An experimental study of partitioning of fluorine between K-richterite,apatite, phlogopite,and melt at 20 kbar

Phase relations have been determined at 20 kbar and primarily under suprasolidus conditions in the Fe−Ti-free F-bearing K-richterite—phlogopite and K-richterite—apatite systems in order to assess the partitioning of F among phlogopite, K-richterite, apatite, and melt under upper-mantle conditions. Both systems are pseudoternary because they contain forsterite, enstatite and a diopside-rich clinopyroxene from the breakdown of the mica and K-richterite. The F-bearing K-richterite systems have lower minimum melting temperatures than the F-bearing phlogopite —apatite system at the same pressure. However in the systems studied, F in phlogopite appears the most effective component in altering minimum liquid compositions whereas comparison between the present study and previous systems suggests that the presence of P₂O₅ during melting may result in more K-enriched melts. Variations in the compositions of the F-bearing phases are primarily controlled by the bulk compositions of the end-member minerals and by temperature, although buffering by non-F bearing minerals (e.g. clinopyroxene) may be effective. Distribution coefficients (as wt% ratios) between F-bearing minerals and coexisting liquids have been determined as functions of bulk composition and temperature for products of experiments. Distribution coefficients between K-richterite—liquid, apatite—liquid, and phlogopite—liquid are ≥1 to slightly <1 for most bulk compositions, indicating thatF is generally a compatible element. This conclusion is in agreement with the sequence ofF distribution for similar phases in ultrapotassic rocks. These results preclude F-bearing mineral reservoirs in the mantle, at depths corresponding to 20 kbar, being capable of producing F-enrichment in ultrapotassic magmas, or being effective in redox melting processes. Editorial responsibility: K. Hodges     

The effect of fluorine on phase relationships in the system KAlSiO4-Mg2SiO4-SiO2 at 28 kbar and the solution mechanism of fluorine in silicate melts

Phase relationships in the system kalsilite-forsterite-quartz with fluorine added by direct substitution for oxygen were examined at 28 kb. A large liquidus field for fluorphlogopite exists with approx. 4 wt% F added to the system and the thermal stability of phlogopite is increased by 300° C relative to the water saturated system. Fluorine expands the phase volume of enstatite relative to forsterite so that the peritectic point PHL+EN+FO+L, a model for melting of a phlogopite harzburgite, lies in the silica-undersaturated field. Experimental phlogopites have excess Si which correlates with F content and are Al-deficient. The high Si contents indicate solid solution with an end member intermediate between tri- and di-octahedral micas. Glasses with compositions analogous to partial melts from phlogopite harzburgite were examined by infrared spectroscopy in the mid- and far-IR regions. Results show that fluorine polymerises the melt by bonding with all the network modifying cations K, Mg and Al. At higher F contents, but still less than 1 wt%, tetrahedral KAlO₂-groups are complexed by fluorine and removed from the aluminosilicate network simultaneously polymerising and increasing the Si/(Si+Al) ratio of the network. However, when HF rather than F is present, the overall effect will be to depolymerise melts due to the effect of OH released by dissolution of HF. The presence of abundant Si-F bonds is considered unlikely even in silica-rich magmas: the viscosity decrease characteristic of fluorine-bearing melts can be attributed to the formation of fluoride complexes.     

Partitioning of F between aqueous fluids and albite granite melt and its petrogenetic and metallogenetic significance

The fluid/melt partitioning experiments on fluorine were carried out in the system albite-H₂O-HF atP = 100 MPa, 770°C ≤T≤800°C: and wt = 2% −6% conditions. The concentrations of fluorine in quenched glasses (melt) were determined by electron microprobe and those of fluorine in the coexisting aqueous fluid were calculated by the method of mass balance. The result shows that the fluorine was concentrated in granitic melt relative to the coexisting fluid. The partition coefficient D_F(wt _F ^F1 /wt _F ^Mt ) ranges from 0.35 to 0.89. It increases with increasing fluorine content in the system. This means that there is not just one single value of partition coefficient for fluorine in the granitic melt-fluid system. The partitioning behavior of fluorine in this system depends critically on fluorine and proton (H⁺) concentrations. Our data suggest that F-rich granitic melts exist in nature and that fluorine may not be an important complexing agent of metal elements in F-bearing fluids. The project was financially supported by both the National Natural Science Foundation of China (No. 49603048) and the State Key Laboratory of Mineral Deposit Research, Nanjing University.     

