Age and isotope geochemistry of the Archaean Pongola and Usushwana suites in Swaziland, southern Africa: a case for crustal contamination of mantle-derived magma

The igneous rocks of the Pongola Supergroup (PS) and Usushwana Intrusive Suite (UIS) represent a case of late Archaean continental magmatism in the southeastern part of the Kaapvaal craton of South Africa and Swaziland.

U-Pb dating on zircons from felsic volcanic rocks of the PS yields a concordia intercept age of 2940 ± 22Ma that is consistent with a Sm-Nd whole rock age of 2934 ± 114Ma determined on the PS basalt-rhyolite suite. The initial ε_Nd of−2.6 ± 0.9 is the lowest value so far reported for Archaean mantle-derived rocks. Rb-Sr whole rock dating of the PS yields a younger isochron age of 2883 ± 69Ma, which is not significantly different form the accepted U-Pb zircon age.

An internal (cpx-opx-plag-whole rock) isochron for a pyroxenite from the younger UIS yields an age of 2871 ± 30 Ma and initial ¹⁴³Nd/¹⁴⁴Nd that lies off the CHUR growth curve by ε_Nd −2.9 ± 0.2. However, Sm-Nd whole-rock data for the UIS yield an excessively high age of 3.1 Ga that conflicts with firm geological evidence showing the UIS to be intrusive into the PS.

The negative deviations of initialε_Nd from the chondritic Nd evolution curve suggest significant contamination of the PS and UIS melts by older continental crust. A mixing process with continental crust after magma segregation is supported by a high initial ⁸⁷Sr/⁸⁶Sr ratio of0.703024 ± 24 for a clinopyroxene sample from a UIS pyroxenite, compared with an expected value of 0.701 for the 2.9 Ga mantle. We therefore interpret the linear array of data points for the UIS gabbros as a mixing line between 2.87 Ga old magma and older continental crust.

Parallel LREE-enriched REE patterns, negative Nb-Ti anomalies, a distinctive and uniform ratio of Ti/Zr 46 and a narrow span of initial Nd indicate a common source for both the PS and UIS suites which is different from primitive mantle.     

Temporal–compositional trends over short and long time-scales in basalts of the Big Pine Volcanic Field, California

Primitive basaltic single eruptions in the Big Pine Volcanic Field (BPVF) of Owens Valley, California show systematic temporal–compositional variation that cannot be described by simple models of fractional crystallization, partial melting of a single source, or crustal contamination. We targeted five monogenetic eruption sequences in the BPVF for detailed chemical and isotopic measurements and ⁴⁰Ar/³⁹Ar dating, focusing primarily on the Papoose Canyon sequence. The vent of the primitive (Mg# = 69) Papoose Canyon sequence (760.8 ± 22.8 ka) produced magmas with systematically decreasing (up to a factor of two) incompatible element concentrations, at roughly constant MgO (9.8 ± 0.3 (1σ) wt.%) and Na₂O. SiO₂ and compatible elements (Cr and Ni) show systematic increases, while ⁸⁷Sr/⁸⁶Sr systematically decreases (0.7063–0.7055) and ε_Nd increases (− 3.4 to − 1.1). ¹⁸⁷Os/¹⁸⁸Os is highly radiogenic (0.20–0.31), but variations among four samples do not correlate with other chemical or isotopic indices, are not systematic with respect to eruption order, and thus the Os system appears to be decoupled from the dominant trends. The single eruption trends likely result from coupled melting and mixing of two isotopically distinct sources, either through melt-rock interaction or melting of a lithologically heterogeneous source. The other four sequences, Jalopy Cone (469.4 ± 9.2 ka), Quarry Cone (90.5 ±17.6 ka), Volcanic Bomb Cone (61.6 ± 23.4 ka), and Goodale Bee Cone (31.8 ± 12.1 ka) show similar systematic temporal decreases in incompatible elements. Monogenetic volcanic fields are often used to decipher tectonic changes on the order of 10⁵–10⁶ yr through long-term changes in lava chemistry. However, the systematic variation found in Papoose Canyon (10⁰–10² yr) nearly spans that of the entire volcanic field, and straddles cutoffs for models of changing tectonic regime over much longer time-scales. Moreover, ten new ⁴⁰Ar/³⁹Ar ages combined with chemistry from all BPVF single eruption sequences show the long-term trend of BPVF evolution comprises the overlapping, temporal–compositional trends of the monogenetic vents. This suggests that the single eruption sequences contain the bulk of the systematic chemical variation, whereas their aggregate compositions define the long-term trend of volcanic field evolution.     

