Wetland ecosystems for denitrification processes in rivers A comparison for implementation in the lower Seine and its estuary (France) ADVIESRAPPORT AUTEUR: NICO DECONINCK ONDERZOEK UITGEVOERD IN OPDRACHT VAN CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, PARIJS, FR. HEERLEN, okt-15 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Colofon Naam document Opdrachtgever Uitgave Projectteam (auteurs) Projectteam (nummer) Projectcoach (docent) Datum (laatst bijgewerkt) Status PWA-NicoDeconinck-IM2010nj.doc Dit onderzoek is uitgevoerd in opdracht van Centre National de la Recherche Scientifique (CNRS), Mevr. Laverman Anniet. InCompany Milieuadvies, faculteit Natuurwetenschappen, Open Universiteit Nederland, Postbus 2960, 6401 DL Heerlen, NL. www.ou.nl/nw Nico Deconinck Team-105, Denitrificatie, IM2010nj Jikke vanwijnen, Open Universiteit Nederland – InCompany Milieuadvies 26-5-2011 12:10 in bewerking voor review (intern: team/projectcoach; extern: opdrachtgever) ter beoordeling definitief InCompany Milieuadvies hanteert de APA 5th Style als norm voor haar wetenschappelijke rapportages. Copyright InCompany Milieuadvies © 2015 Open Universiteit Nederland, Heerlen De auteursrechten op dit materiaal berusten bij de Open Universiteit Nederland. Behoudens uitzonderingen door de Wet gesteld mag zonder schriftelijke toestemming van de rechthebbende(n) op het auteursrecht niets uit deze uitgave worden verveelvoudigd en/of openbaar gemaakt door middel van druk, fotokopie, microfilm of anderszins, hetgeen ook van toepassing is op de gehele of gedeeltelijke bewerking. Copyright on this material is vested in the Open Universiteit Nederland. Save exceptions stated by the law no part of this publication may be reproduced in any form, by print, photoprint, microfilm or other means, included a complete or partial transcription, without the prior written permission of the publisher. InCompany Milieuadvies is het online milieuadviesbureau van de Open Universiteit (www.ou.nl). Studenten werken in teamverband aan echte milieuopdrachten van echte opdrachtgevers. Leren en werken zijn één in deze bijzondere cursus, die de afronding vormt van de wetenschappelijke Bachelor-of-Science opleiding Milieu-natuurwetenschappen VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Projectgegevens Titel (nl) Title (in English) Opdrachtgevende instantie Omschrijving opdracht (nl) Description of the order (in English) Trefwoorden Key words Betrokkene(n) bij opdrachtgeversorganisatie Projectleider team IM Projectcoach Opdrachtgever Examinator Referentie naar dit rapport Wetland ecosystemen voor denitrificatie processen in rivieren. Een vergelijking voor de implementatie in het estuarium van de Seine (Frankrijk) Wetland ecosystems for denitrification processes in rivers. A comparison for implementation in the lower Seine River and its estuary (France) Centre National de la Recherche Scientifique (CNRS)’, Université Pierre et Marie Curie, Parijs, FR. De opdracht bestaat erin een overzicht te geven van mogelijke wetlands, zoals moerassen en overstromingsgebieden die voor denitrificatie in rivieren in aanmerking komen. Hierbij worden een aantal praktische voorbeelden vergeleken en worden de mogelijke milieuomstandigheden besproken. De resultaten van deze studie moeten een overzicht geven van de wetlands, die in functie van de omgevingsfactoren, de denitrificatie of verwijdering van nitraten in het estuarium van de Seine mogelijk maken. This study concerns an overview of potential wetlands, like marshes and floodplains that could be implemented for denitrification in rivers. A few practical cases, related to the environmental conditions will be discussed. The results of this study should give an overview of potential wetlands, related to environmental conditions, which could be considered for implementing in the estuary of the river Seine for denitrification or the removal of nitrates. Nitraat – nitrificatie – denitrificatie – ecosysteem – rivier – wetlands – estuarium – overstromingsgebied Nitrate – nitrification – denitrification – ecosystem – river – wetlands – estuarine – floodplain Mevr. Anniet Laverman, contactpersoon CNRS Nico Deconinck, cursus Virtueel milieuadviesbureau, N5021, 837544374, wo-bachelor Milieu-natuurwetenschappen (B.Sc.), is verantwoordelijk voor contact met Mevr. Laverman + tussentijdse rapportage. Mevr. Jikke vanwijnen, faculteit Natuurwetenschappen, Open Universiteit Nederland, telefonisch (00-31-20-5788425) of per email [email protected] Mevr. Anniet Laverman, UMR 7619 Sisyphe, Université Pierre et Marie Curie, Parijs, FR Dr. Wilfried Ivens, faculteit Natuurwetenschappen, Open Universiteit Nederland, Heerlen, NL Deconinck, N. (2011).Wetland ecosystems for denitrification processes in rivers. A comparison for implementation in the lower Seine River and its estuary (France). Onderzoek uitgevoerd in opdracht van het Centre National de la Recherche Scientifique (CNRS). Parijs, FR. Unpublished Bachelor’s Thesis, Open Universiteit Nederland, Heerlen, NL. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Content Colofon Projectgegevens Inhoud Voorwoord Samenvatting Abstract 1. Introduction Background 1.1. 1.2. Problem definition 1.3. Target of the research 1.4. Criteria for the results 1.5. Conditions 2. Methods 2.1. Literature search 2.2. Analysis 3. Results 3.1. Inventory of types of wetlands 3.2. Denitrification results and wetlands in rivers 4. Discussion and conclusions 4.1. Conclusions 4.2. Discussion 5. Suggestions Literature Annex A Description 8 rivers and their wetlands VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 4 van 50 2 3 4 5 6 7 8 9 9 10 12 21 23 23 23 26 26 28 36 36 38 42 43 47 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Voorwoord Dit adviesrapport bevat de resultaten van een literatuuronderzoek met betrekking tot de denitrificatie in de Seine (Frankrijk) met behulp van wetlands of natte gebieden. Het onderzoek werd in opdracht van het Centre National de la Recherche Scientifique (CNRS) te Parijs uitgevoerd. Met de hulp van Mevrouw Anniet Laverman, tewerkgesteld bij de Université Pierre et Marie Curie te Parijs en met de ondersteuning van de projectcoach Mevrouw Jikke vanwijnen kwam deze studie tot stand. De vrucht van dit werk moet ertoe leiden dat enerzijds het inzicht in de werking van wetlands verbeterd wordt en dat anderzijds de relaties tussen de factoren, die bij de nitraatverwijdering bepalend zijn, verder onderzocht worden. De nadruk komt in dit adviesrapport te liggen bij de Seine als studieobject en meer in het bijzonder het estuarium met een aantal wetlands. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 5 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Samenvatting Wetlands (natte zones) zijn algemeen gekend voor hun denitrificatie en nitraat verwijderingeigenschappen, maar hun efficiëntie kan nogal verschillen volgens het type. Er is bovendien geen algemeen akkoord over de definities van de verschillende wetlands. In deze studie werden 5 indelingen van wetlands gevonden en onderverdeeld in verschillende types en subtypes. Verder werden 5 rivieren met wetlands in de Verenigde Staten en 3 in Europa geselecteerd. Hierbij werden verbonden en geïsoleerde, overstromingszones en estuarium wetlands gedetecteerd. Daarnaast werden in deze studie de denitrificatie efficiëntie resultaten in de wetlands vergeleken op basis van de schaal van Janssen et al. (2005). Verbonden wetlands, overstromingszones en estuarium wetlands gaven de beste resultaten betreffende nitraat verwijdering. De nitraatstromen werden voor 2 wetlands berekend op basis van het NANI model (totale som van antropologische stikstof instroom) en gaven lagere waarden dan deze, bepaald door de auteurs. Als gevolg van een trage waterstroming en een langere contacttijd in verbonden wetlands, werd een hogere nitraat verwijdering en retentie vastgesteld. Deze parameters kunnen door een gecontroleerd pompen van rivierwater in de verbonden wetlands beheerst worden. Verder werd een betere verwijdering in verbonden dan in geïsoleerde wetlands vastgesteld. Zuurstofarme sedimenten toonden de beste denitrificatie waarden in overstromingszones. Relatieve grote oppervlakten en een korte afstand tot de rivier leverden de beste nitraat verwijderingefficiëntie op. In het estuarium gaven een hogere redox potentiaal en een lagere ammonium instroom de beste nitraat verwijderingefficiëntie. Laag moeras (Nuphar advena) gaf betere denitrificatie resultaten dan hoog moeras (Phragmites australis). De kenmerken van de geïdentificeerde wetlands werder verder vergeleken met de wetlands in de zone tussen Caudebec en Honfleur in het estuarium van de Seine. Spijtig genoeg zijn er geen vergelijkbare nitraat verwijderingresultaten te vinden in de literatuur. Marais du Hode, Grande Vasière Nord en Marais Vernier zijn hoofdzakelijk voorzien van verbonden wetlands door een netwerk van kanalen en de waterstroom wordt gecontroleerd door een sluis of openingen in een dam. Marais de la Risle heeft een aantal geïsoleerde wetlands, een modderbank en een kunstmatige meander. In overeenstemming met de resultaten bij de andere rivieren, worden goede prestaties bij Marais du Hode, Grande Vasière Nord en Marais Vernier verwacht. Een aantal kleinere stromen, die verbonden zijn met de Seine, zoals de Eure, de Oise en de Marne, zouden bestudeerd moeten worden om de effecten stroomafwaarts in het estuarium te kunnen bepalen. Als gevolg van hun lagere waterstroming zouden deze rivieren potentieel kunnen bezitten voor het implementeren van optimale retentie en vertragingsmiddelen. Om de complexe samenhang tussen de nitrificatie en denitrificatie parameters te begrijpen, dient meer onderzoek te gebeuren en in het bijzonder in het estuarium door de invloed van de dynamiek van de getijdenstroming. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 6 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Abstract Wetlands are generally recognized for their denitrification and nitrate removal capacities, but their performance can vary seriously. Moreover, a general agreement about the definition of the several kinds of wetlands is still lacking. In this study 5 ways for categorizing wetlands and subdividing them in several types and subtypes. Next, a selection of 5 rivers with wetlands in the United States and 3 in Europe was made. As result, these rivers were associated with connected and isolated, floodplains and estuary wetlands. Furthermore, during this study, A comparison of the denitrification performance results in these wetlands, by using the denitrification performance ranges by Janssen et al. (2005) was made. Connected wetlands, floodplains and estuary wetlands showed the best nitrate removal results. The nitrate fluxes, calculated for 2 wetlands by using the NANI (net sum of anthropological nitrogen inputs) model, were lower than the results observed by the authors. Due to a low water flow rate and a longer contact time in connected wetlands, they show a better nitrate reduction and retention. These parameters could be controlled by pumping river water in the connected wetlands. A better removal performance for connected than isolated wetlands has been found. Oxygen poor flooded sediment showed the best denitrification rate in floodplains. Furthermore, a relative great surface area and a small distance from the riverside enhanced the nitrate removal performance. In the estuary wetlands, a higher redox potential and lower ammonium fluxes gave satisfactory nitrate removal rates. Low marsh (Nuphar advena) showed better denitrification results than higher marsh (Phragmites australis). The characteristics of the identified wetlands were further compared with the wetlands in the region between Caudebec and Honfleur in the estuary of the river Seine. Unfortunately, no comparable nitrate removal results were identified in the literature. Marais du Hode, Grande Vasière Nord and Marais Vernier are mainly provided with connected wetlands by a network of ditches and controlled by a sluice or openings in a dam. Marais de la Risle has a number of isolated wetlands and comprises mudflats and an artificial meander. In accordance with the results of the other rivers, I expect the best nitrate removal performance for Marais du Hode, Grande Vasière Nord and Marais Vernier. A number of smaller streams, which are connected with the Seine, like the Eure, Oise and Marne, should be studied in order to examine the effects downstream in the estuary. Due to their lower water flow rates, these rivers could show potential for implementing optimal retention and velocity decreasing means. Due to the complex interaction between the different parameters in nitrification and denitrification processes, more research should be done for better comprehension, especially in the estuary because of the influence of tidal dynamics. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 7 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS 1. Introduction 1.1. Background Many rivers are overloaded with nutrients, including nitrogen compounds, like nitrates, ammonium or urea from natural and anthropological sources, such as wastewater and agriculture fertilizer by runoff water from agriculture fields. These nutrients can cause harmful algal blooms, especially in the coastal zone. Due to degradation of the algal biomass by heterotrophic bacteria, oxygen depletion in this zone can appear. This process is called eutrophication and has already been reported in 1955 by Ohle (Ohle, 1955). Actually, eutrophication is defined as ‘a change of the natural position of organisms in the food chain in a water body by anthropological influences with negative consequences’ (Van Ballaer et al., 2006). The oxygen depletion, called anoxia or hypoxia, will affect oxygen dependent organisms and so disturb the biodiversity of the ecosystem (Gardner, 2008). Furthermore this riverine nutrient flux will proceed into the sea. The nitrogen flux from the Seine, the Somme and the Scheldt to the sea for the year 2000 has respectively been estimated to 1975, 1333 and 1464 kg N km-2 y-1. In comparison with a more environmental friendly agriculture and without less fertilizer usage (= business-as-usual), an estimation for respectively the Seine, the Somme and the Scheldt to the sea will be 2245, 1623 and 1570 kg N km-2 y-1 (Thieu et al., 2010). Two processes, namely nitrification and denitrification play an important role in nitrogen fluxes in aqueous and terrestrial ecosystems. Nitrification, that converts ammonium into nitrite (NO2-) and nitrate (NO3-), needs oxygen rich conditions. In the contrary, denitrification transforms nitrate into N2O and N2 in oxygen poor concentrations < 0.2 mg O2 L-1, which is indicated with the term ‘suboxic’ or anoxic (Seitzinger et al., 2006). More specific, denitrification is defined as the transformation of nitrite or nitrate into a nitrogen gas, as opposed to the reduction of nitrite or nitrate to ammonia. These gases are nitrous oxide (N2O), considered as a greenhouse gas and NO that contributes to the ozone production, both intermediate products of the reduction from NO3- to N2 in the following sequence NO3→ NO2- → NO → N2O → N2. Contrarily to the previous gases, nitrogen gas (N2) is harmless (Verhoeven, 2002). Overall, microbial denitrification and plant uptake have been identified as the most important natural processes to remove nitrates (Kelly, 2006). Wetland ecosystems, natural or artificially constructed, are able to remove nutrients, such as nitrogen from aquatic systems. Basically, wetlands are distinguished by a) the presence of water at the surface or the root zone b) soil conditions and c) vegetation (Hogan et al., 2000). The indication ‘wetland’ is a very general and broad term that is used for several kinds of ecosystems. In 1971 a convention, the Ramsar Convention was established. The goal of this intergovernmental treaty was to define a better use of wetlands. Articles 1.1 and 2.1 of the convention define wetlands respectively as ‘For the purpose of this Convention wetlands are areas of marsh, fen, peatland or water, whether natural or artificial, permanent or temporary, with water that is static or flowing, fresh, brackish or salt, including areas of marine water the depth of which at low tide does not exceed six meters’ and ‘may incorporate riparian and coastal zones adjacent to the wetlands, and islands or bodies of marine water deeper than six meters at low tide lying within the wetlands’ (Commonwealth, State and Territory Governments of Australia, 2001). VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 8 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS 1.2. Problem definition Denitrification is a critical process that can remove bioavailable nitrogen (N) but it also affects global climate directly by the greenhouse gas nitrous oxide (N2O). Three conditions are required for denitrification: a) available nitrate b) reduced oxygen conditions and c) presence of electron donors, like organic carbon (Seitzinger et al., 2006). Fig.1: Nitrogen pathways (Gardner, 2008). Figure 1 illustrates the major nitrogen pathways. Nitrification and denitrification processes are often coupled. The occurrence of aerobic close to anaerobic zones in shallow surface water and wetlands could promote coupled nitrification/denitrification (Gardner, 2008). This coupling mechanism is regulated by diffusion, which enables to set-up a concentration gradient. NH4+ must diffuse upward in the aerobic zone to be nitrified and NO3- downward in the anaerobic area (Gardner, 2008). Consequently, due to the limited oxygen diffusion in constructed wetlands, nitrification is often the limiting step in the N removal process (Maltais-Landry et al., 2009). Nevertheless, growing plants and tidal influence enhance the oxidizing environment of the rhizosphere and sediment pores, which increases oxygen availability to support nitrification and decrease the diffusion distance between oxygen rich and anoxic sites for respectively nitrifying and denitrifying bacteria (Hamersley & Howes, 2005). Referring to Thieu and colleagues (2010), nitrates create an important problem in the Seine River in France. As well as in the lower river Seine as in the freshwater estuarine, oxygen deficit has been determined due to respectively degradation of organic matter and nitrification of ammonium (Cébron et al., 2003). Furthermore, Billen and colleagues (2007) used a model (the Riverstrahler) to describe nutrient transfer and transformation in the Seine. The model predicts nitrogen retention of 40-60.106 kg N y-1, representing 20 à 30% of the total inputs, with denitrification as the major process. Denitrificaton processes or the microbial transformation of NO3- into N2O and N2 in the Seine have already been examined by a number of scientists. Denitrifying bacteria in aqueous and sedimentary conditions have also been studied universally. Not only the presence of denitrifying bacteria, such as Pseudomonas, Alcaligenes and Flavobacterium is important, but also the environmental conditions will determine the denitrification processes (Gardner, 2008). Three alternate microbial pathways have been identified. Anammox, that concerns the production of N2 (= nitrate reduction) from anaerobic oxidation of ammonium with nitrite, assimilatory nitrate reduction to ammonium (ANRA) and dissimilatory nitrate reduction to ammonium (DNRA) (Gardner, 2008). Denitrification mainly occurs in the benthic phase. Curie and colleagues (2009) found that the riparian zone of the Beauregard stream VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 9 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS (large alluvial floodplain of the Seine) supported denitrification all year long due to river water with levels of dissolved oxygen, high organic carbon content and high temperature. Approximately 65% of the increasing levels of N2O into the atmosphere are due to N transformations in the soil of the Seine basin (Garnier et al., 2006). More particularly, Garnier and colleagues (2006) concluded that N2O emission from 1997 until 2003 was higher in the Seine estuary (between Poses and Caudebec), where salt or brackish water is dynamically mixed with freshwater, than upstream from Paris WWTP (wastewater treatment plant) effluents, but lower than in the effluent’s downstream zone (see fig. 2) The use of wetlands or wetland ecosystems for purifying domestic, agriculture, recreational and industrial wastewater is known since 1950. Besides denitrification by bacteria, still three other processes are important for the nitrate removal in these ecosystems. Plants in the wetland take up nutrients and store them in the upper parts. Next, at the bottom of the wetlands, sedimentary absorption can take place, but ammonium and nitrate absorb rather difficult to soil particles. At last, difficult solvable compounds, due to biochemical reactions can bind to nutrients and store them in sediments (de Vries, 2002). Consequently, different plant species can influence N removal by variation in oxidation and respond differently to seasonal changes (Maltais-Landry et al., 2009) and the oxygen concentration of the substrate of the wetlands, can be determined by the vegetation and more particularly the rhizosphere of the plants (Fisher et Acreman, 2004). Finally, nutrients can be liberated when erosion of the wetland occurs or when plants die (de Vries, 2002). 1.3. Target of the research This study is requested by CNRS (Centre National de la Recherche Scientifique) in Paris in order to identify wetlands and their potential for denitrification and their role in eliminating nitrogen from the Seine rivery (France). The functioning of the Seine river is studied intensively since 1989 by the PIREN-Seine program (Programme Interdisciplinaire de Recherche sur l’Environnement de la Seine). Closely related to this initiative, is the Seine-Aval program that contributes since 1995 to increase the knowledge and the understanding of the physical, chemical and biological processes in the Seine. The goal of this study is to examine the functioning of nitrate removal processes in existing wetlands (natural or artificial) for nitrate removal in the river Seine (France) by comparing examples of wetlands nearby great rivers and determining a number of influencing factors. The removal of nitrates by plant uptake and regularly harvesting these plants as well as waterlogged soil or sediment with a microbially mediated reduction of nitrate (=denitrification) are important processes in wetlands, but this study is not focused on ‘denitrification processes’ as such. The Seine river (France) is 780 km long and has a temperate-oceanic regime, with high flow in winter and low flow in summer. In order to compare the nitrate removal results for the river Seine, a heavy N load zone between Poses (198 km from Paris) and Honfleur (355 km from Paris), with a distance of 157 km, as illustrated in figure 2 has been selected. The Seine river can be divided in a tidal (estuary) and non-tidal (from Poses to Paris) zone, with 4 main basins (upstream Seine, Marne, Oise and Eure rivers) and a dam about 100 km downstream, at Poses forms an obstacle to tidal water movement upstream (Cébron et al., 2003). The Seine river receives treated effluents of 10.106 inhabitants of Paris and its suburbs, as well as nitrogen from intensive agriculture activity (Servais et al., 2007). One of the main sources is the Archères WWTP downstream Paris. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 10 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Fig.2: Lower Seine river + estuaries (Cébron et al., 2003). The zone between Poses and Caudebec has already been studied, according to table 1, that shows total N input (Poses, Eure river and lateral point sources) and output (Caudebec) as well as denitrification rate as result of the difference between N input and output (in 103 kg N d-1) in the river Seine for the years 2000-2003 and differentiated between summer and annual (average) sampling (Garnier et al., 2006). Table 1: Total N input (from Poses, the Eure river and lateral point sources) and output (Caudebec) and denitrification rates obtained as a difference between summer and annual (average) sampling in the Seine river (estuary) in 103 kg N d-1. N input annual N output annual Denitrif. annual N input summer N output summer Denitrif. summer 2000 535 411 -124 299 248 -51 2001 537 462 -75 314 265 -49 2002 375 340 -35 171 142 -29 2003 272 243 -29 109 82 -27 More particularly, this study is focused on the zone between Caudebec and Honfleur, in the Seine estuary, provided with a number of wetlands or ‘wet zones’, like illustrated in the following figure 3. These zones are Grande Vasière Nord (1), characterized by intertidal mudflats, Marais du Hode (2) with reedbeds, Marais de la Risle (4) with river meadows, Marais Vernier (5) with marshy grassland, and Heurteauville, Grand-Mare(6) by peat (Beaumais & Laroutis, 2006). VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 11 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Fig.3 : Wet zones Seine (Beaumais & Laroutis, 2006). 1.4. Criteria for the results In order to evaluate the results of the nitrate removal processes in wetlands in this literature study, a number of criteria have been determined for comparing the characteristics of the study subjects. Firstly, this study needs a clear description of the characteristics of the types of wetlands for comparing the results within different rivers. Next, the nitrate removal results from different studies need to be discussed by critically comparing the measuring methods. Herewith, a division between field and laboratory studies as well as between the nitrate removal paths shall be made. Very often, modeling is used to determine and predict nitrate removal. Fourthly, for determining the impact of vegetation, a short overview will be given. Finally, the areas of the river Seine, that form part of this study will be described. 1.4.1. Terminology ‘wetlands’ Scientists disagree about the characteristics of a wetland due to dynamic processes and their boundaries. More than 50 definitions are used (Turner et al., 2000). A universally acceptable wetland definition has not yet been agreed. Generally, wetlands are defined as ‘intermediate areas between dry land and aquatic ecosystems with several characteristics common with both’ (Hogan et al., 2000). A buffer zone is a more general term. It is described as ‘a piece of land, often having rough or semi-natural vegetation, situated between agricultural land and a surface water body such as a river or lake, and acting to protect that water body from harmful impacts such as high nutrient, pesticide or sediment loadings that might otherwise result from land use practices. It offers protection to a water body through a combination of physical, chemical and biological processes, and some of the most beneficial processes for water quality improvement occur optimally in wetland’ (Hogan et al., 2000). VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 12 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Not all buffer zones are wetlands and not all wetlands act as buffer zones. Wetlands are frequently placed to interact with pollutants. Hydrological connectivity is important for the efficient operation of buffer zones (Maltby et al., 2005). Broadly, Hogan and colleagues (2000) divide river marginal wetlands in those located on floodplains and those on slopes. Floodplains are susceptible to flooding from a river or a stream, while slope units are at more distant locations from rivers or streams. Furthermore, ditches often occur around field margins, minor depressions, scrub or woodland. Backlands are often very wet soils, for holding overbank flooding from the river for prolonged periods and additionally provided with groundwater discharging from foot slope seepage zones. Figure 4 gives an overview of the different locations of wetlands along a river, according to the WFD Guidance Document no.12 (2003) (Maltby et al., 2005). Fig.4: Positions of wetlands in the landscape (Maltby et al., 2005). The Water Framework Directive 2000/60/EC (2003) define the following zones: Riparian zone: is defined as land immediately adjacent to a river and includes parts, like islands and floodplains. It further includes a variety of wetland habitats that rely on over-bank flows. Shore zone: land immediately adjacent to a lake. Intertidal zone: zone between high water spring and low water spring tides. River diversion wetland: a wetland on the adjacent floodplain or behind artificial levees that receives water by pumping or gravity flow from the main channel of a river and includes such floodplain features as oxbow lakes, backwater swamps and other riparian wetlands (Mitsch et al., 2005) Due to the Ramsar Convention (see introduction), a general division in wetland ecosystems is based on natural and constructed wetlands systems (CWS). Maltby and colleagues (2005) classify wetlands, established in artificial water bodies (AWB), as ‘constructed wetlands’ and defined as ‘a wetland which has been and which has not been created by the direct physical alteration of an existing wetland or water body’. Further, Heavily Modified Water Bodies and wetlands (HMWB) are ‘ones which as a result VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 13 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS of physical alterations by human activity are substantially changed in character and cannot, therefore, meet the ‘good ecological status’ (Water Framework Directive (WFD) 2000/60/EC, 2003). Fisher and Acreman (2004) define wetlands that show nutrient retention, those where the nutrient loading of waters that leave the wetlands is lower than the nutrient loading entering the wetlands. 50% of the international studies concerning wetlands and nutrient loading, originate from the US, while approximately 30% has been done in Europe (Fisher & Acreman, 2004). Our examples will be focused on these geographical areas with similar conditions as the river Seine. 1.4.2. Determining nitrate reduction rates in wetlands In order to measure and predict the removal of nitrates from rivers by wetlands, a number of distinctions have to be made. First of all, different measuring methods (1) or models (2) are used. Secondly, several ecosystems are differentiated by their vegetation (3) and the circumstances for the research. At last, in order to compare different environmental conditions retention, accumulation and conversion processes (4), according to 1.2, need to be mentioned. 1.4.2.1 Measuring methods Groffman and colleagues (2006) concluded that several methods for measuring denitrification vary greatly in different environments and at different scales. They evaluated 9 different methods. In the following table 2, we only mention the most frequently used nitrate measuring methods based on a number of literature citations in this study. Table 2: Overview of 4 nitrate measuring methods for wetlands with their references to a number of studies. Nitrate measuring method Short description Reference(s) Acetylene blockage Inhibit reduction N2O/N2 Olentangy River (US), Hernandez & Mitsch, 2007. Des Plaines River (US), Sirivedhin & Gray, 2006. Rhine River (DE), Venterink et al., 2003. Great Ouse River (UK), Machefert & Dise (2004). 15 N Tracer Labeling 15N to NO3Mississippi river (US), Kreiling et al., 2010. Mincio River (IT), Pinardi et al., 2009. Neva estuary (FI), Gran & Pitkänen (1999). Po/Oglio/Mincio (IT), Racchetti et al., (2010). Mississippi River (US), Yu et al., 2006. Seine River (FR), Curie et al., 2009. Mass balance N fluxes Estimating inputs/outputs Mississippi River (US), James et al., 2007; Kreiling et al., 2010; Mitsch et al., 2005 Stoichiometric Mass balance, comparing N 7 rivers Chesapeake Bay with C and P (US), Noe & Hupp, 2009. Delaware river (US), Patrick Center for Environmental Reasearch et al., 1998 VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 14 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS 1.4.2.2. Models A number of models have been developed to predict nitrogen fluxes in rivers. One of these models is the Seneque/Riverstrahler, which makes a difference between landscape and in-stream retention of N and further takes account of root zone processes, groundwater storage, riparian processes as well as sewage treatment, benthic denitrification and sediment storage. Table 3 illustrates the results (in kg N km-2 y-1) obtained by the Seneque/Riverstrahler model for the river Seine (Billen et al., 2009). Table 3: Budget of nitrogen transfers in the river Seine, according to the Seneque/Riverstrahler model for dry (1996) and wet (2001) conditions (in kg N km-2 y-1). Process Root zone Groundwater storage Riparian Benthic Sediment storage River export Total retained in Seine Dry conditions 2875 360 525 135 65 1380 3960 Wet conditions 885 710 1160 105 2310 2925 Another, more simplified model is NANI (= net sum of anthropogenic nitrogen inputs) (in kg N km-2 y-1 (1 km2 = 100 ha)). Howarth and colleagues (1996) proposed the following relationship: Nflx = 0,26 x NANI + 107 and retention = 1 – Nflx/NANI = 1 – (0,00087 x Q – 0,096) and whereby Nflx is the flux of riverine nitrogen exported at the outlet, a fraction (0,26) of the anthropological nitrogen input that is transferred by the river at the outlet and an independent term (107), exported by the river and Q as precipitation or discharge. Billen and colleagues (2009) found a total N retention in the river Seine of 4015 kg N km-2 y-1, which is comparable to the Riverstrahler model. This is illustrated in the following table 4. Table 4: Billen and colleagues (2009) used the available data for the Seine, Somme and Scheldt to test the NANI model and found, in comparison with the Riverstrahler, quite applicable results (table 3). VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 15 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS 1.4.2.3. Nitrate removal In order to compare results from studies with denitrification rates, several nitrate removal processes need to be discussed. A difference has to be to be made between accumulation or retention and conversion or transformation of nitrates. Accumulation or retention means that nitrates in the wetland ecosystem will be stored and hold in the biomass of the vegetation or absorbed in sediments or soils, in contrary to the conversion or transformation to N2O and/or N2. Transformation, immobilization or elimination of nutrients is one the most important functions of ecosystems (Meire et al., 1998). Vegetation can take up nitrates of which a part will be stored in the roots and another part will be liberated due to leaching. Only the removal of the upper part of the plants decreases the nutrient loads in the wetlands (de Vries, 2002). Finally, nitrates can also be stored in groundwater or aquifers. Within the framework of this study, a broader term, namely ‘retention’ will be used. It is according to Billen and colleagues (2009) defined as ‘immobilising reactive nitrogen by storing into a long residence time compartment or to eliminate it by conversion into the non-reactive atmosphere form’. 