Reactions of the feldspar surface with metal ions: Sorption of Pb(II), U(VI) and Np(V), and surface analytical studies of reaction with Pb(II) and U(VI)

Feldspar minerals are thermodynamically unstable in the near-surface environment and their surfaces are well known to react readily with aqueous solutions, leading to incongruent dissolution at low pH values, but congruent dissolution at neutral and high pH values. Interactions with mineral surfaces are an important control on the environmental transport of trace elements and detrital feldspars are abundant in soils and sediments. However, the interactions of metal ions in solution with the reacting feldspar surface have not been widely explored. The interactions of Pb(II), U(VI) and Np(V) ions with the feldspar surface have therefore been studied. Lead is taken up by the microcline surface at pH 6 and 10, but no uptake could be measured at pH 2. There was measurable uptake of Pb(II) on the plagioclase surface at pH 2, 6 and 10. Uptake always increased with pH. In most conditions, Pb(II) reacts through cation exchange process although, at high pH, a discrete phase, probably hydrocerrusite, is observed by atomic force microscopy (AFM) to precipitate on the plagioclase surface. Supersaturation with hydrocerrusite in these conditions is expected from thermodynamic calculations. Uptake of uranyl ion , generally through surface complex formation, could only be measured at pH 6 and 10. At pH 6 and an initial U(VI) concentration above 21.0 μM, precipitation of becquerelite (Ca[(UO₂)₃O₂(OH)₃]₂·8H₂O), identified by AFM and characterised by grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy, is observed on plagioclase. The U(VI) concentration range in which becquerelite precipitation begins (dissolved U(VI) 1-5 μM) is consistent with that predicted from thermodynamic modelling. On plagioclase feldspar, secondary ion mass spectrometry showed diffusion of uranium into the altered surface layer. Uptake of the neptunyl ion (Np(V)) was found at pH 6 and 10 for microcline and at pH 2, 6 and 10 for plagioclase, and was generally lower than uptake of U(VI). By combining batch sorption experiments with imaging and surface analysis, and thermodynamic modelling, it has been possible to gain a mechanistic insight into the reactions of the feldspar surface with metal ions in solution.     

Thermal expansion behavior of Ce2Zr2O7 up to 898 K in conjunction with structural analyses by neutron diffraction

The thermal expansion of cubic pyrochlore Ce₂Zr₂O₇ has been measured from room temperature to 898 K on polycrystalline material in conjunction with structural analyses using neutron diffraction. This compound has a thermal expansion coefficient in line with the other comparable lanthanoide pyrochlore oxides. The coefficient can be expressed as α(T) = 8.418 × 10⁻⁶ + 0.9861 × 10⁻⁹ × T. The structural refinements performed for each measured temperature showed a comparable linear evolution of the Ce–O/Zr–O distances (within 0.57%).     

Geochemistry,isotopic composition (δO, δH,Sr/Sr,Nd/Nd) in the groundwater of French Guiana as indicators of their origin,interrelations

The current use of untreated river water for drinking purposes by the population of French Guiana has important impacts on public health. Consequently, groundwater is of major importance as a possible alternative drinking water supply to reduce these impacts. Since French Guiana belongs to the Guyana Shield, sustainable water management can be expected to depend increasingly on water from fissured aquifers in hard rocks. Groundwater samples were collected from shallow drill holes in the densely populated coastal area, and deeper wells in the basement (around Cayenne and along the Maroni and Oyapock rivers). This study reports on major and trace elements for which Na⁺ and Ca²⁺ excess with regard to Cl reflect the role of water-rock interaction, as well as Sr and Nd isotopes that reflect the role of the different lithologies. δ¹⁸O and δD in waters give constraints on the water cycle (recharge and evaporation processes).     

An intrinsic volatility scale relevant to the Earth and Moon and the status of water in the Moon

The notion of a dry Moon has recently been challenged by the discovery of high water contents in lunar apatites and in melt inclusions within olivine crystals from two pyroclastic glasses. The highest and most compelling water contents were found in pyroclastic glasses that are not very common on the lunar surface. To obtain more representative constraints on the volatile content of the lunar interior, we measured the Zn content, a moderately volatile element, of mineral and rock fragments in lunar soils collected during Apollo missions. We here confirm that the Moon is significantly more depleted in Zn than the Earth. Combining Zn with existing K and Rb data on similar rocks allows us to anchor a new volatility scale based on the bond energy of nonsiderophile elements in their condensed phases. Extrapolating the volatility curve to H shows that the bulk of the lunar interior must be dry (≤1 ppm). This contrasts with the water content of the mantle sources of pyroclastic glasses, inferred to contain up to approximately 40 ppm water based on H₂O/Ce ratios. These observations are best reconciled if the pyroclastic glasses derive from localized water‐rich heterogeneities in a dominantly dry lunar interior. We argue that, although late addition of 0.015% of a chondritic veneer to the Moon seems required to explain the abundance of platinum group elements (Day et al. 2007), the volatile content of the added material was clearly heterogeneous.     

