Magmatic H2O Research Articles

Magmatic initial and saturated water thresholds determine copper endowments: Insights from apatite F-Cl-OH compositions

Magmatic volatiles (H2O, F, Cl), especially water, are critical in the formation of porphyry copper deposit, for its significance as a carrier for metals. However, accurately quantifying the water contents of deep ore-forming magma remain a challenge. Here, we used apatite and forward modelling methods to reconstruct magmatic water evolution histories, with special concern on the control of initial magmatic H2O contents and water saturation threshold to porphyry mineralization. Samples investigated include granitoid rocks and apatite from highly copper-mineralized and barren localities. Generally, our research suggested that both ore-related and ore-barren magma systems are hydrous, the modeled magmatic water contents vary significantly among systems whether mineralized or not, and the major difference lies in the threshold of water saturation (6.0 wt% for barren, and up to 10.0 wt% for highly mineralized). Combined with whole rock geochemistry data (high K2O and Sr/Y contents) and modeling result (high modeled water thresholds), we think the ore-related magmas are stored at deeper depth with higher water solubility. In conclusion, we propose that the level of magmatic water saturation plays a crucial role in the formation of porphyry copper systems. Fertile magma has higher water solubility to which deeper storage depth is a critical contributing factor, and can get significantly water enriched upon saturation.

Early fluid exsolution suppressed sulfide saturation in Triassic arc volcanic rocks from the Gangdese belt: Implications for Cu depletion in arc magmas and mineralization potential

The formation of porphyry–epithermal CuAu deposits depends critically on Cu and Au fertility of arc magmas. Arc magmas commonly exhibit decreasing Cu and Au contents during magmatic differentiation, which is believed to result from sulfide saturation. However, the Cu and Au contents of the arc magmas would also be impacted by fluid exsolution, particularly when magma differentiation occurs in thin arcs. Here we report the variations of chalcophile element contents, including Cu and platinum-group elements (PGEs), with magmatic differentiation in the Qushui–Changguo (QS–CG) arc volcanic rocks from the Gangdese magmatic belt, Tibet. Zircon ages for QS–CG arc volcanic rocks range from 235 to 232 Ma and represent the earliest magmatism correlated to the subduction of the Neo-Tethys Ocean. Magmatic zircons yield an oxygen fugacity of FMQ +1.0 ± 0.6, which is within the range of typical arc magmas worldwide. The crystallization pressures (2.5 kbar) and magmatic H2O contents (5 wt%) estimated from amphibole and clinopyroxene compositions suggest the arc magmas were hydrous and differentiated at low pressures. The primitive rocks have Cu/Pd ratios within the mantle range and relatively high PGE contents, indicating that most chalcophile metals were transferred to the melt during partial melting to form the chalcophile fertile arc magma. The Cu contents decreased from >100 ppm in the primitive rocks to <30 ppm in the evolved rocks (e.g., ∼2 wt% MgO), which resembles the trend observed in global arc magmas. However, the Pt contents exhibit a slight reduction as the MgO decreases, which is in accordance with the crystallization of Pt-rich alloys. No decrease in Pd contents is observed in the samples, and Pd contents increase to ∼10 ppb in the most evolved samples. The absence of a dramatic decrease in PGE contents reveals that the magma did not reach sulfide saturation during differentiation, even in the highly evolved magma after magnetite crystallization. In contrast, the decoupling of Cu and PGE contents in the QS–CG arc magmas and decreasing Cu/Pd ratios are indicative of early aqueous volatile exsolution during magmatic differentiation. We suggest that early volatile exsolution in the arc magmas suppressed sulfide saturation during magmatic differentiation. As a result, early fluid exsolution may also be a key factor in reducing Cu contents in arc magmas in thin arcs, especially for magmas with high volatile contents that undergo differentiation at low pressures. Cu and Au would have been enriched in exsolved fluid prior to sulfide saturation. The Triassic metallogenic potential of the Gangdese belt should be re-evaluated based on recent discoveries. Our results indicate the Triassic magmatism could also be fertile, with the ability to form subduction-related porphyry CuAu deposits in the Gangdese metallogenetic belt.

Decoding degassing modes of magma chamber of arc volcanoes: Insights from CO2/Cl and Cl/H2O ratios of magmatic fluids in groundwater

