Geochemical Perspectives Letters is an internationally peer-reviewed journal of the European Association of Geochemistry, produced by and for the geochemical community:
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Magnetotactic bacteria as a new model for P sequestration in the ferruginous Lake Pavin

The role of microorganisms in the geochemical cycle of P has received great interest in the context of enhanced biological phosphorus removal and phosphorite formation. Here, we combine scanning and transmission electron microscopies, confocal laser scanning microscopy and synchrotron-based x-ray microfluorescence to analyse the distribution of P at the oxic-anoxic interface in the water column of the ferruginous Lake Pavin. We show that magnetotactic bacteria of the Magnetococcaceae family strongly accumulate polyphosphates and appear as P hotspots in the particulate fraction at this depth. This high accumulation may be characteristic of this family and may also relate to the chemical conditions prevailing in the lake. As a result, these magnetotactic cocci can be considered as new models playing a potentially important role in the P geochemical cycle, similar to sulphide oxidising bacteria such as Thiomargarita and Beggiatoa but thriving in a ferruginous, poorly sulphidic environment.

S. Rivas-Lamelo, K. Benzerara, C.T. Lefèvre, C.L. Monteil, D. Jézéquel, N. Menguy, E. Viollier, F. Guyot, C. Férard, M. Poinsot, F. Skouri-Panet, N. Trcera, J. Miot, E. Duprat

Geochem. Persp. Let. (2017) 5, 35–41 | doi: 10.7185/geochemlet.1743 | Published 15 November 2017

Tin isotopic fractionation during igneous differentiation and Earth’s mantle composition

Tin exists both under the 2+ and 4+ oxidation states in igneous systems, and thus its geochemical behaviour changes as a function of oxygen fugacity. To characterise the redox state of Sn during magmatic differentiation and how this affects its isotope composition, we have measured Sn isotopic and elemental abundances in a suite of samples from the Kilauea Iki lava lake. Sn behaves as a highly incompatible element during fractional crystallisation. Lattice strain modelling shows that Sn2+ has mineral-melt partition coefficients (Dmin/melt) ≈1 in plagioclase and clinopyroxene, whereas it is highly incompatible in all phases save for ilmenite, attesting to the sole presence of Sn4+ in basaltic liquid at the Fayalite-Magnetite-Quartz (FMQ) buffer. Furthermore, Sn isotopes are unfractionated during crystallisation of silicates, but decrease to lighter values upon ilmenite precipitation. Isotopic fractionation is onset by the coordination change between Sn4+ in the melt (6- to 8-fold) and ilmenite (6-fold). The Sn isotope composition of komatiites, which are high degree, high temperature partial melts are used to estimate the Sn isotope composition of the bulk silicate Earth (BSE). Komatiites have δ122Sn within the range of the basalts (before ilmenite precipitation) and together provide the best estimate of the BSE of 0.49 ± 0.11 ‰ (2 s.d., n = 9).

N. Badullovich, F. Moynier, J. Creech, F.-Z. Teng, P.A. Sossi

Geochem. Persp. Let. (2017) 5, 24–28 | doi: 10.7185/geochemlet.1741 | Published 15 November 2017

A geochemical link between plume head and tail volcanism

Geodynamical models of mantle plumes often invoke initial, high volume plume ‘head’ magmatism, followed by lower volume plume ‘tails’. However, geochemical links between plume heads, represented by flood basalts such as the Deccan Traps, and plume tails, represented by ocean islands such as La Réunion, are ambiguous, challenging this classical view of mantle plume theory. Using Sr-Nd-Os isotope data, we demonstrate a geochemical link between archetypal plume head and tail volcanism in the Réunion hotspot. Similar plume head-tail relationships have not been definitively shown in previous geochemical studies for Réunion or other global hotspots. Such a link is enabled by use of compatible elements, such as Os, which can circumvent complexities introduced by magmatic assimilation of crust or lithosphere because these elements are scarce in crust compared to primary mantle melts. We calculate Sr-Nd-Os isotopic compositions for the Réunion primary magma and find these are identical to predictions for the Deccan primary magma. Our result provides geochemical evidence for a temporally stable mantle plume that samples a primitive reservoir associated with the African large low-shear-velocity province and with a heritage beginning at the Cretaceous-Palaeogene boundary.

