Raman spectroscopic studies of carbonates part I: High-pressure and high-temperature behaviour of calcite,magnesite, dolomite and aragonite

The room-temperature Raman spectra of aragonite, magnesite and dolomite have been recorded up to 30 GPa and 25 GPa, respectively and no phase changes were observed during compression, unlike calcite. The effect of temperature on the room-pressure Raman spectra of calcite, aragonite, magnesite and dolomite is reported up to 800–1100 K. The measured relative pressure and temperature-shifts of the Raman lines are greater for the lattice modes than for the internal modes of the CO₃ groups. These shifts are used to calculate the mode anharmonic parameters of the observed Raman modes; they are negative and their absolute values are smaller (close to 0) for the internal CO₃ modes than for the lattice modes (4–17 10^?5 K^?1). The temperature shifts of the lattice modes in calcite are considerably larger than those for dolomite and magnesite, and a marked non-linear increase in linewidth is observed above 400° C for calcite. This is consistent with an increasing relaxational component to the libration of the CO₃ groups about their threefold axes, premonitory to the rotational order-disorder transition at higher temperature. This behaviour is not observed for the other calcite structured minerals in this study. We examine systematic variations in the lattice mode frequencies and linewidths with composition, to begin to understand these differences in their anharmonic behaviour. Finally, we have used a simple Debye-Waller model to calculate atomic displacements in calcite, magnesite and dolomite with increasing temperature from the vibrational frequency data, to provide a direct comparison with atomic positional data from high-temperature structure refinements.     

Preliminary Interlaboratory Trial for ISO/DIS 12010: Determination of Short Chain Polychlorinated Alkanes (SCCP) in Water

A first preliminary interlaboratory trial was planned to prepare ISO/DIS 12010: Water quality – determination of short chain polychlorinated alkanes (SCCP) in water – method using GC/MS and electron capture negative ionisation (ECNI). The task was to determine the sum of short chain polychlorinated n‐alkanes with carbon chain lengths of C₁₀–C₁₃ and a chlorine content between 49 and 67% in water by GC‐ECNI‐MS and quantification by multiple linear regression described in ISO/DIS 12010 as the compulsory method. Distributed samples were obtained from a real water extract spiked with a target concentration of 0.4 µg/mL sum of SCCP, i.e. the environmental quality target level according to the Water Framework Directive. The interlaboratory trial included the calibration, a column chromatographic clean up, a concentration step and an integration of chromatographic unresolved humps as well as the quantification with multiple linear regression. Reproducibility standard deviations between 21.5 and 22.9% were achieved by 17 participating laboratories from four countries. The method outlined no significant difference of the results between the standard solution and a real water matrix extract. On the basis of this succeeded preliminary interlaboratory trial the final interlaboratory trial for validation of ISO 12010 was prepared in autumn 2010.     

A Common Reference Material for Cadmium Isotope Studies – NIST SRM 3108

Research into natural mass‐dependent stable isotope fractionation of cadmium has rapidly expanded in the past few years. Methodologies are diverse with MC‐ICP‐MS favoured by all but one laboratory, which uses thermal ionisation mass spectrometry (TIMS). To quantify the isotope fractionation and correct for instrumental mass bias, double‐spike techniques, sample‐calibrator bracketing or element doping has been used. However, easy comparison between data sets has been hampered by the multitude of in‐house Cd solutions used as zero‐delta reference in different laboratories. The lack of a suitable isotopic reference material for Cd is detrimental for progress in the long term. We have conducted a comprehensive round‐robin assay of NIST SRM 3108 and the Cd isotope offsets to commonly used in‐house reference materials. Here, we advocate NIST SRM 3108 both as an isotope standard and the isotopic reference point for Cd and encourage its use as ‘zero‐delta’ in future studies. The purity of NIST SRM 3108 was evaluated regarding isobaric and polyatomic molecular interferences, and the levels of Zn, Pd and Sn found were not significant. The isotope ratio ¹¹⁴Cd/¹¹⁰Cd for NIST SRM 3108 lies within ～ 10 ppm Da^?1 of best estimates for the Bulk Silicate Earth and is validated for all measurement technologies currently in use.     

