Phosphorus and the rare earth elements in felsic magmas: an assessment of the role of apatite

The solubility of fluorapatite in 17 silica-rich melts in the system Na₂O-K₂O-Al₂O₃-SiO₂ (with and without CaO or CaF₂) was determined at 1 kbar water pressure and 750 900°C. Apatite saturation occurs at levels of dissolved P₂O₅ ranging between 0.04 (± 0.02) and 0.28 (± 0.13) wt%. with only 4 values outside the 0.09–0.20 wt% range.The results demonstrate not only that apatite is a common liquidus phase in felsic melts, but also that, under most circumstances, it remains in the residue during episodes of partial fusion of the crust. Given a solubility limit of 0.14 wt% dissolved P₂O₅ (the mean of the experimental values) a source containing as little as 0.05% P₂O₅ must be 35% melted before apatite is lost from the residue and no longer buffers the melt P₂O₅ concentration at the saturation value. Higher abundances of P₂O₅ in the source postpone the loss of residual apatite to still higher degrees of melting, and if the source P₂O₅ content exceeds 0.14 wt%, apatite must be residual for all degrees of melting, increasing in abundance as melting proceeds.The generally secondary influence of apatite on the rare earth element (REE) patterns of melt and residue is most apparent when garnet and/or amphibole is minor or lacking in the residue. Fractional crystallization of intermediate (e.g. andesitic) magmas toward felsic compositions invariably results in saturation in apatite and some consequent depletion of REE in the melt.     

Surface properties, solubility and dissolution kinetics of bamboo phytoliths

Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of “soil” phytoliths ( at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH_IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for “soil” (native) and “heated” (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-pK surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ? pH ? 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation:

     

The aquatic chemistry of rare earth elements in rivers and estuaries

Laboratory experiments were carried out to determine how pH, colloids and salinity control the fractionation of rare earth elements (REEs) in river and estuarine waters. By using natural waters as the reaction media (river water from the Connecticut, Hudson and Mississippi Rivers) geochemical reactions can be studied in isolation from the large temporal and spatial variability inherent in river and estuarine chemistry. Experiments, field studies and chemical models form a consistent picture whereby REE fractionation is controlled by surface/solution reactions. The concentration and fractionation of REEs dissolved in river waters are highly pH dependent. Higher pH results in lower concentrations and more fractionated composition relative to the crustal abundance. With increasing pH the order of REE adsorption onto river particle surfaces is LREEs > MREEs > HREEs. With decreasing pH, REEs are released from surfaces in the same order. Within the dissolved (<0.22 µm) pool of river waters, Fe-organic colloids are major carriers of REEs. Filtration through filters and ultrafilters with progressively finer pore sizes results in filtrates which are lower in absolute concentrations and more fractionated. The order of fractionation with respect to shale, HREEs > MREEs > LREEs, is most pronounced in the solution pool, defined here as <5K and <50K ultrafiltrates. Colloidal particles have shale-like REE compositions and are highly LREE enriched relative to the REE composition of the dissolved and solution pools. The addition of sea water to river water causes the coagulation of colloidal REEs within the dissolved pool. Fractionation accompanies coagulation with the order of sea water-induced removal being LREEs > MREEs > HREEs. While the large scale removal of dissolved river REEs in estuaries is well established, the release of dissolved REEs off river particles is a less studied process. Laboratory experiments show that there is both release and fractionation of REEs when river particles are leached with seawater. The order of sea water-induced release of dissolved REE(III) (LREEs > MREEs > HREEs) from Connecticut River particles is the same as that associated with lowering the pH and the same as that associated with colloidal particles. River waters, stripped of their colloidal particles by coagulation in estuaries, have highly evolved REE composition. That is, the solution pool of REEs in river waters are strongly HREE-enriched and are fractionated to the same extent as that of Atlantic surface seawater. This strengthens the conclusions of previous studies that the evolved REE composition of sea water is coupled to chemical weathering on the continents and reactions in estuaries. Moreover, the release of dissolved Nd from river particles to sea water may help to reconcile the incompatibility between the long oceanic residence times of Nd (7100 yr) and the inter-ocean variations of the Nd isotopic composition of sea water. Using new data on dissolved and particle phases of the Amazon and Mississippi Rivers, a comparison of field and laboratory experiments highlights key features of REE fractionation in major river systems. The dissolved pool of both rivers is highly fractionated (HREE enriched) with respect to the REE composition of their suspended particles. In addition, the dissolved pool of the Mississippi River has a large negative Ce-anomaly suggesting in-situ oxidation of Ce(III). One intriguing feature is the well developed maximum in the middle REE sector of the shale normalized patterns for the dissolved pool of Amazon River water. This feature might reflect competition between surface adsorption and solution complexation with carbonate and phosphate anions.     