B.J. Peters, J.M.D. Day

Geochem. Persp. Let. (2017) 5, 29–34 | doi: 10.7185/geochemlet.1742 | Published 3 November 2017

FeTiMM – A new oxybarometer for mafic to felsic magmas

The oxidation state of magmas is a key parameter that is notoriously difficult to reconstruct. The most common approach is via magnetite–ilmenite oxybarometry. However, many natural magmas do not contain ilmenite, preventing application of this technique. Here we present a new method that allows fO2 to be reconstructed based on the partitioning of Fe and Ti between magnetite and silicate melt. The new method, which we call FeTiMM, is applicable to both ilmenite-free and ilmenite-bearing samples, and even to slowly cooled intrusive rocks such as granites. FeTiMM was calibrated on 109 experiments covering a wide range of oxygen fugacities, temperatures, pressures and silicate melts ranging from basaltic to rhyolitic composition, and returned fO2 values that agree within 0.5 log units with independently constrained fO2 values in all but five cases. A first test on 19 natural samples of dacitic to rhyolitic compositions was equally successful. FeTiMM thus opens the door for numerous new applications in various disciplines of Earth Sciences, including the fields of volcanology, igneous petrology, experimental geochemistry and ore geology.

R. Arató, A. Audétat

Geochem. Persp. Let. (2017) 5, 19–23 | doi: 10.7185/geochemlet.1740 | Published 25 October 2017

Nickel accelerates pyrite nucleation at ambient temperature

Chemical and isotopic compositions of pyrites are used as biogeochemical tracers in Archean to modern sediments. Moreover, pyrite formation from monosulphide precursors has been proposed to be involved in prebiotic chemistry. However, the factors controlling pyrite formation and distribution in the sedimentary record are incompletely understood. Here, we show that Ni2+ ions accelerate ~5 times the nucleation of pyrite at ambient temperature. Using Fe and Ni K-edge EXAFS and TEM-EDXS we demonstrate that Ni(II) is directly involved in the nucleation of pyrite synthesised by reacting Fe(III) with Na2S in the presence of aqueous Ni(II) impurity. Initial formation of a Ni-enriched pyrite core is followed by overgrowth of a Ni-depleted pyrite shell, leading to compositional zoning of the Fe1-xNixS2 nanocrystals (x = 0.05 to 0.0004). The molar Ni/Fe ratio in the final aqueous solution was then 2000 times lower than the starting ratio of 0.01. This enhanced and accelerated trapping of Ni by pyrite could be of prime importance in controlling Ni concentration in the ocean during early diagenesis of marine sediments, and could thus have important implications for interpreting abundances of Ni and pyrite in the sedimentary record. In addition, acceleration of pyrite nucleation in the presence of nickel could help understanding the role of Fe-Ni sulphides in catalysing potential prebiotic reactions.

G. Morin, V. Noël, N. Menguy, J. Brest, B. Baptiste, M. Tharaud, G. Ona-Nguema, M. Ikogou, E. Viollier, F. Juillot

Geochem. Persp. Let. (2017) 5, 6–11 | doi: 10.7185/geochemlet.1738 | Published 18 October 2017

Rapid decrease of MgAlO2.5 component in bridgmanite with pressure

The solubility of the MgAlO2.5 component in bridgmanite was measured at pressures of 27, 35 and 40 GPa and a temperature of 2000 oK using an ultra-high pressure multi-anvil press. Compositional analysis of recovered samples demonstrated that the MgAlO2.5 component decreases with increasing pressure, and approaches virtually zero at 40 GPa. Above this pressure, the MgAlO2.5 component, i.e. the oxygen-vacancy substitution, becomes negligible, and Al is incorporated in bridgmanite by the charge-coupled substitution only. These results are supported by the volume change associated with the change from the oxygen-vacancy substitution to charge-coupled substitution. The present result may explain the seismically observed slab stagnation in the mid-lower mantle. Although bridgmanite has been put forward as a potential host for water and argon in the lower mantle by trapping them in oxygen vacancies, such capabilities will rapidly decrease with depth and be lost in regions deeper than 1000 km.

