Fractional crystallization of high-K arc magmas: biotite- versus amphibole-dominated fractionation series in the Dariv Igneous Complex, Western Mongolia

Many studies have documented hydrous fractionation of calc-alkaline basalts producing tonalitic, granodioritic, and granitic melts, but the origin of more alkaline arc sequences dominated by high-K monzonitic suites has not been thoroughly investigated. This study presents results from a combined field, petrologic, and whole-rock geochemical study of a paleo-arc alkaline fractionation sequence from the Dariv Range of the Mongolian Altaids. The Dariv Igneous Complex of Western Mongolia is composed of a complete, moderately hydrous, alkaline fractionation sequence ranging from phlogopite-bearing ultramafic and mafic cumulates to quartz–monzonites to late-stage felsic (63–75 wt% SiO2) dikes. A volumetrically subordinate more hydrous, amphibole-dominated fractionation sequence is also present and comprises amphibole (±phlogopite) clinopyroxenites, gabbros, and diorites. We present 168 whole-rock analyses for the biotite- and amphibole-dominated series. First, we constrain the liquid line of descent (LLD) of a primitive, alkaline arc melt characterized by biotite as the dominant hydrous phase through a fractionation model that incorporates the stepwise subtraction of cumulates of a fixed composition. The modeled LLD reproduces the geochemical trends observed in the “liquid-like” intrusives of the biotite series (quartz–monzonites and felsic dikes) and follows the water-undersaturated albite–orthoclase cotectic (at 0.2–0.5 GPa). Second, as distinct biotite- and amphibole-dominated fractionation series are observed, we investigate the controls on high-temperature biotite versus amphibole crystallization from hydrous arc melts. Analysis of a compilation of hydrous experimental starting materials and high-Mg basalts saturated in biotite and/or amphibole suggests that the degree of K enrichment controls whether biotite will crystallize as an early high-T phase, whereas the degree of water saturation is the dominant control of amphibole crystallization. Therefore, if a melt has the appropriate major-element composition for early biotite and amphibole crystallization, as is true of the high-Mg basalts from the Dariv Igneous Complex, the relative proximity of these two phases to the liquidus depends on the H2O concentration in the melt. Third, we compare the modeled high-K LLD and whole-rock geochemistry of the Dariv Igneous Complex to the more common calc-alkaline trend. Biotite and K-feldspar fractionation in the alkaline arc series results in the moderation of K2O/Na2O values and LILE concentrations with increasing SiO2 as compared to the more common calc-alkaline series characterized by amphibole and plagioclase crystallization and strong increases in K2O/Na2O values. Lastly, we suggest that common calc-alkaline parental melts involve addition of a moderate pressure, sodic, fluid-dominated slab component while more alkaline primitive melts characterized by early biotite saturation involve the addition of a high-pressure potassic sediment melt

TTG-type plutonic rocks formed in a modern arc batholith by hydrous fractionation in the lower arc crust

We present the geochemistry and intrusion pressures of granitoids from the Kohistan batholith, which represents, together with the intruded volcanic and sedimentary units, the middle and upper arc crust of the Kohistan paleo-island arc. Based on Al-in-hornblende barometry, the batholith records intrusion pressures from ~0.2 GPa in the north (where the volcano-sedimentary cover is intruded) to max. ~0.9 GPa in the southeast. The Al-in-hornblende barometry demonstrates that the Kohistan batholith represents a complete cross section across an arc batholith, reaching from the top at ~8–9 km depth (north) to its bottom at 25–35 km (south-central to southeast). Despite the complete outcropping and accessibility of the entire batholith, there is no observable compositional stratification across the batholith. The geochemical characteristics of the granitoids define three groups. Group 1 is characterized by strongly enriched incompatible elements and unfractionated middle rare earth elements (MREE)/heavy rare earth element patterns (HREE); Group 2 has enriched incompatible element concentrations similar to Group 1 but strongly fractionated MREE/HREE. Group 3 is characterized by only a limited incompatible element enrichment and unfractionated MREE/HREE. The origin of the different groups can be modeled through a relatively hydrous (Group 1 and 2) and of a less hydrous (Group 3) fractional crystallization line from a primitive basaltic parent at different pressures. Appropriate mafic/ultramafic cumulates that explain the chemical characteristics of each group are preserved at the base of the arc. The Kohistan batholith strengthens the conclusion that hydrous fractionation is the most important mechanism to form volumetrically significant amounts of granitoids in arcs. The Kohistan Group 2 granitoids have essentially identical trace element characteristics as Archean tonalite–trondhjemite–granodiorite (TTG) suites. Based on these observations, it is most likely that similar to the Group 2 rocks in the Kohistan arc, TTG gneisses were to a large part formed by hydrous high-pressure differentiation of primitive arc magmas in subduction zones.National Science Foundation (U.S.) (Grant EAR 6920005