Rare earth partitioning between immiscible carbonate and silicate liquids and CO2 vapor: Results and implications for the formation of light rare earth-enriched rocks

Melting relations at 5 and 20 kbar on the composition join sanidine-potassium carbonate are dominated by a two-liquid region that covers over 60% of the join at 1,300 ° C. At this temperature, the silicate melt contains approximately 19 wt% carbonate component at 5 kbar and 32 wt% carbonate component at 20 kbar. The conjugate carbonate melt contains less than 5 wt% silicate component, and it varies less as a function of temperature than does the silicate melt.Partition coefficients for Ce, Sm, and Tm between the immiscible carbonate and silicate melts at 1,200 ° and 1,300 ° C at 5 and 20 kbar are in favor of the carbonate melt by a factor of 2–3 for light REE and 5–8 for heavy REE. The effect of pressure on partitioning cannot be evaluated independently because of complementary changes in melt compositions.Minimum REE partition coefficients for CO₂ vapor/carbonate melt and CO₂ vapor/silicate melt can be calculated from the carbonate melt/silicate melt partition coefficients, the known proportions of melt, and maximum estimates of the proportion of CO₂ vapor. The vapor phase is enriched in light REE relative to both melts at 20 kbar and enriched in all REE, especially the light elements, at 5 kbar. The enrichment of REE in CO₂ vapor relative to both melts is 3–4 orders of magnitude in excess of that in water vapor (Mysen, 1979) at 5 kbar and is approximately the same as that in water vapor at 20 kbar.Mantle metasomatism by a CO₂-rich vapor enriched in light REE, occurring as a precursor to magma genesis, may explain the enhanced REE contents and light REE enrichment of carbonatites, alkali-rich silicate melts, and kimberlites. Light REE enrichment in fenites and the granular suite of nodules from kimberlites attests to the mobility of REE in CO₂-rich fluids under both mantle and crustal conditions.     

Origins of co-existing diverse magmas in a felsic pluton: the Lysterfield Granodiorite,Australia

Numerous batches of initially heterogeneous magma aggregated to form the I-type Lysterfield Granodiorite, with four geochemically distinct series of granodioritic rocks, emplaced in the shallow crust. The compositional heterogeneities originated through variations in the stoichiometries of melting reactions in the protolith terrane and variable degrees of peritectic assemblage entrainment. The high-K series contains igneous, microgranular enclaves that most probably formed through deep-level hybridisation of enriched mantle magmas with crustal melts. In the model presented here, this heterogeneous collection of magmas ascended to form a thin, sheet-like intrusion, quenched against cold wall rocks. Later, laccolithic inflation, through ingress of voluminous more felsic magmas, arched the pluton roof and fragmented the initial sheet, pieces of which fell back into the Granodiorite to become enclaves, some of which were further hybridised by plastic deformation and mechanical incorporation of host-derived crystals. This may be a common mechanism for the formation of such enclave suites.     

Solution of rare earth elements in silicate solid phases; henry's law revisited in light of defect chemistry

It is shown that experimentally observed departures from Henry's law at high dilution conditions for rare earth elements (REE) in garnet, clinopyroxene and plagioclase can be referred to stabilization in the lattice point defects. The solution process involves negative interaction parameters (?500/?3,000 cal for garnet). On the basis of the experimental data, the activity coefficients of the trace REE can be approximated by a model based on trace cation/cationic vacancy binary solid solution, taking into account association phenomena between them as well.     

