High-MgO lavas associated to CFB as indicators of plume-related thermochemical effects: the case of ultra-titaniferous picrite-basalt from the Northern Ethiopian-Yemeni plateau

A comprehensive petrological and geochemical dataset is reported in order to define the thermo-compositional characteristics of Ti (Fe)-enriched picrite-basalt lavas (HT2, TiO2 3-7 wt%), erupted close to the axial zone of the inferred Afar mantle plume, at the centre of the originally continuous Ethiopian-Yemeni CFB plateau (ca. 30Ma) which is zonally arranged with progressively lower Ti basalts (HT1, TiO2 2-4 wt%; LT, TiO2 1-3 wt%) toward the periphery. Integrated petrogenetic modelling based on major and trace element analyses of bulk rocks, minerals and melt inclusions in olivines, as well as Sr-Nd-Pb-He-O isotope compositional variations enables us to make several conclusions. 1) The phase equilibria constraints indicate that HT2 primary picrites were generated at ca. 1570°C mantle potential temperatures (Tp) in the pressure range 4-5 GPa whereas the HT1 and LT primary melts formed at shallower level (< 2 to 3 GPa, Tp 1530 °C for HT1 and 1430°C for LT). Thus the Afar plume head was a thermally and compositionally zoned melting region with maximum excess temperatures of 300-350°C with respect to the ambient mantle. 2) The HT2 primary melts upwelled nearly adiabatically to the base of the continental crust (ca. 1 GPa) where fractionation of olivine, followed by clinopyroxene, led to variably differentiated picritic and basaltic magmas. 3) Trace element modelling requires that the primary HT2 melts were generated - either by fractional or batch melting (F 9-10%) - from a mixed garnet peridotite source (85%) with 15% eclogite (derived from transitional MORB protoliths included in Panafrican terranes) that has to be considered a specific Ti-Fe and incompatible element enriched component entrained by the Afar plume. 4) The LT, HT1 and HT2 lavas have 143Nd/144Nd = 0.5131-0.5128, whereas Sr-Pb isotopes are positively correlated with TiO2, varying from 87 Sr/86Sr 0.7032 and 206Pb/204Pb 18.2 in LT basalts to 87Sr/86Sr 0.7044 and 206Pb/204Pb 19.4 in HT2 picrite-basalts. High 3He/4He (15-20 RA) ratios are exclusively observed in HT2 lavas, confirming earlier evidence that these magmas require a component of deep mantle in addition to eclogite, while the LT basalts may more effectively reflect the signature of the pre-existing mantle domains. The comparison between high-MgO (13-22%) lavas from several Phanerozoic CFB provinces (Karoo, Paranà-Etendeka, Emeishan, Siberia, Deccan, North Atlantic Province) shows that they share extremely high mantle potential temperatures (Tp 1550-1700°C) supporting the view that hot mantle plumes are favoured candidates for triggering many LIPs. However, the high incompatible element and isotopic variability of these high-MgO lavas (and associated CFB) suggest that plume thermal anomalies are not necessarily accompanied by significant and specific chemical effects, which depend on the nature of mantle materials recycled during the plume rise, as well as by the extent of related mantle enrichments (if any) on the pre-existing lithospheric section

