary Fe-Mn phosphates from CaÑada (Spain) and Palermo (USA) pegmatites and petrogenetic implications

Geochemistry of primary Fe-Mn phosphates from CaÑada (Spain) and Palermo (USA) pegmatites and petrogenetic implications

The Mata Azul pegmatitic field, Tocantins/Goiás, central Brazil: geology, genesis and mineralization

In Goias and Tocantins States, Central Brazil, several granitic pegmatites were characterized and grouped for the first time. These pegmatites had been intensely explored by hand in the past, producing mainly gemstone varieties of tourmaline and beryl. Barren, beryl- and tourmaline-bearing pegmatites occur across an area of 2,000 km 2 where they intrude regional metasedimentary rocks and peraluminous granites. K‑feldspar (mostly altered to kaolin), quartz and mica (mainly muscovite) are the major minerals. The main accessory minerals are beryl, tourmaline, garnet, albite, Fe-Mn phosphate aggregates, and trilithionite. The paragneiss surrounding the barren pegmatites was affected by thermal metamorphism and later hydrothermal alteration, producing Ca-silicates, Ti-Nb-Y oxides and sulfides. Leucogranites of the Mata Azul Suite are peraluminous and syn- to post-orogenic with geochemical characteristics of the LCT granite-pegmatite group. LA-ICP-MS U-Pb geochronology in monazite yields an age of 519 ± 2.8 Ma. Additionally, U-Th-Pb chemical dating of uraninite reveals a maximum age between 500 and 560 Ma. These ages, the field relationships, the mineralogy and the geochemical data suggest that the granites of the Mata Azul Suite are the probable sources of the studied pegmatites. The mineral associations and the mineral chemistry are used to define the degree of fractionation of the pegmatites. We propose that the group of studied pegmatites represents a pegmatitic field, called the Mata Azul Suite Pegmatitic Field.

Fosfatos de Fe e Mn primários e secundários em pegmatitos graníticos do Campo Pegmatítico Mata Azul, Jaú do Tocantins, TO, Brasil

No sul do Estado do Tocantins e norte do Estado de Goiás, pegmatitos graníticos estéreis e mineralizados são conhecidos e explorados há muito tempo, mas só recentemente foram caracterizados quanto aos aspectos mineralógicos, composicionais e genéticos e agrupados sob a denominação de Campo Pegmatítico Mata Azul. Em três desses corpos localizados no município de Jaú do Tocantins, com mineralização de berilo, fosfatos de Fe e Mn ocorrem sob a forma de nódulos ou massas centimétricas. Duas associações de fosfatos são diferenciadas. Na primeira delas, hospedada nos pegmatitos São Júlio e Pichorra, foram descritas três fases primárias, identificadas como zwieselita, sarcopsídio e fluorapatita. Processos hidrotermais alteram essas fases, formando rockbridgeíta, uma fase do subgrupo da alluaudita e heterosita. Na segunda associação, presente no pegmatito Fazenda Mesquita, não há sinal de fosfato primário e todas as fases presentes são secundárias. Rockbridgeíta, de cor verde a alaranjada, compõe boa parte do volume das amostras. Fosfosiderita e strengita aparecem como alterações da rockbridgeíta, às vezes preenchendo cavidades nas massas de fosfato. Nas duas associações, óxidos e hidróxidos de Fe e Mn, oriundos da oxidação intempérica, correspondem às últimas fases formadas, podendo constituir crostas que recobrem boa parte dos nódulos e das massas de fosfatos. Em algumas amostras das associações de fosfatos, cristais de uraninita, gahnita, almandina e columbita-(Fe) foram identificados.

Corrigendum to: Phosphate minerals in granitic pegmatites from the Mount Wills District, north-eastern Victoria

Tin- and tantalum-bearing LCT-type granitic pegmatites occur in a 45 km long belt between Eskdale and Mount Wills in north-eastern Victoria. Near Mount Wills, several compositionally zoned rare-element pegmatites contain complex assemblages of primary and secondary phosphate minerals, many of which are rare and previously unrecorded in Victoria. The phosphate assemblages can be divided into Al-rich and Fe–Mn-rich suites, in addition to ubiquitous fluorapatite. The Al-rich phosphate suite includes montebrasite, scorzalite, bertossaite and brazilianite. The Fe‒Mn phosphate suite includes heterosite, phosphoferrite, wolfeite, alluaudite (sp.), arrojadite (sp.) and jahnsite (sp.), derived from the metasomatic alteration of primary triplite. Further hydrothermal alteration of this assemblage has resulted in a secondary suite of strengite, rockbridgeite, phosphosiderite, whiteite, jahnsite and whitmoreite forming in etch cavities and fractures. A Late Silurian age of 420±4 Ma was obtained from one of the dykes via CHIME radiometric dating of monazite, suggesting a similar age for the adjacent Mount Wills Granite, which has not been reliably dated. This highly fractionated, peraluminous granite is presumed to be the source of the rare-element pegmatites based on their close spatial relationship.