The H2O-CO2-Cl composition of the fluids released from the magma chambers for arc volcanoes was calculated based on the solubilities of H2O and CO2 in the silicate melt and the partition coefficient of Cl between the aqueous fluid and melt for the stages defined by a simple evolution model of the magma chamber. The degassing modes consisted of mafic bubbling (MB: first boiling) and felsic bubbling (FB: second boiling) releasing fluids as separate bubbles due to the mafic magma supply and felsic magma formation by differentiation, respectively, and felsic solidification (FS) releasing fluid due to felsic pluton formation. The variations in the CO2/Cl and Cl/H2O ratios of the fluids were examined for each degassing mode at pressures ranging from 150 to 400 MPa and were found to have very large variations at 0.00024–845 for CO2/Cl and 0.00043–0.041 for Cl/H2O. The CO2/Cl is concluded to be a good indicator of magma chamber conditions because each mode has a specific ratio distinguished from that of the other modes; i.e., CO2/Cl > 43 for MB, 0.027–23 for FB, and < 0.62 for FS.The alteration of magmatic composition of fluid during ascent was discussed considering the phase separation of fluid, CO2 bubbling in groundwater, dissolution, and deposition of minerals; furthermore, the limitation of the method when applied to natural groundwater systems were outlined. This method was tested for a natural volcanic system, the Kuju volcano in central Kyusyu, Japan, which is an active volcano complex composed of various magma types from rhyolitic to basaltic, replacing the eruption centers from west to east. Groundwater samples from springs and boreholes were collected and analyzed for chemical and isotopic compositions to determine the magmatic H2O, dissolved inorganic carbon (DIC), and Cl concentrations. The new approach to determine the magmatic CO2 concentration in groundwater using 3He concentration proposed herein cancelled the effect of carbonate deposition/dissolution, addition of DIC from organic matter, and bubbling of CO2. The estimated magmatic CO2/Cl ratios were 0.0009–14, which overlapped consistently with the modeled variation in the CO2/Cl ratio. The spatial variation of magmatic CO2/Cl in groundwater showed that higher-CO2/Cl are found near the central part of the volcanic complex which composed of felsic to mafic volcanoes, and low-CO2/Cl are only found around old felsic volcanoes. The CO2 bubbling springs were found to be associated with younger mafic volcanoes. The condition of the magma chambers, as shown by the spatial variation in CO2/Cl, were consistent with the record of the eruptive activities of the Kuju volcano. The CO2/Cl method proposed in this study using groundwater is useful for estimating magmatic conditions in chambers.

Investigating the Impact of an Exsolved H2O‐CO2 Phase on Magma Chamber Growth and Longevity: A Thermomechanical Model

AbstractMagmatic volatiles drive pressure, temperature, and compositional changes in upper crustal magma chambers and alter the physical properties of stored magmas. Previous studies suggest that magmatic H2O content influences the growth and longevity of silicic chambers through regulating the size and frequency of eruptions and impacting the crystallinity‐temperature curve. However, there has been comparatively little exploration of how CO2 impacts the evolution of magma chambers despite the strong influence of CO2 on H2O solubility and the high concentrations of CO2 often present in mafic systems. In this study, we integrate the thermodynamic effects of dissolved and exsolved H2O and CO2 with the mechanics of open‐system magma chambers that interact thermally and mechanically with the crust. We applied this model to investigate how intrinsic variations in magmatic H2O‐CO2 content influence the growth and longevity of silicic and mafic magma chambers. Our findings indicate that even with a tenfold increase in CO2 content (up to 10,000 ppm), CO2 plays a minimal role in long‐term chamber growth and longevity. While CO2 content affects the magma compressibility, the resulting changes in eruption mass are balanced out by a commensurate change in eruption frequency so that the time‐averaged eruptive flux and long‐term chamber behavior remain similar. In contrast, H2O content strongly influences chamber growth and longevity. In silicic systems, high H2O contents hinder magma chamber growth by increasing the total eruptive flux and steepening the slope of the crystallinity‐temperature curve. In mafic systems, high H2O contents promote magma chamber growth by flattening the slope of the crystallinity‐temperature curve.

Earth's early continental crust formed from wet and oxidizing arc magmas.

Formation of continental crust has shaped the surface and interior of our planet and generated the land and mineral resources on which we rely. However, how the early continental crust of Earth formed is still debated1-7. Modern continental crust is largely formed from wet and oxidizing arc magmas at subduction zones, in which oceanic lithosphere and water recycle into the mantle8-10. The magmatic H2O content and redox state of ancient rocks that constitute the early continental crust, however, are difficult to quantify owing to ubiquitous metamorphism. Here we combine two zircon oxybarometers11,12 to simultaneously determine magmatic oxygen fugacity (fO2) and H2O content of Archaean (4.0-2.5 billion years ago) granitoids that dominate the early continental crust. We show that most Archaean granitoid magmas were ≥1 log unit more oxidizing than Archaean ambient mantle-derived magmas13,14 and had high magmatic H2O contents (6-10 wt%) and high H2O/Ce ratios (>1,000), similar to modern arc magmas. We find that magmatic fO2, H2O contents and H2O/Ce ratios of Archaean granitoids positively correlate with depth of magma formation, requiring transport of large amounts of H2O to the lower crust and mantle. These observations can be readily explained by subduction but are difficult to reconcile with non-subduction models of crustal formation3-7. We note an increase in magmatic fO2 and H2O content between 4.0 and 3.6 billion years ago, probably indicating the onset of subduction during this period.

