New insights on Cu origin and fate from combined chemical extraction and ᵟ⁶⁵Cu isotopic composition: Application to Cu transfers in a Mediterranean vineyard catchment

Repeated use of Cu based fungicides (Bordeaux mixture: Ca(OH)2+CuSO4) to control vine downy hasled to signi!cant increase of Cu in vineyard soils. In Mediterranean catchments, brief and intense flood events can multiply stream discharge by up to 10 and are responsible for important soil leaching and therefore for high "uxes of Cu exported at the outlet of the catchment. In order to assess the origin and fate of Cu measured in the Baillaury catchment (South of France, combined sequential extraction (SCE) and isotopic Cu compositions (δ65Cu) approaches are proposed in this study

Origin and fate of copper in a small Mediterranean vineyard catchment: New insights from combined chemical extraction and δ65Cu isotopic composition

For centuries, many Mediterranean catchments were covered with vineyards in which copper was widely applied to protect grapevines against fungus. In the Mediterranean-type flow regime, brief and intense flood events increase the stream water discharge by up to 10 times and cause soil leaching and storm runoff. Because vineyards are primarily cultivated on steep slopes, high Cu fluxes are discharged by surface water runoff into the rivers. The purpose of this work was to investigate the riverine behavior and transport of anthropogenic Cu by coupling a sequential chemical extraction (SCE) procedure, used to determine Cu partitioning between residual and non-residual fractions, with δ65Cu isotopic measurements in each fraction. In the Baillaury catchment, France, we sampled soils (cultivated and abandoned), river bed sediments (BS), suspended particulate matter (SPM), and river water during the flash flood event of February 2009. Copper partitioning using SCE show that most of Cu in abandoned vineyard soil was in the residual phase (>60%) whereas in cultivated soil, BS and SPM, Cu was mostly (>25%) in non-residual fractions, mainly adsorbed onto iron oxide fractions. A small fraction of Cu was associated with organic matter (5 to 10%). Calculated enrichment factors (EF) are higher than 2 and the anthropogenic contribution was estimated between 50 to 85%. Values for δ65Cu in bulk samples were similar to bedrock therefore; δ65Cu on SCE fractions of superficial soils and SPM allowed for discrimination between Cu origin and distribution. Copper in residual fractions was of natural mineral origin (δ65Cu close to local bedrock, +0.07‰). Copper in water soluble fraction of SPM (δ65Cu = +0.26‰) was similar to dissolved river Cu (δ65Cu = +0.31‰). Copper from fungicide treatment (δ65Cu = −0.35‰) was bound to organic matter (δ65Cu = −0.20‰) without or with slight isotopic fractioning. A preferential adsorption of 65Cu onto iron oxides (δ65Cu = +0.5‰) is shown

Are Cu isotopes a useful tool to trace metal sources and processes in acid mine drainage (AMD) context?

In the South-West Europe (Iberian Pyrite Belt), acid mine drainage (AMD) processes are especially problematic because they affect the environmental quality of watersheds, restricting the use of surface water. Recent studies have shown that Cu isotopes are fractionated during the oxidative dissolution of primary sulfide minerals and could be used to trace metal cycling. However the chemistry of Cu in such environment is complex because Cu is redistributed within numerous secondary minerals and strongly dependent on the hydroclimatic conditions that control key parameters (pH, redox conditions). Finally, it remains difficult to compare the various field studies and deliver some strong general tendencies because of these changing conditions. For these reasons, concerted studies on Cu isotopes fractionation in waters impacted by AMD may help to reveal the sources and transport pathways of this important pollutant. To address this issue, we used a representative scenario of strong contamination by AMD in the Iberian Pyrite Belt (SW Spain), the Cobica River. The aim of our study is to measure the Cu isotopes signature in the waters (river, mine lake, water draining waste) of the small Cobica River system (Huelva, Spain), sampled during a short period (8 h) to avoid any change in the hydro-climatic conditions. This provided an instantaneous image of the isotopic Cu signature in a small mining systems and helped us to constrain both the processes affecting Cu isotopes and their use a potential tracer of metals in contaminated environments.This work was supported by the french national programme EC2CO Biohefect/Ecodyn//Dril/MicrobiEen (INSU/CNRS, France), the Paul Sabatier University (France) and the Department of Mining, Mechanical, Energetic and Construction Engineering of the University of Huelva (Spain)

A Rouse-based method to integrate the chemical composition of river sediments : application to the Ganga basin

Author Posting. © American Geophysical Union, 2011. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research 116 (2011): F04012, doi:10.1029/2010JF001947.The Ganga River is one of the main conveyors of sediments produced by Himalayan erosion. Determining the flux of elements transported through the system is essential to understand the dynamics of the basin. This is hampered by the chemical heterogeneity of sediments observed both in the water column and under variable hydrodynamic conditions. Using Acoustic Doppler Current Profiler (ADCP) acquisitions with sediment depth profile sampling of the Ganga in Bangladesh we build a simple model to derive the annual flux and grain size distributions of the sediments. The model shows that ca. 390 (±30) Mt of sediments are transported on average each year through the Ganga at Haring Bridge (Bangladesh). Modeled average sediment grain size parameters D50 and D84 are 27 (±4) and 123 (±9) μm, respectively. Grain size parameters are used to infer average chemical compositions of the sediments owing to a strong grain size chemical composition relation. The integrated sediment flux is characterized by low Al/Si and Fe/Si ratios that are close to those inferred for the Himalayan crust. This implies that only limited sequestration occurs in the Gangetic floodplain. The stored sediment flux is estimated to c.a. 10% of the initial Himalayan sediment flux by geochemical mass balance. The associated, globally averaged sedimentation rates in the floodplain are found to be ca. 0.08 mm/yr and yield average Himalayan erosion rate of ca. 0.9 mm/yr. This study stresses the need to carefully address the average composition of river sediments before solving large-scale geochemical budgets.This work was supported by INSU program “Relief de la Terre” and ANR Calimero. Valier Galy was supported by the U.S. National Science Foundation (grant OCE‐0851015)