Potassium Stable Isotopic Compositions Measured by High-Resolution MC-ICP-MS

Potassium isotopic (K-41/K-39) compositions are notoriously difficult to measure. TIMS measurements are hindered by variable fractionation patterns throughout individual runs and too few isotopes to apply an internal spike method for instrumental mass fractionation corrections. Internal fractionation corrections via the K-40/K-39 ratio can provide precise values but assume identical K-40/K-39 ratios (e.g. 0.05% (1sigma) in [1]); this is appropriate in some cases (e.g. identifying excess K-41) but not others (e.g., determining mass fractionation effects and metrologically traceable isotopic abundances). SIMS analyses have yielded measurements with 0.25% precisions (1sigma) [2]. ICP-MS analyses are significantly affected by interferences from molecular species such as Ar-38H(+) and Ar-40H(+) and instrument mass bias. Single collector ICP-MS instruments in "cold plasma" mode have yielded uncertainties as low as 2% (1sigma, e.g. [3]). Although these precisions may be acceptable for some concentration determinations, they do not resolve isotopic variation in terrestrial materials. Here we present data from a series of measurements made on the Thermo Scientific NEPTUNE Plus multi-collector ICP-MS that demonstrate the ability to make K-41/K-39 ratio measurements with 0.07% precisions (1sigma). These data, collected on NIST K standards, indicate the potential for MC-ICP-MS measurements to look for K isotopic variations at the sub-permil level. The NEPTUNE Plus can sufficiently resolve 39K and 41K from the interfering 38ArH+ and 40ArH+ peaks in wet cold plasma and high-resolution mode. Measurements were made on small but flat, interference-free, plateaus (ca. 50 ppm by mass width for K-41). Although ICP-MS does not yield accurate K-41/K-39 values due to significant instrumental mass fractionation (ca. 6%), this bias can be sufficiently stable over the time required for several measurements so that relative K-41/K-39 values can be precisely determined via sample-standard bracketing. As cold plasma conditions can amplify matrix effects, experiments were conducted to test the matrix tolerance of measurements; the use of clean, matrix-matched samples and standards is critical. Limitations of the cold-plasma high-resolution MC-ICP-MS methodology with respect to matrix tolerance are discussed and compared with the limitations of TIMS methodologies

Assessing depleted uranium (DU) contamination of soil, plants and earthworms at UK weapons testing sites

Depleted uranium (DU) weapons testing programmes have been conducted at two locations within the UK. An investigation was therefore carried out to assess the extent of any environmental contamination arising from these test programmes using both alpha spectrometry and mass spectrometry techniques. Uranium isotopic signatures indicative of DU contamination were observed in soil, plant and earthworm samples collected in the immediate vicinity of test firing points and targets, but contamination was found to be localised to these areas. The paper demonstrates the superiority of the 235U:238U ratio over the 234U:238U ratio for identifying and quantifying DU contamination in environmental samples and also describes the respective circumstances under which alpha spectrometry or mass spectrometry may be the more appropriate analytical tool

Petrogenesis of the Loch Bà ring-dyke and Centre 3 granites, Isle of Mull, Scotland

The project was supported by Science Foundation Ireland (SFI), the Royal Irish Academy (RIA) and by the Swedish Research Council (VR). Open Access funding provided by Uppsala University.The Loch Bà ring-dyke and the associated Centre 3 granites represent the main events of the final phase of activity at the Palaeogene Mull igneous complex. The Loch Bà ring-dyke is one of the best exposed ring-intrusions in the world and records intense interaction between rhyolitic and basaltic magma. To reconstruct the evolutionary history of the Centre 3 magmas, we present new major- and trace-element, and new Sr isotope data as well as the first Nd and Pb isotope data for the felsic and mafic components of the Loch Bà intrusion and associated Centre 3 granites. We also report new Sr, Nd and Pb isotope data for the various crustal compositions from the region, including Moine and Dalradian metasedimentary rocks, Lewisian gneiss, and Iona Group metasediments. Isotope data for the Loch Bà rhyolite (87Sr/86Sri = 0.716) imply a considerable contribution of local Moine-type metasedimentary crust (87Sr/86Sr = 0.717–0.736), whereas Loch Bà mafic inclusions (87Sr/86Sri = 0.704–0.707) are closer to established mantle values, implying that felsic melts of dominantly crustal origin mixed with newly arriving basalt. The Centre 3 microgranites (87Sr/86Sri = 0.709–0.716), are less intensely affected by crustal assimilation relative to the Loch Bá rhyolite. Pb-isotope data confirm incorporation of Moine metasediments within the Centre 3 granites. Remarkably, the combined Sr–Nd–Pb data indicate that Centre 3 magmas record no detectable interaction with underlying deep Lewisian gneiss basement, in contrast to Centre 1 and 2 lithologies. This implies that Centre 3 magmas ascended through previously depleted or insulated feeding channels into upper-crustal reservoirs where they resided within and interacted with fertile Moine-type upper crust prior to eruption or final emplacement.Publisher PDFPeer reviewe

Stratigraphy of Cretaceous to Lower Pliocene sediments in the northern part of Cyprus based on comparative 87Sr/86Sr isotopic, nannofossil and planktonic foraminiferal dating