The effect of elemental diffusion on the application of olivine-composition-based magmatic thermometry, oxybarometry, and hygrometry: A case study of olivine phenocrysts from the Jiagedaqi basalts, northeast China

Abstract Olivine compositions are widely used to constrain magmatic thermodynamic conditions such as magmatic temperature, oxygen fugacity, and H2O content. However, elemental diffusion may change the initial compositions and lead to large uncertainty on the estimation of these thermodynamic conditions. In this study, we conducted LA-ICP-MS elemental mapping and EPMA analysis of olivine phenocrysts and olivine-hosted spinel from the Jiagedaqi (JGD) alkaline basalts in northeast China to evaluate the influence of elemental diffusion on olivine-composition-based geothermometry, oxybarometry, and hygrometry. The JGD olivines show normal Fo [Mg/(Mg + Fe) × 100 in moles] zoning, with cores having Fo of 77–87 and rims having Fo of 67–73. The constant P contents from core to rim indicate that these compositional zonings were caused mainly by diffusion. Because Al is a slow-diffusing element and its content is relatively constant from core to rim, the temperature calculated by the Al-in-olivine thermometer is not influenced by elemental diffusion and preserves the JGD olivine crystallization temperature up to 1150 °C. The temperatures calculated using the Sc/Y-in-olivine thermometer, the oxygen fugacity calculated using the olivine–spinel oxybarometer, and the H2O content calculated on the basis of Ca partitioning between olivine and melt are strongly influenced by the diffusion of Fo, Sc/Y, and Ca. However, the compositional plateaus in olivine cores, which were not influenced by elemental diffusion, preserve the magmatic temperature (1150 °C), oxygen fugacity (QFM+1.4), and H2O content (4 wt%) that applied during the formation of the JGD olivines. Together, these findings suggest that the mantle source of the JGD basalts was metasomatized by fluids released from the subducted slab. This study highlights that elemental diffusion in olivine phenocrysts can strongly affect the application of olivine-composition-based geothermometers, oxybarometers, and hygrometers. However, primitive olivine cores that have not been influenced by diffusion preserve the initial magmatic thermodynamic conditions.

Mineral–Geochemical and Geotectonic Features of the Lotmvara-II Ultrabasic Sill, Serpentinite Belt (Kola Peninsula)

Abstract —In this paper, we present a description of the characteristics of the Lotmvara-II sill, which is a representative of the Serpentinite Belt (SB) composed of a series of shallowly emplaced ultrabasic intrusive bodies. The Paleoproterozoic SB complexes were derived from a large-scale mantle plume of komatiitic melt. The sill consists predominantly of fine-grained (locally nearly micrograined) harzburgites with subordinate zones of dunites and orthopyroxenites, located in the central and marginal parts, respectively. It formed from an Al-undepleted komatiitic magma of extremely high Mg content and may represent a near-surface laccolithic “ridge.” In general, the sill is comparatively homogeneous and does not have distinct zoning in the distribution of Mg# values in rock compositions (Mg# = 84.2–88.9, average 86.7). Detailed studies show that olivine, chromian spinel, and ilmenite are the most strongly magnesian in the central part of the body. The maximum values of Mg# equal to 90.7–91.4 in the compositions of olivine at the center of the sill are interpreted as “centers of initial crystallization”. The low values of Mg# equal to 73.4–76.4 are attributed to manifestations of the recurrent generation of olivine. The values of Mg# of orthopyroxene in the sill are within the range 84.6 to 92.3. Orthopyroxene grains in a porphyritic texture are surrounded by a rim of calcic amphibole (autometasomatic in origin); they do not differ compositionally from normal grains. The Zn content of the chromian spinel generally decreases toward the marginal parts of the sill. There is an insignificant degree of magmatic differentiation in the sill with respect to the principal components, but incompatible elements (REE and HFSE) locally show increased levels of their relative enrichment, which is reflected in the nature of the mineral associations described. Thus, the sill has a cryptic zonal structure, which is consistent with its overall crystallization from the center to the edges. The data gathered suggest the presence and significant development of volatile components, halogens, CO2, and especially magmatic H2O, which are capable of strongly lowering the liquidus and reducing the density and viscosity of the high-magnesium melt, thereby improving its mobility during ascent from the mantle to the near-surface level of the crust. An increase in fO2 is observed during in situ subvolcanic crystallization of the sill, as noted earlier in the related complexes of the belt. The relatively small volume of the komatiitic magma in the sill crystallized fairly quickly, resulting in unusual mineral intergrowths. Thus, the Lotmvara-II sill is a novel member in the Serpentinite Belt–Tulppio Belt (SB–TB) in the Paleoproterozoic SB–TB megastructure of the Fennoscandian Shield.

A Global Assessment of the Controls on the Fractionation of Arc Magmas

AbstractDuring the differentiation of arc magmas, fractionating liquids follow a series of cotectics, where the co‐crystallization of multiple minerals control the melt compositional trajectories, commonly referred to as liquid lines of descent (LLD). These cotectics are sensitive to intensive properties, including fractionation pressure and melt H2O concentration, and changes in these variables produce systematic differences in the LLDs of arc lavas. Based on a compilation of experimental studies, we develop two major element proxies that exploit differences in LLDs to constrain the fractionation conditions of arc magmas. Near‐primary fractionating magmas evolve along the olivine‐clinopyroxene cotectic, which is pressure‐sensitive. We use this sensitivity to develop a proxy for early fractionation pressure based on the normative mineral compositions of melts with 8 ± 1 wt.% MgO. Fractionation in more evolved magmas is controlled by the clinopyroxene‐plagioclase cotectic, which is strongly sensitive to magmatic H2O contents. We use this relationship to develop an H2O proxy that is calibrated to the normative mineral components of melts with 2–4 wt.% MgO. These two proxies provide new tools for estimating the variations in pressure and temperature between magmatic systems. We applied these proxies to compiled major element data and phenocryst assemblages from modern volcanic arcs and show that in island arcs early fractionation is relatively shallow and magmas are dominantly H2O‐poor, while continental arcs are characterized by more hydrous and deeper early fractionation. These differences likely reflect variations in the relative contributions of decompression and flux melting in combination with distinct upper plate controls on arc melt generation.

