Effect of Fe on garnet–melt trace element partitioning: experiments in FCMAS and quantification of crystal-chemical controls in natural systems

Garnet–melt trace element partitioning experiments were performed in the system FeO–CaO–MgO–Al₂O₃–SiO₂ (FCMAS) at 3 GPa and 1540°C, aimed specifically at studying the effect of garnet Fe²⁺ content on partition coefficients (D^Grt/Melt). D^Grt/Melt, measured by SIMS, for trivalent elements entering the garnet X-site show a small but significant dependence on garnet almandine content. This dependence is rationalised using the lattice strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454], which describes partitioning of an element i with radius r_i and valency Z in terms of three parameters: the effective radius of the site r₀(Z), the strain-free partition coefficient D₀(Z) for a cation with radius r₀(Z), and the apparent compressibility of the garnet X-site given by its Young's modulus E_X(Z). Combination of these results with data in Fe-free systems [Van Westrenen, W., Blundy, J.D., Wood, B.J., 1999. Crystal-chemical controls on trace element partitioning between garnet and anhydrous silicate melt. Am. Mineral. 84, 838–847] and crystal structure data for spessartine, andradite, and uvarovite, leads to the following equations for r₀(3+) and E_X(3+) as a function of garnet composition (X) and pressure (P):

r₀(3+) [Å]=0.930X_Py+0.993X_Gr+0.916X_Alm+0.946X_Spes+1.05(X_And+X_Uv)−0.005(P [GPa]−3.0)(±0.005 Å)

E_X(3+) [GPa]=3.5×10¹²(1.38+r₀(3+) [Å])^−26.7(±30 GPa)

Accuracy of these equations is shown by application to the existing garnet–melt partitioning database, covering a wide range of P and T conditions (1.8 GPa<P<5.0 GPa; 975°C<T<1640°C). D^Grt/Melt for all 3+ elements entering the X-site (REE, Sc and Y) are predicted to within 10–40% at given P, T, and X, when D^Grt/Melt for just one of these elements is known. In the absence of such knowledge, relative element fractionation (e.g. D_Sm^Grt/Melt/D_Nd^Grt/Melt) can be predicted. As an example, we predict that during partial melting of garnet peridotite, group A eclogite, and garnet pyroxenite, r₀(3+) for garnets ranges from 0.939±0.005 to 0.953±0.009 Å. These values are consistently smaller than the ionic radius of the heaviest REE, Lu. The above equations quantify the crystal-chemical controls on garnet–melt partitioning for the REE, Y and Sc. As such, they represent a major advance en route to predicting D^Grt/Melt for these elements as a function of P, T and X.     

The effect of Ca-Tschermaks component on trace element partitioning between clinopyroxene and silicate melt

We have studied the influence of Ca-Tschermaks (Calcium Tschermaks or CaTs) content of clinopyroxene on the partitioning of trace elements between this phase and silicate melt at fixed temperature and pressure. Ion probe analyses of experiments carried out in the system Na₂O–CaO–MgO–Al₂O₃–SiO₂, at 0.1 MPa and 1218°C, produced crystal-melt partition coefficients (D) of 36 trace elements (Li, Cl, Sc, Ti, V, Cr, Fe, Co, Ge, Sr, Y, Zr, Nb, Mo, Ru, Rh, In, Sn, Sb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta and W), for clinopyroxene compositions between 10 and 32 mol% CaTs. Partition coefficients for 2+ to 5+ cations show, for each charge, a near parabolic dependence of log D on ionic radius of the substituting cation, for partitioning into both the M1 and M2 sites of clinopyroxene. Fitting the results to the elastic strain model of Blundy and Wood [Blundy, J.D., Wood, B.J., 1994. Prediction of crystal-melt partition coefficients from elastic moduli. Nature 372, 452–454] we obtain results for the strain-free partition coefficients of theoretical cations (D₀), with site radius r₀, and for the site's Young's Modulus (E).

In agreement with earlier data our results show that increasing ^ivAl concentration in cpx is matched by increasing D, E_M1, E_M2 and D₀ for tri-, tetra- and pentavalent cations. The degree of fractionation between chemically similar elements (i.e. Ta/Nb, Zr/Hf) also increases. In contrast, D values for mono-, di- and hexavalent cations decrease with increasing ^ivAl in the cpx. The large suite of trace elements used has allowed us to study the effects of cation charge on D₀, r₀ and E. We have found that D₀ and r₀ decrease with increasing cation charge, e.g. r₀=0.66 Å for 4+ cations and 0.59 Å for 5+ cations substituting into M1. Values of E_M1 and E_M2 increase with cation charge as well as with increasing ^ivAl content. The increase in E_M2 is linear and close to the trend set by Hazen and Finger [Hazen, R.M., Finger, L.W., 1979. Bulk modulus-volume relationship for cation–anion polyhedra. J. Geophys. Res. 84 (10) 6723–6728] for oxides. E_M1 values are much higher and do not fit the trend predicted by the Hazen and Finger relationship.     

Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

Boundary lines within petrologic diagrams which use oxides of major and minor elements

Use of some petrologic diagrams applied to analyses of volcanic rocks is unnecessarily difficult due to lack of data for construction of discriminant lines between rock series. Coordinates are provided for sufficient points to enable accurate plotting of the boundary lines within seven diagrams, viz.: (1) TAS - total alkalies (Na₂O+K₂O) vs. SiO₂; (2) K₂O vs. SiO₂; (3) AFM; (4) Jensen; (5) KTP - K₂O---TiO₂---P₂O₅; (6) FMS - (FeO^*/MgO) vs. SiO₂; and (7) TAKTIP - K₂O/(Na₂O+K₂O) vs. TiO₂/P₂O₅. Different versions of these boundaries are collated to indicate their variable position, and it is demonstrated that inter-laboratory analytical precision suffices to account for almost all of their spread on the TAS and K₂O vs. SiO₂ diagrams.     

SIMS determination of trace element partition coefficients between garnet, clinopyroxene and hydrous basaltic liquids at 2–7.5 GPa and 1080–1200°C

Trace element partition coefficients (D's) for up to 13 REE, Nb, Ta, Zr, Hf, Sr and Y have been determined by SIMS analysis of seven garnets, four clinopyroxenes, one orthopyroxene and one phlogopite crystallized from an undoped basanite and a lightly doped (200 ppm Nb, Ta and Hf) quartz tholeiite. Experiments were conducted at 2–7.5 GPa, achieving near-liquidus crystallization at relatively low temperatures of 1080–1200°C under strongly hydrous conditions (5–27 wt.% added water). Garnet and pyroxene D_REE show a parabolic pattern when plotted against ionic radius, and conform closely to the lattice strain model of Blundy and Wood (Blundy, J.D., Wood, B.J., 1994. Prediction of crystal–melt partition coefficients from elastic moduli. Nature 372, 452–454). Comparison, at constant pressure, between hydrous and anhydrous values of the strain-free partition coefficient (D₀) for the large cation sites of garnet and clinopyroxene reveals the relative importance of temperature and melt water content on partitioning. In the case of garnet, the effect of lower temperature, which serves to increase D₀, and higher water content, which serves to decrease D₀, counteract each other to the extent that water has little effect on garnet–melt D₀ values. In contrast, the effect of water on clinopyroxene–melt D₀ overwhelms the effect of temperature, such that D₀ is significantly lower under hydrous conditions. For both minerals, however, the lower temperature of the hydrous experiments tends to tighten the partitioning parabolas, increasing fractionation of light from heavy REE compared to anhydrous experiments.

Three sets of near-liquidus clinopyroxene–garnet two-mineral D values increase the range of published experimental determinations, but show significant differences from natural two-mineral D's determined for subsolidus mineral pairs. Similar behaviour is observed for the first experimental data for orthopyroxene–clinopyroxene two-mineral D's when compared with natural data. These differences are in large part of a consequence of the subsolidus equilibration temperatures and compositions of natural mineral pairs. Great care should therefore be taken when using natural mineral–mineral partition coefficients to interpret magmatic processes.

The new data for strongly hydrous compositions suggest that fractionation of Zr–Hf–Sm by garnet decreases with increasing depth. Thus, melts leaving a garnet-dominated residuum at depths of about 200 km or greater may preserve source Zr/Hf and Hf/Sm. This contrasts with melting at shallower depths where both garnet and clinopyroxene will cause Zr–Hf–Sm fractionation. Also, at shallower depths, clinopyroxene-dominated fractionation may produce a positive Sr spike in melts from spinel lherzolite, but for garnet lherzolite melting, no Sr spike will result. Conversely, clinopyroxene megacrysts with negative Sr spikes may crystallize from magmas without anomalous Sr contents when plotted on mantle compatibility diagrams. Because the characteristics of strongly hydrous silicate melt and solute-rich aqueous fluid converge at high pressure, the hydrous data presented here are particularly pertinent to modelling processes in subduction zones, where aqueous fluids may have an important metasomatic role.     

