U-Th-Pb and Lu-Hf isotopic constraints on the evolution of sub-continental lithospheric mantle, French Massif Central

We have carried out a Pb double-spike and Lu-Hf isotope study of clinopyroxenes from spinel-facies mantle xenoliths entrained in Cenozoic intraplate continental volcanism of the French Massif Central (FMC). U-Th-Pb and Lu-Hf isotope systematics verify the existence of different lithospheric domains beneath the northern and southern FMC. Northern FMC clinopyroxenes have extreme Lu/Hf ratios and ultra-radiogenic Hf (ε_Hf = +39.6 to +2586) that reflect ∼15-25% partial melting in Variscan times (depleted mantle model ages ∼360 Ma). Zr, Hf and Th abundances in these clinopyroxenes are low and unaffected by hydrous/carbonatitic metasomatism that overprinted LILE and light REE abundances and caused decoupling of Lu/Hf-Sm/Nd ratios and Nd-Hf isotopes (ε_Nd = +2.1 to +91.2). Pb isotopes of northern FMC clinopyroxenes are radiogenic (²⁰⁶Pb/²⁰⁴Pb > 19), and typically more so than the host intraplate volcanic rocks. ²³⁸U/²⁰⁴Pb ratios range from 17 to 68, and most samples have distinctively low ²³²Th/²³⁸U (<1) and ²³²Th/²⁰⁴Pb (3-22). Clinopyroxenes from southern FMC lherzolites are generally marked by overall incompatible trace element enrichment including Zr, Hf and Th abundances, and have Pb isotopes that are similar to or less radiogenic than the host volcanic rocks. Hf isotope ratios are less radiogenic (ε_Hf = +5.4 to +41.5) than northern FMC mantle and have been overprinted by silicate-melt-dominated metasomatism that affected this part of FMC mantle. Major element and Lu concentrations of clinopyroxenes from southern FMC harzburgites are broadly similar to northern FMC clinopyroxenes and suggest they experienced similar degrees of melt extraction as northern FMC mantle. ²³⁸U/²⁰⁴Pb (53-111) and ²³²Th/²⁰⁴Pb ratios (157-355) of enriched clinopyroxenes from the southern FMC are extreme and significantly higher than the intraplate volcanic rocks. In summary, mantle peridotites from different parts of the FMC record depletion at ∼360 Ma during Variscan subduction, followed by differing styles of enrichment. Northern FMC mantle was overprinted by a fluid/carbonatitic metasomatic agent that carried elements like U, Pb, Sr and light REE. In contrast, much of the southern FMC mantle was metasomatised by a small-degree partial silicate melt resulting in enrichment of all incompatible trace elements. The extreme mantle ²³⁸U/²⁰⁴Pb (northern and southern FMC), ²³²Th/²³⁸U (northern FMC) and ²³²Th/²⁰⁴Pb ratios (southern FMC), coupled with unremarkable present-day Pb isotope ratios, constrain the timing of enrichment. Mantle metasomatism is a young feature related to melting of the upwelling mantle responsible for Cenozoic FMC volcanism, rather than subduction-related metasomatism intimately associated with mantle depletion during the Variscan orogeny. The varying metasomatic styles relate to pre-existing variations in the thickness of the continental lithospheric lid, which controlled the extent to which upwelling mantle could ascend and melt. In the northern FMC, a thicker and more refractory lithospheric lid (?80 km) only allowed incipient degrees of melting resulting in fluid/carbonatitic metasomatism of the overlying sub-continental lithospheric mantle. The thinner lithospheric lid of the southern FMC (?70 km) allowed larger degrees of melting and resulted in silicate-melt-dominated metasomatism, and also focused the location of the volcanic fields of the FMC above this region.     

The U, Th and Pb elemental and isotope compositions of mantle clinopyroxenes and their grain boundary contamination derived from leaching and digestion experiments

Minerals from peridotites are known to be affected by trace element contamination on their grain boundaries. In this contribution we investigate the extent and origin of exogenous contamination associated with mantle clinopyroxenes from various localities (Middle Atlas, Beni Bousera [Morocco], Pyrenean Massif, Massif Central [France]) and test the efficacy of different leaching methodologies used to remove this contamination. In doing so we present new U-Th-Pb (double-spike) isotope and trace elemental data of clinopyroxenes and their leachates from spinel-facies sub-continental lithospheric mantle (SCLM, n = 18).Sequential leaching and dissolution of one clinopyroxene separate shows that multiple and short leaching attacks with dilute HCl at moderate temperatures (e.g., 120 °C) interspersed with rigorous ultra-pure water washes do not induce elemental fractionation and are sufficient to remove grain-boundary contamination. Short attacks with very dilute mixtures of HF and HCl induced strong parent/daughter elemental fractionation and significant elemental loss prior to the clinopyroxene digestion with HF/HNO₃. Such leaching is not suitable for studies investigating parent/daughter elemental or isotope ratios of mantle clinopyroxenes. Fluoride co-precipitates that formed in the presence of moderately dilute HF, used during leaching and typical HF/HNO₃ digestions, are an important sink for all trace elements studied here and lock up at least 60% of the trace elements considered.A suite of clinopyroxene-leachate pairs from Moroccan peridotites confirm extreme grain-boundary contamination and show that up to 65% of U, 82% of Th and 91% of Pb, respectively, are of exogenous origin. Pb isotopes of all leachates considered and nearly all reconstructed unleached clinopyroxenes have highly positive Δ7/4 and ²⁰⁷Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb systematics reminiscent of enriched mantle (particularly EM II), whereas the corresponding extensively leached clinopyroxenes have very different Pb isotope systematics (verified by replicate digestions). Furthermore, the leachates are often marked by remarkably high ²³²Th/²³⁸U (leachate ? bulk silicate Earth) in addition to ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb that are seemingly consistent with depleted mantle (DM) and high ²³⁸U/²⁰⁴Pb (HIMU) mantle mixing. After leaching, clinopyroxenes may have highly elevated ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb that are distinct from typical DM- and HIMU mantle, whereas corresponding leachates bear strong resemblance to anthropogenic Pb recovered from rainwater, snow and aerosols.In the light of the great potential of Pb isotope contamination associated with mantle clinopyroxene we have compiled literature data of mantle peridotites. These data seem to suggest that the SCLM is nearly devoid of HIMU signatures but ostensibly represents an important repository for enriched mantle signatures. However, the dominance of enriched mantle is not verified when ⁸⁷Sr/⁸⁶Sr and ²⁰⁸Pb/²⁰⁴Pb ratios for the same database are considered. We highlight that the scarcity of HIMU-like SCLM and the alleged dominance of EM in continental roots may be reconciled if the current Pb isotope database of SCLM contains samples that were insufficiently leached prior to digestion and thus are contaminated by anthropogenic Pb. We stress the importance of replicate digestions, adequate leaching and leachate analysis to verify the U-Th-Pb elemental and isotope systematics of any given mantle (-derived) sample.     