1.4.2.4. Vegetation Vegetation is an important factor for wetlands, especially for the storage of nutrients in biomass (Hogan et al., 2000). Figure 5 shows the difference between emergent, floating and submerged plants. Fig.5: Plants in wetlands in Dutch, from top to bottom: emergent, floating and submerged (Van Ballaer et al., 2006). Emergent aquatic macrophytes or helophytes are characterized with their roots in the sediment, such as reed (Phragmites australis), broadleaf cattail (Typha latifolia), reed sweetgrass (Glyceria maxima). Marsh or swamp vegetation comprises aquatic floating plants, divided in macrophytes with floating roots or rooted plants, such as common duckweed (Lemna minor), water hyacinth (Eichlornia crassipes), white waterlilly (Nympaea alba). At last, submerged plants depend on oxygen-rich environments with their roots in the sediment, like curly-leaved pondweed (Potamotegon crispus) or American shoreweed (Littorella uniflora). The following table 5 shows the results from 4 studies with nitrate removal or retention and denitrification results (in kg N ha-1 y-1) with plants for some rivers or laboratory conditions (microcosms). For some, a comparison is made with accumulation in bare sediments or soils with floodplains. The results of these studies illustrate that retention with vegetation do not always give the best performance rates. It depends on the kind of vegetation and the environmental conditions. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 16 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Table 5: 4 studies with nitrate accumulation/retention in vegetation (in kg N ha-1 y-1). river/lake or microcosms Mississippi backwater lake (US) Vegetation Retention /denitrification (with vegetation) 108 Floodplains/ Sediments (without vegetation) 1067 Ceratophyllum demersum (submerged macrophyte) Rhine river Flooded 55 (DE) grasslands and reedbeds (emergent macrophyte) Mincio river V. Spiralis 389 304 (IT) (submerged meadows) 18 Floating: 24529* 4905-8585* microcosms Lemna sp. (duckweed) 3679-12264* Submerged: Elodea nuttallii (waterweed) * μmol N m-2 h-1 has been converted to kg N ha-1 y-1 (extrapolation to accumulation/denitrification) reference Kreiling et al., 2010 Venterink et al., 2003 Pinardi et al., 2009 Veraart et al., 2010 annual 1.4.3. The river Seine estuary or basin For comparing a number of rivers with wetlands for nitrate removal, similar characteristics of the river Seine have to be selected. Downstream of Paris, the Seine river is a 7th order river (see figure 6), with a catchment of 44.000 km2 (Garnier et al., 2006) and receives, downstream Paris, a number of rivers, like Marne, Oise and Eure. Fig.6: river order (Strahler, 1957) - http://www.marietta.edu/~biol/biomes/streams.htm (05/12/10) Regarding the target of this study (see point 1.3), the estuarine part of the river Seine in particular two zones with wetlands between Caudebec and Honfleur, is selected to be compared with some international examples. These wetlands are influenced by 1) natural processes and 2) human activities (Alard et al., 2002). The first zone is located in the estuary nearby Honfleur and consists of ‘Marais du Hode’ and ‘Grande Vasière Nord’, illustrated by figure 7. This zone is characterized by wetlands, connected with the Seine. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 17 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Both marshes are characterized by improved denitrification due to subhalophilous grasslands (1) and lesser denitrification in the reed soils (Chabrerie et al., 2001; Alard et al., 2002). They are partially connected to the Seine via a network of ditches, a sluice (2) and openings in a dam (3) in order to drain Seine water. Furthermore a number of creeks connect the river Seine with reed (Phragmites australis), mudflats (4) and an artificial meander (5). Marais du Hode covers an area of 58 km2 (= 5800 ha). 1 2 5 4 3 Fig. 7 : Marais du Hode and Grande Vasière Nord http://seine-aval.fr/ (cd-rom Seine-Aval). A second zone is located closer to Caudebec and comprises ‘Grande-Mare’, ‘Marais Vernier’ and ‘Marais de la Risle’, shown in figures 8 and 10. Grande-Mare is a pool of the Marnier Vernier, connected with the river Seine via the Canal St-Aubin and further with Petit-Mare (figure 9). VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 18 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS 6 7 8 Fig. 8: Marais Vernier http://seine-aval.fr/ (cd-rom Seine-Aval). A number of local reedbeds (6) is located close to the riverside and for some spots; the draining of the river water is regulated by a valve (7). Marais Vernier (8) is the largest remaining wetland system in the lower Seine Valley and is about 4500 ha (Frouin et al., 2006). VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 19 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Fig.9: Grande Mare, connected with the Seine via St-Aubin Canal (Alard et al., 2000). 9 10 Fig.10: Marais de la Risle (cd-rom Seine-Aval). 350 ha of floodplains (mudflats) in the Risle valley are frequently subject to tidal flooding (Bessineton, 2007). This zone is further characterised by isolated wetlands, like ponds or pools (9,10). VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 20 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS 1.5. Conditions Besides the important ecological functions of wetlands, legal, economic and financial aspects for realizing projects have to be taken in consideration. When examining the opportunities for implementing or restoring wetland ecosystems for the river Seine, these aspects have to be calculated within strategic environmental projects. 1.5.1 Legal framework The control of nitrate inputs into the environment, including wetlands, is regulated by the EC Nitrate Directive (91/676/ECC) (Kennedy & Murphy, 2004). An example is the aquifer of Vitoria-Gasteiz (Spain), of which the wetlands (Zurbano wetland) have been restored through the closure of main drainage ditches due to the 91/676/CEE European directive (Garcia-Linares et al., 2003). In the Water Framework Directive, wetlands are not recognized as water bodies per se, but as groundwater bodies or surface water bodies (Merot et al., 2006). The following table 6 gives a summary of the legal framework and non-legal initiatives or projects to assess the role of nutrients in surface waters primarily and the protection of wetlands otherwise. Table 6: Overview legal framework or non-legal initiatives Legal framework Ramsar Convention (1971) Nitrate Directive Second Water Law (1992) EVALUWET (EU project) Water Framework Directive (WFD) 2000 Performance ranges denitrification (Janssen et al., 2005) nutrients >50 mg/l nitrate Water agencies SDAGE • • • wetlands Protection Impact International 91/676/ECC France Ecological functions (WEDSS) Protection High: 10<x<300 kg N ha-1 y-1 Medium: 10<x<80 kg N ha-1 y-1 Low: 5<x<15 kg N ha-1 y-1 EU 2006/60/EU Into new France law With respect to table 6, in this work, only the performance ranges of denitrification, according to Janssen et al. (2005), will be used to evaluate denitrification rates. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 21 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS 1.5.2 Economical/financial The following figure 11 shows the relationship between the ecological and societal context. Several stakeholders calculate, due to the multiple functions of wetlands the benefits for a future strategy. Fig.11: ecosystem services (Maltby et al., 1996; de Groot et al., 2006; Haines et al., 2006, McInnes, 2007). Identifying stakeholders is important to define the functions and the economic value of wetlands. They can be divided in direct extensive and intensive users, agriculture producers, water abstractors, human settlements, indirect users, nature conservation groups and nonusers (Turner et al., 2000). According to EVALUWET, economic analysis of a wetland is an assessment of the functions (Maltby et al., 2005). Tuner and colleagues (2000) refer to the lack of a market for wetland functions and therefore limit the incentive to maintain the wetland. Nevertheless, some wetlands offer some incentives for human consumption, like potential energy by peatlands (Oquist & Svensson, 1996). Schuyt & Brander (2004) calculated the value for a number of wetlands, based on 89 wetland valuation case-studies (Maltby et al., 2005). Unvegetated sediments and freshwater wooded wetlands are identified as having the highest values per unit area, due to their goods and services, like recreation and the wood industry. Merot and colleagues (2006) refers to the PEEW approach (potential, existing and efficient wetland). Potential wetlands are defined as areas which retain the geomorphologic and soil features of wetlands, but are isolated from the river due to artificial drainage and river straightening. Wetlands existing at a given time (soil moisture ascertained) can be defined as existing wetlands. According to a given function (runoff control, water quality, biodiversity,…) wetlands can be defined as efficient wetlands. The foregoing is important to construct or restore wetlands in close relationship to polluted rivers. Four kinds of human implemented wetlands have been identified by Maltby and colleagues (2005): o Constructed wetlands o Created wetlands o Degraded wetlands o Restored wetlands Constructed wetlands are created in locations where no wetland existed before. Low cost, low energy and require no chemical additions for the treatment of water. Contrarily, created wetlands have the objective to simulate all aspects of natural wetlands. Modifications of water bodies, like straightening, embanking and widening result in degradation of riparian wetlands. They’re called degraded wetlands. At last, repairing wetlands to their natural condition or an enhanced situation relative to their degraded condition are called restored wetlands. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 22 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS 2. Methods In a first step, a literature search on the internet has been executed to identify the different kinds of wetlands and further a selection has been made to identify by a few examples of rivers, comparable to the river Seine. These examples are assessed by comparing a number of parameters as identified in point 1.5. Finally, the results are reflected in relation to the characteristics of the river Seine (France). 