A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

Vegetation response to obliquity and precession forcing during the Mid-Pleistocene Transition in Western Mediterranean region (ODP site 976)

The ODP leg 161 Site 976 (Alboran Sea) is a deep-sea section sampled at a water depth of 1108 m in the Western Mediterranean Sea. Pollen analysis provides a vegetation and climate record of the Mid Pleistocene Transition (MPT), roughly one million years ago. The age-model tied to biostratigraphic events was revised by aligning the pollen climate index (PCI) to Mediterranean (KC01b) and global (LR04) oxygen isotope records. The studied time slice spans the interval ～1.09 Ma (MIS 31) to ～0.90 Ma (MIS 23).Across this interval, past phytogeography of nowadays extinct taxa, which were rare, allows a successful application of the modern analogues technique (MAT) to quantitative climate reconstructions for the MPT. Five, long-term, obliquity-related vegetation successions (O1 to O5), and eight short-term, precession-related vegetation successions (P1 to P8) are observed within the studied interval. These vegetation successions, regardless of their duration, show the same pattern: the progressive replacement of temperate trees by mountainous taxa, and then by herbs and steppe maxima. Precession-related successions correspond, therefore, to as dramatic vegetation changes as those driven by obliquity, including a final steppe phase under deteriorated climate conditions.Wavelet analysis of the PCI record shows that the Western Mediterranean experienced a shift at 1.01 Ma from precession-dominated frequencies (1.05–1.01 Ma) to obliquity-dominated frequencies (1.01–0.9 Ma). There is, therefore, an apparent discrepancy between wavelet analysis results and vegetation dynamic analysis (which suggests that obliquity and precession are recorded throughout the entire studied interval). This discrepancy could result from the fact that the PCI record sums, somehow, similar vegetation changes (wet to dry) occurring at different periodicities. Such a complex vegetation dynamics is mathematically rendered through a single parameter (i.e. principal component), which does not successfully catch the subtle combinations of variability occurring at two close periodicities. Furthermore, the pollen-inferred Early Pleistocene vegetation dynamic (and climate) of the Western Mediterranean region does not show a decrease of the obliquity response relative to the precession response at the onset of the MPT.     

Using species traits to guide conservation actions under climate change

Few assessments of species vulnerability to climate change used to inform conservation management consider the intrinsic traits that shape species’ capacity to respond to climate change. This omission is problematic as it may result in management actions that are not optimised for the long-term persistence of species as climates shift. We present a tool for explicitly linking data on plant species’ life history traits and range characteristics to appropriate management actions that maximise their capacity to respond to climate change. We deliberately target data on easily measured and widely available traits (e.g. dispersal syndrome, height, longevity) and range characteristics (e.g. range size, climatic/soil niche breadth), to allow for rapid comparison across many species. We test this framework on 1237 plants, categorising species on the basis of their potential climate change risk as related to four factors affecting their response capacity: reproduction, movement capability, abiotic niche specialisation and spatial coverage. Based on these four factors, species were allocated risk scores, and these were used to test the hypothesis that the current protection status under national legislation and related management actions capture species response capacity to climate change. Our results indicate that 20% of the plant species analysed (242 species) are likely to have a low capacity to respond to climate change based on the traits assessed, and are therefore at high risk. Of the 242 high risk species, only 10% (24 species) are currently listed for protection under conservation legislation. Importantly, many management plans for these listed species fail to address the capacity of species to respond to climate change with appropriate actions: 70% of approved management plans do not include crucial actions which may improve species’ ability to adapt to climate change. We illustrate how the use of easily attainable traits associated with ecological and evolutionary responses to changing environmental conditions can inform conservation actions for plant species globally.     