Plume-lithosphere interaction beneath Mt. Cameroon volcano, West Africa: Constraints from U-Th-Ra and Sr-Nd-Pb isotope systematics

Precise measurements of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria in lavas erupted within the last 100 yr on Mt. Cameroon are presented, together with major and trace elements, and Sr-Nd-Pb isotope ratios, to unravel the source and processes of basaltic magmatism at intraplate tectonic settings. All samples possess ²³⁸U-²³⁰Th-²²⁶Ra disequilibria with ²³⁰Th (18-24%) and ²²⁶Ra (9-21%) excesses, and there exists a positive correlation in a (²²⁶Ra/²³⁰Th)-(²³⁰Th/²³⁸U) diagram. The extent of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria is markedly different in lavas of individual eruption ages, although the (²³⁰Th/²³²Th) ratio is constant irrespective of eruption age. When U-series results are combined with Pb isotope ratios, negative correlations are observed in the (²³⁰Th/²³⁸U)-(²⁰⁶Pb/²⁰⁴Pb) and (²²⁶Ra/²³⁰Th)-(²⁰⁶Pb/²⁰⁴Pb) diagrams. Shallow magma chamber processes like magma mixing, fractional crystallization and wall rock assimilation do not account for the correlations. Crustal contamination is not the cause of the observed isotopic variations because continental crust is considered to have extremely different Pb isotope compositions and U/Th ratios. Melting of a chemically heterogeneous mantle might explain the Mt. Cameroon data, but dynamic melting under conditions of high D_U and D_U/D_Th, long magma ascent time, or disequilibrium mineral/melt partitioning, is required. The most plausible scenario to produce the geochemical characteristics of Mt. Cameroon samples is the interaction of melt derived from the asthenospheric mantle with overlying sub-continental lithospheric mantle which has elevated U/Pb (>0.75) and Pb isotope ratios (²⁰⁶Pb/²⁰⁴Pb > 20.47) due to late Mesozoic metasomatism.     

Timescales of magma differentiation from basalt to andesite beneath Hekla Volcano, Iceland: Constraints from U-series disequilibria in lavas from the last quarter-millennium flows

Measurements of ²³⁸U-²³⁰Th-²²⁶Ra disequilibria, Sr-Nd-Pb-Hf isotopes and major-trace elements have been conducted for lavas erupted in the last quarter-millennium at Hekla volcano, Iceland. The volcanic rocks range from basalt to dacite. Most of the lavas (excluding dacitic samples) display limited compositional variations in radiogenic Sr-Nd-Pb-Hf isotopes (⁸⁷Sr/⁸⁶Sr = 0.70319-0.70322; ¹⁴³Nd/¹⁴⁴Nd = 0.51302-0.51305; ²⁰⁶Pb/²⁰⁴Pb = 19.04-19.06; ²⁰⁷Pb/²⁰⁴Pb = 15.53-15.54; ²⁰⁸Pb/²⁰⁴Pb = 38.61-38.65; ¹⁷⁶Hf/¹⁷⁷Hf = 0.28311-0.28312). All the samples possess (²³⁰Th/²³⁸U) disequilibrium with ²³⁰Th excesses, and they show systematic variations in (²³⁰Th/²³²Th) and (²³⁸U/²³²Th) ratios. The highest ²²⁶Ra excesses occur in the basalt and most differentiated andesite lavas, while some basaltic-andesite lavas have (²²⁶Ra/²³⁰Th) ratio that are close to equilibrium. The ²³⁸U-²³⁰Th-²²⁶Ra disequilibria variations cannot be produced by simple closed-system fractional crystallization with radioactive decay of ²³⁰Th and ²²⁶Ra in a magma chamber. A closed-system fractional crystallization model and assimilation and fractional crystallization (AFC) model indicate that the least differentiated basaltic andesites were derived from basalt by fractional crystallization with a differentiation age of ∼24 ± 11 kyr, whereas the andesites were formed by assimilation of crustal material and fractionation of the basaltic-andesites within 2 kyr. Apatite is inferred to play a key role in fractionating the parent-daughter nuclides in ²³⁰Th-²³⁸U and ²²⁶Ra-²³⁰Th to make the observed variations. Our proposed model is that several batches of basaltic-andesite magmas that formed by fractional crystallization of a basaltic melt from a deeper reservoir, were periodically injected into the shallow crust to form individual magma pockets, and subsequently modifying the original magma compositions via simultaneous assimilation and fractional crystallization. The assimilant is the dacitic melt, which formed by partial melting of the crust.     