Ultrahigh-Temperature Anatexis of Greywackic Granulites Generates Peraluminous Charnockites in the Jining Complex, North China Craton

Abstract Charnockites form an important component of the lower continental crust. Quantitative investigation on the properties of magmas that can stabilize orthopyroxene at solidi is crucial to understanding the petrogenesis of igneous charnockites. This study has performed detailed petrologic analyses and thermodynamic constraints on the Paleoproterozoic high-maficity (FeOT + MgO = 5–14 wt%) and peraluminous charnockites from the Jining Complex in the North China Craton. These charnockites occur as intrusions in granulite facies terranes and contain the mineral assemblages including prevalent perthitic/antiperthitic feldspars and garnet with minor biotite (usually less than ~5 vol%) beside orthopyroxene. The Jining charnockitic magmas were ascertained to have ultrahigh temperatures up to 1050–1100°C, poor H2O contents around 0.14–0.42 wt% and limited aluminum saturation indexes (ASIs) of 1.0–1.3. The stabilization of orthopyroxene at the solidus is attributed to low magmatic H2O contents and ASIs, which have maxima of 1.2 wt% and 1.5, respectively, and are positively correlated to bulk-rock maficity. Such charnockitic magmas could not release H2O-rich fluids near solidi, as the H2O is buffered by the orthopyroxene–biotite pair. Moreover, combined geochemical discrimination and progressive melting modelling reveal that the Jining charnockites were generated by partial melting of a greywackic granulite source, with about 15%–40% entrainment of solid phases in mushy magmas. The melting occurs at temperatures as high as 1050–1100°C, obviously beyond biotite stabilities, and involves quartz, feldspars and garnet as melting reactants, which differs from the previous proposition that peraluminous charnockites are related to biotite dehydration melting. The resultant magmas are substantially enriched in maficity and depleted in H2O due to both the melt compositions per se and the high entraining capability. Such peraluminous charnockite plutons massively emplaced in granulite facies terranes indicate post-orogenic ultrahigh-temperature anatexis of metasedimentary rocks in conditions close to the crustal dry solidus.

APATITE VOLATILE CONTENTS OF PORPHYRY Cu DEPOSITS CONTROLLED BY DEPTH-RELATED FLUID EXSOLUTION PROCESSES

Abstract Porphyry Cu deposits are formed by Cu- and volatile (e.g., Cl, S)-rich fluids exsolved from underlying magma reservoirs. Intuitively, higher magmatic Cl and S contents likely correspond to higher magma fertility. However, the Cl contents of syn-ore magmatic apatite, one of the major Cl-bearing mineral phases in magmas, are highly variable among deposits (from &amp;lt;0.1 to &amp;gt;2 wt %). These variations may be controlled by different timing of apatite crystallization relative to fluid saturation among deposits, but the causes of these different relative timings remain obscure. Here we compile existing chemical data of magmatic apatite and amphibole phenocrysts from 25 porphyry Cu deposits worldwide and use these data to calculate magmatic physical-chemical conditions, such as water contents and magma reservoir depths. We find that the porphyry Cu deposits associated with deeper magma reservoirs are characterized by systematically higher magmatic H2O contents and apatite Cl, but lower apatite F contents and F/Cl ratios compared to shallower deposits. These correlations are best explained by early fluid exsolution and Cl loss that predate apatite crystallization in shallower porphyry Cu systems, which leads to elevated apatite F/Cl ratios. This is supported by the common occurrence of primary fluid inclusions in apatite from shallower systems. Postsubduction porphyry Cu deposits are normally associated with lower apatite Cl contents and shallower magma reservoirs, which is attributed to their formation under relatively extensional tectonic regimes. Our results demonstrate that the magma reservoir depth exerts an important control on the timing of fluid exsolution and accompanying Cl loss. In contrast, relatively high and constant apatite S content among deposits is minimally affected by fluid exsolution, possibly due to buffering of early-saturated sulfate in oxidized and S-rich magmas, and therefore might be used as a better potential fertility indicator than Cl.

