Trace-element partitioning between garnet,clinopyroxene and Fe-rich picritic melts at 3 to 7 GPa

We have determined mineral-melt partition coefficients (D values) for 20 trace elements in garnet-pyroxenite run products, generated in 3 to 7 GPa, 1,425–1,750°C experiments on a high-Fe mantle melt (97SB68) from the Paraná-Etendeka continental-flood-basalt (CFB) province. D values for both garnet (∼Py₆₃Al₂₅Gr₁₂) and clinopyroxene (∼Ca_0.2Mg_0.6Fe_0.2Si₂O₆) show a large variation with temperature but are less dependent on pressure. At 3 GPa, D ^cpx/liq values for pyroxenes in garnet-pyroxenite run products are generally lower than those reported from Ca-rich pyroxenes generated in melting experiments on eclogites and basalts (∼Ca_0.3–0.5Mg_0.3–0.6Fe_0.07–0.2Si₂O₆) but higher than those for Ca-poor pyroxenes from peridotites (∼Ca_0.2Mg_0.7Fe_0.1Si₂O₆). D ^grt/liq values for light and heavy rare-earth elements are ≤0.07 and >0.8, respectively, and are similar to those for peridotitic garnets that have comparable grossular but higher pyrope contents (Py_70–88Al_l7–20Gr_8–14). 97SB68 D _LREE^grt/liq values are higher and D _HREE^grt/liq values lower than those for eclogitic garnets which generally have higher grossular contents but lower pyrope contents (Py_20–70Al_10–50Gr_10–55). D values agree with those predicted by lattice strain modelling and suggest that equilibrium was closely approached for all of our experimental runs. Correlations of D values with lattice-strain parameters and major-element contents suggest that the wollastonite component and pyrope:grossular ratio exert major controls on 97SB68 clinopyroxene and garnet partitioning, respectively. These are controlled by the prevailing pressure and temperature conditions for a given bulk-composition. The composition of co-existing melt was found to have a relatively minor effect on 97SB68 D values. The variations in D values displayed by different mantle lithologies are subtle and our study confirms previous investigations which have suggested that the modal proportions of garnet and clinopyroxene are by far the most influential factor in determining incompatible trace-element concentrations in mantle melts. The trace-element partition coefficients we have determined may be used to place high-pressure constraints on garnet-pyroxenite melting models.     

Aluminum substitution mechanisms in perovskite-type MgSiO<Subscript>3</Subscript>: an investigation by Rietveld analysis

Al-containing MgSiO₃ perovskites of four different compositions were synthesized at 27 GPa and 1,873 K using a Kawai-type high-pressure apparatus: stoichiometric compositions of Mg_0.975Si_0.975Al_0.05O₃ and Mg_0.95Si_0.95Al_0.10O₃ considering only coupled substitution Mg²⁺ + Si⁴⁺ = 2Al³⁺, and nonstoichiometric compositions of Mg_0.99Si_0.96Al_0.05O_2.985 and Mg_0.97Si_0.93Al_0.10O_2.98 taking account of not only the coupled substitution but also oxygen vacancy substitution 2Si⁴⁺ = 2Al³⁺ + V_O¨. Using the X-ray diffraction profiles, Rietveld analyses were performed, and the results were compared between the stoichiometric and nonstoichiometric perovskites. Lattice parameter–composition relations, in space group Pbnm, were obtained as follows. The a parameters of both of the stoichiometric and nonstoichiometric perovskites are almost constant in the X _Al range of 0–0.05, where X _Al is Al number on the basis of total cation of two (X _Al = 2Al/(Mg + Si + Al)), and decrease with further increasing X _Al. The b and c parameters of the stoichiometric perovskites increase linearly with increasing Al content. The change in the b parameter of the nonstoichiometric perovskites with Al content is the same as that of the stoichiometric perovskites within the uncertainties. The c parameter of the nonstoichiometric perovskites is slightly smaller than that of the stoichiometric perovskites at X _Al of 0.10, though they are the same as each other at X _Al of 0.05. The Si(Al)–O1 distance, Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O distance of the nonstoichiometric perovskites keep almost constant up to X _Al of 0.05, and then the Si(Al)–O1 increases and both of the Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O decrease with further Al substitution. These results suggest that the oxygen vacancy substitution may be superior to the coupled substitution up to X _Al of about 0.05 and that more Al could be substituted only by the coupled substitution at 27 GPa. The Si(Al)–O1 distance and one of two independent Si(Al)–O2 distances in Si(Al)O₆ octahedra in the nonstoichiometric perovskites are always shorter than those in the stoichiometric perovskite at the same Al content. These results imply that oxygen defects may exist in the nonstoichiometric perovskites and distribute randomly.     