Isotopic (Sr, Nd, Pb) characteristics of the archean metasomatized mantle—source of the Panozero massif, Karelia

This work addresses the isotopic heterogeneity of the Archean lithospheric mantle by the example of high-Mg, moderate-alkali, LILE and LREE-enriched Panozero sanukitoid massif, which is located in the Central Karelia, southeastern Baltic Shield. Initial Nd and Sr isotope characteristics were determined for mantle source of the massif. ?_Nd(T) in the source are plotted below DM line, varying from + 0.7 to + 1.4 (+1.1, on average). The ⁸⁷Sr/⁸⁶Sr(T) ～ 0.7017 significantly exceeds that of depleted mantle and reflects change of Rb/Sr ratio in the source due to metasomatic reworking of mantle. Data on Pb isotope composition of potassium feldspars indicate that source of monzonites of the Panozero Massif had lower μ (²³⁸U/²⁰⁴Pb) = 8 and higher (²³⁸Th/²³²U) = 4.05 relative to primitive mantle.     

K-Ar ages and Pb,Sr isotopic characteristics of Cenozoic volcanic rocks in Shandong Province,China

28 samples of Cenozoic volcanic rocks collected from Shandong Province have been dated by K-Ar method. They are mainly Neogene with an age range of 4–19 m. y. The basalts from Linqu and Yishui in west Shandong Province are Miocene and those from Penglai and Qixia in east Shandong Province are Miocene and Pliocene in age. The basalts from Wudi in north Shandong Province are Middle-Early Pleistocene in age. In each area the duration of volcanic eruption was estimated at about 2–3 m. y. Pb and Sr isotopic compositions and U, Th, Pb, Rb, Sr, and major elements in most of the samples were determined. The isotopic compositions are:²⁰⁶Pb/²⁰⁴Pb—16.92-18.48,²⁰⁷Pb/²⁰⁴Pb—15.30-15.59,²⁰⁸Pb/²⁰⁴Pb—37.83-38.54, and (⁸⁷Sr/⁸⁶Sr)_i—0.70327-0.70632. There are some positive or negative linear correlations between²⁰⁶Pb/²⁰⁴Pb and²⁰⁷Pb/²⁰⁴Pb, Pb isotopes and Pb content, Pb isotopes and Sr isotopes, and Sr isotopes and other elements. The basaltic rocks from east and west Shandong Province have somewhat differences in isotopic composition and element content. The basalts probably are products of multi-stage evolution of the mantle. They have preserved the primary features of the source, although they were influenced, to some extent, by the contamination of crustal materials.     

Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada

Extreme U and Pb isotope variations produced by disequilibrium in decay chains of ²³⁸U and ²³²Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my⁻¹) contain excess ²⁰⁶Pb and ²⁰⁸Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable ²⁰⁶Pb/²³⁸U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect ²⁰⁷Pb/²³⁵U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages.Opal and calcite from outer (younger) portions of coatings have ²³⁰Th/U ages from 94.6 ± 3.7 to 361.3 ± 9.8 ka and initial ²³⁴U/²³⁸U activity ratios (AR) from 4.351 ± 0.070 to 7.02 ± 0.12, which indicate ²³⁴U enrichment from percolating water. Present-day ²³⁴U/²³⁸U AR is ∼1 in opal/chalcedony from older portions of the coatings. The ²⁰⁷Pb/²³⁵U ages of opal/chalcedony samples range from 0.1329 ± 0.0080 to 9.10 ± 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my⁻¹, in good agreement with previous results. Measured ²³⁴U/²³⁸U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ± 0.006 to 2.091 ± 0.006 and are >1 in most samples. The range of ⁸⁷Sr/⁸⁶Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool.In the U-poor calcite samples, measured ²⁰⁶Pb/²⁰⁷Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both ²⁰⁶Pb and ²⁰⁷Pb derived from Rn diffusion and from direct α-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains ²⁰⁶Pb and ²⁰⁸Pb excesses, but no appreciable ²⁰⁷Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect ²⁰⁶Pb-²³⁸U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.     

Understanding melt generation beneath the slow-spreading Kolbeinsey Ridge using U, Th, and Pa excesses

To examine the petrogenesis and sources of basalts from the Kolbeinsey Ridge, one of the shallowest locations along the global ridge system, we present new measurements of Nd, Sr, Hf, and Pb isotopes and U-series disequilibria on 32 axial basalts. Young Kolbeinsey basalts (full-spreading rate = 1.8 cm/yr; 67°05′-70°26′N) display (²³⁰Th/²³⁸U) < 1 and (²³⁰Th/²³⁸U) > 1 with (²³⁰Th/²³⁸U) from 0.95 to 1.30 and have low U (11.3-65.6 ppb) and Th (33.0 ppb-2.40 ppm) concentrations. Except for characteristic isotopic enrichment near the Jan Mayen region, the otherwise depleted Kolbeinsey basalts (e.g. ⁸⁷Sr/⁸⁶Sr = 0.70272-0.70301, ε_Nd = 8.4-10.5, ε_Hf = 15.4-19.6 (La/Yb)_N = 0.28-0.84) encompass a narrow range of (²³⁰Th/²³²Th) (1.20-1.32) over a large range in (²³⁸U/²³²Th) (0.94-1.32), producing a horizontal array on a (²³⁰Th/²³²Th) vs. (²³⁸U/²³²Th) diagram and a large variation in (²³⁰Th/²³⁸U). However, the (²³⁰Th/²³⁸U) of the Kolbeinsey Ridge basalts (0.96-1.30) are inversely correlated with (²³⁴U/²³⁸U) (1.001-1.031). Samples with low (²³⁰Th/²³⁸U) and elevated (²³⁴U/²³⁸U) reflect alteration by seawater or seawater-derived materials. The unaltered Kolbeinsey lavas with equilibrium ²³⁴U/²³⁸U have high (²³⁰Th/²³⁸U) values (?1.2), which are consistent with melting in the presence of garnet. This is in keeping with the thick crust and anomalously shallow axial depth for the Kolbeinsey Ridge, which is thought to be the product of large degrees of melting in a long melt column. A time-dependent, dynamic melting scenario involving a long, slowly upwelling melting column that initiates well within the garnet peridotite stability zone can, in general, reproduce the (²³⁰Th/²³⁸U) and (²³¹Pa/²³⁵U) ratios in uncontaminated Kolbeinsey lavas, but low (²³¹Pa/²³⁵U) ratios in Eggvin Bank samples suggest eclogite involvement in the source for that ridge segment.     

