Anne Probst

Heavy metal distribution in some French forest soils: evidence for atmospheric contamination

This study is one of very few dealing with the distribution and the origin of heavy metals in French soils from a priori non-polluted forest areas. The abundance of heavy metals measured in these soils decreases as follows: Cr>Zn>Pb>Ni>Cu>Co>>Cd. Total concentrations of Pb, Cr and Ni in some soils exceed the European thresholds for non-polluted soils and even the French association of normalization critical values for sludge spreading. The lowest heavy metal contents are observed in acid soils while the highest concentrations are in the calcaric cambisol and in the mollic andosol, which is rather scarce as compared with the other French forest soils. With the exception of the podzol, Cr and Ni concentrations increase with depth in all soil profiles. The distribution pattern of Co, Cu, Zn depends on the soil characteristics. In some acid soils, however, Cu and Zn decrease with depth. Pb and Cd are accumulated in the upper soil horizons. Heavy metals accumulate in deep soil horizons in relation to important clay content in the dystric planosol and stagnic luvisol. The concentration of each heavy metal is always controlled by different parameters (soil pH, iron and aluminum oxide content, clay content, organic matter and cation exchange capacity), which are heavy metal specific. This study highlights the metal-trapping character of andosol and calcaric soil, the weak heavy metal retention in acid soils, the leaching and trapping character in leached clayed soils, and the migration of heavy metals in the podzol. Pb and Cr concentrations indicate a significant enrichment in surface horizons from various soils in areas which receive significant acid atmospheric pollution. Particularly, the highest Pb content is observed in a soil located in the N-NE part of France. Lead isotope ratios measured in the cambic podzol and the calcaric cambisol, exhibit the importance of the anthropogenic sources and particularly the influence of global atmospheric inputs from leaded gasoline compared to regional and local industrial emissions. The anthropogenic Pb contribution is estimated to 83, 30 and 11%, respectively, for surface, intermediate and deep horizons of the cambic podzol located in the northern part of France, and to 68% in surface horizon of the calcaric cambisol located in the Alps.

REE fractionation during granite weathering and removal by waters and suspended loads: Sr and Nd isotopic evidence

Very few studies deal with REE (rare earth element) mobility within the system soil–soil solution–streamwater. In this article, we try to characterize the fractionation and the migration of the REE in a granite-derived soil system located in a small catchment of the Vosges mountains. ICP-MS and TIMS measurements were performed on both solid samples (“fresh” granite, soil, and suspended load of the stream) and waters (soil solutions, springwater, and streamwater) to determine their respective REE concentrations and Sr and Nd isotopic compositions. The PAAS-normalized REE pattern of the bedrock is characterized by a strong depletion in HREE (heavy REE) and a negative Eu anomaly (0.46). Similarly, the granite-normalized REE distribution patterns of the soil samples show HREE depletions that become more important with decreasing depth. The correlative behavior between P2O5, Th, and REE with depth indicates that, besides apatite, other phosphate minerals such as monazite are the most important phases controlling the Th and REE budget in the soil profile. On the other hand, at greater depth, zircon seems to be another important mineral phase controlling especially the HREE enrichment as shown by the positive relationship between Zr content and the Yb/Ho ratio. Different grain size fractions show similar REE distribution patterns and are only weakly fractionated, compared with bulk soil sample. However, the finest fraction (0–20 μm) is more enriched in Sr and REE, suggesting a stronger concentration of REE-carrying minerals in this fraction. The suspended and dissolved load of the stream show as a whole an enrichment in HREE if compared with the granite or with the different soil samples. However, compared with the uppermost soil samples, the suspended load is significantly more enriched in HREE. Its REE distribution pattern is more similar to that of the finest fraction of the deeper soil sample and to the “fresh” granite. Thus, most probably the REE of the suspended load originated from a source with REE characteristics found in the deep soil horizons. This source might have been situated in the uppermost soil profile, which is actually REE depleted. The weathering process can be compared with a leaching experiment where the waters correspond to the leachate and the soil to the residual phase of the granite. The Sr isotope data indicate that the suspended load originates from the finest soil fraction. The Sr and Nd isotopic data of the suspended load suggest that it contains up to 3% Sr and Nd from apatite and up to 97% from feldspar. Most of the Sr and Nd in the waters originate from apatite leaching or dissolution.

