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Volcanoes formed above the Hawaiian mantle plume exhibit a striking contrast in the geochemical characteristics of the lavas erupted at the northern Kea compared with the southern Loa volcanoes. Isotopic data show that these trends have persisted for more than 5 million years and may mirror compositional heterogeneities in the deep mantle. Linear chains of volcanic ocean islands are one of the most distinctive features on our planet. The longest, the Hawaiian–Emperor Chain, has been active for more than 80 million years, and is thought to have formed as the Pacific Plate moved across the Hawaiian mantle plume, the hottest and most productive of Earth's plumes. Volcanoes fed by the plume today form two adjacent trends, including Mauna Kea and Mauna Loa, that exhibit strikingly different geochemical characteristics. An extensive data set of isotopic analyses shows that lavas with these distinct characteristics have erupted in parallel along the Kea and Loa trends for at least 5 million years. Seismological data suggest that the Hawaiian mantle plume, when projected into the deep mantle, overlies the boundary between typical Pacific lower mantle and a sharply defined layer of apparently different material. This layer exhibits low seismic shear velocities and occurs on the Loa side of the plume. We conclude that the geochemical differences between the Kea and Loa trends reflect preferential sampling of these two distinct sources of deep mantle material. Similar indications of preferential sampling at the limit of a large anomalous low-velocity zone are found in Kerguelen and Tristan da Cunha basalts in the Indian and Atlantic oceans, respectively. We infer that the anomalous low-velocity zones at the core–mantle boundary are storing geochemical anomalies that are enriched in recycled material and sampled by strong mantle plumes.

Kauaʻi shield‐stage lavas are central to understanding the origin of the distinct Kea and Loa Hawaiian geochemical trends in Hawaiian basalts. These trends reflect two geochemically distinct sides in the Hawaiian plume, with Loa to the southwest and Kea to the northeast. The geochemistry and Sr‐Nd‐Hf isotopic compositions of shield‐stage lavas from Kauaʻi show a transition from Kea to Loa across the island with the Loa mantle source becoming dominant as the volcano grew. This geochemical transition is gradual from west to east Kauaʻi and supports the hypothesis that the Kauaʻi volcano sampled both sides of the bilateral Hawaiian plume, a phenomenon that is unusual for a Hawaiian volcano. Notably, Kauaʻi marks the arrival of progressively larger volumes of Loa compositions within the Hawaiian mantle plume. The new data from Kauaʻi, combined with an updated and comprehensive database of Hawaiian shield‐stage major element oxides, trace element concentrations, and isotopic compositions normalized to the same standard values, allows for the Pb‐Sr‐Nd‐Hf isotopic compositions of the Average Loa (‘ALOA’) common geochemical component to be estimated. Despite the bilateral Loa‐Kea geochemical trend beginning at Molokaʻi, Loa compositions dominate the erupted volume of Hawaiian volcanoes younger than 3 Ma, validating the volumetric importance of the Loa source in the lower mantle portion of the Hawaiian plume. Plain Language Summary Hawaiian volcanoes are arranged along two parallel geographic trends named Loa and Kea. Volcanoes belonging to either trend have distinct geochemical compositions that are linked to their deep mantle sources as sampled by the Hawaiian mantle plume. The Kea composition has been present in shield‐stage basalts for ∼81 Ma, however the Loa composition is relatively new and has mainly been measured in volcanoes formed since 3–4 Ma. We used the geochemistry and isotopic compositions of shield‐stage basalts from the island of Kauaʻi to show that Loa compositions began to appear in larger amounts in the Hawaiian plume around 5 Ma. These new data, combined with a large and carefully curated geochemical data set of Hawaiian samples, has allowed us to estimate the average composition of Loa and its associated isotopic end‐member compositions. This work demonstrates that Loa was an important mantle source for the older Hawaiian volcanoes such as Kauaʻi and dominates shield lavas along the Hawaiian chain. Notably, the geochemistry of Kauaʻi’s volcanic rocks represents the long‐term establishment of Loa compositions in the Hawaiian plume. Key Points Radiogenic (Sr‐Nd‐Hf, and Pb) isotopic compositions change from west to east across Kauaʻi and broadly correlate with age Kauaʻi records the first large‐scale and long‐lasting occurrence of Loa‐trend Hawaiian compositions The average Loa composition is constrained in Pb‐Sr‐Nd‐Hf isotopes and dominates compositions along the Hawaiian chain