Evidence for mantle metasomatism: an oxygen and strontium isotope study of the Vulsinian District, Central Italy

This paper presents new O and Sr isotope data for lavas from the northern part of the Roman perpotassic province. The samples comprise the tephritic leucititic to leucite phonolitic lavas and the saturated lavas from the Vulsinian District, the olivine leucite melilitite of San Venanzo, and the kalsilite diopside melilitite of Cupaello. Previous oxygen isotope work on the lavas of the Vulsinian District suggested crustal contamination of “normal” mantle-derived magmas. The new data cover the ranges previously found. O and Sr isotope ratios of evolved lavas of the undersaturated suite indicate assimilation in variable amounts of up to ca. 10% of continental crustal material. The saturated lavas probably assimilated large amounts (up to ca. 50%) of crust. Lavas chemically identified as corresponding to little modified mantle-derived liquids are high in both⁸⁷Sr/⁸⁶Sr andδ¹⁸O: 0.7103−0.7107, +7.8 to +9.4 (Vulsini), 0.7104, +12.3 (San Venanzo) and 0.7112, +14.4 (Cupaello). These high values are interpreted to have been inherited from a metasomatized parental mantle. Hydrous fluids enriched in large-ion lithophile elements and high inδ¹⁸O and⁸⁷Sr/⁸⁶Sr are thought to have mixed with mantle of “normal”δ¹⁸O and⁸⁷Sr/⁸⁶Sr. The fluids probably origi dehydration of continent-derived sediments, which were subducted beneath a mantle wedge in the continent-continent collision of the Corsica-Sardinia block and the Adriatic (Italian) plate. This hypothesis is supported by Pb and Nd isotopic evidence and is probably valid for the entire Roman Province.     

Anomalous strontium and lead isotope signatures in the off-rift Öræfajökull central volcano in south-east Iceland: Evidence for enriched endmember(s) of the Iceland mantle plume?

The currently active off-rift central volcano Öræfajökull in south-east Iceland sits unconformably on much older (10–12 Ma) and eroded crust. The composition of recent volcanics ranges from basalt to rhyolite, but the series is more sodic alkaline than the common rift zone tholeiitic suites. In this study we present Sr, Nd, Pb and O isotopic data for a suite of Öræfajökull samples. The complete suite shows typical mantle values for oxygen isotopes. The ⁸⁷Sr/⁸⁶Sr ratios (average of 15 SAMPLES=0.703702) of the modern Öræfajökull rocks (basalts as well as rhyolites) are much higher than observed so far for any other Icelandic rocks. The ¹⁴³Nd/¹⁴⁴Nd ratios (average=0.512947; n=15) are lower than for rift rocks, but similar to rocks of the off-rift Snæfellsnes volcanic zone. Furthermore, the Öræfajökull rocks are enriched in the ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb isotope ratios compared to Icelandic rift basalts. The enriched nature of the suite indicates that Öræfajökull samples a source component that has characteristics common with EM2 type mantle. Furthermore, it is concluded that the silicic rocks of Öræfajökull formed by fractional crystallization from mafic melts rather than by partial melting of older crust.     

Oxygen isotope evidence for the origin of enriched mantle beneath the mid-Atlantic ridge

Geochemical variations in mid-ocean ridge basalts have been attributed to differing proportions of compositionally distinct mantle components in their sources, some of which may be recycled crust. Oxygen isotopes are strongly fractionated by near-surface interactions of rocks with the hydrosphere, and thus provide a tracer of near-surface materials that have been recycled into the mantle. We present here oxygen isotope analyses of basaltic glasses from the mid-Atlantic ridge south of and across the Azores platform. Variations in δ¹⁸O in these samples are subtle (range of 0.47‰) and may partly reflect shallow fractional crystallization; we present a method to correct for these effects. Relatively high fractionation-corrected δ¹⁸O in these samples is associated with geochemical indices of enrichment, including high La/Sm, Ce/Pb, and ⁸⁷Sr/⁸⁶Sr and low ¹⁴³Nd/¹⁴⁴Nd. Our results suggest two first-order conclusions about these enriched materials: (1) they are derived (directly or indirectly) from recycled upper oceanic crustal rocks and/or sediments; and (2) these materials are present in the north Atlantic MORB sources in abundances of less than 10% (average 2–5%). Modeling of variations of δ¹⁸O with other geochemical variables further indicates that the enriched component is not derived from incorporation of sediment or bulk altered oceanic crust, from metasomatism of the mantle by hydrous or carbonate-rich fluids, or from partial melting of subducted sediment. Instead, the data appear to require a model in which the enriched component is depleted mantle that has been metasomatized by small-degree partial melts of subducted, dehydrated, altered oceanic crust. The age of this partial melting is broadly constrained to 250 Ma. Reconstructed plate motions suggest that the enriched component in the north Atlantic mantle may have originated by subduction along the western margin of Pangea.     

