James S. Scoates

High‐precision isotopic characterization of USGS reference materials by TIMS and MC‐ICP‐MS

The Pacific Centre for Isotopic and Geochemical Research (PCIGR) at the University of British Columbia has undertaken a systematic analysis of the isotopic (Sr, Nd, and Pb) compositions and concentrations of a broad compositional range of U.S. Geological Survey (USGS) reference materials, including basalt (BCR-1, 2; BHVO-1, 2), andesite (AGV-1, 2), rhyolite (RGM-1, 2), syenite (STM-1, 2), granodiorite (GSP-2), and granite (G-2, 3). USGS rock reference materials are geochemically well characterized, but there is neither a systematic methodology nor a database for radiogenic isotopic compositions, even for the widely used BCR-1. This investigation represents the first comprehensive, systematic analysis of the isotopic composition and concentration of USGS reference materials and provides an important database for the isotopic community. In addition, the range of equipment at the PCIGR, including a Nu Instruments Plasma MC-ICP-MS, a Thermo Finnigan Triton TIMS, and a Thermo Finnigan Element2 HR-ICP-MS, permits an assessment and comparison of the precision and accuracy of isotopic analyses determined by both the TIMS and MC-ICP-MS methods (e.g., Nd isotopic compositions). For each of the reference materials, 5 to 10 complete replicate analyses provide coherent isotopic results, all with external precision below 30 ppm (2 SD) for Sr and Nd isotopic compositions (27 and 24 ppm for TIMS and MC-ICP-MS, respectively). Our results also show that the first- and second-generation USGS reference materials have homogeneous Sr and Nd isotopic compositions. Nd isotopic compositions by MC-ICP-MS and TIMS agree to within 15 ppm for all reference materials. Interlaboratory MC-ICP-MS comparisons show excellent agreement for Pb isotopic compositions; however, the reproducibility is not as good as for Sr and Nd. A careful, sequential leaching experiment of three first- and second-generation reference materials (BCR, BHVO, AGV) indicates that the heterogeneity in Pb isotopic compositions, and concentrations, could be directly related to contamination by the steel (mortar/pestle) used to process the materials. Contamination also accounts for the high concentrations of certain other trace elements (e.g., Li, Mo, Cd, Sn, Sb, W) in various USGS reference materials.

Baddeleyite (ZrO2) and zircon (ZrSiO4) from anorthositic rocks of the Laramie anorthosite complex, Wyoming: Petrologic consequences and U-Pb ages

Two types of chromite deposits occur in the Hongguleleng ophiolite in Xinjiang, northwest China. One is located in the mantle sequence, the other occurs in the transition zone between the mantle sequence and layered cumulates. Abundant primary silicate inclusions such as phlogopite, pargasite, clinopyroxene, orthopyroxene, and olivine are found in the segregated chromite, but silicate inclusions occur only rarely in accessory chromite of the ultramafic rocks from the transition zone and cumulates. These silicate phases are considered to have been entrapped as discrete and rare composite inclusions during magmatic precipitation of chromite rather than formed by postmagmatic entrapment. Phlogopite is the most abundant mineral found as inclusions in chromite in the Hongguleleng ophiolite. There are two types of substitutions for K in the phlogopite inclusions: (l) Na substitutes for K, and phlogopite shows a continuous range from almost pure sodium phlogopite to phlogopite; (2) Ca partially substitutes for I! resulting in the formation of Ca-bearing phlogopite. It is proposed that the alkalic aqueous liquid (melt) responsible for the formation of the phlogopite inclusions was derived from the mixture of the K-rich aqueous liquid related to the subduction of the oceanic slab and the Na-rich aqueous liquid from the primary magma of the ophiolite. Two types of phlogopite hydrates, hydrate I and possibly a new hydrate (hydrate H), occur as inclusions in the chromite and result from later hydrothermal processes. The fractures from brittle deformation provided passage for meteoric water to enter and react with the phlogopite inclusions. Compared with those in the transition zone, the inclusions of phlogopite and phlogopite hydrates in the mantle sequence are characterizedby (l) smaller grain size and greater abundance, (2) undulatory extinction, (3) higher Si, Cr, Ni, and Ca, and (4) lower Ti and Al. These differences are possibly due to (l) P, T, and composition of chromite-precipitating magma, (2) subsolidus reequilibration with the host chromite, and (3) postmagrnatic deformation and hydrothermal processes.

