Typologie des eaux souterraines de la molasse entre Chambéry et Linz (France, Suisse, Allemagne, Autriche)

The geochemical typology of natural subsurface waters of the Molasse basin is part of the AQUITYP project, initiated by the Geology Laboratory (GEOLEP) of the Swiss Federal Institute of Technology in Lausanne (EPFL). This study provides an overview of the variation in space of the hydrochemical parameters, especially of trace elements, in order to determine the geological origin of their aquifers. Our data base is mainly made up of two observation networks: a subsurface water network and a deep groundwater network. Complete analyses of all samples have been executed using standard methods for anions and silicium, and high resolution inductively coupled mass spectrometry (HR-ICP-MS) for major cations and trace elements down to the detection limit of about 0.2 µg/l. Subsurface water network It is the main observation network of this investigation and comprises 112 water samples from different springs, collected all over the Molasse basin between Chambéry (France) and Linz (Austria), but mainly in the Swiss Molasse basin. For this region, four groups are generally distinguished, according to the sediment deposition in a continental or marine environment, in ascending stratigraphic order: (1) the Lower Marine Molasse (UMM and North Helvetic "flysch" p.p.), (2) the Lower Freshwater Molasse (USM), (3) the Upper Marine Molasse (OMM) and (4) the Upper Freshwater Molasse (OSM). Our water samples originate from typical sedimentary deposits which we divided in about 30 different sub-type aquifers according to their geological origin and their depositional environment. They are defined on the basis of lithological and structural homogeneity. Therefore, only catchments that completely drain a single, lithologically homogenous, Molasse terrain unit are considered here. Spring catchments selected were generally not affected by runoff from towns, or paved roads. Agricultural activities have been avoided as well as possible. Such spring water should be free of major human influences and only in few cases contain a certain amount of fertilizer products (p.ex: nitrates). Leachate tests of crushed rocks and comparison with snow and soil water compositions allowed to decipher the geogene origin of the dissolved ions in natural groundwaters. The water withdrawn can be generally classified as a calcium-magnesium-hydrogenocarbonate (Ca-Mg-HCO3)-type water. The trace analyses allowed to distinguish several subtypes within this homogenous water type group. The general spacial distribution of the trace elements show, that spring waters in the Bavarian Molasse basin are caracterized by elements as lithium and uranium linked to acid rocks, while those of the Swiss Molasse basin are preferentially influenced by elements derived from mafic or ultramafic rocks, such as chromium and cobalt. The following elements show specific links between aquifer rock type and groundwater. Sulfates: Total mineralisation of spring waters issued from the gypse-bearing Molasse (USM) and the "Glimmersande" (OSM) are highly influenced by high