Pascal Philippot

Deep fluids in subduction zones

The fluid inclusions preserved in high and ultrahigh pressure rocks provide direct information on the compositions of fluid phases evolved during subduction zone metamorphism, and on fluid–rock interactions occurring in such deep environments. Recent experiments and petrologic studies of eclogite–facies rocks demonstrate that stability of a number of hydrous phases in all rock systems allows fluid transport into the mantle sources of arc magmas, as well as into much deeper levels of the Earths mantle. In eclogite–facies rocks, the presence of large ion lithophile elements (LILE) and light rare earths (LREE)-bearing hydrous phases such as epidote and lawsonite, together with HFSE repositories as rutile and other Ti-rich minerals, controls the trace element budget of evolved fluids and fluid-mediated cycling of slab components into the overlying mantle. Studies of fluid inclusions in eclogite–facies terrains suggest that subduction mainly evolves aqueous solutions, melts being produced only locally. Eclogite-facies rocks diffusely record processes of fluid–melt–rock interactions that exerted considerable control on the element and volatile budget of subduction fluids. Trace element fractionation during such interactions needs to be tested and quantified in more detail to achieve the ultimate compositions actually attained by fluids leaving off the slab. Variably saline inclusions with minor CO2 and N2 are trapped in rock-forming high pressure minerals; brines with up to 50% by weight dissolved solute are diffusely found in veins. The latter inclusions are residues after fluid–rock interactions and deposition of complex vein mineralogies: this evidence suggests increased mineral solubility into the fluid and formation, at a certain stage, of silicate-rich aqueous solutions whose geochemical behaviour and transport capacity can approach that of a melt phase. This is supported by experimental work showing high solubility of silicate components in fluids at high pressures. However, natural examples of inclusions trapping such a fluid and quantitative analyses of its major and trace element composition are not yet available. Fluids in high and very high pressure rocks do not move over large scales and the channelways of fluid escape from the slab are not yet identified. This suggests that only part of the slab fluid is lost and returned to the surface via magmatism; the remaining trapped fraction being subducted into deeper levels of the upper mantle, to renew its budget of substances initially stored in the exosphere.

Early Archaean microorganisms preferred elemental sulfur, not sulfate.

Microscopic sulfides with low 34S/32S ratios in marine sulfate deposits from the 3490-million-yearold Dresser Formation, Australia, have been interpreted as evidence for the presence of early sulfate-reducing organisms on Earth. We show that these microscopic sulfides have a mass-independently fractionated sulfur isotopic anomaly (Δ33S) that differs from that of their host sulfate (barite). These microscopic sulfides could not have been produced by sulfate-reducing microbes, nor by abiologic processes that involve reduction of sulfate. Instead, we interpret the combined negative δ34S and positive Δ33S signature of these microscopic sulfides as evidence for the early existence of organisms that disproportionate elemental sulfur.

HIGH SALINITY FLUID INCLUSIONS FORMED FROM RECYCLED SEAWATER IN DEEPLY SUBDUCTED ALPINE SERPENTINITE

The origin of high-pressure brines has been investigated in the Erro-Tobbio peridotite (Western Alps), a mantle slice that was exposed to the seafloor of the Mesozoic Ligurian-Piedmontese Tethys and was later involved in Alpine subduction. Hydrothermal alteration by seawater-derived fluids led to replacement of the mantle assemblage by Cl-bearing serpentine (0.35 wt% Cl), brucite (0.2 wt%), Cl- and alkali-bearing phyllosilicates (0.2 wt% Cl; 0.2–0.55 wt% Na2O; 1–5 wt% K2O). Relics of these hydrous phases occur in olivine + titanian clinohumite + antigorite assemblages formed at 2.5 GPa and 550–600°C during partial devolatilization and veining of the hydrothermally altered peridotite. The high-pressure phases lack chlorine and alkalis and are coeval with fluid inclusions trapped in the syn-eclogitic veins. The inclusions are salt-saturated and contain up to 50 wt% Cl, Na, K, Mg and Fe. High fluid chlorinity was probably achieved during rehydration of relict mantle minerals and deposition of hydrous phases in the veins. The data presented suggest that the seafloor hydrothermal signature was inherited by the eclogitic fluid due to partitioning of chlorine and alkalis into the fluid phase. The presence of salty brines in eclogitized hydrous peridotites can indicate deep recycling of seawater-derived fluids. Hydrous ultramafic systems can therefore act as large-scale carriers of seawater into the mantle.