High-Al gabbros in the Laramie Anorthosite Complex, Wyoming: implications for the composition of melts parental to Proterozoic anorthosite

High-Al gabbro represents one of the latest phases of magmatism in the 1.43 Ga Laramie anorthosite complex (LAC) in southeastern Wyoming. This lithology, which is mineralogically and geochemically the most primitive in the LAC, forms dikes and small intrusions that cross cut monzonitic and anorthositic rocks. High-Al gabbro is characterized by high Al2O3 (15–19 wt%), REE patterns with positive europium anomalies (Eu/Eu*=1.2–3.8), and the lowest initial 87Sr/86Sr (as low as 0.7033) and highest initial ɛNd (up to +2) in the LAC. Their Sr and Nd isotopic characteristics indicate a mantle origin followed by crustal assimilation during ascent. Intermediate plagioclase (An50–60) and mafic silicate (Fo54–63) compositions suggest that they are not primary mantle melts and that they differentiated prior to final emplacement. High-Al gabbros of the LAC are similar compositionally to gabbros from several other Proterozoic anorthosite complexes, including rocks from the Harp Lake complex and the Hettasch intrusion in Labrador and the Adirondack Mountains of New York. These gabbros are considered to be parental to their associated anorthositic rocks, a theory that is supported by recent experimental work. We interpret LAC high-Al gabbros to represent mantle-derived melts produced by the differentiation of a basaltic magma in an upper mantle chamber. Continued evolution of this magma eventually resulted in the formation of plagioclase-rich diapirs which ascended to mid-crustal levels and formed the anorthositic rocks of the LAC. Because these gabbros intrude the anorthositic rocks, they do not represent directly the magma from which anorthosite crystallized and instead are younger samples of magma formed by identical processes.

Relationship between the early Kerguelen plume and continental flood basalts of the paleo-Eastern Gondwanan margins

Abstract Cretaceous basalts recovered during Ocean Drilling Program Leg 183 at Site 1137 on the Kerguelen Plateau show remarkable geochemical similarities to Cretaceous continental tholeiites located on the continental margins of eastern India (Rajmahal Traps) and southwestern Australia (Bunbury basalt). Major and trace element and Sr–Nd–Pb isotopic compositions of the Site 1137 basalts are consistent with assimilation of Gondwanan continental crust (from 5 to 7%) by Kerguelen plume-derived magmas. In light of the requirement for crustal contamination of the Kerguelen Plateau basalts, we re-examine the early tectonic environment of the initial Kerguelen plume head. Although a causal role of the Kerguelen plume in the breakup of Eastern Gondwana cannot be ascertained, we demonstrate the need for the presence of the Kerguelen plume early during continental rifting. Activity resulting from interactions by the newly formed Indian and Australian continental margins and the Kerguelen plume may have resulted in stranded fragments of continental crust, isolated at shallow levels in the Indian Ocean lithosphere.

Orogenic to Post‐Orogenic Origin For the 1.76 Ga Horse Creek Anorthosite Complex, Wyoming, Usa