sulfate contents. It can be demonstrated that sulfate ions are produced from two different sources within this two sub-type aquifers: from the dissolution of gypsum in water, producing high calcium contents as well, and from the oxydation of sulfurous ore minerals, especially pyrite, which are abundant in the "Glimmersande". The "Glimmersand" aquifers in NE Switzerland are furtheron caracterized by high lithium, molybdenum and uranium concentrations, reflecting the granitic composition of this sandstones. High barium contents (>150 µg/l) have been found in spring waters issued from aquifers with a dominant fissure permeability ("Grès de la Cornalle", "Gibloux-Delta" and "Rigi-Schüttung"). Its origin is supposed to be the mineral barite, which tends to precipitate in fractures. Therefore, high barium concentrations may indicate the presence of fracture flow within the aquifer. Considerably high silicon contents are linked to the quartzitic and fine grained aquifers of the brackish marine molasse in Bavaria. Both, petrographical composition and slow flow rate are favouring the water-rock interaction. Caracteristic lithium footprints are found in several waters, as in the aquifers composed of the "Glimmersande", the gypse-bearing molasse, the Rigi-conglomerates, the brackish and the estuarine marine molasse. Chromium strongly marks the waters originating from the Swiss marine Molasse aquifers. It is probably related to ophiolithic detritus derived from the flysch of the Prealpes. A couple of waters show weak anomalies of cobalt, which are nevertheless intimately linked to the presence of ophiolithic components in the sediments. Cobalt might be used as a hydrostratigraphical tool to identify greenstone inputs. Analysed colloidal aluminum may serve as a hydrodynamical parameter, indicating microturbidity within the aquifer. High amounts of aluminum varying in time, have been found in estuarin deposits of the OMM. Generally speaking, we propose three main origins of trace elements in the spring water of the Molasse basin: presence of certain petrographical components within the sediments such as basic and ultrabasic rocks, heavy minerals and evaporites. a small flow rate through interstitial porosity of fine grained sediments, favouring water-rock interaction. the abundance of colloidal material in the waters which depends on the petrographical composition of the aquifer and on sample treatment, e.g. filtration techniques. Deep groundwater network A second observation network composed of 21 borehole waters has been added for comparison. Compared to the subsurface waters, deep water chemistry might differ. The following reasons seem to be responsible: Long residence times of water in the underground favours slow reaction kinetics. Chemistry of very deep water can be influenced by mixing with older formation waters. Most of the deep boreholes in the Swiss Molasse basin are situated in the OMM and therefore represent a likely homogenous lithology. Borehole waters, because of different aquifer rock types and unknown surface and borehole influences, are least likely to represent typical Molasse water composition.