Distribution of REE between clinopyroxene and basaltic melt along a mantle adiabat: effects of major element composition, water, and temperature

The distribution of rare earth elements (REE) between clinopyroxene (cpx) and basaltic melt is important in deciphering the processes of mantle melting. REE and Y partition coefficients from a given cpx-melt partitioning experiment can be quantitatively described by the lattice strain model. We analyzed published REE and Y partitioning data between cpx and basaltic melts using the nonlinear regression method and parameterized key partitioning parameters in the lattice strain model (D ₀, r ₀ and E) as functions of pressure, temperature, and compositions of cpx and melt. D ₀ is found to positively correlate with Al in tetrahedral site (Al ^T ) and Mg in the M2 site (Mg^M2) of cpx and negatively correlate with temperature and water content in the melt. r ₀ is negatively correlated with Al in M1 site (Al^M1) and Mg^M2 in cpx. And E is positively correlated with r ₀. During adiabatic melting of spinel lherzolite, temperature, Al ^T , and Mg^M2 in cpx all decrease systematically as a function of pressure or degree of melting. The competing effects between temperature and cpx composition result in very small variations in REE partition coefficients along a mantle adiabat. A higher potential temperature (1,400°C) gives rise to REE partition coefficients slightly lower than those at a lower potential temperature (1,300°C) because the temperature effect overwhelms the compositional effect. A set of constant REE partition coefficients therefore may be used to accurately model REE fractionation during partial melting of spinel lherzolite along a mantle adiabat. As cpx has low Al and Mg abundances at high temperature during melting in the garnet stability field, REE are more incompatible in cpx. Heavy REE depletion in the melt may imply deep melting of a hydrous garnet lherzolite. Water-dependent cpx partition coefficients need to be considered for modeling low-degree hydrous melting.     

Melting relations and major element partitioning in an oxidized bulk Earth model composition at 15–26 GPa

Melting experiments were performed on an FeO-rich bulk Earth model composition in the CMFAS system in order to investigate the partitioning of major elements between coexisting minerals and melts. The starting material (34.2% SiO₂, 3.86% Al₂O₃, 35.2% FeO, 25.0% MgO and 1.88% CaO), contained in Re-capsules, was a mixture of crystalline forsterite and fayalite, and a glass containing SiO₂, Al₂O₃, and CaO. Olivine is the first liquidus phase at 10 GPa but is replaced by majoritic garnet (ga) in the 15–26 GPa range. Magnesiowüstite (mw) crystallizes close to the liquidus and is joined by perovskite (pv) at 26 GPa.

The quenched melt compositions are homogeneous throughout the melt region of the charges and are only slightly enriched in Si, Ca and Fe, and depleted in Mg, relative to the starting composition. The Fe/Mg and Ca/Al ratios in all of the minerals increase rapidly below the liquidus to become compatible with the bulk composition at the solidus. At 26 GPa, a relative density sequence of mw>pv>melt>ga is observed. This indicates that majorite floating, combined with the sinking of magnesiowüstite and perovskite can be expected during the solidification of a Hadean magma ocean and in hot mantle plumes early in the Earth's history. The mineral–melt partitioning relations indicate that fractional crystallization or partial melting in the transition zone and the upper part of the lower mantle would increase the Fe/Mg and Ca/Al ratios of the melt, even if magnesiowüstite was predominant in the solid fraction. A significant contribution of accumulated mw to the segregation of the protocore is therefore unlikely. The suggested process of perovskite fractionation to the lower mantle is not capable of increasing the Mg/Si ratio in the residual melt, and the combined fractionation of perovskite and magnesiowüstite produces a melt with elevated ratios of Si/Mg, Ca/Al and Fe/Mg.     

Experimental constraints on crystallization differentiation in a deep magma ocean

