Atom‐probe analyses of nanodiamonds from Allende

Atom‐probe tomography (APT) is currently the only analytical technique that, due to its spatial resolution and detection efficiency, has the potential to measure the carbon isotope ratios of individual nanodiamonds. We describe three different sample preparation protocols that we developed for the APT analysis of meteoritic nanodiamonds at sub‐nm resolution and present carbon isotope peak ratios of meteoritic and synthetic nanodiamonds. The results demonstrate an instrumental bias associated with APT that needs to be quantified and corrected to obtain accurate isotope ratios. After this correction is applied, this technique should allow determination of the distribution of ¹²C/¹³C ratios in individual diamond grains, solving the decades‐old question of the origin of meteoritic nanodiamonds: what fraction, if any, formed in the solar system and in presolar environments? Furthermore, APT could help us identify the stellar sources of any presolar nanodiamonds that are detected.     

Development of a hydrogeological conceptual wetland model in the data-scarce north-eastern region of Kilombero Valley,Tanzania

Understanding groundwater/surface-water interactions in wetlands is crucial because wetlands provide not only a high potential for agricultural production, but also sensitive and valuable ecosystems. This is especially true for the Kilombero floodplain wetland in Tanzania, which represents a data-scarce region in terms of hydrological and hydrogeological data. A comprehensive approach combining hydrogeological with tracer-based assessments was conducted, in order to develop a conceptual hydrogeological wetland model of the area around the city of Ifakara in the north-eastern region of Kilombero catchment. Within the study site, a heterogeneous porous aquifer, with a range of hydraulic conductivities, is underlain by a fractured-rock aquifer. Groundwater chemistry is mainly influenced by silicate weathering and depends on groundwater residence times related to the hydraulic conductivities of the porous aquifer. Groundwater flows from the hillside to the river during most of the year. While floodwater close to the river is mainly derived from overbank flow of the river, floodwater at a greater distance from the river mainly originates from precipitation and groundwater discharge. Evaporation effects in floodwater increase with increasing distance from the river. In general, the contribution of flood and stream water to groundwater recharge is negligible. In terms of an intensification of agricultural activities in the wetland, several conclusions can be drawn from the conceptual model. Results of this study are valuable as a base for further research related to groundwater/surface-water interactions and the conceptual model can be used in the future to set up numerical flow and transport models.     

Multi-approach assessment of the spatial distribution of the specific yield: application to the Crau plain aquifer,France

Spatially distributed values of the specific yield, a fundamental parameter for transient groundwater mass balance calculations, were obtained by means of three independent methods for the Crau plain, France. In contrast to its traditional use to assess recharge based on a given specific yield, the water-table fluctuation (WTF) method, applied using major recharging events, gave a first set of reference values. Then, large infiltration processes recorded by monitored boreholes and caused by major precipitation events were interpreted in terms of specific yield by means of a one-dimensional vertical numerical model solving Richards’ equations within the unsaturated zone. Finally, two gravity field campaigns, at low and high piezometric levels, were carried out to assess the groundwater mass variation and thus alternative specific yield values. The range obtained by the WTF method for this aquifer made of alluvial detrital material was 2.9– 26%, in line with the scarce data available so far. The average spatial value of specific yield by the WTF method (9.1%) is consistent with the aquifer scale value from the hydro-gravimetric approach. In this investigation, an estimate of the hitherto unknown spatial distribution of the specific yield over the Crau plain was obtained using the most reliable method (the WTF method). A groundwater mass balance calculation over the domain using this distribution yielded similar results to an independent quantification based on a stable isotope-mixing model. This agreement reinforces the relevance of such estimates, which can be used to build a more accurate transient hydrogeological model.

     

Exploring aberrant bivalve shell ultrastructure and geochemistry as proxies for past sea water acidification

Throughout much of Earth's history, marine carbonates have represented one of the most important geological archives of environmental change. Several pivotal events during the Phanerozoic, such as mass extinctions or hyperthermal events have recently been associated with ocean acidification. Nevertheless, well‐defined geological proxies for past ocean acidification events are, at best, scarce. Here, experimental work explores the response of bivalve shell ultrastructure and isotope geochemistry (δ¹³C, δ¹⁸O and δ²⁶Mg) to stressful environments, in particular to sea water acidification. In this study, the common blue mussel, Mytilus edulis, was cultured (from early juvenile stages to one year of age) at four pH regimes (pH_NBS 7·2 to pH 8·0). Shell growth rate and ultrastructure of mainly the calcitic portion of the shells were compared between experimental treatments. Specimens exposed to low‐pH environments show patches of disordered calcitic fibre orientation in otherwise well‐structured shells. Furthermore, the electron backscattered diffraction analyses reveal that, under acidified conditions, the c‐axis of the calcite prisms exhibits a bimodal or multi‐modal distribution pattern. Similar shell disorder patterns have been reported from mytilids kept under naturally acidified sea water conditions. In contrast, this study found no evidence that different pH regimes affect shell carbon, oxygen or magnesium isotope ratios. Based on these observations, it is proposed that: (i) stressful environments, in this case low sea water pH, predictably affect bivalve biomineralization patterns; and (ii) these findings bear potential as a novel (petrographic) proxy for ancient sea water acidification. An assessment of the applicability of these data to well‐preserved fossil shell material from selected time intervals requires additional work.     

Major,trace element and stable isotope composition of water and muds precipitated from the hot springs of Bolivia: Are the waters of the spring's potential ore forming fluids?