New age data from Sr isotope analysis and both planktonic foraminifera and nannofossils are presented and discussed here for the Upper Eocene–Upper Miocene sedimentary rocks of the Değirmenlik (Kythrea) Group. New dating is also given of some Cretaceous and Pliocene sediments. In a revised stratigraphy the Değirmenlik (Kythrea) Group is divided into ten formations. Different Upper Miocene formations are developed to the north and south of a regionally important, E–W-trending syn-sedimentary fault. The samples were dated wherever possible by three independent methods, namely utilizing Sr isotopes, calcareous nannofossils and planktonic foraminifera. Some of the Sr isotopic dates are incompatible with the nannofossil and/or the planktonic foraminiferal dates. This is mainly due to reworking within gravity-deposited or current-affected sediments. When combined, the reliable age data allow an overall biostratigraphy and chronology to be erected. Several of the boundaries of previously defined formations are revised. Sr data that are incompatible with well-constrained biostratigraphical ages are commonly of Early Miocene age. This is attributed to a regional uplift event located to the east of Cyprus, specifically the collision of the Anatolian (Eurasian) and Arabian (African) plates during Early Miocene time. This study, therefore, demonstrates that analytically sound Sr isotopic ages can yield geologically misleading ages, particularly where extensive sediment reworking has occurred. Convincing ages are obtained when isotopic dating is combined with as many forms of biostratigraphical dating as possible, and this may also reveal previously unsuspected geological events (e.g. tectonic uplift or current activity)

Age constraints on intra-formational unconformities in Upper Jurassic-Lower Cretaceous carbonates in northeast Turkey; geodynamic and hydrocarbon implications

Upper Jurassic-lowermost Cretaceous carbonate build-ups are imaged on seismic data in the Black Sea. They form important, untested, hydrocarbon reservoirs that are the focus of active exploration. Outcrop analogues to these build-ups around the Black Sea contain a series of subaerial exposure surfaces. The hiatuses associated with a number of these subaerial exposure surfaces have been dated in a well exposed Callovian or Upper Oxfordian to Barremian shallow-water inner platform carbonate succession (the Berdiga Formation) in the Eastern Pontides using strontium isotope stratigraphy and foraminiferal biostratigraphy. They span the latest Kimmeridgian to Tithonian or Berriasian, and the Hauterivian to Barremian. Less well constrained, but broadly contemporaneous stratigraphic gaps in multiple successions around the Black Sea provide additional insights and point to a regional driving mechanism. The timing of hiatus formation does not correspond to periods of eustatic lowstand. It does coincide, however, with Late Tithonian to Berriasian and Hauterivian to Early Aptian episodes of rifting in the Greater Caucasus Basin, located farther to the north. Thus, it is possible that subaerial exposure was caused by rift flank uplift during periods of regional extension. Uplift due to slab break off is discounted as a control because it post-dates (rather than pre-dates) locally developed Kimmeridgian magmatism. Rift-flank uplift is likely to have also affected carbonate build-ups on the intervening rift shoulders of the eastern Black Sea, the Shatskiy Ridge and the Mid Black Sea High. At outcrop, subaerial exposure is often associated with karstification and secondary porosity development. Similar processes may have occurred in the offshore helping to enhance the reservoir quality of these exploration targets

Extremely high He isotope ratios in MORB-source mantle from the proto-Iceland plume

The high <sup>3</sup>He/<sup>4</sup>He ratio of volcanic rocks thought to be derived from mantle plumes is taken as evidence for the existence of a mantle reservoir that has remained largely undegassed since the Earth's accretion. The helium isotope composition of this reservoir places constraints on the origin of volatiles within the Earth and on the evolution and structure of the Earth's mantle. Here we show that olivine phenocrysts in picritic basalts presumably derived from the proto-Iceland plume at Baffin Island, Canada, have the highest magmatic <sup>3</sup>He/<sup>4</sup>He ratios yet recorded. A strong correlation between <sup>3</sup>He/<sup>4</sup>He and <sup>87</sup>Sr/<sup>86</sup>Sr, <sup>143</sup>Nd/<sup>144</sup>Nd and trace element ratios demonstrate that the <sup>3</sup>He-rich end-member is present in basalts that are derived from large-volume melts of depleted upper-mantle rocks. This reservoir is consistent with the recharging of depleted upper-mantle rocks by small volumes of primordial volatile-rich lower-mantle material at a thermal boundary layer between convectively isolated reservoirs. The highest <sup>3</sup>He/<sup>4</sup>He basalts from Hawaii and Iceland plot on the observed mixing trend. This indicates that a <sup>3</sup>He-recharged depleted mantle (HRDM) reservoir may be the principal source of high <sup>3</sup>He/<sup>4</sup>He in mantle plumes, and may explain why the helium concentration of the 'plume' component in ocean island basalts is lower than that predicted for a two-layer, steady-state model of mantle structure