Major and trace element mineral/melt partition coefficients are presented for phases on the liquidus of fertile peridotite at 23-23.5 GPa and 2300 °C. Partitioning models, based on lattice-strain theory, are developed for cations in the ‘8-fold’ sites of majorite and Mg-perovskite. Composition-dependant partitioning models are made for cations in the 12-fold site of Ca-perovskite based on previously published data. D^min/melt is extremely variable for many elements in Ca-perovskite and highly correlated with certain melt compositional parameters (e.g. CaO and Al₂O₃ contents). The 8-fold sites in Mg-perovskite and majorite generally have ideal site radii between 0.8 and 0.9 Å for trivalent cations, such that among rare-earth-elements (REE) D^min/melt is maximum for Lu. Lighter REE become increasingly incompatible with increasing ionic radii. The 12-fold site in Ca-perovskite is larger and has an ideal trivalent site radius of ∼1.05 Å, such that the middle REE has the maximum D^min/melt. Trivalent cations are generally compatible to highly compatible in Ca-perovskite giving it considerable leverage in crystallization models. Geochemical models based on these phase relations and partitioning results are used to test for evidence in mantle peridotite of preserved signals of crystal differentiation in a deep, Hadean magma ocean.Model compositions for bulk silicate Earth and convecting mantle are constructed and evaluated. The model compositions for primitive convecting mantle yield superchondritic Mg/Si and Ca/Al ratios, although many refractory lithophile element ratios are near chondritic. Major element mass balance calculations effectively preclude a CI-chondritic bulk silicate Earth composition, and the super-chondritic Mg/Si ratio of the mantle is apparently a primary feature. Mass balance calculations indicate that 10-15% crystal fractionation of an assemblage dominated by Mg-perovskite, but with minor amounts of Ca-perovskite and ferropericlase, from a magma ocean with model peridotite-based bulk silicate Earth composition produces a residual magma that resembles closely the convecting mantle.Partition coefficient based crystal fractionation models are developed that track changes in refractory lithophile major and trace element ratios in the residual magma (e.g. convecting mantle). Monomineralic crystallization of majorite or Mg-perovskite is limited to less than 5% before certain ratios fractionate beyond convecting mantle values. Only trace amounts of Ca-perovskite can be tolerated in isolation due to its remarkable ability to fractionate lithophile elements. Indeed, Ca-perovskite is limited to only a few percent in a deep mantle crystal assemblage. Removal from a magma ocean of approximately 13% of a deep mantle assemblage comprised of Mg-perovskite, Ca-perovskite and ferropericlase in the proportions 93:3:4 produces a residual magma with a superchondritic Ca/Al ratio matching that of the model convecting mantle. This amount of crystal separation generates fractionations in other refractory lithophile elements ratios that generally mimic those observed in the convecting mantle. Further, the residual magma is expected to have subchondritic Sm/Nd and Lu/Hf ratios. Modeling shows that up to 15% crystal separation of the deep mantle assemblage from an early magma ocean could have yielded a convecting mantle reservoir with ¹⁴³Nd/¹⁴⁴Nd and ¹⁷⁶Hf/¹⁷⁷Hf isotopic compositions that remain internal to the array observed for modern oceanic volcanic rocks. If kept in isolation, the residual magma and deep crystal piles would grow model isotopic compositions that are akin to enriched mantle 1 (EM1) and HIMU reservoirs, respectively, in Nd-Hf isotopic space.     

Partitioning of fluorine and chlorine between biotite and granitic melt: experimental calibration at 200 MPa H2O

Experiments from 640 to 680?°C, 200 MPa H₂O at?f _O2?≈?NNO, employing a natural?F-rich?vitrophyric rhyolite from Spor Mountain, Utah, assessed the effect of variable Mg′ [100Mg/(Mg?+?Mn?+?Fe)] on the partitioning of fluorine and chlorine between biotite (Bt) and melt. Over this temperature interval, Bt (?±?fluorite, ?±?quartz) is the sole liquidus phase. Partition coefficients for fluorine between biotite and glass (D_F ^Bt/melt) show a strong dependence on the Mg′ of Bt.?D_F ^Bt/melt varies from???1.5 to 7.2 over the range of Mg′ from 21 to 76. A strong linear correlation between?D_F ^Bt/melt?and Mg′ has a slope of 9.4 and extrapolates through the origin (i.e., D_F ^Bt/melt?≈?0 at Mg′?=?0, an annite-siderophyllite solid solution in these experiments). D_Cl ^Bt/melt values (???1 to 6) in the same experiments vary inversely with Mg′. The Al-content of biotite does not vary with the aluminum saturation index (ASI?=?molar Al₂O₃/Σ alkali and alkaline earth oxides) of melt, but two exchange mechanisms involving Al appear to operate in these micas: (1) Al^vi?+?Al^iv?? Si^iv?+?Mg^iv, and Mg^iv?+?2Al^iv? 2Si^iv?+?□^iv. The effects of other components such as Li or other intensive parameters including f _O2 have yet to be evaluated?systematically. At comparable Mg′ of Bt, however, the Spor Mountain rhyolite yields higher D_F ^Bt/melt values than an Li-rich, strongly peraluminous melt previously investigated. The results indicate that the Mg′ of Bt exerts the principal control on halogen partitioning, with ASI and T as second-order variables. The experimental partition coefficients compare well with other experimental results but not with most volcanic rocks. Magmatic Bt from most rhyolites records higher D_F ^Bt/melt due to reequilibration with degassed (H₂O-depleted) magma and perhaps with F₂O_?1 exchange that may accompany oxidation ([Fe³⁺O] [Fe²⁺OH]_?1). This behavior is evident in magmatic biotite from a zoned peraluminous rhyolite complex near Morococala, Bolivia: Bt is sharply zoned with F-rich rims, but Bt(core)-melt inclusion pairs fall on our experimental curve for D_F ^Bt/melt. These experimental data can be used in part to assess the preservation of magmatic volatile contents in plutonic or volcanic silicic rocks. For plutonic rocks, the actual F-content of melt, not a relative activity ratio involving HF species, can be reasonably estimated if the mica has not undergone subsolidus reequilibration. This information is potentially useful for some shallow-level Ca-poor magmas that are thought to be rich in F (e.g., A- and S-type granites) but do not conserve F well as rocks.     

