Simple Fractional Crystallization Research Articles

Petrogenesis and REE mineralogical characteristics of Shitouping granites in southern Jiangxi Province: Implication for HREE mineralization in South China

The enrichment of heavy rare earth elements (HREE) in the granitic host-rocks is crucial for generating ion-adsorption HREE deposits in South China. The Shitouping pluton, located in the southern part of Jiangxi Province, South China, develops large-scale HREE deposits in its weathering profile identified by recent geological surveys. These granites can be divided into medium to coarse-grained biotite monzogranite (MGBG), medium to coarse-grained syenogranite (MGSG) and fine-grained alkali feldspar granite (FGAG) based on field observations and mineral assemblages. New geochronologic results show that this composite pluton intruded during the Early Cretaceous (ca. 140 Ma). Three granitic units displaying comparable whole-rock Nd [εNd(t) = −4.5 to −3.4] and zircon Hf compositions [εHf(t) = −4.4 to +1.2], combined with mineral association, hydrothermally altered zircon and whole-rock geochemistry, indicate they were derived from partial melting of hybridized crustal source, followed by intense fractional crystallization and fluid metasomatism in the highly evolved granitic system. The MGSG and FGAG have higher Rb, Nb, HREE contents and Rb/Sr ratios, as well as lower Nb/Ta, K/Rb ratios in comparison with the MGBG, implying they are more evolved units. The overlapping magmatic zircon trace element compositions between MGBG and MGSG, coupled with the subvertical contact boundary between the FGAG and the MGBG, suggest that the generation of Shitouping pluton should be attributed to the periodic magma replenishment, remobilization, and differentiation process in the long-lived magmatic system rather than simple fractional crystallization from a single parental magma. Hydrothermally altered zircon with elevated concentration of HREE and the paragenetic relationship between LREE-phosphate and HREE minerals in the MGSG suggest that the fluid metasomatism promotes the migration and accumulation of HREE. This is consistent with the high HREE concentration recorded in the MGSG, which contains abundant HREE minerals associated with fluorites. Thus, this study highlights that magma differentiation and fluid metasomatism during the late magmatic stage could achieve the relatively high HREE contents in granites to favor the formation of ion-adsorption HREE deposits.

The relationship between iron redox states and H2O contents in back-arc basin basaltic glasses from the North Fiji Basin

Island-arc basalts (IAB) from convergent plate margins tend to have both higher iron oxidation states (higher Fe3+/Fe2+) and higher H2O contents than the mid-ocean ridge basalts (MORB) produced by seafloor spreading, which raises the question of whether these two characteristics are causally related. Back-arc basin basalts (BABB) may help with this question, in that they are products of seafloor spreading, like MORB, but sourced from supra-subduction mantle, like IAB. Here we examine the relationship between Fe3+/Fe2+ (determined by XANES spectroscopy) and H2O contents in BABB glasses from the North Fiji Basin (NFB). The glasses cover a range of compositions from 6.1 to 8.5 wt% MgO, and from 0.16 to 1.6 wt% H2O, and have also been analysed for trace elements and Sr-Nd-Pb-isotopes. Measured Fe3+/Fe2+ range from MORB-like to slightly higher values and are positively correlated with H2O and heavy-halogen contents (Cl, Br and I). The correlation is due to lower Fe2+ rather than higher Fe3+ compared to the MORB array. This suite of BABBs is not significantly enriched in trace elements other than H2O and the heavy halogens, with MORB-like Ba/Th and other incompatible-element ratios, suggesting that the H2O and halogens may have come from dehydration of subducted lithospheric serpentinites under subsolidus conditions. Na2O is unusually variable for a suite of samples from such a limited area, and is not correlated with H2O, precluding a relationship between H2O and degree of melting. The link between H2O and low Fe2+ may be explained by H2O-rich fluids entering the transcrustal magma plumbing system, where they increase the proportion of olivine and augite to plagioclase crystallizing during the crustal evolution of the magmas. In this situation, relatively small additions of H2O can have an enhanced effect on major-element chemistry if the crustal evolution proceeds by cycles of replenish-mix-tap-crystallize (RMTX) rather than by simple fractional crystallization without repeated replenishment and tapping. The absence of any increase in Fe3+ with H2O, together with the lack of any correlation between H2O and Fe3+/Fe2+ in MORB glasses generally, suggest that various mechanisms, including more extensive olivine fractionation, were responsible for elevating Fe3+/Fe2+ in H2O-rich basalts from convergent margin settings. Proxy methods based on concentrations of elements with redox-variable partition coefficients (V, Eu) are not sensitive enough to record the subtle variations in Fe3+/Fe2+ observable by XANES spectroscopy.