Melting of hydrous pyroxenites with alkali amphiboles in the continental mantle: 2. Trace element compositions of melts and minerals

The trace element compositions of melts and minerals from high-pressure experiments on hydrous pyroxenites containing K-richterite are presented. The experiments used mixtures of a third each of the natural minerals clinopyroxene, phlogopite and K-richterite, some with the addition of 5% of an accessory phase ilmenite, rutile or apatite. Although the major element compositions of melts resemble natural lamproites, the trace element contents of most trace elements from the three-mineral mixture are much lower than in lamproites. Apatite is required in the source to provide high abundances of the rare earth elements, and either rutile and/or ilmenite is required to provide the high field strength elements Ti, Nb, Ta, Zr and Hf. Phlogopite controls the high levels of Rb, Cs and Ba.Since abundances of trace elements in the various starting mixtures vary strongly because of the use of natural minerals, we calculated mineral/melt partition coefficients (D_Min/melt) using mineral modes and melting reactions and present trace element patterns for different degrees of partial melting of hydrous pyroxenites. Rb, Cs and Ba are compatible in phlogopite and the partition coefficient ratio phlogopite/K-richterite is high for Ba (1 3 6) and Rb (12). All melts have low contents of most of the first row transition elements, particularly Ni and Cu ((0.1–0.01) × primitive mantle). Nickel has high D_Min/melt for all the major minerals (12 for K-richterite, 9.2 for phlogopite and 5.6 for Cpx) and so behaves at least as compatibly as in melting of peridotites. Fluorine/chlorine ratios in melts are high and D_Min/melt for fluorine decreases in the order apatite (2.2) > phlogopite (1.5) > K-richterite (0.87). The requirement for apatite and at least one Ti-oxide in the source of natural lamproites holds for mica pyroxenites that lack K-richterite. The results are used to model isotopic ageing in hydrous pyroxenite source rocks: phlogopite controls Sr isotopes, so that lamproites with relatively low ⁸⁷Sr/⁸⁶Sr must come from phlogopite-poor source rocks, probably dominated by Cpx and K-richterite. At high pressures (>4 GPa), peritectic Cpx holds back Na, explaining the high K₂O/Na₂O of lamproites.     

Fluorine-hydroxyl exchange in apatite and biotite: A potential igneous geothermometer

The free energy data for the simple fluorides, chlorides and hydroxides have been used to predict the distribution of these anions in hydrous minerals. The calculated partition of fluorine in phlogopite agrees well with published results; the distribution of fluorine and hydroxyl between apatite and phlogopite is temperature dependent and has been calculated. The temperatures deduced from analyses of natural apatite-biotite pairs frequently show discrepancies as compared with independent temperature estimates; these probably arise from late-stage exchange of the fluorine in phlogopite with an aqueous fluid, for which independent evidence is available.The fugacity of phosphorus in equilibrium with apatite, a ubiquitous hydrous mineral, has been calculated for various mineral assemblages. The estimates, which are subject to considerable error, are lower for basanites and alkali-basalts than for tholeiites and range from approximately 10^–14 at 1000° C to 10^–16 bars at 750° C for fayalitic rhyolites.     

Partial melting of a phlogopite-clinopyroxenite nodule from south-west Uganda: an experimental study bearing on the origin of highly potassic continental rift volcanics

Melting experiments on a mantle-derived nodule assemblage consisting of clinopyroxene, phlogopite and minor titanomagnetite, sphene and apatite have been done at 20 and 30 kbar between 1,175 and 1,300° C. The nodule composition was selected on the basis of modal and chemical analyses of 84 mantle derived nodules with metasomatic textures from the Katwe-Kikorongo and Bunyaruguru volcanic fields of south-west Uganda. At 30 kbar, 1,225 and 1,250° C, representing 20–30% partial melting, the compositions of glasses compare favourably to those of the average composition of 26 high potassic mafic lavas from the same region. Glasses produced by sufficiently low degrees of partial melting at 20 kbar could not be analysed. Glass compositions obtained for 20–30% melting at 30 kbar have high K₂O (3.07–5.05 wt.%), low SiO₂ (35.0–39.2 wt.%), high K/K + Na (0.54–0.71), K + Na/Al (0.99–1.08) and Mg/ Mg + Fe_T of 0.59–0.62. These results support the suggestion of Lloyd and Bailey (1975) that the nodules represent the source material for the high K-rich lavas of south-west Uganda. If this conclusion is correct it implies that anomalous mantle source of phlogopite clinopyroxenite composition could produced the Ugandan lavas by relatively higher degrees of partial melting than that normally considered for highly alkaline mafic magmas derived from a pyrolitic mantle source. Higher degrees of melting are considered likely from such a different source region, rich in alkalis, water and radioactive elements. Steeper geotherms and increased fluxing of sub-rift mantle by degassing would also produce higher degrees of partial melting.     

