This report attempts to give a survey from literature on the microorganisms involved, on the factors and mechanisms potentially relevant for the susceptibility of drinking water wells to health related microbial contamination. The habitat groundwater accommodates a rich diversity of microorganisms, which has only begun to be identified since the development of molecular detection methods in addition to the conservative cultivation techniques. Characteristics of the subsurface are darkness, low spaces, low nutrient and low oxygen content. Indigenous microorganisms have adapted to these oligotrophic conditions and are able to proliferate in this environment permanently. Other incoming microorganisms generally cannot reproduce under these conditions, but have developed strategies to survive. They can grow only, when the parameters turn favourable. Pathogenic microorganisms comprise bacteria, viruses, and protozoa, which can also survive a certain time in groundwater. Most microorganisms in the subsurface are attached to surfaces and survive best within biofilm populations. Pathogenic microorganisms originate from human or animal faeces. These organisms are not easily detected. The methods are very time and labour consuming. Therefore, other microorganisms regularly present in the faeces are used for detection. Their presence indicates the possibility of a contamination with pathogens. As indicator microorganisms mostly coliform bacteria, E. coli, enterococci and clostridia are used. Contamination with pathogens is reported to derive essentially from communal sources: defects in wastewater treatment plants, sewage tanks, pipes, and waste deposits; from agricultural sources: animal wastes, liquid manure, and grazing; and from point sources like faeces from animals, birds, and humans. Entrance into the subsurface occurs via rainwater and surface waters, as well as by direct contamination of wells. The transport of the microorganisms into the subsurface is influenced by the geologic conditions of a specific site: soil and rock type, presence of fissures, heterogeneity. In sand, microbial movement is less far than e.g. in Karst regions, thus the susceptibility to contamination of groundwater and wells is lower. Pore sizes are crucial for sedimentation and filter efficiency of the soil. Also important is the extent of the unsaturated zone, the flow velocity of the groundwater, the geochemistry and mineralogy of the site. Wells receive their water from the groundwater reservoir of the surrounding soil. The quality of the well water is therefore essentially dependent on the properties of the groundwater and all the factors influencing the groundwater may also be relevant for the well water. The wells represent, in addition, a separate complex system with specific conditions and influencing parameters. This specific habitat involves additional variable adsorption surfaces, more space, higher flow velocity of the water, a mixing of waters from different groundwater layers and thus a different chemical composition. Contamination may also arise from microbial introduction at the open wellhead. Two main processes have been identified which are essentially responsible for the elimination of pathogens during their pathway from top of the soil to the extraction well: inactivation of the microorganisms and their adsorption to the soil particles in the subsurface. Both processes are influenced by a variety of factors and conditions present at a given site. To mention are here properties of (i) The soil: consistence and texture of surfaces, electric charge, hydrophobicity, degree of moisture, coating with organic material. (ii) The groundwater: temperature, pH, presence of cations and ionic strength, presence of organic substances, dissolved oxygen content, activity of indigenous microorganisms. (iii) The microorganisms: forming of flagella, fimbria, hydrophobicity of the cell surface, forming of extracellular polymeric substances, forming of cysts and spores as survival strategies. In addition to the description of the microbial diversity in the subsurface, the sources of pollution and the factors controlling the microbial pathways into groundwater and wells, main methods for the detection of a variety of contaminating microorganisms are given at the end of the report.