Magma Differentiation in Dynamic Mush Domains From the Perspective of Multivariate Statistics: Open‐ Versus Closed‐System Evolution

AbstractOpen‐conduit conditions characterize several of the most hazardous and active volcanic systems of basaltic composition worldwide, persistently refilled by magmatic inputs. Eruptive products with similar bulk compositions, chemically buffered by continual mafic inputs, nevertheless exhibit heterogeneous glass compositions in response to variable magma mixing, crystallization, and differentiation processes within different parts of the plumbing system. Here, we document how multivariate statistics and magma differentiation modeling based on a large data set of glass compositions can be combined to constrain magma differentiation and plumbing system dynamics. Major and trace elements of matrix glasses erupted at Stromboli volcano (Italy) over the last 20 years provide a benchmark against which to test our integrated petrological approach. Principal component analysis, K‐means cluster analysis, and kernel density estimation reveal that trace elements define a multivariate space whose eigenvectors are more readily interpretable in terms of petrological processes than major elements, leading to improved clustering solutions. Comparison between open‐ and closed‐system differentiation models outlines that steady state magma compositions at constantly replenished and erupting magmatic systems approximate simple fractional crystallization trends, due to short magma residence times. Open‐system magma evolution is associated with magma storage crystallinities that are lower than those associated with closed‐system scenarios. Accordingly, open‐system dynamics determine the efficient crystal‐melt separation toward the top of the reservoir, where eruptible melts continuously supply the ordinary activity. Conversely, a mush‐like environment constitutes the bottom of the reservoir, where poorly evolved magmas result from mixing events between mush residual melts and primitive magmas injected from deeper crustal levels.

Enrichment of Incompatible Elements in Alkaline Syenites in Large Igneous Provinces Due to Magma Replenishment and Reactive Porous Flow in a Mush Reservoir

AbstractUnderstanding the petrogenesis of alkaline syenites is important for constraining the mechanisms of rare earth element (REE) and rare-metal mineralization. Here we report a detailed petrological and geochemical study of early Permian syenitic rocks from the southwestern Tarim large igneous province (TLIP) in the Wajilitag area (China). We use these data to investigate the complex magmatic processes responsible for the enrichment of incompatible elements (e.g. REEs and rare metals) in these rocks. The Wajilitag syenitic rocks comprise early hornblende syenite (281 Ma) and later nepheline syenite (278 Ma), both of which are spatially and temporally associated with mafic intrusions (i.e. gabbro and diabase). These syenitic rocks show continuous variations in major elements with the mafic rocks. They also have similar Sr–Nd–Hf isotopic compositions with the nearby mafic rocks, denoting that the Wajilitag syenitic rocks should be derived from the melts represented by these mafic rocks. However, these syenitic rocks, particularly the nepheline syenites, are typically characterized by extreme enrichment of incompatible elements, which is hard to be accounted by simple fractional crystallization of mafic magmas. Some clinopyroxene phenocrysts in the Wajilitag nepheline syenites show oscillatory zoning with strikingly increasing and then gradually decreasing MgO contents, which recorded replenishment of mafic magma at the interval. Low-MgO clinopyroxene mantles and/or rims have much higher incompatible element contents (e.g. Nb, Ce, and Zr) and ratios (e.g. Ce/Y) than their cores, which could reflect melt injection controlled by reactive porous flow in a mush reservoir of a crustal magma chamber. Such processes may also cause the high Ce and/or Nb contents of the mantles and/or rims of zoned titanite and apatite phenocrysts. The injection of reactive porous flow melts is the key process that produces the extreme enrichment of incompatible elements in the alkaline syenites from the western TLIP, as well as other plume-related alkaline syenites that host world-class REE and rare-metal deposits.

Abrolhos Magmatic Province petrogenesis and its link with the Vitória-Trindade Ridge, Southeast Brazilian Margin, South Atlantic Ocean

The Abrolhos Magmatic Province (AMP) is an example of an igneous province with about 63,000 km2 located at the Continent-Ocean Boundary (COB), into the Southeast Brazilian Margin. The AMP emerges as five small islands (Santa Bárbara, Redonda, Siriba, Sueste, and Guarita) which integrate the Abrolhos Archipelago located about 55 km offshore Brazil. The studied rocks belong to a transitional basalt series of alkaline affinity, with evolved rocks with high TiO2 contents. This work presents new detailed fieldwork mapping, petrographic, and whole-rock chemistry data, besides Sr–Nd isotopic compositions from AMP rocks. Mapped magmatic rocks in the Abrolhos Islands have been described as extrusive rocks, but we point out that they are shallow intrusions, mostly sills, and should be grouped into diabase units based on fieldwork and textural features. The AMP lithogeochemical and isotopic data suggest the operation of differentiation processes more complex than simple fractional crystallization or AFC. Our model mixing calculations based on new and compiled Sr-Nd-Pb isotopic data suggest a mixture with a prevailing depleted asthenosphere mantle source (represented by DMM; ca. 80%) metasomatized by an enriched mantle I (EMI) component (≤ 10%) and a possible HIMU-type constituent (up to 10%) in the AMP genesis. The assimilation of subducted slabs of the oceanic crust associated with the HIMU signatures is possibly linked to the Brasiliano Event due to the range of the AMP Nd TDM model ages, from 407 to 767 Ma. A viable mechanism for the EMI end-member contribution could either be a physical detachment of the South American subcontinental lithospheric mantle during the breakup of the Gondwana or lithospheric delamination of the South American plate caused by an edge-driven convection mechanism. The AMP and the Vitória-Trindade Ridge (VTR) show an eastward decreasing age pattern from the older ca. 60 Ma Abrolhos Province to the younger Martin Vaz and Trindade Islands (ca. 4 – 0.1 Ma), located ca. 1200 km away from the Brazilian coastline. The volcanic alignment between the VTR and AMP, along with the overlap of geochemical and isotopic data of their different igneous rocks, cannot be a random feature but instead represent the sampling of similar shallow mantle reservoirs, thus suggesting a cogenetic relationship. Finally, a possible petrogenetic link between the AMP and VTR magmatism is discussed.