Using land cover changes and demographic data to improve hydrological modeling in the Sahel

At the beginning of the drought in the Sahel in the 1970s and 1980s, rainfall decreased markedly, but runoff coefficients and in some cases, absolute runoff increased. This situation was due to the conversion of the land cover from natural vegetation with a low annual runoff coefficient, to cropland and bare soils, whose runoff coefficients are higher. Unless they are adapted, hydrological conceptual models, such as GR2M, are unable to reproduce this increase in runoff. Despite the varying environmental and climatic conditions of the West African Sahel, we show that it is possible to increase the performance of the GR2M model simulations by elaborating a time‐varying soil water holding capacity and to incorporate this value in the annual maximum amount of water to be stored in reservoir A of the model. We looked for interactions between climate, rural society, and the environment. These interactions drive land‐cover changes in the Sahel, which in turn drive the distribution of rainfall between infiltration, evaporation, and runoff and hence the water resources, which are vital in this region. We elaborated several time series of key indicators linked to these interactions. We then integrated these changes in the runoff conditions of the GR2M model through the maximum value of the reservoir capacity. We calculated annual values of water holding capacity using the annual values of four classes of land cover, natural vegetation, cultivated area, bare soil, and surface water. We then used the hydrological model with and without this time‐varying soil value of A and compared the performances of the model under the two scenarios. Whatever the calibration period used, the Nash–Sutcliffe index was always greater in the case of the time‐varying A time series.     

Downscaling projections of climate change in Sao Tome and Principe Islands,Africa

Sao Tome and Principe is a small insular African country extremely vulnerable to rising sea levels and impacts such as inundation, shore line change, and salt water intrusion into underground aquifers. Projections of climate change have considered coarse model resolutions. The objective of this work is to dynamically downscale the global model projections to 4-km resolution and to assess the climate change in the Sao Tome and Principe islands. The global climate projections are provided by the Canadian Earth System Model under two Representative Concentration Pathways greenhouse gas scenarios, RCP4.5 and RCP8.5. The downscaling is produced by the Eta regional climate model. The baseline period is taken between 1971 and 2000, and the future climate period is taken between 2041 and 2070. The 2-m temperature simulations show good agreement with station data. The model simulates temperature more accurately than precipitation. The precipitation simulations systematically show underestimation and delay of the rainy and the dry seasons by about 1 month, a feature inherited from the global climate model. In the middle of the 21st century, projections show the strongest warming in the elevated parts of the Sao Tome Island, especially in February under RCP8.5. Warmer nights and warmer days become more frequent in the islands when compared with those in the present. While under RCP4.5, precipitation increases in the islands; under RCP8.5, it decreases everywhere in both islands. Heavy precipitation rates should increase, especially in the south-southwestern parts of the Sao Tome islands. Detailed spatial variability of the temperature and precipitation changes in the islands can only be revealed at very high spatial model resolution. Implications for the potential energy production from two major river basins are assessed in this work.     

Impact of the Doha outcome on surplus emission allowances and their effect on developed country emissions

The outcome from the December 2012 climate negotiations in Doha has clarified the rules regarding surplus units for the Kyoto Protocol. We summarize these new rules and estimate the resulting effective emissions during the second commitment period using our unit trade model. Other options to deal with surplus emission allowances are employed as benchmarks to assess the Doha outcome. The effective emissions for developed countries as a group under the Doha outcome could be 10–11 % below 1990 levels or 4–5 % points below business-as-usual levels for the second commitment period if we assume that non-Kyoto Protocol countries domestically achieve their targets. However, if mechanisms exist where non-Kyoto Protocol countries can trade units, their emissions could increase and effective emissions for developed countries could be 7–8 % below 1990 levels. In this low-ambition situation we find the main impact of the Doha surplus rules to be the introduction of the historical cap on emissions allowances. Without the effect of the cap, the Doha outcome allows the Parties to the second commitment period to emit at business-as-usual levels until 2020, while still leaving surplus units at the end of the second commitment period.     