Subduction and melting processes inferred from U-Series, Sr-Nd-Pb isotope, and trace element data, Bicol and Bataan arcs, Philippines

We present U-series, Sr-Nd-Pb isotope, and trace element data from the two principal volcanic chains on Luzon Island, developed over oppositely dipping subduction zones, to explore melting and mass transfer processes beneath arcs. The Bataan (western) and Bicol (eastern) arcs are currently subducting terrigenous and pelagic sediments, respectively, which have different trace element and isotopic compositions. The range of (²³⁰Th/²³⁸U) disequilibria for both arcs is 0.85-1.15; only lavas from Mt. Mayon (Bicol arc) have ²³⁰Th activity excesses. Bataan lavas have higher ⁸⁷Sr/⁸⁶Sr and lower ¹⁴³Nd/¹⁴⁴Nd than Bicol lavas (⁸⁷Sr/⁸⁶Sr = 0.7042-0.7046, ¹⁴³Nd/¹⁴⁴Nd = 0.51281-0.51290 vs. ⁸⁷Sr/⁸⁶Sr = 0.70371-0.70391, ¹⁴³Nd/¹⁴⁴Nd = 0.51295-0.51301) and both arcs show steep linear arrays towards sediment values on ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagrams. Analysis of incompatible element and isotopic data allows identification of a sediment component that, at least in part, was transferred as a partial melt to the mantle wedge peridotite. Between 1% and 5% sediment melt addition can explain the isotopic and trace element variability in the rocks from both arcs despite the differences in sediment supply. We therefore propose that sediment transfer to the mantle wedge is likely mechanically or thermally limited. It follows that most sediments are either accreted, reside in the sub-arc lithosphere, or are recycled into the convecting mantle. However, whole-sale sediment recycling into the upper mantle is unlikely in light of the global mid-ocean ridge basalt data. Fluid involvement is more difficult to characterize, but overall the Bicol arc appears to have more fluid influence than the Bataan arc. Rock suites from each arc can be related by a dynamic melting process that allows for ²³⁰Th ingrowth, either by dynamic or continuous flux melting, provided the initial (²³⁰Th/²³²Th) of the source is ∼0.6-0.7. The implication of either model is that inclined arrays on the U-Th equiline diagram may not have chronologic significance. Modeling also suggests that U-series disequilibria are influenced by the tectonic convergence rate, which dictates mantle matrix flow. Thus with slower matrix flow there is a greater degree of ²³⁰Th ingrowth. While other factors such as prior mantle depletion and addition of a subducted component may explain some aspects of U-series data, an overall global correlation between tectonic convergence rate and the extent of U-Th disequilibria may originate from melting processes.     

Direct dating of hydrothermal W mineralization: U-Pb age for hübnerite (MnWO4), Sweet Home Mine, Colorado

We have investigated the potential of hübnerite for U-Pb dating. Hübnerite forms typically at medium to low-temperatures in a wide range of pneumatolytic-hydrothermal mineral deposits, particularly porphyry molybdenum and Sn-specialized granites. Hübnerite from the Sweet Home Mine (Alma, Colorado) formed in a Pb-rich, U-poor environment, but still developed relatively radiogenic Pb isotopic compositions. The low Pb_common contents in hübnerite (0.075 to 0.155 ppm) demonstrate that Pb is efficiently excluded from the crystal lattice. In contrast, U may substitute for Mn. The U-Pb data of hübnerite scatter. Most of the scatter originates from samples with ²⁰⁶Pb/²⁰⁴Pb values below 50, where Pb_blank contributes up to 30% to Pb_total. Using the least radiogenic galena Pb, samples with ²⁰⁶Pb/²⁰⁴Pb values above 70 have overlapping ²⁰⁶Pb∗/²³⁸U and ²⁰⁷Pb∗/²³⁵U values and yield a ²⁰⁶Pb/²³⁸U age of 25.7 ± 0.3 Ma (2σ). Late stage apatite from the Sweet Home Mine yields a ²⁰⁶Pb/²⁰⁴Pb-²³⁸U/²⁰⁴Pb isochron corresponding to an age of 24.8 ± 0.5 Ma (2σ). A comparison of the U-Pb hübnerite ages with literature ⁴⁰Ar/³⁹Ar ages on earlier sericite and the U-Pb age on later apatite suggests that (i) hübnerite yields accurate U-Pb ages and (ii) the evolution of the Sweet Home mineralization from greisen-type mineralization to medium-temperature hydrothermal vein mineralization took place in a few hundred thousand years at most. Aqueous low-N₂-bearing and aqueous inclusions in the dated hübnerite have homogenization temperatures between 325 and 356 °C and moderate salinity (up to 6.7 wt% NaCl equiv.). Thus, hübnerite represents one of the rare examples of a mineral that can be dated accurately and carries petrological information.     