Partitioning of halogens between mantle minerals and aqueous fluids: implications for the fluid flow regime in subduction zones

We have performed phase equilibrium experiments in the system forsterite–enstatite–pyrope-H₂O with MgCl₂ or MgF₂ at 1,100 °C and 2.6 GPa to constrain the solubility of halogens in the peridotite mineral assemblage and the fluid–mineral partition coefficients. The chlorine solubility in forsterite, enstatite and in pyrope is very low, 2.1–3.9 and 4.0–11.4 ppm, respectively, and it is independent of the fluid salinity (0.3–30 wt% Cl), suggesting that some intrinsic saturation limit in the crystal is reached already at very low chlorine concentrations. Chlorine is therefore exceedingly incompatible in upper-mantle minerals. The fluorine solubility is 170–336 ppm in enstatite and 510–1,110 ppm in pyrope, again independent of fluid salinity. Forsterite dissolves 1,750–1,900 ppm up to a fluid salinity of 1.6 wt% F. At higher fluorine contents in the system, forsterite is replaced by the minerals of the humite group. The lower solubility of chlorine by three orders of magnitude when compared to fluorine is consistent with increasing lattice strain. Fluid–mineral partition coefficients are 10⁰–10² for fluorine and 10³–10⁵ for chlorine. Since the latter values are orders of magnitude higher than those for hydroxyl partitioning, fluid flow from the subducting slab through the mantle wedge will lead to an efficient sequestration of H₂O into the nominally anhydrous minerals in the wedge, whereas chlorine becomes enriched in the residual fluid. Simple mass balance calculations reveal that rock–fluid ratios of up to >3,000 are required to produce the elevated Cl/H₂O ratios observed in some primitive arc magmas. Accordingly, fluid flow from the subducted slab into the zone of melting in the mantle wedge does not only occur rapidly in narrow channels, but at least in some subduction zones, fluid pervasively infiltrates the mantle peridotite and interacts with a large volume of the mantle wedge. Together with the Cl/H₂O ratios of primitive arc magmas, our data therefore constrain the fluid flow regime below volcanic arcs.     

Interaction of model peridotite with H2O-KCl fluid: Experiment at 1.9 GPa and its implications for upper mantle metasomatism

Mineralogical and geochemical data suggest that chloride components play an important role in the transformation and partial melting of upper mantle peridotites. The effect of KCl on the transformation of hydrous peridotite rich in Al₂O₃, CaO, and Na₂O was examined in experiments aimed at studying interaction between model NCMAS peridotite with H₂O-KCl fluid under a pressure of 1.9 GPa, temperatures of 900–1200°C, and various initial H₂O/KCl ratios. The experimental results indicate that KCl depresses the solidus temperature of the hydrous peridotite: this temperature is <900°C at 1.9 GPa, which is more than 100°C lower than the solidus temperature (1000–1025°C) of hydrous peridotite in equilibrium with KCl-free fluid. The reason for the decrease in the melting temperature is that the interaction of KCl with silicates prevails over the effect of chloride on the water activity in the fluid. Experimental data highlight the key role of Al₂O₃ as a component controlling the whole interaction process between peridotite and H₂O-KCl fluid. Garnet, spinel, and pargasite-edenite amphibole in association with aluminous orthopyroxene are unstable in the presence of H₂O-KCl fluid at a chloride concentration in the fluid as low as approximately 2 wt % and are replaced by Cl-bearing phlogopite (0.4–1.1 wt % Cl). Interaction with H₂O-KCl fluid does not, however, affect clinopyroxene and forsterite, which are the Al poorest phases of the system. Chlorine stabilizes phlogopite at relatively high temperatures in equilibrium with melt at temperatures much higher than the solidus (>1200°C). The compositional evolution of melt generated during the melting of model peridotite in the presence of H₂O-KCl fluid is controlled, on the one hand, by the solubility of the H₂O-KCl fluid in the melt and, on the other hand, by phlogopite stability above the solidus. At temperatures below 1050°C, at which phlogopite does not actively participate in melting reactions, fluid dissolution results in SiO₂-undersaturated (35–40 wt %) and MgO-enriched (up to 45 wt %) melts containing up to 4–5 wt % K₂O and 2–3 wt % Cl. At higher temperatures, active phlogopite dissolution and, perhaps, also the separation of immiscible aqueous chloride liquid give rise to melts containing >10 wt % K₂O and 0.3–0.5 wt % Cl. Our experimental results corroborate literature data on the transformation of upper mantle peridotites into phlogopite-bearing associations and the formation of ultrapotassic and highly magnesian melts.     