Distribution of rare earth elements and oxyhydroxide phases within a weathered felsic igneous profile in Hong Kong

Variation in type and abundance of oxyhydroxide phases and the fractionation of rare earth elements (REE) within a weathered felsic pyroclastic profile in Hong Kong were investigated in order to assess the key factors and micro-environmental conditions controlling their distribution during weathering at rock and mineral scales. Three types of oxyhydroxide phases (Fe-, Mn- and Ce-rich) were recognized based on their most abundant elements. The Fe-rich types appeared in all samples at different stages of weathering. The Mn-rich types, however, were limited to samples at advanced stages of weathering, while the Ce-rich types were found solely in samples from oxyhydroxide-rich zones. Fractionation of REE likely started at the early stages of weathering, but became evident only at the advanced stages. Characteristics of REE patterns, especially the direction (negative or positive) and extent of Ce-anomalies, correlated very well with the appearance and abundance of Mn-oxyhydroxides, and were attributed to the co-existence of distinct micro-environmental conditions within the profile. These conditions resulted from two major competing processes, “leaching and fixation” and “oxidation (precipitation) and reduction (dissolution)”, which operated simultaneously within the profile at any given stage of weathering.     

Surface chemistry and dissolution kinetics of glassy rocks at 25°C

The weathering rates and mechanisms of three types of glassy rocks were investigated experimentally at 25 °C, pH 1.0 to 6.2, and reaction times as much as to 3 months. Changes in major element chemistry were monitored concurrently as a function of time in the aqueous solution and within the near surface region of the glass. Leach profiles, obtained by a HF leaching technique, displayed near-surface zones depleted in major cations. These zones increased in depth with increasing time and decreasing pH of reactions. Release rates into the aqueous solution were parabolic for Na and K and linear for Si and Al. A coupled weathering model, involving surface dissolution with concurrent diffusion of Na, K, and Al, produced a mass balance between the aqueous and glass phases. Steady state conditions are reached at pH 1.0 after approximately 3 weeks of reaction. Steady-state is not reached even after 3 months at pH 6.2.An interdiffusion model describes observed changes in Na diffusion profiles for perlite at pH 1.0. The calculated Na self-diffusion coefficient of 5 × 10^?19 cm²·s^?1 at 25°C approximates coefficients extrapolated from previously reported high temperature data for obsidian. The self-diffusion coefficient for H₃O⁺, 1.2 × 10^?20 cm²·s^?1, is similar to measured rates of water diffusion during hydration of obsidian to form perlite.     

Composition of rare earth elements in settling particles collected in the highly productive North Pacific Ocean and Bering Sea: Implications for siliceous-matter dissolution kinetics and formation of two REE-enriched phases

Settling particles were sampled monthly for 1 year using an automated time-series sediment trap positioned at similar depths at two sites of high diatomaceous productivity in the North Pacific Ocean and Bering Sea. The particles were analyzed for rare earth elements (REEs) by inductively coupled plasma mass spectrometry (ICP-MS) with and without chemical treatment of the bulk samples to isolate siliceous fractions. The REE composition of the bulk samples is explained largely by the contribution of two distinct components: (i) carbonate with a higher REE concentration, a negative Ce anomaly and lighter REE (LREE) enrichment; (ii) opal with a lower REE concentration, a weaker negative Ce anomaly and heavier REE (HREE) enrichment.The siliceous fractions of settling particles are characterized by high Si/Al ratios (30-190), reflecting high diatom productivity at the studied sites. The La/Al ratio of the siliceous fraction is close to that of the upper crust, but the Lu/Al and Lu/La ratios are significantly higher than those of the upper crust or airborne particles, indicating the presence of excess HREEs in the siliceous fraction. Diatoms are believed to be important carriers of HREEs.The Ce anomaly, Eu anomaly, slope of the REE pattern, and ΣREE of the siliceous fraction vary exponentially with decreasing total mass flux. They can be well-reproduced according to the differential dissolution kinetics of elements in the order of Ce < lighter REEs (LREEs) < Eu = heavier REEs (HREEs) < Si from settling particles, where the dissolution rate is critically reduced through particle aggregation. This order is consistent with the vertical distribution of dissolved REEs and Si in oceans. The differential dissolution kinetics leads to HREE enrichment of the original diatoms and REE enrichment of dissolved diatoms. The Lu/Si ratio of the siliceous fraction of settling particles recovered from some of the highest diatom fluxes is identical to that of the two elements dissolved in deep seawater, providing further evidence for the dissolution of siliceous matter in deep water.     

