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.     

Preliminary data on chemical changes in the Aral Sea during low-level periods from the last 9000 years

The withdrawal of the Aral Sea tributaries (Amu and Syr Daria) for cultures has led to significant falls of its level and an important increase in its salinity. During the Holocene, a succession of low and high water inputs occurred. Silty deposits correspond to the high levels and carbonates to the low levels. This study makes a distinction between the Syr Daria and the Amu Daria water inputs during low-level periods by using mineralogical and chemical compositions of the carbonates deposits. Waters from the Syr Daria are more sulphatic and have a low iron content in comparison with that of the Amu Daria. The Syr Daria was the major tributary around 7500, 4956 and 970 yr?BP, whereas around 6200 and 3610 yr?BP, inflow also from the Amu Daria is observed. To cite this article: L. Le Callonnec et al., C. R. Geoscience 337 (2005).     

Turbulent Transfer Between Street Canyons and the Overlying Atmospheric Boundary Layer

The turbulent exchange of momentum between a two-dimensional cavity and the overlying boundary layer has been studied experimentally, using hot-wire anemometry and particle image velocimetry (PIV). Conditions within the boundary layer were varied by changing the width of the canyons upstream of the test canyon, whilst maintaining the square geometry of the test canyon. The results show that turbulent transfer is due to the coupling between the instabilities generated in the shear layer above the canyons and the turbulent structures in the oncoming boundary layer. As a result, there is no single, unique velocity scale that correctly characterizes all the processes involved in the turbulent exchange of momentum across the boundary layer. Similarly, there is no single velocity scale that can characterize the different properties of the turbulent flow within the canyon, which depends strongly on the way in which turbulence from the outer flow is entrained into the cavity and carried round by the mean flow. The results from this study will be useful in developing simple parametrizations for momentum exchange in the urban canopy, in situations where the street geometry consists principally of relatively long, uniform streets arranged in grid-like patterns; they are unlikely to be applicable to sparse geometries composed of isolated three-dimensional obstacles.     

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.     

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.     

Spatial and Temporal Variability of the CO2 Fluxes in a Tropical, Highly Urbanized Estuary

The spatial and temporal variations of the flux of CO₂ were determined during 2007 in the Recife estuarine system (RES), a tropical estuary that receives anthropogenic loads from one of the most populated and industrialized areas of the Brazilian coast. The RES acts as a source of nutrients (N and P) for coastal waters. The calculated CO₂ fluxes indicate that the upstream inputs of CO₂ from the rivers are largely responsible for the net annual CO₂ emission to the atmosphere of +30 to +48 mmol m^?2 day^?1, depending on the CO₂ exchange calculation used, which mainly occurs during the late austral winter and early summer. The observed inverse relationship between the CO₂ flux and the net ecosystem production (NEP) indicates the high heterotrophy of the system (except for the months of November and December). The NEP varies between ?33 mmol m^?2 day^?1 in summer and ?246 mmol m^?2 day^?1 in winter. The pCO₂ values were permanently high during the study period (average ~4,700 μatm) showing a gradient between the inner (12,900 μatm) and lower (389 μatm) sections on a path of approximately 30 km. This reflects a state of permanent pollution in the basin due to the upstream loading of untreated domestic effluents (N/P?=?1,367:6 μmol kg^?1 and pH?=?6.9 in the inner section), resulting in the continuous mineralization of organic material by heterotrophic organisms and thereby increasing the dissolved CO₂ in estuarine waters.     