Olivine in Hawaiian tholeiitic lavas have high NiO at given forsterite (Fo) contents (e.g., 0.25-0.60 wt% at Fo88) compared to MORB (e.g., 0.10-0.28 wt% at Fo88). This difference is commonly related to source variables such as depth and temperature of melting and/or lithology. Hawaiian olivine NiO contents are also highly variable and can range from 0.25-0.60 wt% at a given Fo. Here we examine the effects of crustal processes (fractional crystallization, magma mixing, diffusive re-equilibration) on the Ni content in olivine from Hawaiian basalts. Olivine compositions for five major Hawaiian volcanoes can be subdivided at ≥Fo88 into high-Ni (0.25-0.60 wt% NiO; Ko'olau, Mauna Loa, and Mauna Kea) and low-Ni (0.25-0.45 wt% NiO; Kilauea and Lo'ihi), groups that are unrelated to major isotopic trends (e.g., Loa and Kea). Within each group, individual volcanoes show up to 2.5× variation in olivine NiO contents at a given Fo. Whole-rock Ni contents from Ko'olau, Mauna Loa, Mauna Kea, and Kilauea lavas overlap significantly and do not correlate with differences in olivine NiO contents. However, inter-volcano variations in parental melt polymerization (NBO/T) and nickel partition coefficients (DNiOl/melt), caused by variable melt SiO2, correlate with observed differences in olivine NiO at Fo90, indicating that an olivine-free source lithology does not produce the inter-volcano groups. Additionally, large intra-volcano variations in olivine NiO can occur with minimal variation in lava SiO2 and NBO/T. Minor variations in parental melt NiO contents (0.09-0.11 wt%) account for the observed range of NiO in ≥Fo88 olivine. High-precision electron microprobe analyses of olivine from Kilauea eruptions (1500-2010 C.E.) show that the primary controls on 50% more likely to preserve original Xpx compared to smaller phenocrysts (400 µm along c-axis) which rarely (6%) recover original Xpx. Sections that are parallel or sub-parallel to the c-axis and/or pass near the core of the crystal best preserve growth signatures. Thus, diffusive re-equilibration, crystal size, and sectioning effects can strongly influence the characterization of mantle source lithologies for Hawaiian volcanoes.

The last 2500 years of activity at Kīlauea Volcano (Hawai‘i) have been characterized by centuries-long periods dominated by either effusive or explosive eruptions. The most recent period of explosive activity produced the Keanakāko‘i Tephra (KT; ca. 1500–1820 C.E.) and occurred after the collapse of the summit caldera (1470–1510 C.E.). Previous studies suggest that KT magmas may have ascended rapidly to the surface, bypassing storage in crustal reservoirs. The storage conditions and rapid ascent hypothesis are tested here using chemical zoning in olivine crystals and thermodynamic modeling. Forsterite contents (Fo; [Mg/(Mg + Fe) × 100]) of olivine core and rim populations are used to identify melt components in Kīlauea’s prehistoric (i.e., pre-1823) plumbing system. Primitive (≥Fo 88 ) cores occur throughout the 300+ years of the KT period; they originated from mantle-derived magmas that were first mixed and stored in a deep crustal reservoir. Bimodal olivine populations (≥Fo 88 and Fo 83–84 ) record repeated mixing of primitive magmas and more differentiated reservoir components shallower in the system, producing a hybrid composition (Fo 85–87 ). Phase equilibria modeling using MELTS shows that liquidus olivine is not stable at depths >17 km. Thus, calculated timescales likely record mixing and storage within the crust. Modeling of Fe–Mg and Ni zoning patterns (normal, reverse, complex) reveal that KT magmas were mixed and stored for a few weeks to several years before eruption, illustrating a more complex storage history than direct and rapid ascent from the mantle as previously inferred for KT magmas. Complexly zoned crystals also have smoothed compositional reversals in the outer 5–20 µm rims that are out of Fe–Mg equilibrium with surrounding glasses. Diffusion models suggest that these rims formed within a few hours to a few days, indicating that at least one additional, late-stage mixing event may have occurred shortly prior to eruption. Our study illustrates that the lifetimes of KT magmas are more complex than previously proposed, and that most KT magmas did not rise rapidly from the mantle without modification during shallow crustal storage.