Isotope and trace element geochemistry of young Pacific seamounts: implications for the scale of upper mantle heterogeneity

Basalts from young seamounts situated within 6.8 m.y. of the East Pacific Rise, between 9° and 14°N latitude, display significant variations in ¹⁴³Nd/¹⁴⁴Nd (0.51295–0.51321), ⁸⁷Sr/⁸⁶Sr (0.7025–0.7031), and(La/Sm)_N (0.415–3.270). Nd and Sr isotope ratios are anti-correlated and form a trend roughly parallel to the “mantle array” on a¹⁴³Nd/¹⁴⁴Nd vs.⁸⁷Sr/⁸⁶Sr variation diagram. Nd and Sr isotope ratios display negative and positive correlations, respectively, with(La/Sm)_N. The geochemical variations observed at the seamounts are nearly as great or greater than those observed over several hundred kilometers of the Reykjanes Ridge, or at the islands of Iceland or Hawaii.

Samples from one particular seamount, Seamount 6, display nearly the entire observed range of chemical variations, offering an ideal opportunity to constrain the nature of heterogeneities in the source mantle. Systematics indicative of magma mixing are recognized when major elements, trace elements, trace element ratios, and isotope ratios are compared with each other in all possible permutations. The source materials required to produce the end-member magmas are: (1) a typical MORB-source-depleted peridotite; and (2) a relatively enriched material which may represent ancient mantle segregations of basaltic melt, incompletely mixed remnants of subducted ocean crust, or metasomatized peridotite such as that found at St. Paul's Rocks or Zabargad Island. Due to the proximity of the seamounts to the East Pacific Rise (EPR), the source materials are thought to comprise an intimate mixture in the mantle immediately underlying the seamounts and the adjacent EPR. Lavas erupted at the ridge axis display a small range of isotopic and incompatible trace element compositions because the large degrees of melting and presence of magma chambers tend to average the chemical characteristics of large volumes of mantle.

If the postulated mantle materials, with large magnitude, small-scale heterogeneities, are ubiquitous in the upper mantle, chemical variations in basalts ranging from MOR tholeiites to island alkali basalts may reflect sampling differences rather than changes in bulk mantle chemistry.     

Trace element and Sr and Nd isotope geochemistry of peridotite xenoliths from the Eifel (West Germany) and their bearing on the evolution of the subcontinental lithosphere

Peridotite xenoliths from the Eifel can be divided into incompatible element-depleted and -enriched members. The depleted group is restricted to dry lherzolites whereas the enriched group encompasses dry harzburgites, dry websterite and amphibole and/or phlogopite-bearing peridotites. Isotopically the depleted group is very diverse with¹⁴³Nd/¹⁴⁴Nd ranging from 0.51302 to 0.51355 and⁸⁷Sr/⁸⁶Sr from 0.7041 to 0.7019, thus occupying a field larger than expected for oceanic-type subcontinental mantle. These xenoliths are derived from a mantle which appears to have diverged from a bulk-earth Nd and Sr isotopic evolution path 2 Ga ago as a consequence of partial melting. The combination of high¹⁴³Nd/¹⁴⁴Nd with high⁸⁷Sr/⁸⁶Sr in some members of the depleted-xenoliths suite is likely to be the result of incipient reaction with incompatible element-enriched fluids in the mantle. In the enriched group such reactions have proceeded further and erased any pre-enrichment isotope memory resulting in a smaller isotopic diversity (¹⁴³Nd/¹⁴⁴Nd 0.51256–0.51273,⁸⁷Sr/⁸⁶Sr 0.7044–0.7032). An evaluation of SmHf and YbHf relationships suggests that the amphibole-bearing lherzolites and harzburgites acquired their high enrichment of light rare earth elements by fluid infiltration into previously depleted peridotite rather than by silicate melt-induced metasomatism. Upper mantle composed of such metasomatized peridotites does not represent a potential source for the basanites and nephelinites from the Eifel. The isotopic and chemical diversity of the subcontinental lithospheric part of the mantle may result from it having remained isolated from the convecting mantle for times > 1 Ga.     