Massive recycling of nitrogen and other fluid-mobile elements (K, Rb, Cs, H) in a cold slab environment: evidence from HP to UHP oceanic metasediments of the Schistes Lustrés nappe (western Alps, Europe)

Abstract Nitrogen and hydrogen isotopic compositions together with N, K, Rb, Cs and H 2 O contents were measured on several high-pressure (HP) to ultrahigh-pressure (UHP) metasediments from the Schistes Lustres nappe (western Alps) and on unmetamorphosed sedimentary protoliths from the Apennines (Italy). These samples represent a sequence of pelagic sediments subducted to different depths down to 90 km along a ‘cold’ geothermal gradient (∼8°C/km). Nitrogen isotopic composition (δ 15 N between +2.6 and +4.8‰) does not show any specific evolution with increasing metamorphic conditions and can be considered constant during subduction. Large variations of the N content (between 169 and 1721 ppm N) together with K, Rb and Cs content are observed but the constancy of K/N (14), K/Rb (385) and K/Cs (10 190) molar ratios in protoliths and metamorphic rocks indicates that none of these fluid-mobile elements was lost through devolatilization processes. This suggests that fluid circulation was limited to sample scale and that the rocks behaved as closed systems during subduction. This interpretation is also supported by the small range of δD values (from −54.1 to −78.0‰). The present results indicate that N, K, Rb and Cs were retained in the subducted sedimentary veneer at least down to the depth locus of island arc magmatism. Based on the correlation between N and K contents, the flux of sedimentary N recycled in subduction zones is estimated at 7.6×10 11 g/yr. Mass balance calculations strongly support the fact that nitrogen is efficiently recycled to the deeper mantle.

Fluid inclusion and mineral isotopic compositions (HCO) in eclogitic rocks as tracers of local fluid migration during high-pressure metamorphism

Eclogite facies metagabbros from the Monviso ophiolitic complex (Italian Western Alps) provide a unique opportunity to trace fluid migration processes in a portion of the oceanic crust that has undergone subduction at a depth of > 40 km. We have determined the omphacites δ18O and the abundance, δD and δ13C of hydrous and carbonaceous compounds present in whole rocks which are believed to trace the residual phases of what was mobilized in the original rocks during subduction. Prograde dehydration reactions and eclogitization of hydrothermally altered oceanic metagabbros was accompanied by approximately 90% fluid loss. The remaining fluid was trapped as primary water-rich fluid inclusions in omphacite megacrysts that developed at the expense of the precursor magmatic pyroxene. Deformation of the eclogitic rocks resulted in continuous recycling of fluid between mylonites and omphacite veins without further fluid loss from the host ductile shear zone. Oxygen isotopes of omphacite (omp) and hydrogen isotopes of water in the fluid inclusions (FI), analyzed in low-strain rocks, mylonites and undeformed/deformed veins show marked variations, δ18Oomp and δDFI values ranging from +3.0 to +5.3‰ and from −31 to −93‰, respectively. Detailed isotopic analysis of several individual vein-wallrock pairs show that the scale of isotopic equilibration is of the order of one centimeter. Therefore, the eclogitic minerals and fluids filling the veins are concluded to be locally derived. Our results argue against recent models which suggest large-scale mass flushing of isotopically homogeneous fluids during subduction zone metamorphism. On average, the H2O contents and δDFI value are within the upper mantle range. The carbon has been inherited from the metamorphic transformation of the original carbon present in the oceanic crust and has a mean δ13C value of −24.2 ± 1.2‰. Two carbonaceous components can be recognized, condensed carbon which represents the major carbon species and carbonate daughter crystals present in fluid inclusions. δ18Oomp values are significantly lower than those reported for mantle minerals and are similar to pyroxene and whole-rock values from hydrothermally altered oceanic crust. It is suggested that the isotopic imprint of the Monviso eclogitic minerals and fluids represents the signature of mid-ocean ridge hydrothermal alteration and subduction zone eclogitization processes. The rocks studied could be the missing link between altered oceanic gabbros and eclogitic xenoliths. In addition, the range in δ18Oomp values recorded in the different microstructural domains covers most of the δ18O values reported in type A, B and C eclogitic xenoliths, implying that caution must be exercised when using oxygen isotopes as an indicator of the origin of eclogitic xenoliths.

Extreme 15N-enrichments in 2.72-Gyr-old sediments: evidence for a turning point in the nitrogen cycle.

Although nitrogen is a key element in organic molecules such as nucleic acids and proteins, the timing of the emergence of its modern biogeochemical cycle is poorly known. Recent studies on the antiquity of the nitrogen cycle and its interaction with free oxygen suggests the establishment of a complete aerobic N biogeochemical cycle with nitrification, denitrification, and nitrogen fixation at about 2.68 Gyr. Here, we report new bulk nitrogen isotope data for the 2.72 billion-year-old sedimentary succession of the Tumbiana Formation (Pilbara Craton, Western Australia). The nitrogen isotopic compositions vary widely from +8.6‰ up to +50.4‰ and are inversely correlated with the very low δ(13)C values of associated organic matter defining the Fortescue excursion (down to about -56‰). We propose that this (15)N-enrichment records the onset of nitrification coupled to the continuous removal of its derivatives (nitrite and nitrate) by denitrification. This finding implies an increase in the availability of electron acceptors and probably oxygen in the Tumbiana depositional environment, 300 million years before the oxygenation of the Earths atmosphere.