We report here the first occurrence of celestine (SrSO4) in recent oceanic basalts. Celestine was found in moderately altered accidental volcanic blocks from Ka'ula Island, a rejuvenated tuff cone in the northern Hawaiian Islands. This occurrence is novel not only for the presence of celestine but also for the absence of barite, the sulfate mineral most commonly found in oceanic hydrothermal deposits. Celestine was found lining vesicles and partially fillings voids within the matrix of several high Sr (2200-6400 ppm) Ka'ula basalts. High-quality wavelength-dispersive microprobe analyses of celestine are reported here for near end-member celestine (>90%). The Ka'ula celestine deposits are compositionally heterogeneous with large variations in Ba content (0.9-7.5 wt%) within single mineral aggregates. The most likely source of the Sr for celestine in the Ka'ula basalts was the host basalt, which contains ∼1200 ppm. This is about 10 times higher than normally found in mid-ocean ridge basalts and 4 times greater than commonly observed in Hawaiian basalts. Hydrothermal alteration by S-bearing fluids related to the eruption that transported these accidentally fragments probably mobilized Sr in the blocks. These S-rich solutions later precipitated celestine during or following the eruption. We were unable to confirm the origin for the Sr via Sr isotope measures because the Ka'ula celestine was too fine grained, friable, and widely dispersed to be concentrated for Sr isotope analyses. Future studies of basalts from active volcanoes on oceanic islands, especially for basalts with elevated Sr contents (>1000 ppm), should be aware of the possible presence of celestine in moderately altered lavas.

New major and trace element abundances, and Pb, Sr, and Nd isotopic ratios of Quaternary lavas from two adjacent volcanoes (South Pagan and the Central Volcanic Region, or CVR) located on Pagan Island allow us to investigate the mantle source (i.e., slab components) and melting dynamics within the Mariana intra-oceanic arc. Geologic mapping reveals a pre-caldera (780–9.4 ka) and post-caldera (<9.4 ka) eruptive stage for South Pagan, whereas the eruptive history of the older CVR is poorly constrained. Crystal fractionation and magma mixing were important crustal processes for lavas from both volcanoes. Geochemical and isotopic variations indicate that South Pagan and CVR lavas, and lavas from the northern volcano on the island, Mt. Pagan, originated from compositionally distinct parental magmas due to variations in slab contributions (sediment and aqueous fluid) to the mantle wedge and the extent of mantle partial melting. A mixing model based on Pb and Nd isotopic ratios suggests that the average amount of sediment in the source of CVR (~2.1%) and South Pagan (~1.8%) lavas is slightly higher than Mt. Pagan (~1.4%) lavas. These estimates span the range of sediment-poor Guguan (~1.3%) and sediment-rich Agrigan (~2.0%) lavas for the Mariana arc. Melt modeling demonstrates that the saucer-shaped normalized rare earth element (REE) patterns observed in Pagan lavas can arise from partial melting of a mixed source of depleted mantle and enriched sediment, and do not require amphibole interaction or fractionation to depress the middle REE abundances of the lavas. The modeled degree of mantle partial melting for Agrigan (2–5%), Pagan (3–7%), and Guguan (9–15%) lavas correlates with indicators of fluid addition (e.g., Ba/Th). This relationship suggests that the fluid flux to the mantle wedge is the dominant control on the extent of partial melting beneath Mariana arc volcanoes. A decrease in the amount of fluid addition (lower Ba/Th) and extent of melting (higher Sm/Yb), and an increase in the sediment contribution (higher Th/Nb, La/Sm, and Pb isotopic ratios) from Mt. Pagan to South Pagan could reflect systematic cross-arc or irregular along-arc melting variations. These observations indicate that the length scale of compositional heterogeneity in the mantle wedge beneath Mariana arc volcanoes is small (~10 km).

For more than half a century, exploring a complete sequence of the oceanic crust from the seafloor through the Mohorovičić discontinuity (Moho) and into the uppermost mantle has been one of the most challenging missions of scientific ocean drilling. Such a scientific and technological achievement would provide humankind with profound insights into the largest realm of our planet and expand our fundamental understanding of Earth's deep interior and its geodynamic behavior. The formation of new oceanic crust at mid-ocean ridges and its subsequent aging over millions of years, leading to subduction, arc volcanism, and recycling of some components into the mantle, comprise the dominant geological cycle of matter and energy on Earth. Although previous scientific ocean drilling has cored some drill holes into old (> 110 Ma) and young (< 20 Ma) ocean crust, our sampling remains relatively shallow (< 2 km into intact crust) and unrepresentative of average oceanic crust. To date, no hole penetrates more than 100 m into intact average-aged oceanic crust that records the long-term history of seawater–basalt exchange (60 to 90 Myr). In addition, the nature, extent, and evolution of the deep subseafloor biosphere within oceanic crust remains poorly unknown. To address these fundamentally significant scientific issues, an international workshop “Exploring Deep Oceanic Crust off Hawai`i” brought together 106 scientists and engineers from 16 countries that represented the entire spectrum of disciplines, including petrologists, geophysicists, geochemists, microbiologists, geodynamic modelers, and drilling/logging engineers. The aim of the workshop was to develop a full International Ocean Discovery Program (IODP) proposal to drill a 2.5 km deep hole into oceanic crust on the North Arch off Hawai`i with the drilling research vessel Chikyu. This drill hole would provide samples down to cumulate gabbros of mature (∼ 80 Ma) oceanic crust formed at a half spreading rate of ∼ 3.5 cm a−1. A Moho reflection has been observed at ∼ 5.5 km below the seafloor at this site, and the workshop concluded that the proposed 2.5 km deep scientific drilling on the North Arch off Hawai`i would provide an essential “pilot hole” to inform the design of future mantle drilling.