Orbital timing of the Indian,East Asian and African boreal monsoons and the concept of a ‘global monsoon’

Our understanding of monsoon circulation timing’s at the orbital scale is currently a matter of debate. Here, we compare previous and recently published results of Indian, East Asian, West African and East African monsoon variability. We note different timings between the East African, West African, Indian and East-Asian monsoon systems for the most recent 45 ka, where the age models are constrained by AMS dating. On this basis, we construct different orbital forcing “reference curves” and apply them to the 200 ka time period for the different monsoon systems. Our results indicate that the ‘global monsoon’ concept at the orbital scale is a misnomer. We find real regional differences in the timing of the monsoon response to orbital forcing and differences in the weight of precession and obliquity in the monsoon records. This work highlights the necessity of studies aimed at understanding the underlying physics of these regional response patterns. This is crucial to a better understanding of monsoon dynamics and improved climate model simulations and comparisons with proxy data.     

Using Mg Isotopes to Trace Cyanobacterially Mediated Magnesium Carbonate Precipitation in Alkaline Lakes

This study assesses the potential use of Mg isotopes to trace Mg carbonate precipitation in natural waters. Salda Lake (SW Turkey) was chosen for this study because it is one of the few modern environments where hydrous Mg carbonates are the dominant precipitating minerals. Stromatolites, consisting mainly of hydromagnesite, are abundant in this lake. The Mg isotope composition of incoming streams, groundwaters, lake waters, stromatolites, and hydromagnesite-rich sediments were measured. Because Salda Lake is located in a closed basin, mass balance requires that the Mg isotopic offset between Lake Salda water and precipitated hydromagnesite be comparable to the corresponding offset between Salda Lake and its water inputs. This is consistent with observations; a ??²⁶Mg offset of 0.8?C1.4??? is observed between Salda Lake water and it is the incoming streams and groundwaters, and precipitated hydromagnesite has a ??²⁶Mg 0.9?C1.1??? more negative than its corresponding fluid phase. This isotopic offset also matches closely that measured in the laboratory during both biotic and abiotic hydrous Mg carbonate precipitation by cyanobacteria (Mavromatis, V., Pearce, C., Shirokova, L. S., Bundeleva, I. A., Pokrovsky, O. S., Benezeth, P. and Oelkers, E.H.: Magnesium isotope fractionation during inorganic and cyanobacteria-induced hydrous magnesium carbonate precipitation, Geochim. Cosmochim. Acta, 2012a. 76, 161?C174). Batch reactor experiments performed in the presence of Salda Lake cyanobacteria and stromatolites resulted in the precipitation of dypingite (Mg₅(CO₃)₄(OH)₂·5(H₂O)) and hydromagnesite (Mg₅(CO₃)₄(OH)₂·4H₂O) with morphological features similar to those of natural samples. Concurrent abiotic control experiments did not exhibit carbonate precipitation demonstrating the critical role of cyanobacteria in the precipitation process.     

Effet de la turbidité sur la dégradation des pigments phytoplanctoniques dans l'estuaire de la GirondeEffect of turbidity on phytoplanktonic pigments degradation in the Gironde Estuary

In the Gironde Estuary, most part of phytoplanktonic material carried by the rivers is mineralised in the maximum turbidity zone (MTZ). In order to follow the degradation of the phytoplanktonic material into the MTZ, we developed an in vitro approach based on the monitoring of phytoplanktonic pigments. Algal material from two chlorophytes (Scenedesmus suspicatus Chaudat and Chlamydomonas sp.) was incubated in the dark during 28 days into water samples from the Gironde estuary MTZ, at variable suspended solid concentrations (SPM) as well as in a sterilised turbid sample. First order decay constants of chlorophylls a and b and lutein increased by a factor 3 to 5 between SPM of 0 and $\text{3 }\text{g}\text{l}{}^{\mathrm{?1}}$. The production of pheophytin a in the presence of particles and the lack of degradation in the sterilised turbid sample confirmed the effect of attached bacteria on the particles. To cite this article: E. Lemaire et al., C. R. Geoscience 334 (2002) 251–258.     

