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The Δ47 clumped isotope thermometer has been applied to multiple studies aimed at reconstructing the paleoelevation and paleoclimate of sedimentary basins and paleosol sequences. Ideally, this technique directly preserves the temperature of carbonate formation, avoiding any speculation on the composition of surface water from which the carbonate precipitated. Recently, however, concerns about post-depositional alteration of the Δ47 isotope signature from the effects of burial and/or diagenetic alteration have arisen, potentially complicating the application of the Δ47 clumped isotope thermometer for determining paleo-surface temperatures. Here we investigate the effect of burial history on mass-47 clumped isotope. To this purpose we collected samples, from the surface and from drill cores, in two different areas of the Greater Green River basin: the Washakie Basin near Rock Springs, Wyoming and the Green River Basin near Pinedale, Wyoming. Both basins are filled with a thick sequence of Eocene lacustrine strata and the thermal histories of both basins are well documented from petroleum prospecting studies. Clumped isotope Δ47 compositions were measured from lacustrine micritic limestones with a range of peak burial depths from 1 to 6.5 km. For samples from the Washakie Basin that did not experience burial depths exceeding ∼2000 meters, the measured Δ47 values vary from 0.623‰ to 0.684‰, yielding carbonate formation temperatures consistent with previously hypothesized Paleocene-Eocene surface temperatures. In contrast, samples from the Green River Basin, collected from greater burial depths, demonstrate significantly lower Δ47 values (higher temperatures). The consistency of δ18O values and lack of CL evidence for recrystallization suggest closed-system resetting of the clumped isotope thermometer by either partial solid-state re-ordering or carbonate reprecipitation during burial. The Δ47 values of the deeply buried samples have been compared to values derived from recrystallization and temperature history reordering models (THRMs). Both recrystallization and reordering models are successful at predicting Δ47 reordering at burial temperatures >100 °C. These observations, from samples collected from a basin with a remarkably well-constrained thermal history and geothermal gradient, highlight the challenges in elucidating burial histories or diagenetic processes solely from clumped isotopic compositions.

Clumped isotopes thermometry (Δ47) and U-Pb dating of carbonates have been used to elucidate the temperature-time conditions of 10 tectonic calcite veins in the hanging wall of the South Pyrenean Frontal Thrust (Spain), the youngest thrust unit in the south-central Pyrenees. The Δ47 values indicate precipitation temperatures below ∼90 °C, in agreement with fluid inclusion analyses. 6 veins have been successfully dated, giving ages between 61 and 14.5 Ma with all but one value below 24 Ma. On the basis of our new results, we propose that several the studied veins record the end of Pyrenean tectonics in the area during the Burdigalian, possibly up to the Serravalian, younger than estimates based on magnetostratigraphic data from continental syn-tectonic deposits. Calculated δ18O values of the precipitating fluid are either very positive, suggesting a local source that has interacted with the host rock, or negative, suggesting the downward incursion of meteoric waters. For undated or pre-burial veins, the Δ47 values derived from temperature history reordering model (THRM) show that the measured Δ47 values may have been significantly altered during burial, preventing their use as a reliable thermal or paleohydrological marker. Although applied to a limited number of samples, these results highlight the great potential of the U-Pb/Δ47 approach to decipher the history of vein or cement formation and fluid flow in complex tectonic zones, provided that (i) the thermal evolution is known and (ii) the extent of clumped isotope reordering is systematically modelled., This work benefited from a PhD grant of the French Ministry of Research (MESR) to NC. All analyses and field work performed in the course of this study were funded by a “CNRS excellence chair” grant to GH.

Syntectonic veins commonly have been used to assess the composition and source of fluids involved in fault zone activity. Such veins also provide information on the ambient stress conditions during deformation and mineralization. Based on bulk sampling and bulk O- and C-isotope analysis, combined with fluid inclusion microthermometry, many studies have demonstrated that syntectonic veins provide snapshots of fluid composition and stress conditions over the course of fault history. This is widely acknowledged for mode I extension veins that develop in the damage zones of faults. However, an important and unanswered question is the extent to which such veins record a more detailed fault history at the micron scale. In this study, we present new detailed in-situ micron-scale δ 18 O data, measured using Secondary Ion Mass Spectrometry (SIMS), combined with detailed fluid inclusion microthermometry and Δ47 clumped isotope thermometry to document the fluid and temperature conditions during mode I vein growth related to deformation along the Cotiella thrust fault (Pyrenees). All the studied veins show three distinct episodes of vein opening, recording a complex history of varying fluid composition and temperature. Results show that the studied fault portion passed from a hydrological rock-buffered system, in which formation waters were in isotopic equilibrium with the host sediments, to a fluid-buffered system involving meteoric water. However, such information is only achievable at the micron scale using Secondary Ion Mass Spectrometry. This study demonstrates the potential of these new micro-beam techniques for investigating fault behavior in more detail than previously available, particularly with respect to the nature of the fluids involved and the P–T conditions extant during fault activity.