Fractional crystallization of high-K arc magmas: biotite- versus amphibole-dominated fractionation series in the Dariv Igneous Complex, Western Mongolia

Many studies have documented hydrous fractionation of calc-alkaline basalts producing tonalitic, granodioritic, and granitic melts, but the origin of more alkaline arc sequences dominated by high-K monzonitic suites has not been thoroughly investigated. This study presents results from a combined field, petrologic, and whole-rock geochemical study of a paleo-arc alkaline fractionation sequence from the Dariv Range of the Mongolian Altaids. The Dariv Igneous Complex of Western Mongolia is composed of a complete, moderately hydrous, alkaline fractionation sequence ranging from phlogopite-bearing ultramafic and mafic cumulates to quartz–monzonites to late-stage felsic (63–75 wt% SiO2) dikes. A volumetrically subordinate more hydrous, amphibole-dominated fractionation sequence is also present and comprises amphibole (±phlogopite) clinopyroxenites, gabbros, and diorites. We present 168 whole-rock analyses for the biotite- and amphibole-dominated series. First, we constrain the liquid line of descent (LLD) of a primitive, alkaline arc melt characterized by biotite as the dominant hydrous phase through a fractionation model that incorporates the stepwise subtraction of cumulates of a fixed composition. The modeled LLD reproduces the geochemical trends observed in the “liquid-like” intrusives of the biotite series (quartz–monzonites and felsic dikes) and follows the water-undersaturated albite–orthoclase cotectic (at 0.2–0.5 GPa). Second, as distinct biotite- and amphibole-dominated fractionation series are observed, we investigate the controls on high-temperature biotite versus amphibole crystallization from hydrous arc melts. Analysis of a compilation of hydrous experimental starting materials and high-Mg basalts saturated in biotite and/or amphibole suggests that the degree of K enrichment controls whether biotite will crystallize as an early high-T phase, whereas the degree of water saturation is the dominant control of amphibole crystallization. Therefore, if a melt has the appropriate major-element composition for early biotite and amphibole crystallization, as is true of the high-Mg basalts from the Dariv Igneous Complex, the relative proximity of these two phases to the liquidus depends on the H2O concentration in the melt. Third, we compare the modeled high-K LLD and whole-rock geochemistry of the Dariv Igneous Complex to the more common calc-alkaline trend. Biotite and K-feldspar fractionation in the alkaline arc series results in the moderation of K2O/Na2O values and LILE concentrations with increasing SiO2 as compared to the more common calc-alkaline series characterized by amphibole and plagioclase crystallization and strong increases in K2O/Na2O values. Lastly, we suggest that common calc-alkaline parental melts involve addition of a moderate pressure, sodic, fluid-dominated slab component while more alkaline primitive melts characterized by early biotite saturation involve the addition of a high-pressure potassic sediment melt

Oxygen Isotope Trajectories of Crystallizing Melts: Insights from Modeling and the Plutonic Record