Iron partitioning in pyrolitic lower mantle

The partitioning of iron between Mg-rich perovskite (Pv) and ferropericlase (Fp) was investigated for a pyrolitic bulk composition over a wide range of simulated lower-mantle pressures and temperatures from 28 to 114 GPa and from 1,900 to 2,300 K, in a laser-heated diamond anvil cell (DAC). The recovered DAC samples are chemically homogeneous, indicating a relatively small temperature gradient during laser heating. The chemical compositions of coexisting Pv, Fp, and Ca-rich perovskite (CaPv) were determined by energy-dispersive X-ray spectroscopy (EDS) using an EDS instrument attached to a transmission electron microscope. Our results demonstrate that at pressures above 90 GPa, Pv becomes more Fe-rich with increasing pressure, which is likely due to the effects of high-spin to low-spin crossover of Fe³⁺ in Pv. We highlight that such a change in Fe–Mg partitioning between Pv and Fp should have a strong influence on the physical properties of the deep lower mantle.     

CaAl ratio and composition of the Earth's upper mantle

Undifferentiated meteorites (chondrites) have the same relative abundances of refractory lithophile elements (Ca, Al, Ti, Sc, REE, etc.), despite variable absolute concentrations. The reasonable assumption of chondritic ratios among refractory elements in the bulk Earth is used to constrain the chemical composition of the upper mantle in the following way: Correlations of the compatible refractory elements Ca, Al, Ti, Sc and Yb with MgO are worldwide very similar in suites of spinel-lherzolite xenoliths from basaltic rocks. Such suites represent upper mantle material depleted to differing degrees by extraction of partial melts. From these refractory elements vs. MgO correlations, ratios of pairs of refractory elements were calculated at various MgO contents. Chondritic $\text{Al}\text{Ti}$ and $\text{Sc}\text{Ti}$ ratios were only obtained for MgO contents below 36%. A chrondritic $\text{Sc}\text{Yb}$ ratio requires an MgO content above 35%. We therefore accept 35.5% as the most reasonable MgO content of undepleted upper mantle. This MgO content is slightly below the spinel-lherzolite with the lowest measured MgO content (36.22%). The corresponding Al₂O₃ content of 4.75% is higher than in previous estimates of upper mantle composition. The concentrations of other elements were obtained from similar correlations at a MgO content of 35.5%. The resulting present upper mantle composition is enriched in refractory elements by a factor of 1.49 relative to Si and Cl and by a factor of 1.12 for Mg relative to Si and Cl. These enrichments are in the same range as those for the Vigarano type carbonaceous chondrites. The Mg/Mg + Fe ratio of 89 is slightly lower than previous estimates.The $\text{Ca}\text{Al}$ ratio in spinel lherzolite suites is, however, uniformly higher worldwide than the chondritic ratio by about 15%. Orogenic peridotites as well as komatiites appear to have similar non-chondritic $\text{Ca}\text{Al}$ ratios. It is therefore suggested that this non-chondritic $\text{Ca}\text{Al}$ ratio is a characteristic of the upper mantle, possibly since the Archean. A minor fractionation of about 4% of garnet in an early, global melting event (deep magma ocean?) is presented as the most likely cause for the high $\text{Ca}\text{Al}\text{-}\text{ratio}$. In this case the addition of 4% of such a garnet component to the undepleted present upper mantle would be required to obtain the composition of the primordial upper mantle. The $\text{Ca}\text{Al}\text{-}\text{ratio}$ of this primordial mantle would be 15% higher than that of the undepleted present upper mantle, resulting in an enrichment of refractory elements of 1.70 ($\text{Al}\text{Si}$ relative to Cl) for the primordial upper mantle.     