Effects of a melted greenland ice sheet on climate, vegetation, and the cryosphere

This paper investigates the possible implications for the earth-system of a melting of the Greenland ice-sheet. Such a melting is a possible result of increased high latitude temperatures due to increasing anthropogenic greenhouse gas emissions. Using an atmosphere-ocean general circulation model (AOGCM), we investigate the effects of the removal of the ice sheet on atmospheric temperatures, circulation, and precipitation. We find that locally over Greenland, there is a warming associated directly with the altitude change in winter, and the altitude and albedo change in summer. Outside of Greenland, the largest signal is a cooling over the Barents sea in winter. We attribute this cooling to a decrease in poleward heat transport in the region due to changes to the time mean circulation and eddies, and interaction with sea-ice. The simulated climate is used to force a vegetation model and an ice-sheet model. We find that the Greenland climate in the absence of an ice sheet supports the growth of trees in southern Greenland, and grass in central Greenland. We find that the ice sheet is likely to regrow following a melting of the Greenland ice sheet, the subsequent rebound of its bedrock, and a return to present day atmospheric CO₂ concentrations. This regrowth is due to the high altitude bedrock in eastern Greenland which allows the growth of glaciers which develop into an ice sheet.     

Suspended sediment dynamics in a large drainage basin: the River Rhine

The behaviour of suspended sediment in rivers is often a function of energy conditions, i.e. sediment is stored at low flow and transported under high discharge conditions. The timing of maximum sediment transport can, however, also be related to mixing and routing of water and sediment from different sources. In this study suspended sediment transport was studied in the River Rhine between Kaub and the German–Dutch border. As concentrations decrease over a runoff season and as the relationship between water discharge and suspended sediment concentrations during most floods is characterized by clockwise hysteresis, it is concluded that sediment depletion occurs during a hydrological year and during individual floods. However, analyses of the sediment contribution from the River Mosel indicate that clockwise hysteresis may result from sediment depletion as well as from early sediment supply from a tributary. Thus, although the suspended sediment behaviour in the downstream part of the River Rhine is partly a transport phenomenon related to energy conditions, mixing and routing of water from different sources also plays an important role. Suspended sediment transport during floods was modelled using a ‘supply‐based’ model. Addition of a sediment supply term to the sediment rating curve leads to a model that produces better estimates of instantaneous suspended sediment concentrations during high discharge events. A major constriction of the model is that it cannot be used to predict suspended sediment concentrations as long as the amount of sediment in storage and the timing of sediment supply are unknown. Copyright © 1999 John Wiley & Sons, Ltd.     

Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Experimental determination of magnesium isotope fractionation during higher plant growth

Two higher plant species (rye grass and clover) were cultivated under laboratory conditions on two substrates (solution, phlogopite) in order to constrain the corresponding Mg isotope fractionations during plant growth and Mg uptake. We show that bulk plants are systematically enriched in heavy isotopes relative to their nutrient source. The Δ²⁶Mg_plant-source range from 0.72‰ to 0.26‰ for rye grass and from 1.05‰ to 0.41‰ for clover. Plants grown on phlogopite display Mg isotope signatures (relative to the Mg source) ∼0.3‰ lower than hydroponic plants. For a given substrate, rye grass display lower δ²⁶Mg (by ∼0.3‰) relative to clover. Magnesium desorbed from rye grass roots display a δ²⁶Mg greater than the nutrient solution. Adsorption experiments on dead and living rye grass roots also indicate a significant enrichment in heavy isotopes of the Mg adsorbed on the root surface. Our results indicate that the key processes responsible for heavy isotope enrichment in plants are located at the root level. Both species also exhibit an enrichment in light isotopes from roots to shoots (Δ²⁶Mg_leaf-root = −0.65‰ and −0.34‰ for rye grass and clover grown on phlogopite respectively, and Δ²⁶Mg_leaf-root of −0.06‰ and −0.22‰ for the same species grown hydroponically). This heavy isotope depletion in leaves can be explained by biological processes that affect leaves and roots differently: (1) organo-Mg complex (including chlorophyll) formation, and (2) Mg transport within plant. For both species, a positive correlation between δ²⁶Mg and K/Mg was observed among the various organs. This correlation is consistent with the link between K and Mg internal cycles, as well as with formation of organo-magnesium compounds associated with enrichment in heavy isotopes. Considering our results together with the published range for δ²⁶Mg of natural plants and rivers, we estimate that a significant change in continental vegetation would induce a change of the mean river δ²⁶Mg that is comparable to analytical uncertainties.     