Z. Liu, T. Ishii, T. Katsura

Geochem. Persp. Let. (2017) 5, 12–18 | doi: 10.7185/geochemlet.1739 | Published 12 October 2017

The solubility of heat-producing elements in Earth’s core

The long term thermal and dynamic evolution of Earth’s core depends on its energy budget, and models have shown that radioactive decay due to K and U disintegration can contribute significantly to core dynamics and thermal evolution if substantial amounts of heat-producing elements are dissolved in the core during differentiation. Here we performed laser-heated diamond anvil cell experiments and measured K and U solubility in molten iron alloy at core formation conditions. Pyrolitic and basaltic silicate melts were equilibrated with metallic S–Si–O-bearing iron alloys at pressures of 49 to 81 GPa and temperatures of 3500 to 4100 K. We found that the metal-silicate partitioning of K is independent of silicate or metal composition and increases with pressure. Conversely, U partitioning is independent of pressure and silicate composition but it strongly increases with temperature and oxygen concentration in the metal. We subsequently modelled U and K concentration in the core during core formation, and found a maximum of 26 ppm K and 3.5 ppb U dissolved in the core, producing up to 7.5 TW of heat 4.5 Gyr ago. While higher than previous estimates, this is insufficient to power an early geodynamo, appreciably reduce initial core temperature, or significantly alter its thermal evolution and the (apparently young) age of the inner core.

I. Blanchard, J. Siebert, S. Borensztajn J. Badro

Geochem. Persp. Let. (2017) 5, 1-5 | doi: 10.7185/geochemlet.1737 | Published 4 October 2017

Magma dynamics of ancient Mt. Etna inferred from clinopyroxene isotopic and trace element systematics

Dynamic magmatic processes driving volcanic eruptions, including melting, fractionation, and assimilation, provide critical insights into plumbing systems supporting long-lived magmatism. Here we describe an approach combining in situ elemental analyses in clinopyroxene phenocrysts, integrated thermobarometry models, and bulk crystalline Hf, Nd, and Pb isotopic studies to reconstruct a key period of ancient eruptions of Mount Etna (Sicily), Europe’s largest, most active volcano. Trace element signatures recorded in clinopyroxene from 220 to 100 ka are consistent with derivation from a heterogeneous mantle of hydrated peridotite and ~10 % pyroxenite, also consistent with sources feeding recent Etna eruptions. Isotopic data from Mount Etna alkaline lava clinopyroxene, crystallised between 0.5 and 0.2 GPa, insignificantly vary from whole rock values, ruling out substantive assimilation of material during magma ascent from the onset of clinopyroxene fractionation through the mid-crust, storage, and eruption. Together, our results suggest that varying contributions of well-mixed hydrated peridotite and pyroxenite melts have been consistent features of magma assembly beneath Mt. Etna since the development of ancient alkaline centres.

S.A. Miller, M. Myers, M.F. Fahnestock, J. Bryce, J. Blichert-Toft

Geochem. Persp. Let. (2017) 4, 47-52 | doi: 10.7185/geochemlet.1735 | Published 28 September 2017

The gravitas of gravitational isotope fractionation revealed in an isolated aquifer

Despite the ubiquitous effects of gravitation on Earth, its potential influence on relative distribution of isotopic substances has remained elusive – and so far only identified in confined gaseous systems (Craig et al., 1988, 1998). Yet, in a motionless and chemically homogeneous water column, dissolved isotopic substances must be distributed according to their masses. Here we report the first resolvable isotopic variations resulting from gravitational effects on solutes, identified on dissolved chloride (Cl-) and bromide (Br-) in a sedimentary aquifer from the Illinois Basin (USA). We show that the correlations between depth and both 37Cl/35Cl and 81Br/79Br – varying by 1.1 ‰ and 1.6 ‰ respectively – reflect the evolution toward a gravity-diffusion equilibrium of porewater in the sediment column. This observation reveals that these deep groundwaters have been mostly stagnant for at least 20 Myr, possibly up to 300 Myr. As chloride and bromide are often conservative in groundwater systems, we highlight their essential role in unravelling the hydrodynamics and residence times of isolated aquifers. Furthermore, this study reveals gravitational fractionation as a viable process, potentially affecting other isotopic systems in various geological settings.