Plate tectonic processes introduce basaltic crust (as eclogite) into the peridotitic mantle. The proportions of these two sources in mantle melts are poorly understood. Silica-rich melts formed from eclogite react with peridotite, converting it to olivine-free pyroxenite. Partial melts of this hybrid pyroxenite are higher in nickel and silicon but poorer in manganese, calcium, and magnesium than melts of peridotite. Olivine phenocrysts' compositions record these differences and were used to quantify the contributions of pyroxenite-derived melts in mid-ocean ridge basalts (10 to 30%), ocean island and continental basalts (many >60%), and komatiites (20 to 30%). These results imply involvement of 2 to 20% (up to 28%) of recycled crust in mantle melting.

Fourteen whole rock samples were analyzed for 40 Ar/ 39 Ar geochronology to determine the timing of an important transition in mantle source geochemistry that occurred on the island of Kaua‘i, located at the junction between the Northwest Hawaiian Ridge and the Hawaiian Islands. Kaua‘i’s shield-stage lavas have lead (Pb) isotopic compositions that change from west to east across the island. Given previous age constraints, it was unclear whether western and eastern portions of the shield were coeval. The new dates from this study range from 4.95 ± 0.19 Ma to 4.02 ± 0.04 Ma, decrease broadly from west to east Kaua‘i, and correlate with Pb isotopic ratios. The results indicate that the transition from Kea to Loa isotopic compositions across Kaua‘i occurred between ~4.7 and 4.4 Ma. The new 40 Ar/ 39 Ar geochronological results require a modification of the order of shield-building events for Kaua‘i. The easternmost lavas of the Nāpali Member formed after the westernmost lavas and are unlikely their stratigraphic equivalents, as previously inferred from mapping and structural observations. The easternmost lavas of the Nāpali Member likely represent the final period of shield-stage volcanism on Kaua‘i, which is supported by the location of the residual gravity anomaly beneath the Līhu‘e Basin in eastern Kaua‘i. This work highlights the importance of combining field-based observations with geochemical, isotopic, and geochronological data when assessing the shield-stage evolution of Hawaiian volcanoes.

New geochronologic constraints refine the growth history of Mauna Loa volcano and enhance interpretations of the petrologic, geochemical, and isotopic evolution of Hawaiian magmatism. We report results of 40Ar/39Ar incremental heating experiments on low‐K, tholeiitic lavas from the 1.6 km high Kahuku landslide scarp cutting Mauna Loa's submarine southwest rift zone, and from lavas in a deeper section of the rift. Obtaining precise40Ar/39Ar ages from young, tholeiitic lavas containing only 0.2–0.3 wt.% K2O is challenging due to their extremely low radiogenic 40Ar contents. Analyses of groundmass from 45 lavas yield 14 new age determinations (31% success rate) with plateau and isochron ages that agree with stratigraphic constraints. Lavas collected from a 1250 m thick section in the landslide scarp headwall were all erupted around 470 ± 10 ka, implying an extraordinary period of accumulation of ∼25 mm/yr, possibly correlating with the peak of the shield‐building stage. This rate is three times higher than the estimated vertical lava accumulation rate for shield‐building at Mauna Kea (8.6 ± 3.1 mm/yr) based on results from the Hawaii Scientific Drilling Project. Between ∼470 and 273 ka, the lava accumulation rate along the southwest rift zone decreased dramatically to ∼1 mm/yr. We propose that the marked reduction in lava accumulation rate does not mark the onset of post‐shield volcanism as previously suggested, but rather indicates the upward migration of the magma system as Mauna Loa evolved from a submarine stage of growth to one that is predominantly subaerial, thereby cutting off supply to the distal rift zone. Prior to ∼250 ka, lavas with Loihi‐like isotopic signatures were erupted along with lavas having typical Mauna Loa values, implying greater heterogeneity in the plume source earlier in Mauna Loa's growth. In addition to refining accumulation rates and the isotopic evolution of the lavas erupted along the southwest rift zone, our new40Ar/39Ar results constrain the eruption of the Ninole Basalts from 227 to 108 ka and provide maximum estimates on the timing of the Ka Lae and South Kona landslides. Key Points At ~470 ka, an extraordinary period of lava accumulation occurred Prior to ~250 ka, there was greater heterogeneity in the plume source Ninole basalts erupted from 227‐108 ka