The evolution of fluorine-rich felsic magmas: source dichotomy, magmatic convergence and the origins of topaz granite

Topaz granite is alkali-feldspar granite that contains essential albite, quartz, K-feldspar, lithium-mica, and topaz. As a group topaz granites are characterized by their extreme enrichment in F (up to 3 wt%) and a wide variety of lithophile elements. They can be subdivided into a 'low-P₂O₅ subtype' (P₂O₅ < 0.1 wt%, Al₂O₃ < 14.5 wt%, SiO₂ > 73 wt%) and a 'high-P₂O₅ subtype' (P₂O₅ > 0.4 wt%, Al₂O₃ > 14.5 wt%, SiO₂ < 73 wt%), the δ¹⁸O values of which indicate a dichotomy of source rock: the low-P₂O₅ subtype (δ¹⁸O < 10‰) having a meta-igneous protolith and the high-P₂O₅ subtype (δ¹⁸O > 10 ‰) a source with a significant component of pelitic material. The unusually high F contents enhance the efficacy of melt segregation and crystal-melt fractionation and so facilitate extreme differentiation in topaz granite magmas. Very low melt volumes restrict the bulk composition of the partial melts regardless of the nature of the source; and extreme fractionation forces them along a path of magmatic convergence, to produce a group of granitic rocks with near-minimum compositions so enriched in a variety of lithophile elements (Li, Nb, Ta, Sn) that economic mineralization often results.     

Partitioning of rare earth elements between an aqueous chloride fluid phase and melt during the decompression-driven degassing of granite magmas

This paper reports the results of numerical simulation for the behavior of rare earth elements (REE) during decompression degassing of H₂O- and Cl-bearing granite melts at pressures decreasing from 3 to 0.5–0.3 kbar under near isothermal conditions (800 ± 25°C). Fluid phase in equilibrium with the melt contains mainly chloride REE complexes, and their behavior during magma degassing is, therefore, intimately related to the behavior of chlorine. It was shown that the contents and distribution patterns of REE in the aqueous chloride fluid phase formed during decompression vary considerably depending on (1) the contents of volatiles (Cl and H₂O) in the initial melt, (2) the redox state of the magma, and (3) the dynamics of fluid phase separation from magmas during their ascent toward the Earth’s surface. During decompressiondriven degassing, the contents of both Cl and REE in the fluid decrease, especially dramatically under opensystem conditions. The REE patterns of the fluid phase compared with those of the melt are characterized by a higher degree of light to heavy REE fractionation. A weak negative Eu anomaly may be present in the REE patterns of Cl-rich fluids formed during the early stages of degassing at relatively high pressures. At a further decrease in pressure and Cl content in the fluid, it is transformed into a positive Eu anomaly increasing during decompression degassing. Such an anomalous behavior of Eu during degassing is related to its occurrence in magmatic melts in two valence states, Eu³⁺ and Eu²⁺, whereas the other REE occur in melts mainly as (REE)³⁺. The Eu³⁺/Eu²⁺ ratio of melt is controlled by the redox state of the magmatic system. The higher the degree of melt reduction, the more pronounced the anomalous behavior of Eu during decompression degassing. The amount of REE extracted by fluid from melt during various stages of degassing does not significantly influence the content and distribution patterns of REE in the melt.     

Geochemistry of the Sweetwater Wash Pluton,California: Implications for “anomalous” trace element behavior during differentiation of felsic magmas

