Micropollutants in Large Lakes: From Potential Pollution to Risk Assessments

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.

Sources, Spreading and Fate of Antibiotic Resistance Genes and Resistant Bacteria in Vidy Bay, Lake Geneva, Switzerland

Nadine Czekalski

Increasing numbers of multiresistant bacterial pathogens cause severe health problems on a global scale. Large quantities of bacteria and their resistance genes are discharged into natural environments via human and animal waste. Not much is known so far about the fate and further spread of resistance determinants in the environment. There is evidence that aquatic environments may function as important compartments for preserving and exchanging antibiotic resistance genes (ARG) from sewage and drinking water. Lake Geneva is the largest fresh water reservoir of Western Europe and supplies the surrounding cities. At the same time these cities discharge sewage into the lake. Lausanne is the largest city in the lake’s catchment and discharges the highest amount of treated, as well as in case of heavy rain events, partly untreated waste waters. Also two rivers, Chambering and Flown, transport untreated sewage (bypass), in case of storm events. Only 3.4 km from the sewage discharge point lake water is pumped for drinking water preparation for Lausanne. Many studies have reported on contamination of the bay with heavy metals, inorganic nutrients, organic carbon and fecal indicator bacteria due to the sewage discharge. The present thesis aimed on investigating the sources, spreading and fate of antibiotic resistant bacteria and antibiotic resistance genes in the Vida bay, Lake Geneva. In the first part of this dissertation, a screening for antibiotic- and specifically multi-resistant bacteria was carried out as one of the first studies in a Swiss waste water stream and the receiving fresh water lake. For this purpose, a combined set of culture based (viable bacterial counts on nutrient media supplemented with antibiotics) and molecular tools (detection and quantitation of antibiotic resistance genes from environmental DNA-extracts using quantitative real-time PCR) was applied. Raw hospital and communal sewage, as well as partly treated/mixed sewage, which is discharged into the lake via an effluent pipe 700 m off shore, were taken into account. Furthermore lake water samples nearby the end of the waste water discharge pipe and the drinking water pump as well as close to the two river mouths were analyzed. Finally, the role of Lausannes WTP was evaluated for its potential to remove resistant and multiresistant bacteria, as well ARG. Results show highest levels of multiresistant bacteria and ARG in both hospital and communal sewage. Incidence was found that the WTP is a selective environment for multiresistant bacteria and resistance genes. Moreover, lake water and sediments nearby the end of the WTP discharge pipe and the two river mouths exhibited significantly higher levels of resistant determinants as compared to samples from the drinking water uptake. If the level of antibiotic resistance close to the drinking water uptake represents the natural background level of the lake or whether it is impacted by the WTP plume remained open during this first survey. The spatial distribution and persistence of ARG discharged via waste water into lake systems has been evaluated for the first time in the second part of this thesis. 22 sediment cores were sampled along two major transects (leading either into the deep lake or along the south-western shore line to the drinking water uptake) and in the vicinity of the WTP discharge pipe in the Vidy bay. A subset of samples was also analyzed for contamination with a “conventional” pollutant of sewage (mercury), for which a similar transport behavior (particle bound) as for bacteria and their resistance genes is assumed. The microbial community composition in all sediment as well as in waste water samples was analyzed using ARISA. Strong pollution with both ARG and mercury was detected in close proximity of the WTP discharge pipe and both contaminants significantly decreased along the transect into the deep lake. In general however, the spatial contamination of mercury and ARG was only moderately correlated. While the mercury contaminated sediment surface area tended to have a pollution tail in south eastern direction, ARG showed only a slow decrease along the south western transect. These findings imply differences in transport and fate of mercury and ARG in the bay, or additional sources of ARG contamination. Analysis of the microbial diversity in the samples support these hypotheses. This study revealed feasibility of qPCR as a tool to semi-quantitatively track spatial ARG contamination in fresh water lake sediments. Not much is known yet on the antibiotic resistance background level of fresh water lakes and how this may be influenced by anthropogenic activities in the surrounding catchment. Water samples from 21 Swiss lakes have been collected and were analyzed for the prevalence of different ARG (2 sulfonamide resistance genes sul1 & sul2, 3 tetracycline resistance genes tetB, tetM, tetW and one plasmid mediated fluoroquinolone resistance gene qnrA). In order to document the abundance of these genes in the bacterial populations, they were normalized to bacterial 16S rRNA gene copy numbers. The lakes differ in size, geographical position, land use pattern, and trophical status. The composition of the microbial community of all lakes was analyzed using ARISA. Sulfonamide resistance genes were detected in all investigated lakes (0.2-4%, sul1 and 0.01-0.3%, sul2), with highest levels in Lake Baldegger (21%). Lake Baldegger also contained all of the three tetracycline resistance genes, which were found in only 4 other lakes. None of the lakes was positive for qnrA. Important anthropogenic catchment activities linked to sul gene prevalence could not be identified based on our data and may require further analysis and an additional variables to complete our data set. However, our study demonstrates contamination of Swiss lakes with sulfonamide resistance genes and the potential of fresh water lakes preserve these genes, even remote from direct sources of pollution.

EPFL2013

Passive sampling for monitoring organic contaminants in aquatic systems

Sylvain Coudret, Luiz Felippe De Alencastro, Nicolas Estoppey, Dominique Grandjean, Adrien Schopfer

Passive sampling has been shown to be a good alternative to grab sampling. Because of the in-situ accumulation in samplers, limits of quantitation are low enough to measure organic pollutants in water. In addition, integrative passive samplers enable to sequester pollutants from episodic pollution and provide time weighted average (TWA) concentrations. Finally, they do not require a power supply in the field and are flexible enough to be deployed at sites that are difficult to access. This study will present the interest and efficiency of passive sampling to reveal industrial and agricultural pollution trends. Two practical applications for nonpolar and polar contaminants are presented. Low-density polyethylene (LDPE) and Silicon rubber (SR) samplers were deployed in rivers to monitor indicator PCBs (iPCBs, IUPAC nos. 28, 52, 101, 138, 153 and 180). The results showed that the impact of PCBs emissions into the river is higher in summer than other seasons due to the low flow rate of the river during the summer period. Polar organic chemical integrative samplers (POCIS) were deployed in another river to investigate herbicides coming from vineyards. The results showed an increase of water contamination due to the studied agricultural area. The maximal contamination was observed in April and corresponds to the period of herbicide application on the crops. The use of performance reference compounds (PRCs) to estimate aqueous concentrations is also presented and illustrated by examples.

2017

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

Jordi Batlle-Aguilar

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.