Elevated oxygen isotope values in igneous rocks are often used to fingerprint supracrustal alteration or assimilation of material that once resided near the surface of the earth. The δ^(18)O value of a melt, however, can also increase through closed-system fractional crystallization. In order to quantify the change in melt δ^(18)O due to crystallization, we develop a detailed closed-system fractional crystallization mass balance model and apply it to six experimentally- and naturally-determined liquid lines of descent (LLDs), which cover nearly complete crystallization intervals (melt fractions of 1 to <0.1). The studied LLDs vary from anhydrous tholeiitic basalts to hydrous high-K and calc-alkaline basalts and are characterized by distinct melt temperature-SiO_2 trajectories, as well as, crystallizing phase relationships. Our model results demonstrate that melt fraction-temperature-SiO_2 relationships of crystallizing melts, which are strongly a function of magmatic water content, will control the specific δ^(18)O path of a crystallizing melt. Hydrous melts, typical of subduction zones, undergo larger increases in δ^(18)O during early stages of crystallization due to their lower magmatic temperatures, greater initial increases in SiO_2 content, and high temperature stability of low δ^(18)O phases, such as oxides, amphibole, and anorthitic plagioclase (versus albite). Conversely, relatively dry, tholeiitic melts only experience significant increases in δ^(18)O at degrees of crystallization greater than 80%. Total calculated increases in melt δ^(18)O of 1.0 to 1.5‰ can be attributed to crystallization from ∼50 to 70 wt.% SiO_2 for modeled closed-system crystallizing melt compositions. As an example application, we compare our closed system model results to oxygen isotope mineral data from two natural plutonic sequences, a relatively dry, tholeiitic sequence from the Upper and Upper Main Zones (UUMZ) of the Bushveld Complex (South Africa) and a high-K, hydrous sequence from the arc-related Dariv Igneous Complex (Mongolia). These two sequences were chosen as their major and trace element compositions appear to have been predominantly controlled by closed-system fractional crystallization and their LLDs have been modeled in detail. We calculated equilibrium melt δ^(18)O values using the measured mineral δ^(18)O values and calculated mineral-melt fractionation factors. Increases of 2-3‰ and 1-1.5‰ in the equilibrium melts are observed for the Dariv Igneous Complex and the UUMZ of the Bushveld Complex, respectively. Closed-system fractional crystallization model results reproduce the 1‰ increase observed in the equilibrium melt δ^(18)O for the Bushveld UUMZ, whereas for the Dariv Igneous Complex assimilation of high δ^(18)O material is necessary to account for the increase in melt δ^(18)O values. Assimilation of evolved supracrustal material is also confirmed with Sr and Nd isotope analyses of clinopyroxene from the sequence. Beginning with a range of mantle-derived basalt δ^(18)O values of 5.7‰ (“pristine” mantle) to ∼7.0‰ (heavily subduction-influenced mantle), our model results demonstrated that high-silica melts (i.e. granites) with δ^(18)O of up to 8.5‰ can be produced through fractional crystallization alone. Lastly, we model the zircon-melt δ^(18)O fractionations of different LLDs, emphasizing their dependence on the specific SiO_2-T relationships of a given crystallizing melt. Wet, relatively cool granitic melts will have larger zircon-melt fractionations, potentially by ∼1.5‰, compared to hot, dry granites. Therefore, it is critical to constrain zircon-melt fractionations specific to a system of interest when using zircon δ^(18)O values to calculate melt δ^(18)O

Fractional crystallization of high-K arc magmas: biotite- versus amphibole-dominated fractionation series in the Dariv Igneous Complex, Western Mongolia