Tracking caldera cycles in the Aso magmatic system – Applications of magnetite composition as a proxy for differentiation

Caldera-forming eruptions are among the most hazardous natural events on Earth and pose a significant risk for global consequences in the future. Recent petrological re-evaluations of pre-, syn-, and post-caldera deposits in several volcanic systems worldwide suggest a cyclic behavior in the evolution of the subvolcanic reservoirs feeding these eruptions. Such caldera cycles are usually subdivided into maturation, fermentation and recovery phases, each characterized by distinct petrological features (e.g. variations in mineral and glass compositions). Combined with trends in intensive parameters and geophysical information about the eruptive behavior of the system, these characteristics can be used to determine the current state of a reservoir within the caldera cycle framework. Here, we test the application of this caldera cycle model on the Aso volcanic complex in Central Kyushu (Japan) by analyzing pre-, syn-, and post-caldera activity between the Aso-4 and Aso-3 events and evaluate the recent activity of Aso based on mineral and glass geochemistry. Widely overlapping compositions in most minerals (here plagioclase and orthopyroxene) and melt, as well as similar ranges in intensive parameters (e.g. magmatic H2O content), make it difficult to pinpoint chemical differences between pre- or post-caldera eruptions. Tracing the MnO/Al2O3 ratio in titanomagnetite, on the other hand, appears as a useful proxy to trace the level of differentiation within the reservoir prior to eruption. Titanomagnetite is an abundant mineral phase known to chemically re-equilibrate fast with melt and hence records “average” conditions prevailing just prior to eruption, with MnO showing a typical incompatible behavior during magma evolution, while Al2O3 is typically compatible. The assessment of different case studies revealed clear evolutionary patterns common in all these caldera cycles with low Mn (associated with low levels of differentiation) during recovery, progressively increasing during maturation, and culminating at highest levels (and associated levels of differentiation) during the fermentation phase, right before the next caldera-forming event. The MnO/Al2O3 ratio in titanomagnetite is analytically easy and quick to determine by electron microprobe, and gives valuable information about the current position of a system within the caldera cycle framework. Based on the evaluation of recent eruptive products in context with the current volcanic activity, we conclude that Aso is presently still in recovery after the massive Aso-4 eruption. Depending on magma supply from depth, the system can either enter renewed maturation or activity could decline leading to the cessation of the system.

Corona-Type Textures in Ultrabasic Complexes of the Serpentinite Belt, Kola Peninsula, Russia

For the first time, corona-type textures are described in ultrabasic rocks in three complexes of the Serpentinite Belt on the Kola Peninsula in the northeastern Fennoscandian Shield. Three variants of the corona texture formed at different stages during the crystallization of a komatiitic, Al-undepleted melt emplaced in a subvolcanic setting. The first type crystallized at an early stage (Mg# Ol = 87) in a fine-grained harzburgite of the Chapesvara-I sill, with the following order in the corona: Ol → Opx → Cpx → Pl → Amp (aluminous sodic-calcic). The second type displays the sequence Opx → Cpx → Amp → Pl → Qz, which is observed in the orthopyroxenite zone in the Lotmvara-I sill. The third type involves a symplectitic corona in a plagioclase-bearing orthopyroxenite in the Lyavaraka complex, in which the inferred order is: Cpx → Amp (aluminous hornblende) + symplectitic Qz, formed in direct contact with grains of Pl. The corona-type textures occur in fresh rocks and are not related to regional metamorphism. They likely formed as consequences of two important factors: (1) rapid cooling, leading to unsteady conditions of crystallization in a shallow setting; and (2) an intrinsic enrichment in H2O and other volatiles in the parental magma, giving rise to fluid-saturated environments at advanced stages of crystallization. This was followed by a deuteric deposition of Amp rims as a result of the accumulation of H2O and reaction of H2O-bearing fluid with early grains of pyroxene and late plagioclase. The likely existence of a close relationship is suggested by the drusites of the Belomorian complex, which are coeval. In addition, unusual occurrences of lamellar inclusions of phlogopite and Al2SiO5 are documented, hosted by interstitial grains of plagioclase in the orthopyroxenite zone of the Lotmvara-I sill. These are attributed to crystallization from late portions of remaining melt enriched in Al, K, Na, H2O, and Cl, which is indicated by the recorded occurrence of chlorapatite in this association. Thus, our findings indicate the presence and abundance of intrinsic volatiles, Cl, F, CO2, and especially magmatic H2O, which were important to lower the liquidus, decrease the density and viscosity of the highly magnesian melt of Al-undepleted komatiite, thus enabling its transport from the mantle to a shallow level in the crust.

Development of major element proxies for magmatic H2O content in oceanic basalts

Analysis of H2O concentrations in quenched glass has enabled significant improvements in our understanding of its role in mantle melting, magma differentiation, eruption dynamics, and the origin of mantle heterogeneity. Direct measurements of dissolved H2O in glass, however, are not always possible, and we lack robust methods of constraining magmatic H2O contents in aphyric, bulk rock samples that lack glass. Here, we present a major element hygrometer for mid-ocean ridge (MOR) and back-arc basin (BAB) basalt magmas based on the sensitivity of phenocryst phase assemblages to magmatic H2O contents, which translate into resolvable differences in liquid lines of descent (LLDs) as a function of magmatic H2O concentrations. Existing hygrometers lack sufficient resolution to be useful at the low H2O concentrations typical of MOR and BAB basalts (<1.0 wt%). We develop the major element proxy, Al2O3/FeO*(7.0) (fractionation-corrected to 7 wt% MgO), for determining magmatic H2O contents using cogenetic suites of oceanic basalts with well-defined LLDs and well-constrained H2O contents. H2O(7.0) positively correlates with Al2O3/FeO*(7.0) in the mid-ocean ridge basalt dataset, and this relationship is maintained in back-arc basin basalts with a broader range of water contents (up to 2.0 wt%). The main petrological control over this covariation is the role of H2O in suppressing plagioclase crystallization, while crystallization pressure and magmatic oxygen fugacity play lesser roles. Herein, we present an empirical model that uses Al2O3/FeO*(7.0) to estimate the magmatic water content in plagioclase-saturated oceanic basaltic magmas: H2O(7.0) = 1.109Al2O3/FeO∗(7.0) − 1.111. This model enables the estimation of magmatic H2O content using whole-rock major element data, which can be readily determined for aphyric or crystalline lavas that lack quenched glassy rinds, melt inclusions, or appropriate phenocryst assemblages.