2.1 Literature search With the objective to give 1) an overview of the different types of wetlands 2) a few examples of denitrification results with wetlands in rivers and 3) an overview of influencing environmental factors, in a first step, a keyword search on the internet was undertaken to identify scientific articles. The following keywords have been used separately or combined: ‘nitrate’, ‘nitrification’, ‘denitrification’, ‘ecosystem’, ‘river’, ‘wetland’, ‘estuarine’, ‘floodplain’. A second step consists of identifying the opportunities for the implementation of wetlands near the river Seine (France). In this literature, a number of rivers with comparable conditions of the Seine are selected. The articles have been selected from the following databases ‘PubMed’, ‘ScienceDirect’, ‘Wiley Online Library’, ‘ESA Online Journals’, ‘SpringerLink’ and ‘Hydrology and Earth Systems Sciences (HESS)’. Full-text articles are ordered in our internal library and examined. CNRS offered a number of full-text journals and a CD-rom of the Seine. 2.2 Analysis 2.2.1 Study area In this work, 8 different studies with river-wetland relationships are compared. Different types of wetlands (3 in EU and 5 in the US) will be evaluated in relation to the criteria and their relevance to the river Seine. The following references are used: country, name and river order, author(s), surface, type and origin of wetland (see 1.4.1), climate, hydrological, location and N fluxes, duration and/or period, measuring (see 1.4.2.1), vegetation (see 1.4.2.4). For Europe, 3 studies: the Great Ouse River (UK) (Machefert & Dise, 2004), the Neva estuary (FI) (Gran & Pitkänen, 1999) and the rivers Po/Mincio/Oglio (IT) (Racchetti et al., 2010) were selected. For the US, the following 5 studies were selected: Mississippi (Davis Pond-Louisiana) (Yu et al., 2006), 7 rivers of the Chesapeake Bay watershed (Noe & Hupp, 2009), a comparison of Olentangy river (Ohio) and Caernarvon wetland (Mississippi/Louisiana) (Mitsch et al., 2005), Delaware river estuary (Patrick Center for Environmental Reasearch et al., 1998) and Mississippi (Finger lakes) (James (2010)). These rivers were primarily selected on their different types of wetlands and secondly on their relevance for implementing in the estuary of the Seine river. A detailed table (enclosed as annex A), gives an overview of the several characteristics of the rivers and their wetlands. Hereafter, their relevance in relation to the estuary of the Seine river will be shortly explained. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 23 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS • Estuary denitrification rates and the influence of tidal flooding are characteristics of The Neva estuary and the estuary of the Delaware river, with an upper and lower zone. Furthermore the impact of emergent aquatic vegetation will be examined for the latter (see figure 12) Fig.12: Delaware (Patrick Center for Environmental Reasearch et al., 1998). Mantua Creek is the lower zone (619 ha marsh) and Rancocas Creek forms the upper zone (793 ha marsh). • • Floodplains, their surface and position for N retention is important in the Great Ouse river and the 7 rivers of the Chesapeake Bay watershed. The % water filled pore space (WFPS) is also important in the former. Connected wetlands with a river are described in diversion wetlands of the Mississippi river like Davis Pond (figure 13), Olentangy/Caernarvon (figure 14) and the backwater of Finger Lakes. Experimental connected and isolated wetlands are compared in the rivers Po-MincioOglio. Hydraulic connectivity, vegetation and residence time are compared. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 24 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Fig.13: Davis Pond, Mississippi river (Yu et al., 2006). Davis Pond is a freshwater marsh, connected by an inflow channel with the Mississippi river and outflow via Lake Cataouatche. Fig.14: left: Olentangy River; right: Mississippi river, Caernarvon (Mitsch et al., 2005) For the Olentangy river, a diversion wetland basin has been created, while for the Mississippi river, the diversion wetland Caernarvon has been restored. 2.2.2 Evaluation and models The nitrogen removal/retention will primarily be evaluated by using the performance ranges denitrification scale by Janssen et al.(2005), mentioned in point 1.5.1. The results of the denitrification/retention/removal of the several studies were converted to kg N ha-1 y-1 for comparison. Furthermore in 6 of the 8 studies with river/wetlands, a denitrification model was used and in all studies, denitrification rates were based on estimations. Next, the NANI model (see point 1.4.2.2) will be used to compare the calculated ‘theoretical’ retention and the results obtained in the studies. The NANI model uses kg N km-2 y-1 (Howarth et al., 1996; Billen et al., 2009). In order to compare results: μmol N m-2 h-1 need to be converted, 1 μmol N = 1.10-6 mol N = 1.10-6 x 14 g/mol = 0,000014 g = 0,000000014 kg; km2 = 1.106 m2; 1 y = 365 d = 8760 h. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 25 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS The nitrate removal results of the different studies will be converted into kg N ha-1 y-1 or kg N km-2 y-1. Based on the results, environmental conditions will be discussed and evaluated in the framework of the results found in the river Seine (see table 1: Garnier et al., 2006) 3.Results 3.1 Inventory of types of wetlands In this study, five ways of typing the kinds of wetlands (categories) (I→V) have been identified. Each category has a number of types and subtypes, as shown in table 7. Table 7: Overview inventory wetlands Category Origin (I) Habitats (II) Types -Natural (a) Subtypes -Inland (non-tidal)(1) -Coastal (tidal)(2) -Artificial (b) -Constructed (1) -Created (2) -Degraded (3) -Restored (4) -Grass (1) -Woodland (2) -Scrub (3) -Fen (4) -Ecological (a) -Vegetation type (1’) -Primary production (2’) -C cycling (3’) -Nutrient cycling (4’) Landscape (III) -floodplain (a) -valley slopes (b) -flat area (c) -slope (d) -depression (e) -valley bottom (f) -Unvegetated (1’’) -Freshwater wood (2’’) -Salt/brackish marsh (3’’) -Freshwater marsh (4’’) -Mangrove (5’’) -depressions (+ditches) (1) -backland (+ditches) (1) -flat upland (1) -flat lowland (2) -surface water (1) -ground water (2) -surface water (1) -groundwater (2) -surface water (1) VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 26 van 50 Reference(s) Boudreau et al., 2004 Bruland et al., 2006 Commonwealth (2001) Maltby et al., 2005 Hogan et al., 2000 Wheeler & Shaw, (2000) ; Maltby et al. 2005 Gosselink & Turner (1978) ; Maltby et al. 2005 Maltby et al., 2005 ; Schuyt & Brander (2004) Hogan et al., 2000 Maltby et al., 2005 Bullock & Acreman, 2003 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS -coastal (g) -underground (h) Hydrology (IV) -over-bank flooding from river (a) -high levels of groundwater (b) -groundwater (2) -surface water (1) -groundwater (2) -groundwater (1) -slope (outlet contact with river) (1) -depression (outlet no contact with river) (2) -precipitation (1’) -evapotranspiration (2’) -runoff (3’) -lateral inflow (4’) -drainage (5’) -over bank flow (6’) -out flow (7’) -pumping (8’) -tidal inflow (9’) -tidal outflow (10’) -spring (11’) -slope (outlet contact with river) (1) -depression (outlet no contact with river (2) -groundwater discharge (1’) -groundwater recharge (2’) -groundwater seepage (3’) Regional (V) (biogeochemical) -seasonal (a) -flooding (b) -temperature (1) -water table height (2) -rainfall (3) -sunlight (4) -plant activity (5) -sediment (1) deposition -trace elements (2) storage in floodplains VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 27 van 50 Bullock & Acreman, 2003; Hogan et al. 2000 Acreman (2004); Maltby et al., 2005 Bullock & Acreman, 2003; Hogan et al. 2000 Acreman (2004); Maltby et al., 2005 Maltby et al., 2005 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS 3.2 Denitrification results and wetlands in rivers The following table 8 gives an overview of the denitrification removal rates in the 8 studies with wetlands (mentioned in 2.2.1) and associated with the codes of these corresponding wetland types according table 7. Table 8: Overview N retention/removal rates in 8 wetland/river relationships River Wetland type (3.1) Great Ouse (UK) Neva estuary (FI) Po/Mincio/Oglio (IT) IIId1 Mississippi (Davis Pond) (US) Chesapeake Bay watershed (US) – 7 rivers Ia2 IVa1 (C) IVa1’(I) IVa3’(I) IVb1’(I) IVa8’ IIa4’’ IIIa IIa2 Olentangy (US) Ib2 IVa8’ Mississippi (US) Ib4 IVa8’ Delaware river (US) IIa4’’ IVa9’ Mississippi (Finger Lakes) (US) IIIb1 N retention/ removal/denit. (kg N ha-1 y-1) (s)* (m)** Target Important 5 (mid/top) 71,7 (bottom) 0,4 (inner) 64,2 (outer) 43-2315 (C) 2,4-283,3 (I) N2/N2O WFPS (>70%) Slope/River Sediment 147 1,5 % N2O emission retention 4749 ha – 93 (s) 307 ha – 36 (m) 1707 ha – 70 (s) 2132 ha – 76 (m) 1668 ha – 44 (m) 2856 ha – 44 (m) 3674 ha – 54 (s) 1 ha - 390 (average) NH4+ Denitr. Summer > winter Surface wetland 2,6 ha - 460 (average) Lower: 1654 (Mantua Creek – 256 ha/4,3 RM***) Upper: 28710 (Rancocas Creek – 466 ha/15,3 RM) 500 -Water retention time -Temp. Surface floodplain Emergent aquatic vegetation (EAV) retention NH4+ * (s) SPARROW watershed model ** (m) measured *** RM river miles VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 28 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS With the nitrate removal results from the 8 studies, I constructed the following graph (figure 15). One result (Rancocas Creek) is not included in this graph, due to the extreme high value. Denitrification results in 8 rivers with wetlands (EU/US) kg N /ha/y 2500 2000 1500 1000 500 7,5ha Lower Connected 1ha 2,6ha 3800ha Isolated 4749ha 2132ha Bottom 1707ha Outer estuary 1668ha 2856ha 307ha 3674ha Top Mid Inner estuary Finger Lakes Po/Mincio/Oglio Neva Delaware Great Ouse Chesapeake Davis Pond Olentangy Caernarvon 0 Fig.15: Graph with comparison of denitrification/retention rates in 8 studies (Rancocas Creek (Delaware river) is not mentioned in this graph). The precedent graph (fig.15) shows on the right hand side, the best nitrate removal results, observed in the 8 studies. Connected wetlands (Racchetti et al., 2010) and the lower marsh of the river Delaware (Patrick Center for Environmental Reasearch et al., 1998) gave the best nitrate removal results, respectively followed by the 7,5 ha backwater of Finger Lakes (Mississippi river) (James (2010)), diversion wetland Caernarvon (Mississippi river) and pumping water from Olentangy river (Mitsch et al., 2005), according to the performance ranges of Janssen et al., 2005 (see point 1.6.1). Hence, the N removal results were far above the maximal performance range, namely 300 kg N ha-1 y-1. The Chesapeake Bay floodplains gave denitrification results between 40 and 100 kg N ha-1 y-1 which is still in the high performance range of Janssen et al. (2005). The inner Neva estuary showed the lowest nitrate removal results (Gran and Pitkänen, 1999). Next, a more detailed analysis of the nitrate removal results will be illustrated. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 29 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Connected and isolated wetlands (cat. IV (table 7)) When comparing the nitrate removal results (fig. 15) of connected (Davis Pond, Olentangy, Caernarvon, Finger Lakes, Po/Mincio/Oglio) and isolated (Po/Mincio/Oglio) wetlands, a more favorable position is found for the first category. The connected wetlands, related to the Po/Mincio/Oglio (Racchetti et al., 2010) are identified as ‘over bank flooding with slope, connected with the outlet to the river’. The nitrate removal results are two orders higher than with the isolated wetlands, categorized as ‘over bank flooding with precipitation and run-off’ or as ‘high groundwater level and discharge’. Furthermore Racchetti and colleagues (2010) found that during summertime (2007), the anoxic sediment denitrification was higher than coupled denitrification/nitrification. Mitsch and colleagues (2005) calculated better nitrate removal results for connected wetlands of the Mississippi, a 9th order river (Caernarvon), than for the Olentangy river (4th order river), knowing that the surface area of the first is at least twice the surface of the latter but with a higher N load for Olentangy. They found respectively a retention of 55 and 35 %. At Davis Pond (Mississippi), Yu and colleagues (2006) determined a denitrification rate in a forested marsh, connected to Lake Cataouatche (fig.13) and calculated at a concentration of 1 mg N l-1, 147 kg N ha-1 y-1 removal and 1,5 % N2O production. Furthermore respectively, 96 and 48 % nitrate reduction was calculated when water passed through the marsh at 25 m3 s-1 and 78 m3 s-1. Figure 16 illustrates the pumping of river water in the wetlands, related to Mitsch and colleagues (2005) and Yu and colleagues (2010). Fig.16: connected wetlands, pumping (Maltby et al., 2005) Finally, James (2010) measured a denitrification rate of 500 kg N ha-1 y-1, with a nitrate load of 931 kg N ha-1 y-1 and an output of 431 kg N ha-1 y-1. This results in an efficiency of 54%. 86% was covered by floating Lemna sp., 21% by N. odorata and between 46 – 65% by C. demersum. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 30 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Floodplains (cat. III (table 7)) Figure 17 shows a number of floodplains, according to the Great Ouse river and the Chesapeake Bay. Fig.17: Backland depression and floodplain (Maltby et al., 2005). Machefert and Dise (2004) found that annual denitrification was about 15 times higher near-stream (= bottom) (Great Ouse river) than higher up the slope (= top) of the floodplains. Generally, they concluded that for high denitrification rates, a threshold moisture of about 65 – 70% WFPS has to be reached. Noe and Hupp (2009) found a positive correlation between the surface area of the forested floodplains and the nitrate accumulation rates. Figure 18 was constructed with the results of table 8 to show a relation between surface area and nitrate removal rates. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 31 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Nitrate removal results: Chesapeake floodplains 5000 4500 4000 surface area (ha) 3500 3000 2500 2000 1500 1000 500 0 0 10 20 30 40 50 60 70 80 90 100 nitrate removal (kg N /ha/y) Fig 18: relationship between nitrate removal (kg N ha-1 y-1) and floodplain surface area (ha) (data source: Noe & Hupp (2009)) Estuaries (cat. I (table 5)) Mass balance calculations indicate a denitrification rate of 50 kg N ha-1 y-1 for the Neva estuary. When comparing inner and outer estuary, Gran and Pitkänen (1999) found respectively, 0,4 kg N ha-1 y-1 (redox 26 mV) denitrified and 44,9 kg NH4+ ha-1 y-1 outflux and 64,2 kg N ha-1 y-1 (redox 457 mV) denitrified and 5,4 NH4+ ha-1 y-1 outflux. Very ‘important’ denitrification results were found in the upper zone of the Delaware river, the Rancocas Creek. 20,4 mg N g-1 dw has been measured in low marsh (Nuphar advena), and 12 mg N g1 dw in high marsh (Zizania aquatica, Typha sp., Phragmites australis), while similar results were measured in the lower zone (Mantua Creek). Generally, Patrick Center for Environmental Reasearch et al., 1998 measured between 0,5 and 131 kg N RM-1 d-1 (av.65 kg N RM-1 d-1) incorporated in biomass. Respectively for Rancocas, 51 kg N ha-1 y-1 (466 ha = 15,3 RM) and for Mantua, 91 kg N ha-1 y-1 (256 ha = 4,3 RM). NANI model I calculated the river nitrate flux (Nflx) (see 1.4.2.2) by using the NANI model in order to compare the nitrate removal results for the rivers Olentangy and Mississippi (Mitsch et al., 2005) and for Finger Lakes (James (2010)). I only used the nitrate input loads, cited by the authors, which is not necessarily the total anthropological input. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 32 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS For the Olentangy river, Nflx = 0,26 X 108000 + 107 = 28187 kg N km-2 y-1 is calculated with the NANI model, while Mitsch et al., 2005 calculated a river output of 70200 kg N km-2 y-1. For the Mississippi river, Nflx = 0,26 X 84000 + 107 = 21947 kg N km-2 y-1 but a river output of 37800 kg N km-2 y-1 determined by Mitsch et al., 2005. For Finger Lakes, with the NANI model, Nflx = 0,26 X 93075 + 107 = 24307 kg N km-2 y-1 and James (2010) calculated a river output of 43070 kg N km-2 y-1. The Nflx results obtained with the NANI model were much lower than the observed results by the authors, which means that the calculated results by the NANI model overestimate the retention rates. 3.3 Influencing factors for denitrification: Before listing the potential factors that could influence nitrate removal, regarding this literature study, I compare the nitrate budget results from Kreiling and colleagues (2010) for Third Lake (Finger Lakes, US) with the nitrate budgets of the Riverstrahler model for the Seine River (Billen et al., 2009). The following graphs (fig.19) show that for Finger Lakes (left graph), the plant uptake (=root zone) and the denitrification/nitrification coupling are of minor importance for nitrate removal in relation to discharge and sediment uptake, compared to the right graph, based on calculations by the Riverstrahler model for the Seine. Budget of nitrogen transfers in the Seine (FR) according to the Seneque/Riverstrahler model Nitrate mass balance estimation in a Mississippi backwater lake: Finger Lakes (US) 17% 2% 39% 45% 53% 27% 10% SEDIMENT 1% 6% ROOT ZONE NITR/DENITR DISCHARGE AQUIFERS IN STREAM ROOT ZONE SEDIMENT DISCHARGE Fig.19: left graph shows the nitrate mass balance for Finger Lakes (US), a Mississippi backwater lake (data source: Kreiling et al., 2010); in this model, aquifers and in stream nitrate removal are not explicitly considered; right graph illustrates the Seneque/Riverstrahler model for the Seine (FR) (data source: Billen et al., 2009); nitrification-denitrification coupling is not independently considered. a) climate, season and temperature: Mitsch and colleagues (2005) explain the higher denitrification rate of the Mississippi river compared to the Olentangy river due to the subtropical climate with higher temperatures and a longer growing season for vegetation. Racchetti and colleagues (2010) also found significantly higher denitrification rates in summer than in winter. Yu and colleagues (2006) mentioned also the importance of the temperature in relation to the biological reaction rate. Sirivedhin & Gray (2006) found a higher sediment denitrification potential at 25°C than at 4°C, but in relation to a higher nitrate concentration. In general, denitrification rates increase with higher temperatures. b) wetland surface area: Three determinants have been identified, namely, the distance from the river and the soil volumetric water content (Machefert and Dise, 2004), as well as the floodplain surface (see fig.18) (Noe and VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 33 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Hupp, 2009). Furthermore, they found that for larger riverine loads a smaller proportion of that load was retained on the floodplains. Mitsch and colleagues (2005) indicated that a removal of 40% of total nitrate, requires the creation or restoration of 22000 km2. Mainly, a larger wetland surface area enhances nitrate retention, but is dependent of the N load. c) vegetation: James (2010) suggested that biotic uptake (C. demersum and Lemna sp.) was responsible for retaining nitrate, because denitrification was only responsible for 57 %. Fig.20: Comparison of denitrification in different vegetation conditions (Veraart et al., 2010) Another study showed that the highest denitrification rates were observed under a closed mat of floating macrophytes (upper graph in fig.20), with low oxygen conditions and nitrate removal was dominated by plant uptake (Veraart et al., 2010). Nitrate retention can thus be directly related to vegetation by uptake or indirectly by the creation of favorable conditions by the plants. Vegetation will preferentially assimilate ammonium over nitrate (Kreiling et al., 2010). d) water velocity and retention time: A lower water velocity (25 m3 s-1) in the wetland resulted in a 96 % nitrate reduction, while at 78 m3 s-1 only a 48 % reduction was measured. For a retention time of 1 to 5 days in the wetlands, respectively 42, 68, 82, 90 and 95 % of the nitrate was removed (Yu et al., 2006). Venterink et al. (2003) suggested that a low N retention in the deep and fast flowing River Rhine may be explained by a very low contact time between river nitrate and sediment. Sirivedhin & Gray (2006) observed a greater nitrate removal in a shallow, young and well-mixed constructed wetland. Apparently, a strong correlation between a lower water velocity and a longer water retention time with increasing N retention capacity was found. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 34 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS e) hydraulic connectivity: Racchetti and colleagues (2010) showed that within connective wetlands, denitrification was mainly determined by nitrate diffusing into anoxic sediments from the water column. Nitrate influx to sediment were greater in anoxic versus oxic conditions (James (2010)). Fig.21: Comparison of denitrification between sediment and periphyton (Venterink et al., 2003) Denitrification reached maximal rates in oxygen-poor flooded sediment’, but no great differences were found between reedbeds and grasslands, according to fig.21 (Venterink et al., 2003). Improved denitrification is related to hydraulic connectivity by oxygen-poor flooded sediments. f) redox potential: In the outer Neva estuary, higher denitrification rates were determined at higher redox potentials and lower ammonium fluxes (Gran & Pitkänen, 1999). Based on the results of Gran & Pitkänen (1999), a relation can be observed between the location in the estuary (inner/outer), the redox potential and the denitrification rate (fig. 22). VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 35 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Ratio redox and denitrification in the inner and outer Neva estuary 600 500 Denitrification (mg N m-2 d-1) 400 300 inner outer Linear (outer) Linear (inner ) 200 100 0 0 2 4 6 8 10 12 14 -100 -200 redox (mV) Fig.22: Comparison of redox and denitrification rate in the inner (blue line) and outer (pink line) Neva estuary (FI) (data source: Gran & Pitkänen, 1999). NH4+ efflux from the sediment was highest in anoxic conditions (18469 kg km-2 y-1), compared to oxic conditions (9746 kg km-2 y-1) in Finger Lakes (James (2010)). This is probably due to a nitrification process in oxic sediments. Brion and colleagues (2000) observed decreasing ammonium concentrations in the Seine estuary and increasing nitrate concentration. A higher redox potential and lower ammonium concentrations improve denitrification in the estuary due to higher nitrate availability, which is confirmed by fig.22. 