The age and inferred tectonic setting of the 1.76 Ga Horse Creek anorthosite complex (HCAC) in the Laramie Mountains of southeastern Wyoming place important constraints on the origin of middle Proterozoic anorthosite complexes. The 100 km2 HCAC consists of strongly recrystallized anorthosite and two small intrusions of monzonite and granite. U‐Pb crystallization ages from euhedral zircons in anorthosite and monzonite are 1761.5 ± 2 Ma and 1754.5 ± 2.2 Ma, respectively. An additional period of zircon growth in the anorthosite occurred at 1753.4 ± 2 Ma, as represented by a small population of anhedral zircon. We attribute the origin of this second morphological variety of zircon in the anorthosite to the loss of Zr from ilmenite during reaction with plagioclase to form sphene. This reaction took place in response to heat and fluid influx during intrusion of the adjacent monzonite. The HCAC and the younger 1.43 Ga Laramie anorthosite complex to the north were intruded along or near a Paleoproterozoic suture zone, the Cheyenne belt, marking the boundary between Archean rocks of the Wyoming Province to the north and Proterozoic island arc terranes to the south. We propose that the the HCAC was emplaced into young crust during or several million years after collision along the suture in an environment of late‐to post‐orogenic transtension. The presence of pre‐existing crustal structures, especially Archean/Proterozoic boundaries, strongly influences the generation and emplacement of many middle Proterozoic anorthosite complexes.

Residual-liquid origin for a monzonitic intrusion in a mid-Proterozoic anorthosite complex: The Sybille intrusion, Laramie anorthosite complex, Wyoming

The Sybille intrusion (≈100 km 2) is one of three large monzonitic intrusions in the 1.43 Ga Laramie anorthosite complex of southeastern Wyoming. The petrographic, geochemical, isotopic, and geophysical characteristics of Sybille monzonitic rocks are consistent with an origin by extensive crystallization of liquids residual to nearby anorthositic cumulates (ferrodiorites) and contamination by Archean wall rocks. The exposed part of the intrusion is composed mainly of coarse-grained monzosyenites with abundant alkali feldspar phenocrysts. The monzosyenites preserve mineralogical evidence for high crystallization temperatures (>1000 °C), mid-crustal emplacement pressures (≈3 kbar), relatively reduced crystallization conditions (2 log units below the fayalite + magnetite + quartz [FMQ] oxygen buffer), and they crystallized in the presence of a CO2-rich fluid phase (Fuhrman et al., 1988; Frost and Touret, 1989). The eastern monzosyenites, those adjacent to contemporaneous anorthosite, are distinguished by an anhydrous mineral assemblage (Fo16-Fo8 olivine, high-Ca pyroxene) lacking modal quartz, silica contents of 60 wt%, and smaller Eu anomalies (Eu/Eu* = 1.2 to 1.3). Abundant xenoliths of Archean wall rocks and anorthosite from the adjacent intrusions in all monzosyenites attest to a stoping emplacement mechanism near the roof of the chamber. We propose that the monzosyenites represent a relatively thin, 0.5-1.0-km-thick, roof to a magma chamber dominated by dense ferrodioritic cumulates at depth. Extensive, open-system fractionation of a ferrodioritic parent magma, residual after crystallization of anorthosite, produced Fe-enriched monzodioritic and/or monzonitic magma in the upper part of the chamber and complementary Fe- and Ti-rich cumulates in the lower levels. We have corroborated the production of monzonitic liquids from crystallization of ferrodiorite through a series of reconnaissance equilibrium-crystallization experiments. The presence of dense ferrodioritic cumulates at depth is consistent with the prominent positive gravity anomaly associated with the Sybille intrusion (Hodge et al., 1973). In the upper parts of the chamber, the fractionated monzodioritic and/or monzonitic magmas eventually became saturated in alkali feldspar. Owing to density contrasts, the alkali feldspar phenocrysts floated to the roof of the chamber, thus producing the exposed porphyritic monzosyenites. In addition, the roof of the chamber was the site of significant melting of Archean gneiss and, locally, metapelite. The Sr and Nd isotopic compositions of the monzosyenites, with Sr isotopic ratios becoming increasingly radiogenic from east ( I Sr = 0.7059 and initial ϵNd = −2.5) to west ( I Sr = 0.7092 and initial ϵNd = −2.6), are consistent with a 5% to 15% addition of Archean orthogneiss to a ferrodioritic parent magma that had isotopic characteristics similar to adjacent anorthositic rocks. The stratigraphic and compositional similarity of the Sybille monzosyenites to mangerites in the Bjerkreim-Sokndal intrusion of the Rogaland anorthosite complex, southern Norway, indicates that similar open-system magmatic processes are capable of having produced high-temperature, K-rich monzonitic rocks in other Proterozoic anorthosite complexes.