The Kettara shear zone is a regional wrench shear zone within the Jebilet massif of Western Morocco, part of the Variscan orogenic belt. This massif is characterized by bimodal magmatism, largely intrusive, and by a number of polymetallic massive sulfide deposits. A syntectonic mafic-ultramafic intrusion and an adjacent, deformed pyrrhotite-rich massive sulfide deposit are located within a ‘compressional jog’ of the shear zone. Hydrothermal alteration in both the intrusion and the wall rocks adjacent to the deposit is characterized by syntectonic replacement processes leading to formation of chlorite-schists and quartz ± calcite veins. Fluid inclusions in mineralized (pyrrhotite-bearing) quartz veins from the wall rocks adjacent to the deposit and in veins associated with chlorite-schists within the intrusion indicate a prevalence of H2O-CO2-CH4-N2 and H2O-salt fluid systems. In the mineralized veins the fluid shows reducing conditions, with gas dominated by CH4 and N2 and salinities around 7.5 wt% NaCl, whereas in the chlorite shear zones fluid is CO2 dominated and salinities are higher than 23 wt% NaCl. Hydrogen and oxygen isotopic compositions of chlorite and quartz are similar and demonstrate involvement of metamorphic water in both the deposit and the intrusion. The data are consistent with a regional metamorphic fluid flow through the Kettara shear zone. The migrating metamorphic fluids were reduced in the organic matter-rich host rocks leading to deposition of sulfides in the mineralized veins. There are two possible hypotheses for the origin of these mineralized veins: either they were formed during deformation and remobilization of a syn-sedimentary massive sulfide deposit, or they were formed synchronously with the sulfide deposit during development of the Kettara shear zone.

The pace and degree of nutrient limitation are among the most critical uncertainties in predicting terrestrial ecosystem responses to global change. In the northeastern United States, forest growth has recently declined along with decreased soil calcium (Ca) availability, suggesting that acid rain has depleted soil Ca to the point where it may be a limiting nutrient. However, it is unknown whether the past 60 y of changes in Ca availability are strictly anthropogenic or partly a natural consequence of long-term ecosystem development. Here, we report a high-resolution millennial-scale record of Ca and 16 other elements from the sediments of Mirror Lake, a 15-ha lake in the White Mountains of New Hampshire surrounded by northern hardwood forest. We found that sedimentary Ca concentrations had been declining steadily for 900 y before regional Euro-American settlement. This Ca decline was not a result of serial episodic disturbances but instead the gradual weathering of soils and soil Ca availability. As Ca availability was declining, nitrogen availability concurrently was increasing. These data indicate that nutrient availability on base-poor, parent materials is sensitive to acidifying processes on millennial timescales. Forest harvesting and acid rain in the postsettlement period mobilized significant amounts of Ca from watershed soils, but these effects were exacerbated by the long-term pattern. Shifting nutrient limitation can potentially occur within 10,000 y of ecosystem development, which alters our assessments of the speed and trajectory of nutrient limitation in forests, and could require reformulation of global models of forest productivity.