4.Discussion en Conclusions 4.1 Conclusions In this work, 8 studies with river-wetland relationships, 3 wetland types were identified with a high nitrate removal performance, in decreasing performance order: connected, floodplains and estuary wetlands. More specifically, according to table 7, these wetlands are identified as over bank flooding with a slope (IVa1), freshwater marsh (IIa4’’) with tidal inflow (IVa9’), floodplain depressions (IIIb1), woodland (IIa2) and coastal wetlands with tidal influence (Ia2). In addition to that, nitrate removal or denitrification rates in these 8 studies were estimated by using models and based on extrapolations. The NANI model that I used for 2 calculations showed higher retention rates than observed in the studies. VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 36 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Within this study, a number of factors that could influence nitrate removal have been cited by a number of authors. I scheduled (fig.23) these factors in relation to the type of wetland. created connected restored velocity vegetation retention time wetlands surface area floodplains estuary distance anoxic redox oxic Fig.23: Schematic overview of the wetland types (green) identified in this study and their characteristics (blue), oxygen status (orange). The connected wetlands in this study showed a high nitrate removal performance, which was less for isolated wetlands. Related to the nitrate removal performance of these connected wetlands are water velocity, contact time and retention. Lower water velocity in the wetland enhances the nitrate reduction (Yu et al., 2006). A very low contact time between the river nitrate and the sediment could reduce the nitrate retention (Venterink et al., 2003). Vegetation and biotic uptake are able to retain nitrate (James, 2010; Veraart et al., 2010). However, Venterink and colleagues (2003) found no great differences in nitrate removal between reedbeds and grasslands. High nitrate removal has also been observed in floodplains, in relation to a relative great surface area and close to the riverside (Noe and Hupp, 2009). They further observed that the larger the nitrate load, the smaller the retention on the floodplain. Oxygen poor flooded sediment showed the best denitrification rate (Venterink et al., 2003). This also illustrated in the model by Kreiling et al., 2010 in Finger Lakes (fig.19) with a major impact of the sediment nitrate removal, compared to biotic and nitrification-denitrification coupling. In estuaries, these zones with a higher redox potential and lower ammonium fluxes showed an important denitrification performance (Gran & Pitkänen, 1999). Low marsh (Nuphar advena) showed better denitrification results than high marsh (Zizania aquatica, Typha sp., Phragmites australis) (Patrick Center for Environmental Reasearch et al., 1998). The Seine estuary from Caudebec to Honfleur has already a number of created or restored wetlands. Nevertheless, I did not find nitrate removal performance results for this zone. Brion and colleagues (2000) mentioned an increasing nitrate concentration and a decreasing ammonium concentration in the Seine estuary up to Caudebec. This could indicate that in this oxygen rich zone, ammonium conversion has been executed by nitrifying bacteria. Otherwise, in estuary sediments, vegetation preferentially assimilates NH4+ over NO3- (Kreiling et al., 2010). Furthermore, VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 37 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS temperature plays a role in the performance of biological processes and could so influence nitrate removal. 4.2 Discussion Referring to the nitrogen pathways (fig.1) denitrification and nitrate retention/removal are influenced by a number of processes like nitrification/denitrification coupling, microbial transformation, sediment absorption and plant uptake. Arrigoni and colleagues (2008) stated that observed nitrate removal may be due to multiple processes and different controlling factors. Plant uptake, microbial immobilization and denitrification are all functioning at high rates in tidal wetlands. Sirivedhin & Gray (2006) also confirm that a variety of factors influence the process of denitrification but that it is impossible to provide a rank order of importance. When comparing the different nitrate removal processes in relation to the characteristics of the wetlands that have been identified in this study and the wetlands in the estuary of the Seine River (from Caudebec to Honfleur), a number of similarities could be found. Eventhough, the relationship between the different factors is difficult to determine, an attempt to indicate important factor will be given below. Denitrification is determined by available nitrate, reduced oxygen conditions and electron donors. This means a sufficiently nitrate load, anoxic or suboxic conditions and the availability of organic matter. Furthermore, environmental conditions (anaerobic and aerobic) determine the coupling denitrification/nitrification. Like already stated in the beginning of this study, Maltais-Landry and colleagues (2009) mentioned that, due to limited oxygen diffusion in constructed wetlands, nitrification is often the limiting step in the denitrification process. In order to improve the balance between oxic and anoxic conditions, a number of environmental conditions have been adapted, like in restored or created wetlands. In the Des Plaines River Wetlands Demonstration Project (DPRWDP)(US), shallow and young, wellmixed constructed wetlands showed consistently greater nitrate removal than mature, less-mixed wetlands (Sirivedhin & Gray, 2006). This is also mentioned by Fisher and Acreman (2004), referring in their study to the percentage of nutrient removal, that is inversely related to loading and the number of years that the wetland received anthropogenic nutrient loading. This means that a good contact zone between anoxic and oxic conditions stimulates the nitrate removal process, but also that the nitrate removal performance of older wetlands decreases with the years. In connected wetlands, low water velocity and retention increase the contact zone. River water can be drained into ponds or marshes in a controlled way by regulation means, like pumps, sluices or dams. Craig and colleagues (2008) found that low velocity environments and increasing hydraulic retention allow greater contact between the water and the benthos and can so improve N removal. Grande-Mare, a pool of Marnier Vernier is connected to the Seine by a 5 km long canal, St-Aubin. Furthermore, in Marais du Hode and Grande Vasière Nord, several grasslands are connected with the river Seine by a network of ditches and controlled by draining regulating systems (sluice, opening in dam). Marais de la Risle has a number of disconnected wetlands, like pools and ponds. Small streams (1st to 3rd order) with considerable loads during low or moderate flows, could offer opportunities for N removal (Craig et al., 2008). In the deep and fast flowing river Rhine, a very low N retention was found, which could be explained by a very low contact-time between river nitrate and sediment (Venterink et al., 2003). On the contrary, Montreuil and colleagues (2010) found that the reduction in nitrate fluxes was greater in catchments of high stream orders and that the proportion of fluxes depleted during transfer with a increasing distance. In the Scorff River basin (FR), a 6th order river, Montreuil and colleagues (2010) cited a maximum of 91% reduction (= 16,79 kg N ha-1 y-1) at low water with an increasing residence time. The largest part of the retention processes occurs in the downstream sectors of the drainage network, with stream order ≥ 5 (Billen et al., 2007). Fisher & Acreman (2004) further mentioned that the oxygen concentration of sediments in wetlands can be determined by vegetation, more particularly in the root zone. Emergent macrophytes in low marsh zones, that were permanently flooded, favored the organic matter supply for denitrification and VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 38 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS they stimulate water movement into the soil, which facilitates the diffusion of nitrates to the anoxic zones for denitrification (Hernandez & Mitsch, 2007). On the other hand, submerged vegetation in tidal channels can alter oxygen concentrations (Arrigoni et al., 2008). According to the results of the studies with the 8 rivers and wetlands, seasonal differences and temperature were mentioned as important factors for denitrification rates. Denitrification activity slows down significantly below 4° C (Sirivedhin & Gray, 2006). Moreover, during autumn an increase of soluble nutrient loading has been cited in many studies due to a lower plant uptake and so stimulates flushing and diluting of nutrient outputs. Contrarily, vegetation decay can increase microbial activity, which could promote denitrification and mineralization of nutrients in the wetlands (Fisher & Acreman, 2004). Yu and colleagues (2006) refer to the importance of the temperature in biological reaction rates. Regarding fig.19, Kreiling and colleagues (2010) showed that denitrification/nitrification coupling and plant uptake was of minor importance for nitrate removal, which is confirmed by Venterink et al. 2003, according to fig.21. However, in this study low marsh (Nuphar advena) showed better nitrate removal results than high marsh (Zizania aquatica, Typha sp., Phragmites australis) (Patrick Center for Environmental Reasearch et al., 1998). Marais du Hode, Grande Vasière Nord and Marais Vernier are provided with reedbeds (Phragmites australis) and subhalophilus grasslands. Chabrerie and colleagues (2001) found in Marais du Hode, three different zones, namely grasslands, mesophilous grassland and reedbeds. They mentioned that denitrification rate was highest in the second zone. In the first zone, low denitrification rates were explained by the soil properties, low organic C content, due to tillage and low availability of oxygen. Sabater and colleagues (2003) did not find clear N removal patterns between herbaceous and forested zones nor significant seasonal differences in 14 riparian sites throughout Europe. The presence of NH4+ for the transformation to NO3- is another condition. Brion and colleagues (2000) examined nitrate and ammonium flux in the Seine from Paris to the estuary (Caudebec) for the period July and September 1995 and July 1996 and found increasing nitrate and decreasing ammonium concentrations to the estuary. Gran and Pitkänen (1999) found that the zones in the estuary with a higher redox potential and lower ammonium fluxes, showed an important denitrification performance. Anammox (anaerobic ammonium oxidation) could be a plausible reason for this phenomenon. KoopJakobsen & Giblin (2009) found that the highest relative importance of anammox was found in sediments of freshwater marshes, namely only 3%, while it was less important in saline marsh sediments. They further found that the decrease of anammox was due denitrification. However, aerated environments showed the best denitrification performance, according to MaltaisLandry et al. (2009) and Curie et al. (2009). Floodplains and mudflats showed great nitrate retention close to the river and when the surface area was large enough (Noe and Hupp, 2009). Racchetti and colleagues (2010) refer to Verhoeven et al. (2006), who stated that wetlands have to account for at least 10% of the watershed area in order to contribute significantly to water quality improvement. Maltby and colleagues (2005) mentioned that when pore spaces within soil are filled with water, the diffusion