Horizontal and vertical zoning of heterogeneities in the Hawaiian mantle plume from the geochemistry of consecutive postshield volcano pairs: Kohala‐Mahukona and Mauna Kea–Hualalai

[1] Sr-Nd-Pb-Hf isotopic compositions of postshield lavas from two pairs of Hawaiian volcanoes, Mauna Kea and Kohala (Kea trend) and Hualalai and Mahukona (Loa trend), allow for identification of smallscale (tens of kilometers) heterogeneities in the Hawaiian mantle plume and provide constraints on their distribution. The postshield lavas range from transitional/alkalic basalt to trachyte and are enriched in incompatible trace elements (e.g., LaN/YbN = 6.0–16.2). These lavas are characterized by a limited range of Sr-Nd-Hf isotopic compositions ( 87 Sr/ 86 Sr = 0.70343–0.70365, 143 Nd/ 144 Nd = 0.51292–0.51301, and 176 Hf/ 177 Hf = 0.28311–0.28314) and have distinct Pb isotopic compositions ( 206 Pb/ 204 Pb = 17.89–18.44, 207 Pb/ 204 Pb = 15.44–15.49, and 208 Pb/ 204 Pb = 37.68–38.01) that correspond to their respective Kea or Loa side of the Pb-Pb isotopic boundary. Mauna Kea lavas show a systematic shift to less radiogenic Pb isotopic compositions from the shield to postshield stage and they trend to low 87 Sr/ 86 Sr toward, but not as extreme as, compositions characteristic of rejuvenated stage lavas. Hualalai postshield lavas lie distinctly above the Hf-Nd Hawaiian array and have much lower Pb isotopic ratios than shield lavas, including some of the least radiogenic values (e.g., 206 Pb/ 204 Pb = 17.89–18.01) of recent Hawaiian volcanoes. In contrast, comparison of Kohala with the adjacent Mahukona volcano shows that these older postshield lavas become more radiogenic in Pb during the late stages of volcanism. The isotope systematics of the postshield lavas cannot be explained by mixing between Hawaiian plume end-members (e.g., Kea, Koolau, and Loihi) or by assimilation of Pacific lithosphere and are consistent with the presence of ancient recycled lower oceanic crust (±sediments) in their source. More than one depleted component is sampled by the postshield lavas and these components are long-lived features of the Hawaiian plume that are present in both the Kea and Loa source regions. The depleted components in the postshield lavas, particularly as sampled at Hualalai, are different from the much more homogeneous component present in rejuvenated lavas. The geochemistry of the postshield lavas provides evidence for a bilateral symmetry to the plume where the compositional boundary between the Kea and Loa sources is complex and vertical components of heterogeneity are significant.

A strontium and neodymium isotopic investigation of the Laramie anorthosites, Wyoming, USA: Implications for magma chamber processes and the evolution of magma conduits in Proterozoic anorthosites

