Jean-Luc Probst

Identifying the origins of local atmospheric deposition in the steel industry basin of Luxembourg using the chemical and isotopic composition of the lichen Xanthoria parietina

Trace metal atmospheric contamination was assessed in one of the oldest European industrial sites of steel production situated in the southern part of the Grand-Duchy of Luxembourg. Using elemental ratios as well as Pb, Sr, and Nd isotopic compositions as tracers, we found preliminary results concerning the trace metal enrichment and the chemical/isotopic signatures of the most important emission sources using the lichen Xanthoria parietina sampled at 15 sites along a SW-NE transect. The concentrations of these elements decreased with increasing distance from the historical and actual steel-work areas. The combination of the different tracers (major elements, Rare Earth Element ratios, Pb, Sr and Nd isotopes) enabled us to distinguish between three principal sources: the historical steel production (old tailings corresponding to blast-furnace residues), the present steel production (industrial sites with arc electric furnace units) and the regional background (baseline) components. Other anthropogenic sources including a waste incinerator and major roads had only weak impacts on lichen chemistry and isotopic ratios. The correlation between the Sr and Nd isotope ratios indicated that the Sr-Nd isotope systems represented useful tools to trace atmospheric emissions of factories using scrap metal for steel production.

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 δ(65)Cu 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 δ(65)Cu in bulk samples were similar to bedrock therefore; δ(65)Cu 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 (δ(65)Cu close to local bedrock, +0.07‰). Copper in water soluble fraction of SPM (δ(65)Cu=+0.26‰) was similar to dissolved river Cu (δ(65)Cu=+0.31‰). Copper from fungicide treatment (δ(65)Cu=-0.35‰) was bound to organic matter (δ(65)Cu=-0.20‰) without or with slight isotopic fractioning. A preferential adsorption of (65)Cu onto iron oxides (δ(65)Cu=+0.5‰) is shown.

Stable carbon isotope evidence for nitrogenous fertilizer impact on carbonate weathering in a small agricultural watershed.

The isotopic signature of Dissolved Inorganic Carbon (DIC), δ(13)C(DIC), has been investigated in the surface waters of a small agricultural catchment on calcareous substratum, Montoussé, located at Auradé (south-west France). The Montoussé catchment is subjected to intense farming (wheat/sunflower rotation) and a moderated application of nitrogenous fertilizers. During the nitrification of the NH(4)(+), supplied by fertilization, nitrate and H(+) ions are produced in the soil. This anthropogenic acidity is combined with the natural acidity due to carbonic acid in weathering processes. From an isotopic point of view, with natural weathering, using carbonic acid, δ(13)C(DIC) is intermediate between the δ(13)C of soil CO(2) produced by organic matter oxidation and that of the carbonate rocks, while it has the same value as the carbonates when carbonic acid is substituted by another acid like nitric acid derived from nitrogen fertilizer. The δ(13)C(DIC) values range from -17.1‰ to -10.7‰ in Montoussé stream waters. We also measured the δ(13)C of calcareous molassic deposits (average -7.9‰) and of soil organic carbon (between -24.1‰ and -26‰) to identify the different sources of DIC and to estimate their contribution. The δ(13) C(DIC) value indicates that weathering largely follows the carbonic acid pathway at the springs (sources of the stream). At the outlet of the basin, H(+) ions, produced during the nitrification of N-fertilizer, also contribute to weathering, especially during flood events. This result is illustrated by the relationship between δ(13)C(DIC) and the molar ratio NO(3)(-)/(Ca(2+) + Mg(2+)). Consequently, when the contribution of nitrate increases, the δ(13)C(DIC) increases towards the calcareous end-member. This new isotopic result provides evidence for the direct influence of nitrogen fertilizer inputs on weathering, CO(2) consumption and base cation leaching and confirms previous results obtained using the chemistry of the major ions present in the field, and in soil column experiments.

Isotopic characteristics of the Garonne River and its tributaries

The Garonne is the largest river in the south-west of France, and its drainage basin stretches between the Pyrénées and the Massif Central mountains. Until now, no water stable isotope study has been performed on the whole Garonne river basin which is composed of different geological substrata, and where the water resources are limited during the dry summer period. This study focuses on the Garonne river and its tributaries from the Pyrénées foothill upstream to its confluence with the Lot River downstream. The aim of the study is to determine the origins of the surface waters using their chemical and stable isotopic compositions ((18)O, D and (13)C), to better understand their circulation within the drainage basin and to assess the anthropogenic influences. The Garonne displays a specific (18)O seasonal effect, and keeps its Pyrénean characteristics until its confluence with the Tarn River. The difference in the dissolved inorganic carbon (DIC) comes mainly from the change in lithology between the Pyrénées and the Massif Central mountains. Agriculture activity is only detected in the small tributaries.