REE diffusion in calcite

Chemical diffusion of four rare-earth elements (La, Nd, Dy and Yb) has been measured in natural calcite under anhydrous conditions, using rare-earth carbonate powders as the source of diffusants. Experiments were run in sealed silica capsules along with finely ground calcite to ensure stability of the single-crystal samples during diffusion anneals. Rutherford backscattering spectroscopy (RBS) was used to measure diffusion profiles. The following Arrhenius relations were obtained over the temperature range 600–850°C: D_La =2.6×10⁻¹⁴ exp(−147±14 kJ mol⁻¹/RT) m² s⁻¹, D_Nd =2.4×10⁻¹⁴ exp(−150±13 kJ mol⁻¹/RT) m² s⁻¹, D_Dy =2.9×10⁻¹⁴ exp(−145±25 kJ mol⁻¹/RT) m² s⁻¹, D_Yb =3.9×10⁻¹² exp(−186±23 kJ mol⁻¹/RT) m² s⁻¹. In contrast to previous findings for refractory silicates (e.g. zircon), differences in transport rates among the REE are not pronounced over the range of temperature conditions investigated in this study. Diffusion of the REE is significantly slower than diffusion of the divalent cations Sr and Pb and slower than transport of Ca and C at temperatures above 650°C. Fine-scale zoning and isotopic and REE chemical signatures may be retained in calcites under many conditions if diffusion is the dominant process affecting alteration.     

Origin of Baotoudong syenites in North China Craton: Petrological,mineralogical and geochemical evidence

Baotoudong syenite pluton is located to the east of Baotou City, Inner Mongolia, the westernmost part of the Triassic alkaline magmatic belt along the northern margin of the North China Craton(NCC). Zircon U-Pb age, petrological, mineralogical and geochemical data of the pluton were obtained in this paper, to constrain its origin and mantle source characteristics. The pluton is composed of nepheline-clinopyroxene syenite and alkali-feldspar syenite, with zircon U-Pb age of 214.7±1.1 Ma. Diopside(cores)-aegirine-augite(rims), biotite, orthoclase and nepheline are the major minerals. The Baotoudong syenites have high contents of rare earth elements(REE), and are characterized by enrichment in light rare earth elements(LREE) and large ion lithophile elements(LILE; e.g., Rb, Ba, Sr), depletion in heavy rare earth elements(HREE) and high field strength elements(HFSE). They show enriched Sr-Nd isotopic compositions with initial ~87Sr/~86Sr ranging from 0.7061 to 0.7067 and ε_Nd(t) values from –9.0 to –11.2. Mineralogy, petrology and geochemical studies show that the parental magma of the syenites is SiO_2-undersaturated potassic-ultrapotassic, and is characterized by high contents of Ca O, Fe_2O_3, K_2O, Na_2O and fluid compositions(H_2O), and by high temperature and high oxygen fugacity. The syenites were originated from a phlogopite-rich, enriched lithospheric mantle source in garnet-stable area(80 km). The occurrence of the Baotoudong syenites, together with many other ultrapotassic, alkaline complexes of similar ages on the northern margin of the NCC in Late Triassic implies that the lithospheric mantle beneath the northern margin of the NCC was previously metasomatized by melts/fluids from the subducted, altered paleo-Mongolian oceanic crust, and the northern margin of the craton has entered into an extensively extensional regime as a destructive continental margin in Late Triassic.     

Precise Re–Os mineral isochron and Pb–Nd–Os isotope systematics of a mafic–ultramafic sill in the 2.0 Ga Onega plateau (Baltic Shield)

We present Re–Os, Sm–Nd and Pb–Pb isotope and trace element data for the Konchozero sill, a layered mafic–ultramafic intrusion in the Early Proterozoic Onega plateau, one of the oldest continental flood basalt provinces on Earth. The Sm–Nd and Pb–Pb combined mineral and whole-rock isochron ages of 1988±34 and 1985±57 Ma for the sill coincide with the age of ferropicrites from Pechenga (the Kola Peninsula). The lithostratigraphic, chemical and isotope evidence suggest the derivation of Pechenga lavas and the Onega plateau volcanics from a single mantle plume. Peridotite and gabbro whole-rock samples, and primary ulvospinel and ilmenite mineral separates from the sill yield a Re–Os isochron with a slope corresponding to an age of 1969±18 Ma, γ_Os(T) =−0.61±5.9. This age is consistent with the other isotope data, and indicates the closed-system behavior of Re and Os in the rocks. The peridotites and ulvospinel have high Os concentrations (2.5–14 ppb) and low ¹⁸⁷Re/¹⁸⁸Os ratios (0.35–1.1), thus allowing a more accurate determination of the weighted average initial ¹⁸⁷Os/¹⁸⁸Os of 0.1144±0.0019 (2σ_pop), γ_Os(T) =+0.77±1.7. This value is lower than that determined by Walker et al. (Geochim. Cosmochim. Acta 61 (1997) 3145–3160) for the Pechenga lavas (γ_Os(T) =+6.1±0.7), and implies a substantial Os-isotope heterogeneity in this ancient plume. Compared to the Onega plateau primary basalt magma, Pechenga ferropicrites are relatively enriched in iron and Ni, have lower (Nb/Th)_N ratios (2.1 vs 1.1) and less radiogenic Nd-isotope compositions (_Nd(T) = +3.1 and +1.4, respectively), but share similar low-radiogenic Pb-isotope characteristics (μ₁=8.57 and 8.60). Incorporation of small amounts (1.5%) of outer core material into the hotter central part of the plume and subsequent contamination of the Pechenga ferropicritic magmas with the 2.9 Ga Belomorian gneisses can explain the observed chemical and isotope variations in the two provinces provided that the core had <0.25 ppm of Pb.     