The Los Burros gold deposit is located within the Franciscan complex of the Nacimiento block, California. Although this deposit was mined during the late 19th and early 20th centuries, its origin and its relationship with the regional metamorphism and deformation are unclear. In order to better understand the mode of formation of the deposit, and its possible link with a post-subduction thermal anomaly, we performed a detailed geological and structural mapping within the Los Burros district, coupled with a (U-Th)/He thermochronological study on apatite and zircon. Fluid-inclusion and stable isotope (O and C) analyses of the ore deposit provide constraints on the temperature and potential source of the fluid(s) responsible for the Los Burros gold formation. Our results demonstrate that the Los Burros Au deposit formed from a metamorphic aqueous CO2-CH4 fluid at temperatures of ~300 °C. Results from Raman Spectroscopy of Carbonaceous Materials confirm the presence of a thermal anomaly in the range 260–320 °C near the Los Burros Mining District as previously inferred by vitrinite reflectance techniques. Our structural and preliminary thermochronological analyses show that the Los Burros Au deposit consists of a series of meter-wide, quartz-calcite-sulfide “en-echelon” veins, formed during a late transpressive event related to San Andreas fault activity and the subduction of a slab-window during the past 30 Ma. Our new data suggest that the thermal anomaly recorded in the vicinity of the Los Burros Mining District is not associated with a magmatic-derived hydrothermal system such as described within the epithermal McLaughlin deposit in Northern California, but rather with a late transpressive deformation event that uplifted deeply buried metamorphic rocks, possibly connected to a local metamorphic overprint.

One-dimensional carbon nanomaterials such as carbon nanotubes (CNTs) and graphene nanoribbons (GNRs) are promising for future applications in nanoelectronics and nanophotonics due to their unique characteristics such as topological edge states, chirality, and quantum confinement. Despite the chemical unzipping method of producing GNRs from CNTs, using energetic photons to control light–matter interaction and shape materials at the nanoscale has great promise, especially for chemical-free and on-demand manufacturing. Here, we exploit the high electromagnetic field from a Ti:Sapphire femtosecond laser to interact with CNTs, causing ultrafast energy transfer between the photons and the nanotubes and converting them to GNRs and carbon nanocrystals. Probed with scattering-type scanning near-field optical microscopy, the nanoribbons are identified as semiconducting and/or insulating, a strikingly different electronic phase compared with the original metallic CNTs. Our method of employing high-field and nonequilibrium processes with an ultrafast laser to alter the shape and transform the electronic properties is scalable, does not necessitate high-temperature processes, and is highly spatially controllable—conditions that pave the way for manufacturing nanoscale hybrid materials and devices.

The chemical and isotopic compositions of clay minerals such as illite and chlorite are commonly used to quantify diagenetic and low-grade metamorphic conditions, an approach that is also used in the present study of the Monte Perdido thrust fault from the South Pyrenean fold-and-thrust belt. The Monte Perdido thrust fault is a shallow thrust juxtaposing upper Cretaceous-Paleocene platform carbonates and Lower Eocene marls and turbidites from the Jaca basin. The core zone of the fault, about 6 m thick, consists of intensely deformed clay-bearing rocks bounded by major shear surfaces. Illite and chlorite are the main hydrous minerals in the fault zone. Illite is oriented along cleavage planes while chlorite formed along shear veins (< 50 mu m in thickness). Authigenic chlorite provides essential information about the origin of fluids and their temperature. delta O-18 and delta D values of newly formed chlorite support equilibration with sedimentary interstitial water, directly derived from the local hanging wall and footwall during deformation. Given the absence of large-scale fluid flow, the mineralization observed in the thrust faults records the P-T conditions of thrust activity. Temperatures of chlorite formation of about 240A degrees C are obtained via two independent methods: chlorite compositional thermometers and oxygen isotope fractionation between cogenetic chlorite and quartz. Burial depth conditions of 7 km are determined for the Monte Perdido thrust reactivation, coupling calculated temperature and fluid inclusion isochores. The present study demonstrates that both isotopic and thermodynamic methods applied to clay minerals formed in thrust fault are useful to help constrain diagenetic and low-grade metamorphic conditions.

Observations from deep boreholes at several locations worldwide, laboratory measurements of frictional strength on quartzo-feldspathic materials, and earthquake focal mechanisms indicate that crustal faults are strong (apparent friction μ ≥ 0.6). However, friction experiments on phyllosilicate-rich rocks and some geophysical data have demonstrated that some major faults are considerably weaker. This weakness is commonly considered to be characteristic of mature faults in which rocks are altered by prolonged deformation and fluid-rock interaction (i.e., San Andreas, Zuccale, and Nankai Faults). In contrast, in this study we document fault weakening occurring along a marly shear zone in its infancy (