Detailed petrogenesis of the unsampled Oceanus Procellarum: The case of the Chang'e-5 mare basalts

Lunar mare basalts provide a probe to study the magmatic and thermal evolution of the Moon. The Chang'e-5 (CE-5) mission returned samples from a young and hitherto unsampled mare terrain, providing fresh opportunities to understand lunar volcanic history. A detailed petrologic survey was conducted in this study on basalt fragments and glasses from the returned CE-5 soil samples. Relatively large-sized (100–400 μm) basaltic fragments were hand-picked and examined for texture, mineral assemblage and mineral chemistries. Basaltic fragments exhibit dominantly subophitic textures and are phenocryst-free, with low to intermediate-Ti (2.1–5.5 wt%) and low Mg# (Mg/(Mg + Fe) × 100, 19–47, with an average whole-rock Mg# of 33) consistent with olivine-melt equilibrium calculation (Mg# = 34). A range of highly evolved basaltic materials have been identified, in which abundant fayalitic olivine, symplectitic intergrowths, and Si + K-rich mesostasis co-exist were found resulting from late-stage silicate liquid immiscibility. Basaltic glass compositions largely overlap with basaltic fragment compositions suggesting they are locally derived. The CE-5 basalts have a relatively limited range of eruption temperatures of 1150–1230 °C. Based on their petrographic and geochemical characteristics, some CE-5 mare basalts are highly evolved and some of the resultant basaltic melt products underwent high crystallization. Thermodynamic modeling using MELTS suggests highly evolved basaltic magma was produced by a low-pressure and simple fractional crystallization under reduced conditions. This may have occurred at the surface in the inflated Em4/P58 flow with a thickness of ~50 m. The low degree of partial melting mantle source of the parental melts is the late-stage lunar magma ocean cumulates in a similar manner to some evolved low-Ti mare basalt meteorites, although the source of CE-5 basalts may have been slightly more Ti-rich.

Chemical study of group IIIF iron meteorites and the potentially related pallasites Zinder and Northwest Africa 1911

Group IIIF was established as a magmatic iron-meteorite group based on similar Ga and Ge abundances, unusually high Ga/Ge ratios, and the IIIAB-like interelement trends in its members; recent Mo and Ru isotopic data indicate that three of its members exhibit the isotopic signature of carbonaceous-chondrite (CC) irons. Here we report the elemental chemistry of this group and model its crystallization history. Included are new elemental data for IIIF irons acquired by both instrumental neutron activation analysis (INAA) and laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS). A fractional-crystallization model was used to evaluate the IIIF compositional trends for 19 elements and was unable to explain the observed fractionation trends for several key elements (Co, Ga, Ge). In particular, the inability of this model to match Co in the IIIF irons is striking because (1) group IIIF has the widest Co variation among all magmatic iron groups and (2) none of the tested initial S contents (0–20 wt.%) explains both the wide Co variation and steep Co-As slope. Attempts to fit subsets of the IIIF irons were also unsuccessful. In addition, group IIIF has the greatest variety of structural classes and kamacite bandwidths among all established magmatic iron groups. If the IIIF irons constitute a coherent group, they were derived from a parent body that experienced more complex processes than simple fractional crystallization of the core.The Zinder and Northwest Africa (NWA) 1911 pyroxene-bearing pallasites were recently suggested to be related to group IIIF based on their Ga and Ge contents, and we completed a petrographic study of the pallasite silicates and LA-ICP-MS analyses of their metal fractions. The two pallasites are related to one another: they have nearly identical mineralogical, elemental and O-isotopic compositions in their silicates and metals. Their metallic compositions resemble those of the IIIF irons Moonbi, St. Genevieve County, and Cerro del Inca, but their O-isotopic compositions resemble those of non-carbonaceous (NC) achondrites. Additional isotopic measurements are needed to test the potential genetic relationship to group IIIF.

Genesis of Megacrystalline Uraninite: A Case Study of the Haita Area of the Western Margin of the Yangtze Block, China

Megacrystalline uraninite (up to one centimeter in size) represents one of the most important discoveries in uranium mineralogy in the western margin of the Yangtze Block and even in China in recent years. However, the genesis of megacrystalline uraninite remains controversial. In this study, the megacrystalline uraninite found in the felsic and quartz veins in the Haita area is examined for the first time. The study examined the geochemical characteristics of uraninite in the two veins and resulted in two primary findings. (1) The genesis of the uraninite was likely intrusive and was closely related to partial melting. (2) The quartz vein and feldspar vein are cogenetic and have a simple differentiation evolution relationship. Therefore, the partial melting of felsic materials during migmatization may be the most important mechanism of uranium mineralization in the study area. Furthermore, further simple fractional crystallization may be another important mechanism for the formation of megacrystalline uraninite. This study enriches the REE database of uraninite in uranium deposits worldwide, which is meaningful for studying the genesis of megacrystalline uraninite.