Phosphate minerals in granitic pegmatites from the Mount Wills District, north-eastern Victoria

Tin- and tantalum-bearing LCT-type granitic pegmatites occur in a 45 km long belt between Eskdale and Mount Wills in north-eastern Victoria. Near Mount Wills, several compositionally zoned rare-element pegmatites contain complex assemblages of primary and secondary phosphate minerals, many of which are rare and previously unrecorded in Victoria. The phosphate assemblages can be divided into Al-rich and Fe–Mn-rich suites, in addition to ubiquitous fluorapatite. The Al-rich phosphate suite includes montebrasite, scorzalite, bertossaite and brazilianite. The Fe‒Mn phosphate suite includes heterosite, phosphoferrite, wolfeite, alluaudite (sp.), arrojadite (sp.) and jahnsite (sp.), derived from the metasomatic alteration of primary triplite. Further hydrothermal alteration of this assemblage has resulted in a secondary suite of strengite, rockbridgeite, phosphosiderite, whiteite, jahnsite and whitmoreite forming in etch cavities and fractures. A Late Silurian age of 420±4 Ma was obtained from one of the dykes via CHIME radiometric dating of monazite, suggesting a similar age for the adjacent Mount Wills Granite, which has not been reliably dated. This highly fractionated, peraluminous granite is presumed to be the source of the rare-element pegmatites based on their close spatial relationship.

Tourmaline as a petrogenetic monitor of the origin and evolution of the Berry-Havey pegmatite (Maine, U.S.A.)

The Berry-Havey pegmatite (Oxford pegmatite field, Androscoggin County, Maine, U.S.A.), enriched in Li, F, B, Be, and P, is intruded in hornblende-rich amphibolite, with minor biotite or diopside. The pegmatite has a complex internal structure, with four texturally and compositionally different zones that show an increasing degree of evolution inward: wall zone, intermediate zone, core margin, and core zone. The main minerals are quartz, feldspars, Al-micas, tourmaline, with minor Fe-micas, garnet, beryl, amblygonite-montebrasite, Fe-Mn phosphates, and apatite. Tourmaline is present in all zones of the pegmatite, showing different textures: black anhedral crystals in the wall and intermediate zones; black prisms of up to 40 cm in length in the intermediate zone; black tapered prisms, surrounded by a pseudo-graphic intergrowth of quartz or albite with black ± green/bluish tourmaline, and constituting a continuous layer under the core zone; multicolored and “watermelon” zoned crystals in the core zone; and gemmy deep green and color-zoned “watermelon” tourmaline prisms, up to 15 cm length, inside the pockets. A complete chemical evolution from Mg-rich schorl in the wall zone to elbaite with an important deprotonation in the pockets inside the core zone is observed. The most plausible exchange vectors for this chemical evolution are FeMg −1 , Y Al W O[ Y R 2+W (OH)] −1 and Al[X] X (R 2+ Na) −1 (where R 2+ = Fe 2+ +Mg 2+ +Mn 2+ +Zn 2+ ), for the tourmalines from the wall and intermediate zones. In the core margin, tourmaline composition evolves from schorl toward Li-rich species through the substitution ( Y Al Y Li Y R 2+ −2 ). Later, during the crystallization of the core zone, this exchange vector combined with the substitution ([X] Y Al 0.5 X Na −1 Y Li −0.5 ). Finally, the gemmy tourmalines from the pockets show a deprotonation related to the exchange vector Y Al W O 2 Y Li −1 W (OH) −2 and may be classified as darrellhenryite. These substitutions may reflect an increase in oxygen fugacity and a decrease in Li and F related to the crystallization of lepidolite and amblygonite-montebrasite in the core zone adjacent to or within the pockets. The crystallization of these minerals would reduce the availability of Li and F for the very latest tourmaline crystals, growing inside the pockets, where the deprotonation becomes important. Chemical and textural variation in tourmaline is consistent with a fractional crystallization process for the internal evolution of the Berry-Havey pegmatite. Crystallization of the tourmaline layer under the core zone may be related to the exsolution of the fluid phase implied in the formation of pockets.

