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Ferro-ferri-holmquistite (IMA2022-020), ideal formula □Li2(Fe32+Fe23+)Si8O22(OH)2, was found in albitized granite from the Iwagi islet, Ehime, Japan. Ferro-ferri-holmquistite is a CFe2+Fe3+ analogue of holmquistite and belongs to the lithium-subgroup amphiboles. It commonly occurs as acicular aggregate and/or isolated crystals in quartz, albite and K-feldspar and is blue with a bluish-grey streak and a vitreous luster. It has a Mohs hardness of 5 1/2. Its cleavage is perfect on {210}. Measured and calculated densities are Dmeas.=3.2 g cm−3 and Dcalc.=3.317 g cm−3, respectively. Ferro-ferri-holmquistite is optically biaxial (-), with α=1.685, β=1.713 and γ=1.727, and is pleochroic, with X= pale blue ∼ pale yellowish blue, Y= deep blue ∼ brownish blue and Z= deep blue ∼ deep bluish violet; X>Z>Y. The magnetic susceptibility is similar to the associated biotite. Ferro-ferri-holmquistite is insoluble in HCl, HNO3 and H2SO4. The empirical formula calculated on the basis of Σ(C+T) = 13 on the results obtained by electron microprobe analyzer (EPMA), and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is A(K0.01Na0.06)Σ0.07B(Li1.95Na0.04Ca0.01)Σ2.00C(Fe2.822+Fe1.393+Al0.51Mg0.22Mn0.052+Ti0.01)Σ5.00T(Si7.98Al0.02)Σ8.00O22(OH)1.94F0.06. Structure refinement converged to R1= 4.22 %. The space group is orthorhombic Pnma, and the unit-cell parameters are a= 18.5437(2) Å, b= 17.9222(1) Å, c= 5.3123(1) Å and V= 1765.51(1) Å3. Based on the refined site occupancies, the structural formula can be written as ANa0.062M4(Li1.952Na0.048)Σ2.000M1(Fe1.7702+Mg0.230)Σ2.000M2(Fe1.4463+Fe0.1022+Al0.452)Σ2.000M3(Fe0.8912+Mg0.109)Σ1.000TSi8O22(OH)2 (Z= 4). Three OH-stretching IR bands, centered at 3614, 3631 and 3644 cm−1, are assigned to the local configuration M1M1M3= FeFeFe, MgFeFe (including FeMgFe and FeFeMg) and MgMgFe (including MgFeMg and FeMgMg), respectively, based on the IR studies of the orthorhombic Pnma amphiboles.

Oomurodashi is a newly discovered active, shallow, silicic submarine volcano only 60 km from Tokyo Bay. We reveal its past eruptive activity, and potential future hazards, by examining volatile contents of its subaerial and submarine pumice and lava deposits. These novel data for shallow silicic submarine eruption products were obtained using new Fourier transform infrared spectroscopy (FTIR) analytical techniques for vesicular and hydrated glasses. All matrix glasses have H2O species data consistent with low-temperature hydration following eruption. We therefore used unaltered OH data to investigate past eruptions. Geochemistry confirmed that Oomurodashi was the source of a ca. 13.5 ka subaerial tephra deposit on nearby inhabited islands. We infer from pumice OH contents and tephra characteristics that this deposit was formed by explosive submarine phreatomagmatic activity that produced the shallow crater in the submarine edifice. OH contents of in-place submarine lavas are lower than expected for their current water depth; comparison with past sea level implies that these lavas erupted at ca. 7–10 ka and ca. 14 ka when sea level was lower. Oomurodashi has also erupted submarine pumice with different densities, quench depths, and dispersal histories; however, any pumice sufficiently buoyant to produce floating pumice rafts will have been lost from the local geological record, so pumice rafts remain a potential future hazard.

In this study, the Sr isotope ratios (IRs; 87Sr/86Sr) of ferromanganese (Fe–Mn) crusts are analyzed through laser ablation inductively coupled plasma multiple-collector mass spectrometry. A sample collected from off Minamitorishima Island showed uniform Sr IRs (0.70906–0.70927) similar to that of present-day seawater with more than 36 mm thickness. Meanwhile, a detritus-rich sample collected from off northeast (NE) Japan showed a wide variation in Sr IRs (0.707761–0.709963). The Sr IR variation in the Fe–Mn crust from off NE Japan suggests detrital influx contributions from both the NE Japan arc (0.718). Detrital flux from the NE Japan arc increases from the bottom to middle layers, possibly due to the uplift of the Ou backbone range that occurred after ~2 Ma. The increased influx of the aeolian dust in the outer layer is attributable to global cooling in the Quaternary that increased the loess dust transportation from China to the western North Pacific Ocean. Meanwhile, the influence of the detrital influx on the sample from off Minamitorishima Island appeared to be negligible. The Sr IR analysis with high spatial resolution proposed in this study possibly improves the burial history of Fe–Mn nodules.