Partitioning behavior of chlorine and fluorine in the system apatite-silicate melt-fluid

The partitioning behavior of Cl among apatite, mafic silicate melt, and aqueous fluid and of F between apatite and melt have been determined in experiments conducted at 1066 to 1150 °C and 199-205 MPa. The value of D_Cl^apatite/melt (wt. fraction of Cl in apatite/Cl in melt) ≈0.8 for silicate melt containing less than ∼3.8 wt.% Cl. At higher melt Cl contents, small increases in melt Cl concentration are accompanied by large increases in apatite Cl concentration, forcing D_Cl^apatite/melt to increase as well. Melt containing less than 3.8% Cl coexists with water-rich vapor; that containing more Cl coexists with saline fluid, the salinity of which increases rapidly with small increases in melt Cl content, analogous to the dependency of apatite composition on melt Cl content. This behavior is due to the fact that the solubility of Cl in silicate melt depends strongly on the composition of the melt, particularly its Mg, Ca, Fe, and Si contents. Once the melt becomes “saturated” in Cl, additional Cl must be accommodated by coexisting fluid, apatite, or other phases rather than the melt itself. Because Cl solubility depends on composition, the Cl concentration at which D_Cl^apatite/melt and D_Cl^fluid/melt begin to increase also depends on composition. The experiments reveal that D_F^apatite/melt ≈3.4. In contrast to Cl, the concentration of F in silicate melt is only weakly dependent on composition (mainly on melt Ca contents), so D_F^apatite/melt is constant for a wide range of composition.The experimental data demonstrate that the fluids present in the waning stages of the solidification of the Stillwater and Bushveld complexes were highly saline. The Cl-rich apatite in these bodies crystallized from interstitial melt with high Cl/(F + OH) ratio. The latter was generated by the combined processes of fractional crystallization and dehydration by its reaction with the relatively large mass of initially anhydrous pyroxene through which it percolated.     

Non-modal melting in an upwelling mantle column: Steady-state models with applications to REE depletion in abyssal peridotites and the dynamics of melt migration in the mantle

Simple models for trace element fractionation during concurrent melting and melt migration in an upwelling steady-state mantle were developed. Based on petrologic considerations, we divided the mantle column into two regions: a single-lithology lower region that consists of partially molten garnet and spinel lherzolites and a double-lithology upper region where high-porosity dunite channels or melt-filled fractures are embedded in a porous lherzolite/harzburgite matrix. Analytical solutions for the case of a constant and uniform relative melting suction rate and a linearly variable relative melt suction rate were obtained. Key parameters and the first order characteristics of melting and melt migration in a 1-D steady-state mantle column were examined through forward calculations and Monte Carlo simulations. Melting in the upwelling single-lithology column is equivalent to non-modal batch melting, whereas melting and melt migration in the double-lithology region can be viewed as a nonlinear combination of batch melting and fractional melting, depending on the amount of melt extracted to the channel. The degree of melting (F), the degree of melting at the depth of melt-channel initiation (F_d) and the relative rate of melt suction (R) are important in controlling the extent of depletion of the incompatible trace element in the matrix. Spatially variable R affects the abundance of an incompatible trace element in the melt and residual solid the most in near fractional melting. There is a strong nonlinear trade off among the three parameters. Given F_d, it is possible to constrain F and R from incompatible trace element abundances in residual peridotite.To explore the dynamics of melt migration in the mantle, we used the two melting models developed in this study and published REE and Y abundances in diopside in abyssal peridotites from the Central Indian Ridge to infer their melting and melt migration history. Overall, the degrees of melting inferred from the trace element data are not sensitive to the value of F_d used in the inversion and ranges from 10% to 15%. The relative rate of melt suction depends slightly on the choice of F_d and ranges from 0.85 to 1.0 for F_d = 0.05 and 0.75 to 0.97 for F_d = 0. Further, the estimated R is inversely correlated with F, a robust feature independent of the choice of F_d. The upward decrease of R in an upwelling mantle column can be understood in terms of melt focusing in the lower part of the double-lithology region. And finally, given F and R, we found that the permeability and porosity of the lherzolite/harzburgite matrix also increase as a function of F in the melting column, with melt fractions ranging from 0.2% to 0.7% for a grain size of 5 mm.     

