Geochemical Perspectives Letters is a new internationally peer-reviewed journal of the EAG:
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Latest articles
Oxygenation of the mid-Proterozoic atmosphere: clues from chromium isotopes in carbonates

Chromium (Cr) isotopes in marine sedimentary rocks can be used as a sensitive proxy for ancient atmospheric oxygen because Cr-isotope fractionation during terrestrial weathering only occurs when pO2 exceeds a threshold value. This is a useful system when applied to rocks of mid-Proterozoic age, where fundamental questions persist about atmospheric pO2 and its relationship to biological innovation. Whereas previous studies have focused on temporally limited iron-rich sedimentary rocks, we present new Cr-isotope data from a suite of mid-Proterozoic marine carbonate rocks. Application of the Cr-isotope proxy to carbonate rocks has the potential to greatly enhance the temporal resolution of Proterozoic palaeo-redox data. Here we report positive δ53Cr values in four carbonate successions, extending the mid-Proterozoic record of Cr-isotope fractionation – and thus pO2 above threshold values – back to ~1.1 Ga. These data suggest that pO2 sufficient for the origin of animals was transiently in place well before their Neoproterozoic appearance, although uncertainty in the pO2 threshold required for Cr-isotope fractionation precludes definitive biological interpretation. This study provides a proof of concept that the Cr-isotopic composition of carbonate rocks can provide important new constraints on the oxygen content of the ancient atmosphere.  

G.J. Gilleaudeau, R. Frei, A.J. Kaufman, L.C. Kah, K. Azmy, J.K. Bartley, P. Chernyavskiy, A.H. Knoll

Geochem. Persp. Let. (2016) 2, 178-187 | doi: 10.7185/geochemlet.1618 | Published 24 May 2016

CO2-fluxing collapses metal mobility in magmatic vapour

Magmatic systems host many types of ore deposits, including world-class deposits of copper and gold. Magmas are commonly an important source of metals and ore-forming fluids in these systems. In many magmatic-hydrothermal systems, low-density aqueous fluids, or vapours, are significant metal carriers. Such vapours are water-dominated shallowly, but fluxing of CO2-rich vapour exsolved from deeper magma is now recognised as ubiquitous during open-system magma degassing. Here, we show that such CO2-fluxing leads to a sharp drop in element solubility, up to a factor of 10,000 for Cu, and thereby provides a highly efficient, but as yet unrecognised mechanism for metal deposition.  

V.J. van Hinsberg, K. Berlo, A.A. Migdisov, A.E. Williams-Jones

Geochem. Persp. Let. (2016) 2, 169-177 | doi: 10.7185/geochemlet.1617 | Published 18 May 2016

Molecular hydrogen in mantle minerals

Current models assume that hydrogen was delivered to Earth already in oxidised form as water or OH groups in minerals; similarly, it is generally believed that hydrogen is stored in the present mantle mostly as OH. Here we show by experiments at 2-7 GPa and 1100-1300 °C that, under reducing conditions, molecular hydrogen (H2) has an appreciable solubility in various upper mantle minerals. This observation suggests that during the accretion of the Earth, nebular H2 could have been delivered to the growing solid planet by direct dissolution in a magma ocean and subsequent incorporation in silicates. Moreover, the presence of dissolved molecular H2 in the minerals of the lower mantle could explain why magmas sourced in this region are rich in hydrogen, despite the fact that lower mantle minerals contain almost no OH groups.  

X. Yang, H. Keppler, Y. Li

Geochem. Persp. Let. (2016) 2, 160-168 | doi: 10.7185/geochemlet.1616 | Published 18 May 2016

