Northern latitude chemical weathering rates: clues from the Mackenzie River Basin, Canada

The main scope of this study is to investigate parameters controlling chemical weathering rates for a large river system submitted to subarctic climate. More than 110 river water samples from the Mackenzie River system (northern Canada) have been sampled and analyzed for major and trace elements and Sr isotopic ratios in the dissolved phase. The three main morphological units are reflected in water chemistry. Rivers from the Canadian Shield are very dilute, dominated by silicate weathering (Millot et al., 2002), whereas the rivers of the Rocky and Mackenzie Mountains as well as the rivers of the sedimentary Interior Platform are dominated by carbonate weathering and are SO₄ rich. Compared to the rivers of the Mackenzie and Rocky Mountains, the rivers of the interior plains are organic, silica, and Na rich and constitute the dominant input term to the Mackenzie River mainstream. Rivers of the Canadian Shield area do not significantly contribute to the Mackenzie River system. Using elemental ratios and Sr isotopic ratios, a mathematical inversion procedure is presented that distinguishes between solutes derived from silicate weathering and solutes derived from carbonate weathering. Carbonate weathering rates are mostly controlled by runoff, which is higher in the mountainous part of the Mackenzie basin. These rates are comparable to the carbonate weathering rates of warmer areas of the world. It is possible that part of the carbonate weathering is controlled by sulfide oxidative weathering, but its extent remains difficult to assess. Conversely to what was stated by Edmond and Huh (1997), overall silicate weathering rates in the Mackenzie basin are low, ranging from 0.13 to 4.3 tons/km²/yr (Na + K + Ca + Mg), and confirm the negative action of temperature on silicate weathering rates for river basins in cold climates. In contrast to what has been observed in other large river systems such as the Amazon and Ganges Rivers, silicate weathering rates appear 3 to 4 times more elevated in the plains than in the mountainous headwaters. This contradicts the “Raymo hypothesis” (Raymo and Ruddiman, 1992). Isotopic characterization of suspended material clearly shows that the higher weathering rates reported for the plains are not due to the weathering of fine sediments produced in the mountains (e.g., by glaciers) and deposited in the plains. Rather, the relatively high chemical denudation rates in the plains are attributed to lithology (uncompacted shales), high mechanical denudation, and the abundance of soil organic matter derived from incomplete degradation and promoting crystal lattice degradation by element complexation. The three- to fourfold factor of chemical weathering enhancement between the plains and mountains is similar to the fourfold factor of enhancement found by Moulton et al. (2000) between unvegetated and vegetated watershed. This study confirms the negative action of temperature on silicate weathering for cold climate but shows that additional factors, such as organic matter, associated with northern watersheds are able to counteract the effect of temperature. This acceleration by a factor of 4 in the plains is equivalent to a 6°C increase in temperature.     

New U-Pb zircon and Ar/Ar muscovite age constraints on the emplacement of the Lizio syn-tectonic granite (Armorican Massif, France)

LA-ICP-MS U-Pb analyses performed on zircon grains from the Lizio granite yielded an emplacement age of 316 ± 6 Ma. Typical S-C structures show that the Lizio granite was emplaced contemporaneously with dextral shearing along the northern branch of the South Armorican Shear Zone and that it was therefore active at that time. ⁴⁰Ar/³⁹Ar analyses performed on muscovite grains yielded plateau dates ranging between 311.5 and 308.2 Ma. Muscovite chemistry is typical of primary magmatic muscovite, which precludes a late fluids-induced resetting of the K-Ar isotopic system. ⁴⁰Ar/³⁹Ar dates thus likely correspond to the cooling ages below the argon closure temperature. Considering the uncertainties on the measured ages, we can propose that either the Lizio granite cooled down quickly in less than a million of years or that it remained in a hot environment for several millions of years after its emplacement. This latter scenario could have been sustained by shear heating during dextral shearing along the northern branch of the South Armorican Shear Zone.     

Characterization of mesostasis regions in lunar basalts: Understanding late‐stage melt evolution and its influence on apatite formation

Recent studies geared toward understanding the volatile abundances of the lunar interior have focused on the volatile‐bearing accessory mineral apatite. Translating measurements of volatile abundances in lunar apatite into the volatile inventory of the silicate melts from which they crystallized, and ultimately of the mantle source regions of lunar magmas, however, has proved more difficult than initially thought. In this contribution, we report a detailed characterization of mesostasis regions in four Apollo mare basalts (10044, 12064, 15058, and 70035) in order to ascertain the compositions of the melts from which apatite crystallized. The texture, modal mineralogy, and reconstructed bulk composition of these mesostasis regions vary greatly within and between samples. There is no clear relationship between bulk‐rock basaltic composition and that of bulk‐mesostasis regions, indicating that bulk‐rock composition may have little influence on mesostasis compositions. The development of individual melt pockets, combined with the occurrence of silicate liquid immiscibility, exerts greater control on the composition and texture of mesostasis regions. In general, the reconstructed late‐stage lunar melts have roughly andesitic to dacitic compositions with low alkali contents, displaying much higher SiO₂ abundances than the bulk compositions of their host magmatic rocks. Relevant partition coefficients for apatite‐melt volatile partitioning under lunar conditions should, therefore, be derived from experiments conducted using intermediate compositions instead of compositions representing mare basalts.     