The petrogenesis of granitoid rocks unusually rich in apatite in the Western Tatra Mts. (S-Poland, Western Carpathians)

In the bottom part of the tongue-shaped, layered granitoid intrusion, exposed in the Western Tatra Mts., apatite-rich granitic rocks occur as pseudo-layers and pockets between I-type hybrid mafic precursors and homogeneous S-type felsic granitoids. The apatite-rich rocks are peraluminous (ASI?=?1.12–1.61), with P₂O₅ contents ranging from 0.05 to 3.41 wt.% (<7.5 vol.% apatite), shoshonitic to high-K calc-alkaline. Apatite is present as long-prismatic zoned crystals (Ap₁) and as large xenomorphic unzoned crystals (Ap₂). Ap₁ apatite and biotite represent an early cumulate. Feldspar and Ap₂ textural relations may reflect the interaction of the crystal faces of both minerals and support a model based on local saturation of (P, Ca, F) versus (K, Na, Al, Si, Ba) in the border zones. Chondrite-normalized REE patterns for the apatite rocks and for pure apatite suggest apatite was a main REE carrier in these rocks. Minerals characteristics and the whole rock chemistry suggest both reduced S-type and I-type magma influenced the apatite-rich rocks. The field observations, mineral and rock chemistry as well as mass-balance calculations point out that the presence of apatite-rich rocks may be linked to the continuous mixing of felsic and mafic magmas, creating unique phosphorus- and aluminium-rich magma portions. Formation of these rocks was initially dominated by the complex flowage-controlled and to some extent also gravity-driven separation of early-formed zoned minerals and, subsequently, by local saturation in the border zones of growing feldspar and apatite crystals. Slow diffusion in the phosphorus-rich magma pockets favoured the local saturation and simultaneous crystallization of apatite and feldspars in a crystal-ladden melt.     

Fluorine geochemistry of basaltic rocks from continental and oceanic regions and petrogenetic application

Fluorine contents in about 300 samples of various types of basalts and related rocks from continental (southwestern U.S.A.; Zaire; Deccan and South Africa) and oceanic regions (Hawaii and Mid-Atlantic Ridge between 23° N and 40° N) were determined by a selective ion-electrode method.Of all of the major components in these basaltic rocks, F shows good correlation only with K₂O. It increases regularly from tholeiite to perpotassic basalt on continents, and from tholeiite to nephelinite on Hawaii. In the F-K₂O diagram all the basaltic rocks from continents and Hawaii plot between the origin of the coordinate axes and the field of phlogopite in peridotite xenoliths in South African kimberlites. Accordingly, the major proportions of F, K₂O and also H₂O in these basaltic magmas are derived from phlogopite at the source regions in the upper mantle. On the other hand, F in abyssal tholeiites is relatively higher than that of the other tholeiites at equal K₂O content, and it is suggested that most of F, K₂O and H₂O are derived from pargasites.When it is assumed that the upper mantle phlogopite contains about 10% K₂O, 0.4% (0.3–0.5%) F and 4% H₂O, H₂O content in basaltic magmas from continental including island arc and oceanic island regions can be qualitatively estimated based on their proportions of K₂OFH₂O. Similarly, H₂O content in abyssal basaltic rocks is also estimated on the basis of FH₂O in pargasites (Table 2).A suite of Deccan tholeiites shows remarkable F enrichment with increasing K₂O due to separation of anhydrous and K-free minerals during fractionation. F in tholeiitic and alkali basalt magmas in Hawaii also increases regularly with K₂O during progressive fractionation until the later stages, where rhyodacite and trachyte exhibit a relative decrease owing to the effective subtraction of F-bearing amphibole and apatite in addition to anhydrous minerals.     

The effect of fluorine on liquidus phase relationships in the system Qz-Ab-Or with excess water at 1 kb

Liquidus phase relationships have been determined experimentally for the system Qz-Ab-Or with excess water and 1, 2, and 4 wt.% added fluorine at 1 kb pressure. With increasing fluorine content the position of the quartz-alkali feldspar field boundary moves away from the quartz apex. The position of the minimum melting composition and the minimum liquidus temperature change progressively from Qz₃₇Ab₃₄Or₂₉ and 730° C for the fluorine free system (Tuttle and Bowen 1958) to Qz₁₅Ab₅₈Or₂₇ and 630° C for the system with 4 wt.% added fluorine. Exploratory experiments have been carried out below the liquidus, and have indicated that for certain bulk compositions an assemblage consisting of two alkali feldspars, quartz, melt and vapour can exist at temperatures as low as 550° C at 1 kb.The experimental results suggest that there may be an interaction between fluorine and aluminosilicate complexes present within the melt, to produce aluminofluoride (AlF ₆ ^3– ) complex anions (Manning et al. 1980). The observed changes in liquidus phase relationships with increasing fluorine content indicate that the compositions of certain fluorine-rich granitic rocks are consistent with an origin by crystallisation of residual melts enriched in fluorine by magmatic differentiation. Such residual melts may exist at relatively low temperatures, and may form part of a continuum between granite magmatism and associated hydrothermal activity. Because of the observed preference of fluorine for aluminosilicate phases at the magmatic stage, the presence of fluorine alone is not considered to play a direct part in the generation of residual mineralising hydrothermal fluids.     