U,U andTh in seawater

We have developed techniques to determine²³⁸U,²³⁴U and²³²Th concentrations in seawater by isotope dilution mass spectrometry. U measurements are made using a²³³U²³⁶U double spike to correct for instrumental fractionation. Measurements on uranium standards demonstrate that²³⁴U/²³⁸U ratios can be measured accurately and reproducibly.²³⁴U/²³⁸U can be measured routinely to ± 5‰ (2σ) for a sample of 5 × 10⁹ atoms of²³⁴U (3 × 10⁻⁸ g of total U, 10 ml of seawater). Data acquisition time is 1 hour. The small sample size, high precision and short data acquisition time are superior to-counting techniques.²³⁸U is measured to ± 2‰ (2σ) for a sample of 8 × 10¹² atoms of²³⁸U ( 3 × 10⁻⁹ g of U, 1 ml of seawater).²³²Th is measured to ± 20‰ with 3 × 10¹¹²³²Th atoms (10⁻¹⁰ g²³²Th, 1 1 of seawater). This small sample size will greatly facilitate investigation of the²³²Th concentration in the oceans. Using these techniques, we have measured²³⁸U,²³⁴U and²³²Th in vertical profiles of unfiltered, acidified seawater from the Atlantic and²³⁸U and²³⁴U in vertical profiles from the Pacific. Determinations of²³⁴U/²³⁸U at depths ranging from 0 to 4900 m in the Atlantic (7°44′N, 40°43′W) and the Pacific (14°41′N, 160°01′W) Oceans are the same within experimental error (± 5‰,2σ). The average of these²³⁴U/²³⁸U measurements is 144 ± 2‰ (2σ) higher than the equilibrium ratio of 5.472 × 10⁻⁵. U concentrations, normalized to 35‰ salinity, range from 3.162 to 3.281 ng/g, a range of 3.8%. The average concentration of the Pacific samples (31°4′N, 159°1′W) is 1% higher than that of the Atlantic (7°44′N, 40°43′W and 31°49′N, 64°6′W).²³²Th concentrations from an Atlantic profile range from 0.092 to 0.145 pg/g. The observed constancy of the²³⁴U/²³⁸U ratio is consistent with the predicted range of²³⁴U/²³⁸U using a simple two-☐ model and the residence time of deep water in the ocean determined from¹⁴C. The variation in salinity-normalized U concentrations suggests that U may be much more reactive in the marine environment than previously thought.     

Martian mantle mineralogy investigated by the Lu–Hf and Sm–Nd systematics of shergottites

Chemical heterogeneities in the Martian mantle are believed to result from the crystallization of a magma ocean in the first 100 million years of its history. Shergottite meteorites from Mars are thought to retain a compositional record of such early differentiation and the resulting mineralogy at different depths. The coupled ¹⁷⁶Lu–¹⁷⁶Hf and ¹⁴⁷Sm–¹⁴³Nd isotope systematics in 9 shergottites are used here to investigate these issues. Three compositional groups in the shergottites display distinct isotope systematics. One group, commonly termed as depleted, is characterized by positive ¹⁷⁶Hf_i from + 46.2 to + 50.4 and ¹⁴³Nd_i from + 36.2 to + 39.1. Another, termed as enriched, has negative ¹⁷⁶Hf_i = − 16.5 to − 13.2 and ¹⁴³Nd_i = − 7.0 to − 6.5. The third group is intermediate between the depleted and enriched groups with positive ¹⁷⁶Hf_i = + 30.0 to + 33.4 and ¹⁴³Nd_i = + 16.9. Together, they describe mixing curves between ¹⁷⁶Hf/¹⁷⁷Hf, ¹⁴³Nd/¹⁴⁴Nd, Lu/Hf, and Sm/Nd, implying that they sample two distinct sources in the Martian mantle. All shergottites are characterized by (Sm/Nd)_source < (Sm/Nd)_sample, but (Lu/Hf)_source > (Lu/Hf)_sample. This decoupling can be explained by two successive partial melting episodes in the depleted shergottite source and localized in the Martian upper mantle. The genesis of shergottites can be modeled using non-modal equilibrium partial melting in a source initially composed of 60% olivine, 21% clinopyroxene, 9% orthopyroxene, and 10% garnet, with degrees of partial melting of 8.8% and 3.9%, respectively, for the two successive events. The enriched end-member of the shergottite mixing curve is best modeled by late-stage quenched residual melt resulting from the crystallization of a magma ocean. The depleted shergottite source may be modeled as a mixture of cumulates and residual melt, as convection in the Martian magma ocean is expected to reduce the incompatible trace element heterogeneity in the final solidified layers. Consequently, equilibrium crystallization is preferred to model the crystallization of the Martian magma ocean. The models that best explain the shergottite data are those where the magma ocean is at a depth of at least 1350 km in Mars.     