Better understanding metallogenesis in oceanic crust depends on costly sea-floor drilling projects in areas where metal-bearing deposits, such as sea-floor massive sulfide deposits, are currently forming. In 2018, International Ocean Discovery Program (IODP) Expedition 376 recovered drill cores from an active hydrothermal field at Brothers volcano, in the Kermadec arc. These provide insight into the formation of mineral deposits along arcs, the structure and permeability of hydrothermal sites, and the relationship between the discharge of magmatic fluids and the deep biosphere. We report whole-rock major and trace element compositions and the Re-Os isotope geochemistry of hydrothermally altered volcanic rocks in a core from Hole U1530A, extending 453 m beneath the sea floor, and unaltered volcanic rocks in cores from four other drilling sites, and interpret these data to better understand subseafloor mixing of hydrothermal fluids and ambient seawater. The core exhibits more radiogenic 187Os/188Os values than typical basal values in four intervals. We propose two causal mechanisms of these radiogenic values: (1) mixing between seawater and hydrothermal fluid, associated with abundant deposition of sulfide or sulfate minerals; and (2) ingress of seawater with radiogenic 187Os/188Os values, associated with abundant chlorite and high porosity. Extreme Os enrichments up to 61.5 ppb are interpreted as the result of mobilization of Os as OsO4 or OsF6 and transport by volcanic gas, which also affected the Re-Os geochemistry of the rocks from the other Expedition 376 holes. Mobilization and transport of Os by volcanic gas may be an appreciable factor in the influx of unradiogenic Os into the ocean.

The Re–Os isotopic system is a powerful tool for both geochronology and tracing various geochemical processes. Because the Os isotopic ratio (187Os/188Os) distinctly differs between modern seawater (∼1.06) and hydrothermal fluid (∼0.13), the Re–Os isotopic system is potentially a sensitive tracer of subseafloor fluid flow and the release or uptake of hydrogenous/magmatic Re and Os. The effect of alteration on the Re–Os budget in oceanic crust has been examined for mid-ocean ridge basalt (MORB) and lower oceanic crustal gabbro. In contrast, applications of the Re–Os system in intraoceanic arc settings are limited mainly to fresh igneous rocks; the role of hydrothermal alteration has not yet been examined.Here, we provide a depth profile of Re–Os geochemistry at Site U1527, located on the NW caldera rim of the Brothers volcano hydrothermal field in the Kermadec arc, which was drilled during International Ocean Discovery Program (IODP) Expedition 376 in 2018. Volcaniclastic rocks from Hole U1527C that had experienced various degrees of high- and low-temperature hydrothermal alteration were analyzed for bulk chemical composition as well as Re–Os concentrations and isotopes. The concentration of Re varied from 0.172 to 18.7 ppb, and that of Os ranges from 9.7 to 147.1 ppt. Hydrothermal alteration usually resulted in the Re uptake by rocks, but a part of Re was released into the ocean by later oxidative weathering. Compared with Re, Os mobility resulting from hydrothermal alteration was limited. Before alteration, our samples likely had homogenous 187Os/188Os of between 0.13 and 0.14, whereas alteration added hydrogenous Os to some drill core sections in two different ways. Elevated 187Os/188Os with Ba enrichment and abundant pyrite occurrence suggests Os precipitation induced by subseafloor mixing of seawater and high-temperature hydrothermal fluid. The highest Re and Os concentrations at Hole U1527C, found in the same interval, were associated with high concentrations of Bi, Sb, and Tl. In contrast, elevated 187Os/188Os without Ba and Os enrichment can be explained by adsorption of seawater-derived radiogenic Os onto Fe hydroxide during seawater ingress into volcaniclastic rocks with a high matrix volume.Intense Re enrichment at Hole U1527 relative to the high-temperature alteration zone in altered MORB may be related to abundant pyrite precipitation and high Re content in primary arc magmas. We propose that degassed Re from shallow intraoceanic arc magmas may be sequestered by subseafloor high-temperature alteration. Part of the stored Re might also be released into the ocean by later oxidative seawater circulation and seafloor weathering, raising a question about the role of alteration zones in the Re cycle in subduction zones. This study is one of the first attempts to apply the Re–Os system to altered rocks in arc settings, and future research should provide more information about the fate of Re in intraoceanic arcs and the detailed role of hydrothermal alteration in the Re cycle on the Earth.

