Hydrodynamic characterisation of a groundwater - surface water system and evaluation of BTEX, PAHs decay and heavy metals fate

Most contaminated sites related to past industrial activities in Europe are adjacent to rivers and urbanized areas. These sites pose a major problem for water authorities and policy makers in terms of contaminants mobility, natural attenuation (or degradation) and risk assessment for environment and humans. Natural attenuation in groundwater is only effective if hydrogeochemical conditions of the system are favourable and contaminant degrading microorganisms are present. To evaluate this effectiveness, many site specific factors have to be considered, among which the dynamics of groundwater fluxes and groundwater – surface water interactions and biogeochemical processes. The site of concern in this study is a brownfield located in the north bank of the Meuse River, upstream of the city of Liège, Belgium. The soil, the unsaturated zone and the gravel aquifer are heavily contaminated by organic pollutants (BTEX and PAHs) and metals due to past industrial activities of coke production in the XXth Century. Various point sources of contaminants were delineated in the site. Benzene and Toluene concentrations in groundwater were found up to 50.000 μg l-1 and 23.000 μg l-1 respectively in source areas, while pollution due to metals was less important, with presence of Fe (> 6400 μg l-1), Zn (40 μg l-1), Co (18 μg l-1), Cu (>9 μg l-1), Pb (>100 μg l-1) and Cr (2 μg l-1) mainly with higher concentrations in some hot spots. The Meuse River level is established at around 59.5 meters a.s.l. by dams. However, river water levels fluctuate continuously with amplitude varying between a few centimetres up to 2 meters during winter and spring seasons. The main objectives of the research investigations were 1) to evaluate whether an interaction exists, at the level of the mentioned brownfield, between groundwater and the neighbouring river; 2) to assess the dynamics of such interactions and to quantify groundwater fluxes as the main potential vector of mobility of contaminants offsite; 3) to determine the potential of bacterial degradation of organic compounds and fate of metals contaminants in the specific environment of the site; and 4) to integrate groundwater – surface water dynamics with potential degradation of contaminants in order to evaluate further evolutions of contaminants in the aquifer. A detailed monitoring of groundwater and surface water levels, together with a series of field tests like pumping and tracer tests, contributed to a good knowledge in hydrodynamics of the contaminated aquifer. Groundwater and surface water monitoring datasets were analyzed in order to characterize hydraulic dynamics of the groundwater – surface water system. Groundwater heads observed were strongly influenced by Meuse River stages, and groundwater flow in the transition zone (seepage) was oriented in the direction going from the aquifer to the river under normal conditions. The use of an analytical model, however, pointed out that small changes on water river level were enough for a groundwater flow inversion, so seepage going from the Meuse River into the aquifer. Organic compounds (mainly benzene and low weight PAHs) have been studied with respect to their intrinsic bacterial degradation potential. Two independent stable isotope-based approaches (laboratory and field) were used to determine in situ biodegradation rates for benzene, and for the two- and three-ring aromatic hydrocarbons naphthalene and acenaphthene. In the laboratory, microcosms were set up with 13C-labeled substrates as well as with groundwater and with sediments from the site. The increase in 13C-CO2 over time was monitored by GC-IRMS analysis and used to calculate biodegradation rates. Benzene, naphthalene and acenaphthene were found to be biodegradable by the intrinsic microbial community under in situ-like conditions. The respective biodegradation rates decreased with increasing number of aromatic rings and were significantly lower under anoxic conditions. Apart from the microcosm study, in situ-biodegradation rates could be retrieved in a field study from 13C/12C signatures of residual groundwater contaminants using first-order kinetics. Biodegradation rates of lab- and field-based approaches were found to be in good agreement. Batch tests revealed that the heavy metals could be precipitated under sulphate (present at the site) reducing conditions. This in situ bioprecipitation process can be induced by the presence of electron donors and plays an important role in the natural attenuation process. Other conditions as aerobic or nitrate reducing conditions, did not lead to heavy metal immobilization. This gives specific indications about future site management and land use. It was also proved that the present heavy metal concentration did not influence the PAH biodegradation. However, PAH biodegradation under aerobic conditions is very slow. Further investigations will be necessary to evaluate the effect of aerobic biodegradation (addition of air) on the mobilization of the heavy metals, bound to the aquifer. The continuous changes of the groundwater flow direction observed in the studied site, lead to surface water flowing into the aquifer. This is likely to be an additional source of oxygen for the aquifer. This influx of oxygen-saturate water could enhance the degradation of BTEX and PAHs in the regions of the aquifer which are affected. Further investigations are needed to come to a qualitative evaluation to what extent oxygen from river water contributes to the removal of BTEX and PAHs at the site.