Release of subducted sedimentary nitrogen throughout Earth’s mantle

The dynamic process of subduction represents the principal means to introduce chemical heterogeneities into Earth's interior. In the case of nitrogen (N) - atmosphere's most abundant gas - biological-activity converts N2 into ammonium ions (NH4+), which are chemically-bound within seafloor sediments and altered oceanic crust that comprise the subducting slab. Although some subducted N re-emerges via arc-related volcanism (Sano et al., 1998), the majority likely bypasses sub-arc depths (150-200 km) and supplies the deeper mantle (Li et al., 2007; Mitchell et al., 2010; Johnson and Goldblatt, 2015; Bebout et al., 2016). However, the fate of subducted N remains enigmatic: is it incorporated by the shallow convecting mantle - the source of ridge volcanism, or is the deeper mantle - nominally associated with mantle plumes - its ultimate repository? Here, we present N-He-Ne-Ar isotope data for oceanic basalts from the Central Indian Ridge (CIR)-Réunion plume region to address this issue. All on-axis samples with depleted MORB mantle (DMM) affinities (3He/4He = 8 ± 1 RA; Graham, 2002) have low N-isotopes (mean δ15N = -2.1 ‰), whereas those with plume-like 3He/4He display higher values (mean δ15N = 1.3 ‰). We explain these data within the framework of a new mantle reference model to predict a time-integrated net N regassing flux to the mantle of ~3.4 × 1010 mol/yr, with the plume-source mantle representing the preferential destination by a factor of 2-3. The model has implications for the present-day imbalance between N subducted at trenches and N emitted via arc-related volcanism, the N-content of Earth's early atmosphere, as well as relationships between N2 and the noble gases in mantle reservoirs, including 3He/4He-δ15N relationships in plume-derived lavas.  

P.H. Barry, D.R. Hilton

Geochem. Persp. Let. (2016) 2, 148-159 | doi: 10.7185/geochemlet.1615 | Published 3 May 2016

Nitrogen isotope fractionation during terrestrial core-mantle separation

The origin and evolution of the terrestrial nitrogen remains largely unresolved. In order to understand the potential influence of core-mantle separation on terrestrial nitrogen evolution, experiments were performed at 1.5 to 7.0 GPa and 1600 to 1800 °C to study nitrogen isotope fractionation between coexisting liquid Fe-rich metal and silicate melt. The results show that the metal/silicate partition coefficient of nitrogen FORMULA ranges from 1 to 150 and the nitrogen isotope fractionation Δ15Nmetal-silicate is −3.5 ± 1.7 ‰. Calculations show that the bulk Earth is more depleted in δ15N than the present-day mantle, and that the present-day mantle δ15N of −5 ‰ could be derived from an enstatite chondrite composition via terrestrial core-mantle separation, with or without the addition of carbonaceous chondrites. These results strongly support the notion that enstatite chondrites may be a main component from which the Earth formed and a main source of the terrestrial nitrogen. Moreover, in the deep reduced mantle, the Fe-rich metal phase may store most of the nitrogen, and partial melting of the coexisting silicates may generate oceanic island basalts (OIBs) with slightly positive δ15N values.  

Y. Li, B. Marty, S. Shcheka, L. Zimmermann, H. Keppler

Geochem. Persp. Let. (2016) 2, 138-147 | doi: 10.7185/geochemlet.1614 | Published 21 April 2016

A glimpse into the Roman finances of the Second Punic War through silver isotopes

The defeat of Hannibal’s armies at the culmination of the Second Punic War (218 BC–201 BC) was a defining moment in Western world history. One of the underappreciated consequences of the conflict was the Roman monetary reform of 211 BC, which ushered in a monetary system that would sustain Roman power for the next many centuries. This system would encapsulate many of the issues plaguing finances of governments until today, such as inflation, debasement, and the size of monetary mass. Here we approach the issue of financial fluxes using a newly developed powerful tracer, that of silver isotopic compositions, in conjunction with Pb isotopes, both of which we measured in Roman coinage minted before and after the 211 BC monetary reform. The results indicate that pre-reform silver was minted from Spanish metal supplied by Carthage as war penalty after the First Punic War, whereas post-reform silver was isotopically distinct and dominated by plunder, most likely from Syracuse and Capua. The 211 BC monetary reform and the end of debasement, therefore, were aimed at accommodating new sources of silver rather than being the response to financial duress. The drastic weight reduction of silver coins implemented by the Roman mint was not motivated by metal shortage but by the need to block inflation after a major surge of war booty.