Fate of volatile fluorinated compounds in the subsurface

Christian Balsiger

Since their discovery around 1930, the synthetic compounds of the class of chlorofluorocarbons (CFCs) have been produced and used worldwide at very large scale. Their physico-chemical properties (non-flammability, chemical inertia, miscibility with water and oil, compatibility with many metals and plastics, solvent capacity) have made them ideal candidates for several applications, such as refrigerant fluids, aerosol propellants, foam blowing agents, or as solvents or intermediates of chemical synthesis. In the 70', it was demonstrated that following their release in the atmosphere, they are implicated in the process leading to the commonly called stratospheric ozone hole. The governments of several industrialised country have thus signed a protocol with the objective to stop the production and use of CFCs. CFCs have been increasingly replaced by compounds with similar structure, the hydrochlorofluorocarbons (HCFCs), but whose reactivity in the lower layers of the atmosphere is quite different from that of CFCs. Due to their chemical inertia, CFCs has been used as tracers for surface and groundwater datation. During such investigations, the biodegradability of these compounds and the existence of punctual pollution sources in soil and groundwater have been evidenced. It has been demonstrated that some of these compounds can be dechlorinated under anoxic conditions producing other compounds with sometimes higher toxicity and higher water solubility, and resulting in a risk linked to the consumption of natural groundwater. The goal of this thesis was to get indications about reductive transformations of CFCs and especially HCFCs in Swiss aquifers and landfills, on the potential of different microbial communities to reductively dechlorinate certain compounds, and under which redox conditions the transformations occur in aquifer systems. Data concerning the production, use, emission, regulation, as well as the biodegradability and toxicity of these compounds are presented in chapter 1 and in the appendix. The analytical methods developed and used during this work are presented in chapter 2. Particularly, a versatile analytical system allowing the measure of trace but also higher concentrations in different media, solid or aqueous, has been set up and used during this work. CFCs and HCFCs were analyzed at 3 sites in Switzerland. Samples were collected from a natural groundwater in which a chloroethene plume had been observed, from an old landfill closed in 1980, and from a more recent bioactive landfill constructed in horizontal layers. In addition, the behaviour of different CFCs and HCFCs was studied in microcosms inoculated with sludge originating from several sewage treatment plants in the canton of Vaud, and with a sediment originating from a contaminated aquifer in Holland. The studied CFCs and HCFCs were furthermore injected at the inlet of a 1.2 m height column filled with the aquifer sediment from Holland. In this quasi natural aquifer, the oxido-reductive conditions were modified during the experiment in order to investigate the conditions at which the biodegradation occurred. The field studies showed that CFCs and HCFCs are present in aquifers and landfills, and there were indications that their transformation also occurs there. Estimations of half-life times indicated that the reductive dechlorination occurred at slow rates. This could be due to the low temperatures of natural groundwater systems and other factors linked to the hydro-geological properties of the natural environment such as dispersion, sorption or partitionning. In the microcosms inoculated with sludge, CFC-11 was transformed to HCFC-21, the latter being further dechlorinated to HCFC-31. HCFC-123a and chlorotrifluoroethene (CTFE) were produced simultaneously from CFC-113. Inhibition of methanogesis with 2 bromoethane sulfonate decreased significantly the degradation rate of CFC-11, emphasizing the importance of the role of methanogens in the degradation process. In the microcosms inoculated with the contaminated sediment, the transformation of CFC-11 also occurred, but was not accompanied with methane production, as it was the case in the suldge microcosms. Moreover, the presence of acetate, lactate and butyrate in the microcosms containing CFC-11 suggested that methanogens were inhibited in the presence of CFC-11. CFC-113 was transformed in the same way as in the microcosms inoculated with the sludge; however, the produced CTFE was further transformed to trifluoroethene (TFE). Production of HCFC-151b from HCFC-141b was also observed. In the column filled with aquifer material, only the transformations of CFC-11 and CFC-113 were observed, which is probably due to the short residence time in the column (~10 days), during which the transformation of the other compounds was not sufficiently pronounced. The increasingly reducing conditions in the column were accompanied with an increase of the degradation rates of CFC-11 and CFC-113, with a maximum reached in presence of methanogenesis. The addition of sulfate in the artificial groundwater decreased the biodegradation rates of the two compounds, and the concentration of their transformation products was simultaneously increased. This suggests that these products become more persistent under sulfate-reducing conditions. Natural attenuation designates all the processes leading to the decrease of the concentration of organic compounds migrating from a pollution source throughout a natural environment. Whereas natural attenuation or enhanced natural attenuation seem adequate for several classes of compounds, the absence of defluorination reaction of CFCs and HCFCs reported in this work suggests the use of other remediation techniques for the decontamination of sites polluted with these compounds. Indeed, the transformation products of CFCs and HCFCs still contain a fluorine atom and are not less harmfull to the environment than the parent compounds. In addition, the use of CFCs as age-dating tracers in groundwater is not recommended under anoxic conditions, as it was demonstrated here that they are not stable in such environments. The HCFCs on the other hand seem to be more persistent, and it is primordial to decrease rapidly their production and release in the environment.