Many studies have documented hydrous fractionation of calc-alkaline basalts producing tonalitic, granodioritic, and granitic melts, but the origin of more alkaline arc sequences dominated by high-K monzonitic suites has not been thoroughly investigated. This study presents results from a combined field, petrologic, and whole-rock geochemical study of a paleo-arc alkaline fractionation sequence from the Dariv Range of the Mongolian Altaids. The Dariv Igneous Complex of Western Mongolia is composed of a complete, moderately hydrous, alkaline fractionation sequence ranging from phlogopite-bearing ultramafic and mafic cumulates to quartz–monzonites to late-stage felsic (63–75 wt% SiO[subscript 2]) dikes. A volumetrically subordinate more hydrous, amphibole-dominated fractionation sequence is also present and comprises amphibole (±phlogopite) clinopyroxenites, gabbros, and diorites. We present 168 whole-rock analyses for the biotite- and amphibole-dominated series. First, we constrain the liquid line of descent (LLD) of a primitive, alkaline arc melt characterized by biotite as the dominant hydrous phase through a fractionation model that incorporates the stepwise subtraction of cumulates of a fixed composition. The modeled LLD reproduces the geochemical trends observed in the “liquid-like” intrusives of the biotite series (quartz–monzonites and felsic dikes) and follows the water-undersaturated albite–orthoclase cotectic (at 0.2–0.5 GPa). Second, as distinct biotite- and amphibole-dominated fractionation series are observed, we investigate the controls on high-temperature biotite versus amphibole crystallization from hydrous arc melts. Analysis of a compilation of hydrous experimental starting materials and high-Mg basalts saturated in biotite and/or amphibole suggests that the degree of K enrichment controls whether biotite will crystallize as an early high-T phase, whereas the degree of water saturation is the dominant control of amphibole crystallization. Therefore, if a melt has the appropriate major-element composition for early biotite and amphibole crystallization, as is true of the high-Mg basalts from the Dariv Igneous Complex, the relative proximity of these two phases to the liquidus depends on the H[subscript 2]O concentration in the melt. Third, we compare the modeled high-K LLD and whole-rock geochemistry of the Dariv Igneous Complex to the more common calc-alkaline trend. Biotite and K-feldspar fractionation in the alkaline arc series results in the moderation of K[subscript 2]O/Na[subscript 2]O values and LILE concentrations with increasing SiO[subscript 2] as compared to the more common calc-alkaline series characterized by amphibole and plagioclase crystallization and strong increases in K[subscript 2]O/Na[subscript 2]O values. Lastly, we suggest that common calc-alkaline parental melts involve addition of a moderate pressure, sodic, fluid-dominated slab component while more alkaline primitive melts characterized by early biotite saturation involve the addition of a high-pressure potassic sediment melt

Exhumation of the UHP Tso Morari eclogite as a diapir rising through the mantle wedge

Ultrahigh-pressure (UHP) rocks such as the coesite-bearing eclogites, occurring as boudins within felsic gneisses of the Tso Morari dome in northwestern Himalayas, originated through subduction of the northern continental margin of India during its early Eocene collision with the Kohistan–Ladakh arc. These rocks are believed to be exhumed through a low-viscosity channel along the top surface of the subducting slab. However, details of the exhumation mechanism are poorly known. We present new constraints on the P–T evolution of hydrous and carbonate-rich samples of the Tso Morari eclogite between 2.2–2.3 GPa/400–425 °C and ~0.4 GPa/450 °C using thermobarometry and calculated P–T– M[subscript CO[subscript 2]] phase equilibria. Our results indicate that the eclogites were strongly heated at high pressures from 400–425 °C at 2.2–2.3 GPa to 670–720 °C at 1.8–1.9 GPa during the early stages of exhumation. Diffusion modeling of Ca variation across the core–rim interface of garnet indicates that the heating stage lasted only <0.1 Myr, in accordance with geochronological constraints and fast exhumation rates. Our P–T path is at odds with exhumation of the eclogites along a subduction channel as model calculations indicate that the intermediate P–T conditions of 1.8–1.9 GPa/670–720 °C are not achieved along the subducting slab. Instead, the constrained P–T conditions are consistent with heating within the mantle wedge overlying the subducting slab. Therefore, we conclude that the Tso Morari eclogites were possibly exhumed as part of a low-density, felsic diapir rising through the mantle wedge. Based on low viscosity values (1.7 × 10[superscript 19]–5.0 × 10[superscript 19] Pa s) of mantle wedges associated with modern subduction zones, the calculated exhumation rate for the Tso Morari eclogite is extremely fast (29–147 mm/yr) and at par with that constrained for other northwestern Himalayan UHP rocks.National Science Foundation (U.S.) (NSF EAR 0910644