Chemical and isotopic (Pb,Sr) zonation in a peraluminous granite pluton: role of fluid fractionation

The Davis Lake pluton (DLP, ~800 km²) of southwestern Nova Scotia, Canada, part of the large peraluminous South Mountain batholith of ca. 380 Ma (U/Pb zircon, Ar/Ar mica), consists of granite and subordinate topaz–muscovite leucogranite that hosts greisen tin-base metal mineralization. A new Pb–Pb isochron age for leucogranite from the most evolved part of the DLP indicates a crystallization age of 378±3.6 Ma, coincident with other radiometric ages of the DLP (Rb–Sr, Re–Os, Pb–Pb). The intrusion displays a compositional zonation defined by lead and strontium isotopic ratios, as well as some major elements (e.g., Si, F), incompatible trace elements (e.g., Li, Rb, Ta, U, Sn), and elemental ratios (e.g., K/Rb and Nb/Ta). The greisens and the leucogranites that host them are characterized by extreme radiogenic compositions for Pb and Sr, and their chemical-isotopic trends are extensions of the trends displayed by the less evolved granites. The covariations of the isotopic ratios with several major and trace elements and elemental ratios as well as the Pb–Pb and Rb–Sr isochrones indicate that all phases of the intrusion originated from a homogeneous parental magma. The granitoid magma underwent extensive fractional crystallization of feldspars, minor biotite and accessory minerals (monazite, apatite and zircon) in a compositionally zoned magma chamber that was subsequently accompanied by fluid fractionation, during which time the internally derived fluorine-rich fluids modified the Rb/Sr, U/Pb and Th/Pb ratios, leading to distinct variations of ⁸⁷Sr/⁸⁶Sr, ²⁰⁶Pb/²⁰⁴Pb, ²³⁸U/²⁰⁴Pb and ²³²Th/²⁰⁴Pb isotopic ratios. These data therefore document the evolution of a granitic magma through magmatic (i.e., crystal fractionation), orthomagmatic (i.e., crystal-fluid fractionation) and hydrothermal (i.e., fluid fractionation) stages that culminated in the formation of a tin-base metal deposit. The Pb isotope data also constrain the source region for the DLP as being Avalonian basement that, by inference, must underlie much of the Meguma Terrane.Editorial responsibility: T.L. Grove     

Lead Isotope Characteristics of the Mindyak Gold Deposit,Southern Urals: Evidence for the Source of Metals

The isotopic composition of Pb in pyrite of the Mindyak orogenic gold deposit located in the Main Ural Fault Zone, the Southern Urals, has been studied by the high-precision MC-ICP-MS method. Orebodies at the deposit are composed of early pyrite and late polysulfide–carbonate–quartz mineral assemblages. The orebodies are localized in olistostrome with carbonaceous clayey-cherty cement. Pyrites from early and late mineral assemblages are close in Pb isotope ratios. For early pyrite ²⁰⁶Pb/²⁰⁴Pb = 18.250–18.336, ²⁰⁷Pb/²⁰⁴Pb = 15.645–15.653, ²⁰⁸Pb/²⁰⁴Pb = 38.179–38.461; while for late pyrite ²⁰⁶Pb/²⁰⁴Pb = 18.102–18.378, ²⁰⁷Pb/²⁰⁴Pb = 15.635–15.646, ²⁰⁸Pb/²⁰⁴Pb = 38.149–38.320. The model parameters μ₂ (²³⁸U/²⁰⁴Pb = 9.91 ± 2), ω₂ (²³²Th/²⁰⁴Pb = 38.5 ± 4), and ²³²Th/²³⁸U = 3.88 ± 3 indicate that an upper crustal Pb source played a leading role in ore formation. Carbonaceous shale as an olistostrome cement and syngenetic sulfide mineralization are considered to be the main Pb sources of both early and late mineral assemblages. An additional recept in apparently magmatic lead is suggested for the late veinlet mineralization. The involvement of lead from several sources in ore formation is consistent with the genetic model, which assumes a two-stage formation of orebodies at the Mindyak deposit.     

The origin of geochemical diversity of lunar mantle sources inferred from the combined U-Pb, Rb-Sr, and Sm-Nd isotope systematics of mare basalt 10017

The results of our combined U-Pb, Rb-Sr, and Sm-Nd isotope study of mare basalt 10017 contribute to the understanding of the petrogenetic processes involved in the origin of geochemical diversity in lunar mare basalt sources, as well as the U-Pb isotope systematics of the Moon. The Rb-Sr, Sm-Nd, and ²³⁸U-²⁰⁶Pb isotope systems yield concordant crystallization ages of 3.633 ± 0.057 Ga, 3.678 ± 0.069 Ga, and 3.616 ± 0.098 Ga, respectively. The ²³⁵U-²⁰⁷Pb isochron yields an older, though still concordant, age of 3.80 ± 0.12 Ga. Neither the ²⁰⁶Pb-²⁰⁷Pb system nor U-Pb concordia system yields an age for 10017 that is concordant with the age determined from the Sm-Nd, Rb-Sr, and ²³⁸U-²⁰⁶Pb systems. The initial ⁸⁷Sr/⁸⁶Sr of 10017 is 0.69941 ± 7 and the initial ε_Nd is +3.2 ± 0.4. Initial Pb isotopic compositions, determined from the U-Pb isochrons, are ²⁰⁶Pb/²⁰⁴Pb_i = 31 ± 11 and ²⁰⁷Pb/²⁰⁴Pb_i = 34 ± 15. Together, these initial Pb compositions constrain the μ value of the 10017 source to be 70 ± 30, assuming a single-stage Pb growth model. This is considerably lower than μ values typically estimated for mare basalt sources (∼100-600). Regardless, the μ values calculated for the sources of mare basalts, as well as other lunar samples, show a range that is larger than can be explained by fractionation of U from Pb solely by crystallization of silicate phases and ilmenite during magma ocean solidification and formation of lunar mantle sources. The U-Pb isotope systematics may reflect late-stage formation of a sulfide phase, which strongly fractionates Pb from U but has minimal effect on Rb/Sr or Sm/Nd compositions, during crystallization of the lunar magma ocean.     