F. Albarède, J. Blichert-Toft, M. Rivoal, P. Telouk

Geochem. Persp. Let. (2016) 2, 127-137 | doi: 10.7185/geochemlet.1613 | Published 15 April 2016

Compositional symmetry between Earth’s crustal building blocks

Arc magmatism drives the production of modern continental crust. However, the mode of crustal differentiation in the geologic past, particularly in the Archean, remains controversial. Herein I adopt a compositional approach to interrogate a global, igneous geochemical database (EarthChem Library) and document the evolving compositional history of basalt, andesite, and rhyolite, which represent the three main crustal building blocks. Basalt and andesite share synced geochemical histories and progressively incompatible-element-rich and compatible-element-poor compositions that are consistent with extensive partial mantle-melting during the Archean. Post-Archean basaltic to andesitic rocks also tend to be more alkaline in character, which coupled with their high field-strength- and large-ion lithophile-element signature, points to the increased influence of Phanerozoic-style intra-plate magmatism on the global, rock record. Coeval rhyolitic rocks are depleted in these same elements, suggesting that post-Archean felsic magmas track the evolving compositions of their basaltic to andesitic source, which are, in turn, controlled by the partial melting trend. These complementary, or symmetric, geochemical trends between rock types shifted during the Proterozoic and heralded the onset of modern compositional relationships between crustal building blocks.

C.J.M. Lawley

Geochem. Persp. Let. (2016) 2, 117-126 | doi: 10.7185/geochemlet.1612 | Published 11 March 2016

Experimental evidence that microbial activity lowers the albedo of glaciers

Darkening of glacier and ice sheet surfaces is an important positive feedback to increasing global temperatures. Deposition of impurities on glaciers is primarily believed to reduce surface albedo, resulting in greater melt and mass loss. However, no study has yet included the effects of biological activity in albedo reduction models. Here, we provide the first experimental evidence that microbial activity can significantly decrease glacier surface albedo. Indeed, the addition of nutrients at ice meltwater concentrations to microbe-impurity mixtures resulted in extensive microbial organic carbon fixation and accumulation in Greenland Ice Sheet surface debris. Accumulated organic carbon, over the period of a melt season, darkened the glacial debris in our experiments from 31.1 % to 15.6 % surface reflectivity (used as an analogue for albedo in our calculations), generating a strongly absorbing surface. Our experiments are the first to quantify the microbially-induced potential melt increase for the Greenland Ice Sheet (up to an average of 17.3±2.5 Gt yr-1 at present and up to ~85 Gt yr-1 by 2100, based on our first order calculations). Mass loss from glaciers will conceivably intensify through enhanced microbial activity, resulting from longer melt seasons and fertilisation from anthropogenic sources.

M. Musilova, M. Tranter, J.L. Bamber, N. Takeuchi, A.M. Anesio

Geochem. Persp. Let. (2016) 2, 106-116 | doi: 10.7185/geochemlet.1611 | Published 11 March 2016

Mononuclear U(IV) complexes and ningyoite as major uranium species in lake sediments

Natural attenuation of uranium in subsurface environments is generally assigned to immobilisation processes due to microbial reduction of U(VI). Recent laboratory studies have established that the end products of such a process include both low solubility biogenic uraninite and more labile non-crystalline U(IV) species. Indeed, biogenic uraninite formation may be inhibited in the presence of organic or inorganic phosphoryl ligands, leading to the formation of non-crystalline U(IV)-phosphate complexes or nanoscale U(IV)-phosphate solids. Such species have been observed in shallow contaminated alluvial aquifers and can thus be suspected to form in other important environments, among which lacustrine sediments have a global environmental significance since they may represent major uranium accumulation reservoirs in riverine watersheds. Here, on the basis of microscopic, spectroscopic and chemical extraction analyses, we report the occurrence of mononuclear U(IV)-phosphate/silicate complexes, accompanied by nano-crystalline ningyoite-like U(IV)-phosphate minerals, as major scavengers for uranium in lacustrine sediments downstream from a former uranium mine in France. This observation reveals that uranium trapping mechanisms during early diagenesis of lacustrine sediments can virtually exclude uraninite formation, which has important implications for better modelling uranium cycling in natural and contaminated freshwaters. Moreover, our results raise issues concerning the long term fate of mononuclear U(IV) complexes and U(IV) phosphate nano-minerals, especially with respect to re-oxidation events.