Melting rates beneath Hawaii: Evidence from uranium series isotopes in recent lavas

²³⁸U, ²³²Th, ²³⁰Th and ²²⁶Ra abundances have been measured in six samples of recent Hawaiian basalt by high precision mass spectrometry, in an attempt to compare the melting process in plumes and at spreading ridges. The data reveal a very small range in (²³⁰Th/²³⁸U) activity ratio up to a maximum value of 1.02 ± 0.01, and (²²⁶Ra/²³⁰Th) activity ratios which lie between 1.10 ± 0.015 and 1.19 ± 0.02. UTh and RaTh abundances are linearly correlated demonstrating that the disequilibria predate crystallisation and differentiation. Using recently published estimates for the bulk partition coefficients of U and Th, the results are consistent with melting rates > 10⁻³ kg m⁻³ a⁻¹ at porosities < 10⁻³ for dynamic fractional melting in the garnet stability field.     

Ferrobasalts from the Spiess Ridge segment of the Southwest Indian Ridge

Highly vesicular, microporphyritic basaltic rocks have been dredged from the slow-spreading Spiess Ridge segment of the Southwest Indian Ridge. All the samples recovered are hyalocrystalline with plagioclase, clinopyroxene and olivine as phenocryst and microphenocryst phases. Titanomagnetite occurs as euhedral microphenocrysts in some of the more evolved samples. In terms of bulk rock and quench glass chemistry the lavas are characterised by highly evolved compositions(e.g. FeO*=10.3−14.2%;TiO₂=2.0−3.4%;K₂O=0.50−1.1%;MgO=6.0−3.5%;Zr=160−274ppm;Nb=14−32ppm) and can be classified as ferrobasalts. Isotopic and incompatible element ratios of the lavas(e.g.⁸⁷Sr/⁸⁶Sr=0.70325−0.70333;Zr/Nb=8.4−11.3;Y/Nb=2.3−1.4) indicate their strongly “enriched” nature (see also Dickey et al. [6]).

Quantitative major and trace element modelling indicates that most of the compositional variations observed can be attributed to low-pressure fractional crystallisation of plagioclase, clinopyroxene and minor olivine and titanomagnetite. The range in composition can be accounted for by up to 65% fractional crystallisation.

We suggest that the extreme differentiation of the Spiess Ridge lavas is related not to spreading rate, but to rate of magma supply. The basaltic melts appear to have evolved in a newly established zone of magmatic activity, associated with the most recent northward jump of the Bouvet triple junction, where they were effectively isolated from significant admixture of primitive magmas.     

Uranium and thorium diffusion in diopside

This paper presents new experimental data on the tracer diffusion rates of U and Th in diopside at 1 atm and 1150–1300°C. Diffusion couples were prepared by depositing a thin layer of U–Th oxide onto the polished surface of a natural diopside single crystal, and diffusion profiles were measured by ion microprobe depth profiling. For diffusion parallel to [001] the following Arrhenius relations were obtained: log₁₀D_U=(−5.75±0.98)−(418±28 kJ/mol)/2.303RT log₁₀D_Th=(−7.77±0.92)−(356±26 kJ/mol)/2.303RT. The diffusion data are used to assess the extent to which equilibrium is obtained during near fractional melting of a high-Ca pyroxene bearing mantle peridotite. We find that the diffusion rates for both elements are slow and that disequilibrium between solid and melt will occur under certain melting conditions. For near-fractional adiabatic decompression melting at ascent rates >3 cm/yr, high-Ca pyroxene will exhibit disequilibrium effects. High-Ca pyroxene will become zoned in U and Th and the melts extracted will be depleted in these incompatible elements relative to melts produced by equilibrium fractional melting. U and Th diffusivities in high-Ca pyroxene are similar, and diffusive fractionation of these elements will be limited. Numerical solutions to a dynamic melting model with diffusion-controlled chemical equilibration indicate that the activity ratio [²³⁰Th/²³⁸U] in a partial melt of spinel peridotite will be slightly less than 1 for a broad range of melting parameters. This result reinforces the already widely accepted conclusion that melting of spinel peridotite cannot account for ²³⁰Th excesses in mid-ocean ridge and ocean island basalts, and that garnet must therefore be present over part of the melting column.     