Lead isotopic evidence for interaction between plume and lower crust during emplacement of peralkaline Lovozero rocks and related rare-metal deposits,East Fennoscandia,Kola Peninsula,Russia

The Lovozero alkaline massif—an agpaitic nepheline syenite layered intrusion—is located in the central part of the Kola Peninsula, Russia, and belongs to the Kola ultramafic alkaline and carbonatitic province (KACP) of Devonian age. Associated loparite and eudialyte deposits, which contain immense resources of REE, Nb, Ta, and Zr, constitute a world class mineral district. Previous Sr, Nd, and Hf isotope investigations demonstrated that these rocks and mineral deposits were derived from a depleted mantle source. However, because the Sr, Nd, and Hf abundances in the Kola alkaline rocks are significantly elevated, their isotopic compositions were relatively insensitive to contamination by the underlying crustal rocks through which the intruding magmas passed. Pb occurring in relatively lower abundance in the KACP rocks, by contrast, would have been a more sensitive indicator of an acquired crustal component. Here, we investigate the lead isotopic signature of representative types of Lovozero rocks in order to further characterize their sources. The measured Pb isotopic composition was corrected using the determined U and Th concentrations to the age of the crystallization of the intrusion (376?±?28 Ma, based on a ²⁰⁶Pb/²⁰⁴Pb versus ²³⁸U/²⁰⁴Pb isochron and 373?±?9 Ma, from a ²⁰⁸Pb/²⁰⁴Pb versus ²³²Th/²⁰⁴Pb isochron). Unlike the previously investigated Sr, Nd, and Hf isotopes, the lead isotopic composition plot was well outside the FOZO field. The ²⁰⁶Pb/²⁰⁴Pb values fall within the depleted MORB field, with some rocks having lower ²⁰⁷Pb/²⁰⁴Pb but higher ²⁰⁸Pb/²⁰⁴Pb values. Together with other related carbonatites having both lower and higher ²⁰⁶Pb/²⁰⁴Pb values, the combined KACP rocks form an extended linear array defining either a?~2.5-Ga secondary isochron or a mixing line. The projection of this isotopic array toward the very unradiogenic composition of underlying 2.4–2.5-Ga basaltic rocks of the Matachewan superplume and associated Archean granulite facies country rock provides strong evidence that this old lower crust was the contaminant responsible for the deviation of the Lovozero rocks from a presumed original FOZO lead isotopic composition. Evaluating the presence of such a lower crustal component in the Lovozero rock samples suggests a 5–10% contamination by such rocks. Contamination by upper crustal rock is limited to only a negligible amount.     

Variable initial Pb isotopic compositions of rocks associated with the UG2 chromitite, eastern Bushveld Complex

An investigation of the Pb isotopic compositions of plagioclase and sulfide in a stratigraphic interval including the UG2 chromitite of the eastern Bushveld Complex has been conducted to determine the Pb isotopic composition(s) of the magma(s) that crystallized to form this part of the intrusion, gain a better understanding of why coexisting plagioclase and sulfide commonly exhibit widely different Pb isotopic compositions, and explore the use of Pb isotopes in deducing post-accumulation history. Analyses were obtained in situ with a NuPlasma multicollector ICP-MS coupled with 193 nm Excimer or 213 nm lasers.Most plagioclase compositions fall on the ²⁰⁷Pb/²⁰⁴Pb vs ²⁰⁶Pb/²⁰⁴Pb geochron of 2.06 Ga, which is the solidification age of the intrusion. The measured ratios have not been affected by radiogenic ingrowth, and plagioclase generally remained closed to Pb exchange after initial cooling. The array of plagioclase compositions on the geochron is significantly larger than that defined by analytical error. This indicates that in terms of Pb at least two different magma compositions were present. The composition of the least radiogenic magma was approximated by that of the contemporaneous BSE with μ (²³⁸U/²⁰⁴Pb) and ω (²³²Th/²⁰⁴Pb) values of ≈9.0 and 35, respectively, suggesting a mantle derivation with little or no involvement of the continental crust, while the second magma possessed a Pb isotopic composition similar to the upper crust with μ ≈ 9.6.Compared to plagioclase, sulfides generally possess slightly higher ²⁰⁶Pb/²⁰⁴Pb ratios for equivalent ²⁰⁷Pb/²⁰⁴Pb ratios such that their compositions fall between the 2.06 and 1.86 Ga geochrons. The latter age is much younger than the cooling age. The data are interpreted to mean that the Bushveld Complex remained buried in the crust at temperatures of several hundred °C for about 200 Ma after solidification, and that any sulfides accessible to fluid continued to re-equilibrated during this time with more radiogenic Pb. The sulfide Pb may have been transported into the Bushveld Complex by fluids from an external reservoir when the rocks were still partially molten and thus permeable. Alternatively, the sulfide Pb may have originated mainly from radiogenic decay of U and Th present in minerals other than the sulfides in the immediately surrounding Bushveld rocks, followed by local redistribution of Pb by whatever fluid was present. Indeed, some sulfides are characterized by ²⁰⁸Pb/²⁰⁴Pb ratios sufficiently high that an external source is unlikely. This observation and the fact that the sulfides display small-scale heterogeneity suggest that most, if not all, of the radiogenic sulfide Pb was locally derived. It also implies that during the post-solidification, re-equilibration period there was no large-scale fluid-flow through the microfracture network because otherwise the isotopic heterogeneities would not have been preserved. The minerals in 2 of the 19 samples studied contain young Pb, presumably introduced by meteoric waters that permeated the macrofracture network.     