The importance of H2O in arc magmas for the formation of porphyry Cu deposits

Porphyry copper deposits (PCDs) hosted in subvolcanic intrusions at convergent margins are the primary world's copper resources. However, the set of magmatic processes that lead to the generation of ore-bearing magmatic provinces remains unclear. In this paper we review the systematic of Cu evolution during arc magma differentiation using new and existing global compilations of whole rock geochemistry data. We trace the Cu evolution from primitive arc magmas through lower crustal plutonic to volcanic rocks. We focus on the well-known tholeiitic and calc-alkaline fractionation sequences, where arc tholeiitic series represents damp primitive melts (2 wt% H₂O) that differentiate with iron depletion. Our study shows that the Cu concentration in primitive arc basalts (~80 ppm) is indistinguishable from that of primitive melts formed at mid-ocean ridges (MORBs) implying that Cu is mainly sourced from the mantle wedge in arcs with a limited contribution from the subducted oceanic lithosphere. A global compilation of plutonic rocks whole rock geochemistry (lower crustal cumulates and derivative melts) indicate no systematic difference in Cu concentrations between cumulates associated with tholeiitic or calc-alkaline series. Yet a complementary global compilation of arc volcanic whole rock geochemistry highlights the contrasting behavior of Cu in tholeiitic and calc-alkaline series during magmatic differentiation. In tholeiitic arc series, Cu shows an incompatible or compatible behavior during magma differentiation influenced by the crustal thickness. In calk-alkaline arc series, Cu is compatible during magma differentiation independently to the crustal thickness. This relates to the timing of sulfide saturation, which is controlled by the liquid lines of descent (LLD) and/or crustal thickness at redox conditions relevant for arc magmas. We demonstrate that the initial melt H₂O content in primitive arc melts controls the LLD and the volume of remaining melt mass at fluid saturation. We show that the remaining H₂O-saturated melt mass positively correlates with the total mass of Cu transferred into degassing fluids. The mass of extractable Cu ranges from ~3 to ~10 Mt (i.e., large PCD) for calc-alkaline series, and ranges from ~0.3 to ~2.5 Mt for tholeiitic series. The ore-forming potential of calc-alkaline arc magmas is at least ~4 to ~10 times higher relative to tholeiitic arc magmas. Despite the compatible behavior of Cu during magmatic differentiation, we propose that a single stage model for the formation of large economic PCDs (as opposed to multi-stage model for Cu-sulfides storage and remobilization) is most applicable for the calc-alkaline melts. The importance of the initial melt H₂O content ultimately reflects the key role of flux melting associated with wet calc-alkaline series and high ore-forming potential, in opposition to decompression melting associated with damp tholeiitic series in arc.National Science Foundation (Grant EAR-1552202

Evidence for polybaric fractional crystallization in a continental arc: Hidden Lakes mafic complex, Sierra Nevada batholith, California

Although the voluminous granitoids that constitute the upper crust of the Sierra Nevada batholith (California) have been investigated in detail, comparatively few studies focus on the origin of mafic bodies at similar crustal levels. Here, we present field and petrographic observations, geochronology, and geochemistry of the Hidden Lakes mafic complex in the central-eastern Sierra Nevada batholith. Our results show that the complex comprises norites, gabbros, monzondiorites, and monzonites that record fractional crystallization of a hydrous (~ 3 wt% H2O), non-primitive basalt within the upper crust (0.3 GPa) at c. 95–96 Ma. To quantitatively model the generation of the observed lithologies, we construct a two-stage polybaric crystallization model based on cumulate and melt-like bulk-rock compositions. In the first step, we model fractionation of a primitive, mantle-derived basalt at > 30 km depth, generating dominantly pyroxenite cumulates. The evolution of the derivative melt (67% of melt mass remaining) is then modeled to fractionate at 12 km depth to produce the observed lithologies within the Hidden Lakes mafic complex. Extension of this model to higher-silica melt compositions (> 65 wt% SiO2) replicates observed granodiorite compositions in the batholith, suggesting that polybaric crystallization could be an important process for the generation of arc granitoid melts. The depth of differentiation in continental arcs is debated, as field observations indicate abundant lower crustal fractionation while experimental data suggest that high-pressure crystallization of hydrous basalts cannot produce the non-peraluminous granitoid compositions observed in continental arc batholiths. Our model supports polybaric differentiation as one potential mechanism to resolve this inconsistency