The relationship between plutonic and volcanic components of magmatic plumbing systems continues to be a question of intense debate. The Oki-Dōzen Islands, Sea of Japan, preserve outcrops of temporally associated plutonic, hypabyssal, and volcanic rocks. Post-intrusion uplift juxtaposed Miocene syenites in inferred faulted contact with volcanic trachytes that are cut by rhyolite hypabyssal dikes. This provides a window deep into the timing and origins of magma storage architecture and dynamics. Zircon is ubiquitous in all samples; our aim is to determine what its age and composition can reveal about the plutonic-volcanic connection. Here we show magma source characteristics are recorded in zircon Hf isotopes; source composition and assimilation of heterogeneous hydrothermally altered crust in zircon O isotopes; and extensive fractional crystallization in zircon trace elements. Combined with new UTh-Pb SHRIMP zircon ages, 6.4–5.7 Ma, compositional data show pluton formation was by protracted amalgamation of discrete magma pulses. The rhyolite dike preserves an evolved fraction segregated from these discrete magmas. Synchronous with plutonism was a volcanic eruption of trachyte magma derived from the same source, which may have stalled at a relatively shallow depth prior to eruption. Stalling occurred at least above the amphibole stability zone because amphibole-compatible Sc and Ti were not depleted in the trachyte melt resulting in elevated values of these in volcanic compared to plutonic zircon. Identifying smaller episodic magma pulses in a larger magmatic complex places constraints on potential magma fluxes and eruptible volumes. High-flux, large volume, plume-related ocean island magmatic systems may have extensive vertically distributed multi-stage magmatic reservoirs and subduction-related systems transcrustal magma reservoirs. By contrast, Oki-Dōzen was a low-flux system with incremental pluton growth and small- to moderate-scale eruptions.

The architecture, formation, and modification of oceanic plates are fundamental to our understanding of key geologic processes of the Earth. Geophysical surveys were conducted around a site near the Hawaiian Islands (northeastern Hawaiian North Arch region; Hawaiian North Arch hereafter), which is one of three potential sites for an International Ocean Discovery Program mantle drilling proposal for the Pacific plate that was submitted in 2012. The Hawaiian North Arch site is located in 78–81 Ma Cretaceous crust, which had an estimated full spreading rate of 7–8 cm yr−1. This site fills a major gap in our understanding of oceanic crust. Previously drilling has been skewed to young or older crust ( or >110 Ma) and slow-spread crust. P-wave velocity structure in the uppermost mantle of the Hawaiian North Arch shows a strong azimuthal anisotropy, whereas Moho reflections below the basement are variable: strong and continuous, weak, diffuse, or unclear. We assume that the strength of the Moho reflection is related to the aging of the oceanic plate. The Hawaiian volcanic chain (200 km to the southwest of the proposed drill site) and the nearby North Arch magmatism on the proposed Hawaiian North Arch sites might also have affected recognition of the Moho via deformation and/or magma intrusion into the lower crust of the uppermost mantle. This workshop report describes scientific targets for 2 km deep-ocean drilling in the Hawaiian North Arch region in order to provide information about the lower crust from unrecovered age and spreading rate gaps from previous ocean drillings. Other scientific objectives to be achieved by drilling cores before reaching the target depth of the project are also described in this report.

The lithophile elements and isotopic compositions of oceanic basalts suggest they derive from different mantle components. We present new analytical results of un-degassed deep-marine basaltic glasses from various regions, and we find strong linear correlations of R2 ≥ 0.997 between H2O and F as well as H2O and Ce, for which we propose mantle trends. The mantle trends represent global variations of mantle components, ranging from a depleted dry peridotite of mid-ocean ridge basalt (MORB) (DMM, depleted MORB source mantle: H2O = 100 ppm; H2O/Ce = 200; H2O/F = 10) to a hydrous peridotite of Hawaiian ocean island basalt (OIB) of deep mantle origin (FOZO, focal zone: H2O = 750 ppm; H2O/Ce = 200; H2O/F = 18.5). Accordingly, we defined the correlation as a volatile DMM–FOZO trend. Based on our findings, we report novel H2O–F–Ce systematics to discriminate the degree of water depletion in the source mantle and the rehydration of the mantle with recycled surface water through oceanic plate subduction. Using this method, most OIBs are distinguished clearly from the DMM–FOZO trend, and we find that the water in their sources originates from recycled water derived from the hydrated oceanic crust and sediment after various degrees of dehydration (75–95%) in subduction zones.