Isotope geochemistry of Pantelleria volcanic fluids, Sicily Channel rift: a mantle volatile end-member for volcanism in southern Europe

Chemical and isotopic ratio (He, C, H and O) analysis of hydrothermal manifestations on Pantelleria island, the southernmost active volcano in Italy, provides us with the first data upon mantle degassing through the Sicily Channel rift zone, south of the African–European collision plate boundary. We find that Pantelleria fluids contain a CO₂–He-rich gas component of mantle magmatic derivation which, at shallow depth, variably interacts with a main thermal (100°C) aquifer of mixed marine–meteoric water. The measured ³He/⁴He ratios and δ¹³C of both the free gases (4.5–7.3 R_a and −5.8 to −4.2‰, respectively) and dissolved helium and carbon in waters (1.0–6.3 R_a and −7.1 to −0.9‰), together with their covariation with the He/CO₂ ratio, constrain a ³He/⁴He ratio of 7.3±0.1 R_a and a δ¹³C of ca. −4‰ for the magmatic end-member. These latter are best preserved in fluids emanating inside the active caldera of Pantelleria, in agreement with a higher heat flow across this structure and other indications of an underlying crustal magma reservoir. Outside the caldera, the magmatic component is more affected by air dilution and, at a few sites, by mixing with either organic carbon and/or radiogenic ⁴He leached from the U–Th-rich trachytic host rocks of the aquifer. Pantelleria magmatic end-member is richer in ³He and has a lower (closer to MORB) δ¹³C than all fluids yet analyzed in volcanic regions of Italy and southern Europe, including Mt. Etna in Sicily (6.9±0.2 R_a, δ¹³C=−3±1‰). This observation is consistent with a south to north increasing imprint of subducted crustal material in the products of Italian volcanoes, whose He and C (but also O and Sr) isotopic ratios gradually evolve towards crustal values northward of the African–Eurasian plate collision boundary. Our results for Pantelleria extend this regional isotopic pattern further south and suggest the presence of a slightly most pristine or ‘less contaminated’, ³He-richer mantle source beneath the Sicily Channel rift zone. The lower than MORB ³He/⁴He ratio but higher than MORB CO₂/³He ratio of Pantelleria volatile end-member are compatible with petro-geochemical evidence that this mantle source includes an upwelling HIMU–EM1-type asthenospheric plume component whose origin, according to recent seismic data, may be in the lower mantle.     

The early Paleozoic carbon cycle

A review of O, C, Sr and S isotope trends for the entire Phanerozoic shows that the present-day values of isotope signals are similar to those at the Proterozoic termination. The sharp rise in ⁸⁷Sr/⁸⁶Sr since 65 Ma has been attributed to an uplift and subsequent metamorphism and erosion associated with the Himalayas and Tibet. This orogenic evolution has been postulated to have influenced the global organic and inorganic carbon cycles and climate as well. A similar large-scale orogeny, the Pan-African event, also dominated the Neoproterozoic (Vendian) times, and the similarity of modern and Neoproterozoic isotope values for seawater may therefore have had a comparable tectonic cause. In this contribution, we present the results of a numerical model of the coupled C–alkalinity–S–Sr cycles suggesting that the early Paleozoic (from early Cambrian to late Devonian) evolution of Sr, O, C and S seawater isotope signals could have been the consequence of progressive oxidation of a large reduced carbon reservoir exhumed during the Pan-African orogeny. The δ¹⁸O measured in brachiopod shells is used as a forcing of the model, postulating that any change in the oxygen isotopic composition of seawater is the result of a disequilibrium in the organic carbon subcycle through the coupling of the oxygen isotopic and carbon cycles. The calculated δ¹³C, ⁸⁷Sr/⁸⁶Sr and δ³⁴S are in good agreement with the data, as is the reasonable calculated history for atmospheric pCO₂ and its relation to global climate.     