Hydrograph separation using isotopic, chemical and hydrological approaches (Strengbach catchment, France)

The streamflow components were determined in a small catchment located in Eastern France for a 40 mm rain event using isotopic and chemical tracing with particular focus on the spatial and temporal variations of catchment sources. Precipitation, soil solution, springwater and streamwaters were sampled and analysed for stable water isotopes (18O and 2H), major chemical parameters (SO42−, NO3−, Cl−, Na+, K+, Ca2+, Mg2+, NH4+, H+, H4SiO4, alkalinity and conductivity), dissolved organic carbon (DOC) and trace elements (Al, Rb, Sr, Ba, Pb and U). 18O, Si, DOC, Ba and U were finally selected to assess the different contributing sources using mass balance equations and end-member mixing diagrams. Isotopic hydrograph separation shows that the pre-event water only contributes to 2% at the beginning of the stormflow to 13% at the main peak flow. DOC associated to Si and U to Ba allow to identify the different contributing areas (upper layers of the saturated areas, deep layers of the hillslope and rainwater). The streamflow (70%) originates from the deep layers of the hillslope, the remaining being supplied by the small saturated areas. The combination of chemical (both trace and major elements) and isotopic tracers allows to identify the origin of water pathways. During the first stage of the storm event, a significant part of the runoff (30-39%) comes from the small extended saturated areas located down part of the basin (overland runoff then groundwater ridging). During the second stage, the contribution of waters from the deep layers of the hillslope in the upper subcatchment becomes more significant. The final state is characterised by a balanced contribution between aquifers located in moraine and downslopes. Indeed, this study demonstrates the interest of combining a variety of hydrometric data, geochemical and isotopic tracers to identify the components of the streamwater in such conditions

Strontium as a tracer of weathering processes in a silicate catchment polluted by acid atmospheric inputs, Strengbach, France

This paper determines the weathering and atmospheric contributions of Ca in surface water from a small spruce forested silicate catchment (N–E France) receiving acid atmospheric inputs. The bedrock is a granite with K-feldspar and albite as dominant phases. The calcium content in plagioclase is low and the Ca/Na ratio in surface water is high, reflecting other sources of calcium from those expected from the weathering of major mineral phases. The biotite content is low. Only traces of apatite were detected while no calcite was found in spite of a major hydrothermal event having affected the granite. The strontium isotopic ratio 87Sr/86Sr and Sr content was used as a tracer of weathering and was determined in minerals and bulk bedrock, open field precipitation, throughfall, soil solution, spring and stream water. The Sr isotopic ratio of the reacting weathering end-member was predicted by simulating the alteration of the granite minerals by incorporating strontium into the water–rock interaction kinetic code KINDIS. In the early stages of water–rock interaction, K-feldspar and biotite strongly influence the isotopic composition of the weathering solution whereas, the Na-rich plagioclase appears to be the main long-term reactive weathering end-member. Approximately 50% of dissolved Sr in streamwater are atmospherically derived. The 87Sr/86Sr ratios of exchangeable Sr in the fine fraction at 1-m depth from a soil profile indicate that the amount of exchangeable Sr seems essentially controlled by atmospheric inputs. The exception is the deep saprolite where weathering processes could supply the Sr (and Ca). Na-Plagioclase weathering obviously control the chemistry and the isotopic composition of surface waters. The weathering of trace mineral plays a secondary role, the exception is for apatite when plagioclase is absent. Our hydrochemical, mineralogical and isotopic investigations show that a major part of the strong Ca losses detected in catchment hydrochemical budgets that result from the neutralization of acid precipitation has an atmospheric origin. Consequently, in the long term, in such areas, the availability of such an exchangeable base cation might be strongly limited and surface waters consequently acidified.