The assessment of methods for the diagnosis and distinction of well ageing types and processes with the aim to recommend methods and tools for further fieldwork was part of work package 1 of the preparatory phase WellMa1. Therefore, field tests were carried out at selected well sites with a variety of methods covering standard monitoring methods to assess the constructive state of a well (TV inspections, borehole geophysical methods) and its performance (pump tests) as well as methods aiming at a better process understanding such as the hydrochemical and microbiological analysis of the raw water and clogging deposits. Altogether ten methods were applied at 21 different wells of the Berliner Wasserbetriebe (BWB) covering (i) exposure of object slides during operation and rest periods for microbiological investigations, (ii) BART with test kits for iron-related bacteria (IRB) and slime-forming bacteria (SLYM), (iii) water sampling for the investigation of pristine groundwater organisms, (iv) online measurements of chemical parameters O2, Eh, pH and T and water sampling for chemical analyses (main cations and anions), (v) TV inspections, (vi) three-step pumping tests, (vii) borehole geophysics with Gamma-Gamma-Density scan (GG.D), NeutronNeutron log (NN), Flowmeter (Flow) and Packer-Flowmeter measurement and (ix) Particle countings. The assessment and comparison should originally be completed by a horizontally directed core sampling from different depths from the screen sections of three of the chosen wells. Due to technical difficulties, this was not achieved during this phase of the project. The investigations led to a development and refinement of the methods and approaches. Because of their limited accessibility to the different parts of a well, a combination of methods is always necessary. Especially for the indirect methods like borehole geophysics, an initial assessment of the well condition directly subsequent to construction is essential to provide a basis for the assessment of the well performance development. Generally, the applied standard monitoring methods and diagnosis tools provided the expected identification of a performance deterioration and evidence for the presence of starting materials for clogging processes such as iron, oxygen, iron-related bacteria and particles. Room for improvement could be identified with regard to the reliability, information value and comparability of the tested methods, e.g. by a stepwise combination and extension of the methods to determine the interacting processes from the composition of the deposits. Further investigations should aim at method validation, especially for well monitoring during routine operation (e.g. use of delta h, development of standards for Qs-measurements and TV inspections), and further method development for the ongoing project with scientific investigations to obtain deeper process understanding, e.g. investigating shares of deposits resulting from the different processes (chemical, biological, physical) and relations between the rate of clogging or the location of deposits to well characteristics and site conditions to separate the different well ageing processes. This will then lead to the identification of key parameters that may be influenced to slow down well ageing and keep the well performance and water quality at an optimum.

The Aquisafe project aims at mitigation of diffuse pollution from agricultural sources to protect surface water resources. The first project phase (2007-2009) focused on the review of available information and preliminary tests regarding (i) most relevant contaminants, (ii) system-analytical tools to assess sources and pathways of diffuse agricultural pollution, (iii) the potential of mitigation zones, such as wetlands or riparian buffers, to reduce diffuse agricultural pollution of surface waters and (iv) experimental setups to simulate mitigation zones under controlled conditions. The present report deals with (i), providing information on trace substances, which enter surface water predominantly via diffuse sources in rural or semi-rural environments. In particular, it provides a priority list of relevant substances to aid planning of monitoring programs at waterworks, which abstract surface water from rural watersheds, for which information on substance use is sparse. As this ranking is limited to substances for which broad data sets are available from literature, it is compared to actual screening programs in predominantly rural catchments in Brittany (France) and Indiana (USA). The literature review identified pesticides as the dominant known diffuse contaminant group in rural and semi-rural settings (section 2.1). This is confirmed for the agriculturally dominated Ic Catchment in France and Upper White River Watershed in the USA, where pesticides were found to dominate the diffuse source compounds (section 3). Seven agricultural pesticides were detected in the Ic Catchment with AMPA and atrazine being the most common compounds, detected in 54 % and 41 % of all the samples, respectively. In the White River Basin 26 of the 38 detected compounds were pesticides making them the largest group of chemicals detected. Based on literature values on pesticide detection in surface waters in Germany, France and the USA, a priority list was established in section 2.2 of this report (see Table on page vi). Only seven substances were among the 20 most relevant pesticides, both in the USA and in Europe. Accordingly, US and European substances are distinguished in the priority list. Most frequently detected substances were atrazine, metolachlor and simazine for the USA, AMPA (metabolite of glyphosate), diuron and atrazine for France and diuron, atrazine and isoproturon for Germany. The importance of atrazine in Europe is interesting, since it was already banned at the time of the monitoring, indicating the high persistency of atrazine in groundwater. In some cases in Germany, concentrations in surface waters were found to follow typical seasonal application patterns, indicating illegal use (pers. Comm.. M. Bach). Although the list of substances in the USA and in Europe differ, there is an agreement to the fact that many of the pesticides applied in agriculture find their way into surface waters. The concentrations found are often beyond 0.1 µg/L. For the EU this level already corresponds to the drinking water limit. Thus, if surface water is used for drinking water production pesticides seem to be of high relevance. In finished drinking water, frequently-used Isoproturon and Bentazon were most frequently detected in Germany and France. The importance for drinking water production is emphasized by frequent detections above 0.1 µg/L in finished drinking water in nine waterworks in the US. Regarding drinking water regulation, the thresholds in the USA are substance-specific and generally more than one magnitude higher than 0.1 µg/L. As a result threshold exceedance was mainly found for Atrazine. In terms of treatability in water works, the priority list includes the efficiency of classical treatment (flocculation, filtration, ozonation) and of powdered activated carbon (PAC), which is often added in emergency situations. Particularly problematic are triazines (such as atrazine), phenoxy-type substances (such as 2,4-D and Mecoprop) and Anilides/Anilines (such as Metolachlor and Acetochlor). The pesticides found in the screenings are in good agreement with the priority list of most problematic pesticides for the US and Europe. AMPA and atrazine, the substances detected most frequently in the Ic catchment, as well as 2,4-D and dichlorprop, which were found in high concentrations > 0.1 µg/L in one sample are all included in the Europe top 20 of the priority list. Other substances on the list may not have been found because they were not measured, because of relatively high analytical detection limits of the screening or simply because they are not used in the basin, dominated by corn and wheat cultures. In the White River Basin, atrazine, acetochlor and simazine were detected at concentrations exceeding early warning levels utilized by several states in the United States, indicating their high relevance concerning drinking water production. They are also included in the US top 20 of the priority list. The priority list is a reliable basis for potentially problematic pesticides. It can thus be used as a starting point for monitoring programs in rural catchments, where no specific information on pesticide use are available. If looking for pesticides in surface water, it is important to take times of application of regarded pesticides into consideration, as shown by strong fluctuations in atrazine concentrations in the source water of a waterworks in Indiana (Figure 12 of this report). The screening results indicate that also other contaminants than pesticides may play a role in rural catchments. In the screening in the semi-rural catchments in Indiana, twelve of the detected 38 substances were not pesticides, but belonged to other groups, such as domestic use products, manufacturing additives or gasoline hydrocarbons. Of these twelve substances, seven were only found in one of the two catchments, showing a strong catchment-specific relationship. The findings indicate that other substances than pesticides may be of local importance, though in the case study all 12 substances were at least 50-fold below human health benchmarks (if defined). We conclude that the pesticide priority list given below is a good starting point for diffuse pollution screening even though it may possibly not be sufficient if major local influences, such as factories, large roads with stormwater discharges, CSO or specific local pesticide uses are present.