The deposition of metal-rich black or reddish muds by many thermal springs in the Cordilleras and the Altiplano of Bolivia suggest that these geothermal waters may be related to those that once formed the world-class Bolivian tin, silver and gold mineralisation. The discharge temperatures of these springs are as high as 70 °C. According to δ¹⁸O, δD, tritium data and Ar/N₂ ratios these waters are predominantly of meteoric origin. Less than 10% of the discharging thermal water represents deep-seated metal-rich thermal brines of at least 530 °C according to carbon exchange between CO₂ and CH₄. These brines ascend along tectonic faults and mix with low-temperature meteoric water in surface-near aquifers. The meteoric component of the thermal water is recharged in the high Cordilleras with residence times exceeding 50 years. The chemical composition of the thermal water is dominated by the rather inefficient low-temperature leaching of the surface-near aquifer rocks by meteoric water. The small fraction of metal-rich hot deep-seated water is not able to increase the metal content of the water mix to a level sufficient to classify these thermal waters as ore-bearing. Surface-near leaching is supported, e.g., by the B/Li ratios of the spring water of the Western Cordillera and Caleras/Pulacayo in the Eastern Cordillera that correspond very closely to that of the easily leachable glassy inclusions of the outcropping andesitic lavas. The often remarkable metal content of the muds deposited by the springs originate from efficient scavenging of heavy metals by ferric oxyhydroxides. Under the given arid to semi-arid climate the muds are additionally enriched in metals by wind-transported dust. The present study does support a relation of the actual thermal waters with neither the classical subduction-related Upper Tertiary tin, silver and gold mineralisation nor the supposed younger Sb mineralisation of Bolivia.     

A new systematic approach using the Modified Gaussian Model: Insight for the characterization of chemical composition of olivines, pyroxenes and olivine-pyroxene mixtures

An automatic procedure has been implemented on the original MGM approach (Sunshine et al., 1990) in order to deal with an a priori unknown mafic mineralogy observed in the visible-near infrared by reflectance spectroscopy in the case of laboratory or natural rock spectra. We consider all the mixture possibilities involving orthopyroxene, clinopyroxene and olivine, and use accordingly for each configuration different numbers of Gaussians, depending on the potential complexity of the mixture. A key issue is to initialize the MGM procedure with a proper setting for the Gaussians parameters. An automatic analysis of the shape of the spectrum is first performed. The continuum is handled with a second order polynomial adjusted on the local maxima along the spectrum and Gaussians parameters initial settings are made on the basis of laboratory results available in the literature in the case of simple mixtures of mafic minerals. The returned MGM solutions are then assessed on spectroscopic grounds and either validated or discarded, on the basis of a mineralogical sorting.The results presented in this paper are a first quantitative step to characterize both modal and chemical compositions of pyroxenes and olivines. A demonstration of the methodology on specific examples of binary and ternary olivine-pyroxenes mixtures has been made, which shows that the different non-linear effects which affect the Gaussian parameters (center and strength) can be successfully handled. Of note is the fact that the band center positions associated with the different mafic minerals are not set here in the inverse problem, and thus the MGM outputs are truly informative of the chemical composition of pyroxenes and olivines. With the consideration of some limits on the detection thresholds, these results are quite promising for increasing the operational use of the Modified Gaussian Model with large hyperspectral data sets in view of establishing detailed mineralogical mappings of magmatic units.     

A watershed-scale study of climate change impacts on groundwater recharge (Annapolis Valley,Nova Scotia,Canada)

Abstract

The potential impacts of future climate change on the evolution of groundwater recharge are examined at a local scale for a 546-km² watershed in eastern Canada. Recharge is estimated using the infiltration model Hydrologic Evaluation of Landfill Performance (HELP), with inputs derived from five climate runs generated by a regional climate model in combination with the A2 greenhouse gas emissions scenario. The model runs project an increase in annual recharge over the 2041–2070 period. On a seasonal basis, however, a marked decrease in recharge during the summer and a marked increase during the winter are observed. The results suggest that increased evapotranspiration resulting from higher temperatures does not offset the large increase in winter infiltration. In terms of individual water budget components, clear differences are obtained for the different climate change scenarios. Monthly recharge values are also found to be quite variable, even for a given climate scenario. These findings are compared with results from two regional-scale studies.

Editor D. Koutsoyiannis; Associate editor M. Besbes     

Multi-tracer assessment of seasonal water source changes in coastal water systems along the southeastern coast of Ivory Coast (West Africa)

ABSTRACT

Proper management of coastal freshwater resources depends on an understanding of processes controlling their chemistry and seasonal flowpaths. A quantitative approach involving the coupling of major solutes and isotopes (δ¹⁸O, δ²H) of 180 samples in end-member mixing analysis (EMMA) was adopted to elucidate seasonal patterns of hydraulic exchanges amongst coastal waters along the Ebrié Lagoon catchment, Ivory Coast. The results show that the Ebrié Lagoon is a hydrologically dynamic system. In the dry season, evaporation and seawater inflow are the dominating processes, while in the wet season, river discharge is the main water source in the lagoon. Regional geology plays a significant role in aquifer recharge patterns. The Quaternary aquifer responds faster to precipitation, while the Mio-Pliocene aquifer is recharged indirectly via floodplain seepages. Salinization of over 90% of wells arises from hydrological exchanges with the Ebrié Lagoon. A diluted seawater effect was recorded in wells during the wet season owing to the relative increase in freshwater inflow.     

A model for conductive faults with non-matching grids

In this paper, we are interested in modeling single-phase flow in a porous medium with known faults seen as interfaces. We mainly focus on how to handle non-matching grids problems arising from rock displacement along the fault. We describe a model that can be extended to multi-phase flow where faults are treated as interfaces. The model is validated in an academic framework and is then extended to 3D non K-orthogonal grids, and a realistic case is presented.