Opaque Mineralogy as a Tracer of Magmatic History of Volcanic Rocks:an Example from the Neogene-Quaternary Harrat Rahat Intercontinental Volcanic Field, North Western Saudi Arabia

The Neogene-Quaternary Harrat Rahat volcanic field is part of the major intercontinental Harrat fields in western Saudi Arabia.It comprises lava flows of olivine basalt and hawaiite,in addition to mugearite,benmorite,and trachyte that occur mainly as domes,tuff cones and lava flows.Based on opaque mineralogy and mineral chemistry,the Harrat Rahat volcanic varieties are distinguished into Group I(olivine basalt and hawaiite) and Group II(mugearite,benmorite and trachyte).The maximum forsterite content(~85) is encountered in zoned forsteritic olivine of Group I,whereas olivine of Group II is characterized by intermediate(Fo=50),fayalitic(Fo=25) and pure fayalite in the mugearite,benmorite and trachyte,respectively.The more evolved varieties of Group II contain minerals that show enrichment of Fe2+,Mn2+and Na+that indicates normal fractional crystallization.The common occurrence of coarse apatite with titanomagnetite in the benmorite indicates that P5+becomes saturated in this rock variety and drops again in trachyte.Cr-spinel is recorded in Group I varieties only and the Cr#(0.5) suggests lherzolite as a possible restite of the Harrat Rahat volcanics.The plots of Cr# vs.the forsterite content(Fo) suggest two distinct trends,which are typical of mixing of two basaltic magmas of different sources and different degrees of partial melting.The bimodality of Harrat Rahat Cr-spinel suggests possible derivation from recycled MORB slab in the mantle as indicated by the presence of high-Al spinel.It is believed that the subcontinental lithospheric mantle was modified by pervious subduction process and played the leading role in the genesis of the Harrat Rahat intraplate volcanics.The trachytes of the Harrat Rahat volcanic field were formed most probably by melting of a lower crust at the mantle-crust boundary.The increase in fO2 causes a decrease in Cr2 O3,and Al2 O3,and a strong increase in the proportion of Fe3+and Mg# of spinel crystallizing from the basaltic melt at T ~1200°C.The olivine-pyroxene and olivine-spinel geothermometers yielded equilibrium temperature in the range of 935-1025°C,whereas the range of <500-850°C from single-pyroxene thermometry indicates either post crystallization reequilibrium of the clinopyroxene,or the mineral is xenocrystic and re-equilibrated in a cooling basaltic magma.     

Inclusions in chrysolite from the Kovdor Massif: Genetic and gemmological significance

Gem-quality chrysolite (peridot) from a phlogopite deposit related to the Kovdor ultrabasic-alkaline massif in the Kola Peninsula, Russia, was studied using a variety of techniques (optical mineralogical microscopy, chemical, Mössbauer spectroscopy, and photoluminescence) to determine its chemical composition, the Fe²⁺/Fe³⁺ ratio, refraction indexes, density, as well as to examine inclusions in it. Much attention was devoted to the microprobe identification of crystalline inclusions in the host chrysolite (apatite, tetraferriphlogopite, amphibole, and magnetite), its exsolution products (diopside and magnetite), and the daughter phases of melt inclusions in this mineral (which were subdivided into primary and secondary genetic types). The daughter phases of these melt inclusions are silicates (forsterite, diopside, tetraferriphlogopite, clinohumite, and serpentine), various carbonates (Ca-dominated carbonates are characteristic of the primary inclusions, whereas Mg-rich carbonates were found only in the secondary inclusions), magnetite, djerfisherite (alkali sulfide), and Ba-Sr-REE carbonates. The presence of melt inclusions testifies to a magnatic genesis of the gem, and the simultaneous occurrence of these inclusions with crystalline inclusions can be used as an additional identification feature of gem chrysolite from the Kovdor Massif.     

Sulfur partitioning between apatite and melt and effect of sulfur on apatite solubility at oxidizing conditions

The effect of sulfur on phosphorus solubility in rhyolitic melt and the sulfur distribution between apatite, ±anhydrite, melt and fluid have been determined at 200 MPa and 800–1,100 °C via apatite crystallization and dissolution experiments. The presence of a small amount of sulfur in the system (0.5 wt.% S) under oxidizing conditions increases the solubility of phosphorus in the melt, probably due to changing calcium activity in the melt as a result of the formation of Ca-S complexing cations. Apatite solubility geothermometers tend to overestimate temperature in Ca-poor, S-bearing system at oxidizing conditions. In crystallization experiments, the sulfur content in apatite decreases with decreasing temperature and also with decreasing sulfur content of the melt. The sulfur partition coefficient between apatite and rhyolitic melt increases with decreasing temperature (Kd_S^apatite/melt=4.5–14.2 at T=1,100–900 °C) under sulfur-undersaturated conditions (no anhydrite). The sulfur partition coefficient is lower in anhydrite-saturated melt (~8 at 800 °C) than in anhydrite-undersaturated melt, suggesting that Kd_S^apatite/melt depends not only on the temperature but also on the sulfur content of the melt. These first results indicate that the sulfur content in apatite can be used to track the evolution of sulfur content in a magmatic system at oxidizing conditions.Editorial responsibility: J. Hoefs     

