The export of agricultural contaminants from agricultural landscapes of the US Midwest has contributed to the impairment of surface waters throughout the Mississippi River Basin and has been linked to various human health concerns. Natural treatment systems (wetlands, bioswales, bioreactors) can capture agricultural runoff and significantly reduce nutrient loading to downstream waters but there is a paucity of data on the effectiveness of these treatment systems to attenuate the suite of pollutants (nutrients and synthetic organics) typically found in agricultural runoff. This understanding is important given that the degradation of different pollutants involves metabolic pathways that often require different redox environments. As part of the Aquisafe-2 project, a bioretention swale comprising two treatment cells (a subsurface cell in series with a surface cell) was monitored, and its performance evaluated over a three-year period (2011 - 2013). Results showed that the bioswale was moderately efficient with regard to nitrate (NO3-; retention range: 16-58 %). N removal averaging 30 % was measured during a series of wetting events during which the bioswale operated at an estimated average hydraulic retention time (HRT) of 0.97 day. Spatial analysis of the data showed that almost all the NO3- removal occurred in the subsurface cell; however, N removal was also measured in the surface cell under low flow conditions (estimated HRT: 2.5 days). The highest rates of N removal (~ 58 %) were measured when the bioswale stayed wet for several days probably due to the development of a more optimum environment for denitrifying microbes. Nitrate removal capacity was limited by NO3- availability, short retention times during high flows, and the frequent fluctuation between oxic and anoxic conditions, but not by water temperature (8.3-16.6 oC) and dissolved organic carbon (DOC; 1.9 - 29.2 mg C L-1). The bioswale performance with regard to soluble reactive phosphorus (SRP) and atrazine was more variable, with net retention during some periods and net release at other times. The bioswale was a net source of P during most sampling periods with an average SRP release corresponding to 13 % of input, probably due to desorption of water soluble P from the topsoil applied during construction. This interpretation is supported by the progressive decline in P release observed between the first and third year of monitoring. The subsurface and the surface cells contributed almost equally to the fate of P in the bioswale. Likewise, the bioswale was at times a small/moderate sink (13-31 % retention) for atrazine, and a net source (-38 % to -15 %) during periods when the bioswale received overland runoff from the adjacent crop field which bypassed the subsurface cell. Results suggested that competition between atrazine and DOC for sorption sites is a possible mechanism affecting atrazine removal efficiency. Additional work is needed to compare the efficiency of the subsurface and surface cells with regard to atrazine, and elucidate the biogeochemical factors controlling its fate in the bioswale.

The present laboratory study tests the hypothesis that straw-bark mulch bioreactors are capable of concurrently retaining nitrate (NO3-) and the herbicides atrazine or bentazone at short hydraulic residence times (HRT). In a 1 year column experiment at HRT of ~4h three organic carbon sources, straw of common wheat (Triticum aestivum L.), bark mulch of pine tree (Pinus sp.) and a mixture of both materials, showed high reduction of continuously dosed NO3- (100mgL-1) with average denitrification rates of 23.4g-Nd-1m-3, 8.4g-Nd-1m-3 and 20.5g-Nd-1m-3, respectively. Under denitrifying conditions, fast and substantial retention of continuously dosed atrazine (20µgL-1) was observed with estimated dissipation times (DT50) between 0.12 and 0.49 days in the straw-bark mulch bioreactor. In parallel batch experiments, it could be confirmed that atrazine retention is based on adsorption to bark mulch and on degradation processes supplied by the organic materials as continual sources of carbon. In contrast, bentazone was not significantly reduced under the experimental conditions. While aging of materials was clearly observed in a reduction of denitrification by 60-70% during the experiment, systems still worked very well until the end of the experiment. The results indicate that the combined use of straw and bark mulch could increase the efficiency of mitigation systems, which are installed to improve the quality of drainage water before its release to surface waters. Further, the addition of these materials has the potential of parallel retention of NO3- and less mobile herbicides like atrazine, even during high flow events, as expected at the outlet of agricultural drainage systems. High removal is expected for mitigation system designed to remain saturated most of the time, whereas bioreactors that run periodically dry are not covered by this study. However, further experiments with the tested materials at technical or field scale under more realistic climate conditions need to be carried out.

The AQUISAFE research project aims at mitigation of diffuse pollution from agricultural sources to protect surface water resources. The project has several objectives including optimizing system-analytical tools for the planning and implementation of mitigation zones, demonstrating the effectiveness of mitigation zones in international case studies in the US Midwest and Brittany, France and developing recommendations for the implementation of near-natural mitigation zones, which are efficient in attenuating nutrients and selected pesticides. A series of different types of mitigation systems, including constructed wetlands and reactive trenches are being constructed in 2010 at identified agricultural sites in France and the USA. A preliminary monitoring of a drainage-fed surface flow wetland showed good nitrate retention when water infiltrated or had significant residence times, but no discernable effect during major storm events. As a result, future designs aim at higher reaction times by adapting size of end-of-drainage solutions to expected flows and by developing new mitigation systems for existing drainage ditches. Moreover, reaction rates are improved by forming favourable conditions for underground passage and by addition of organic carbon sources, such as straw or wood chips. Whereas nutrients are the focus for the field sites in France, both nutrients and atrazine are the focus in the US. Reactive trenches are being tested for pesticide retention at laboratory and technical scale at the experimental field of the German Federal Environment Agency. In the latter experiments, Bentazon and Atrazine are used as test substances, given their relevance for European and US surface waters, respectivelyseveral objectives including optimizing system-analytical tools for the planning and implementation of mitigation zones, demonstrating the effectiveness of mitigation zones in international case studies in the US Midwest and Brittany, France, and developing recommendations for the implementation of near-natural mitigation zones, which are efficient in attenuating nutrients and selected pesticides. A series of different types of mitigation systems, including constructed wetlands and reactive trenches are being constructed in 2010 at identified agricultural sites in France and the USA. A preliminary monitoring of a drainage-fed surface flow wetland showed good nitrate retention when water infiltrated or had significant residence times, but no discernable effect during major storm events. As a result, future designs aim at higher reaction times by adapting size of end-of-drainage solutions to expected flows and by developing new mitigation systems for existing drainage ditches. Moreover, reaction rates are improved by forming favourable conditions for underground passage and by addition of organic carbon sources, such as straw or wood chips. Whereas nutrients are the focus for the field sites in France, both nutrients and atrazine are the focus in the US. Reactive trenches are being tested for pesticide retention at laboratory and technical scale at the experimental field of the German Federal Environment Agency. In the latter experiments, Bentazon and Atrazine are used as test substances, given their relevance for European and US surface waters, respectively.