Strontium diffusion in sanidine and albite, and general comments on strontium diffusion in alkali feldspars

Strontium chemical diffusion has been measured in albite and sanidine under dry, 1 atm, and QFM buffered conditions. Strontium oxide-aluminosilicate powdered sources were used to introduce the diffusant and Rutherford Backscattering Spectroscopy (RBS) used to measure diffusion profiles. For the 1 atm experiments, the following Arrhenius relations were obtained:

Sanidine (Or₆₁), temperature range 725–1075°C, diffusion normal to (001): D=8.4 exp(−450±13 kJ mol⁻¹/RT) m²s⁻¹. Albite (Or₁), temperature range 675–1025°C, diffusion normal to (001): D=2.9 × exp(−224±11 kJ mol⁻¹/RT) m²s⁻¹.

The alkali feldspars in this and earlier work display a broad range of activation energies for Sr diffusion, which may be a consequence of the thermodynamic non-ideality of the alkali feldspar system and/or the mixed alkali effect.     

Liquid immiscibility and its role at the magmatic–hydrothermal transition: a summary of experimental studies

Several types of fluid immiscibility may affect the evolution of volatile-rich magmatic systems at the magmatic–hydrothermal transition. The topology of silicate–salt–H₂O systems implies that three-fluid immiscibility (silicate melt+hydrosaline melt+vapour) should be stable in a broad range of compositions and P–T conditions. The most important factor controlling the immiscibility appears to be the Coulombic properties (electric charges Z and ionic radii r) of the main network-modifying cations and the capacity for immiscibility appears to decrease in the following sequence: Mg>Ca>Sr>Ba>Li>Na>K. Liquid immiscibility is enhanced in peralkaline compositions and in the presence of nonsilicate anions such as F⁻, Cl⁻, CO₃²⁻ and BO₃³⁻. In volatile-rich magmatic systems, the H₂O is likely to react with the chloride, fluoride, borate and carbonate species and the chemical effects of high-temperature hydrolysis may be greatly enhanced by phase separation in systems with multiple immiscible fluid phases. Natural granitic magmas can thus exsolve a range of chemically and physically diverse hydrosaline liquids and the role of these fluid phases is likely to be especially significant in pegmatites and Li–F rare-metal granites.     

Partitioning of boron among melt, brine and vapor in the system haplogranite–H2O–NaCl at 800 °C and 100 MPa

Fluid-saturated experiments were conducted to investigate the partitioning of boron among haplogranitic melt, aqueous vapor and brine at 800 °C and 100 MPa. Experiments were carried out in cold-seal pressure vessels for 1 to 21 days, and utilized powdered synthetic subaluminous haplogranite glass doped with 1000 ppm B (crystalline H₃BO₃) and variable amounts of NaCl and H₂O at a fluid/haplogranite mass RATIO=1:1. Run-product glasses were analyzed for boron concentration by secondary ion mass spectrometry (SIMS) and for major elements and chlorine by electron microprobe. The composition of the coexisting fluid was calculated by mass balance. Boron partition coefficients between aqueous vapor and hydrous granitic melt range from 3.1 to 6.3, and demonstrate a clear preference of boron for the vapor over the hydrous melt. Partition coefficients between brine and hydrous granitic melt vary from 0.45 to 1.1, suggesting that boron has no preference for the brine or the melt. The bulk fluid–melt partition coefficients for low-salinity and high-salinity experiments are D_B^(vapor/melt)=4.6±1.3 and D_B^(brine/melt)=0.91±0.49, respectively. The corresponding vapor–brine partition coefficient is 5.0±3.1, demonstrating that boron partitions preferentially into the vapor over the brine at the conditions of this study. The preferential incorporation of boron in the aqueous vapor is controlled by borate speciation and solution mechanism. The dominant borate species in aqueous fluids, H₃BO₃^o, is highly soluble in aqueous vapor (X_B2O3=0.187); however, B₂O₃ is immiscible in NaCl liquid. Consequently, concentrations of boron in aqueous vapor are significantly higher than in the coexisting brine. Furthermore, Na–B complexing in the melt at high chlorine fluid contents stabilizes boron in the melt thereby contributing to the non-preferential partitioning of boron between brine and melt. The commonly observed association of tourmalinization (boron metasomatism), brecciation and ore deposition in nature is consistent with the preferential partitioning of boron into aqueous vapor of magmatic-hydrothermal systems predicted by this study.     