Partitioning behavior of chlorine and fluorine in the system apatite-melt-fluid. II: Felsic silicate systems at 200 MPa

Hydrothermal experiments were conducted to determine the partitioning of Cl between rhyolitic to rhyodacitic melts, apatite, and aqueous fluid(s) and the partitioning of F between apatite and these melts at ca. 200 MPa and 900-924 °C. The number of fluid phases in our experiments is unknown; they may have involved a single fluid or vapor plus saline liquid. The partitioning behavior of Cl between apatite and melt is non-Nernstian and is a complex function of melt composition and the Cl concentration of the system. Values of D_Cl^apat/melt (wt. fraction of: Cl in apatite/Cl in melt) vary from 1 to 4.5 and are largest when the Cl concentrations of the melt are at or near the Cl-saturation value of the melt. The Cl-saturation concentrations of silicate melts are lowest in evolved, silica-rich melts, so with elevated Cl concentrations in a system and with all else equal, the maximum values of D_Cl^apat/melt occur with the most felsic melt. In contrast, values of D_F^apat/melt range from 11 to 40 for these felsic melts, and many of these are an order of magnitude greater than those applying to basaltic melts at 200 MPa and 1066-1150 °C. The Cl concentration of apatite is a simple and linear function of the concentration of Cl in fluid. Values of D_Cl^fluid/apat for these experiments range from 9 to 43, and some values are an order of magnitude greater than those determined in 200-MPa experiments involving basaltic melts at 1066-1150 °C.In order to determine the concentrations and interpret the behavior of volatile components in magmas, the experimental data have been applied to the halogen concentrations of apatite grains from chemically evolved rocks of Augustine volcano, Alaska; Krakatau volcano, Indonesia; Mt. Pinatubo, Philippines; Mt. St. Helens, Washington; Mt. Mazama, Oregon; Lascar volcano, Chile; Santorini volcano, Greece, and the Bishop Tuff, California. The F concentrations of these magmas estimated from apatite-melt equilibria range from 0.06 to 0.12 wt% and are generally equivalent to the concentrations of F determined in the melt inclusions. In contrast, the Cl concentrations of the magmas estimated from apatite-melt equilibria (e.g., ca. 0.3-0.9 wt%) greatly exceed those determined in the melt inclusions from all of these volcanic systems except for the Bishop Tuff where the agreement is good. This discrepancy in estimated Cl concentrations of melt could result from several processes, including the hypothesis that the composition of apatite represents a comparatively Cl-enriched stage of magma evolution that precedes melt inclusion entrapment prior to the sequestration of Cl by coexisting magmatic aqueous and/or saline fluid(s).     

Features of the Early Palaeozoic Mantle beneath Langao County and Its Formation Mechanism

Phlogopite-amphibole pyroxenite xenoliths contained in an Early Palaeozoic alkali subvolcanic lam-prophyre complex in Langao County, Shaanxi Province, are metasomatized mantle xenoliths, composed mainly of clinopyroxene, amphibole, phlogopite, apatite, pervoskite, ilmenite and sphene with well-developed subsolidus metamorphism-deformation textures, such as "triple points" and "cataclastic boundaries" . Minerological studies indicate that clinopyroxene is rich in SiO2 and MgO and poor in TiO2 and Al2O3, which is notably different from magmatogenic deep-seated megacrysts and phenocrysts formed in the range of mantle pressure. Amphibole and phlogopite have the compositional feature of mantle-derived amphibole and phlogopite. Sm-Nd isotope studies suggest that the metasomatized mantle beneath Langao County is the product of metasomatism of primitive mantle by melt (fluid) derived from the mantle plume, and the mantle metasomatism occurred 650 Ma ago. The process of mantle metasomatism changed from mantle me     

The high PT stability of apatite and Cl partitioning between apatite and hydrous potassic phases in peridotite: an experimental study to 19 GPa with implications for the transport of P,Cl and K in the upper mantle