Thermochemical study of Mg–Fe chlorites

The thermochemical study of two natural trioctahedral Mg–Fe chlorites—clinochlores was carried out using high-temperature melt solution calorimetry with a Tian–Calvet microcalorimeter. The enthalpies of formation of clinochlores of compositions (Mg_4.9Fe _0.3 ²⁺ Al_0.8)[Si_3.2Al_0.8O₁₀](OH)₈ (–8811 ± 12 kJ/mol) and (Mg_4.3Fe _0.7 ²⁺ Al_1.0)[Si_3.0Al_1.0O₁₀](OH)₈ (–8696 ± 13 kJ/mol) from elements were determined. The values of the standard entropies and the Gibbs energies of formation of the studied natural minerals as well as thermodynamic properties of Mg–Fe chlorites of theoretical composition were estimated.     

Silicate perovskite-melt partitioning of trace elements and geochemical signature of a deep perovskitic reservoir

We have determined the partitioning of a wide range of trace elements between silicate melts and CaSiO₃ and MgSiO₃ perovskites using both laser ablation-ICPMS and ion microprobe techniques. Our results show that, with the exception of Sc, Zr, and Hf, all trace elements we considered are incompatible in MgSiO₃ perovskite, from highly incompatible for U, Th, Ba, La, Sr and monovalent elements to slightly incompatible for heavy rare earth elements. MgSiO₃ perovskite-melt partition coefficients increase slightly with Al content in the perovskite. These observations contrast strongly with partitioning between CaSiO₃ perovskite and silicate melts. In the latter case, all rare earth elements are clearly compatible as are U and Th. Our data also suggest that, contrary to pressure and temperature, melt composition can significantly affect CaSiO₃ perovskite-melt partitioning; partition coefficients for rare earth elements and U and Th increase with decreasing CaO melt content. The presence of ∼0.4 wt% water in melt makes little difference, however. Partitioning of trace elements into the large site of both MgSiO₃ and CaSiO₃ perovskites follows the near-parabolic dependence on ionic radius predicted from the lattice strain model. The peaks of the parabolae are much higher for the CaSiO₃ phase, perhaps suggesting that the mechanisms of charge compensation for heterovalent substitution are different in the two cases. Our partitioning data have been used to assess the potential effect of perovskite fractionation into the lower mantle during early Earth history. Crystallisation of less than 8% of a mixture of CaSiO₃ and MgSiO₃ perovskites could have led to a ‘layer’ enriched in U and Th without disturbing the chondritic pattern of refractory lithophile elements in the primitive upper mantle. The resultant reservoir could have high Sm/Nd, U/Pb, Sr/Rb, Lu/Hf ratios similar to the HIMU component of ocean island basalts, but would not balance the observed depletion of the primitive upper mantle in Si and Nb.     

Effects of Mg and Si ions on the symmetry of δ-AlOOH

We conducted powder neutron diffraction for δ-AlOOH samples with and without Mg and Si ions under ambient conditions in order to investigate the long-standing problem of the symmetry of this phase. The observed reflection conditions clearly show that the space group of pure δ-AlOOH is P2₁ nm with ordered hydrogen bonds, whereas that of δ-(Al_0.86Mg_0.07Si_0.07)OOH is Pnnm or Pnn2 with disordered hydrogen bonds. It is more likely that the space group of δ-(Al_0.86Mg_0.07Si_0.07)OOH is Pnnm, because cation or hydrogen ordering that breaks the mirror plane perpendicular to c axis in the Pnnm structure would not occur. The previously reported inconsistency for the space group of this phase was caused by the substitution of Mg and Si ions to Al site, i.e., the disordered cations with different valences may fluctuate hydrogen positions, and the disordered hydrogen causes the symmetry change.     

Kimberlite petrogenesis: Insights from clinopyroxene-melt partitioning experiments at 6 GPa in the CaO-MgO-Al2O3-SiO2-CO2 system