Nitrogen Isotopic Composition and Density of the Archean Atmosphere

Same As It Ever Was Nitrogen constitutes approximately 78% by volume of Earths atmosphere and is a key component in its chemical and physical characteristics. It is not clear whether N2 has been so abundant throughout Earths geological history. Marty et al. (p. 101, published online 19 September) analyzed the isotopic compositions of nitrogen and argon from fluid inclusions trapped in hydrothermal quartz formed 3 to 3.5 billion years ago. The partial pressure and isotopic composition of atmospheric N2 were similar to todays. Thus, other factors are needed to explain why liquid water existed on Earths surface despite the Sun being 30% less luminous. Earth’s Archean atmosphere contained roughly as much nitrogen between 3.0 and 3.5 billion years ago as it does today. Understanding the atmosphere’s composition during the Archean eon is fundamental to unraveling ancient environmental conditions. We show from the analysis of nitrogen and argon isotopes in fluid inclusions trapped in 3.0- to 3.5-billion-year-old hydrothermal quartz that the partial pressure of N2 of the Archean atmosphere was lower than 1.1 bar, possibly as low as 0.5 bar, and had a nitrogen isotopic composition comparable to the present-day one. These results imply that dinitrogen did not play a significant role in the thermal budget of the ancient Earth and that the Archean partial pressure of CO2 was probably lower than 0.7 bar.

The ineluctable requirement for the trans-iron elements molybdenum and/or tungsten in the origin of life.

An evolutionary tree of key enzymes from the Complex-Iron-Sulfur-Molybdoenzyme (CISM) superfamily distinguishes “ancient” members, i.e. enzymes present already in the last universal common ancestor (LUCA) of prokaryotes, from more recently evolved subfamilies. The majority of the presented subfamilies and, as a consequence, the Molybdo-enzyme superfamily as a whole, appear to have existed in LUCA. The results are discussed with respect to the nature of bioenergetic substrates available to early life and to problems arising from the low solubility of molybdenum under conditions of the primordial Earth.

Ammonium quantification in muscovite by infrared spectroscopy

Abstract Single muscovite grains of different chemical composition (in particular Si-content from 3.05 to 3.69 per formulae unit (pfu)) and origin (metamorphic and granitic rocks) were analysed by infrared (IR) spectroscopy. Their ammonium concentrations were subsequently measured by capacitance manometry after extraction as N2 using a sealed-tube combustion technique. The values range from 0 to 2203 ppm NH4+. Correlation between ammonium concentration and ammonium IR absorbance corresponding to NH4+ bending permits an assessment of the ammonium molecular absorptivity at 1430 cm−1 (eN–H1430=462±32 l mol−1 cm−1). In order to avoid uncertainties on thickness estimates using an optical technique, a relationship between sample thickness and IR absorbance was determined. Ammonium concentration of muscovite can be directly derived from its IR spectrum using the relationship [NH4+] (ppm)=1142.5×[(AN–H1430−A2514)/(A1282−A2514)]−606 where A1282, AN–H1430 and A2514 are absorbances corresponding to wavenumbers 1282 (Si–O vibration peak), 1430 (NH4+ bending) and 2514 cm−1 (silicate network vibration), respectively. The precision of ammonium concentration estimates using this method is better than 20% (2σ) for muscovites thicker than 30 μm. This is independent of mineral composition, thus implying that the ammonium concentration vs. IR absorbance relationship is independent of the muscovite–celadonite solid solution.

Argon isotopic composition of Archaean atmosphere probes early Earth geodynamics

Understanding the growth rate of the continental crust through time is a fundamental issue in Earth sciences. The isotopic signatures of noble gases in the silicate Earth (mantle, crust) and in the atmosphere afford exceptional insight into the evolution through time of these geochemical reservoirs. However, no data for the compositions of these reservoirs exists for the distant past, and temporal exchange rates between Earth’s interior and its surface are severely under-constrained owing to a lack of samples preserving the original signature of the atmosphere at the time of their formation. Here, we report the analysis of argon in Archaean (3.5-billion-year-old) hydrothermal quartz. Noble gases are hosted in primary fluid inclusions containing a mixture of Archaean freshwater and hydrothermal fluid. Our analysis reveals Archaean atmospheric argon with a 40Ar/36Ar value of 143 ± 24, lower than the present-day value of 298.6 (for which 40Ar has been produced by the radioactive decay of the potassium isotope 40K, with a half-life of 1.25 billion years; 36Ar is primordial in origin). This ratio is consistent with an early development of the felsic crust, which might have had an important role in climate variability during the first half of Earth’s history.