Micropollutants in Large Lakes: From Potential Pollution to Risk Assessments

David Andrew Barry, Florence Bonvin, Neil Graham, Luca Rossi

This book is divided into six additional chapters: Chapter 2 deals with the agricultural source of micropollutants; Chapter 3 with the urban source of micropollutants; Chapter 4 with lake circulation; Chapter 5 with the influence of a wastewater treatment plant on a bay; Chapter 6 with the input of sediments and their transport in a bay; and Chapter 7 with the risk assessment of the mixture of the compounds present in lake water. A last chapter (8) synthesizes the main findings and presents perspectives for future studies. More specifically: Chapter 2 is dedicated to the micropollutants that enter lakes through agriculture. These are mainly pesticides. After a review of the different types of compounds, the authors will put forth the main pathways these compounds follow to enter lakes. The case of glyphosate, an herbicide used worldwide, will be discussed. Chapter 3 illustrates the urban sources of pollutants with pharmaceuticals and biocides. Two models will be covered that allow estimating the load and dynamics of these chemicals that may exit from an urban catchment and therefore reach lakes. Special attention will be paid to the “end of pipe” removal of these compounds at a WWTP. Chapter 4 is dedicated to lake circulation. The aim of this chapter is to present an overall description of lake hydrodynamics, which is driven by three factors: wind, temperature and Coriolis forces. The main inflow to Lake Geneva is provided by the Rhône River. In addition, the topography surrounding the lake varies rapidly, for example, with mountains in the eastern part. As a consequence, the lake’s currents can vary markedly. To achieve our objective, we will utilise hydrodynamic modelling. A model will be proposed that permits describing the behavior of the top layer of the lake based on wind direction. The importance of stable hydrogen and oxygen isotopes for characterising the sources of water and mixing processes in the lake will be described and illustrated with the example of the Rhône river interflow to it. The measured variations of the isotopic compositions within the lake can serve as verification of the lake hydrodynamic models. However, the emphasis of the chapter will be on explaining the major current features and how they relate to wind forcing, which is one of the main drivers. Chapter 5 and 6 are devoted to the Vidy Bay in the Lausanne area of Lake Geneva. This bay receives the treated effluents of the largest wastewater treatment plant of the lake catchment. The latter represents therefore one of the major point sources of contaminants for the lake. These two chapters will focus on the various processes that control the transfer of contaminants (associated with particles or in a dissolved state) discharged into the bay and transported to the lake’s main water body. More specifically, Chapter 5 describes the WWTP plume dynamics. In relation to hydrodynamics (Chapter 4), specifically the behaviour of the plume formed through the treatment plant effluent release, field measurements are utilised to attempt to determine the plume behavior under various lake conditions. Furthermore, it investigates the degradation of organic pollutants. Photodegradation and other degradation processes are studied with theoretical, experimental and modelling approaches. Chapter 6 focuses on sediment path tracing. The pollutants associated with particles (trace metals, hydrophobic components, etc.) settle to the lakebed, but can be remobilized and transported to deeper parts of the lake. Bottom currents, and other physical forces, can cause resuspension and advection. Tracers used to identify this advection comprise natural and anthropogenic radioisotopes along with mercury as a major toxic trace element. Chapter 7 concentrates on one major issue of micropollutants in aquatic systems, like lakes, i.e., the risk of the mixture. The evaluation of the risk of mixture of micropollutants is not trivial and we will first present critically the models that allow doing so. We will also demonstrate their validity as predictive tools with the example of herbicide mixtures in Lake Geneva. Finally, we will map the risk of micropollutants around the lake. Finally in Chapter 8, we synthesize the main findings of all chapters and discuss recommendations for the management of mid-sized lakes regarding micropollution.

CRC Press & EPFL Press2018

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

Benzene dispersion and natural attenuation in an alluvial aquifer with strong interactions with surface water

Jordi Batlle-Aguilar, David Hunkeler

Field and laboratory investigations have been conducted at a former coke plant, discharging to an adjacent river, in order to assess pollutant attenuation in a contaminated alluvial aquifer. Various organic (BTEX, PAHs, mineral oils) and inorganic (As, Zn, Cd) compounds were found in the aquifer and in concentrations exceeding the obligatory limit values. Due to redox conditions of the aquifer, heavy metals were almost immobile, thus not posing a major risk of dispersion off-site the brownfield. Field and laboratory investigations demonstrated that benzene, among organic pollutants, presented the major worry for off-site dispersion, mainly due to its mobility and high concentration, i.e. up to 750 mg L-1 in the source zone. However, benzene could never be detected near the river which is about 160 m downgradient the main source. Redox conditions together with benzene concentrations determined in the aquifer have suggested that degradation mainly occurred within 100 m distance from the contaminant source under anoxic conditions, and most probably with sulphate as main oxidant. A numerical groundwater flow and transport model, calibrated under transient conditions, was used to simulate benzene attenuation in the alluvial aquifer towards the Meuse River. The mean benzene degradation rate used in the model was quantified in situ along the groundwater flow path using compound-specific carbon isotope analysis (CSIA). The results of the solute transport simulations confirmed that benzene concentrations decreased almost 5 orders of magnitude 70 m downgradient the source. Simulated concentrations have been found to be below the detection limit in the zone adjacent to the river and agreed well with the absence of benzene downgradient river-close piezometers reported in groundwater sampling campaigns. In a transient model scenario including groundwater – surface water dynamics, benzene concentrations were observed to be inversely correlated to the river water levels, leading to the hypothesis that benzene dispersion is mainly controlled by natural attenuation.

2009