In this experimental study, we examine the mineral-melt partitioning of major and trace elements between clinopyroxene and CO₂-rich kimberlitic melts at a pressure of 6 GPa and temperatures of 1410°C and 1430°C. The melts produced contain ∼ 28 wt% dissolved CO₂, and are saturated with olivine and clinopyroxene. To assess the effects of temperature, crystal and melt compositions on trace element partitioning, experiments were performed in the model CaO-MgO-Al₂O₃-SiO₂-CO₂ system. Our results reveal that all the elements studied, except Al, Mg, Si, and Ga, are incompatible in clinopyroxene. Partition coefficients show a considerable range in magnitude, from ∼ 10⁻³ for D_U and D_Ba to ∼ 2.5 for D_Si. The two experimental runs show similar overall partitioning patterns with the D values being lower at 1430°C. Rare earth elements display a wide range of partition coefficients, D_La (0.012-0.026) being approximately one order of magnitude lower than D_Lu (0.18-0.23). Partition coefficients for the 2+ and 3+ cations entering the M2-site exhibit a near-parabolic dependence on radius of the incorporated cations as predicted from the lattice strain model. This underlines the contribution made by the crystal structure toward controlling the distribution of trace elements. Using data obtained in this study combined with that in the published literature, we also discuss the effects that other important parameters, namely, melt composition, pressure, and temperature, could have on partitioning.Our partition coefficients have been used to model the generation of the Group I (GI) kimberlites from South Africa. The numerical modeling shows that kimberlitic melts can be produced by ∼0.5% melting of a MORB-type depleted source that has been enriched by small-degree melts originating from a similar depleted source. This result suggests that the source of GI kimberlites may be located at the lithosphere-asthenosphere transition. Percolation of small degree melts from the asthenosphere would essentially create a metasomatic horizon near the bottom of the non-convecting sublithospheric mantle. Accumulation of such small degree melts together with the presence of volatiles and conductive heating would trigger melting of the ambient mantle and subsequently lead to eruption of kimberlitic melts. Additionally, our model shows that the GI source can be generated by metasomatism of a 2 Ga old MORB source ca. 1 Ga ago. Assuming that MORB-type mantle is the most depleted source of magmas on earth, then this is the oldest age at which the GI source could have existed. However, this age most likely reflects the average age of a series of metasomatic events than that of a single event.     

Evidence for a Deep-Mantle Origin of a NaPX-EN Inclusion in Diamond

A diamond mineral inclusion (NaPx-En) with a garnet structure and unusual composition (16 mol% Na₂MgSi₅O₁₂—84% Mg₄Si₄O₁₂) was reported from a Chinese diamond and demonstrated to be from the Earth's transition zone (Wang and Sueno, 1996; Gasparik and Hutchison, 2000). Concentrations of LREEs in the inclusion increase gradually with the atomic number; the MREE and HREE are about 7-10 times chondrite.

Trace-element partitionings between NaPx-En garnet and CO₂-rich melt were experimentally determined at 1900°C and 23 GPa with a split-sphere anvil apparatus (USSA-2000). Partitioning coefficients increase regularly from 0.002 for La to 0.8 for Yb. The calculated concentrations of REEs and Ti, Sr, Y, and Zr in hypothetical melt coexisting with the NaPx-En inclusion in the source region are consistent with those typical of natural carbonatite melts. We propose that the NaPx-En inclusion formed originally in the lower mantle as MgSiO₃ perovskite. It was later converted to garnet by reaction with a carbonatite melt upon mantle diapir movement into the transition zone. It was only then encapsulated as a diamond inclusion.     

Potassic primary melts of vulsini (Roman Province): evidence from mineralogy and melt inclusions

The origin and the relationships between the high potassic (HKS) and potassic (KS) suites of the Roman Comagmatic Province and the nature of their primary magmas have been intensively debated over the past 35 years. We have addressed these problems by a study of mineralogy (olivine Fo_92-87, Cr-spinel and diopside) and melt inclusions in olivine phenocrysts from a scoria sample of Montefiascone (Vulsini area). This rock is considered as one of the most primitive (MgO=13.5 wt%, NiO=340 ppm; Cr=1275 ppm) in the northern part of the Roman Comagmatic Province. The compositions of both the olivine and their melt inclusions are controlled by two main processes. In the case of the olivine Fo<90.5, fractional crystallization (olivine + diopside + minor spinel) was the principal mechanism of the magma evolution. The olivine (Fo_92-90.5) and the Cr-spinel (Cr#=100. Cr/(Cr+Al)=63-73) represent a near-primary liquidus assemblage and indicate the mantle origin of their parental magmas. The compositions of melt inclusions in these olivine phenocrysts correspond to those of poorly fractionated H₂O-rich ( 1 wt%) primary melts (MgO=8.4-9.7 wt%,FeO^total=6-7.5 wt%). They evidence a wide compositional range (in wt%: SiO₂=46.5-50, K₂O=5.3-2.8, P₂O₅=0.4-0.2, S=0.26-0.12; Cl=0.05-0.03, and CaO/Al₂O₃= 0.8-1.15), with negative correlations between SiO₂ and K₂O, Al₂O₃ and CaO, as well as positive correlations between K₂O, and P₂O₅, S, Cl, with nearly constant ratios between these elements. These results are discussed in terms of segregation of various mantle-derived melts. The high and constant Mg# [100.Mg/(Mg+Fe²⁺)] 73-75 of studied melts and their variable Si, K, P, Ca, Al, S contents could be explained by the melting of a refractory lithospheric mantle source, heterogeneously enriched in phlogopite and clinopyroxene (veined mantle source).     