Although slab-derived fluid significantly affects melt generation and dynamics within subduction zones, its amount and distribution are not sufficiently constrained at present. Herein, we use isotopic systematics of arc volcanic rocks, subducting materials, and intrinsic mantle components prior to metasomatism, to quantify the contribution of the slab-derived fluid that metasomatizes the overlying mantle wedge beneath the entire area of Japan arcs. Simultaneous application of several multivariate statistical analyses (clustering analysis and principal/independent component analyses) to the isotopic data set allows Japan arcs to be broadly divided into eastern and western parts at the first order. Moreover, a clear higher-order inter-arc segmentation is observed, together with some intra-arc variations that possibly correspond to the heterogeneity of incoming plates. Inter-arc segmentation is shown to be primarily controlled by the geometrical parameters of the slab and the arc (e.g., subduction of a single plate or double plates beneath either oceanic or continental crust), which results in differences between mantle wedge and slab thermal conditions. Accordingly, the Kuril and Izu arcs, which have thin arc crusts (~20 km), exhibit the lowest extent of slab-derived fluid addition (0.1 wt%) to the mantle wedge, while the NE Japan arc, with a thicker arc crust (up to 36 km), features a higher value of 0.2 wt%, although the slab thermal parameters for these three arcs are essentially the same. The Central Japan arc shows the highest extent of slab-derived fluid addition (>1.0 wt%) because of the overlapping subduction of Pacific and Philippine Sea slabs, while the SW Japan and Ryukyu arcs feature moderate values of ~0.5 wt%. Moreover, a clear exotic plume zone and spots are observed in SW Japan and the Japan Sea. In addition to the variability of slab-derived fluid composition, the intrinsic mantle composition (before slab-derived fluid–induced metasomatism) shows a clear along-arc variation that is possibly caused by a large-scale mantle flow from the continental side. Thus, slab-derived fluid addition and mantle composition variability equally contribute to inter-arc segmentation, which highlights the importance of both local and regional thermal flow structures of slab-mantle systems.

The Pb isotope compositions of galena in hydrothermal deposits obtained by drillings from two hydrothermal fields in the middle Okinawa Trough were studied. One of the study fields was the Iheya North field located on a volcanic complex and the other was the Izena field located in the sediment-filled caldera structure. LA-MC-ICP-MS was applied to directly measure Pb isotope compositions in individual galena grains which highlighted variations not only in regional scale, but also in microscopic scale so that changes of Pb isotope compositions within a galena grain can be tracked. Homogeneous Pb isotope compositions were found within the same hydrothermal site, irrespective of the mineral assemblage, texture and sampling depth beneath the seafloor. In contrast, the isotope compositions varied significantly between the two hydrothermal fields. The Pb isotope composition from the Iheya North field was isotopically close to the volcanic rocks of the Okinawa Trough, whereas that from the Izena field was more radiogenic with values intermediate between sediments and volcanic rocks of the Okinawa Trough. Within the Iheya North field, intra-field variation of Pb isotope compositions was recognized between two active sites 2.5 km apart from each other. The intra-field variation was recognized also in the Izena field. The sub-seafloor massive sulfide layer has a more sediment-like Pb isotope composition, compared to the inactive sulfide mound. These results illustrate that the Pb-mineralizing hydrothermal fluids originate from their local host rocks with/without sediment and that the isotope compositions of the galena grains reflect their metal sources; either the volcanic rocks and/or the sediments via water-rock interactions.

Serpentinites and serpentinized mantle peridotites with various tectonic origins occur in the Franciscan Complex of the Northern California Cordillera, USA. Boron isotopes of serpentinites differentiate with fluid-mediated processes, and have great potential for key geologic markers in convergent margins. To understand boron isotope behavior within the Franciscan subduction zone system, we apply a newly developed ablation volume correction (AVC) method for in-situ isotope/elemental analyses using a laser-ablation multiple collector inductively-coupled-plasma mass spectrometry (LA-MC-ICPMS) on seventeen different Franciscan serpentinites (sensu lato) collected from eight separate areas. Boron abundances and isotope compositions of the studied serpentinites show large variations B = 1.6–239 μg·g−1, δ11B = −12.0 to +24.4‰, which allow to discriminate the serpentinites into two groups: (1) a lighter δ11B of −12.0 to +8.8‰ with a lesser B ~2 GPa. Preferential partitioning of 11B into fluids released from the subducted slab at shallow leaves lighter δ11B in the slab resulting in lighter δ11B in the deep slab fluids. In contrast, the blueschist-absent serpentinites with heavier δ11B may have formed at a shallow environment where shallow slab or hydrothermal fluids with heavier 11B were present. Lesser versus greater amounts of B in the deep versus shallow serpentinites are also consistent with the dehydration profile of B from a slab. Our results show the versatility of boron isotopes and composition for identification of the origin of serpentinite in Pacific-type orogenic belts.