Analogue models of the effect of long-term basement fault movement on volcanic edifices

Long-term fault movement under volcanoes can control the edifice structure and can generate collapse events. To study faulting effects, we explore a wide range of fault geometries and motions, from normal, through vertical to reverse and dip-slip to strike-slip, using simple analogue models. We explore the effect of cumulative sub-volcanic fault motions and find that there is a strong influence on the structural evolution and potential instability of volcanoes. The variety of fault types and geometries are tested with realistically scaled displacements, demonstrating a general tendency to produce regions of instability parallel to fault strike, whatever the fault motion. Where there is oblique-slip faulting, the instability is always on the downthrown side and usually in the volcano flank sector facing the strike-slip sense of motion. Different positions of the fault beneath the volcano change the location, type and magnitude of the instability produced. For example, the further the fault is from the central axis, the larger the destabilised sector. Also, with greater fault offset from the central axis larger unstable volumes are generated. Such failures are normal to fault strike. Using simple geometric dimensionless numbers, such as the fault dip, degree of oblique motion (angle of obliquity), and the fault position, we graphically display the geometry of structures produced. The models are applied to volcanoes with known underlying faults, and we demonstrate the importance of these faults in determining volcanic structures and slope instability. Using the knowledge of fault patterns gained from these experiments, geological mapping on volcanoes can locate fault influence and unstable zones, and hence monitoring of unstable flanks could be carried out to determine the actual response to faulting in specific cases.     

Intensity predictive attenuation models calibrated in Mw for metropolitan France

In the framework of the SIGMA project, a study was launched to develop a parametric earthquake catalog for the historical period, covering the metropolitan territory and calibrated in Mw. A set of candidate calibration events was selected corresponding to earthquakes felt over a part of the French metropolitan territory, which are fairly well documented both in terms of macroseismic intensity distributions (SisFrance BRGM-EDF-IRSN) and magnitude estimates. The detailed analysis of the macroseismic data led us to retain only 30 events out of 65 with Mw ranging from 3.6 to 5.8. In order to supplement the dataset with data from larger magnitude events, Italian earthquakes were also considered (11 events posterior to 1900 with Mw?≥?6.0 out of 15 in total), using both the DBMI11 macroseismic database (Locati et al. in Seismol Resour Lett 85(3):727–734, 2014) and the parametric information from the CPTI11 (Rovida et al. in CPTI11, la versione 2011 del Catalogo Parametrico dei Terremoti Italiani Istituto Nazionale di Geofisica et Vulcanologia, Milano, Bologna, 2011.  https://doi.org/10.6092/ingv.it-cpti11). To avoid introducing bias related to the differences in terms of intensity scales (MSK vs. MCS), only intensities smaller than or equal to VII were considered (Traversa et al. in On the use of cross-border macroseismic data to improve the estimation of past earthquakes seismological parameters, 2014). Mw and depth metadata were defined according to the Si-Hex catalogue (Cara et al. in Bull Soc Géol Fr 186:3–19, 2015.  https://doi.org/10.2113/qssqfbull.186.1.3), published information, and to the specific worked conducted within SIGMA related to early instrumental recordings (Benjumea et al. in Study of instrumented earthquakes that occurred during the first part of the 20th century (1905–1962), 2015). For the depth estimates, we also performed a macroseismic analysis to evaluate the range of plausible estimates and check the consistency of the solutions. Uncertainties on the metadata related to the calibration earthquakes were evaluated using the range of available alternative estimates. The intensity attenuation models were developed using a one-step maximum likelihood scheme. Several mathematical formulations and sub-datasets were considered to evaluate the robustness of the results (similarly to Baumont and Scotti in Accounting for data and modeling uncertainties in empirical macroseismic predictive equations (EMPEs). Towards “European” EMPEs based on SISFRANCE, DBMI, ECOS macroseismic database, 2008). In particular, as the region of interest may be characterized by significant laterally varying attenuation properties (Bakun and Scotti in Geophys J Int 164:596–610, 2006; Gasperini in Bull Seismol Soc Am 91:826–841, 2001), we introduced regional attenuation terms to account for this variability. Two zonation schemes were tested, one at the national scale (France/Italy), another at the regional scale based on the studies of Mayor et al. (Bull Earthq Eng, 2017.  https://doi.org/10.1007/s10518-017-0124-8) for France and Gasperini (2001) for Italy. Between and within event residuals were analyzed in detail to identify the best models, that is, the ones associated with the best misfit and most limited residual trends with intensity and distance. This analysis led us to select four sets of models for which no significant trend in the between- and within-event residuals is detected. These models are considered to be valid over a wide range of Mw covering?~?3.5–7.0.