The Aquisafe project aims at mitigation of diffuse pollution from agricultural sources to protect surface water resources. The first project phase (2007-2009) focused on the review of available information and preliminary tests regarding (i) most relevant contaminants, (ii) system-analytical tools to assess sources and pathways of diffuse agricultural pollution, (iii) the potential of mitigation zones, such as wetlands or riparian buffers, to reduce diffuse agricultural pollution of surface waters and (iv) experimental setups to simulate mitigation zones under controlled conditions. The present report deals with (ii) and aims at identifying numerical modelling tools that can assess the origin of contaminants as well as the impact of different mitigation measures regarding water quality aspects on a catchment scale. In order to test the identified modelling tool in the further course of the Aquisafe project a case study was found in Brittany (France) in agreement with Veolia Eau: the small watershed of the river Ic. Due to intensive agricultural land use the nitrate concentration exceeds the threshold for surface water used for drinking water purpose (which is the main concern of Veolia Eau). Additionally, trace contaminants (pesticides) were detected in the surface water ever since measurements have been carried out. Therefore modelling shall mainly support the water supplier in actions aiming at reducing the nitrate concentration in the surface water. An additional task could later on be the application of the model in order to assess the effectiveness of mitigation measures against trace contamination. In order to choose the most appropriate model a model comparison was carried out using a three step approach. The first step was a screening of different information sources and resulted in the identification of 44 existing models. The second step was a pre-selection according to essential criteria in order to identify models that fulfil the basic requirements for a) the Ic nitrate issue and b) the Aquisafe trace contaminant issue. In a third step a multicriteria analysis was carried out using 6 additional criteria followed by a final recommendation. The essential criteria used for the pre-selection of the models were a) the inclusion of major hydrological processes, b) the inclusion of the nitrogen cycle (for the Ic nitrate issue) or the inclusion of trace contaminants (for the Aquisafe trace contaminant issue) c) the size of catchments that can be modelled, d) the temporal and spatial resolution and e) the possibility to include management options and/or mitigation measures. For the Ic nitrate issue this resulted in the selection of the models: HBV-NP, HSPF, SWIM, SWAT, WASMOD and Mike She. For the Aquisafe trace contaminant issue only four models remained after the pre-selection process: DRIPS, HSPF, SWAT and Mike She. Additional criteria were then applied and resulted in the recommendation to use the model SWAT for further investigations in both cases due to sufficient accuracy and included processes (full hydrological model with water quality simulation (nutrients and trace contaminants) as well as a wide range of successful applications (amongst others). This report presents a wide range of models with their capabilities and limits. It contains criteria which were identified with the stakeholders in order to choose the most appropriate model. The approach presented in this report shall support the decision process of selecting a model for a certain problem regarding water quality and includes only a recommendation. The final decision on which model shall be applied, will be taken in agreement with the stakeholders Veolia Eau and Goel’Eaux.

The Aquisafe project aims at mitigation of diffuse pollution from agricultural sources to protect surface water resources. The first project phase (2007-2009) focused on the review of available information and preliminary tests regarding (i) most relevant contaminants, (ii) system-analytical tools to assess sources and pathways of diffuse agricultural pollution, (iii) the potential of mitigation zones, such as wetlands or riparian buffers, to reduce diffuse agricultural pollution of surface waters and (iv) experimental setups to simulate mitigation zones under controlled conditions. The present report deals with (ii), presenting existing diagnostic methods for agricultural diffuse pollution on a river basin scale. The report focuses on methods with low to moderate data requirements and analytical effort. Generally no numerical models but mostly GIS based approaches have been considered. The described methods were distinguished along two questions: 1. Does diffuse agricultural pollution play an important role in a given catchment? 2. Which areas within the catchment contribute highly to diffuse pollution of the receiving river, i.e. which areas are critical source areas (CSAs)? Question 1 can be answered by using nutrient measurements, mass balance approaches or land use based methods. For most catchments some nutrient measurements and land use data are available, which allow a first assessment whether diffuse pollution could play a role. For question 2, the identification of CSAs, a number of GIS-based methods was found in scientific literature. Since most available methods focus on nutrients and since spatial data on other contaminants, such as pesticides, are typically not available, the report outlines methods for the two critical nutrients nitrogen and phosphorus. Each method can be looked up separately, as they are summarized in a similar structure. Moreover Table 8 in Appendix G provides a quick overview of all the presented methods. All the described approaches focus on nutrients, as they are a major concern and often in the focus of research projects. In general the presented methods consider three aspects to assess the risk of pollution from an area within a river basin: 1. The source of nutrients on agricultural land is included through fertilizer application, livestock numbers or indirectly via land use. 2. Transport to the river is mainly assessed via soil type, land cover, elevation and distance to the river 3. In addition several methods take retention processes into account during transport to or within the river It is important that different contaminants show different behaviour. For instance, phosphorus is pre-dominantly particle-bound, enters rivers via soil erosion and can be retained by adsorption or plant export. Nitrate, the dominant form of nitrogen, is very well soluble, is lost mostly through leaching and most efficiently retained by denitrification. Consequently, methodologies for the assessment of CSAs for phosphorus and nitrogen were looked at separately. While many promising methods with limited data requirements and analytical efforts were identified in the report, few concepts (such as the Universal Soil Loss Equation for phosphorus) seem to be well established. Most literature concerns specific local or regional case studies. As a result, transferability to other catchments is questionable. The highest potential is seen in qualitative, multi-criteria methods (such as the scoring approach by Trepel and Palmeri, 2002), which can be adapted by the user depending on the diagnostic aim as well as local data availability. In summary, it is recommended to test several of the presented GIS methods on one or two catchments to gain experience in their handling and their transferability.