Fully characterising the exchange of volatile elements between the Earth’s interior and surface layers has been a longstanding challenge. Volatiles scavenged from seawater by hydrothermally altered oceanic crust have been transferred to the upper mantle during subduction of the oceanic crust, but whether these volatiles are carried deeper into the lower mantle is poorly understood. Here we present evidence of the deep-mantle Cl cycle recorded in melt inclusions in olivine crystals in ocean island basalts sourced from the lower mantle. We show that Cl-rich melt inclusions are associated with radiogenic Pb isotopes, indicating ancient subducted oceanic crust in basalt sources, together with lithophile elements characteristic of melts from a carbonated source. These signatures collectively indicate that seawater-altered and carbonated oceanic crust conveyed surface Cl downward to the lower mantle, forming a Cl-rich reservoir that accounts for 13–26% or an even greater proportion of the total Cl in the mantle., Volatile exchange between the Earth’s interior and surface layers is one of the central issues in mantle geochemistry. Here the authors present evidence that chlorine is transferred from the surface to the deep mantle by subducted oceanic crust, forming a chlorine-rich mantle reservoir.

nternational Ocean Discovery Program Expedition 369 drilled four sites on the southwestern Australian continental margin, in the deep water Mentelle Basin (MB) and on the neighboring Naturaliste Plateau (NP). The drillsites are located on continental crust that continued rifting after seafloor spreading began further north on the Perth Abyssal Plain (PAP) between magnetochrons M11r and M11n (133–132 Ma), ending when spreading began west of the NP between chrons M5n and M3n (126–124 Ma). Drilling recovered the first in situ samples of basalt flows overlying the breakup unconformity on the NP, establishing a magnetostratigraphically constrained eruption age of >131–133 Ma, and confirming a minimal late Valanginian age for the breakup unconformity (coeval with the onset of PAP seafloor spreading). Petrogenetic modeling indicates the basalts were generated by 25% melting at 1.5 GPa and a potential temperature of 1380°C–1410°C, consistent with proximity of the Kerguelen plume during breakup. Benthic foraminiferal fossils indicate that the NP remained at upper bathyal or shallower depths during the last 6 Myr of rifting and for 3–5 Myr after breakup between India and Australia. The limited subsidence is attributed to heat from the nearby Kerguelen plume and PAP spreading ridge. The margin subsided to middle bathyal depths by Albian time and to lower bathyal (NP) or greater (MB) depths by late Paleogene time. Periods of rapid sedimentation accompanied a westward jump of the PAP spreading ridge (108 Ma), rifting on the southern margin (100–84 Ma), and opening of the southern seaway between Australia and Antarctica (60–47 Ma).

Volcanoes in the East Asian/Pacific region have been the source of some of the largest magnitude eruptions during the Late Quaternary, and accurately evaluating their eruptive histories is essential for hazard assessments. To overcome difficulties in resolving and precisely dating eruptions in the near‐source realm, the high‐resolution (varved) sediments of Lake Suigetsu (central Honshu, Japan) were examined for the presence of non‐visible (cryptotephra) layers from 50 ka up until the 30 ka Aira‐Tanzawa (AT) caldera‐forming event of Aira volcano. Cryptotephra layers are four times more frequently preserved than visible markers in the Suigetsu sediments, meaning that this archive provides a unique and unprecedented record of eruptions that were dispersed over the densely populated regions of central Honshu. Major and trace element volcanic glass chemistry is used to fingerprint the ash layers and pinpoint their volcanic origin. Tephras are found throughout the investigated sediments, but the highest abundance of ash fall events are recorded between 39 and 30 ka, capturing a period of intense volcanism at calderas on Kyushu Island (Japan). The augmented Suigetsu tephrostratigraphy records at least seven eruptions from Aso caldera (southern Kyushu) that post‐date the widespread ACP‐4 Plinian eruption (ca. 50 ka) and four explosive events from Aira (central Kyushu) that occurred leading up to the catastrophic caldera‐forming AT eruption (ca. 30 ka).

The deep-sea clay that covers wide areas of the pelagic ocean bottom provides key information about open-ocean environments but lacks age-diagnostic calcareous or siliceous microfossils. The marine osmium isotope record has varied in response to environmental changes and can therefore be a useful stratigraphic marker. In this study, we used osmium isotope ratios to determine the depositional ages of pelagic clays extraordinarily rich in fish debris. Much fish debris was deposited in the western North and central South Pacific sites roughly 34.4 million years ago, concurrent with a late Eocene event, a temporal expansion of Antarctic ice preceding the Eocene-Oligocene climate transition. The enhanced northward flow of bottom water formed around Antarctica probably caused upwelling of deep-ocean nutrients at topographic highs and stimulated biological productivity that resulted in the proliferation of fish in pelagic realms. The abundant fish debris is now a highly concentrated source of industrially critical rare-earth elements.