Multistage growth of Fe–Mg–carpholite and Fe–Mg–chloritoid,from field evidence to thermodynamic modelling

We provide new insights into the prograde evolution of HP/LT metasedimentary rocks on the basis of detailed petrologic examination, element-partitioning analysis, and thermodynamic modelling of well-preserved Fe–Mg–carpholite- and Fe–Mg–chloritoid-bearing rocks from the Afyon Zone (Anatolia). We document continuous and discontinuous compositional (ferromagnesian substitution) zoning of carpholite (overall X _Mg = 0.27–0.73) and chloritoid (overall X _Mg = 0.07–0.30), as well as clear equilibrium and disequilibrium (i.e., reaction-related) textures involving carpholite and chloritoid, which consistently account for the consistent enrichment in Mg of both minerals through time, and the progressive replacement of carpholite by chloritoid. Mg/Fe distribution coefficients calculated between carpholite and chloritoid vary widely within samples (2.2–20.0). Among this range, only values of 7–11 correlate with equilibrium textures, in agreement with data from the literature. Equilibrium phase diagrams for metapelitic compositions are calculated using a newly modified thermodynamic dataset, including most recent data for carpholite, chloritoid, chlorite, and white mica, as well as further refinements for Fe–carpholite, and both chloritoid end-members, as required to reproduce accurately petrologic observations (phase relations, experimental constraints, Mg/Fe partitioning). Modelling reveals that Mg/Fe partitioning between carpholite and chloritoid is greatly sensitive to temperature and calls for a future evaluation of possible use as a thermometer. In addition, calculations show significant effective bulk composition changes during prograde metamorphism due to the fractionation of chloritoid formed at the expense of carpholite. We retrieve P–T conditions for several carpholite and chloritoid growth stages (1) during prograde stages using unfractionated, bulk-rock XRF analyses, and (2) at peak conditions using compositions fractionated for chloritoid. The P–T paths reconstructed for the Kütahya and Afyon areas shed light on contrasting temperature conditions for these areas during prograde and peak stages.     

On the Use of Hydrological Models and Satellite Data to Study the Water Budget of River Basins Affected by Human Activities: Examples from the Garonne Basin of France

Natural and anthropogenic forcing factors and their changes significantly impact water resources in many river basins around the world. Information on such changes can be derived from fine scale in situ and satellite observations, used in combination with hydrological models. The latter need to account for hydrological changes caused by human activities to correctly estimate the actual water resource. In this study, we consider the catchment area of the Garonne river (in France) to investigate the capabilities of space-based observations and up-to-date hydrological modeling in estimating water resources of a river basin modified by human activities and a changing climate. Using the ISBA–MODCOU and SWAT hydrological models, we find that the water resources of the Garonne basin display a negative climate trend since 1960. The snow component of the two models is validated using the moderate-resolution imaging spectroradiometer snow cover extent climatology. Crop sowing dates based on remote sensing studies are also considered in the validation procedure. Use of this dataset improves the simulated evapotranspiration and river discharge amounts when compared to conventional data. Finally, we investigate the benefit of using the MAELIA multi-agent model that accounts for a realistic agricultural and management scenario. Among other results, we find that changes in crop systems have significant impacts on water uptake for agriculture. This work constitutes a basis for the construction of a future modeling framework of the sociological and hydrological system of the Garonne river region.     

Geothermal waters from the Taupo Volcanic Zone,New Zealand: Li,B and Sr isotopes characterization

Chemical and isotopic data for 23 geothermal water samples collected in New Zealand within the Taupo Volcanic Zone (TVZ) are reported. Major and trace elements including Li, B and Sr and their isotopic compositions (δ⁷Li, δ¹¹B, ⁸⁷Sr/⁸⁶Sr) were determined in high temperature geothermal waters collected from deep boreholes in different geothermal fields (Ohaaki, Wairakei, Mokai, Kawerau and Rotokawa geothermal systems). Lithium concentrations are high (from 4.5 to 19.9 mg/L) and Li isotopic compositions (δ⁷Li) are homogeneous, ranging between −0.5‰ and +1.4‰. In particular, it is noteworthy that, except for the samples from the Kawerau geothermal field having slightly higher δ⁷Li values (+1.4%), the other geothermal waters have a near constant δ⁷Li signature around a mean value of 0‰ ± 0.6 (2σ, n = 21). Boron concentrations are also high and relatively homogeneous for the geothermal samples, falling between 17.5 and 82.1 mg/L. Boron isotopic compositions (δ¹¹B) are all negative, and display a range between −6.7‰ and −1.9‰. These B isotope compositions are in agreement with those of the Ngawha geothermal field in New Zealand. Lithium and B isotope signatures are in a good agreement with a fluid signature mainly derived from water/rock interaction involving magmatic rocks with no evidence of seawater input. On the other hand, Sr concentrations are lower and more heterogeneous and fall between 2 and 165 μg/L. The ⁸⁷Sr/⁸⁶Sr ratios range from 0.70549 to 0.70961. These Sr isotope compositions overlap those of the Rotorua geothermal field in New Zealand, confirming that some geothermal waters (with more radiogenic Sr) have interacted with bedrocks from the metasedimentary basement. Each of these isotope systems on their own reveals important information about particular aspects of either water source or water/rock interaction processes, but, considered together, provide a more integrated understanding of the geothermal systems from the TVZ in New Zealand.     