Field relations, mineralogy and major and trace element data for the very felsic, peraluminous Sweetwater Wash pluton establish a differentiation sequence dominantly controlled by fractional crystallization processes. Elements Ba and Sr show depletion by factors of 50–60X from the earliest granite unit analyzed to the late-stage pegmatites and aplites. The strong Ba depletion is largely due to the partitioning behavior of this element in K-feldspar, while the Sr depletion is due to the combined effects of the two feldspars. The 4-fold increase in Rb during crystallization is also predictable from mineral/ melt partition coefficients.Coefficients for the light rare-earth elements (LREE) in major mineral species predict that these elements should behave incompatibly during crystallization and increase with fractionation. In fact, the LREE abundances decrease by a factor of 10–20X during crystallization. This anomalous behavior is commonly observed in felsic plutonic and volcanic sequences. In the Sweetwater Wash pluton monazite occurs in minute quantities, but it is sufficiently abundant to govern the partitioning of LREE and Th during crystallization. Petrographic observations indicate that monazite was on the liquidus throughout most of the crystallization. Analyses of silicate mineral separates suggest that the monazite contains more than 75% of the LREE in the whole rocks.Fractionation of REE-rich accessories (in particular monazite) from felsic magmas may be the general cause of REE depletion during differentiation of these melts. Monazite can easily be mistaken for zircon and, because it typically contains 50% LREE, extremely minute and easily overlooked quantities of monazite can control LREE abundances.     

Development of viscous fingering between mafic and felsic magmas: evidence from the Terra Nova Intrusive Complex (Antarctica)

Summary A wide range of types of contact morphology among mafic and felsic magmas are observed in outcrops on Vegetation Island (Terra Nova Intrusive Complex, Antarctica). Image analysis and fractal geometry techniques were applied for in-depth study of the mafic/felsic interface, with the aim of studying the origin of the varied morphologies. In particular, the length (IP_N) and fractal dimension (D_box) of interfaces were measured. Results indicate that there is a close exponential dependence of IP_N on D_box.The observed morphologies are identical to those observed during viscous fingering processes induced by the displacement of a more viscous fluid by a less viscous one. To test if viscous fingering was responsible in this case too, IP_N and D_box values were measured on viscous fingering structures obtained experimentally using various viscosity ratios (V_R) from the literature. Results indicate that, as in the natural case, there is an exponential dependence of IP_N on D_box, leading to the conclusion that the varied interface morphologies between mafic and felsic magmas are the result of viscous fingering dynamics. In addition, experimental studies clearly show that there is an exponential relationship between the viscosity ratio of fluids and the interface fractal dimension (D_box), and the ratio between the two types of magma was estimated using this relationship. It is shown that viscosity contrasts between mafic and felsic magmas varied considerably, ratios ranging from ca. 6 to 49. These results, together with outcrop evidence, provide indications regarding the evolution of the magmatic system, which generated the actual mafic/felsic associations on Vegetation Island.     

A simple thermodynamic model for estimating the solubility of H2O in magmas

A symmetrical, strictly regular solution model is used to estimate H₂O solubilities in silicate melts. The standard state chemical potential of dissolved H₂O and the adjustable parameter in the activity coefficient are determined by least squares analyses of data on H₂O solubility in silicate melts. The adjustable parameter in the expression for the activity coefficient (In) is a function only of the anhydrous melt composition and eleven values are provided for melts ranging in composition from picrite to rhyolite. At the 95% confidence level, the model should estimate H₂O contents to within 4.8% of the amount present if the amount present is less than 10 wt.%. This compares to the reproducibility of 2.25% of the amount present for experimental determinations. To apply the model to rocks and magmas estimates ofT, P, and the fugacity of H₂O are required.Variation of the H₂O content of the melt changes the activity of other components. Knowledge of this variation removes the requirement that the fugacity of H₂O be estimated. Application of the properties of exact differentials to the Gibbs function for the hydrous melt provides an expression relating the chemical potential of a feldspar component to the H₂O content of the melt. This expression contains a second adjustable parameter which depends on the anhydrous melt composition. Using this second expression, the H₂O content can be estimated ifT, P, and feldspar composition are known. Data are too meagre to evaluate the quantitative success of the second method.     