Contrasting Volcanic Deformation in Arc and Ocean Island Settings Due To Exsolution of Magmatic Water

AbstractTwo of the most widely observed co‐eruptive volcanic phenomena—Ground deformation and volcanic outgassing—Are fundamentally linked via the mechanism of magma degassing and the development of compressibility, which controls how the volume of magma changes in response to a change in pressure. Here we use thermodynamic models—Constrained by petrological data—To reconstruct volatile exsolution and the consequent changes in magma properties. We use the fraction of SO2 exsolved during decompression to predict co‐eruptive SO2 flux and magma compressibility to predict co‐eruptive surface deformation (both normalized by erupted volume). We conduct sensitivity tests using properties of typical basalts to assess how varying magma volatile content, crustal properties, and chamber geometry affect co‐eruptive deformation and degassing. We find that magmatic H2O content has the most impact on both SO2 flux and volume change. Our findings have general implications for typical basaltic systems in arc and ocean island settings. The higher water content of arc magmas makes them more compressible than ocean island magmas and leads to muted or non‐existent deformation being observed during arc eruptions. Our models are consistent with observation: Deformation has been detected during 48% of basaltic eruptions in ocean island settings (16/33) during the satellite era (2005–2020), but only 11% of basaltic eruptions in arc settings (7/61).

Sampling Volcanic Plume Using a Drone-Borne SelPS for Remotely Determined Stable Isotopic Compositions of Fumarolic Carbon Dioxide

Both chemical and isotopic compositions of concentrated volcanic plumes are highly useful in evaluating the present status of active volcanoes. Monitoring their temporal changes is useful for forecasting volcanic eruptions as well. Recently, we developed a drone-borne automatic volcanic plume sampler, called SelPS, wherein an output signal from a sulfur dioxide (SO2) sensor triggered a pump to collect plume samples when the SO2 concentration exceeded a predefined threshold. In this study, we added a radio transmission function to the sampler, which enabled our operator to monitor real-time SO2 concentration during flights and thus obtain more concentrated volcanic plume samples through precise adjustment of the hovering position. We attached the improved SelPS to a drone at Nakadake crater, Aso volcano (Japan), and successfully obtained volcanic plume samples ejected from the crater more concentrated than those obtained by using previous version of SelPS in 2019. Additionally, we found a significant linear correlation between the reciprocal of the concentration and isotopic ratios for the 2H/1H ratios of H2, 18O/16O ratios of CO2, and 13C/12C ratios of CO2 within the plume samples. Based on the isotopic ratios of fumarolic H2 (δ2H = −239 ± 6‰) and fumarolic CO2 (δ13C = −3.58 ± 0.85‰ and δ18O = +22.01 ± 0.68‰) determined from the linear correlations, we estimated the apparent equilibrium temperatures (AETs) with magmatic H2O simultaneously and precisely for the first time in erupting volcanoes, assuming hydrogen isotope exchange equilibrium between H2 and H2O (AETD = 629 ± 32°C) and oxygen isotope exchange equilibrium between CO2 and H2O (AET18O = 266 ± 65°C). We found that the AET18O was significantly lower than the AETD in the crater. While the temperature of the magmatic gases was originally 600°C or more, most of the gases cooled just beneath the crater to temperatures around the boiling point of water. The improved SelPS enable us to determine both AETD and AET18O in eruptive volcanoes, wherein fumaroles are inaccessible. Simultaneous and precise determination of both the AET18O and AETD can provide novel information on each volcano, such as the physicochemical conditions of magma degassing and the development of fluid circulation systems beneath each volcano.

