222Rn as Natural Tracer for LNAPL Recovery in a Crude Oil‐Contaminated Aquifer

The objective of this study was to investigate whether ²²²Rn in groundwater can be used as a tracer for light non‐aqueous phase liquid (LNAPL) quantification at a field site treated by dual‐phase LNAPL removal. After the break of a pipeline, 5 ha of soil in the nature reserve Coussouls de Crau in southern France was contaminated by 5100 m³ of crude oil. Part of this oil seeped into the underlying gravel aquifer and formed a floating oil body of about 3.9 ha. The remediation consists of plume management by hydraulic groundwater barriers and LNAPL extraction in the source zone. ²²²Rn measurements were performed in 21 wells in and outside the source zone during 15 months. In uncontaminated groundwater, the radon activity was relatively constant and remained always >11 Bq/L. The variability of radon activity measurements in wells affected by the pump‐and‐skim system was consistent with the measurements in wells that were not impacted by the system. The mean activities in wells in the source zone were, in general, significantly lower than in wells upgradient of the source zone, owing to partitioning of ²²²Rn into the oil phase. The lowest activities were found in zones with high non‐aqueous phase liquid (NAPL) recovery. LNAPL saturations around each recovery well were furthermore calculated during a period of high groundwater level, using a laboratory‐determined crude oil–water partitioning coefficient of 38.5 ± 2.9. This yielded an estimated volume of residual crude oil of 309 ± 93 m³ below the capillary fringe. We find that ²²²Rn is a useful and cheap groundwater tracer for finding zones of good LNAPL recovery in an aquifer treated by dual‐phase LNAPL removal, but that quantification of NAPL saturation using Rn is highly uncertain.     

A case study of the mesoscale dynamics in the North-Western Mediterranean Sea: a combined data–model approach

The Northern current is the main circulation feature of the North-Western Mediterranean Sea. While the large-scale to mesoscale variability of the northern current (NC) is well known and widely documented for the Ligurian region, off Nice or along the Gulf of Lions shelf, few is known about the current instabilities and its associated mesoscale dynamics in the intermediate area, off Toulon. Here, we took advantage of an oceanographic cruise of opportunity, the start of a HF radar monitoring programme in the Toulon area and the availability of regular satellite sea surface temperature and chlorophyll a data, to evaluate the realism of a NEMO-based regional high-resolution model and the added value brought by HF radar. The combined analysis of a 1/64° configuration, named GLAZUR64, and of all data sets revealed the occurrence of an anticyclonic coastal trapped eddy, generated inside a NC meander and passing the Toulon area during the field campaign. We show that this anticyclonic eddy is advected downstream along the French Riviera up to the study region and disturbs the Northern current flow. This study aims to show the importance of combining observations and modelling when dealing with mesoscale processes, as well as the importance of high-resolution modelling.     

Large wavenumber convection in the rotating annulus

Abstract

The annulus model considers convection between concentric cylinders with sloping endwalls. It is used as a simplified model of convection in a rapidly rotating sphere. Large azimuthal wavenumbers are preferred in this problem, and this has been exploited to develop an asymptotic approach to nonlinear convection in the annulus. The problem is further reduced because the Taylor-Proudman constraint simplifies the dependence in the direction of the rotation vector, so that a nonlinear system dependent only on the radial variable and time results. As Rayleigh number is increased a sequence of bifurcations is found, from steady solutions to periodic solutions and 2-tori, typically ending in chaotic behaviour. Both the magnetic (MHD convection) and non-magnetic problem has been considered, and in the non-magnetic case our bifurcation sequence can be compared with those found by previous two-dimensional numerical simulations.     

Links between NAO fluctuations and inter-annual variability of winter-months precipitation in the Seine River watershed (north-western France)

The inter-annual to multi-decadal winter variability (DJFM) of precipitation on the Seine River watershed (France) was analysed using continuous wavelet transform analysis and compared to the winter North Atlantic Oscillation Index (NAOI). Nine weather stations were used over the 1951 to 2004 period and confirmed the homogeneity of inter-annual fluctuations for all stations but one. Wavelet coherence between SLP over the Icelandic and Azores regions and precipitation highlighted coherence for different scales of variability according to the centre of action considered. Segmentation and wavelet analysis and coherence between precipitation and NAOI over a long period of time (1873–2004) showed: i) increasing variability across the last century at most time scales, especially for NAOI; ii) the existence of change points for the mean and variance of both signals; iii) overall discontinuity of the coherence whatever the scale considered, especially between ∼1910 and ∼1955 for inter-decennial to pluri-decennial scales.     