Geochemistry of the Uintjiesberg kimberlite, South Africa: petrogenesis of an off-craton, group I, kimberlite

The Uintjiesberg kimberlite diatreme occurs within the Proterozoic Namaqua–Natal Belt, South Africa, approximately 60 km to the southwest of the Kaapvaal craton boundary. It is a group I, calcite kimberlite that has an emplacement age of 100 Ma. Major and trace element data, in combination with petrography, are used to evaluate its petrogenesis and the nature of its source region. Macrocryst phases are predominantly olivine with lesser phlogopite, with very rare garnet and Cr-rich clinopyroxene. Geochemical variation amongst the macrocrystic samples (Mg# 0.85–0.87, SiO₂=27.0–29.3%, MgO=26.1–30.5%, CaO=10.9–13.5%) is shown to result from 10% to 40% entrainment and partial assimilation of peridotite xenoliths, whereas that shown by the aphanitic samples (Mg# 0.80–0.83, SiO₂=19.1–23.0%, MgO=17.9–23.9%, CaO=16.5–23.7%) is consistent with 7–25% crystal fractionation of olivine and minor phlogopite. Changing trajectories on chemical variation diagrams allow postulation of a primary magma composition with 25% SiO₂, 26% MgO, 2.3% Al₂O₃, 5%H₂O, 8.6% CO₂ and Mg#=0.85.

Forward melting models, assuming 0.5% melting, indicate derivation of the primary Uintjiesberg kimberlite magma from a source enriched in light rare earth elements (LREE) by 10× chondrite and heavy REE (HREE) by 0.8–2× chondrite, the latter being dependent on the proportion of residual garnet. Significant negative Rb, K, Sr, Hf and Ti anomalies present in the inferred primary magma composition are superimposed on otherwise generally smooth primitive mantle-normalized trace element patterns, and are inferred to be a characteristic of the primary magma composition. The further requirement for a source with chondritic or lower HREE abundances, residual olivine with high Fo content (Fo₉₄) suggests derivation from a mantle previously depleted in mafic melt but subsequently enriched in highly incompatible elements prior to kimberlite genesis. These requirements are interpreted in the context of melting of continental lithospheric mantle previously enriched by metasomatic fluids derived from a sublithospheric (plume?) source.     

Mineralogy and petrology of cretaceous subsurface lamproite sills, southeastern Kansas, USA

Cores and cuttings of lamproite sills and host sedimentary country rocks in southeastern Kansas from up to 312 m depth were analyzed for major elements in whole rocks and minerals, certain trace elements in whole rocks (including the REE) and Sr isotopic composition of the whole rocks. The lamproites are ultrapotassic (K₂O/Na₂O = 2.0–19.9), alkalic [molecular (K₂O/Na₂O)/Al₂O₃ = 1.3-2.8], enriched in mantle-incompatible elements (light REE, Ba, Rb, Sr, Th, Hf, Ta) and have nearly homogeneous initial Sr isotopic compositions (0.707764-0.708114).

These lamproites could have formed by variable degrees of partial melting of harzburgite country rock and cross-cutting veins composed of phlogopite, K-Ti richterite, titanite, diopside, K-Ti silicates, or K-Ba-phosphate under high H₂O/CO₂ ratios and reducing conditions. Variability in melting of veins and wall rock and variable composition of the metasomatized veins could explain the significantly different composition of the Kansas lamproites.

Least squares fractionation models preclude the derivation of the Kansas lamproites by fractional crystallization from magmas similar in composition to higher silica phlogopite-sanidine lamproites some believe to be primary lamproite melts found elsewhere. In all but one case, least squares fractionation models also preclude the derivation of magmas similar in composition to any of the Kansas lamproites from one another. A magma similar in composition to the average composition of the higher SiO₂ Ecco Ranch lamproite (237.5–247.5 m depth) could, however, have marginally crystallized about 12% richterite, 12% sanidine, 7% diopside and 6% phlogopite to produce the average composition of the Guess lamproite (305–312 m depth).

Lamproite from the Ecco Ranch core is internally fractionated in K₂O, Al₂O₃, Ba, MgO, Fe₂O₃, Co and Cr most likely by crystal accumulation-removal of ferromagnesian minerals and sanidine. In contrast, the Guess core (305–312 m depth) has little fractionation throughout most of the sill except in several narrow zones. Lamproite in the Guess core has large enrichments in TiO₂, Ba, REE, Th, Ta and Sc and depletions in MgO, Cr, Co and Rb possibly concentrated in these narrow zones during the last dregs of crystallization of this magma.

The Ecco Ranch sill did not show any evidence of loss of volatiles or soluble elements into the country rock. This contrasts to the previously studied, shallow Silver City lamproite which did apparently lose H₂O-rich fluid to the country rock. Perhaps a greater confining pressure and lesser amount of H₂O-rich fluid prevented it from escaping.     