The mobility of the rare earth elements: Evidence and implications from selected terrains affected by burial metamorphism

The mobility of the rare earth element (REE) during hydrous burial metamorphism is described from three localities. Comparison of REE abundances in relict domains and metadomains from flood lavas in the Maddina Volcanics, Fortescue Group, Western Australia shows that, relative to the relict domains, REE may be strongly depleted in certain metadomains. Strong variations in La/Yb, La/Sm and Eu may also occur due to postcrystallization secondary processes. Similar comparisons in flood lavas from Mamainse Point in the Canadian Keweenawan Series show that REE are mobile and increase in abundance in metadomains. Spilites from U.S. Virgin Islands also show evidence for REE mobility during low grade burial metamorphism. In this case light REE (LREE) have been preferentially mobilized with heavy REE (HREE) remaining parallel or sub-parallel on chondrite normalized plots.REE analyses from these locations together with an evaluation of published work suggests that the mobility of REE can be described by: 1. gross REE and selective LREE enrichment; 2. REE movement around a primary mean; 3. gross REE depletion; 4. selective REE mobility. Failure to take into account REE mobility may lead to incorrect conclusions concerning petrogenetic models based on altered basic sequences. The coherence of REE with other key trace elements during alteration is also discussed.     

Monazite begets monazite: evidence for dissolution of detrital monazite and reprecipitation of syntectonic monazite during low-grade regional metamorphism

Back-scattered electron (BSE) imaging and X-ray element mapping of monazite in low-grade metasedimentary rocks from the Paleoproterozoic Stirling Range Formation, southwestern Australia, reveal the presence of distinct, high-Th cores surrounded by low-Th, inclusion-rich rims. Previous geochronology has shown that the monazite cores are older than 1.9 Ga and overlap with the ages of detrital zircon grains (∼3.5–2.0 Ga), consistent with a detrital origin. Many cores have scalloped and embayed surfaces indicating partial dissolution of former detrital grains. Textural evidence links the growth of the monazite rims (∼1.2 Ga) to deformation and regional metamorphism during the Mesoproterozoic Albany-Fraser orogeny. These results indicate that high-Th detrital monazite is unstable under low-grade metamorphic conditions (<400°C) and was partially or completely dissolved. Dissolution was followed by near-instantaneous reprecipitation and the formation of low-Th monazite and ThSiO₄. This reaction is likely to operate in other low-grade metasedimentary rocks, resulting in the progressive replacement of detrital monazite by metamorphic monazite during regional prograde metamorphism.     

Progressive hybridisation between Late Devonian mafic-intermediate and felsic magmas in the Meguma Zone of Nova Scotia, Canada

Two felsic plutons of Late Devonian (385–370 Ma) age in the Meguma Zone of southwestern Nova Scotia contain three circa 376 Ma synplutonic mafic-intermediate intrusions that collectively record progressive stages of in situ hybridisation. A 5 m wide spessartite dyke in the Port Mouton Pluton probably underwent rapid cooling and crystallisation immediately after intrusion, which heated and coarsened the adjacent tonalite. An 85 m long sheet of pillowed kersantite (also in tonalite of the Port Mouton Pluton) presumably contained residual magma after quenching and obtained K, P, Ba, Rb, more radiogenic Sr, Zr, Nb, and light REE from the tonalite during magma mingling. The third synplutonic body, a >100 m wide diorite sheet, intrudes granodiorite of the adjacent Shelburne Pluton and has a circa 45 m wide gradational contact of metaluminous hornblende-tonalite. This tonalite dominantly records magma mixing by the transfer of Ti, Mg, Fe, Ca, and V in hornblende, biotite, plagioclase, and (at least in part) apatite xenocrysts derived from dioritic pillows that were originally disaggregated in the granodiorite, probably in response to convection. Scattered data points, unusual “concave-down” variation trends for Al₂O₃, P₂O₅, and Sr, and non-hyperbolic Sr-Nd isotopic characteristics in the tonalite, apparently reflect syn- or post-mixing fractionation and accumulation of xenocrysts from residual magma. Phosphorus may have assisted diffusion of Sr, Zr, Nb, and light REE, and caused premature quenching of the hybrids at Mcleods Cove and Birchtown, during magma mingling and mixing. Received: 1 January 1996 / Accepted: 3 August 1996     

Archean granulite gneisses from eastern Hebei Province,China: rare earth geochemistry and tectonic implications