Abstract A strontium and neodymium isotopic investigation of plagioclase-rich cumulate rocks in the 1.43 Ga Laramie anorthosite complex (LAC) provides new insights into the evolution of magma chambers and underlying magma plumbing systems during the crystallization of Proterozoic anorthosites. The 725 km2 LAC intruded the boundary between Archean rocks of the Wyoming Province in the north and Proterozoic island arc terranes in the south, the Cheyenne belt, at pressures of 3–4 kilobars. Initial strontium and eND isotopic ratios from the three large composite anorthositic intrusions (Poe Mountain, Chugwater, and Snow Creek) and late troctolitic intrusions range from 0.7034–0.7055 and +0.9 to −4.9, respectively. The isotopic ratios in the cumulates vary as a result of (1) the isotopic composition of the parental mantle-derived high-Al gabbroic magmas, (2) the amount of contamination by Archean rocks during ascent through the crust, and (3) mixing of replenishing magmas and resident magmas with different isotopic compositions in the magma chamber at the final level of emplacement. Strontium isotopic and normative An variations across the 5–7 km thick stratigraphic section of layered plagioclase-rich cumulates in the 200 km2 Poe Mountain anorthosite indicate that multiple inputs of magma are needed to construct even relatively small intrusions in Proterozoic anorthosites. The earliest and stratigraphically lowest intrusion was emplaced as a plagioclase-rich magma that crystallized large volumes of compositionally homogeneous anorthosite. At least three subsequent chamber-wide episodes of magma replenishment, followed by mixing, are indicated by abrupt shifts in ISr and/or normative An in the stratigraphically higher levels of the Poe Mountain anorthosite. Strontium and neodymium isotopic disequilibrium between a high-Al clinopyroxene megacryst and the layered cumulates is consistent with a high-pressure origin for Al-rich pyroxene megacrysts in Proterozoic anorthosites. The megacryst crystallized in a magma chamber at pressures of 10–12 kilobars from relatively uncontaminated basaltic parent magma (high-Al gabbro) and was transported through the crust in progressively contaminated anorthositic magma. The range of observed isotopic compositions in the anorthositic rocks is nearly identical to that of high-Al gabbroic dikes in the LAC, supporting the proposition that high-Al gabbros are parental to anorthosite (Mitchell et al., 1995). The isotopic data require that the anorthositic parental magmas were contaminated during ascent through the crust by Archean orthogneisses and/or metapelitic rocks. Decreasing ISr and increasing eNd with a relative decrease in age of the intrusions (Snow Creek → Poe Mountain/Chugwater → troctolites) indicates that the magma conduit became increasingly insulated from crustal contamination over time. This study indicates that the strontium and neodymium isotopic systems can be used to distinguish between processes that occurred at lower crustal/upper mantle pressures, during the ascent of magma diapirs, and within individual magma chambers in Proterozoic anorthosites, and underscores the need for stratigraphic control when addressing the origin of plagioclase-rich cumulates.

The architecture of oceanic plateaus revealed by the volcanic stratigraphy of the accreted Wrangellia oceanic plateau

The accreted Wrangellia flood basalts and associated sedimentary rocks that compose the prevolcanic and postvolcanic stratigraphy provide an unparalleled view of the architecture, eruptive environment, and accumulation and subsidence history of an oceanic plateau. This Triassic large igneous province extends for ∼2300 km in the Pacific Northwest of North America, from central Alaska and western Yukon (Nikolai Formation) to Vancouver Island (Karmutsen Formation), and contains exposures of submarine and subaerial volcanic rocks representing composite stratigraphic thicknesses of 3.5–6 km. Here we provide a model for the construction of the Wrangellia oceanic plateau using the following information and visualization tools: (1) stratigraphic summaries for different areas of Wrangellia; (2) new 40Ar/39Ar geochronology results; (3) compilation and assessment of geochronology and biostratigraphy for Wrangellia; (4) compiled digital geologic maps; (5) an online photographic archive of field relationships; and (6) a Google Earth file showing the mapped extent of Wrangellia flood basalts and linked field photographs. Based on combined radiometric (U-Pb, 40Ar/39Ar, K-Ar), paleontological, and magnetostratigraphic age constraints, the Wrangellia flood basalts were emplaced during a single phase of tholeiitic volcanism ca. 230–225 Ma, and possibly within as few as 2 Myr, onto preexisting submerged arc crust. There are distinct differences in volcanic stratigraphy and basement composition between Northern and Southern Wrangellia. On Vancouver Island, ∼6 km of high-Ti basalts, with minor amounts of picrites, record an emergent sequence of pillow basalt, pillow breccia and hyaloclastite, and subaerial flows that overlie Devonian–Mississippian (ca. 380–355 Ma) island arc rocks and Mississippian–Permian marine sedimentary strata. In contrast, Alaska and Yukon contain 1–3.5-km-thick sequences of mostly subaerial high-Ti basalt flows, with low-Ti basalt and submarine pillow basalts in the lowest parts of the stratigraphy, that overlie Pennsylvanian–Permian (312–280 Ma) volcanic and sedimentary rocks. Subsidence of the entire plateau occurred during and after volcanism, based on late-stage interflow sedimentary lenses in the upper stratigraphic levels and the presence of hundreds of meters to >1000 m of overlying marine sedimentary rocks, predominantly limestone. The main factors that controlled the resulting volcanic architecture of the Wrangellia oceanic plateau include high effusion rates and the formation of extensive compound flow fields from low-viscosity, high-temperature tholeiitic basalts, sill-dominated feeder systems, limited repose time between flows (absence of weathering, erosion, sedimentation), submarine versus subaerial emplacement, and relative water depth (e.g., pillow basalt–volcaniclastic transition).