High PT experiments were performed in the range 2.5–19 GPa and 800–1,500°C using a synthetic peridotite doped with trace elements and OH-apatite or with Cl-apatite + phlogopite. The aim of the study was (1) to investigate the stability and phase relations of apatite and its high PT breakdown products, (2) to study the compositional evolution with P and T of phosphate and coexisting silicate phases and (3) to measure the Cl-OH partitioning between apatite and coexisting calcic amphibole, phlogopite and K-richterite. Apatite is stable in a garnet-lherzolite assemblage in the range 2.5–8.7 GPa and 800–1,100°C. The high-P breakdown product of apatite is tuite γ-Ca₃ (PO₄)₂, which is stable in the range 8–15 GPa and 1,100–1,300°C. Coexisting apatite and tuite were observed at 8 GPa/1,050°C and 8.7 GPa/1,000°C. MgO in apatite increases with P from 0.8 wt% at 2.5 GPa to 3.2 wt% at 8.7 GPa. Both apatite and tuite may contain significant Na, Sr and REE with a correlation indicating 2 Ca²⁺=Na⁺ + REE³⁺. Tuite has always higher Sr and REE and lower Fe and Mg than apatite. Phosphorus in the peridotite phases decreases in the order P_melt ≫ P_grt ≫ P_Mg2SiO4 > P_cpx > P_opx. The phosphate-saturated P₂O₅ content of garnet increases from 0.07 wt% at 2.5 GPa to 1.5 wt% at 12.8 GPa. Due to the low bulk Na content of the peridotite, ^[8]Na^[4]P^[8]M²⁺ ₋₁ ^[4]Si₋₁ only plays a minor role in controlling the phosphorus content of garnet. Instead, element correlations indicate a major contribution of ^[6]M^2+[4]P^[6]M³⁺ ₋₁ ^[4]Si₋₁. Pyroxenes contain ~200–500 ppm P and olivine has 0.14–0.23 wt% P₂O₅ in the P range 4–8.7 GPa without correlation with P, T or X_Mg. At ≥12.7 GPa, all Mg₂SiO₄ polymorphs have <200 ppm P. Coexisting olivine and wadsleyite show an equal preference for phosphorus. In case of coexisting wadsleyite and ringwoodite, the latter fractionates phosphorus. Although garnet shows by far the highest phosphorus concentrations of any peridotite silicate phase, olivine is no less important as phosphorus carrier and could store the entire bulk phosphorus budget of primitive mantle. In the Cl-apatite + phlogopite-doped peridotite, apatite contains 0.65–1.35 wt% Cl in the PT range 2.5–8.7 GPa/800–1,000°C. Apatite coexists with calcic amphibole at 2.5 GPa, phlogopite at 2.5–5 GPa and K-richterite at 7 GPa, and all silicates contain between 0.2 and 0.6 wt% Cl. No solid potassic phase is stable between 5 and 8.7 GPa. Cl strongly increases the solubility of K in hydrous fluids. This may lead to the breakdown of phlogopite and give rise to the local presence in the mantle of fluids strongly enriched in K, Cl, P and incompatible trace elements. Such fluids may get trapped as micro-inclusions in diamonds and provide bulk compositions suitable for the formation of unusual phases such as KCl or hypersilicic Cl-rich mica.     

Phlogopite-Amphibole-Pyroxenite Xenoliths in Langao,Shaanxi Province,China:evidence for Mantle Metasomatism

Phlogopite-amphibole-pyroxenite xenoliths contained in the alkali basic-ultrabasic subvolcanic complex in Langao, Shaanxi Province, are composed of diopside, Ti-rich pargasite, phlogopite apatite, sphene and ilmenite, which have subsolidus metamorphism-deformation textures such as triple-points, cataclastic boundaries and kink-bands. Mineral chemical characteristics show that the diposide, Ti-rich paragasite and phlogopite are derived from the mantle and are the products of mantle metasomatism. Compared with normal mantle-derived spinel-lherzolites, the xenoliths are enriched in TiO₂, Fe₂O₃, CaO, Na₂O and K₂O, with apparent depletion in MgO. Chondrite-normalized REE patterns and primordial-mantle normalized trace elements data show that they are enriched in REE (especially LREE) and incompatible trace elements. The petrographic, mineralogical and petrochemical characteristics indicate that the xenoliths are metasomatized mantle xenoliths, which offers the evidence for mantle metasomatism and represents the anomalous mantle beneath the Early Paleozoic rift in northern Daba Mountains. The agents of mantle metasomatism are probably derived from the rising of mantle hot plumes. The processes of metasomatism varied from limited-range fluid metasomatism in deep mantle (>90 km) to pervasive metasomatism of silicate melt. This project was financially supported by the National Natural Science Foundation of China (No. 49402035).