The nature of the sub-continental mantle: constraints from the major-element composition of continental flood basalts

Many continental flood basalts (CFB) have isotope and trace-element signatures that differ from those of oceanic basalts and much interest concerns the extent to which these reflect differences in their upper mantle source regions. A review of selected data sets from the Mesozoic and Tertiary CFB confirms significant differences in their major- and trace-element compositions compared with those of basalts erupted through oceanic lithosphere. In general, those CFB suites characterised by low Nb/La, high (⁸⁷Sr/⁸⁶Sr)_i and low εNd_i tend to exhibit relatively low TiO₂, CaO/Al₂O₃, Na₂O and/or Fe₂O₃, and relatively high SiO₂. In contrast, those which have high Nb/La, low (⁸⁷Sr/⁸⁶Sr)_i and high εNd_i ratios, like the upper units in the Deccan Traps, have major- and trace-element compositions similar to oceanic basalts. It would appear that those CFB that have distinctive isotope and trace-element ratios also exhibit distinctive major-element contents, suggesting that major and trace elements have not been decoupled significantly during magma generation and differentiation.

When compared (at 8% MgO) with oceanic basalt trends, the displacement of many CFB to lower Na₂O, Fe₂O₃^*, TiO₂ and CaO/Al₂O₃, but higher SiO₂, at similar Mg#, is not readily explicable by crustal contamination. Rather, it reflects source composition and/or the effects of the melting processes. The model compositions of melts produced by decompression of mantle plumes beneath continental lithosphere have relatively low SiO₂ and high Fe₂O₃^*. In contrast, the available experimental data indicate that partial melts of peridotite have low TiO₂, Na₂O and Fe₂O₃^*CaO/Al₂O₃, if the peridotite has been previously depleted by melt extraction. Moreover, melting of hydrated, depleted peridotite yields SiO₂-rich, Fe₂O₃- and CaO-poor melts. Since anhydrous, depleted peridotite has a high-temperature solidus, it is argued that the source of these CFB was variably melt depleted and hydrated mantle, inferred to be within the lithosphere. Isotope data suggest these source regions were often old and relatively enriched in incompatible trace elements, and it is envisaged that H₂O±CO₂ were added at the same time as the incompatible elements. An implication is that a significant proportion of the new continental crust generated since the Permian reflected multistage processes involving mobilization of continental mantle lithosphere that was enriched in minor and trace elements during the Proterozoic.     

Status report on stability of K-rich phases at mantle conditions

Experimental research on K-rich phases and observations from diamond inclusions, UHP metamorphic rocks, and xenoliths provide insights about the hosts for potassium at mantle conditions. K-rich clinopyroxene (Kcpx–KM³⁺Si₂O₆) can be an important component in clinopyroxenes at P>4 GPa, dependent upon coexisting K-bearing phases (solid or liquid) but not, apparently, upon temperature. Maximum Kcpx content can reach 25 mol%, with 17 mol% the highest reported in nature. Partitioning ^(K)D_(cpx/liquid) above 7 GPa=0.1–0.2 require ultrapotassic liquids to form highly potassic cpx or critical solid reactions, e.g., between Kspar and Di. Phlogopite can be stable to about 8 GPa at 1250 °C where either amphibole or liquid forms. When fluorine is present, it generally increases in Phl upon increasing P (and probably T) to about 6 GPa, but reactions forming amphibole and/or KMgF₃ limit F content between 6 and 8 GPa. The perovskite KMgF₃ is stable up to 10 GPa and 1400 °C as subsolidus breakdown products of phlogopite upon increasing P. ^(M4)K-substituted potassic richterite (ideally K(KCa)Mg₅Si₈O₂₂(OH,F)₂) is produced in K-rich peridotites above 6 GPa and in Di+Phl from 6 to 13 GPa. K content of amphibole is positively correlated with P; Al and F content decrease with P. In the system 1Kspar+1H₂O K-cymrite (hydrous hexasanidine–KAlSi₃O₈·nH₂O–Kcym) is stable from 2.5 GPa at 400 to 1200 °C and 9 GPa; Kcym can be a supersolidus phase. Formation of Kcym is sensitive to water content, not forming within experiments with H₂O2O>Kspar. Phase X, a potassium di-magnesium acid disilicate ((K_1−x−n)₂(Mg_1−nM_n³⁺)₂Si₂O₇H_2x), forms in mafic compositions at T=1150–1400 °C and P=9–17 GPa and is a potential host for K and H₂O at mantle conditions with a low-T geotherm or in subducting slabs. The composition of phase-X is not fixed but actually represents a solid solution in the stoichiometries □₂Mg₂Si₂O₇H₂–(K□)Mg₂Si₂O₇H–K₂Mg₂Si₂O₇ (□=vacancy), apparently stable only near the central composition. K-hollandite, KAlSi₃O₈, is possibly the most important K-rich phase at very high pressure, as it appears to be stable to conditions near the core–mantle boundary, 95 GPa and 2300 °C. Other K-rich phases are considered.     