The Aquisafe project aims at mitigation of diffuse pollution from agricultural sources to protect surface water resources. The first project phase (2007-2009) focused on the review of available information and preliminary tests regarding (i) most relevant contaminants, (ii) system-analytical tools to assess sources and pathways of diffuse agricultural pollution, (iii) the potential of mitigation zones, such as wetlands or riparian buffers, to reduce diffuse agricultural pollution of surface waters and (iv) experimental setups to simulate mitigation zones under controlled conditions.

The Aquisafe project aims at mitigation of diffuse pollution from agricultural sources to protect surface water resources. The first project phase (2007-2009) focused on the review of available information and preliminary tests regarding (i) most relevant contaminants, (ii) system-analytical tools to assess sources and pathways of diffuse agricultural pollution, (iii) the potential of mitigation zones, such as wetlands or riparian buffers, to reduce diffuse agricultural pollution of surface waters and (iv) experimental setups to simulate mitigation zones under controlled conditions. The present report deals with (iv) and evaluates the suitability of the technical scale experimental site at the UBA in Berlin, Marienfelde for simulating processes that impact the fate and transformation of nutrients in wetlands / riparian zones. A 3-month pilot investigation (Sep. to mid Nov. 2007) was conducted in order to assess the impact of vegetation on nitrate (NO3-) removal in slow-sand filters (SSFs) and identifying possible interference of glyphosate with N and C cycling processes in these systems. SSFs are engineered bio-reactors that can mitigate the transfer of a wide range of pollutants including nutrients and organic contaminants to water bodies. Two vertical-flow experimental SSFs (average area: 60 and 68 m2, depth: 0.8 and 1.2 m, respectively) at the UBA facilities in Berlin were used in this study: one unplanted and the other vegetated with Phragmites australis. The SSFs received water amended with nitrate (NO3-) and phosphate (PO4 -) without and with glyphosate (added for 2 weeks). Mineral N concentration at the mixing cell, SSF surface, 40 cm depth and at the SSF outlet was measured at least twice per week to calculate N removal rates. Physical water properties (pH, redox potential, temperature) and greenhouse gas emission (CO2, CH4 and N2O) were also monitored to gain insights into controlling processes. Results showed that N removal rates were several-fold higher in the vegetated than in the non-vegetated SSFs averaging 663 mg N m-2 d-1 (57 % of input) and 114 mg N m-2 d-1 (14 % of input), respectively. In both systems, most of the N removal occurred in the top 40 cm of the SSFs. Marked temporal variation in N removal rates was also detected with rates in general 3 times higher in late summer compared to mid/late autumn. In the latter period, a net release of N was observed in the non-vegetated SSF. The seasonal variation in N removal could be related to a lack of vegetation growth and thus plant N uptake, and may also reflect of the sensitivity of denitrification to climatic factors as suggested by strong (r2 > 0.77) linear relationships between weekly N removal rates and SSF water temperature. A clear impact of glyphosate addition on nitrate concentrations could not be observed. Denitrification, the process most responsible for the removal of nitrogen from waters and soils seems to be unaffected by the addition of glyphosate under the conditions in the experiment. The impact of glyphosate, if any, was probably much smaller compared to the strong influence of temperature on N dynamics in the SSFs. Difficulty of maintaining a constant concentration of glyphosate during dosing may have also contributed to this outcome. Nitrous oxide emission accounted for < 3 % of the total N removed was always lower in the vegetated (< 0.1 - 0.3 mg N2O-N m-2 d-1) than in the non-vegetated SSF (0.2 - 3.8 mg N2O-N m-2 d-1). Conversely, CH4 emission was always higher in the vegetated (range: +0.4 to +49.5 mg CH4-C m-2 d-1) than in the non-vegetated SSF (range: -2.1 to +1.32 mg CH4-C d-1). These results, in connection with much lower