of oxygen is greatly reduced, which gives a soil with low oxygen content and low redox potential. Venterink et al. (2003) found that oxygen poor flooded sediments showed the best denitrification rate. In Marais du Hode, an artificial meander has been created to reduce the water velocity and to improve the contact between the river water and the sediment (fig.7 (5)). The formation of N2O as greenhouse gas is related to the nitrate conversion process. In the Great Ouse river (UK), the highest N2O concentrations were found at the upper slope, further away from the river and so related to the soil moisture of the water-filled pore space (WFPS). With soil volumetric water contents below 35%, gaseous N was emitted as 50% N2O and 50% N2 at the lower, intermediate and upper zones, while for soil water contents above 35%, the near-stream zone showed 20% N2O, and 80% N2, the intermediate 10% N2O and 90% N2 and the upper zone 40% N2O and 60% N2 (Machefert & Dise, 2004). Furthermore, Hernandez and Mitsch (2007) concluded that N2O production was higher in high marsh and edge zones than in low marsh and increased in cold seasons (autumn and winter) in a created riverine wetland (Olentangy River). Permanently flooded low marsh zones had lower N2O ratios of emissions than less frequently flooded high marsh and edge zones. This could be explained by more aerobic conditions in high marsh. However, Garnier and colleagues (2006) VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 39 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS concluded that the N2O emissions in the freshwater Seine estuary was less than 0,1% of both denitrification and nitrification fluxes. Concerning the methodology of this study the NANI model and the performance ranges denitrification have been used. The NANI model (Howarth et al., 1996; Billen et al., 2009) for Olentangy/Mississippi (Mitsch et al., 2005) and Finger Lakes (James (2010)), showed a much higher retention efficiency than measured or calculated. These differences can be explained by the simplicity of the model and probably by the difference between the N input loads measured and the total anthropological N sources. Furthermore, I used the denitrification performance ranges by Janssen et al., 2005 to interpret the nitrate removal performance in the wetlands. I did not find another reference point in order to compare these ranges. Most of the rivers with wetlands that have been analyzed in this study were only examined for short periods by the authors. Consequently, it is difficult to interpret the results over a long time. Furthermore, estimations were made by models. The wetlands of the Seine estuary (Marais du Hode, Grande Vasière Nord, Grande-Mare, Marais Vernier, Marais de la Risle) are mainly characterized by tidal flooding with seawater, brackish and freshwater over grasslands, reedbeds and mudflats and a connection with a backwater. According to the results of my study with the list of different types of wetlands (table 7), the foregoing wetlands can be indicated as Ib2 (artificial-created), IIa1 (grasslands), IIIa1 (floodplain-depression), IVa5’ (hydrology-drainage), IVa9’ (hydrology-tidal inflow) and Vb (biogeochemical-flooding). Table 9: Comparison wetland characteristics Seine estuary and the opportunities for implementation Wetland characteristics 1. Connected wetlands Created Velocity Vegetation 2. Floodplains Surface area Distance 3. Estuary Redox ‘What is’ ‘Could be’ Location in Seine estuary ditches, sluice, openings in dam valve drainage shallow, young and well-mixed subhalophilous grasslands reedbeds; peat low marsh; floating macrophytes; woodland Marais du Hode Grande Vasière Nord Marais Vernier Marais du Hode Grande Vasière Nord Marais du Hode Grande Vasière Nord Marais Vernier mudflats; artificial meander close to riverbank controlled pumping slope; low marsh tidal flooding; isolated ponds and pools turbulence stimulation; vegetation Marais du Hode Grande Vasière Nord Marais de la Risle Marais du Hode Grande Vasière Nord Marais de la Risle Marais Vernier I compare the current situation (strengths and weaknesses) and the potential future risks and opportunities for the above mentioned wetlands with the aid of table 9. Strengths: Marais du Hode, Grande Vasière Nord and Marais Vernier are all characterized by wetlands that are connected with the Seine River by ditches or creeks. The draining is regulated by a sluice or openings VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 40 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS in a dam. This enables to control the water velocity and retention into the wetlands. The river Seine is in Marais Vernier connected to Grand-Mare, a pool for delivering water in dry periods. This is comparable with the connected wetlands (Mitsch and colleagues (2005), Racchetti et al., 2010, Yu et al., 2006). In Marais du Hode, the highest denitrification rate is found in dry subhalophilous grasslands and the lowest rate in reedbeds (Alard et al. 2002). Marais du Hode is further provided with mudflats and an artificial meander. In 2002, a surface of 47 ha of Marais de la Risle valley was reconnected within the Seine estuary, as well as the grasslands of Marais du Hode in 2004 and 2005. The cost was respectively € 6800 and € 99000 (Bessinton, 2007). In the framework of a cost-benefit approach, it is important to have a reference fee for future developments. The French water management system encouraged public-private partnerships by setting up contracts. The role of the Seine-Normandy Water Agency (AESN, Agence de l’Eau Seine-Normandie) at the river basin level is to ensure a balance between the water quality and the civil needs. The AESN has encouraged efforts to restore wetlands by awarding prizes. They invested 1.6 million Euro in wetlands in 2000 (AESN, 2002). Weaknesses: Marais de la Risle is characterized by a number of isolated wetlands. In this study, isolated wetlands showed a lesser nitrate removal performance than connected wetlands. Marais du Hode and Marais Vernier are provided with reedbeds. Higher denitrification was found in grasslands than in reedbeds (Chabrerie et al., 2001; Alard et al., 2002). Unfortunately, no comparable data of nitrate removal for these zones of the Seine estuary, in relation to the effects of floodplains or mudflats, has been found in the literature. Opportunities: The Seine is fed by the Oise, Marne and Eure rivers. These smaller streams with a lower stream order (< 7th order river) could be examined for implementing a wetland strategy, according to Craig and colleagues (2008). This has already been done with valley bottom wetlands in agricultural landscapes, located in headwater catchments (1st to 3rd order streams) (Merot et al., 2006). A combination of grasslands (wet meadows) as wider buffer zones (10 - 50 m) and forest communities as buffer strips (5 – 10 m) on stream banks can be useful (Mander et al., 2005). Nuphar advena, low vegetation marsh, gave favorable denitrification results in a tidal freshwater estuarine of the Delaware River (Patrick Center for Environmental Reasearch et al., 1998). Craig and colleagues (2008) mentioned that low velocity environments and increasing hydraulic retention can improve nitrate removal processes. They also refer to the creation of denitrification hotspots by providing energy for denitrifying energy, stimulation anoxia and slowing water velocities for improving the contact time with denitrifiers. This could be tested in the creeks or ditches. Societal importance indicates that unvegetated sediment wetlands are found to have the highest economical values ($ 374 ha-1 y-1), because of their storm protection, recreation and commercial impact. Only freshwater marshes, present in riparian floodplains provide fresh drinking, watering or irrigation water (Malty et al., 2005). The PEEW approach of Merot and colleagues (2006), already mentioned in point 1.5.2 could help to determine ‘efficient’ wetlands with the goal to focus investments on ‘efficient wetlands’. For wetland conservation decisions, cost-benefit analysis (CBA) based on economic efficiency criteria offers a method for decision makers. This requests improved information that can be obtained from integrated ecological-economic models (Turner et al., 2000). Threats: Due to the complexity and the uncertainty of the relationship between the different factors that could influence denitrification, precaution has to be taken in account when implementing great changes. Furthermore, interactions that are made upstream could have consequences lower in the river estuary. Lack of a market for wetland functions could limit the incentives for stakeholders to improve wetland quality. Maltby and colleagues (2005) concluded that unvegetated sediments and wooded wetlands VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 41 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS showed the highest value per unit area. Dependent from the perspective of the different stakeholders, opposite visions could lead to a standby situation. Chabrerie and colleagues (2001) found in Marais du Hode a lower denitrification rate in grasslands due to tillage. Contrary, nitrates could be removed by harvesting the vegetation biomass. 5.Suggestions Most of the research to denitrification effects in the Seine River is limited to the region between Poses and the estuary at Caudebec. In order to determine the nitrate removal performance of the existing wetlands from Caudebec to Honfleur, multiple studies for each kind of wetland should be set-up. Furthermore, a number of studies should be focused on lower order rivers like the Marne, Oise and Eure in order to examine the impact of the nitrate removal effects downstream in the estuary of the Seine River. The collected data can be used to estimate or extrapolate nitrate removal by a model, preferably the Riverstrahler model. Besides the denitrification performance range according to Janssen et al., 2005, another reference framework would be useful to compare nitrate removal results. This could be discussed in a legal context. A better understanding of the relation between the different factors that influence nitrification and denitrification, as well as the importance of the interaction between the processes is the next challenge. This insight in the interaction could help to influence a number of parameters. One example is to study the influence of harvesting vegetation in relation to the removal of the carbon source for denitrification. Due to the importance of the greenhouse gas effect of N2O, the influence of the denitrification or dissimilatory nitrate reduction in the production of N2O in the estuary of the Seine is not clear (Garnier et al., 2006). Further research of N2O production in the estuarine wetlands would be useful in order to estimate the effects. 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VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 46 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS Annex A: Description 8 rivers and their wetlands VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 47 van 50 WETLAND ECOSYSTEMS FOR DENITRIFICATION PROCESSES IN RIVERS VMAB2010nj-M105-DENITRIFICATIE-PWADeconinck-20110526.doc Pagina 48 van 50 faculteit Natuurwetenschappen/School of Science Open Universiteit Nederland Postbus 2960 6401 DL Heerlen, NL tel. +31 45 576 2877 [email protected] www.ou.nl/nw www.Incompany-milieuadvies.nl
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