Geochemical evolution of a shallow magma plumbing system during the last 500 years, Miyakejima volcano, Japan: Constraints from U-Th-Ra systematics

In order to unravel magma processes and the geochemical evolution of shallow plumbing systems beneath active volcanoes, we investigated U-series disequilibria of rocks erupted over the past 500 years (1469-2000 AD) from Miyakejima volcano, Izu arc, Japan. Miyakejima volcanic rocks show ²³⁸U-²³⁰Th-²²⁶Ra disequilibria with excess ²³⁸U and ²²⁶Ra, due to the addition of slab-derived fluids to the mantle wedge. Basaltic bombs of the 2000 AD eruption have the lowest (²³⁰Th/²³²Th) ratio compared to older Miyakejima eruptives, yielding the youngest ²³⁸U-²³⁰Th model age of 2 kyr. This reinforces our previous model that fluid release from the slab and subsequent magma generation in the mantle wedge beneath Miyakejima occur episodically on a several-kyr timescale. In the last 500 years, Miyakejima eruptives show: (1) a vertical trend in a (²³⁰Th/²³²Th)-(²³⁸U/²³²Th) diagram and (2) a positive linear correlation in a (²²⁶Ra/²³⁰Th)₀ − 1/²³⁰Th diagram, which is also observed in lavas from some of the single eruptions (e.g., 1940, 1962, and 1983 AD). The variations cannot be produced by simple fractional crystallization in a magma chamber with radioactive decay of ²³⁰Th and ²²⁶Ra, but it is possibly produced by synchronous generation of melts in the mantle wedge with different upwelling rate or addition of multiple slab-derived fluids. A much more favorable scenario is that some basaltic magmas were intermittently supplied from deep in the mantle and injected into the crust, subsequently modifying the original magma composition and producing variations in (²³⁰Th/²³²Th) and (²²⁶Ra/²³⁰Th)₀ ratios via assimilation and fractional crystallization (AFC). The assimilant of the AFC process would be a volcanic edifice of previous Miyakejima magmatism. Due to the relatively short timescales involved, the interaction between the assimilant and recent Miyakejima magmatism has not been recorded by the Sr-Nd-Pb isotopic systems. In such cases, Th isotopes and (²²⁶Ra/²³⁰Th) ratio are excellent geochemical tracers of magmatic evolution.     

Isotopic composition of Pb and Th in interplinian volcanics from Somma–Vesuvius volcano, Italy

Summary We present a detailed isotopic study of volcanic rocks emitted from Somma–Vesuvius volcano during three periods of interplinian activity: Protohistoric (3550 y B.P. to 79 A.D.), Ancient Historic (79 to 472 A.D.) and Medieval (472 to 1631 A.D.). Pb isotopic compositions of two acid leached fractions and whole rock residues of 37 whole rock samples (determined by Somma et al., 2001) show that each of the three interplinian periods is distinguished by small, systematic, and unique uranogenic and thorogenic Pb isotopic trends. This key and novel feature is compatible with the notion that the Pb isotopic data reflect small-scale source heterogeneity operating over relatively short periods of time. From this representative group of samples, a selected set of nine whole rocks were analysed for Th isotopes. ²³²Th/²³⁸U ratios in the source can be obtained independently from Pb and from Th isotopes. Those obtained from Pb isotopes represent source ratios, time-integrated over the whole age of the Earth; they range from 3.9 to 4.1. ²³²Th/²³⁸U obtained from Th isotopes are those of the present source. They are lower, and cluster around 3.5; this difference probably indicates recent U enrichment of the present source.The behaviour of Pb, as inferred by its isotopic ratios, is quite distinct from that of Sr and Nd isotopes: Pb isotope variations are not correlated to Sr or Nd isotope variations. The isotopic contrast is compatible with the idea that the isotopes were decoupled during magmatic production, evolution, and ascent through the crust. Thus, the Pb isotopes do not reflect the effects of the same processes as in the case of the Sr and Nd isotopes, or, as we also favor, they do not necessarily reflect the same source contributions into the magmas. Moreover, the Pb isotopic evolution of the interplinian rocks chiefly reflects mixing, driven by processes that are superimposed on, and independent of, other source contributions that determine the isotopic compositions of Sr and Nd. We suggest that reactions between magmas and fluids transported Pb and U, but not Sr. These data show that isotope mixing in the mantle is active at different times and scales.     