Développements analytiques en spectrométrie de masse à thermo-ionisation pour l'analyse isotopique de faibles quantités

TOULOUSE3-BU Sciences (315552104) / SudocSudocFranceF

Behavior of Sm and Nd in a lateritic soil profile

A study of lateritic soils and samples of ground and river waters was carried out in the Nsimi-Zoetele, a tropical watershed in the southern Cameroon. The Nd isotopic compositions and concentrations of Nd and Sm were determined. It was found that the Nd isotopic composition of the river waters was much more radiogenic than the parent rocks, and that the Nd in the waters is not homogeneous but is carried by different dissolved and complexed components that are not isotopically homogenized. The soil profile shows a regular increase in ε_(Nd) going from the parent rock (ε_(Nd) = −36) to ε_(Nd) = −18 near the top of the profile. The Nd transported in the river is thus not representative of the parent rock but reflects the results of differential weathering of constituent minerals and the redeposition of REE in phosphates and a significant contribution of radiogenic Nd from dust. The concentration of Nd in the river water is far above that found in temperate climate rivers and thus this type of tropical river may play a dominant role in the marine Nd and REE budget. It is suggested that the correlation of REE with DOC is related to DOC fixing some dissolved REE but that the REE in solution is governed by other mechanisms. No major shifts were found in Sm/Nd; however, a regular progression from the parent rock through the lateritic profile was found. The upper laterite profile shows large, almost uniform depletions in all REE below Tb and enrichment above. Complementary behavior was found in the lower part of the section. The concentration of Nd relative to the immobile elements Zr and Ti in the laterite is depleted by a factor of ∼10. Th, Nd and Sm are enriched in the lowest zone sampled and must reflect redeposition of REE from the upper part of the weathering section and is associated with phosphate formation. It is concluded that the soil evolution involves both differential dissolution of primary phases from the parent rock, significant to major input of REE from atmospheric dust from other regions, and the formation of diagenetic phases, particularly phosphates

5. Eau, climat et biodiversité

La planète Terre, en raison de sa position particulière autour du Soleil, présente de l’eau en surface sous forme liquide, solide et gazeuse. Cette eau provient du dégazage de la Terre par le biais du volcanisme et de l’intense bombardement météoritique qu’a connu la planète, principalement entre 4,5 et 4 milliards d’années avant notre ère. D’après les données isotopiques obtenues sur des roches très anciennes, la Terre était à cette époque beaucoup plus chaude qu’actuellement. Puis, le clima..

Etude biogéochimique d'un système lacustre de la plaine d'inondation amazonienne

TOULOUSE3-BU Sciences (315552104) / SudocTOULOUSE-Observ. Midi Pyréné (315552299) / SudocSudocFranceF

Limited iron isotope variations in recent lateritic soils from Nsimi, Cameroon: Implications for the global Fe geochemical cycle

International audienceLaterites are oxidized Fe-rich soils covering one third of the continents and are drained by half of the continental waters. They therefore represent a key component of the iron geochemical cycle at the Earth's surface, yet no iron isotope study has been conducted on recent laterites so far. Building on previous integrated morpho-pedological studies of soils located in an equatorial rainforest, Southern Cameroon, we have undertaken a mineralogical, elemental and isotopic study of iron in two lateritic profiles. One is a borehole 3620 cm deep going to the parent granodioritic rock, located at the top of a hill, whereas the other is 675 cm deep and is located downhill. Mossbauer spectroscopy reveals that typically >= 96% of the soil's iron is held in nanocrystalline hematite and goethite. Iron isotope measurements performed by plasma source mass spectrometry show that Fe isotopic equilibrium was rarely reached between these iron oxide and hydroxide despite their small size. Overall, it is found that most samples display iron isotope signatures very close to the mean crustal value, with a maximum range of 0.2 parts per thousand in delta Fe-57. Given that lateritic soils evolve over millions of years, show large variations in Fe concentrations and mineralogical abundances, this range is surprisingly small when compared to other Fe isotope studies of soils from different climatological contexts, that can easily show delta Fe-57 ranges in excess of 1 parts per thousand. at the bulk sample scale. The most likely explanation of this finding is that despite notable vertical and lateral Fe mobility in the studied laterites from Cameroon, as computed using the open-system mass fraction transport function, tau(Fe,w), iron remained mostly in the oxidized form as shown by Mossbauer spectroscopy. This probably results from the strong bioturbation and pedoturbation of these lateritic soils that lead them to remain porous over a large thickness and facilitated the flow of oxygenated waters from the surface down to the saprolite horizon. This study therefore reveals that soils that remained as an open system for iron do not necessarily show large Fe isotopic variations. It is suggested that the Fe drained from such lateritic soils should have delta Fe-57 values within similar to 0.1 parts per thousand. of that of the continental crust. This is in contrast with previous soil studies, notably from sites located at higher latitudes, that imply that these soils should release isotopically more variable Fe to surface waters. Such possible contrasted isotopic signatures from different surface waters will likely lead to an isotopically heterogeneous ocean given the short residence time of Fe in seawater