oxidation reduction potential readings in the vegetated filter, suggest that the reduction of N2O to N2 was important in the SSF systems and that N2 was the dominant N gas produced. Thus, N2 production must be quantified in order to establish N mass balance of SSF systems. The results show that technical-scale experiments can realistically simulate mitigation systems, while having control over contaminant loading, flow conditions and monitoring. Important lessons learnt for future applications are the following (i) Denitrifying conditions can be established in both SSF of the experimental site by adjusting to low flow conditions (0.23 m³/h) and dosing nitrate. (ii) Dosing of trace contaminants (in this case glyphosate) needs to be improved, but will remain difficult for the large amounts of water involved. The results underline the importance of measurements in the mixing cell. (iii) Since seasonal effects play an important role in mitigation zone performance, any experiments need to be done in parallel, rather than in succession to be able to compare the results.

The Aquisafe project aims at mitigation of diffuse pollution from agricultural sources to protect surface water resources. The first project phase (2007-2009) focused on the review of available information and preliminary tests regarding (i) most relevant contaminants, (ii) system-analytical tools to assess sources and pathways of diffuse agricultural pollution, (iii) the potential of mitigation zones, such as wetlands or riparian buffers, to reduce diffuse agricultural pollution of surface waters and (iv) experimental setups to simulate mitigation zones under controlled conditions. The present report deals with (iii), providing a review of the potential of constructed wetlands to protect surface waters from diffuse agricultural pollution. Population growth and industrialization have lead to the demise of large majorities of natural wetland systems. Recent research continues to suggest the importance of these often saturated areas in the natural remediation of pollutants in water, as well as being aesthetically pleasing and acting as potential habitat for declining species. The drastic losses in wetland areas, combined with the realization of their importance, have stimulated recent attempts at wetland restoration and even construction of wetlands where they would not have naturally occurred. In terms of substance remediation, constructed wetlands were traditionally used for the treatment of point sources, such as urban or industrial waste water. Recently they have also become increasingly popular for the treatment of diffuse pollution from agriculture and urban storm runoff. Constructed wetlands have been shown to be efficient in the treatment of nutrients, organic matter and heavy metals. Few studies also show their potential against trace organics, such as pesticides and pharmaceutical residues and against pathogens. Retention efficiencies vary significantly among case studies. In agricultural settings the following design criteria should be considered: (i) Water residence time in wetlands is critical. Some studies concerning nutrient removal suggest that a constructed wetland should be about 5 % of the watershed area and assure water residence time of 7 days. (ii) Vegetation is important to slow down flow and increase sedimentation. Regular cutting and removal of plants is controversially discussed, since it may reduce their beneficial effect on wetland hydrology. (iii) Constant redox conditions are important to avoid release of sedimented or adsorbed pollutants. (iv) A combination of constructed wetlands with buffer strips showed very positive results.

The Aquisafe project aims at mitigation of diffuse pollution from agricultural sources to protect surface water resources. The first project phase (2007-2009) focused on the review of available information and preliminary tests regarding (i) most relevant contaminants, (ii) system-analytical tools to assess sources and pathways of diffuse agricultural pollution, (iii) the potential of mitigation zones, such as wetlands or riparian buffers, to reduce diffuse agricultural pollution of surface waters and (iv) experimental setups to simulate mitigation zones under controlled conditions.