EPFL2004

Typologie géochimique des eaux des aquifères carbonatés des chaînes alpines d'Europe centrale et méridionale

This study describes the spatial heterogeneousness of the chemical composition of underground waters, particularly the trace elements, and the carbon-13 isotope in several carbonate aquifers of the alpine belt in Europe. The research forms part of the AQUITYP project which have been worked on the last 14 years by the Geology laboratory of the Swiss Federal Institute of Technology in Lausanne (GEOLEP). The main aim of the project is to define the typology of the aquifers, based on the chemical characterisation of underground waters. The carbonate aquifers has been divided in several groups chosen after geological, geographical and hydrological criterias. The geological criterias are petrography and depositional environments of carbonates. The geographical criteria is the altitude of the catchment area. The criteria hydrology is the type of flow in karstic systems. The first stage of this research consisted of a selection of 87 carbonate aquifers divided in 13 regions of study in the alpine belt between France and Greece. Aquifers were selected in order to guarantee the absence of external contamination in groundwaters. Sampling were carried out in a period of base-flow, when groundwaters are equilibrated with rocks. The analyse of 112 samples of water provided the basis of the observations of the various chemical and isotopic composition of groundwaters of carbonate aquifers. Lixiviation of rocks forming aquifers provides information about geogenic origin of some trace elements. The geological and hydrogeological context of aquifers The aquifers studied are composed of platform and basin limestones, that form part of the paleogeographic domain of the Tethys. One example of Devonian limestone belongs to the complex of the Palaeozoic of Graz is also included. Each aquifer has homogenous petrographic composition, but from one aquifer to another the petrographic composition may differ. In this research are included pure limestones, marly limestones and dolomites. From a hydrogeological point of view the 87 aquifers show different degrees of karstification, they are placed either in regions of mountains (caracterised by an important hydraulic gradient), either in region of plateau. The surface of the catchment areas is variable between ten km2 (for example the karstic plateau in Slovenia) and a few km2 (for example the Parmelan massif from subalpine belt in France). Discharges of springs are also variable, between 1 and 1000 l/s. The chemical characterisation of water The study of the chemical typology of the waters of carbonate aquifers are carried out on non thermal water rich in oxygen (median values: temperature 8.8°C, dissolved oxygen 11.8 mg/l, Eh 0.4 V, pH 7.2). The total dissolved solids differs between 100 and 600 mg/l. Underground waters are calcium bicarbonate type. Within these facies in some cases, the Mg and S04 content can be superior, thus defining two sub-facies. The iodine content in the groundwaters of carbonate aquifers usually shows higher values than the other types of aquifers of the project AQUITYP. Concentration in the groundwaters of carbonate aquifers is variable between 10 and 60 µg/l. The origin of iodine is caused by the oxidation of fossil organic matter present in the carbonate rocks. Trace elements allows to distinguish groups of aquifers composed of pure limestones, dolomite or deep sea limestones : pure limestones. The aquifers composed of pure limestones are marked by a very small concentration of trace elements. This can be explained by the poorness of the detrital materials (clays, Fe-Mn oxides, heavy minerals) and the compact lithology that reduces the surface of water-rock interaction. dolomite. The typical elements of dolomite aquifers are Mg, U and Mo. The high primary porosity and the brittle deformation of this type of rock favorise a better water rock interaction compared to poor reef limestone aquifers. Examples of this group of aquifers have been selected in the Italian Dolomites and in the Zone of Karavanke in Slovenia deep sea limestones. The barium is a geogenic tracer in some aquifers composed of basin limestones. The aquifers of the Maiolica and of the Scaglia in the Apennine and the Malm aquifer (spring of Grandchamp) in the Prealpes in Switzerland have a high level of Ba in groundwater (between 60 and 220 µg/l). The limiting factor of Ba mobility in this carbonate environment is the concentration of SO42- in the water. The SO42- makes the Ba precipitate in shape of barytes. This process explains the presence of barytes in fractures found in the aquifer of the Calcare Massiccio in the Apennines. The content of carbonate-13 in groundwaters allows to make a distinction between waters infiltrated in catchment areas with or without vegetation and soils. This isotope is also interpreted as a tracer of the type of underground flow in Karstic system (rapid flow in Karstic channels or slow flow in little fractures of the rock). For the project an example has been taken in Tanneben karst, in Austria. This karst shows that water with a slow flow from blocks has a higher 13C content in comparison with fast flow channel water. Finally some analysis of waters from the bottom of soils on the Jura belt in Switzerland showed that during little rain periods the content of isotope is comparable to the one of slow flow waters of the unsaturated zone in the karst. This demonstrate that the isotopic exchange with rock is completed at low horizon in the soil. The vanadium is a geogenic tracer in the Malm aquifer of the Jura belt in Switzerland and in the Cretaceous aquifer in the region of Trieste, in Italy. The origin of vanadium differs in these two examples. In the Jura belt the vanadium comes probably from marly layers of limestones of the low Portlandien. In the region of Trieste the element vanadium is present in bituminous carbonate sediments from inner platform (Calcari bituminosi from Paleocene). In conclusion the importance and the limits of the chemical criterion for the typology of aquifers are shown. This method of distinction of groups of limestone aquifers is one of the tools which permit the determination of the origin of water sources, particularly in underground and borehole construction projects.