Lead isotopes of the carbonate-hosted Kabwe, Tsumeb, and Kipushi Pb-Zn-Cu sulphide deposits in relation to Pan African orogenesis in the Damaran-Lufilian Fold Belt of Central Africa

Lead isotope ratios of galena from the carbonate-hosted massive sulphide deposits of Kabwe (Pb-Zn) and Tsumeb (Pb-Zn-Cu) in Zambia and Namibia, respectively, have been measured and found to be homogeneous and characteristic of upper crustal source rocks. Kabwe galena has average isotope ratios of ^206/204Pb = 17.997 ± 0.007, ^207/204Pb = 15.713 ± 0.010 and ^208/204Pb = 38.410 ± 0.033. Tsumeb galena has slightly higher ^206/204Pb (18.112 ± 0.035) and slightly lower ^207/204Pb (15.674 ± 0.016) and ^208/204Pb (38.276 ± 0.073) ratios than Kabwe galena. The isotopic differences are attributed to local differences in the age and composition of the respective source rocks for Kabwe and Tsumeb. The homogeneity of the ore lead in the two epigenetic deposits suggests lead sources of uniform isotopic composition or, alternatively, thorough mixing of lead derived from sources with relatively similar isotopic compositions. Both deposits have relatively high ²³⁸U/²⁰⁴Pb ratios of 10.31 and 10.09 for Kabwe and Tsumeb galenas, respectively. These isotope ratios are considered to be typical of the upper continental crust in the Damaran-Lufilian orogenic belt, as also indicated by basement rocks and Cu-Co sulphides in stratiform Katangan metasediments which have a mean μ-value of 10.25 ± 0.12 in the Copperbelt region of Zambia and the Democratic Republic of Congo (formerly Zaire). The ²³²Th/²⁰⁴Pb isotope ratios of 43.08 and 40.42 for Kabwe and Tsumeb suggest Th-enriched source regions with ²³²Th/²³⁵U (κ-values) of 4.18 and 4.01, respectively. Model isotopic ages determined for the Kabwe (680 Ma) and Tsumeb (530 Ma) deposits indicate that the timing of the mineralisation was probably related to phases of orogenic activity associated with the Pan-African Lufilian and Damaran orogenies, respectively. Galena from the carbonate-hosted Kipushi Cu-Pb-Zn massive sulphide deposit in the Congo also has homogeneous lead isotope ratios, but its isotopic composition is comparable to that of the average global lead evolution curve for conformable massive sulphide deposits. The μ (9.84) and κ (3.69) values indicate a significant mantle component, and the isotopic age of the Kipushi deposit (456 Ma) suggests that the emplacement of the mineralisation was related to a post-tectonic phase of igneous activity in the Lufilian belt. The isotope ratios (^206/204Pb, ^207/204Pb, ^208/204Pb) of the three deposits are markedly different from the heterogeneous lead ratios of the Katangan Cu-Co stratiform mineralisation of the Copperbelt as well as those of the volcanogenic Nampundwe massive pyrite deposit in the Zambezi belt which typically define radiogenic linear trends on lead-lead plots. The host-rock dolomite of the Kabwe deposit also has homogeneous lead isotope ratios identical to the ore galena. This observation indicates contamination of the Kabwe Dolomite Formation with ore lead during mineralisation. Received: 8 September 1997 / Accepted: 21 August 1998     

Uranium-lead isotope systematics of Mars inferred from the basaltic shergottite QUE 94201

Uranium-lead ratios (commonly represented as ²³⁸U/²⁰⁴Pb = μ) calculated for the sources of martian basalts preserve a record of petrogenetic processes that were active during early planetary differentiation and formation of martian geochemical reservoirs. To better define the range of μ values represented by the source regions of martian basalts, we completed U-Pb elemental and isotopic analyses on whole rock, mineral and leachate fractions from the martian meteorite Queen Alexandra Range 94201 (QUE 94201). The whole rock and silicate mineral fractions have unradiogenic Pb isotopic compositions that define a narrow range (²⁰⁶Pb/²⁰⁴Pb = 11.16-11.61). In contrast, the Pb isotopic compositions of weak HCl leachates are more variable and radiogenic. The intersection of the QUE 94201 data array with terrestrial Pb in ²⁰⁶Pb/²⁰⁴Pb-²⁰⁷Pb/²⁰⁴Pb-²⁰⁸Pb/²⁰⁴Pb compositional space is consistent with varying amounts of terrestrial contamination in these fractions. We calculate that only 1-7% contamination is present in the purified silicate mineral and whole rock fractions, whereas the HCl leachates contain up to 86% terrestrial Pb. This terrestrial Pb contamination generated a ²⁰⁶Pb-²⁰⁷Pb array in the QUE fractions that appears to represent an ancient age, which contrasts with a much younger crystallization age of 327 ± 10 Ma derived from Rb-Sr and Sm-Nd isochrons (Borg L. E., Nyquist L. E., Taylor L. A., Wiesmann H. and Shih C. -Y. (1997) Constraints on Martian differentiation processes from Rb-Sr and Sm-Nd isotopic analyses of the basaltic shergottite QUE 94201. Geochim. Cosmochim. Acta61, 4915-4931). Despite the contamination, and accepting 327 ± 10 Ma as the crystallization age, we use the U-Pb data to determine the initial ²⁰⁶Pb/²⁰⁴Pb of QUE 94201 to be 11.086 ± 0.008 and to calculate the μ value of its mantle source to be 1.82 ± 0.01. The μ value calculated for the QUE 94201 source is the lowest determined for any martian basalt source, and, when compared to the highest values determined for martian basalt sources, indicates that μ values in martian source reservoirs vary by at least a factor of two. Additionally, the range of source μ values indicates that the μ value of bulk silicate Mars is approximately three. The amount of variation in the μ values of the mantle sources (μ ∼ 2-4) is greater than can be explained by igneous processes involving silicate phases alone. We suggest the possibility that a small amount of sulfide crystallization may generate greater extents of U-Pb fractionation during formation of the mantle sources of martian basalts.