International audience; The present work aims at understanding the tectonic evolution of the Jebilet massif, Morocco, during the Late Paleozoic as constrained by structural, metamorphic and geochronological studies. From Late Devonian to Early Carboniferous, bordering faults controlled the opening of the Jebilet intracontinental basin (D0 stage) as shown by sedimentary infill. This episode was accompanied by a magmatic activity, newly dated between 358±7 Ma and 336±4 Ma. The first record of the Variscan event affected the Jebilet by the Late Visean‐Namurian and is represented by allochthonous superficial nappes emplaced at shallow depth in a moderately lithified sedimentary succession. D1 also developed regional‐scale recumbent folds trending E‐W that may suggest N‐S crustal shortening not generating crustal thickening, nor contributing to metamorphism. The main Variscan D2 episode consists of a progressive evolution from bulk coaxial deformation to non‐coaxial dextral transpression consistent with NW‐SE horizontal shortening, resulting in a moderate thickening. This episode was accompanied by HT‐LP metamorphism and syntectonic intrusions controlled by an inherited thermal anomaly in relation with the intracontinental rifting stage (D0). Based on previous age determinations from syntectonic leucogranite and metamorphic rocks, D2 is dated between 310 and 280 Ma. The tectono‐metamorphic evolution of the Jebilet massif can be correlated with a plate‐tectonic scenario evolving from, first a Late Devonian–Early Carboniferous basin formation during stretching of the north‐Gondwana margin and initiation of the Paleotethys Ocean, and, second, to a Late Carboniferous‐Early Permian ocean closure (Rheic or Paleotethys Oceans depending of scenarios) that resulted in the final Variscan‐Alleghanian tectonics.

In orogens, shortening is mainly accommodated by thrusts, which constitute preferential zones for fluid–rock interactions. Fluid flow, mass transfer, and mineralogical reactions taking place along thrusts have been intensely investigated, especially in sedimentary basins for petroleum and uranium research. This study combines petrological investigations, mineralogical quantifications, and geochemical characterizations with a wide range of analytical tools with the aim of defining the fluid properties (nature, origin, temperature, and redox) and fluid–host rock interactions (mass transfers, recrystallization mechanisms, and newly formed synkinematic mineralization) in the Pic-de-Port-Vieux thrust fault zone (Pyrenees, Spain). We demonstrate that two geochemically contrasted rocks have been transformed by fluid flow under low-grade metamorphism conditions during thrusting. The hanging-wall Triassic red pelite was locally bleached, while the footwall Cretaceous dolomitic limestone was mylonitized. The results suggest that thrusting was accompanied by a dynamic calcite recrystallization in the dolomitic limestone as well as by leaching of iron via destabilization of iron oxides and phyllosilicate crystallization in the pelite. Geochemical and physical changes highlighted in this study have strong implications on the understanding of the thrust behavior (tectonic and hydraulic), and improve our knowledge of fluid–rock interactions in open fluid systems in the crust.

ACL; International audience; This study aims at understanding the origin and nature of syn-orogenic fluid flow in the Jaca basin from the South Pyrenean fold and thrust-belt, as recorded in calcite and quartz veins of the Sierras Interiores (Spain) and the turbiditic basin, which cover upper Cretaceous to Late Eocene syntectonic deposits. The fracture network consists of a classical pattern of transverse and longitudinal fractures related to Layer Parallel Shortening (LPS) and folding respectively. Veins filled equally about the third of fractures in the carbonate shelf and turbidites. Carbon and oxygen isotopes of calcite veins mostly indicate precipitation from isotopically buffered water, consistent with high water-rock interaction. In the Sierras Interiores, petrographical observations and fluid inclusion microthermometry are consistent with two distinct stages of precipitation. The first stage is characterized by relatively low Th and low salinities (155-205 °C and 0.5-3.2 wt% eq. NaCl). The second stage, which was characterized both by the formation of mode-I joints and by mode-I reactivation of pre-existing veins, shows higher Th and salinities (215-270 °C and 2.2-5.7 wt% eq. NaCl). Waters recorded in the second stage are interpreted to have interacted with underlying Triassic evaporites and flowed along major thrusts before vein precipitation, which are locally in thermal disequilibrium with host-rocks. We suggest the transition from a rather closed hydrological system during the first stage of vein formation, interpreted to have occurred during Eaux-chaudes thrusting (upper Lutetian-Bartonian), to a more open hydrological system during the second stage, which likely occurred during Gavarnie thrusting (Priabonian-early Rupelian). Finally, we also document the migration in space and time of hydrothermal pulses along the South Pyrenean Foreland Basin, related to the westward propagation of major thrusts during the Pyrenean orogeny. © 2017 John Wiley & Sons Ltd, European Association of Geoscientists & Engineers and International Association of Sedimentologists.