Trace elements in stream bed sediments from agricultural catchments (Gascogne region, S-W France): Where do they come from?

The Gascogne region (SW of France) is cultivated for more than 75% of the area. 83 samples of stream bed sediments were collected in three main Gascogne river basins (Gers, Save and Touch, left tributaries of the Garonne river) to evaluate the impact of agricultural practices on trace elements behavior. Eight potential harmful elements (PHE) (Cr, Co, Ni, Cu, Zn, As, Cd and Pb), four reference elements for normalization (Sc, Cs, Al and Fe) and four major elements (Mn, Ca, Mg and P) were considered. The average trace element concentrations in the fine fractions (<63 microm) are in the decreasing order: Zn>Cr>Ni>Pb>Cu>Co>As>Sc>Cs>Cd. Geochemical investigations and an original approach combining regression analysis and chemical sequential extraction allowed to select the most adequate reference material (regional molasse) and reference element (Cs) for normalization procedure. The enrichment factor (EF) is generally lower than 2.5, particularly for Cr, Ni, Cu, As, Zn; however, 23% of the sampling stations are more contaminated (2.5<EF<4.5), particularly for Cd, Pb and Co. The PHE in the Gascogne river sediments are mainly originated from natural weathering processes; nevertheless, anthropogenic contribution could represent up to 34% of the total sediment content. For lead, geochemical and isotopic methods gave very similar anthropogenic contributions (24% and 22%, respectively). The enrichment of Cu, Pb, Zn, Co, As, Ni, Cr was mainly related to global and local atmospheric deposition of industrial emissions and gasoline combustion, and was associated to forested catchments. All PHEs are controlled by clay and oxi-hydroxides minerals. Cd was the only PHE enriched downstream cultivated catchments and this enrichment was linked to Ca and P. This indicates a major origin of Cd from fertilizer inputs and a main control by carbonate minerals.

Influence of acid atmospheric inputs on surface water chemistry and mineral fluxes in a declining spruce stand within a small granitic catchment (Vosges Massif, France).

Abstract The characteristics of surface and soil waters draining an old declining spruce stand, and their chemical behaviour under acid input influence within a small catchment are described using open field precipitations, throughfalls, soil solutions, spring and streamwater data. Element fluxes are calculated in the different ecosystem compartments, and the proton mass balance has been assessed. The results show the importance of acid occult deposits and, more generally, of acid atmospheric inputs, in explaining present soil acidification. This acidification is characterized by the base cation deficiencies observed in spruce thereby showing symptoms of decline. However, stream waters and spring waters are not yet acidified owing to the neutralization of acid inputs by weathering in the regolith. Nevertheless, streamwater chemistry is dominated by strong acid anions which are not characteristic of waters draining granitic bedrock in pristine areas.

δ13C pattern of dissolved inorganic carbon in a small granitic catchment: the Strengbach case study (Vosges mountains, France)

Abstract The transfers and origins of dissolved inorganic carbon (DIC) were studied for a year in a soil–spring–stream system in the Strengbach catchment, Vosges mountains, France. This 80 ha experimental research basin is located on the eastern side of the mountains, at an altitude ranging from 883 to 1146 m.a.s.l. and is mainly covered by spruce (80%). Brown acid and podzolic soils developed on a granitic basement, and, as a result, the DIC originates solely from CO2 generated by oxidation of soil organic matter. The ( δ 13 C DIC ) in catchment waters is highly variable, from about −22‰ in the springs and piezometers to about −12‰ in the stream at the outlet of the catchment. In the springs, pronounced seasonal variations of δ 13 C DIC exist, with the DIC in isotopic equilibrium with the soil CO2 that has estimated δ 13 C of about −24‰ in winter and −20‰ in summer. These seasonal variations reflect an isotopic fractionation that seems only induced by molecular diffusion of soil CO2 in summer. In stream water, seasonal variations are small and the relatively heavy DIC (−12‰ on average) is a result of isotopic equilibration of the aqueous CO2 with atmospheric CO2.