The granulite gneisses and their retrograded products of the Qianxi Group from eastern Hebei Province, China, have been investigated for their isotope and trace element geochemistry. A consistent age of about 2.5 AE has been obtained by the Rb-Sr and Sm-Nd whole-rock isochron methods, in agreement with the zircon U-Pb data (Pidgeon 1980; D.Y. Liu, unpubl.). Geochemical arguments from initial isotopic ratios (I_Sr and I_Nd) and elemental distribution patterns have led us to conclude that this age of about 2.5 AE represents the time of granulite facies metamorphism, which must have followed closely the primary emplacement of their protoliths. Previous claims for early Archean ages (>3.5 AE) of these granulites are not substantiated. The mineral isotope systematics register an important thermal event at about 1.7 AE, roughly corresponding to the time of the widespread Luliang Orogeny (Ma and Wu 1981) or Chungtiao Movement (Huang 1978).The granulites of the Qianxi Group have diverse compositions ranging from ultrabasic through basic-intermediate to acid. Discriminant function calculations suggest that most analyzed samples have igneous parentage. Only a few show characteristics of metasedimentary rocks. The igneous protoliths apparently belong to two series — tholeiitic and calc-alkaline, with the latter dominating in abundance. The majority of the acid granulites have compositions corresponding to tonalite-granodiorite.Except for ultrabasic and metasedimentary rocks, all REE patterns are significantly fractionated with LREE enrichment. The degree of fractionation, as measured by the (La/Yb)_N ratios, is most important in the acid granulites. These rocks often show positive Eu anomalies and HREE depletions that are typical of Archean TTG rocks (tonalitetrondhjemite-granodiorite).The existence of komatiites has been previously reported in this region. Although a few rocks have a major element chemistry similar to that for peridotitic komatiites, the lack of associated members in a komatiitic series and the scarcity of REE data have not confirmed the true komatiite occurrence in this region.Many Qianxi granulites are highly depleted in Rb relative to K and Sr. This preferential Rb depletion during granulite facies metamorphism has led to very high K/Rb and very low Rb/Sr ratios. The most comparable case is found in Lewisian granulites.Although the fractionated REE patterns of the basic granulites somewhat resemble those of continental flood basalts, the highly different abundances in other incompatible elements (Ti, Zr, and Ba) readily distinguish them from each other. Nevertheless, the LREE enriched patterns of the basic granulites may suggest an origin of their protoliths by partial melting of LREE-enriched mantle sources. On the other hand, the REE patterns of acid granulites suggest that their protoliths could be derived by partial melting of quartz eclogite, amphibolite or basic granulite.The close time relationship for a series of geologic events, namely, from initial melting of mantle peridotites, through fractional crystallisation of basaltic magmas, to granulite facies metamorphism, seems to occur in many granulite terrains. This relationship, together with the juxtaposition of lithologies of different origins and the exceptionally high pressure conditions (>10 Kb) can be best explained by crustal underplating combined with intracrustal thin-skinned thrusting and stacking of crustal slices. The andesitic or island arc model for the formation of the lower continental crust is not in good agreement with the present geochemical data.     

An experimental study of anorthosite dissolution in lunar picritic magmas: Implications for crustal assimilation processes

Experiments characterizing the kinetics of anorthosite dissolution in lunar picritic magmas (very low-Ti, low-Ti, and high-Ti picritic glasses) were conducted at 0.6 GPa and 1250-1400 °C using the dissolution couple method. Reaction between the anorthosite and lunar picritic magmas at 1250-1300 °C produced a spinel + melt layer. Reaction between the anorthosite and an olivine-saturated low-Ti magma at 1250-1300 °C produced a crystal-free region between the spinel + melt layer and the olivine-saturated magma. The anorthosite dissolution experiments conducted at 1400 °C simply dissolved anorthosite and did not result in a crystal-bearing region. The rate of anorthosite dissolution strongly depends on temperature and composition of the reacting melt. Concentration profiles that develop during anorthosite dissolution are nonlinear and extend from the picritic glass compositions to anorthite. These profiles feature a large and continuous variation in melt density and viscosity from the anorthosite-melt interface to the initial picritic magmas. In both the low-Ti and high-Ti magmas the diffusive fluxes of TiO₂, Al₂O₃, and SiO₂ are strongly coupled to the concentration gradients of CaO and FeO. Anorthosite dissolution may play an important role in producing the chemical variability of the lunar picritic magmas, the origin of spinel in the lunar basalts and picritic glasses, and the petrogenesis of the high-Al basalts.