Early Cretaceous gabbroic rocks from the Taihang Mountains: Implications for a paleosubduction-related lithospheric mantle beneath the central North China Craton

SHRIMP zircon U–Pb ages and geochemical and Sr–Nd–Pb isotopic data are presented for the gabbroic intrusive from the southern Taihang Mountains to characterize the nature of the Mesozoic lithospheric mantle beneath the central North China Craton (NCC). The gabbroic rocks emplaced at 125 Ma and are composed of plagioclase (40–50%), amphibole (20–30%), clinopyroxene (10–15%), olivine (5–10%) and biotite (5–7%). Olivines have high MgO (Fo = 78–85) and NiO content. Clinopyroxenes are high in MgO and CaO with the dominant ones having the formula of En_42–46Wo_41–50Fs_8–13. Plagioclases are dominantly andesine–labradorite (An = 46–78%) and have normal zonation from bytownite in the core to andesine in the rim. Amphiboles are mainly magnesio and actinolitic hornblende, distinct from those in the Precambrian high-pressure granulites of the NCC. These gabbroic rocks are characterized by high MgO (9.0–11.04%) and SiO₂ (52.66–55.52%), and low Al₂O₃, FeOt and TiO₂, and could be classified as high-mg basaltic andesites. They are enriched in LILEs and LREEs, depleted in HFSEs and HREEs, and exhibit (⁸⁷Sr/⁸⁶Sr)_i = 0.70492–0.70539, ε_Nd(t) = − 12.47–15.07, (²⁰⁶Pb/²⁰⁴Pb)_i = 16.63–17.10, Δ8/4 = 70.1–107.2 and Δ7/4 = − 2.1 to − 9.4, i.e., an EMI-like isotopic signatures. Such geochemical features indicate that these early Cretaceous gabbroic rocks were originated from a refractory pyroxenitic veined-plus-peridotite source previously modified by an SiO₂-rich melt that may have been derived from Paleoproterozoic subducted crustal materials. Late Mesozoic lithospheric extension might have induced the melting of the metasomatised lithospheric mantle in response to the upwelling of the asthenosphere to generate these gabbroic rocks in the southern Taihang Mountains.     

The Bjerkreim-Sokndal Layered Intrusion, Rogaland, SW Norway: Evidence from marginal rocks for a jotunite parent magma

The Late-Proterozoic Bjerkreim-Sokndal Layered Intrusion (BKSK) consists of andesine anorthosite, leuconorite, troctolite, norite, gabbronorite, jotunite, mangerite, quartz mangerite and charnockite. The sequence of appearance of cumulus minerals and their compositions suggest a parent magma that was evolved, had plagioclase (±olivine) on the liquidus, was sufficiently TiO₂-rich for hemo-ilmenite to crystallise early, and low in CaO and CaO/Al₂O₃compared to basalts as reflected by the sodic plagioclases and the delayed appearance of cumulus augite. Fine- to medium-grained jotunites found along the northern contact of the BKSK consist of plagioclase (An_45–53), inverted pigeonite (Mg# = 55-50), sparse augite (Mg# = 69-59), Fe-Ti oxides, K-feldspar, quartz and apatite. They are basic to intermediate rocks with relatively high FeO^total, high TiO₂, low MgO/MgO + FeO, moderate Al₂O₃ and low CaO and normative diopside. The jotunites have compositions that are consistent with the parental magma for the lower part of the BKSK Layered Series, and are interpreted as being marginal chills. Similar, but slightly more differentiated, jotunite magmas were subsequently emplaced into the BKSK and the surrounding region as broad dykes and small plutons. Jotunite is a minor rock type in most massif-type anorthosite provinces but may have an important petrological significance.     

Oxidative dissolution of pyritic sludge from the Aznalcóllar mine (SW Spain)

As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m² g⁻¹).

The dissolution rate law of sludge obtained is r=10^{−6.1(±0.3)} [O₂(aq)]^0.41(±0.04) a_H+^0.09(±0.06) g_sludge m⁻² s⁻¹ (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10^{−7.8(±0.3)} [O₂(aq)]^0.50(±0.04) a_H+^0.10(±0.08) mol m⁻² s⁻¹ (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively.

A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O₂ onto pyrite surface is proposed.     