Evidence of hydration of the peridotite mantle wedge recorded in low-CaO olivines from Los Tuxtlas Volcanic Field, Veracruz, Mexico

Los Tuxtlas Volcanic Field (LTVF) is an isolated volcanic center located between the Trans-Mexican Volcanic Belt and the Central America Volcanic Arc. Its volcanic products include alkaline and sub-alkaline rocks with variable subduction signatures, some of them considered as high-MgO rocks and some also include ultramafic xenoliths. Most suites show MgO contents ranging from 11 to 16 wt%, reflecting peridotite-derived melts with a primitive character (Mg# ≥ 66) that suffered crystal settling in magma batches during its ascent from the mantle to surface. Parental magma compositions were reconstructed using the significant forsterite compositions (Fo88 to Fo83) to estimate magmatic temperatures that range from 1095 to 1372 °C. Reconstructed parental magmas and low-CaO magmatic olivines allowed us to determine two main groups with water content between 4 and 6% and 8–9%. These magmatic parameters are consistent with those inferred by thermal models, supporting that magmatic products are derived from the melting of a mantle-wedge peridotite at relatively high temperature and wet conditions. Isotopic compositions point to the existence of a high-μ signature (HIMU; μ = 238U/204Pb) in the mantle source similar to that identified at a regional scale from northern Mexico to South America. Low-CaO olivines and their use as a proxy for magmatic H2O content provide evidence of hydration of the mantle wedge by fluids derived from the slab. Hydrous slab-derived contribution induces a higher extent of melting and formation of wet magmas with high LILE/HFSE ratios. Relatively high-NiO olivine compositions record slight metasomatism of the mantle wedge by a small amount of silicic-rich slab components and the contribution of larger proportions of peridotite mantle to the melt over the slightly metasomatized mantle domains. In general, most of the magmatic products record stages of melting and metasomatism triggered and induced by fluids and melts of the slab into an enriched mantle peridotite wedge.

Comparative analysis of exploration potential within the Urumieh Dokhtar Magmatic Arc, Iran, with a detailed example from mineral chemistry of the Marshenan intrusion

The Early Miocene Marshenan intrusion, in the central part of the Urumieh-Dokhtar magmatic arc (UDMA), central Iran, includes granodiorite-granite and diorite; it is a classic example of a CuAu barren intrusive system. Zircon U-Pb dating indicates that the diorite display an age of 20.32 ± 0.36 Ma, coeval with granodiorite rocks (20.5 ± 0.8 Ma). These rocks are composed of feldspar, quartz, amphibole, biotite, titanite, and magnetite. In the granodiorites, the plagioclase composition ranges from oligoclase to bytownite, the amphiboles are magnesio-hornblende and biotites is Mg rich, related to calc-alkaline orogenic suites in the region. Plagioclase phenocrysts exhibits oscillatory zoning and marked changes in the abundance of elements, such as Ba, Sr, and Fe, suggesting magma mixing/mingling may have had a role in generating these parental magmas. The average calculated P–T conditions of the granodiorite and diorite rocks are about 730 °C and 2.1 kbar and 733 °C and 1.7 kbar, respectively, corresponding to near solidus conditions equal to emplacement depths of ~7 to 8 km. Magmatic H2O contents and ƒO2 calculated from crystallized amphiboles indicate that the Marshenan granodiorite had initial magmatic H2O contents ~5 wt% and relatively high ƒO2 (ΔNNO; ave. 1.3) and the diorite had initial magmatic H2O contents ~4.7 wt% and relatively high ƒO2 (ΔNNO; ave. 1.5), both consistent with the presence of phases, such as hornblende, biotite, magnetite, and titanite. In comparison with other intrusions in the UDMA, the Marshenan intrusion formed via the same physico-chemical mechanisms like other barren intrusions, whereas the fertile intrusions exhibit slightly higher temperatures, pressures, ƒO2, and H2O values than the barren intrusions. These compiled data suggest that, in spite of the high magmatic H2O and ƒO2 contents, the Marshenan and other barren intrusions in the UDMA will not produce porphyry Cu mineralization, unlike the giant Kerman deposit, probably due to magma source, magmatic evolution processes, timing of volatile exsolution, pre-existing crustal-scale fractures, coeval volcanism, and extended duration of volatile saturated crystallization to subsolidus conditions.

Crystallization and melt extraction of a garnet-bearing charnockite from South China: Constraints from petrography, geochemistry, mineral thermometry, and rhyolite-MELTS modeling

AbstractSince granitic rocks in high-grade terranes commonly undergo amphibolite-granulite facies meta-morphic overprint, recovering magmatic records from the metamorphic modification remains a major challenge. Here, we report an early Paleozoic, garnet-bearing Yunlu charnockite that outcropped in the Yunkai terrane of the Cathaysia block from South China and underwent amphibole-grade metamorphic overprint in the late Devonian. Field observation, micro-texture, and mineral geochemistry combined with diffusion modeling constrain that the metamorphic overprint with an extremely short duration of ~0.2–0.5 Ma only influences a narrow rim of &amp;lt;100 μm for most minerals. The magmatic information can be retrieved by combining rhyolite-MELTS modeling with mineral thermobarometry using mineral core compositions to quantitatively estimate magmatic pressure, temperature, and melt H2O contents. Rhyolite-MELTS modeling results are evaluated by comparison with experimentally determined phase relations for a peraluminous granite with ~69.83 wt% SiO2 at a pressure of ~500 MPa. The comparison suggests that the modeling reproduces phase relationships of feldspars and quartz within 20–60 °C when the melt H2O contents are below 7.0 wt%, but fails to account properly for all the phases when the melt H2O contents are higher than 7.0 wt%. The modeling results using reconstructed primary magma composition of the Yunlu charnockite combined with the orthopyroxene-garnet-plagioclase-quartz thermobarometry and fluid inclusion analyses suggest that the magma was emplaced at a pressure of ~600 MPa, a temperature of &amp;gt;900 °C, and an initial H2O content of ~4.0 wt% with rare CO2 components. The orthopyroxene-garnet, biotite-garnet, and biotite-orthopyroxene thermometers yield a consistent temperature range of 770–820 ± 60 °C, which is significantly higher than the H2O-saturated solidus temperature of ~630 °C estimated from experimental results and two-feldspar thermometry. These results indicate that the early crystallized minerals (e.g., garnet, orthopyroxene, and some euhedral biotite) of the Yunlu charnockite equilibrate at higher temperatures with crystallinities of ~30–45%, rather than the H2O-saturated solidus conditions. We thus propose a hypothesis of melt extraction at 780–820 °C in a deep-seated, slowly cooling, partially crystalline magma reservoir. The melt extraction physically segregates the early crystallized minerals from residual interstitial melts, which inhibits element diffusion equilibration between these minerals and interstitial melts. Granite thermometry commonly yields a large range of temperature estimations, which may be related to melt extraction events. Our study shows that melt extraction recorded in granites can be identified by combining micro-texture, mineral thermometry and rhyolite-MELTS modeling, which further provides quantitative insights into the fractionation process of silicic magmas.