EPFL1995

Road runoff over the shoulder diffuse infiltration

Pascal Piguet

A new concept of road runoff management, based on diffuse infiltration over the shoulder, was tested in a real-scale experimentation site located near Grandson, Switzerland. This new concept consists in diffusely infiltrating the road runoff in the infiltration slope adjoining the road shoulder; where road contaminants are retained. This presupposed that the road shoulder was as tightened as possible to effectively drive the road runoff to the slope, and that the infiltration slope effectively retains all road pollutants. Those two main postulates needed strong scientific verification. For this purpose, five different shoulder designs were tested in Grandson to assess which one presented the best hydraulic performance, i.e. which shoulder was the most impervious. Those designs were made of gravel mixed with humus (SGL), gravel mixed with clay (SGC), gravel seeded with lawn (SGL), a prolonged HMF road base (SH), and a bentonitic geotextile tightening (SB). Also, to verify the retention of pollutant, two infiltration slopes adjoining SGL (LW) and SH (LH) were set as lysimeter (basal geomembrane collecting road effluents); the third infiltration slope (LB) had a direct connection with the aquifer which was closely monitored (6 piezometers located up- and downstream from the road; influence of the road runoff was thus emphasized). Finally, to ensure that this new concept do not lower the road bearing capacity, deflectometers were placed in the road structure; 3 campaigns of leveling assessed the road settlement. Hydraulic assessment of the shoulders, based on 112 natural precipitation as well as 3 artificial watering tests, showed strong discrepancies between all shoulders behaviours. They had to deal with potentially high amount of water. Lag times ranged from a few minutes to several hours. Results showed that lag times were only function of the precipitation mean intensity. The infiltration process could be assessed by a modified Green & Ampt equation. The moisturizing front was frank and linearly progressed downward. Shoulders vertical hydraulic conductivities ranged from 4.6·10-6 (SGC) to 2.2·10-5 m·s-1 (SGL). The exfiltration volume is function of the water volume available at the shoulder surface. The drought preceding the rain event has no influence on the stock variation or the exfiltration volume. Road runoff used two different infiltration paths: the macroporosity drives the water efficiently and rapidly, while the microporosity is less efficient and retains the moisture longer. Tracer tests (Brine) proved that the contamination first flush passed over the shoulders. This is also confirmed by the flux calculation. Runoff coefficients CR ranged from 0.3 (SGL) to 0.9 (SB). This coefficient decreased rapidly once the shoulder is wet. Only SB really fulfilled its task, letting water through only in harsh hydraulic conditions (100 mm; 40mm/h). It is highly recommended for further road development: for new roads as well as old roads being refurbished. The shoulder SH proved to be inefficient for structural and material reasons. Other shoulders are comparatively ineffective. SGC must be enhanced; in that case it could offer a valuable alternative. The bearing capacity of the road was very good. The road lifetime was evaluated to more than 20 years (1·109 residual standard axle load). The Grandson experimental site could not conclusively demonstrate a worsening of the geotechnical behaviour of the road. This is due to the particularly good material and road pavement thickness used for this road. Infiltrations in shoulders are high enough and would have doubtless caused a loss of bearing capacity in case the road would have been more modestly dimensioned. It is therefore clear that the shoulder must be tightened. Geochemical results concerned six families of contaminant: MTE, PAH, Cx, BTEX, MTBE, and PCB. Batch and column tests allowed calculating MTE and PAH distribution coefficient Kd in the Grandson soils, as well as in other typical Swiss soils. Results showed that mobile elements are B, Br, Mo, Ba, Sb, Zn, and V (0 < Kd < 90). Less mobile elements are Ni, Cd, Cr, and Rb (200 < Kd < 300). Elements with very low mobility are Pb, Mn, and Ti (1500 < Kd < 3500). PAH mobility was high for the light PAH (naphthalene, acenaphtene, fluorene, anthracene; Kd < 75). Heavy PAH had lower mobility (Kd > 175). Comparisons with other typical soils enlightened the predominant influence of the pH. Batch test performed with acidic soils (pH = 5.5) confirmed lower MTE Kd. MTE are thus more mobile in acidic soils. Other physicochemical parameters have a smaller influence. The column test performed with a synthetically loaded solution (MTE and PAH) infiltrating the Grandson soils showed