G. Morin, A. Mangeret, G. Othmane, L. Stetten, M. Seder-Colomina, J. Brest, G. Ona-Nguema, S. Bassot, C. Courbet, J. Guillevic, A. Thouvenot, O. Mathon, O. Proux, J.R. Bargar

Geochem. Persp. Let. (2016) 2, 95-105 | doi: 10.7185/geochemlet.1610 | Published 16 February 2016

Intramolecular fractionation of hydrogen isotopes in silicate quenched melts

The interplay between the chemical composition and the molecular structure of silicate melts was central to the evolution of the Earth’s crust, mantle and core. This interplay also affects geochemical records such as the partitioning of isotopes between minerals, melts and fluids in the Earth’s interior. For instance, large 2H/1H fractionations between silicate melts and aqueous fluids have been observed at high temperature and pressure. Such behaviour may be promoted by the occurrence of 2H/1H intramolecular fractionation within the molecular structure of silicate melts. New Raman spectroscopy and 1H and 2H Nuclear Magnetic Resonance (NMR) spectroscopy data reveal the source of such 2H/1H intramolecular isotopic fractionation, showing that 1H and 2H fractionate between the silicate tetrahedral units. Such a process might affect other isotopic systems (e.g., N, C, or S) where the isotopes interact with the melt silicate network.

C. Le Losq, B.O. Mysen, G.D. Cody

Geochem. Persp. Let. (2016) 2, 87-94 | doi: 10.7185/geochemlet.1609 | Published 16 February 2016

A stable isotope doping method to test the range of applicability of detailed balance

The principle of detailed balance (PDB) has been a cornerstone for irreversible thermodynamics and chemical kinetics for a long time (Wegscheider, 1901; Lewis, 1925; Onsager, 1931), and its wide application in geochemistry has mostly been implicit and without experimental testing of its applicability. Nevertheless, many extrapolations based on PDB without experimental validation have far reaching impacts on society’s mega environmental enterprises. Here we report an isotope doping method that independently measures simultaneous dissolution and precipitation rates and can test this principle. The technique reacts a solution enriched in a rare isotope of an element with a solid having natural isotopic abundances (Beck et al., 1992; Gaillardet, 2008; Gruber et al., 2013). Dissolution and precipitation rates are found from the changing isotopic ratios. Our quartz experiment doped with 29Si showed that the equilibrium dissolution rate remains unchanged at all degrees of undersaturation. We recommend this approach to test the validity of using the detailed balance relationship in rate equations for other substances.

Z. Liu, J.D. Rimstidt, Y. Zhang, H. Yuan, C. Zhu

Geochem. Persp. Let. (2016) 2, 78-86 | doi: 10.7185/geochemlet.1608 | Published 15 February 2016

Rapid cooling of planetesimal core-mantle reaction zones from Mn-Cr isotopes in pallasites

Pallasite meteorites, which consist of olivine-metal mixtures and accessory phosphates crystallised from silico-phosphate melts, are thought to represent core-mantle reaction zones of early differentiating planetesimals. Pallasite meteorites can be linked to five distinct planetesimals, indicating that they are default products of differentiation. However, their formation modes (deep, shallow, and impact environments) and age are still elusive. We have investigated the trace element and Mn-Cr isotopic signatures of Main-Group pallasite olivine, finding enhanced Mn, P and 53Cr/52Cr near crystal rims which indicates early ingrowth of radiogenic 53Cr* in silico-phosphate melts. Mn-Cr isotopic data corroborate previous Hf-W isotopic data, indicating an early metal-silicate separation event but additionally that rapid cooling generated silico-phosphate eutectic melts with high Mn/Cr within ~2.5 to 4 Myr of Solar System formation. These melts formed before most known samples of planetesimal crusts (eucrite and angrite meteorites) and are among the earliest evolved planetary silicates. Additionally, Mn-rich phosphates in other, non-Main-Group pallasite meteorites suggest that core-mantle reaction zones are generic, datable features of differentiation.

