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 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 (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.