Copper-Gold Fertility of Arc Volcanic Rocks: A Case Study from the Early Permian Lizzie Creek Volcanic Group, NE Queensland, Australia

Abstract The Early Permian Lizzie Creek Volcanic Group of the northern Bowen Basin, NE Queensland, Australia, has compositions that range from basalt through andesite to rhyolite with geochemical signatures (e.g., enrichment in Cs, Rb, Ba, U, Th, and Pb, depletion in Nb and Ta) that are typical of arc lavas. In the Mount Carlton district the Lizzie Creek Volcanic Group is host to high-sulfidation epithermal Cu-Au-Ag mineralization, whereas farther to the south near Collinsville (~50 km from Mount Carlton) these volcanic sequences are barren of magmatic-related mineralization. Here, we assess whether geochemical indicators of magma fertility (e.g., Sr/Y, La/Yb, V/Sc) can be applied to volcanic rocks through study of coeval volcanic sequences from these two locations. The two volcanic suites share similar petrographic and major element geochemical characteristics, and both have undergone appreciable hydrothermal alteration during, or after, emplacement. Nevertheless, the two suites have distinct differences in alteration-immobile trace element (V, Sc, Zr, Ti, REE, Y) concentrations. The unmineralized suite has relatively low V/Sc and La/Yb, particularly in the high SiO2 rocks, which is related to magma evolution dominated by fractionation of clinopyroxene, plagioclase, and magnetite. By contrast, the mineralized suite has relatively high V/Sc but includes high SiO2 rocks with depleted HREE and Y contents, and hence high La/Yb. These trends are interpreted to reflect magma evolution under high magmatic H2O conditions leading to enhanced amphibole crystallization and suppressed plagioclase and magnetite crystallization. These rocks have somewhat elevated Sr/Y compared to the unmineralized suite, but as Sr is likely affected by hydrothermal mobility, Sr/Y is not considered to be a reliable indicator of magmatic conditions. Our data show that geochemical proxies such as V/Sc and La/Yb that are used to assess Cu-Au fertility of porphyry intrusions can also be applied to cogenetic volcanic sequences, provided elemental trends with fractionation can be assessed for a volcanic suite. These geochemical tools may aid regional-scale exploration for Cu-Au mineralization in convergent margin terranes, especially in areas that have undergone limited exhumation or where epithermal and porphyry mineralization may be buried beneath cogenetic volcanic successions.

Taking the pulse of volcanic eruptions using plagioclase glomerocrysts

Crystallization timescales in subvolcanic systems and the consequences of interaction between ascending magmas and gases remain largely unconstrained, as do links between these processes and monitoring signals at restless volcanoes. We apply diffusion chronometry to radially-oriented plagioclase and associated olivine in a glomerocryst from Tolbachik volcano (Kamchatka, Russia) to elucidate such processes. We show that cm-size glomerocrysts grow in a few days prior to, or during, eruption. Melt inclusions from these glomerocrysts show no compositional evolution during crystallization, implying growth in a melt-rich and dynamic environment. Volatile elements in melt inclusions show significant variability, with increasing CO2 as H2O decreases. This behaviour is inconsistent with normal degassing processes, and more likely reflects CO2-fluxing. On the basis of short residence timescales of glomerocrysts and sharp changes in melt inclusion volatile abundances, we propose that rapid (pre-)eruptive crystallization is controlled by rhythmic fluxing of magmatic H2O and CO2 through the sub-volcanic conduit. This implies that compositional zoning in plagioclase, from resorption textures to oscillatory zoning, record short-term CO2- and H2O-fluxing episodes, consistent with strombolian eruption dynamics. We propose that volcanic glomerocrysts represent the counterpart of vertical igneous layering (or comb layering) in shallow plutons. Magmatic layering and glomerocrysts dominated by radial plagioclase offer novel ways of targeting short-term crystallization and degassing processes in subvolcanic systems.