A Crystal Mush Perspective Explains Magma Variability at La Fossa Volcano (Vulcano, Italy)

The eruptive products of the last 1000 years at La Fossa volcano on the island of Vulcano (Italy) are characterized by abrupt changes of chemical composition that span from latite to rhyolite. The wide variety of textural features of these products has given rise to several petrological models dealing with the mingling/mixing processes involving mafic-intermediate and rhyolitic magmas. In this paper, we use published whole-rock data for the erupted products of La Fossa and combine them in geochemical and thermodynamic modelling in order to provide new constrains for the interpretations of the dynamics of the active magmatic system. The obtained results allow us to picture a polybaric plumbing system characterized by multiple magma reservoirs and related crystal mushes, formed from time to time during the differentiation of shoshonitic magmas, to produce latites, trachytes and rhyolites. The residing crystal mushes are periodically perturbated by new, fresh magma injections that, on one hand, induce the partial melting of the mush and, on the other hand, favor the extraction of highly differentiated interstitial melts. The subsequent mixing and mingling of mush-derived melts ultimately determine the formation of magmas erupted at La Fossa, whose textural and chemical features are otherwise not explained by simple assimilation and fractional crystallization models. In such a system, the compositional variability of the erupted products reflects the complexity of the physical and chemical interactions among recharging magmas and the crystal mushes.

Differentiation of magma composition: Reactivation of mush and melt reaction in a magma chamber

Understanding the storage and evolution of magma in the Earth's crust is of great significance for the study of igneous rocks. In recent years, the low melt state is considered to be the normal state in a magma chamber for long periods of time, while the high melt state is relatively short-lived and closely related to magma eruption. Under this condition, the effect of fractional crystallization at a low melt state has been questioned. The separation of minerals is seriously restricted under the condition of low temperature and low melt. It is necessary to recognize the differentiation and evolution of magma. Therefore, based on the whole rock geochemistry, trace element composition of zircons, and thermodynamic simulation of Mesozoic trachytic volcanic rock samples from a typical volcanic basin in the Suolun area, we evaluated the reaction process in the magma chamber. The results showed that the trachytic volcanic rock samples exhibited obvious characteristics of K-feldspar accumulation, which could not be explained by simple fractional crystallization. The results of the thermodynamic simulation indicated that the differentiation of magma in the study area is mainly the result of a crystal-melt reaction in the magma chamber as oppose to the traditional view of separation crystallization. This process may be universal in low temperature magma chambers dominated by low melt. This conclusion provides a new perspective for us to understand the formation of magma, and it can help us understand the formation of deposits which related to magmatic evolution, such as rare metal granite deposits.

Mosaic zircon petrochronology and implications for the ultra-slow spreading process of Southwest Indian Ridge

Here we report the discovery of mosaic zircons in Hole U1473A on the Atlantis Bank in the Southwest Indian Ridge. Oxygen isotope, UPb dating, and geochemical analyses of the zircons were carried out directly in petrographic thin-sections. The mosaic zircons are from diorite and oxide gabbro at shallow depths, whereas the nonmosaic zircons occur in oxide gabbronorite and tonalite at greater depths. The majority of zircons have δ18O of 5.5 ± 0.1‰, which are mantle-like values, reflecting formation by simple fractional crystallization. No correlation exist between UPb ages, δ18O values, and the mosaic microstructures. The mosaic subdomains in a single zircon are well correlated with some trace elements and fractures. Therefore, the variable trace element contents were produced during crystallization, and associated with secondary brittle deformation due to movement on mid-ocean ridge detachment faults. The pervasive brittle deformation weakened the originally rigid zircon and triggered fracturing. The fractures became highly permeable pathways, allowing rapid grain-boundary diffusive loss of Pb, which resulted in the relatively young age of 11.42 ± 0.41 Ma for the mosaic zircons as compared with 12.16 ± 0.14 Ma for the non-mosaic zircons. The zircon trace element patterns are all indistinguishable from global oceanic zircons. However, the trace element abundances and ratios require a significantly depleted normal-type mid-ocean ridge basalt mantle source.

MushPEC: Correcting Post-entrapment Processes Affecting Melt Inclusions Hosted in Olivine Antecrysts