S.J. McKibbin, T.R. Ireland, P. Holden, H.St.C. O’Neill, G. Mallmann

Geochem. Persp. Let. (2016) 2, 68-77 | doi: 10.7185/geochemlet.1607 | Published 28 January 2016

North Atlantic hotspot-ridge interaction near Jan Mayen Island

At slow to ultraslow spreading rates along mid-ocean ridges, thicker lithosphere typically impedes magma generation and tectonic extension can play a more significant role in crustal production (Dick et al., 2003). The source of anomalously high magma supply thus remains unclear along ridges with ultraslow-spreading rates adjacent to Jan Mayen Island in the North Atlantic (Neumann and Schilling, 1984; Mertz et al., 1991; Haase et al., 1996; Schilling et al., 1999; Trønnes et al., 1999; Haase et al., 2003; Mertz et al., 2004; Blichert-Toft et al., 2005; Debaille et al., 2009). Here we show that Jan Mayen volcanism is likely the surface expression of a small mantle plume, which exerts significant influence on nearby mid-ocean ridge tectonics and volcanism. Progressive dilution of Jan Mayen geochemical signatures with distance from the hotspot is observed in lava samples from the immediately adjacent Mohns Ridge, and morphological indicators of enhanced magma supply are observed on both the Mohns Ridge and the nearby Kolbeinsey Ridge, which additionally locally overlies a highly heterogeneous, eclogite-bearing mantle source. These morphological and geochemical influences underscore the importance of heterogeneous mantle sources in modifying melt supply and thus the local expression of tectonic boundaries.

L.J. Elkins, C. Hamelin, J. Blichert-Toft, S.R. Scott, K.W.W. Sims, I.A. Yeo, C.W. Devey, R.B. Pedersen

Geochem. Persp. Let. (2016) 2, 55-67 | doi: 10.7185/geochemlet.1606 | Published 22 January 2016

Processes controlling carbon cycling in Antarctic glacier surface ecosystems

Glacier surface ecosystems, including cryoconite holes and cryolakes, are significant contributors to regional carbon cycles. Incubation experiments to determine the net production (NEP) of organic matter in cryoconite typically have durations of 6-24 hours, and produce a wide range of results, many of which indicate that the system is net heterotrophic. We employ longer term incubations to examine the temporal variation of NEP in cryoconite from the McMurdo Dry Valleys, Antarctica to examine the effect of sediment disturbance on system production, and to understand processes controlling production over the lifetimes of glacier surface ecosystems. The shorter-term incubations have durations of one week and show net heterotrophy. The longer term incubations of approximately one year show net autotrophy, but only after a period of about 40 days (~1000 hours). The control on net organic carbon production is a combination of the rate of diffusion of dissolved inorganic carbon from heterotrophic activity within cryoconite into the water, the rate of carbonate dissolution, and the saturation of carbonate in the water (which is a result of photosynthesis in a closed system). We demonstrate that sediment on glacier surfaces has the potential to accumulate carbon over timescales of months to years.

E.A. Bagshaw, M. Tranter, J.L. Wadham, A.G. Fountain, A. Dubnick, S. Fitzsimmons

Geochem. Persp. Let. (2016) 2, 44-54 | doi: 10.7185/geochemlet.1605 | Published 21 January 2016

Carbon isotope discrimination in C3 land plants is independent of natural variations in pCO2

The δ13C of terrestrial C3 plant tissues and soil organic matter is important for understanding the carbon cycle, inferring past climatic and ecological conditions, and predicting responses of vegetation to future climate change. Plant δ13C depends on the δ13C of atmospheric CO2 and mean annual precipitation (MAP), but an unresolved decades-long debate centres on whether terrestrial C3 plant δ13C responds to pCO2. In this study, the pCO2-dependence of C3 land plant δ13C was tested using isotopic records from low- and high-pCO2 times spanning historical through Eocene data. Historical data do not resolve a clear pCO2-effect (-1.2 ± 1.0 to 0.6 ± 1.0 ‰/100 ppmv). Organic carbon records across the Pleistocene-Holocene transition are too affected by changes in MAP, carbon sources, and potential differential degradation to quantify pCO2-effects directly, but limits of ≤1.0 ‰/100 ppmv or ~0 ‰/100 ppmv are permissible. Fossil collagen and tooth enamel data constrain pCO2-effects most tightly to -0.03 ± 0.13 and -0.03 ± 0.24 ‰/100 ppmv between 200 and 700 ppmv. Combining all constraints yields a preferred value of 0.0 ± 0.3 ‰/100 ppmv (2 s.e.). Recent models of pCO2-dependence imply unrealistic MAP for Cenozoic records.

M.J. Kohn

Geochem. Persp. Let. (2016) 2, 35-43 | doi: 10.7185/geochemlet.1604 | Published 8 January 2016