Diffusion gradients in an eclogite xenolith from the Roberts Victor kimberlite pipe: (2) kinetics and implications for petrogenesis

In a bimineralic eclogite xenolith (sample JJG41) from the Roberts Victor kimberlite, compositional gradients in clinopyroxene are related to garnet exsolution. Two principal reactions involving clinopyroxene and garnet occur: (i) The net-transfer Al₂Si^-1Mg^-1 which is responsible for garnet growth according to the equation 2Di+Al₂Si^-1Mg^-1=Grossular+MgCa^-1 (reaction 1). This has created substantial compositional gradients in Al, Si and Mg within clinopyroxene. (ii) The exchange of Fe–Mg between garnet and clinopyroxene (reaction 2). During the stage of garnet growth (reaction 1) the lamellae crystallized sequentially as a result of a temperature decrease from around 1400 to 1200° C. This exsolution growth-stage was under the control of Al diffusion in clinopyroxene and at around 1200° C further growth of garnet lamellae became impeded by the sluggishness of Al diffusion in the clinopyroxene host. However, reaction 2 continued during further cooling down to about 1000° C; this temperature being inferred from the constant Fe–Mg partitioning at clinopyroxene-garnet interfaces for the whole set of lamellae. The initial clinopyroxene in JJG41 was probably formed by crystallization from a melt in Archaean time. The cessation of Fe–Mg exchange between garnet and clinopyroxene at about 1000° C may well predate the eruption of the eclogite in kimberlite at around 100 Ma. Kinetic models of reaction are examined for both reactions. Modelling of reaction 1, involving both diffusion and interface migration, allows several means of estimating the diffusion coefficient of Al in clinopyroxene; the estimates are in the range 10^-16-10^-20 cm²/s at 1200° C. These estimates bracket the experimentally determined data for Al diffusion in clinopyroxene, and from these experimental data a preferred cooling rate of about 300° C/Ma is obtained for the period of growth of garnet exsolution lamellae. A geospeedometry approach (Lasaga 1983) suitable for a pure-exchange process (reaction 2) is used to estimate the cooling rate in the later stages of the thermal history (after garnet growth); values 4–40° C/Ma are consistent with the shape of the Fe-diffusion gradients in the clinopyroxene. The extensive thermal history recorded by JJG41, including probable melt involvement at ca. 1400° C, demonstrates the complex evolution of rocks within the mantle. Whilst the notion of formation of mantle eclogites from subducted oceanic crust has become fashionable, it is clear that tracing eclogite geochemical and P-T characteristics backwards from their nature at the time of xenolith eruption, through high-temperature mantle events to the characteristics of the original subducted oceanic crust, will be very complex.     

Prediction of high-temperature oxygen isotope fractionation factors between mantle minerals

The increment method is adopted to calculate oxygen isotope fractionation factors for mantle minerals, particularly for the polymorphic phases of MgSiO₃ and Mg₂SiO₄. The results predict the following sequence of ¹⁸O-enrichment: pyroxene (Mg,Fe,Ca)₂Si₂O₆>olivine (Mg,Fe)₂SiO₄>spinel (Mg,Fe)₂SiO₄>ilmenite (Mg,Fe, Ca)SiO₃>perovskite (Mg,Fe,Ca)SiO₃. The calculated fractionations for the calcite-perovskite (CaTiO₃) system are in excellent agreement with experimental calibrations. If there would be complete isotopic equilibration in the mantle, the spinel-structured silicates in the transition zone are predicted to be enriched in ¹⁸O relative to the perovskite-structured silicates in the lower mantle but depleted in ¹⁸O relative to olivines and pyroxenes in the upper mantle. The oxygen isotope layering of the mantle would essentially result from differences in the chemical composition and crystal structure of mineral phases at different mantle depths. Assuming isotopic equilibrium on a whole earth scale, the chemical structure of the Earth's interior can be described by the following sequence of ¹⁸O-enrichment: uppr crust>lower crust>upper mantle>transition zone>lower mantle >core.     