Olivine-hosted melt inclusions (MIs) are widely used as a tool to study the early stages of magmatic evolution. There are a series of processes that affect MI compositions after trapping, including post-entrapment crystallization (PEC) of the host mineral at the MI boundaries, exsolution of volatile phases into a “shrinkage bubble” and diffusive exchange between a MI and its host. Classical correction schemes applied to olivine-hosted MIs include PEC correction through addition of olivine back to the melt until it reaches equilibrium with the host composition and “Fe-loss” correction due to Fe-Mg diffusive exchange. These corrections rely on the assumption that the original host composition is preserved. However, for many volcanic samples the crystal cargo is thought to be antecrystic, and the olivine composition may thus have been completely re-equilibrated during long crystal storage times. Here, we develop a novel MI correction scheme that is applicable when the original host crystal composition has not been preserved and the initial MI composition variability can be represented by simple fractional crystallization (FC). The new scheme allows correction of MI compositions in antecrystic hosts with long and varied temperature histories. The correction fits a set of MI compositions to modelled liquid lines of descent generated by FC. A MATLAB®script (called MushPEC) iterates FC simulations using the rhyolite-MELTS algorithm. In addition to obtaining the corrected MI compositions, the application of this methodology provides estimations of magmatic conditions during MI entrapment. A set of MIs hosted in olivine crystals of homogeneous composition (Fo77–78) from a basaltic tephra of Akita-Komagatake volcano was used to test the methodology. The tephra sample shows evidence of re-equilibration of the MIs to a narrow Mg# range equivalent to the carrier melt composition. The correction shows that olivine hosts were stored in the upper crust (c.125 – 150 MPa) at undersaturated H2O contents ofc. 1 – 2 wt% H2O).

Late Permian–Triassic tectonic nature of the eastern Central Asian Orogenic Belt: Constraints from the geochronology and geochemistry of igneous rocks in the Bureya Massif

The late Paleozoic–early Mesozoic tectonic nature of the eastern Central Asian Orogenic Belt (CAOB) has been subject to debate, and the late Paleozoic–early Mesozoic magmatism in the Bureya Massif provides an opportunity to address this issue. We report new zircon UPb ages, Hf isotope data, and whole-rock major and trace element data for late Paleozoic–early Mesozoic igneous rocks from the south of the Bureya Massif. These data provide insight into the petrogenesis of the igneous rocks, and constrain the late Paleozoic–early Mesozoic tectonic nature of the eastern CAOB. Zircon UPb ages indicate that the late Permian (ca. 255 Ma) and Middle–Late Triassic (ca. 216 Ma) magmatic events are identified in the south of the Bureya Massif. The late Permian igneous rocks consist mainly of bimodal rock suites, which include quartz monzodiorites, gneissic monzogranites, and A-type gneissic syenogranites. The Middle–Late Triassic igneous rocks are dominated by porphyritic syenogranites, and A-type granite porphyries, syenogranites, and gneissic macroporphyritic quartz syenites. The quartz monzodiorites have low SiO2 contents (53.9–56.1 wt%), high Mg# (56–57), and Cr (160–175 ppm), Co (25.2–27.8 ppm), and Ni (61.2–72.3 ppm) contents, and are enriched in light rare earth elements (LREE) and large-ion lithophile elements (LILE; e.g., K, Rb, Sr, and Ba). These characteristics, along with enriched zircon Hf compositions [εHf(t) = −8.31 to −0.44], suggest that their primary magma was derived from the partial melting of lithospheric mantle that had been metasomatized by fluids released from a fossil subducted slab. The granitoids have high SiO2, and low MgO contents, and are enriched in LILE, depleted in high field strength elements (HFSE), and yield εHf(t) values of −11.5 to +2.87 and two-stage model ages (TDM2) ages of 1968–1024 Ma. These characteristics suggest that they were derived from the partial melting of Paleoproterozoic–Mesoproterozoic accreted crustal material; however, these granitoids have distinct, heterogeneous geochemical compositions, precluding simple fractional crystallization of a single parental melt, and strongly suggesting that they were originated from distinct petrogenetic processes. The late Permian–Triassic bimodal igneous rock suites and A-type granites imply an extensional environment in the eastern CAOB.

Geochemical modelling of granitoid magma diversity at Capo Vaticano Promontory (Serre Batholith, southern Italy)

Late-Variscan metaluminous/weakly peraluminous (quartz-diorites and tonalites) and strongly peraluminous (two mica porphyritic granodiorites and granites) granitoids represent two magmatic associations making up the Capo Vaticano Promontory (central Calabria, Italy). They characterize a portion of a complete continental crustal section exposed in continuity from NW to SE in the adjacent Serre Batholith. In this paper, we deal with geochemical modelling trying to understand the evolutionary processes responsible for the CVP granitoid genesis. We have investigated the main processes such as fractional crystallization, variable entrainment of peritectic mineral phases in the melt (Stevens et al., 2007; Clemens and Stevens, 2012), restite-unmixing (White and Chappell, 1977) and magma mixing to explain the geochemical variability in major and trace elements of these magmatic suites. The quartz-diorites and tonalites, representing the deepest seated rocks, are constituted by various amount of Pl + Bt + Amph + Qtz. Bt-rich and Pl-rich quartz-diorite are characterized by cumulus of Bt and Pl, respectively. A multi-step articulated fractional crystallization process was able to reproduce the quartz-diorite/tonalitic trends. Starting from a tonalitic parental magma, three different cumulates were produced: a mafic (Bt-rich) cumulate (75 % Bt, 10 % Pl and 5 % Ap) after F = 10 %, a second cumulate composed by Pl (45 %), Bt (30 %) and Amph (5 %) after F = 20 % and Pl-rich quartz-diorite (60 % Pl, 20 % Bt and 20 % Amph) as the third cumulates, after F = 30 %. Among the source-related models, restitic unmixing could have played a minor role in the quartz-diorite and tonalite genesis, defining them as products derived from partial melting of I-type sources. Pl + Kfs + Qtz + Bt + Ms are the main phases constituting the porphyritic granodiorites and granites. A simple fractional crystallization from less evolved granodiorites sample (KA2) has reproduced the more evolved liquid composition (PA27), after F = 27 %. In addition, PAE modelling is consistent with partial melting of a metapelitic source with entrainment of 20 to 5 % vol. of a peritectic assemblage made of orthopyroxene and garnet.Magma mixing modelling with mafic end-members (a basalt, a basaltic andesite and the MME of CVP) excluded any additional contribution from the mantle.Finally, geochemical modelling highlights the fractional crystallization as the main responsible process in the CVP granitoids differentiation, whereas PAE and restite unmixing processes do not provide evidence about source contributions. This study supports the idea that granitoid rocks represent recycled crustal material in the Capo Vaticano Promontory.