that MTE are more mobile in dynamic conditions. This is easily explained by the reduced contact time between the contaminant and the soil aggregates. PAH were not detected at the column outlet, thus showing a very good retention in the column soil. Soil layers analyses demonstrated that PAH were mostly retained in the surface layers. Also, MTE with low mobility show the same behaviour. Mobile elements showed no preferential retention layer. Concerning the infiltration slope, lag times were usually greater than those encountered for the shoulders. Lag time were function of the rain mean intensity. The influence of the preceding drought was significant. Exfiltration volumes EL were high in case of large event; it could be approximated by a simple equation function of the API and surface available water. Moisture redistribution processes occurred in the soils as long as there is a volumetric water content θ gradient. Fluxes strongly varied in magnitude and direction during a precipitation event: usually from about 1·10-8 to 1·10-5 m·s-1 and from up- to downward (evaporation to infiltration). The first flush effect was poor to medium. NaCl signal was highly buffered. The pH was also completely buffered by the soil high carbonate content. It thus shifted from 6.5 in the rainwater to 8 in the LW exfiltration water. To especially emphasize the geochemical behaviour, an artificial precipitation test was created to control every aspect of the rainfall. It was judged very representative of a natural storm. MTE and PAH contaminants had two different behaviours: mobile elements moved mainly in solute and have concentration correlated with EC. Elements with low mobility had higher concentrations correlated with the turbidity peaks. They were transported sorbed to particles. Comparison between the particular and solute form concentrations confirmed that mobile elements are measured in similar concentrations whether the sample was filtered at 0.45 µm, at 1 µm, or not filtered at all prior to acidification. On the contrary, less mobile elements are easily sorbed to particles. The MTE concentrations under sorbed form range from 5% (Rb, Sb) to 98% (Pb) of the total concentration. They had strong first flush effects. B, V, Cr, Mn, Ni, CU, Zn, Br, Mo, Cd, Sb, and Pb were identified as road tracers. Fe and Al represented 80% of the road runoff. Overall, the total MTE concentration in the lysimeter first water collected decreased to 1/30th of the road runoff first flush concentration. Mobile elements were less retained. The PAH total concentration in the lysimeter first collected water was about 1'000 times lower than in the road runoff first flush. The PAH concentration was mainly constituted by mobile PAH naphthalene and phenanthrene. Cx were well represented in the road runoff. However, only heavy species were commonly found. C32 was the most common specie. The triplet C16-C18-C20 was always present in high concentration in the lysimeter exfiltration water. This triple is a great road tracer. BTEX, while present in the road runoff, were not detected in the lysimeter exfiltration water. The alluvial aquifer was also monitored. It is confined between the Arnon (north) and a basement till which shallows up southward. Eastern and western limit are less known but might coincide with the river. The aquifer is clearly linked to the river. This is proved by the piezometric level, EC and T follow-up. EC and temperature also emphasized the higher activity in downstream piezometer. The road runoff infiltration could not be emphasized by the NaCl tracer test. The infiltrated water concentration was possibly buffered by the aquifer volume. Also, the brine was heavier than the aquifer water: it could have plunged to the bottom of the aquifer. All families of contaminant are presented in the aquifer. However, the provenance of those contaminants remains uncertain. The groundwater was indeed as concentrated upstream as downstream. Moreover, the river concentrations had similar, or even higher, values. The contamination provenance is thus either the aerial deposition (equally distributed up- and downstream), either the Arnon River infiltrating the aquifer. The contaminant behaviours in the aquifer could be described. It confirmed the contaminant mobility previously noted during the batch, column and test precipitation experiments. Mobile substances are seen in higher concentrations, whereas substances with low mobility are sparsely found. This project thus demonstrated that the new "over the shoulder diffuse infiltration" concept is clearly implementable. Aquifer concentrations were compared to Swiss legal concentration limits. Except for Cr, the aquifer water was of drinkable quality. This proved that the concept is robust, environmental-friendly and conclusive.

EPFL2007