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) and has the purpose to provide a brief overview of the current state of knowledge related to the role of riparian zones as best management practices for water quality improvement at the watershed scale. Research indicates that landscape hydrogeological characteristics such as topography and surficial geology influence both riparian zone hydrology and biogeochemistry. Topography, depth to a confining layer and soil hydraulic conductivity all affect groundwater input to riparian zones and the water table fluctuation regime throughout the year. Research also indicates that although most biologically mediated reactions in soil are redox dependant, landscape hydrogeology, by affecting riparian hydrology, affects the redox conditions in the soil profile. In turn, microbial processes and changes in element concentrations are predictable as a function of the redox state of the soil.Variations in biogeochemical conditions directly affect the fate of multiple contaminants in riparian systems. In particular, variations in soil redox potential in riparian zones can affect the evolution of numerous contaminants and solutes within riparian zones like pesticides, phosphorus, NO3-, N2O, NH4+, SO42-, CH4, Fe2+/Fe3+ or Dissolved Organic Carbon (DOC). Of all the solutes/contaminants mentioned above, nitrate is one of the most important concerning water quality in many areas of the US and Western Europe. Consequently, many studies have investigated nitrate removal in riparian systems. Depending on site conditions, nitrate retention generally varies between 60 and 90 %; however, there are situations where nitrate removal is less or even where a riparian zone becomes a source of N to the stream. Although the riparian literature is clearly dominated by nitrate removal studies, many studies also focus on phosphorus, sediments, pesticides, chloride, bromide and bacteria. Although there are situations where riparian zones have been shown to be sources of P, Atrazine, bromide, E. coli or E. streptococci bacteria, riparian zones generally contribute to the reduction of most contaminants in subsurface flow and overland flow. Nevertheless, although conditions favorable to the reduction or oxidation of a given contaminant at the microbial level are often known, more research needs to be conducted to determine the variables controlling the fate of contaminants other than nitrate in soil at the riparian zone scale.Finally, although many studies have investigated the hydrological and biogeochemical functioning of riparian zones in the past few decades, much research remains to be conducted in order to quantify and predict the impact of riparian zones on water quality at the watershed scale in a variety of climatic and hydrogeological settings. In particular, better strategies and/or tools to generalize riparian function at the watershed scale need to be developed. Particular areas where research is needed to achieve this goal include: 1) the development of strategies to quantify and model the cumulative impact of individual riparian zones on water quality at the watershed scale; 2) a better quantification of the importance of spatial and temporal variability in hydrologic and biogeochemical riparian functioning relative to annual nutrient transport; 3) a better understanding of the role of vegetation in terms of its impact on riparian biogeochemical processes and the response of these processes to manipulations of vegetative cover; 4) a better understanding of the impact of human activities and infrastructure on riparian zone function in both urban and rural landscapes; 5) a better understanding of the fate of emerging contaminants in riparian systems.

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 (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.

Major reservoirs are a key element for public water supply in many countries. In Europe over 800 major reservoirs serve primarily this purpose. Eutrophication affects significant numbers of lakes and reservoirs, and is the well-known issue currently impacting drinking water supply reservoirs. In most cases, phosphorus is the principal cause of eutrophication, and therefore has been studied intensively. The presence of micro pollutants (e.g. pesticides, pharmaceutically active compounds - PhaCs) is not systematically monitored but some substances are very mobile and tend to resist degradation. Such contaminants have been detected in numerous surface water bodies (lakes, reservoirs and rivers). As agriculture is intensifying and land use is changing in many areas, the impact of diffuse pollution on water quality is expected to be more pervasive in the future. The project Aquisafe proposes to investigate the topic in a multi-step approach which will include: i) an analysis of the nature, occurrence and risk of surface water contamination, ii) a modelling approach to quantify the contaminants origin, load and repartition to assess the effects of adapted controlled measures, and iii) the development, adaptation or optimisation of the design and operation of mitigation zones (riparian corridors and small scale wetlands) to reduce downstream loads of pollutants. Thus, Aquisafe is a first step to establish the state-of-the-knowledge on current existing solutions, identify emerging issues and assess the feasibility of using models for the evaluation of mitigation zones for contaminants removal. Within the Aquisafe project it will expected: i) a recommendation on potential key substances to be targeted, also for further investigations, ii) an identification of drinking water source vulnerability to emerging contaminants using a coupled modelling approaches, and iii) an analysis of existing mitigation methods and scientific background for the construction of riparian corridors and/or constructed wetlands in order to mitigate trace contaminants entering the surface water.