Low-latitude arc–continent collision as a driver for global cooling

New constraints on the tectonic evolution of the Neo-Tethys Ocean indicate that at ∼90–70 Ma and at ∼50–40 Ma, vast quantities of mafic and ultramafic rocks were emplaced at low latitude onto continental crust within the tropical humid belt. These emplacement events correspond temporally with, and are potential agents for, the global climatic cooling events that terminated the Cretaceous Thermal Maximum and the Early Eocene Climatic Optimum. We model the temporal effects of CO[subscript 2] drawdown from the atmosphere due to chemical weathering of these obducted ophiolites, and of CO[subscript 2] addition to the atmosphere from arc volcanism in the Neo-Tethys, between 100 and 40 Ma. Modeled variations in net CO[subscript 2]-drawdown variation of ocean bottom water temperatures over this time interval, indicating that ophiolite emplacement may have played a major role in changing global climate. We demonstrate that both the lithology of the obducted rocks (mafic/ultramafic) and a tropical humid climate with high precipitation rate are needed to produce significant consumption of CO[subscript 2]. Based on these results, we suggest that the low-latitude closure of ocean basins along east–west trending plate boundaries may also have initiated other long-term global cooling events, such as Middle to Late Ordovician cooling and glaciation associated with the closure of the Iapetus Ocean

Phlogopite- and clinopyroxene-dominated fractional crystallization of an alkaline primitive melt: petrology and mineral chemistry of the Dariv Igneous Complex, Western Mongolia

We present field relationships, petrography, and mineral major and trace element data for the Neoproterozoic Dariv Igneous Complex of the Altaids of Western Mongolia. This unique complex of high-K plutonic rocks is composed of well-exposed, km-scale igneous intrusions of wehrlites, phlogopite wehrlites, apatite-bearing phlogopite clinopyroxenites, monzogabbros, monzodiorites, and clinopyroxene-bearing monzonites, all of which are intruded by late stage lamprophyric and aplitic dikes. The biotite-dominated igneous complex intrudes depleted harzburgitic serpentinite. The observed lithological variability and petrographic observations suggest that the plutonic rocks can be ascribed to a fractionation sequence defined by olivine + clinopyroxene ± Fe–Ti oxides → phlogopite + apatite → K-feldspar + plagioclase → amphibole + quartz. Notably, phlogopite is the dominant hydrous mafic mineral. Petrogenesis of the observed lithologies through a common fractionation sequence is supported by a gradual decrease in the Mg# [molar Mg/(Fe_(total) + Mg) × 100] of mafic minerals. Crystallization conditions are derived from experimental phase petrology and mineral chemistry. The most primitive ultramafic cumulates crystallized at ≤0.5 GPa and 1,210–1,100 °C and oxygen fugacity (fO_2) of +2–3 ∆FMQ (log units above the fayalite–quartz–magnetite buffer). Trace element modeling using clinopyroxene and apatite rare earth element compositions indicates that the dominant mechanism of differentiation was fractional crystallization. The trace element composition of a parental melt was calculated from primitive clinopyroxene compositions and compares favorably with the compositions of syn-magmatic lamprophyres that crosscut the fractionation sequence. The parental melt composition is highly enriched in Th, U, large ion lithophile elements, and light rare earth elements and has a pronounced negative Nb–Ta depletion, suggestive of an alkaline primitive melt originating from a subduction-imprinted mantle. Comparison with a global compilation of primitive arc melts demonstrates that Dariv primitive melts are similar in composition to high-K primitive melts found in some continental arcs. Thus, the high-K fractionation sequence exposed in the Dariv Igneous Complex may be a previously unrecognized important fractionation sequence resulting in alkali-rich upper crustal granitoids in continental arc settings