The pace and degree of nutrient limitation are among the most critical uncertainties in predicting terrestrial ecosystem responses to global change. In the northeastern United States, forest growth has recently declined along with decreased soil calcium (Ca) availability, suggesting that acid rain has depleted soil Ca to the point where it may be a limiting nutrient. However, it is unknown whether the past 60 y of changes in Ca availability are strictly anthropogenic or partly a natural consequence of long-term ecosystem development. Here, we report a high-resolution millennial-scale record of Ca and 16 other elements from the sediments of Mirror Lake, a 15-ha lake in the White Mountains of New Hampshire surrounded by northern hardwood forest. We found that sedimentary Ca concentrations had been declining steadily for 900 y before regional Euro-American settlement. This Ca decline was not a result of serial episodic disturbances but instead the gradual weathering of soils and soil Ca availability. As Ca availability was declining, nitrogen availability concurrently was increasing. These data indicate that nutrient availability on base-poor, parent materials is sensitive to acidifying processes on millennial timescales. Forest harvesting and acid rain in the postsettlement period mobilized significant amounts of Ca from watershed soils, but these effects were exacerbated by the long-term pattern. Shifting nutrient limitation can potentially occur within 10,000 y of ecosystem development, which alters our assessments of the speed and trajectory of nutrient limitation in forests, and could require reformulation of global models of forest productivity.

International audience; During compressive events, deformation in sedimentary basins is mainly accommodated by thrust faulting and related fold growth. Thrust faults are generally rooted in the basement and may act as conduits or barriers for crustal fluid flow. Most of recent studies suggest that fluid flow through such discontinuities is not apparent and depends on the structural levels of the thrust within the fold-and-thrust belt. In order to constrain the paleofluid flow through the Jaca thrust-sheet-top basin (Paleogene southwest-Pyrenean fold-and-thrust belt) this study compares on different thrust faults located at different structural levels. The microstructures in the different fault zones studied are similar and consist of pervasive cleavage, calcite shear veins (SV1), extension veins (EV1) and late dilatation veins (EV3). In order to constrain the nature and the source of fluids involved in fluid-rock interactions within fault zones, a geochemical approach, based on oxygen and carbon stable isotope and trace element compositions of calcite from different vein generations and host rocks was adopted. The results suggest a high complexity in the paleohydrological behaviors of thrust faults providing evidence for a fluid-flow compartmentalization within the basin. Previous studies in the southern part of the Axial Zone (North of the Jaca basin) indicates a circulation of deep metamorphic water, probably derived from the Paleozoic basement, along fault zones related to the major basement Gavarnie thrust. In contrast, in northern part of the Jaca basin, the Monte Perdido thrust fault is affected by a closed hydrological fluid system involving formation water during its activity. The Jaca and Cotiella thrust faults, in turn, both located more to the south in the basin, are characterized by a composite fluid flow system. Indeed, stable isotope and trace element compositions of the first generations of calcite veins suggest a relatively closed paleohydrological system, whereas the late calcite vein generations, which are probably associated with the late tectonic activity of the basin, support a contribution of both meteoric and marine waters. Based on these results, a schematic fluid-flow model is presented. This model allows visualization of three main fluid flow compartments along a N-S transect.