Geochemical and isotopic constraints on the evolution of magma plumbing system at Damavand Volcano, N Iran

Damavand is a Quaternary stratovolcano in N Iran, associated with small volumes of under-saturated to weakly-saturated mafic lavas (Tephrite-Basanite-Alkali olivine basalt), and large volumes of saturated lavas (trachyandesite-trachyte (TT)) together with minor pyroclastic rocks. TT rocks are characterized by LILE and HFSE enrichments, whereas the mafic rocks have higher REE and other incompatible elements (except Rb, Th) than TT suite rocks, contradicting the assumed derivation of TT magmas from mafic magmas by simple fractional crystallization processes. The similar whole-rock isotope ratios of mafic rocks, TT suites and their enclaves do suggest a common origin. Magmatic enclaves in TT suites show decoupled major and some trace elements from their host while they have similar geochemistry to the mafic lavas. Trace element modeling including assimilation-fractional crystallization (AFC) and energy-constrained recharge-assimilation fractional crystallization (EC-RAFC) suggest that the Damavand TT rocks were formed by multi-stage fractionation of mafic magma with minor effects of open system processes. Differentiation started at high pressures (6–8 kbar, initial temperature of magma (Tm) = 1180 °C) involving anhydrous minerals (mainly clinopyroxene-orthopyroxene), accompanied by recharge and wall-rock assimilation at equilibration temperature (Teq) of 1050 °C as the magma reached the threshold for extraction from crystal mush (Mm = 0.49) (stage-1). These processes resulted in the enrichment of the residual liquid in incompatible elements. The fractionation of oligoclase-andesine, anorthoclase, phlogopite and apatite from intermediate enriched melts occurred at shallow crustal levels (0.5–3 kbar, Tm = 1050 and Teq = 830 °C): here, FC processes and further recharge and assimilation of crustal materials reduced LILE and REE concentration in the residual liquid (stage-2). The role of enriched melts is supported by unusual trace element composition of key minerals, for instance, feldspars have variable concentrations of Ba (132–5495 ppm), Sr (1471-14413 ppm) and unusual Rb, La and Ce contents. Based upon melt extraction modeling, physical removal of residual melts at stage-2 could produce cumulate residues with trace element compositions comparable to enclaves in TT suites (stage-3). Disruption of crystal mush due to recharge, followed by mixing of enclave material with evolved trachytic melts caused buffering of magma at trachyandesitic composition (stage-4). The results affirm the advantages of using a range of compositional and textural records in modeling of petrogenetic processes in all magmatic plumbing systems.

Diffusion-driven extreme Mg and Fe isotope fractionation in Panzhihua ilmenite: Implications for the origin of mafic intrusion

To investigate the petrogenesis of Fe-Ti oxide ore deposits, we report Mg and Fe isotopic compositions for coexisting olivine, clinopyroxene and ilmenite in Fe-Ti oxide ores, magnetite-bearing gabbros and gabbros from the Panzhihua Fe-Ti-oxide-bearing layered mafic intrusion, Southwest China. Olivine and clinopyroxene have δ26Mg values ranging from −0.47 to −0.32‰ and −0.40 to −0.18‰, and δ57Fe values from −0.21 to +0.23‰ and −0.16 to +0.20‰, respectively. Most of these mineral pairs display disequilibrium inter-mineral fractionation as they fall off the theoretically predicted equilibrium fractionation lines. Ilmenites from oxide ores and magnetite-bearing gabbros (Group 1) have mantle-like or lower δ26Mg values of −0.80 to −0.13‰ and δ57Fe values of −0.33 to −0.23‰, and those from gabbros (Group 2) display slightly to extremely higher δ26Mg values of +0.48 to +23.10‰ and much lower δ57Fe values of −0.59 to −0.33‰. The δ26Mg negatively correlates with δ57Fe in all ilmenites, which cannot be explained by simple extensive fractional crystallization or Soret diffusion. Instead, the negative correlations between δ26Mg and δ57Fe and between MgO and FeO in ilmenites result from Mg-Fe inter-diffusion among ilmenite, silicate minerals and high-Ti basaltic melts. The extremely large isotopic variations were produced by the large Mg activity gradient between different types of ilmenites and melts, which was enhanced by interstitial liquid immiscibility process. Our study therefore demonstrates that combined Mg-Fe isotopes can be used to trace the genesis of Fe-Ti-oxide-bearing ore.