How new subduction zones form is an ongoing scientific question with key implications for our understanding of how this process influences the behavior of the overriding plate. Here we focus on the effects of a Late Cretaceous subduction-initiation (SI) event in Iran and show how SI caused enough extension to open a back-arc basin in NE Iran. The Late Cretaceous Torbat-e-Heydarieh ophiolite (THO) is well exposed as part of the Sabzevar-Torbat-e-Heydarieh ophiolite belt. It is dominated by mantle peridotite, with a thin crustal sequence. The THO mantle sequence consists of harzburgite, clinopyroxene-harzburgite, plagioclase lherzolite, impregnated lherzolite, and dunite. Spinel in THO mantle peridotites show variable Cr# (10–63), similar to both abyssal and fore-arc peridotites. The igneous rocks (gabbros and dikes intruding mantle peridotite, pillowed and massive lavas, amphibole gabbros, plagiogranites and associated diorites, and diabase dikes) display rare earth element patterns similar to MORB, arc tholeiite and back-arc basin basalt. Zircons from six samples, including plagiogranites and dikes within mantle peridotite, yield U-Pb ages of ca. 99–92 Ma, indicating that the THO formed during the Late Cretaceous and was magmatically active for ∼7 m.y. THO igneous rocks have variable εNd(t) of +5.7 to +8.2 and εHf(t) ranging from +14.9 to +21.5; zircons have εHf(t) of +8.1 to +18.5. These isotopic compositions indicate that the THO rocks were derived from an isotopically depleted mantle source similar to that of the Indian Ocean, which was slightly affected by the recycling of subducted sediments. We conclude that the THO and other Sabzevar-Torbat-e-Heydarieh ophiolites formed in a back-arc basin well to the north of the Late Cretaceous fore-arc, now represented by the Zagros ophiolites, testifying that a broad region of Iran was affected by upper-plate extension accompanying Late Cretaceous subduction initiation.

Mafic magmatism of the rifting Taupo Volcanic Zone (TVZ) of the North Island, New Zealand, is volumetrically minor, but is thought to tap the material that provides the heat source for voluminous rhyolite production through partial melting of the crust, which ultimately results in very large volume explosive eruptions. We have studied the major and trace element chemistry of 14 mafic samples from across the entire TVZ, and the U isotopic composition of whole-rocks, groundmasses and separates of mafic mineral phases from a selection of nine samples (with the remaining five too sparsely phyric for mineral separation). Some minerals yield significant 234U enrichments despite groundmass and whole-rock close to 238U–234U secular equilibrium, pointing to uptake of variably hydrothermally altered antecrystic minerals prior to the eruption of originally sparsely phyric to aphyric mafic magmas. However, incompatible trace element patterns indicate that there are three chemically distinct groups of samples, and that samples may be used to derive primary melt compositions. We employ the latest version of the Arc Basalt Simulator (ABS5) to forward model these compositions, deriving mantle source parameters including mantle fertility, slab liquid flux, mantle volatile content, degree of melting, and P–T conditions of melt segregation. We show that mafic rocks erupted in areas of old, now inactive calderas constitute low-degree, deep melts, whereas those in areas of active caldera-volcanism are high-degree partial melts segregated from a less depleted source at an intermediate depth. Finally, high-Mg basaltic andesites erupted in the SW and NE of the TVZ point to a fertile, shallow mantle source. Our data are consistent with a petrogenetic model in which mantle melting is dominated by decompression, rather than fluid fluxing, and progresses from shallow to deeper levels with time. Melt volumes initially increase to a tipping point, at which large-scale crustal melting and caldera volcanism become prominent, and then decrease owing to progressive depletion of the mantle wedge by melting, resulting in the dearth of heat provided and eventual cessation of very large volume rhyolitic volcanism. ABS5 modelling therefore supports the notion of a direct link between the chemistry of recently erupted mafic magmas and the long-term activity and evolution of rhyolitic volcanism in the TVZ.

The International Ocean Discovery Program Expedition 350 drilled between two Izu rear‐arc seamount chains at Site U1437 and recovered the first complete succession of rear‐arc rocks. The drilling reached 1806.5 m below seafloor. In situ hyaloclastites, which had erupted before the rear‐arc seamounts came into existence at this site, were recovered in the deepest part of the hole (∼15-16 Ma). Here it is found that the composition of the oldest rocks recovered does not have rear‐arc seamount chain geochemical signatures, but instead shows affinities with volcanic front or some of the extensional zone basalts between the present volcanic front and the rear‐arc seamount chains. It is suggested that following the opening of the Shikoku back‐arc Basin, Site U1437 was a volcanic front or a rifting zone just behind the volcanic front, and was followed at ∼ 9 Ma by the start of rear‐arc seamount chains volcanism. This geochemical change records variations in the subduction components with time, which might have followed eastward moving of hot fingers in the mantle wedge and deepening of the subducting slab below Site U1437 after the cessation of Shikoku back‐arc Basin opening.