Quantifying internal variability in a regional climate model: a case study for Southern Africa

This study aims at presenting various methodologies to separate the reproducible and irreproducible components of seasonal and intraseasonal climate variability simulated by a regional climate model over Southern Africa (south of 15°S), during an austral summer rainy season representative of the climatology. To that end, a 30-member ensemble simulation is performed using WRF laterally forced by the ERA40 reanalyses. Retained metrics include the analysis of weather regimes, signal-to-noise ratio, inter-member standard deviation and coefficient of variation. At the seasonal timescale, simulated rainfall amounts generally show a strong reproducibility, except in the subtropics and over the southern part of the Mozambique Channel. There, the number of rainy days is roughly similar in all members, while their average intensity varies extensively. At the intraseasonal timescale, the chronology of weather regimes, derived from the 500?hPa geopotential height, is highly reproducible. Rainfall variability is much less reproducible, especially in the central parts of the domain and near its outflow boundaries. Analysis of a South African regional index nonetheless indicates that both wet and dry spells tend to be accurately simulated and occur in phase in most members, demonstrating that they are embedded in large-scale variability patterns. Internal variability is lastly related to the lateral forcings along the domain boundaries. An objective classification of inflow/outflow mass fluxes allows identification of the recurrent synoptic configurations that favor strong or weak regional reproducibility. The main uncertainties concern the basic morphological features of rain-bearing systems (i.e., their spatial extension, location and propagation speed). Consequences for tropical-temperate interactions are then discussed.     

Deep inside a neoproterozoic intra-oceanic arc: growth,differentiation and exhumation of the Amalaoulaou complex (Gourma,Mali)

We show here that the Amalaoulaou complex, in the Pan-African belt of West Africa (Gourma, Mali), corresponds to the lower and middle sections of a Neoproterozoic intra-oceanic arc. This complex records a 90–130-Ma-long evolution of magmatic inputs and differentiation above a subducting oceanic slab. Early c. 793 Ma-old metagabbros crystallised at lower crustal or uppermost mantle depths (25–30 km) and have geochemical characteristic of high-alumina basalts extracted from a depleted mantle source slightly enriched by slab-derived sedimentary components ((La/Sm)_N < 1; ε_Nd: +5.4–6.2; ⁸⁷Sr/⁸⁶Sr: 0.7027–0.7029). In response to crustal thickening, these mafic rocks were recrystallised into garnet-granulites (850–1,000°C; 10–12 kbar) and subject to local dehydration–melting reactions, forming trondhjemititic leucosomes with garnet–clinopyroxene–rutile residues. Slightly after the granulitic event, the arc root was subject to strong HT shearing during partial exhumation (detachment faults/rifting or thrusting), coeval with the emplacement of spinel- and garnet-pyroxenite dykes crystallised from a high-Mg andesitic parental magma. Quartz and hornblende-gabbros (700–660 Ma) with composition typical of hydrous volcanic rocks from mature arcs ((La/Sm)_N: 0.9–1.8; ε_Nd: +4.6 to +5.2; ⁸⁷Sr/⁸⁶Sr: 0.7028–0.7031) were subsequently emplaced at mid-arc crust levels (~15 km). Trace element and isotopic data indicate that magmas tapped a depleted mantle source significantly more enriched in oceanic sedimentary components (0.2%). Exhumation occurred either in two stages (700–660 and 623 Ma) or in one stage (623 Ma) with a final exhumation of the arc root along cold P-T path (550°C, 6–9 kbar; epidote–amphibolite and greenschist facies conditions) during the main Pan-African collision event (620–580 Ma). The composition of magmas forming the Cryogenian Amalaoulaou arc and the processes leading to intra-arc differentiation are strikingly comparable to those observed in the deep section of exposed Mezosoic oceanic arcs, namely the Kohistan and Talkeetna complex. This evolution of the Amalaoulaou oceanic arc and its accretion towards the West African craton belong to the life and closure of the Pharusian Ocean that eventually led to the formation of the Greater Gondwana supercontinent, a similar story having occurred on the other side of the Sahara with the Mozambique Ocean.     

U redox fronts and kaolinisation in basement-hosted unconformity-related U ores of the Athabasca Basin (Canada): late U remobilisation by meteoric fluids