Thermochemical study Mg–Fe amphiboles

The paper presents data on the thermochemical study (high-temperature melt calorimetry in a Tian–Calvet microcalorometer) of two natural Mg–Fe amphiboles: anthophyllite Mg_2.0(Mg_4.8Fe_0.2 ²⁺)[Si_8.0O₂₂](OH)₂ from Kukh-i-Lal, southwestern Pamirs, Tajikistan, and gedrite Na_0.4Mg_2.0(Mg_1.7Fe_0.2 ²⁺Al_1.3)[Si_6.3Al_1.7O₂₂](OH)₂ from the Kola Peninsula, Russia. The enthalpy of formation from elements is obtained as–12021 ± 20 kJ/mol for anthophyllite and as–11545 ± 12 kJ/mol for gedrite. The standard entropy, enthalpy, and Gibbs energy of formation are evaluated for Mg–Fe amphiboles of theoretical composition.     

Composition of barian mica in multiphase solid inclusions from orogenic garnet peridotites as evidence of mantle metasomatism in a subduction zone setting

Multiphase solid inclusions in minerals formed at ultra-high-pressure (UHP) provide evidence for the presence of fluids during deep subduction. This study focuses on barian mica, which is a common phase in multiphase solid inclusions enclosed in garnet from mantle-derived UHP garnet peridotites in the Saxothuringian basement of the northern Bohemian Massif. The documented compositional variability and substitution trends provide constraints on crystallization medium of the barian mica and allow making inferences on its source. Barian mica in the multiphase solid inclusions belongs to trioctahedral micas and represents a solid solution of phlogopite KMg₃(Si₃Al)O₁₀(OH)₂, kinoshitalite BaMg₃(Al₂Si₂)O₁₀(OH)₂ and ferrokinoshitalite BaFe₃(Al₂Si₂)O₁₀(OH)₂. In addition to Ba (0.24–0.67 apfu), mica is significantly enriched in Mg (X_Mg ~ 0.85 to 0.95), Cr (0.03–0.43 apfu) and Cl (0.04–0.34 apfu). The substitution vector involving Ba in the I-site which describes the observed chemical variability can be expressed as BaFe^IVAlClK_?1Mg_?1Si_?1(OH)_?1. A minor amount of Cr and ^VIAl enters octahedral sites following a substitution vector ^VI(Cr,Al)₂□^VI(Mg,Fe)_?3 towards chromphyllite and muscovite. As demonstrated by variable Ba and Cl contents positively correlating with Fe, barian mica composition is partly controlled by its crystal structure. Textural evidence shows that barian mica, together with other minerals in multiphase solid inclusions, crystallized from fluids trapped during garnet growth. The unusual chemical composition of mica reflects the mixing of two distinct sources: (1) an internal source, i.e. the host peridotite and its garnet, providing Mg, Fe, Al, Cr, and (2) an external source, represented by crustal-derived subduction-zone fluids supplying Ba, K and Cl. At UHP–UHT conditions recorded by the associated diamond-bearing metasediments (c. 1100 °C and 4.5 GPa) located above the second critical point in the pelitic system, the produced subduction-zone fluids transporting the elements into the overlying mantle wedge had a solute-rich composition with properties of a hydrous melt. The occurrence of barian mica with a specific chemistry in barium-poor mantle rocks demonstrates the importance of its thorough chemical characterization.     

The major-element chemistry of suspended matter in the Amazon Estuary

Suspended matter from the surface waters of the Amazon Estuary were collected during May and June 1976 on the ‘R/V Alpha Helix’, and their major-element compositions (Al, Si, Ti, K, Mg, Ca, P, Fe and Mn) were measured.Between salinities of 0 and 10%. the suspended material, predominantly terrigenous in derivation, decreases in load from 500 to 3 mg/l, but has a chemical composition which remains essentially constant. With the onset of a large amount of biological productivity at approximately 10%. salinity, there are large increases in the ratios of $\text{Si}\text{Al}$, $\text{P}\text{Al}$, $\text{Ca}\text{Al}$, $\text{Mg}\text{Al}$, $\text{Ti}\text{Al}$ and $\text{Mn}\text{Al}$ which are maintained at higher salinities. Calculations of “excess” concentrations of elements held in the non-terrigenous components of the suspended material further support our main conclusion that Si, P, Ca, Mg, Ti and Mn are incorporated into the skeletal and organic phases of marine phytoplankton (predominately diatoms) of the Amazon Estuary. The data suggest, but with less certainty, that Fe and K follow the above elements.This study has demonstrated that the chemical composition of river-introduced suspended matter can be significantly altered by biological activity within estuarine waters as can be the geochemical cycle of inorganic elements.