PEGMATITIC BERYL AS INDICATOR OF MELT EVOLUTION: EXAMPLE FROM THE VELASCO DISTRICT, PAMPEANA PEGMATITE PROVINCE, ARGENTINA, AND REVIEW OF WORLDWIDE OCCURRENCES

Fil: Sardi, Fernando Guillermo. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Tucuman. Instituto Superior de Correlacion Geologica; Argentina

In vitro and in vivo corrosion properties of new iron-manganese alloys designed for cardiovascular applications.

The principle of biodegradation for the production of temporary implant materials (e.g. stents) plays an important role in the treatment of congenital heart defects. In the last decade several attempts have been made with different alloy materials-mainly based on iron and magnesium. None of the currently available materials in this field have demonstrated satisfying results and have therefore not found entry into broad clinical practice. While magnesium or magnesium alloy systems corrode too fast, the corrosion rate of pure iron-stents is too slow for cardiovascular applications. In the last years FeMn alloy systems were developed with the idea that galvanic effects, caused by different electrochemical properties of Fe and Mn, would increase the corrosion rate. In vitro tests with alloys containing up to 30% Mn showed promising results in terms of biocompatibility. This study deals with the development of new FeMn alloy systems with lower Mn concentrations (FeMn 0.5 wt %, FeMn 2.7 wt %, FeMn 6.9 wt %) to avoid Mn toxicity. Our results show, that these alloys exhibit good mechanical features as well as suitable in vitro biocompatibility and corrosion properties. In contrast, the evaluation of these alloys in a mouse model led to unexpected results-even after 9 months no significant corrosion was detectable. Preliminary SEM investigations showed that passivation layers (FeMn phosphates) might be the reason for corrosion resistance. If this can be proved in further experiments, strategies to prevent or dissolve those layers need to be developed to expedite the in vivo corrosion of FeMn alloys.

ON THE GEOCHEMICAL CHARACTER OF PRIMARY Fe-Mn PHOSPHATES BELONGING TO THE TRIPHYLITE-LITHIOPHILITE, GRAFTONITE-BEUSITE, AND TRIPLITE-ZWIESELITE SERIES: FIRST RESULTS AND IMPLICATIONS FOR PEGMATITE PETROGENESIS

Iron-Mn phosphate minerals are common accessory phases in pegmatites, some granites and, rarely, in some hydrothermal quartz-rich dikes. A comprehensive textural and geochemical characterization of primary phosphate minerals belonging to the triplite-zwieselite, triphylite-lithiophilite, and graftonite-beusite series has been done. Chemical data, including major and trace elements contents, have been obtained by electron microprobe (EMP) and laser-ablation inductively coupled-plasma mass-spectrometry (LA-ICP-MS) techniques. The concentration of trace elements shows important differences for the three series of primary Fe-Mn phosphate minerals. Members of the triphylite-lithiophilite series are the poorest in trace elements, with Zn as the only element that may occur in important amounts. This low concentration in trace elements could be related to structural constrains. Graftonite-beusite members are the richest in REE, most probably due to the substitution of Ca by the rare earths. Members of the triplite-zwieselite series are the richest in certain HFSE, such as Nb and Ta. There is an important difference in the shape of multi-element diagrams of triplite-zwieselite samples associated with pegmatites, all of them showing a strong negative Eu anomaly, and those of samples from a quartz-rich dike, with no Eu anomaly. This difference is interpreted as the result of the Eu fractionation in pegmatites due to the previous crystallization of plagioclase. No correlation has been found between the Fe/(Fe+Mn) ratio and the different trace element contents of the primary phosphate series. Moreover, the concentrations of trace elements are not simply related to the pegmatite type, its paragenesis or its geological setting. Further investigation of mineral association, textural relationships, partition coefficients, and geology and history of crystallization of the pegmatitic bodies appears necessary in order to determine the factors controlling the variability in the trace elements content for the different primary phosphate series.

Phosphate nodules containing two distinct assemblages in the Cema granitic pegmatite, San Luis province, Argentina: Paragenesis, composition and significance

Nodules of Fe–Mn phosphates are common in the outer core zone of the Cema pegmatite, San Luis Range, Argentina. Two different complex phosphates associations have been distinguished in these nodules. One of them is beusite–wyllieite–sicklerite-rich (BWS), with varulite and staněkite among the main products of replacement, Fe/(Fe + Mn) values between 0.46 and 0.48 for sicklerite, and MgO values up to 2.14 wt%. The other association is lithiophilite–sicklerite-rich (LS), with varulite and hureaulite among the main secondary products, lower Fe/(Fe + Mn) values, in the range 0.37–0.39 for lithiophilite, and lower MgO contents, invariably below 1 wt%. According to the mineral-chemistry data of these Fe–Mn phosphate nodules, a higher temperature of crystallization is proposed for the BWS association compared to the LS one. The Mn enrichment observed in these phosphates, in a pegmatite that is not highly fractionated, could be explained as a result of the early crystallization of other Fe–(Mg–Mn)-rich minerals, such as schorl, in the border and wall zones of this pegmatite. The crystallization of this silicate would have strongly depleted the activity of Fe in the remaining pegmatite-forming melt.