Proterozoic basement-hosted unconformity-related uranium deposits of the Athabasca Basin (Saskatchewan, Canada) were affected by significant uranium redistribution along oxidation–reduction redox fronts related to cold and late meteoric fluid infiltration. These redox fronts exhibit the same mineralogical and geochemical features as the well-studied uranium roll-front deposits in siliclastic rocks. The primary hydrothermal uranium mineralisation (1.6–1.3 Ga) of basement-hosted deposits is strongly reworked to new disseminated ores comprising three distinctly coloured zones: a white-green zone corresponding to the previous clay-rich alteration halo contemporaneous with hydrothermal ores, a uranium front corresponding to the uranium deposition zone of the redox front (brownish zone, rich in goethite) and a hematite-rich red zone marking the front progression. The three zones directly reflect the mineralogical zonation related to uranium oxides (pitchblende), sulphides, iron minerals (hematite and goethite) and alumino-phosphate-sulphate (APS) minerals. The zoning can be explained by processes of dissolution–precipitation along a redox interface and was produced by the infiltration of cold (<50°C) meteoric fluids to the hydrothermally altered areas. U, Fe, Ca, Pb, S, REE, V, Y, W, Mo and Se were the main mobile elements in this process, and their distribution within the three zones was, for most of them, directly dependent on their redox potential. The elements concentrated in the redox fronts were sourced by the alteration of previously crystallised hydrothermal minerals, such as uranium oxides and light rare earth element (LREE)-rich APS. The uranium oxides from the redox front are characterised by LREE-enriched patterns, which differ from those of unconformity-related ores and clearly demonstrate their distinct conditions of formation. Uranium redox front formation is thought to be linked to fluid circulation episodes initiated during the 400–300 Ma period during uplift and erosion of the Athabasca Basin when it was near the Equator and to have been still active during the last million years. A major kaolinisation event was caused by changes in the fluid circulation regime, reworking the primary uranium redox fronts and causing the redistribution of elements originally concentrated in the uranium-enriched meteoric-related redox fronts.     

Weathering of ordinary chondrites from the Atacama Desert,Chile, by Mössbauer spectroscopy and synchrotron radiation X‐ray diffraction

Some terrestrial areas have climatic and geomorphologic features that favor the preservation, and therefore, accumulation of meteorites. The Atacama Desert in Chile is among the most important of such areas, known as DCA. This desert is the driest on Earth, one of the most arid, uninhabitable localities with semiarid, arid, and hyper‐arid conditions. The meteorites studied here were collected from within the DCA of San Juan and Pampa de Mejillones, located, respectively, in the Central Depression and the Coastal Range of the Atacama Desert. ⁵⁷Fe Mössbauer spectroscopy was used for quantitative analysis of the degree of weathering of the meteorites, through the determination of the proportions of the various Fe‐bearing phases and in particular the amount of oxidized iron in terrestrial alteration products. The abundance of ferric ions in weathered chondrites can be related to specific precursor compositions and to the level of terrestrial weathering. The aim of the study was the identification, quantification, and differentiation of the weathering products in the ordinary chondrites found in the San Juan and the Pampa de Mejillones areas of the Atacama Desert. The ⁵⁷Fe Mössbauer spectroscopy study was complemented by synchrotron radiation X‐ray diffraction and magnetic susceptibility measurements. The results allow a clear differentiation of the rate of weathering in meteorite samples collected from the San Juan versus the Pampa de Mejillones areas of the Atacama Desert.     

Ab initio calculations of the Fe(II) and Fe(III) isotopic effects in citrates,nicotianamine, and phytosiderophore,and new Fe isotopic measurements in higher plants

Iron is one of the most abundant transition metal in higher plants and variations in its isotopic compositions can be used to trace its utilization. In order to better understand the effect of plant-induced isotopic fractionation on the global Fe cycling, we have estimated by quantum chemical calculations the magnitude of the isotopic fractionation between different Fe species relevant to the transport and storage of Fe in higher plants: Fe(II)-citrate, Fe(III)-citrate, Fe(II)-nicotianamine, and Fe(III)-phytosiderophore. The ab initio calculations show firstly, that Fe(II)-nicotianamine is ～3‰ (⁵⁶Fe/⁵⁴Fe) isotopically lighter than Fe(III)-phytosiderophore; secondly, even in the absence of redox changes of Fe, change in the speciation alone can create up to ～1.5‰ isotopic fractionation. For example, Fe(III)-phytosiderophore is up to 1.5‰ heavier than Fe(III)-citrate₂ and Fe(II)-nicotianamine is up to 1‰ heavier than Fe(II)-citrate. In addition, in order to better understand the Fe isotopic fractionation between different plant components, we have analyzed the iron isotopic composition of different organs (roots, seeds, germinated seeds, leaves and stems) from six species of higher plants: the dicot lentil (Lens culinaris), and the graminaceous monocots Virginia wild rye (Elymus virginicus), Johnsongrass (Sorghum halepense), Kentucky bluegrass (Poa pratensis), river oat (Uniola latifolia), and Indian goosegrass (Eleusine indica). The calculations may explain that the roots of strategy-II plants (Fe(III)-phytosiderophore) are isotopically heavier (by about 1‰ for the δ⁵⁶Fe) than the upper parts of the plants (Fe transported as Fe(III)-citrate in the xylem or Fe(II)-nicotianamine in the phloem). In addition, we suggest that the isotopic variations observed between younger and older leaves could be explained by mixing of Fe received from the xylem and the phloem.