Mineral phase compositions in silica-undersaturated ‘leucite’ lamproites from the Bucak area, Isparta, SW Turkey

Ultrapotassic rocks in the Bucak area of Isparta Angle, SW Turkey, show unusually low SiO₂ (46.8–49.2 wt.%) and high MgO (10.4–11.6 wt.%) contents, and lamproitic affinity (K/Na, > 2.5; Mg#, 73–75; Al₂O₃, 9.2–11 wt.%, CaO 7.4–10.6 wt.%, Cr, 525–675 ppm; Ni, 442–615 ppm). They are made up by phlogopite (30–40 vol.%), leucite (25–30 vol.%), olivine (5–20 vol.%), which rarely contain Cr-spinel, clinopyroxene (5–10 vol.%), sanidine (5 vol.%) and richterite, with accessory apatite, magnetite and ilmenite. One sample also include negligible sodalite in groundmass, which is unusual mineral in lamproites. Mineral phase variation and textures record discrete phases of pre-eruptive crystallization: (1) early appearance of (Cr-spinel-bearing) olivine, Ti poor phlogopite ± apatite at pressures of ca. 1.0–2.0 GPa, at or close to the lithospheric Mechanical Boundary Layer (MBL), and (2) later appearance of Ti rich phlogopite, clinopyroxene, richterite, leucite, sanidine, and other minor phases, at pressures of ca. 0.1–1.0 GPa, indicating discrete, pressure-specific fractionation events. The Bucak silica poor ‘leucite’ lamproites were probably generated by partial melting of phlogopite-bearing, refractory peridotite at pressures of ca. 1.5–2 GPa, higher than those proposed for SiO₂-saturated ‘phlogopite’ lamproites (ca. 1–1.5 GPa) from Afyon, to the North. The depth (total pressure) of melt segregation probably dominates over volatile partial pressures (e.g. of CO₂, F, H₂O) in determining the SiO₂-undersaturated character of Bucak magmas.     

江南造山带西段桂北四堡地区830 Ma辉长岩锆石SIMS U-Pb年代学和岩石地球化学特征及其岩石成因研究

本次研究对象为江南造山带西段桂北四堡地区新元古代辉长岩,主要由斜长石和单斜辉石组成,含有少量的橄榄石和钛铁氧化物,表明在岩浆演化过程中发生了斜长石和单斜辉石以及少量橄榄石的分离结晶作用。辉长岩锆石SIMS U-Pb谐和年龄为(830±7)Ma,指示其侵位年龄约为830 Ma。全岩具有低SiO₂含量(48.46%~53.99%)、高MgO含量(9.27%~25.22%)、Mg^#值较高(62~79)的特征。辉长岩为钙碱性系列岩石,其稀土元素球粒陨石标准化和微量元素原始地幔标准化与典型的弧岩浆相似,具有相对富集轻稀土元素((La/Yb)_N=2.2~3.7,(La/Sm)_N=2.5~2.9)和大离子亲石元素,明显的高场强元素(Nb、Ta和Ti)亏损的特征,还具有较高的Th/Nb比值(0.7~0.8)和低Nb/La比值(0.4~0.6)。辉长岩具有负的ε_Nd(t)值(-6.3~-3.0)和正的ε_Hf(t)值(8.0~12.1),指示其源区为亏损地幔,但有富集组分加入。结合区域地质特征,推测辉长岩形成于活动大陆边缘俯冲构造背景,起源于受沉积物流体交代了的楔地幔。     

Experimental petrochemistry of some highly siderophile elements at high temperatures, and some implications for core formation and the mantle''s early history

The highly siderophile elements (HSE's: Ru, Rh, Pd, Re, Os, Ir, Pt and Au) and those elements with distribution coefficients between Fe-rich metal and silicate phases which exceed 10⁴. The large magnitude of these distribution coefficients makes them exceedingly difficult to measure experimentally. We describe a new experimental campaign aimed at obtaining reliable values of D_M^{mets/sil melt} for selected HSE's indirectly, by measuring the solubilities of the pure metals (or simple HSE alloys) in haplobasaltic melts as a function of oxygen fugacity.

Preliminary results for Pd, Au, Ir and Re indicate that the HSE's may dissolve in silicate melts in unusually low valence states, e.g., 2+ for Ir and 1+ for the others. These unusual valence states may be important in understanding the geochemical properties of the HSE's. Inferred values of D_M^{met/sil melt} from the solubility data at 1400°C and IW −1 are 10⁷ for Pd and Au, and 10⁹−10¹² for Ir. Metal/silicate partition coefficients are thus confirmed to be very large, and are also different for the different HSE's.

A review of the abundance of the HSE's in the Earth's upper mantle shows that they are all present at 0.8% of chondritic, i.e. they have the same relative abundance, and the ratios of their concentrations are chondritic (e.g., Re/Os). Both the low degree of depletion (compared to the high values of D_M^{met/sil melt}) and the chondritic relative abundances support the idea that the mantle's HSE's were added in a “late veneer” after the cessation of core formation. Sulfur is even more depleted in the mantle relative to CI chondrites than the HSE's: this implies a late veneer which was depleted in volatile elements, and which was added to a mantle stripped of S. Since considerable S dissolves in silicate melt, this further implies that core formation in the Earth either occurred under P−T conditions below the solicate solidus, or, if the process occurred over a range of temperatures in a cooling Earth, then the process continued down to conditions below the silicate solidus.