Characterization and migration of atmospheric REE in soils and surface waters

Abstract Rainwater and snow collected from three different sites in France (Vosges Mountains, French Alps and Strasbourg) show more or less similar shapes of their REE distribution patterns. Rainwater from Strasbourg is the most REE enriched sample, whereas precipitations from the two mountainous, less polluted catchments are less REE enriched and have concentrations close to seawater. They are all strongly LREE depleted. Different water samples from an Alpine watershed comprising snow, interstitial, puddle and streamwater show similar REE distributions with LREE enrichment (rainwater normalized) but MREE and HREE depletion. In this environment, where water transfer from the soil to the river is very quick due to the low thickness of the soils, it appears that REE in streamwater mainly originate from atmospheric inputs. Different is the behaviour of the REE in the spring- and streamwaters from the Vosges Mountains. These waters of long residence time in the deep soil horizons react with soil and bedrock REE carrying minerals and show especially significant negative Eu anomalies compared to atmospheric inputs. Their Sr and Nd isotopic data suggest that most of the Sr and Nd originate from apatite leaching or dissolution. Soil solutions and soil leachates from the upper soil horizons due to alteration processes strongly depleted in REE carrying minerals, have REE distribution patterns close to those of lichens and throughfall. Throughfall is slightly more enriched especially in light REE than filtered rainwater probably due to leaching of atmospheric particles deposited on the foliage and also to leaf excretion. Data suggest that Sr and Nd isotopes of the soil solutions in the upper soil horizons originate from two different sources: 1) An atmospheric source with fertilizer, dust and seawater components and 2) A source mainly determined by mineral dissolution in the soil. These two different sources are also recognizable in the Sr and Nd isotopic composition of the tree’s throughfall solution. The atmospheric contributions of Sr and Nd to throughfall and soil solution are of 20 to 70 and 20%, respectively. In springwater, however, the atmospheric Sr and REE contribution is not detectable.

Hydrochemical budgets of a small forested granitic catchment exposed to acid deposition: The strengbach catchment case study (Vosges massif, France)

Hydrochemical budgets have been obtained for the 3-yr period 1986–89 at Strengbach, a small granitic basin in the Vosges mountains (north-eastern France). Here, the spruce forest shows both yellowing and crown thinning, symptoms of forest decline. Water amount and surface water chemistry were monitored in each ecosystem compartment. Bulk precipitation is acidic. Some pollution episodes occur in winter and early spring, but the annual bulk deposition acidity is rather low. Throughfall however, is much more concentrated, particularly for H+ and associated strong acid anions. These inputs come as occult deposits which comprise major ecosystem inputs, as confirmed by the chloride balance for the catchment. Input-output budgets for the catchment indicate a net deficit of base cations, especially calcium. Sulfate also shows a net loss while N budget is well balanced. As the soil exchange capacity is nearly exhausted for base cations, and dominated by H+ and Al, the neutralization of incident acid inputs occurs mainly in the weathered bedrock. Silicate weathering processes lead to high losses of cations and of silica. Aluminium hydroxide is precipitated; however, bicarbonate remains very low indicating poorly-buffered surface water.

Interception in a mountainous declining spruce stand in the Strengbach catchment (Vosges, France)

In a over-mature (declining) 90-year-old Norway spruce stand (Picea abies) in the Vosges mountain area, gross precipitation, throughfall, stemflow and meteorological variables have been measured for three periods in the summers of 1988, 1989 and 1990; transpiration was measured from June to August 1989. Throughfall, interception and stemflow represent, respectively, 65.3%, 34.2% and 0.5% of the incident rainfall. A semi-logarithmic relationship between interception and gross precipitation is given. Transpiration of the stand determined by sap-flow measurements represents only 27% of the potential evapotranspiration.