From granite to highly evolved pegmatite: A case study of the Pinilla de Fermoselle granite–pegmatite system (Zamora, Spain)

The Pinilla de Fermoselle pegmatite is a cap-like body with an asymmetrical vertical zoning, from a granitic facies at the bottom to the upper contact with the metamorphic country-rocks. The granite grades imperceptibly into the pegmatite, which includes three main zones with different degrees of enrichment in Li+F+B (±P, Rb, Cs, Be, Sn). The essential minerals are quartz, feldspar, Al-micas from the muscovite–lepidolite series, Fe-micas (biotite and zinnwaldite), tourmaline (schorl–elbaite–rossmanite) and Fe–Mn phosphates. Apatite, beryl, cassiterite and cookeite are the most significant accessory minerals.The trace elements Li, Be and Sr show similar trends in feldspar, micas and tourmaline, with an increase in the Li and Be contents and a decrease in Sr from the granite to the most evolved pegmatitic zone. Similar trends are shown by Rb, Cs and Ba for micas and K-feldspar, Rb and Cs increasing gradually from the granite to most evolved pegmatitic zones, simultaneously to the decrease of Ba. In tourmaline Nb and Ta contents increase upwards whereas Zn contents decrease in the same way. The Mn contents increase until intermediate degrees of evolution, and decrease again in the pinkish elbaite.Combined field, petrographic and geochemical data are consistent with a fractional crystallization model from a granitic melt, with a clear petrogenetic relationship between the underlying peraluminous granite and the pegmatite body. K-feldspar and, particularly, micas and tourmaline appear as good geochemical monitors using trace elements such as Li, Rb, Be, Sr and Ba, which offer intriguing insights into the petrogenesis of pegmatites.

Fe-Mn phosphate associations as indicators of the magmatic-hydrothermal and supergene evolution of the Jálama batholith in the Navasfrías Sn-W District, Salamanca, Spain

AbstractThe residual melts that remained after the consolidation of the Jálama batholith crystallized to form a group of intra-granitic pegmatite dykes, which are hosted by its outermost facies (the External Unit), and the most evolved residual melts migrated through fractures to form the Cruz del Rayo field of pegmatite dykes, which are hosted by pre-Ordovician low-grade metasedimentary rocks. The increasing activity of phosphorus as magmatic differentiation took place led to the crystallization of primary phosphates, including members of the triplite–zwieselite and the amblygonite–montebrasite series. A strong albitization of the granitic and pegmatite rocks led to the replacement of the primary assemblage by other phosphates such as alluaudite. The influx of post-magmatic hydrothermal fluids, produced quartz veins, gave rise to the crystallizationof ore minerals and triplite, and altered the granites, aplites and pegmatites, replacing some of the phosphate minerals and feldspars and depositing goyazite, montebrasite and childrenite–eosphorite. The interaction of the residual hydrothermal fluids with those from the surrounding metamorphic rocks during later alteration events resulted in the influx of large quantities of Ca and Mg, and produced phosphate assemblages enriched in those elements. Finally, late goyazite, hydroxylapatite and an unidentified Fe-rich phosphate were formed as a result of supergene alterationby percolating meteoric waters, which added Ca, Sr and other elements into the system, and increased fO2.

Chemical variations and significance of phosphates from the Fregeneda-Almendra pegmatite field, Central Iberian Zone (Spain and Portugal)

Granitic pegmatites are widespread within a schist-metagreywacke complex in the Fregeneda-Almendra area (Central Iberian Zone). They intrude pre-Ordovician metasedimentary rocks and show a zonal distribution relative to the Meda-Penedono-Lumbrales granitic complex, from barren bodies to those enriched in Li, F, Sn, Nb>Ta, P and Be. Based on mineralogical criteria, these pegmatites are classified into three main categories: barren, intermediate and rare-element pegmatites, with each type including various subtypes. Phosphates are present in many pegmatites that usually occur as fine-grained accessory minerals. The most complex association of such minerals includes numerous Fe–Mn phosphates that occur in intermediate pegmatites. Al-phosphates are characteristic of Li-rich pegmatites. Electron microprobe analyses of representative phosphates reflect compositional differences depending on the pegmatite type. The Fe/(Fe+Mn) ratio of phosphates tends to decrease as the evolution degree of the pegmatites increases.