The chondritic relative abundances of the HSE's in the upper mantle argue for a chemically unstratified primitive mantle, unless the late veneer was mixed only into the upper mantle.     

Origin of lamprophyres by the mixing of basic and alkaline melts in magma chamber in Beiya area, western Yunnan, China

Lamprophyres consisting mainly of diopside, phlogopite and K-feldspar formed in the early Tertiary around 60 Ma in the Beiya area and are characterized by low SiO₂ ± 46–50 wt.%), Rb (31–45 ppm) and Sr (225–262 ppm), high Al₂O₃, (11.2–13.1 wt.%), CaO (8.0–8.7 wt.%), MgO (11.5–12.1 wt.%), K₂O(4.9–5.5 wt.%), TiO₂ (2.9–3.3 wt.%) and REE (174–177 ppm), and compatible elements (e.g. Sc, Cr and Ni) and HSF elements (e.g. Th, U, Zr, Nb, Ta, Ti and Y), and low ¹⁴³Nd/¹⁴⁴Nd 0.512372–0.512536, middle ⁸⁷Sr/⁸⁶Sr 0.707322–0.707395, middle ²⁰⁶Pb/²⁰⁴Pb 18.50–18.59, ²⁰⁷Pb/²⁰⁴Pb 15.60–15.65 and ²⁰⁸Pb/²⁰⁴Pb 38.75–38.8. These rocks developed peculiar quartz megacrysts with poly-layer reaction zones, melt inclusions, and partial melted K-feldspar and plagioclase inclusions, and plastic shapes. Important features of these rocks include: (1) hybrid composition of elements, (2) abrupt increase of SiO₂ content of the melt, recorded by zoned diopside, (3) development of sanidine and aegirine-augite reaction zones, (4) alkaline melt and partial melted K-feldspar and plagioclase inclusions, (5) deformed quartz inclusions associated with quartz megacrysts, (6) the presence of quartz megacrysts in plastic shape with their parent melts, (7) the occurrence of olivine, high-MgO ilmenite and spinel inclusions within earlier formed diopside, phlogopite and magnetite. Median ⁸⁷Sr/⁸⁶Sr values between Tertiary alkaline porphyries in the Beiya area and the western Yunnan and Tertiary basalt in the western Yunnan indicate that the Beiya lamprophyre melts were derivative and resulted from the mixing between basic melts that were related to the partial melting of phenocrysts of spinel iherzolite from a mantle source. The alkaline melts originated from partial melting along the Jinshajiang subduction ductile shear zone at the contact between the buried Palaeo-Tethyan oceanic lithosphere and the upper mantle lithosphere. The alkaline melts are composed of 65% sanidine (Or₇₀Ab₂₈An₂) and 35% SiO₂. The melt mixing occurred in magma chambers in the middle-shallow crust at 8–10 km before the derivative lamprophyre melts intruded into the shallow cover in Beiya area. This mixing of basic and alkaline melts might represent a general process for the formation of lamprophyre in the western Yunnan.     

A review and analysis of silicate mineral dissolution experiments in natural silicate melts

We present a database and a graphical analysis of published experimental results for dissolution rates of olivine, quartz plagioclase, clinopyroxene, orthopyroxene, spinel, and garnet in basaltic and andesitic melts covering a range of experimental temperatures (1100–1500°C) and pressures (10⁵ Pa-3.0 GPa). The published datasets of Donaldson (1985, 1990) and Brearly and Scarfe (1986) are the most complete. Experimental dissolution rates from all datasets are recalculated and normalized to a constant oxygen basis to allow for direct comparison of dissolution rates between different minerals. Dissolution rates (ν) range from 5·10⁻¹⁰ oxygen equivalent moles (o.e.m.) cm⁻² s⁻¹ for olivine in a basaltic melt to 1.3·10⁻⁵ o.e.m. cm⁻² s⁻¹ for garnet in a basaltic melt. Values of ln ν are Arthenian for the experiments examined and activation energies range from 118 to 1800 kJ/o.e.m. for quartz and clinopyroxene, respectively.

The relationship between calculated A/RT for the dissolution reactions, where A is the thermodynamic potential affinity, and values of ν is linear for olivine, plagioclase, and quartz. We interpret this as strong evidence in support of using calculated A as a predictor of ν for, at least, superliquidus melt conditions.