The origin of plagioclase phenocrysts in basalts from continental monogenetic volcanoes of the Kaikohe-Bay of Islands field,New Zealand: implications for magmatic assembly and ascent

Late Quaternary, porphyritic basalts erupted in the Kaikohe-Bay of Islands area, New Zealand, provide an opportunity to explore the crystallization and ascent history of small volume magmas in an intra-continental monogenetic volcano field. The plagioclase phenocrysts represent a diverse crystal cargo. Most of the crystals have a rim growth that is compositionally similar to groundmass plagioclase (~?An₆₅) and is in equilibrium with the host basalt rock. The rims surround a resorbed core that is either less calcic (~?An_20–45) or more calcic (>?An₇₀), having crystallized in more differentiated or more primitive melts, respectively. The relic cores, particularly those that are less calcic (<?~?An₄₅), have ⁸⁷Sr/⁸⁶Sr ratios that are either mantle-like (~?0.7030) or crustal-like (~?0.7040 to 0.7060), indicating some are antecrysts formed in melts fractionated from plutonic basaltic forerunners, while others are true xenocrysts from greywacke basement and/or Miocene arc volcanics. It is envisaged that intrusive basaltic forerunners produced a zone where various degrees of crustal assimilation and fractional crystallization occurred. The erupted basalts represent mafic recharge of this system, as indicated by the final crystal rim growths around the entrained antecrystic and xenocrystic cargo. The recharge also entrained cognate gabbros that occur as inclusions, and produced mingled groundmasses. Multi-stage magmatic ascent and interaction is indicated, and is consistent with the presence of a partial melt body in the lower crust detected by geophysical methods. This crystallization history contrasts with traditional concepts of low-flux basaltic systems where rapid ascent from the mantle is inferred. From a hazards perspective, the magmatic system inferred here increases the likelihood of detecting eruption precursor phenomena such as seismicity, degassing and surface deformation.     

Petrographical and geochemical characterization of Comblanchien limestone (Bourgogne,France): A fingerprint of the building stone provenance

The Comblanchien limestone is a well-known building stone that deserves a quantitative characterization in order to be able to certify its origin. We compare petrographical and geochemical characteristics of limestones commercialized under the name of Comblanchien to those of one of their competitors (VATC, a Portuguese coated grain-bearing limestone). From macroscopic and microscopic observations, the distinction is somehow difficult but the coated grain-bearing Comblanchien samples have δ¹³C values (from +1.75 to +2.25‰) different from those of the VATC sample (negative δ¹³C value). As an example of application of these results, three samples from a building site near Paris are also studied in order to verify their provenance. We conclude that they do not come from quarries from the Comblanchien area, but likely from Portugal. The study shows that a detailed analysis of building limestones may provide a robust tool for discriminating between currently mined stones of different provenances, and thus open the possibility to attach to a given limestone a fingerprint, an identity card, and if required a commercial label.     

The timing of sea-level high-stands during Marine Isotope Stages 7.5 and 9: Constraints from the uranium-series dating of fossil corals from Henderson Island

Direct dating of fossil coral reefs using the U-series chronometer provides an important independent test of the Milankovitch orbital forcing theory of climate change. However, well-dated fossil corals pre-dating the last interglacial period (>130 thousand years ago; ka) are scarce due to, (1) a lack of sampling localities, (2) insufficient analytical precision in U-series dating methods, and (3) diagenesis which acts to violate the assumption of closed-system U-series isotopic decay in fossil corals. Here we present 50 new high-precision U-series age determinations for fossil corals from Henderson Island, an emergent coral atoll in the central South Pacific. U-series age determinations associated with the Marine Isotope Stage (MIS) 9 interglacial and MIS 7.5 interstadial periods are reported. The fossil corals show relatively little open-system U-series behaviour in comparison to other localities with fossil coral reefs formed prior to the last glacial cycle, however, open-system U-series behaviour is still evident in most of the dated corals. In particular, percent-level shifts in the [²³⁰Th/²³⁸U]_act composition are observed, leading to conventional U-series ages that are significantly younger or older than the true sample age. This open-system U-series behaviour is not accounted for by any of the open-system U-series models, indicating that new models should be derived. The new U-series ages reported here support and extend earlier findings reported in Stirling et al. (2001), providing evidence of prolific coral reef development on Henderson Island at ∼320 ka, most likely correlated with MIS 9.3, and subsequent reef development at ∼307 ka during MIS 9.1, while relative sea-level was potentially ∼20 m lower than during MIS 9.3. The U-series ages for additional well-preserved fossil corals are suggestive of minor reef development on Henderson Island during MIS 7.5 (245-230 ka) at 240.3 ± 0.8 and 234.7 ± 1.3 ka. All U-series observations are consistent with the Milankovitch theory of climate change, in terms of the timing of onset and termination of the dated interglacial and interstadial periods. The best preserved samples also suggest that the oceanic ²³⁴U/²³⁸U during MIS 9 and MIS 7.5 was within five permil of the modern open ocean composition.