A multi-dimensional assessment of urban vulnerability to climate change in Sub-Saharan Africa

In this paper, we develop and apply a multi-dimensional vulnerability assessment framework for understanding the impacts of climate change-induced hazards in Sub-Saharan African cities. The research was carried out within the European/African FP7 project CLimate change and Urban Vulnerability in Africa, which investigated climate change-induced risks, assessed vulnerability and proposed policy initiatives in five African cities. Dar es Salaam (Tanzania) was used as a main case with a particular focus on urban flooding. The multi-dimensional assessment covered the physical, institutional, attitudinal and asset factors influencing urban vulnerability. Multiple methods were applied to cover the full range of vulnerabilities and to identify potential response strategies, including: model-based forecasts, spatial analyses, document studies, interviews and stakeholder workshops. We demonstrate the potential of the approach to assessing several dimensions of vulnerability and illustrate the complexity of urban vulnerability at different scales: households (e.g., lacking assets); communities (e.g., situated in low-lying areas, lacking urban services and green areas); and entire cities (e.g., facing encroachment on green and flood-prone land). Scenario modeling suggests that vulnerability will continue to increase strongly due to the expected loss of agricultural land at the urban fringes and loss of green space within the city. However, weak institutional commitment and capacity limit the potential for strategic coordination and action. To better adapt to urban flooding and thereby reduce vulnerability and build resilience, we suggest working across dimensions and scales, integrating climate change issues in city-level plans and strategies and enabling local actions to initiate a ‘learning-by-doing’ process of adaptation.     

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.     

Continuous real‐time analysis of the isotopic composition of precipitation during tropical rain events: Insights into tropical convection

To investigate stable isotopic variability of precipitation in Singapore, we continuously analysed the δ‐value of individual rain events from November 2014 to August 2017 using an online system composed of a diffusion sampler coupled to Cavity Ring‐Down Spectrometer. Over this period, the average value (δ¹⁸O_Avg), the lowest value (δ¹⁸O_Low), and the initial value (δ¹⁸O_Init) varied significantly, ranging from ?0.45 to ?15.54‰, ?0.9 to ?17.65‰, and 0 to ?13.13‰, respectively. All 3 values share similar variability, and events with low δ¹⁸O_Low and δ¹⁸O_Avg values have low δ¹⁸O_Init value. Individual events have limited intraevent variability in δ‐value (Δδ) with the majority having a Δδ below 4‰. Correlation of δ¹⁸O_Low and δ¹⁸O_Avg with δ¹⁸O_Init is much higher than that with Δδ, suggesting that convective activities prior to events have more control over δ‐value than on‐site convective activities. The d‐excess of events also varies considerably in response to the seasonal variation in moisture sources. A 2‐month running mean analysis of δ¹⁸O reveals clear seasonal and interannual variability. Seasonal variability is associated with the meridional movement of the Intertropical Convergence Zone and evolution of the Asian monsoon. El Niño–Southern Oscillation is a likely driver of interannual variability. During 2015–2016, the strongest El Niño year in recorded history, the majority of events have a δ¹⁸O value higher than the weighted average δ¹⁸O of daily precipitation. δ¹⁸O shows a positive correlation with outgoing longwave radiation in the western Pacific and the Asian monsoon region, and also with Oceanic Niño Index. During El Niño, the convection centre shifts eastward to the central/eastern Pacific, weakening convective activities in Southeast Asia. Our study shows that precipitation δ‐value contains information about El Niño–Southern Oscillation and the Intertropical Convergence Zone, which has a significant implication for the interpretation of water isotope data and understanding of hydrological processes in tropical regions.     

Comparison of direct statistical and indirect statistical-deterministic frameworks in downscaling river low-flow indices

ABSTRACT

This work explores the ability of two methodologies in downscaling hydrological indices characterizing the low flow regime of three salmon rivers in Eastern Canada: Moisie, Romaine and Ouelle. The selected indices describe four aspects of the low flow regime of these rivers: amplitude, frequency, variability and timing. The first methodology (direct downscaling) ascertains a direct link between large-scale atmospheric variables (the predictors) and low flow indices (the predictands). The second (indirect downscaling) involves downscaling precipitation and air temperature (local climate variables) that are introduced into a hydrological model to simulate flows. Synthetic flow time series are subsequently used to calculate the low flow indices. The statistical models used for downscaling low flow hydrological indices and local climate variables are: Sparse Bayesian Learning and Multiple Linear Regression. The results showed that direct downscaling using Sparse Bayesian Learning surpassed the other approaches with respect to goodness of fit and generalization ability.

Editor D. Koutsoyiannis; Associate editor K. Hamed