T. Giunta, O. Devauchelle, M. Ader, R. Locke, P. Louvat, M. Bonifacie, F. Métivier, P. Agrinier

Geochem. Persp. Let. (2017) 4, 53-58 | doi: 10.7185/geochemlet.1736 | Published 26 September 2017

Climate driven carbon and microbial signatures through the last ice age

Ice cores preserve diverse materials as millennial-scale proxies for Earth’s history. While major ions and elemental analyses are commonly investigated in palaeoclimate reconstructions, the integration of biological measurements is rapidly developing. Although the limited number of data herein impose constraints on broader generalisations, we show that microbial assemblages and organic matter (OM) composition from Byrd Station and West Antarctic Ice Sheet Divide ice cores may serve as palaeoecological markers from the Last Glacial Maximum (LGM; section ~20.5 ka BP) and last deglaciation periods (LD; section ~14.5 ka BP), reflecting environmental changes. Fluorescent analyses determined OM from both cores to have similar amino acid-like signatures; however, more comprehensive molecular characterisation showed only 12 % overlap in molecular formulae, with Byrd OM being more chemically labile. Microbial diversity in both cores was low, and together with predicted metabolic capabilities, differed significantly between communities. Variation in OM composition and microbial diversity reflects changes in environmental sources and deposition patterns onto the Antarctic Ice Sheet during distinct climate periods, with OM composition potentially shaping microbial communities post-deposition. Combining detailed microbial and OM composition analyses created a unique window into the past, providing a way to characterise carbon composition and potential metabolic processes as a function of environmental change.

J. D’Andrilli, H.J. Smith, M. Dieser, C.M. Foreman

Geochem. Persp. Let. (2017) 4, 29-34 | doi: 10.7185/geochemlet.1732 | Published 21 September 2017

Running out of gas: Zircon 18O-Hf-U/Pb evidence for Snowball Earth preconditioned by low degassing

The general long-term stability of Earth’s climate over geologic time was punctuated by dramatic excursions. Between ca. 2.5 and 0.5 billion years ago (Ga), these events included the globally extensive glaciations known as Snowball Earths, when ice extended to tropical latitudes. Such anomalous periods of time provide unique opportunities for understanding the mechanisms regulating planetary climate and habitability. However, the causes of these events remain enigmatic, in part because there is little information about fluxes in the global carbon cycle in deep time. We propose that the oxygen stable isotope composition in zircons (δ18Ozircon) contains information about past weathering conditions on the continents, imparted during the time between separation of parent material from the mantle (reflected in the Hf model age) and zircon crystallisation (the U/Pb age). A new compilation of coupled 18O-Hf-U/Pb isotopic data shows that the mean δ18Ozircon value varied particularly between 2.5 Ga and 0.5 Ga. The maximum in the δ18Ozircon record, which we interpret as a time of intense weathering, is associated with the Lomagundi Event (~2.22–2.07 Ga), a dramatic carbon isotope excursion thought to reflect enhanced organic carbon burial facilitated by the release of phosphorous during rock weathering. The onset of the Neoproterozoic Snowball Earth events coincides with the minimum in δ18Ozircon, suggesting low silicate weathering rates at the time. This evidence suggests that long-term decreases in the rate of CO2 release to the atmosphere from solid Earth degassing may have preconditioned the global climate system for intense glaciations.

J. Hartmann, G. Li, A.J. West

Geochem. Persp. Let. (2017) 4, 41-46 | doi: 10.7185/geochemlet.1734 | Published 15 September 2017