Bacterial dissolution of fluorapatite as a possible source of elevated dissolved phosphate in the environment

In order to understand the contribution of geogenic phosphorus to lake eutrophication, we have investigated the rate and extent of fluorapatite dissolution in the presence of two common soil bacteria (Pantoea agglomerans and Bacillus megaterium) at T = 25 °C for 26 days. The release of calcium (Ca), phosphorus (P), and rare earth elements (REE) under biotic and abiotic conditions was compared to investigate the effect of microorganism on apatite dissolution. The release of Ca and P was enhanced under the influence of bacteria. Apatite dissolution rates obtained from solution Ca concentration in the biotic reactors increased above error compared with abiotic controls. Chemical analysis of biomass showed that bacteria scavenged Ca, P, and REE during their growth, which lowered their fluid concentrations, leading to apparent lower release rates. The temporal evolution of pH in the reactors reflected the balance of apatite weathering, solution reactions, bacterial metabolism, and potentially secondary precipitation, which was implied in the variety of REE patterns in the biotic and abiotic reactors. Light rare earth elements (LREE) were preferentially adsorbed to cell surfaces, whereas heavy rare earth elements (HREE) were retained in the fluid phase. Decoupling of LREE and HREE could possibly be due to preferential release of HREE from apatite or selective secondary precipitation of LREE enriched phosphates, especially in the presence of bacteria. When corrected for intracellular concentrations, both biotic reactors showed high P and REE release compared with the abiotic control. We speculate that lack of this correction explains the conflicting findings about the role of bacteria in mineral weathering rates. The observation that bacteria enhance the release rate of P and REE from apatite could account for some of the phosphorus burden and metal pollution in aquatic environments

Triple oxygen isotopic composition of the high-³He/⁴He mantle

Measurements of Xe isotope ratios in ocean island basalts (OIB) suggest that Earth’s mantle accreted heterogeneously, and that compositional remnants of accretion are sampled by modern, high-3He/4He OIB associated with the Icelandic and Samoan plumes. If so, the high-3He/4He source may also have a distinct oxygen isotopic composition from the rest of the mantle. Here, we test if the major elements of the high-3He/4He source preserve any evidence of heterogeneous accretion using measurements of three oxygen isotopes on olivine from a variety of high-3He/4He OIB locations. To high precision, the Δ17O value of high-3He/4He olivines from Hawaii, Pitcairn, Baffin Island and Samoa, are indistinguishable from bulk mantle olivine (Δ17OBulk Mantle − Δ17OHigh 3He/4He olivine = −0.002 ± 0.004 (2 × SEM)‰). Thus, there is no resolvable oxygen isotope evidence for heterogeneous accretion in the high-3He/4He source. Modelling of mixing processes indicates that if an early-forming, oxygen-isotope distinct mantle did exist, either the anomaly was extremely small, or the anomaly was homogenised away by later mantle convection. The δ18O values of olivine with the highest 3He/4He ratios from a variety of OIB locations have a relatively uniform composition (∼5‰). This composition is intermediate to values associated with the depleted MORB mantle and the average mantle. Similarly, δ18O values of olivine from high-3He/4He OIB correlate with radiogenic isotope ratios of He, Sr, and Nd. Combined, this suggests that magmatic oxygen is sourced from the same mantle as other, more incompatible elements and that the intermediate δ18O value is a feature of the high-3He/4He mantle source. The processes responsible for the δ18O signature of high-3He/4He mantle are not certain, but δ18O–87Sr/86Sr correlations indicate that it may be connected to a predominance of a HIMU-like (high U/Pb) component or other moderate δ18O components recycled into the high-3He/4He source