Thrusting fault zone in foreland basins are characterized by highly foliated zones generally enriched in phyllosilicates which can play a major role on the mechanical behaviour of the fault. In this context, investigations of synkinematic clay minerals permit to determine the origin of the fluid from which they precipitated as well as the mechanisms of deformation. Our study is focused on clay mineral assemblages (illite and chlorite) in a major thrust fault located in the Monte Perdido massif (southern Pyrenees), a shallow thrust that affects upper cretaceous-paleocene platform carbonates and lower Eocene marls and turbidites. It implied 3 km of displacement of the Monte Perdido thrust unit with respect to the underlying Gavarnie unit. In this area the cleavage development by pressure-solution is linked to the Monte Perdido and Gavarnie thrust activity. The core zone of the fault, about 6 m thick, consists of an interval of intensely deformed clay-bearing rocks bounded by major shear surfaces. The deformed sediment is markedly darker than the protolith. Calcite-quartz shear veins along the shear planes are abundant. Detailed SEM and TEM observations of highly deformed fault zone samples indicate that clay mineral enrichment in the core zone of the fault is not only related to passive increase by pressure-solution mechanism but that dissolution–recrystallization of phyllosilicates occurs during deformation. A mineral segregation is observed in the highly deformed zone. Newly formed 2M 1 muscovite is present along the cleavage whereas IIb chlorite crystals fill SV2 shear veins suggesting syntectonic growth of phyllosilicates in the presence of fluids in low-grade metamorphic conditions. These mineralogical reactions act as weakening processes and would favour Monte Perdido fault creeping.

The Monte Perdido thrust fault (southern Pyrenees) consists of a 6-m-thick interval of intensely deformed clay-bearing rocks. The fault zone is affected by a pervasive pressure solution seam and numerous shear surfaces. Calcite extensional-shear veins are present along the shear surfaces. The angular relationships between the two structures indicate that shear surfaces developed at a high angle (70°) to the local principal maximum stress axis σ1. Two main stages of deformation are present. The first stage corresponds to the development of calcite shear veins by a combination of shear surface reactivation and extensional mode I rupture. The second stage of deformation corresponds to chlorite precipitation along the previously reactivated shear surfaces. The pore fluid factor λ computed for the two deformation episodes indicates high fluid pressures during the Monte Perdido thrust activity. During the first stage of deformation, the reactivation of the shear surface was facilitated by a suprahydrostatic fluid pressure with a pore fluid factor λ equal to 0.89. For the second stage, the fluid pressure remained still high (with a λ value ranging between 0.77 and 0.84) even with the presence of weak chlorite along the shear surfaces. Furthermore, evidence of hydrostatic fluid pressure during calcite cement precipitation supports that incremental shear surface reactivations are correlated with cyclic fluid pressure fluctuations consistent with a fault-valve model.

International audience; In orogenic systems, thrust faults play a major role in stacking different tectonic units and may act as conduits for the expulsion of large amounts of fluid of different origins (metamorphic, diagenetic, meteoric). This study focuses on the Monte Perdido thrust unit emplaced in the Paleogene Jaca thrust-sheet-top basin, in the SW-central Pyrenees. We aim to decipher the mechanisms and P-T conditions of deformation in fault zones and characterize the related fluid involvement, through combined microstructural, geochemical and microthermometry analyses. Two thrust faults cutting platform limestones, marls and siliciclastic turbidites of the lower part of the basin-fill (Paleocene-lower Eocene) have been studied. The fault zones are characterized by metre-thick shear zones with highly deformed, foliated clay-rich sediments. Foliation is underlined by preferentially oriented phyllosilicates. Several generations of shear and extension calcite, quartz and chlorite-bearing veins attest to fluid-rock interactions during a multi-stage deformation. Microstructural observations and stable isotope analyses on calcite from veins and host sediments suggest that deformation was aseismic and dominated by diffusive mass transfer from pressure solution sites along cleavage and stylolites to the precipitation sites in veins, with mineralizing fluids in equilibrium with the host sediments. Our results suggest an essentially closed hydrologic system, and imply the absence of significant fluid flow along the studied fault zones. Microthermometric study on fluid inclusions present in calcite and quartz veins, and calcite-quartz oxygen isotopic fractionation determined for the first generation shear veins, allow a geothermal gradient of 34 degrees C/km to be estimated. Analytical results demonstrate an evolution of the fault zones in three stages. The first stage was related to the emplacement of the Monte Perdido thrust unit during the middle Eocene at a temperature of similar to 208 degrees C and a burial depth of similar to 5.7 km. The second stage corresponds to a fault reactivation at a temperature of similar to 240 degrees C and a burial depth of similar to 6.5 km. The latter deformation may have been related to folding of the Monte Perdido thrust unit during the emplacement of the underlying Gavarnie thrust unit during the late Eocene-early Oligocene, with deeper burial resulting from aggradation of the thrust-sheet-top basin-fill. The last event corresponds to the formation of a dilatant vein system likely related to the exhumation of the massif.