In subduction zones, fluids rise from the slab to the mantle, causing metasomatism and flux melting of the mantle to produce arc magmas. The transfer of material from slab to mantle and, in turn, to arc crust is an important control on the long-term chemical evolution of the mantle and continental crust. In this study, we investigate the transport of K in subduction zones by exploring the systematics of K stable-isotope variations in lavas of the Izu arc. We find that the Izu lavas have isotopically heavy K relative to estimates for midocean ridge basalt (MORB)-source upper mantle. Moreover, the δ 41 K values of the lavas are clearly heavier than those of subducting sediments and are probably heavier than subducting altered ocean crust. An across-arc decrease in δ 41 K values is apparent. Arc-front lavas are heavier than the mantle by about 0.22‰ (median), whereas rear-arc lavas are heavier by only about 0.08‰ (median). The heavy K-isotope compositions of the arc lavas may arise from isotopic fractionation during slab dehydration, where light K is preferentially retained in phases such as phengite in the slab. The across-arc decrease in δ 41 K values may be due to progressive breakdown of these phases, and to associated depletion of the slab in heavy K. Variations in the relative contributions of different source materials—igneous ocean crust, sediment, and mantle peridotite—may also play a role. In particular, we explore a possibility, motivated by radiogenic-isotope studies, that the slab signal in K isotopes may be attenuated in the rear arc as a result of extensive fluid-mantle interaction. If K isotopes do track slab dehydration, then K isotopes provide insight into the transfer of K and similarly mobile elements out of the slab and into the upper mantle and arc crust. Lastly, we observe extreme isotopic variations in some of the lavas, which we interpret to result from crustal-level or Earth-surface processes that affect only a subset of the lavas.

Lawsonite is a hydrous Ca-Al silicate mineral which is broadly stable under modern style subduction conditions. In order to understand the elemental fractionation and the sources of subducted materials, lawsonite crystals in lawsonite-eclogite facies basaltic and sedimentary rocks from South Motagua Melange of Guatemala were investigated using LA-ICPMS and LA-MC-ICPMS. Mass balance calculation based on in-situ trace element and modal compositions in an eclogite with a low-variance mineral assemblage confirmed that lawsonite hosts most of the light rare earth element (LREE), Sr, Pb, Th and U in the bulk. In-situ Sr-Pb isotope analyses of eclogite-facies lawsonite crystals revealed isotopic variations reflecting their protoliths. Isotopic zoning was also detected in some crystals. Lawsonite crystals in a phengite-rich eclogite have relatively low 87Sr/86Sr = 0.70335–0.70355 with variations in 207Pb/206Pb = 0.8401–0.8512 and 208Pb/206Pb = 2.0757–2.0911. Lawsonite crystals from another eclogite are remarkably zoned. The cores have 87Sr/86Sr = 0.70558–0.70601 and the rims have relatively elevated 87Sr/86Sr = 0.70636–0.70662, exhibiting MORB-like 207Pb/206Pb = 0.843–0.844 at the cores and more enriched 207Pb/206Pb = 0.839–0.841 at the rims. The radiogenic Sr isotope composition would have been derived from seafloor alteration before subduction. In fact, lawsonite crystals in a metachert have higher 87Sr/86Sr = 0.70697–0.70757 with 208Pb/206Pb = ∼2.07. However, the isotopically zoned metabasaltic lawsonite crystals with MORB-like core compositions suggest that metasomatism by an external fluid from sediment protolith occurred during overgrowth of their rims. Our study indicates that lawsonite crystals record both the isotopic compositions of the protoliths and metasomatic fluids from different protoliths. The in-situ Sr-Pb isotope analysis has a potential to reveal records of the complicated metamorphic processes.

Lithium behavior in slab-derived fluids has been constrained using isotope geochemistry of subduction-related metamorphic and volcanic rocks. We investigated a veined jadeitite from the New Idria serpentinite diapir, California, which is regarded as direct precipitates from slab-derived fluids and therefore records slab-derived fluid signatures. We applied an in-situ measurement of Li concentration and δ7Li composition using an ablation volume correction (AVC) LA-MC-ICPMS. This method enabled determinations of millimeter- to submillimeter-scale isotopic variations in the jadeitite veins and host rocks (jadeite matrix), allowing immediate observations on fluid–rock interactions. Multiple-stage jadeite veins and their host rocks showed a wide range of Li concentrations from 4 to 68 μg/g and δ7Li compositions from −11.7 to +6.7‰, with a curvilinear correlation between them. Individual veins formed in different generations also showed wide isotopic variations as large as ~14‰. Those isotopic and compositional variations within/among veins can be readily explained by variable mixing between the matrix and infiltrated fluids. The initial infiltrated fluid compositions were estimated to be between +6.7 and +12.3‰, based on the δ7Li values of jadeites in the veins that were supposed to be unmodified by interactions with their matrices. The estimated fluid composition is mostly consistent with those inferred for slab-derived fluids proposed by previous studies. The New Idria jadeitite provides a line of evidence for the presence of high δ7Li fluids in the mantle wedge at the forearc depth. Our study also demonstrates that the high δ7Li composition of slab-derived fluids can be easily modified by interactions with surrounding rocks along their pathways.