Melt inclusion evidence for long term steady-state volcanism at Las Sierras-Masaya volcano, Nicaragua

Las Sierras-Masaya volcanic system is a persistently active basaltic caldera complex in Nicaragua. While there has been almost no juvenile material erupted since 1772, Masaya volcano has been persistently degassing for >150 years. An additional unusual behaviour for the Las Sierras-Masaya volcanic complex is its ability to produce large caldera-forming basaltic Plinian eruptions with the most recent occurring about 1800 years ago.Here we present melt inclusion analyses that provide constraints on the magmatic system over time. Melt inclusions hosted in plagioclase and olivine crystals were analyzed for major, trace and volatile elements (S, Cl, F, H2O). The data supports a consistent parental magmatic source with restricted compositional variability explained by simple fractional crystallization of plagioclase, olivine, clinopyroxene and magnetite at a nearly constant temperature. This broadly agrees with previous whole rock geochemical studies showing that the overall chemical signature of volcanic products at Masaya has remained largely unchanged for ~60,000 years and that both shallow fractionation and degassing processes dominate the whole evolution of the magmatic series. Based on volatile element in melt inclusions and gas composition and flux measurements, we determine the magmatic flux to be ~0.19 km3 yr−1 implying that up to 47 km3 of magma may have degassed since the last effusive eruption. As at other persistently active basaltic volcanoes (e.g., Mt. Etna, Italy; Kilauea, Hawaii, USA), this magmatic flux must involve significant endogenous storage which is likely accommodated by extensional tectonics. However, Masaya volcano differs in its apparent simplicity with respect to its stable chemistry and its fully interconnected magmatic system.

Volatile concentrations in olivine-hosted melt inclusions from meimechite and melanephelinite lavas of the Siberian Traps Large Igneous Province: Evidence for flux-related high-Ti, high-Mg magmatism

The origin of high-Mg melts remains one of the most highly debated questions in igneous petrology. There are two contrasting points of view, namely, (1) melt initiation in a rising high-temperature plume, and (2) mantle melting due to fluxing by water. To address this question we determined H2O, CO2, F, Cl and S concentrations in olivine-hosted melt inclusions of high-Mg volcanic rocks of the Siberian Traps Large Igneous Province that bracket the main pulse of volcanism at about 252–250 Ma, and can be classified as melanephelinites and meimechites. Both rock types belong to the high-Ti rock series. Correcting measured H2O, CO2, F, Cl and S concentrations in homogenized primary meimechite melt inclusions to primary meimechite melt composition using experimental melt compositions resulted in corrected melt-inclusion, volatile compositions of ~3.88 wt% H2O, ~1477 ppm CO2, ~4214 ppm F, ~2.08 wt% Cl and ~2490 ppm S. These values are viewed as minimum estimates for the original volatile concentrations in the melt because of the high probability for degassing during melt crystallization and/or during experiment homogenization. Olivine-hosted homogenized melt inclusions from melanephelinites yielded lower corrected concentrations of ~1.06 wt% H2O, ~998 ppm CO2, ~3242 ppm F, ~607 ppm Cl and ~2131 ppm S. We also measured water concentrations in clinopyroxenes of melanephelinites by FTIR, obtaining values as high as 133 ppm H2O, which corresponds to 0.91 wt% in the melt, in general agreement with data obtained by SIMS on the olivine-hosted melt inclusions. Olivine grains from melanephelinites are characterized by evolved compositions (Fo 0.80–0.86). Extrapolation to a primitive melanephelinite melt by simple fractional crystallization suggests that it could also contain high H2O concentrations (up to ~ 3 wt%). Analyzed meimechite and melanephelinite whole-rock samples are characterized by trace-element patterns that are typical of mantle-derived melts and by Sr-Nd isotope ratios that exclude crustal contamination or derivation from ancient lithospheric mantle. Thus, high volatile concentrations can be attributed to sublithospheric mantle source regions. This supports the notion that high-Mg melts form by volatile fluxing of the asthenospheric mantle rather than by decompression melting under relatively dry conditions of a rising abnormally high-temperature mantle plume.