Drastic shift in lava geochemistry in the volcanic-front to rear-arc region of the Southern Kamchatkan subduction zone: Evidence for the transition from slab surface dehydration to sediment melting

The shift of lava geochemistry between volcanic front to rear-arc volcanoes in active subduction zones is a widespread phenomenon. It is somehow linked to an increase of the slab surface depth of the subducting oceanic lithosphere and increasing thickness of the mantle wedge and new constraints for its causes may improve our understanding of magma generation and element recycling in subduction zones in general. As a case study, this paper focuses on the geochemical composition of lavas from two adjacent volcanic centres from the volcanic front (VF) to rear-arc (RA) transition of the Southern Kamchatkan subduction zone, with the aim to examine whether the shift in lava geochemistry is associated with processes in the mantle wedge or in the subducted oceanic lithosphere or both. The trace element and O-Sr-Nd-Hf-Pb (double-spike)-isotopic composition of the mafic Mutnovsky (VF) and Gorely (RA) lavas in conjunction with geochemical modelling provides constraints for the degree of partial melting in the mantle wedge and the nature of their slab components. Degrees of partial melting are inferred to be significantly higher beneath Mutnovsky (∼18%) than Gorely (∼10%). The Mutnovsky (VF) slab component is dominated by hydrous fluids, derived from subducted sediments and altered oceanic crust, eventually containing minor but variable amounts of sediment melts. The composition of the Gorely slab component strongly points to a hydrous silicate melt, most likely mainly stemming from subducted sediments, although additional fluid-contribution from the underlying altered oceanic crust (AOC) is likely. Moreover, the Hf-Nd-isotope data combined with geochemical modelling suggest progressive break-down of accessory zircon in the melting metasediments. Therefore, the drastic VF to RA shift in basalt chemistry mainly arises from the transition of the nature of the slab component (from hydrous fluid to melt) in conjunction with decreasing degrees of partial melting within ∼15 km across-arc. Finally, systematic variations of key inter-element with high-precision Pb-isotope ratios provide geochemical evidence for a pollution of the Mutnovsky mantle source with Gorely melt components but not vice versa, most likely resulting from trench-ward mantle wedge corner flow. We also present a geodynamic model integrating the location of the Mutnovsky and Gorely volcanic centres and their lava geochemistry with the recently proposed thermal structure of the southern Kamchatkan arc and constraints about phase equilibria in subducted sediments and AOC. Herein, the slab surface hosting the subducted sediments suffers a transition from dehydration to melting above a continuously dehydrating layer of AOC. Wider implications of this study are that an onset of (flush-) sediment melting may ultimately be the main trigger for the VF to RA transition of lava geochemistry in subduction zones.     

The November 2002 eruption of Piton de la Fournaise,Réunion: tracking the pre-eruptive thermal evolution of magma using melt inclusions

The November 2002 eruption of Piton de la Fournaise in the Indian Ocean was typical of the activity of the volcano from 1999 to 2006 in terms of duration and volume of magma ejected. The first magma erupted was a basaltic liquid with a small proportion of olivine phenocrysts (Fo₈₁) that contain small numbers of melt inclusions. In subsequent flows, olivine crystals were more abundant and richer in Mg (Fo_83–84). These crystals contain numerous melt and fluid inclusions, healed fractures, and dislocation features such as kink bands. The major element composition of melt inclusions in this later olivine (Fo_83–84) is out of equilibrium with that of its host as a result of extensive post-entrapment crystallization and Fe²⁺ loss by diffusion during cooling. Melt inclusions in Fo₈₁ olivine are also chemically out of equilibrium with their hosts but to a lesser degree. Using olivine–melt geothermometry, we determined that melt inclusions in Fo₈₁ olivine were trapped at lower temperature (1,182 ± 1°C) than inclusions in Fo_83–84 olivine (1,199–1,227°C). This methodology was also used to estimate eruption temperatures. The November 2002 melt inclusion compositions suggest that they were at temperatures between 1,070°C and 1,133°C immediately before eruption and quenching. This relatively wide temperature range may reflect the fact that most of the melt inclusions were from olivine in lava samples and therefore likely underwent minor but variable amounts of post-eruptive crystallization and Fe²⁺ loss by diffusion due to their relatively slow cooling on the surface. In contrast, melt inclusions in tephra samples from past major eruptions yielded a narrower range of higher eruption temperatures (1,163–1,181°C). The melt inclusion data presented here and in earlier publications are consistent with a model of magma recharge from depth during major eruptions, followed by storage, cooling, and crystallization at shallow levels prior to expulsion during events similar in magnitude to the relatively small November 2002 eruption.