Geochemical and Hf–Pb–Sr–Nd isotopic constraints on the origin of the Amsterdam–St. Paul (Indian Ocean) hotspot basalts

The Amsterdam–St. Paul (ASP) Plateau is a recent (≤5 Ma) volcanic rise constructed along the Southeast Indian Ridge (SEIR) by the combined effects of a relatively small mantle plume and a mid-oceanic ridge. The Amsterdam and St. Paul islands are located 100 km away from each other and formed during the last 0.4 Myr; they are the only subaerial features of the ASP Plateau and the two islands are structurally separated by the presence of a SW–NE transform fault. New geochemical analyses and Hf–Pb–Sr–Nd isotopic compositions of 20 basaltic rocks from Amsterdam and St. Paul Islands constrain the nature and origin of the sources involved in the genesis of the ASP hotspot basalts. Aphyric basalts from St. Paul are mildly alkalic, incompatible element-enriched and highly fractionated; they are distinct from the tholeiitic basalts from Amsterdam, from the recently discovered Boomerang active seamount on the ASP Plateau, and from the Kerguelen Archipelago basalts on the Antarctic Plate. The St. Paul and Amsterdam basalts have very limited isotopic variations with distinct 206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb, and 176Hf/177Hf isotopic compositions (19.08±0.07, 15.61±0.02, 39.45±0.12, 0.28313±0.00003 for Amsterdam, and 18.70±0.08, 15.56±0.01, 38.87±0.05, 0.28306±0.00002 for St. Paul, respectively) that are not compatible with any direct contribution of the enriched Kerguelen plume end-member. Pb–Nd–Sr isotopic compositions of the St. Paul basalts appear consistent with simple binary mixtures between heterogeneous ambient upper mantle and a highly radiogenic Pb plume component (the ASP plume end-member), particularly expressed in the isotopic compositions of the Amsterdam basalts. However, the Amsterdam basalts have distinctly higher ϵHf than the St. Paul basalts (+13 and +10, respectively) for a given ϵNd (+4) and are inconsistent with such a simple binary mixing scenario. Isotopic systematics in the Amsterdam and St. Paul basalts indicate that the Amsterdam and St. Paul volcanoes were formed by sampling isotopically distinct zones of the ASP plume at a lateral distance of 100 km. Less than 1% variation in the proportion of recycled altered oceanic crust relative to pelagic sediment, combined with minor variations in the proportion of recycled material within the Amsterdam and St. Paul plume sources themselves relative to a peridotitic mantle source, could account for the isotopic differences between the compositions of basalts from these two islands. The particularly high 206Pb/204Pb component recorded in the Amsterdam and St. Paul basalts is also locally recorded at different times and locations within other Indian Ocean basalts (e.g. Ninetyeast Ridge basalts, 38 Ma) and such a component has also contaminated the source of SEIR basalts to varying degrees. The particularly high 206Pb/204Pb component is therefore not exclusive to the Amsterdam–St. Paul plume but is heterogeneously distributed within the Indian Ocean upper mantle. This may reflect the role of the Indian mantle plumes in dispersing recycled material within the Indian upper mantle.