Geochemistry of the Serifos calc-alkaline granodiorite pluton, Greece: constraining the crust and mantle contributions to I-type granitoids

The Late Miocene (11.6–9.5 Ma) granitoid intrusion on the island of Serifos (Western Cyclades, Aegean Sea) is composed of syn- to post-tectonic granodiorite with quartz monzodiorite enclaves, cut by dacitic and aplitic dikes. The granitoid, a typical I-type metaluminous calcic amphibole-bearing calc-alkaline pluton, intruded the Cycladic Blueschists during thinning of the Aegean plate. Combining field, textural, geochemical and new Sr–Nd–O isotope data presented in this paper, we postulate that the Serifos intrusion is a single-zoned pluton. The central facies has initial ^(87)Sr/^(86)Sr = 0.70906 to 0.7106, e_(Nd)(t) = − 5.9 to − 7.5 and δ^(18)Ο_(qtz) = + 10 to + 10.6‰, whereas the marginal zone (or border facies) has higher initial ^(87)Sr/^(86)Sr = 0.711 to 0.7112, lower e_(Nd)(t) = − 7.3 to − 8.3, and higher δ^(18)Ο_(qtz) = + 10.6 to + 11.9‰. The small range in initial Sr and Nd isotopic values throughout the pluton is paired with a remarkable uniformity in trace element patterns, despite a large range in silica contents (58.8 to 72 wt% SiO_2). Assimilation of a crustally derived partial melt into the mafic parental magma would progressively add incompatible trace elements and SiO2 to the evolving mafic starting liquid, but the opposite trend, of trace element depletion during magma evolution, is observed in the Serifos granodiorites. Thermodynamic modeling of whole-rock compositions during simple fractional crystallization (FC) or assimilation-fractional crystallization (AFC) processes of major rock-forming minerals—at a variety of pressure, oxidation state, and water activity conditions—fails to reproduce simultaneously the major element and trace element variations among the Serifos granitoids, implying a critical role for minor phases in controlling trace element fractionation. Both saturation of accessory phases such as allanite and titanite (at SiO_2 ≥ 71 wt%)(to satisfy trace element constraints) and assimilation of partial melts from a metasedimentary component (to match isotopic data) must have accompanied fractional crystallization of the major phases.

Discovery and implications of the chaotic attractor from zoned pyroxene in Qixiangzhan comenditic lava, Tianchi volcano, NE China

Mineral compositional analysis is a powerful tool for identifying both volcanic and petrogenetic processes. This property is observed because spatial variations in the composition of magmatic minerals record chemical and physical changes in the magma from which they crystallized. Thus, these variations can also be used to decipher the history of a magmatic system and its triggering mechanism prior to eruption. The Tianchi volcano, located in the Changbaishan volcanic region, is one of the most active and dangerous volcanoes in East Asia; however, the eruptional mechanism of most recent eruptions are not well-resolved, especially the comenditic lava flow in the Qixiangzhan stage, Tianchi volcano. We focused on the zoned patterns in pyroxene phenocrysts of the comenditic lava to decipher the magma process and triggering mechanism of this silicic lava eruption. We analyzed major and minor element concentrations by point measurement and line-scan across a zoned pyroxene grain using the electron probe micro-analyzer (EPMA) equipped with the energy-dispersive (ED) spectrum. We also extracted a compositional time series by considering the variation of zone thickness across oscillatory zoning and reconstructed the phase space of the compositional time series using the optimal time delay method. First, we calculated the optimal time delay of phase space reconstruction obtained from the first minimum method of mutual information, and we later determined the embedded dimension. Using two parameters (i.e., time delay and embedded dimension), we subsequently reconstructed the phase space. We also present the Poincare section of the reconstructed system. The results of EPMA point measurement (Table 1 and Figure 4) showed that the zoned pyroxenes have higher MgO (2 wt%–2.12 wt%) and lower Na2O (1.26 wt%–1.39 wt%) in the core compared with the rim (MgO, 1.22 wt%–1.54 wt%; Na2O, 1.71 wt%–1.92 wt%). The results of the line-scan of EPMA-ED showed that the normalized concentration of each minor element (MgO, Na2O, MnO) exhibits an intense oscillatory variation (Figure 4). Meanwhile, in the reconstructed phase space (Figure 5(c)) and the Poincare section (Figure 5(d)), the compositional time series of Mg exhibits a chaotic attractor. This attractor is different from the periodic oscillation attractor and the completely random oscillatory dynamic system (Figure 3). These features indicated that the pyroxene phenocrysts grow in a system with a high degree of freedom and complexity and the magma composition around pyroxene changed notably and quickly during crystallization. These features lead us to believe that the oscillatory zoning observed in the Qixiangzhan comenditic lava is not the result of a simple fractional crystallization process, which generally occurred in the stable magma chamber. Although such a process may lead to compositional zoning in the pyroxenes, it cannot form oscillatory zoning. A simple, closed-system fractional crystallization process will produce a periodic oscillation attractor instead of a strange attractor in their reconstructed phase space. A feasible process that may account for the oscillatory zoning features in the Qixiangzhan comenditic lava is an interaction between two (or more) compositionally distinct magmas (magma mixing). This process can create strong heterogeneities within magma bodies in a short time and on a very short length scale. More importantly, this process can produce a strange attractor in the reconstructed phase space of a zoning mineral. These features are all consistent with what we have obtained from the zoned pyroxene in the Qixiangzhan comenditic lava. Thus, we believe that the Qixiangzhan comenditic lava results from magma mixing or the magma recharge process. The mixing and convection processes of infilled primary magma and evolved magma can accelerate the vesiculation of the magma chamber, thereby causing an eruption. Combined with the frequent occurrence of magma recharge or magma mixing evidence in the latest eruptions of the Tianchi volcano, we believe that the infilling of primitive magmas plays a key role in the triggering mechanism of the Tianchi volcano.