Late Pleistocene climatic change in the French Jura (Gigny) recorded in the δO of phosphate from ungulate tooth enamel

Oxygen isotope compositions of phosphate in tooth enamel from large mammals (i.e. horse and red deer) were measured to quantify past mean annual air temperatures and seasonal variations between 145 ka and 33 ka in eastern France. The method is based on interdependent relationships between the δ¹⁸O of apatite phosphate, environmental waters and air temperatures. Horse (Equus caballus germanicus) and red deer (Cervus elaphus) remains have δ¹⁸O values that range from 14.2‰ to 17.2‰, indicating mean air temperatures between 7°C and 13°C. Oxygen isotope time series obtained from two of the six horse teeth show a sinusoidal-like signal that could have been forced by temperature variations of seasonal origin. Intra-tooth oxygen isotope variations reveal that at 145 ka, winters were colder (? 7 ± 2°C) than at present (3 ± 1°C) while summer temperatures were similar. Winter temperatures mark a well-developed West–East thermal gradient in France of about ? 9°C, much stronger than the ?4°C difference recorded presently. Negative winter temperatures were likely responsible for the extent and duration of the snow cover, thus limiting the food resources available for large ungulates with repercussions for Neanderthal predators.     

Stepwise palaeoclimate change across the Eocene–Oligocene transition recorded in continental NW Europe by mineralogical assemblages and δ15Norg (Rennes Basin,France)

The Eocene–Oligocene transition (EOT, ~34 Ma) is the largest global cooling of the Cenozoic Era and led the Earth's climatic system to change from a greenhouse to an icehouse mode. Although it is well documented in marine settings, the few studies focusing on continental environments have demonstrated regional heterogeneities. The study core CDB1, located in the Rennes Basin (Western France), is a unique terrestrial (lacustrine–palustrine) record comprising well‐preserved and terrestrial‐derived organic‐rich sediments encompassing the EOT. Clay minerals and the first organic nitrogen isotope record (δ¹⁵N_org) of terrestrial origin for this period are used to reconstruct palaeoclimate changes across this key interval. As suggested in worldwide marine and a few continental records, a stepwise transition from warm/humid conditions in the Late Eocene to cooler/drier conditions in the Early Oligocene is confirmed in the area. In addition, an episode of drier conditions in the Late Eocene and humid/dry cycles in the Early Oligocene are suggested.     

From subduction to collision: Thermal overprint of HP/LT meta-sediments in the north-eastern Lepontine Dome (Swiss Alps) and consequences regarding the tectono-metamorphic evolution of the Alpine orogenic wedge

The Cenozoic-age metamorphic structure of the Alps consists of a throughgoing pressure-dominated belt (blueschists and eclogites) that strikes parallel to the orogen and was later truncated by two thermal domes characterised by Barrow-type metamorphism (Lepontine dome and Tauern window). This study documents for the first time that relics of Fe-Mg carpholite occur also within meta-sedimentary units that are part of the north-eastern Lepontine structural and metamorphic dome, where so far exclusively Barrovian assemblages were found. They occur in meta-sediments of both Valais Oceanderived Lower Penninic Bündnerschiefer and structurally lower Europe-derived Sub-Penninic cover nappes and slices. These high-pressure units were subsequently overprinted by a thermal event, as is documented by the growth of new minerals typical for Barrovian metamorphism.We present evidence for a two-stage metamorphic evolution in the northern part of the Lepontine dome: (1) Early subduction-related syn-D1 (Safien phase) HP/LT metamorphism under blueschist facies conditions (350–400 °C and 1.2–1.4 GPa) was immediately followed by “cold” isothermal (or cooling) decompression during D2 nappe-stacking (Ferrera phase). (2) Collisionrelated Barrovian overprint (500–570 °C and 0.5–0.8 GPa) postdates the D3 nappe-refolding event (Domleschg phase) and represents a late heating pulse, separated by D2 and D3 from the D1 high-pressure event. It occurred before and/or during the initial stages of D4 (Chiéra phase) representing a second nappe-refolding event.In discussing possible heat sources for the late Barrow-type heating pulse it is argued that heat release from radioactive decay of accreted material may play an important role in contributing much to heat production. Based on the field evidence, we conclude that heat transfer was essentially conductive during these latest stages of the thermal evolution.