Deep inside a neoproterozoic intra-oceanic arc: growth,differentiation and exhumation of the Amalaoulaou complex (Gourma,Mali)

We show here that the Amalaoulaou complex, in the Pan-African belt of West Africa (Gourma, Mali), corresponds to the lower and middle sections of a Neoproterozoic intra-oceanic arc. This complex records a 90–130-Ma-long evolution of magmatic inputs and differentiation above a subducting oceanic slab. Early c. 793 Ma-old metagabbros crystallised at lower crustal or uppermost mantle depths (25–30 km) and have geochemical characteristic of high-alumina basalts extracted from a depleted mantle source slightly enriched by slab-derived sedimentary components ((La/Sm)_N < 1; ε_Nd: +5.4–6.2; ⁸⁷Sr/⁸⁶Sr: 0.7027–0.7029). In response to crustal thickening, these mafic rocks were recrystallised into garnet-granulites (850–1,000°C; 10–12 kbar) and subject to local dehydration–melting reactions, forming trondhjemititic leucosomes with garnet–clinopyroxene–rutile residues. Slightly after the granulitic event, the arc root was subject to strong HT shearing during partial exhumation (detachment faults/rifting or thrusting), coeval with the emplacement of spinel- and garnet-pyroxenite dykes crystallised from a high-Mg andesitic parental magma. Quartz and hornblende-gabbros (700–660 Ma) with composition typical of hydrous volcanic rocks from mature arcs ((La/Sm)_N: 0.9–1.8; ε_Nd: +4.6 to +5.2; ⁸⁷Sr/⁸⁶Sr: 0.7028–0.7031) were subsequently emplaced at mid-arc crust levels (~15 km). Trace element and isotopic data indicate that magmas tapped a depleted mantle source significantly more enriched in oceanic sedimentary components (0.2%). Exhumation occurred either in two stages (700–660 and 623 Ma) or in one stage (623 Ma) with a final exhumation of the arc root along cold P-T path (550°C, 6–9 kbar; epidote–amphibolite and greenschist facies conditions) during the main Pan-African collision event (620–580 Ma). The composition of magmas forming the Cryogenian Amalaoulaou arc and the processes leading to intra-arc differentiation are strikingly comparable to those observed in the deep section of exposed Mezosoic oceanic arcs, namely the Kohistan and Talkeetna complex. This evolution of the Amalaoulaou oceanic arc and its accretion towards the West African craton belong to the life and closure of the Pharusian Ocean that eventually led to the formation of the Greater Gondwana supercontinent, a similar story having occurred on the other side of the Sahara with the Mozambique Ocean.     

U redox fronts and kaolinisation in basement-hosted unconformity-related U ores of the Athabasca Basin (Canada): late U remobilisation by meteoric fluids

Proterozoic basement-hosted unconformity-related uranium deposits of the Athabasca Basin (Saskatchewan, Canada) were affected by significant uranium redistribution along oxidation–reduction redox fronts related to cold and late meteoric fluid infiltration. These redox fronts exhibit the same mineralogical and geochemical features as the well-studied uranium roll-front deposits in siliclastic rocks. The primary hydrothermal uranium mineralisation (1.6–1.3 Ga) of basement-hosted deposits is strongly reworked to new disseminated ores comprising three distinctly coloured zones: a white-green zone corresponding to the previous clay-rich alteration halo contemporaneous with hydrothermal ores, a uranium front corresponding to the uranium deposition zone of the redox front (brownish zone, rich in goethite) and a hematite-rich red zone marking the front progression. The three zones directly reflect the mineralogical zonation related to uranium oxides (pitchblende), sulphides, iron minerals (hematite and goethite) and alumino-phosphate-sulphate (APS) minerals. The zoning can be explained by processes of dissolution–precipitation along a redox interface and was produced by the infiltration of cold (<50°C) meteoric fluids to the hydrothermally altered areas. U, Fe, Ca, Pb, S, REE, V, Y, W, Mo and Se were the main mobile elements in this process, and their distribution within the three zones was, for most of them, directly dependent on their redox potential. The elements concentrated in the redox fronts were sourced by the alteration of previously crystallised hydrothermal minerals, such as uranium oxides and light rare earth element (LREE)-rich APS. The uranium oxides from the redox front are characterised by LREE-enriched patterns, which differ from those of unconformity-related ores and clearly demonstrate their distinct conditions of formation. Uranium redox front formation is thought to be linked to fluid circulation episodes initiated during the 400–300 Ma period during uplift and erosion of the Athabasca Basin when it was near the Equator and to have been still active during the last million years. A major kaolinisation event was caused by changes in the fluid circulation regime, reworking the primary uranium redox fronts and causing the redistribution of elements originally concentrated in the uranium-enriched meteoric-related redox fronts.     

Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates,nicotianamine, and phytosiderophore,and new Fe isotopic measurements in higher plants

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ～3‰ (⁵⁶Fe/⁵⁴Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ～1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate₂ and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ⁵⁶Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.     

Analytical direct planetary perturbations on the orbital motion of satellites

An analytical expansion of the disturbing function arising from direct planetary perturbations on the motion of satellites is derived. As a Fourier series, it allows the investigation of the secular effects of these direct perturbations, as well as of every argument present in the perturbation. In particular, we construct an analytical model describing the evection resonance between the longitude of pericenter of the satellite orbit and the longitude of a planet, and study briefly its dynamic. The expansion developed in this paper is valid in the case of planar and circular planetary orbits, but not limited in eccentricity or inclination of the satellite orbit.     

Uniwavelength lidar sensitivity to spherical aerosol microphysical properties for the interpretation of Lagrangian stratospheric observations

The determination of stratospheric particle microphysical properties from multiwavelength lidar, including Rayleigh and/or Raman detection, has been widely investigated. However, most lidar systems are uniwavelength operating at 532 nm. Although the information content of such lidar data is too limited to allow the retrieval of the full size distribution, the coupling of two or more uniwavelength lidar measurements probing the same moving air parcel may provide some meaningful size information. Within the ORACLE-O3 IPY project, the coordination of several ground-based lidars and the CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation) space-borne lidar is planned during measurement campaigns called MATCH-PSC (Polar Stratospheric Clouds). While probing the same moving air masses, the evolution of the measured backscatter coefficient (BC) should reflect the variation of particles microphysical properties. A sensitivity study of 532 nm lidar particle backscatter to variations of particles size distribution parameters is carried out. For simplicity, the particles are assumed to be spherical (liquid) particles and the size distribution is represented with a unimodal log-normal distribution. Each of the four microphysical parameters (i.e. log-normal size distribution parameters, refractive index) are analysed separately, while the three others are remained set to constant reference values. Overall, the BC behaviour is not affected by the initial values taken as references. The total concentration (N₀) is the parameter to which BC is least sensitive, whereas it is most sensitive to the refractive index (m). A 2% variation of m induces a 15% variation of the lidar BC, while the uncertainty on the BC retrieval can also reach 15%. This result underlines the importance of having both an accurate lidar inversion method and a good knowledge of the temperature for size distribution retrieval techniques. The standard deviation (σ) is the second parameter to which BC is most sensitive to. Yet, the impact of m and σ on BC variations is limited by the realistic range of their variations. The mean radius (r_m) of the size distribution is thus the key parameter for BC, as it can vary several-fold. BC is most sensitive to the presence of large particles. The sensitivity of BC to r_m and σ variations increases when the initial size distributions are characterized by low r_m and large σ. This makes lidar more suitable to detect particles growing on background aerosols than on volcanic aerosols.     

Constraints on the thermal evolution of continental lithosphere from U-Pb accessory mineral thermochronometry of lower crustal xenoliths,southern Africa

U-Pb isotopic thermochronometry of rutile, apatite and titanite from kimberlite-borne lower crustal granulite xenoliths has been used to constrain the thermal evolution of Archean cratonic and Proterozoic off-craton continental lithosphere beneath southern Africa. The relatively low closure temperature of the U-Pb rutile thermochronometer (~400-450 °C) allows its use as a particularly sensitive recorder of the establishment of "cratonic" lithospheric geotherms, as well as subsequent thermal perturbations to the lithosphere. Contrasting lower crustal thermal histories are revealed between intracratonic and craton margin regions. Discordant Proterozoic (1.8 to 1.0 Ga) rutile ages in Archean (2.9 to 2.7 Ga) granulites from within the craton are indicative of isotopic resetting by marginal orogenic thermal perturbations influencing the deep crust of the cratonic nucleus. In Proterozoic (1.1 to 1.0 Ga) granulite xenoliths from the craton-bounding orogenic belts, rutiles define discordia arrays with Neoproterozoic (0.8 to 0.6 Ga) upper intercepts and lower intercepts equivalent to Mesozoic exhumation upon kimberlite entrainment. In combination with coexisting titanite and apatite dates, these results are interpreted as a record of postorogenic cooling at an integrated rate of approximately 1 °C/Ma, and subsequent variable Pb loss in the apatite and rutile systems during a Mesozoic thermal perturbation to the deep lithosphere. Closure of the rutile thermochronometer signals temperatures of 𙠂 °C in the lower crust during attainment of cratonic lithospheric conductive geotherms, and such closure in the examined portions of the "off-craton" Proterozoic domains of southern Africa indicates that their lithospheric thermal profiles were essentially cratonic from the Neoproterozoic through to the Late Jurassic. These results suggest similar lithospheric thickness and potential for diamond stability beneath both Proterozoic and Archean domains of southern Africa. Subsequent partial resetting of U-Pb rutile and apatite systematics in the cratonic margin lower crust records a transient Mesozoic thermal modification of the lithosphere, and modeling of the diffusive Pb loss from lower crustal rutile constrains the temperature and duration of Mesozoic heating to 𙡦 °C for ₞ ka. This result indicates that the thermal perturbation is not simply a kimberlite-related magmatic phenomenon, but is rather a more protracted manifestation of lithospheric heating, likely related to mantle upwelling and rifting of Gondwana during the Late Jurassic to Cretaceous. The manifestation of this thermal pulse in the lower crust is spatially and temporally correlated with anomalously elevated and/or kinked Cretaceous mantle paleogeotherms, and evidence for metasomatic modification in cratonic mantle peridotite suites. It is argued that most of the geographic differences in lithospheric thermal structure inferred from mantle xenolith thermobarometry are likewise due to the heterogeneous propagation of this broad upper mantle thermal anomaly. The differential manifestation of heating between cratonic margin and cratonic interior indicates the importance of advective heat transport along pre-existing lithosphere-scale discontinuities. Within this model, kimberlite magmatism was a similarly complex, space- and time-dependent response to Late Mesozoic lithospheric thermal perturbation.     

Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics

Molybdenum disulfide (MoS₂), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS₂ is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia.     

Mesozoic thermal evolution of the southern African mantle lithosphere

The thermal structure of Archean and Proterozoic lithospheric terranes in southern Africa during the Mesozoic was evaluated by thermobarometry of mantle peridotite xenoliths erupted in alkaline magmas between 180 and 60 Ma. For cratonic xenoliths, the presence of a 150–200 °C isobaric temperature range at 5–6 GPa confirms original interpretations of a conductive geotherm, which is perturbed at depth, and therefore does not record steady state lithospheric mantle structure.

Xenoliths from both Archean and Proterozoic terranes record conductive limb temperatures characteristic of a “cratonic” geotherm (40 mW m⁻²), indicating cooling of Proterozoic mantle following the last major tectonothermal event in the region at 1 Ga and the probability of thick off-craton lithosphere capable of hosting diamond. This inference is supported by U–Pb thermochronology of lower crustal xenoliths [Schmitz and Bowring, 2003. Contrib. Mineral. Petrol. 144, 592–618].

The entire region then suffered a protracted regional heating event in the Mesozoic, affecting both mantle and lower crust. In the mantle, the event is recorded at 150 Ma to the southeast of the craton, propagating to the west by 108–74 Ma, the craton interior by 85–90 Ma and the far southwest and northwest by 65–70 Ma. The heating penetrated to shallower levels in the off-craton areas than on the craton, and is more apparent on the southern margin of the craton than in its western interior. The focus and spatial progression mimic inferred patterns of plume activity and supercontinent breakup 30–100 Ma earlier and are probably connected.

Contrasting thermal profiles from Archean and Proterozoic mantle result from penetration to shallower levels of the Proterozoic lithosphere by heat transporting magmas. Extent of penetration is related not to original lithospheric thickness, but to its more fertile character and the presence of structurally weak zones of old tectonism. The present day distribution of surface heat flow in southern Africa is related to this dynamic event and is not a direct reflection of the pre-existing lithospheric architecture.     

Climate variability and trends in downscaled high-resolution simulations and projections over Metropolitan France

In order to fulfill the society demand for climate information at the spatial scale allowing impact studies, long-term high-resolution climate simulations are produced, over an area covering metropolitan France. One of the major goals of this article is to investigate whether such simulations appropriately simulate the spatial and temporal variability of the current climate, using two simulation chains. These start from the global IPSL-CM4 climate model, using two regional models (LMDz and MM5) at moderate resolution (15–20 km), followed with a statistical downscaling method in order to reach a target resolution of 8 km. The statistical downscaling technique includes a non-parametric method that corrects the distribution by using high-resolution analyses over France. First the uncorrected simulations are evaluated against a set of high-resolution analyses, with a focus on temperature and precipitation. Uncorrected downscaled temperatures suffer from a cold bias that is present in the global model as well. Precipitations biases have a season- and model-dependent behavior. Dynamical models overestimate rainfall but with different patterns and amplitude, but both have underestimations in the South-Eastern area (Cevennes mountains) in winter. A variance decomposition shows that uncorrected simulations fairly well capture observed variances from inter-annual to high-frequency intra-seasonal time scales. After correction, distributions match with analyses by construction, but it is shown that spatial coherence, persistence properties of warm, cold and dry episodes also match to a certain extent. Another aim of the article is to describe the changes for future climate obtained using these simulations under Scenario A1B. Results are presented on the changes between current and mid-term future (2021–2050) averages and variability over France. Interestingly, even though the same global climate model is used at the boundaries, regional climate change responses from the two models significantly differ.