First assessment of water and carbon cycles in two tropical coastal rivers of south‐west India: an isotopic approach

RATIONALEnThe contribution of tropical coastal rivers to the global carbon budget remains unmeasured, despite their high water dynamics, i.e. higher run-off with their basin characteristic of warm temperature. Two rivers draining the western part of the Western Ghats, the Swarna (length 80 km) and Nethravati (147 km) Rivers, were studied for water and carbon cycles.nnnMETHODSnThe stable isotope ratios of oxygen (δ(18) O values), hydrogen (δ(2) H values) and carbon (δ(13) C values) were used to understand the water circulation, the weathering processes and the carbon biogeochemical cycle. The river water samples were collected during the dry post-monsoonal season (November 2011).nnnRESULTSnThe δ(18) O and δ(2) H values of river water suggested that the monsoonal vapour source and its high recycling have a dominant role because of the orographical and tropical conditions. The absence of calcareous rocks has led to dissolved inorganic carbon (DIC) mainly originating from atmospheric/soil CO2 , via rock-weathering processes, and the low soil organic matter combined with high run-off intensity has led to low riverine dissolved organic carbon (DOC) contents. The δ(13) C values increase from upstream to downstream and decrease with increasing pCO2 . There is a positive relationship between the δ(13) CDIC values and the DOC concentrations in these two rivers that is contrary to that in most of the studied rivers of the world.nnnCONCLUSIONSnThe higher evapotranspiration supported by tropical conditions suggests that there are higher vapour recycling process in the Swarna and Nethravati basins as studied from the water δ(18) O and δ(2) H values. The basin characteristics of higher rainfall/run-off accompanied by warm temperature suggest that the δ(13) C value of riverine DIC is mainly controlled by the weathering of source rocks (silicates) with variation along the river course by CO2 degassing from the river water to the atmosphere and is less dominated by the oxidation of DOC.

Trace Element and Pesticide Dynamics During a Flood Event in the Save Agricultural Watershed: Soil-River Transfer Pathways and Controlling Factors

Agricultural practices are the main source of water contamination in rural areas. Rainfall events, and subsequently, soil leaching and storm runoff are mainly controlling the transfer of pollutants from diffuse sources in watersheds during floods. These periods are also very important to better understand their dynamics, particularly their different soil-river transfer pathways (surface runoff SR, subsurface runoff SSR, and groundwater flow GF). This study focuses on riverine transfers of both pesticides and trace elements. High-resolution monitoring of water discharge and water sampling were performed during a flood event that occured in May 2010 in an agricultural catchment of SW France. Chemical composition of major and trace elements, silica, alkalinity, pH and conductivity, DOC and POC, TSM, and commonly used pesticides were analyzed with a high sampling frequency. The different stream flow components (SR, SSR, and GF) were assessed using two independent hydrograph separation methods: a hydrological approach based on Maillet’s formula (1905) for the recession period and a chemical approach based on physico-chemical tracers, TSM for SR and PO43− for GF. Both methods exhibited important contributions of SR (33 %) and SSR (40 %) to the total riverine pollutant transfers. The contribution of different components was also visible using concentration-discharge relationships which exhibited hysteresis phenomenon between the rising and the falling limbs of the hydrograph. Higher concentrations during the rising period (clockwise hysteresis) were characteristic of pollutants mainly exported by SR (trifluralin, Cd). Anticlockwise hysteresis with higher concentration during the recession period showed pollutants mainly exported by SSR (metolachlor, Cu). Moreover, significant relationships were highlighted between the controlling factors (DOC, POC, and TSM) and SR, SSR, and GF contributions: DOC and the complexed pollutants were highly correlated to SSR while POC, TSM, and the adsorbed pollutants were linked to SR. During the flood, Kd of most pollutants increased, particularly at the beginning, and therefore, future studies should investigate their availability to living organisms and thus their toxicity. An additional characteristic equation between Kd and Kow of the different pesticides was proposed to help future management, modelling, and estimation of pollutant transfers during floods.

Anthropogenic contribution and influencing factors on metal features in fluvial sediments from a semi-arid Mediterranean river basin (Tafna River, Algeria): A multi-indices approach

Metals in river sediments from a semi-arid Mediterranean basin were investigated from upstream to downstream during contrasting hydrological conditions in 2014 and 2015. The level and origin of the contamination were evaluated using several geochemical and isotopic indicators. Elements were grouped by their level of contamination: high (Pbu202f>u202fCdu202f>u202fZnu202f>u202fCu) and low (Al, Fe, Cr, Co, Ni). Multiple local sources of contamination were identified (industrial, agricultural and domestic waste), as well as very specific ones (gasoline station) and diffuse pollution from atmospheric deposition (gasoline, ores, aerosols). During storm events, the upstream dams can either be secondary sources of contamination or dilutors through particles derived from natural erosion. The contamination was slowed downstream due to the river geomorphology, but eventually washed into the Mediterranean Sea by intense storm events. Naturally derived elements (Co, Ni, Cr, As) were associated with Al, Fe and Mn oxides or clays, and anthropogenic originated metals with phosphorus (Cd and Zn), sulphur (Cu) and POC (Pb enrichment). Cadmium and Pb were the most available metals upstream and at the outlet, but their availability was not strictly related to their degree of contamination. These conclusions could be drawn thanks to an approach by multiple indicators.