Santorini volcano sits ~145 km above the Aegean Wadati-Benioff zone, where the African plate subducts northward beneath Eurasia. There are only a few localities in the whole Aegean where basaltic lavas primitive enough to constrain mantle processes beneath the Aegean arc can be found; in this work we analyzed one such locality, a basalt lava from the southern part of Santorini. We apply a suite of petrological tools (PRIMACALC2 and ABS5) in sequence to estimate magma chamber conditions, primary magma composition, mantle melting conditions, and slab dehydration conditions. Back-calculation modeling based on major-element chemistry yields shallow magma chamber conditions of P = 0.02 GPa, fO 2 = QFM + 2, and ~1 wt% H 2 O in the primary magma. The estimated major element composition of this primary magma then leads to estimated mantle melting conditions of 2.1 GPa, 1353 °C, and F = 8%; whereas a more precise estimate derived from trace element modeling implies 1.7 GPa, 1323 °C, and F = 18%. Furthermore, the trace element model implies a slab flux derived from 4.6 GPa (~150 km slab depth). The estimated slab depth, magma segregation conditions, and magma chamber depth are all consistent with seismic observations, supporting slab dehydration in the seismically imaged steep slab interval and flux melting in a relatively hot mantle wedge.

The extreme Sr, Nd, Hf, and Pb isotopic compositions found in Pitcairn Island basalts have been labeled enriched mantle 1 (EM1), characterizing them as one of the isotopic mantle end members. The EM1 origin has been vigorously debated for over 25 years, with interpretations ranging from delaminated subcontinental lithosphere, to recycled lower continental crust, to recycled oceanic crust carrying ancient pelagic sediments, all of which may potentially generate the requisite radiogenic isotopic composition. Here we find that δ(26)Mg ratios in Pitcairn EM1 basalts are significantly lower than in normal mantle and are the lowest values so far recorded in oceanic basalts. A global survey of Mg isotopic compositions of potentially recycled components shows that marine carbonates constitute the most common and typical reservoir invariably characterized by extremely low δ(26)Mg values. We therefore infer that the subnormal δ(26)Mg of the Pitcairn EM1 component originates from subducted marine carbonates. This, combined with previously published evidence showing exceptionally unradiogenic Pb as well as sulfur isotopes affected by mass-independent fractionation, suggests that the Pitcairn EM1 component is most likely derived from late Archean subducted carbonate-bearing sediments. However, the low Ca/Al ratios of Pitcairn lavas are inconsistent with experimental evidence showing high Ca/Al ratios in melts derived from carbonate-bearing mantle sources. We suggest that carbonate–silicate reactions in the late Archean subducted sediments exhausted the carbonates, but the isotopically light magnesium of the carbonate was incorporated in the silicates, which then entered the lower mantle and ultimately became the Pitcairn plume source.

Sr isotope analysis of plutonic rocks is an important method for deriving the provenance and age of ancient magmatic episodes, and the petrogenetic processes operating during intrusive activity. We determined the 87 Sr/ 86 Sr isotopic compositions of fresh and variably altered feldspars from the 1.14 Ga gabbroic Great Abitibi Dyke, Ontario, Canada, through the use of Laser Ablation Inductively-Coupled Plasma Mass Spectrometry (LA-ICPMS). The data show an alteration trend between fresh, low-Rb plagioclase with 87 Sr/ 86 Sr ratios of 0.7045 and high-Rb alkali feldspar with 87 Sr/ 86 Sr ratios of 0.7059, which may be used to constrain the 87 Sr/ 86 Sr ratio of the mantle source. This trend is incompatible with simple mixing and instead has age significance. As post-intrusive alteration through hydrothermal circulation starts immediately following emplacement, LA-ICPMS analysis allows rapid estimation of initial 87 Sr/ 86 Sr ratios and intrusive age, suitable for sample screening and selection for more precise dating. For the Great Abitibi Dyke, the Rb-Sr age estimate of emplacement of 1.10 ± 0.23 Ga (2σ) is concordant with the precise U-Pb emplacement age of the dyke (1140.6 ± 2.0 Ma). The most altered high-Rb alkali feldspars return younger ages, suggesting that post-intrusive alteration lasted several hundred million years. This study highlights the need for microanalysis to differentiate between alteration and magmatic processes on basis of Sr isotopic signatures, and outlines a rapid method to determine initial 87 Sr/ 86 Sr ratios and to estimate Rb-Sr ages of plutonic rocks in terranes with long histories of multiple intrusive magmatic episodes.