Carbon isotopes in submarine basalts

High-sensitivity stepped extraction reveals two isotopically distinct forms of carbon in submarine basalt glasses: an isotopically light carbon component released by combustion from 200 to 600°C and an isotopically heavy CO₂ liberated from vesicles (magmatic carbon) from 600 to 1200°C. The δ¹³C_PDB of the low release temperature carbon varies from −24 to −30‰ and is believed to be surficial organic contamination. A survey of various types of oceanic glasses demonstrates that the δ¹³C of magmatic CO₂ varies from −4.2 to −7.5‰ in mid-ocean ridge basalt (MORB), from −2.8 to −6.7‰ in glasses from Hawaii and Explorer Seamount and from −7.7 to −16.3‰ in glasses from the Scotia Sea and Mariana Trough. Magmatic CO₂ in back-arc basin basalts (BABB) is on average 5‰ lighter than equivalent CO₂ in MORB and can be explained by the mixing in the source regions for BABB magmas of juvenile (MORB-like) CO₂ with an organic carbon component from subducted pelagic sediments. It is inferred that significant amounts of pelagic carbonate carbon (δ¹³C 0‰) must be recycled into the mantle.     

The Vendian record of Sr and C isotopic variations in seawater: Implications for tectonics and paleoclimate

New Sr and C isotopic data, both obtained on the same samples of marine carbonates, provide a relatively detailed record of isotopic variation in seawater through the latest Proterozoic and allow, for the first time, direct correlation of these isotopic changes in the Vendian ( 540–610 Ma). The strong isotope variations determined in this study record significant environmental and tectonic changes. Together with a fairly poorly constrained Nd isotopic record, the Sr and C isotopic records can be used to constrain rates of erosion, hydrothermal alteration and organic C burial. Further, comparison of these records with those of the Cenozoic permit investigation of the general relationship between global tectonics and continental glaciation. In particular, results of this study show a very large change in the ⁸⁷Sr/⁸⁶Sr of marine carbonates from low pre-Vendian ( > 610 Ma) values ( 0.7066) to high Middle Cambrian values ( 0.7090). This change is greater in magnitude than the significant increase in seawater ⁸⁷Sr/⁸⁶Sr through the Cenozoic. Both changes are attributed to high erosion rates associated with continent-continent collisions (Pan-African and Himalayan-Tibetan). In the latest Proterozoic these high erosion rates, probably coupled with high organic productivity and anoxic bottom-water conditions, contributed to a significant increase in the burial rate of organic C. Ice ages mark both the Neoproterozoic and Cenozoic, but different stratigraphic relationships between the Sr isotopic increase and continental glaciation indicate that uplift-driven models proposed to explain Cenozoic climatic change cannot account for the latest Proterozoic ice ages.     

Helium isotope geochemistry of mid-ocean ridge basalts from the South Atlantic

We report new helium isotope results for 49 basalt glass samples from the Mid-Atlantic Ridge between 1°N and 47°S.³He/⁴He in South Atlantic mid-ocean ridge basalts (MORB) varies between 6.5 and 9.0 R_A (R_A is the atmospheric ratio of1.39 × 10⁻⁶), encompassing the range of previously reported values for MORB erupted away from high³He/⁴He hotspots such as Iceland. He, Sr and Pb isotopes show systematic relationships along the ridge axis. The ridge axis is segmented with respect to geochemical variations, and local spike-like anomalies in³He/⁴He, Pb and Sr isotopes, and trace element ratios such as(La/Sm)_N are prevalent at the latitudes of the islands of St. Helena, Tristan da Cunha and Gough to the east of the ridge. The isotope systematics are consistent with injection beneath the ridge of mantle “blobs” enriched in radiogenic He, Pb and Sr, derived from off-axis hotspot sources. The variability in³He/⁴He along the ridge can be used to refine the hotspot source-migrating-ridge sink model.

MORB from the 2–7°S segment are systematically the least radiogenic samples found along the mid-ocean ridge system to date. Here the depleted mantle source is characterized by⁸⁷Sr/⁸⁶Sr of 0.7022, Pb isotopes close to the geochron and with²⁰⁶Pb/²⁰⁴Pb of 17.7, and³He/⁴He of 8.6–8.9 R_A. The “background contamination” of the subridge mantle, by radiogenic helium derived from off-ridge hotspots, displays a maximum between 20 and 24°S. The HePb and HeSr isotope relations along the ridge indicate that the³He/⁴He ratios are lower for the hotspot sources of St. Helena, Tristan da Cunha and Gough than for the MORB source, consistent with direct measurements of³He/⁴He ratios in the island lavas. Details of the HeSrPb isotope systematics between 12 and 22°S are consistent with early, widespread dispersion of the St. Helena plume into the asthenosphere, probably during flattening of the plume head beneath the thick lithosphere prior to continental breakup. The geographical variation in theHe/Pbratio deduced from the isotope systematics suggests only minor degassing of the plume during this stage. Subsequently, it appears that the plume component reaching the mid-Atlantic ridge was partially outgassed of He during off-ridge hotspot volcanism and related melting activity.

Overall, the similar behavior of He and Pb isotopes along the ridge indicates that the respective mantle sources have evolved under conditions which produced related He and Pb isotope variations.